1. Introduction {#sec1-ijms-20-03660}
===============

The International Energy Agency defines a biorefinery as "the sustainable processing of biomass into a spectrum of marketable products and energy", which is the most comprehensive and commonly accepted definition \[[@B1-ijms-20-03660]\]. Because inexpensive petroleum-derived chemicals are already mass produced, the production of bio-based chemicals has been limited to those with structures that are too complex for the fine-chemicals market to justify their expensive production costs \[[@B2-ijms-20-03660]\]. However, nonrenewable resources are limited despite population growth. Accordingly, the increased consumer demand for environmentally friendly products has become a driving force for the use of biorefineries \[[@B2-ijms-20-03660]\]. Emerging economies (e.g., the countries of Brazil, Russia, India and China (BRIC)) require increasing amounts of oil and other fossil-based products, in addition to the security of chemical and energy supplies for isolated regions such as islands \[[@B2-ijms-20-03660]\]. Carboxylic acids have attracted considerable attention among the raw materials for bioderived chemicals. The US Department of Energy (DOE) has selected twelve chemicals from more than three hundred biomass-derived chemicals, based on cooperative research with industry and academia, to be developed using biorefinery production methods \[[@B3-ijms-20-03660]\]. More than half of the twelve selected chemicals are carboxylic acids. Carboxylic acids obtained by the oxidation of monosaccharides and oligosaccharides are referred to as sugar acids \[[@B4-ijms-20-03660],[@B5-ijms-20-03660],[@B6-ijms-20-03660]\]. The oxidation of aldose (aldohexose when the carbon number is six) at its aldehyde group to form a carboxyl group produces aldonic acid (aldohexonic acid), whereas the corresponding oxidation at its terminal hydroxy group results in a different monocarboxylic acid, (aldo)uronic acid ((aldo)hexuronic acid). Aldaric acid (hexaric acid) is a dicarboxylic acid produced by oxidizing both groups ([Figure 1](#ijms-20-03660-f001){ref-type="fig"}). Because aldaric acids have been studied for numerous types of applications, improved methods for their production are urgently needed. [d]{.smallcaps}-Glucaric acid, the aldaric acid of [d]{.smallcaps}-glucose or [l]{.smallcaps}-gulose, was selected by the DOE as one of the twelve chemicals \[[@B3-ijms-20-03660]\]. Hence, this article summarizes biorefinery methods relating to aldaric acids with six carbon atoms (hexaric acids; [Figure 1](#ijms-20-03660-f001){ref-type="fig"}), including [d]{.smallcaps}-glucaric acid.

2. Classification of Aldohexoses and Hexaric Acids {#sec2-ijms-20-03660}
==================================================

Aldohexoses have four stereocenters, resulting in sixteen configurational isomers ([Figure 1](#ijms-20-03660-f001){ref-type="fig"}). Relative-configuration classification divides these stereoisomers into eight groups with the following common names: altrose, allose, idose, galactose, glucose, gulose, talose, and mannose. In contrast, hexaric acids have the same functional group at both ends of their structure; thus, the hexaric acids of altrose and talose and those of glucose and gulose are the same compounds. Moreover, the hexaric acids of allose and galactose are *meso*-compounds, because of their symmetry. In short, relative-configuration classification divides hexaric acids into altraric acid, allaric acid, idaric acid, galactaric acid, glucaric acid, and mannaric acid; because allaric acid and galactaric acid are *meso*-compounds, the total number of configurational isomers is ten ([Figure 2](#ijms-20-03660-f002){ref-type="fig"}) \[[@B7-ijms-20-03660]\]. Because hexaric acids have four stereochemically diverse secondary hydroxy groups and two carboxyl groups, their applications as platform chemicals have been studied as described below. Of the hexaric acids, [d]{.smallcaps}-glucaric, *meso*-galactaric, and [d]{.smallcaps}-mannaric acids have been the most studied as starting compounds for biorefineries, in part because the raw materials for these hexaric acids are abundant. Therefore, several compounds, such as [l]{.smallcaps}-mannaric acid \[[@B8-ijms-20-03660],[@B9-ijms-20-03660]\] and [d]{.smallcaps}-idaric acid, \[[@B10-ijms-20-03660],[@B11-ijms-20-03660]\] which are used as the starting compounds for human immunodeficiency virus (HIV) protease inhibitors, are regarded as exceptions in this report. The focus of this article is on studies investigating the applications and production methods for [d]{.smallcaps}-glucaric acid, *meso*-galactaric acid, and [d]{.smallcaps}-mannaric acid.

3. Applications of Hexaric Acids {#sec3-ijms-20-03660}
================================

Because hexaric acids have four stereochemically diverse secondary hydroxy groups and two carboxyl groups, they have been studied since the 1950s as platform chemicals for producing chelating agents and corrosion inhibitors \[[@B10-ijms-20-03660],[@B11-ijms-20-03660],[@B12-ijms-20-03660],[@B13-ijms-20-03660],[@B14-ijms-20-03660],[@B15-ijms-20-03660],[@B16-ijms-20-03660],[@B17-ijms-20-03660],[@B18-ijms-20-03660],[@B19-ijms-20-03660],[@B20-ijms-20-03660],[@B21-ijms-20-03660]\], precursors for polyamides \[[@B22-ijms-20-03660],[@B23-ijms-20-03660],[@B24-ijms-20-03660],[@B25-ijms-20-03660],[@B26-ijms-20-03660],[@B27-ijms-20-03660],[@B28-ijms-20-03660],[@B29-ijms-20-03660],[@B30-ijms-20-03660],[@B31-ijms-20-03660],[@B32-ijms-20-03660],[@B33-ijms-20-03660],[@B34-ijms-20-03660],[@B35-ijms-20-03660],[@B36-ijms-20-03660]\], polyesters \[[@B37-ijms-20-03660],[@B38-ijms-20-03660],[@B39-ijms-20-03660],[@B40-ijms-20-03660],[@B41-ijms-20-03660]\], polyanhydrides \[[@B42-ijms-20-03660]\], polycations \[[@B43-ijms-20-03660]\], coordination polymers including metal--organic frameworks \[[@B44-ijms-20-03660],[@B45-ijms-20-03660],[@B46-ijms-20-03660],[@B47-ijms-20-03660],[@B48-ijms-20-03660]\], pendant polymers \[[@B49-ijms-20-03660]\], macromolecules \[[@B50-ijms-20-03660],[@B51-ijms-20-03660]\], cross-linkers in hydrogels \[[@B52-ijms-20-03660]\], medicines \[[@B8-ijms-20-03660],[@B9-ijms-20-03660],[@B10-ijms-20-03660],[@B11-ijms-20-03660],[@B49-ijms-20-03660],[@B51-ijms-20-03660],[@B53-ijms-20-03660]\], and other compounds including platform chemicals, like adipic acid and furan dicarboxylic acid \[[@B54-ijms-20-03660],[@B55-ijms-20-03660],[@B56-ijms-20-03660],[@B57-ijms-20-03660],[@B58-ijms-20-03660],[@B59-ijms-20-03660],[@B60-ijms-20-03660],[@B61-ijms-20-03660],[@B62-ijms-20-03660]\].

3.1. Monomers {#sec3dot1-ijms-20-03660}
-------------

The use of hexaric acids as monomers produces polycondensates that are nontoxic, biodegradable, and more hydrophilic than those derived from petrochemicals \[[@B36-ijms-20-03660]\]. Research on polyamide syntheses derived from hexaric acids started in the 1950s \[[@B22-ijms-20-03660]\] and continues, particularly in the laboratory of Kiely. This group has synthesized polyamides from three monomers, [d]{.smallcaps}-glucaric acid, *meso*-galactaric acid, and [d]{.smallcaps}-mannaric acid, to investigate the influence of stereochemistry on the physical properties of polymers \[[@B31-ijms-20-03660]\]. The polyamides were synthesized in methanol from either a hexaric acid diester or a methylated hexaric acid lactone, which were synthesized by a condensation reaction of a hexaric acid and methanol, with even-number-chain-length alkylenediamines having two to twelve carbon atoms as the monomers ([Figure 3](#ijms-20-03660-f003){ref-type="fig"}A--C).

A comparison between poly(alkylene galactaramide)s synthesized from *meso*-galactaric acid and poly(alkylene [d]{.smallcaps}-glucaramide)s from [d]{.smallcaps}-glucaric acid revealed that the melting points of poly(alkylene galactaramide)s were all higher than those of poly(alkylene [d]{.smallcaps}-glucaramide)s when the length of the alkylenediamine used was the same. Furthermore, it was found that, while the poly(alkylene [d]{.smallcaps}-glucaramide)s composed of alkylenediamines with two and four carbon atoms were water soluble, only the poly(alkylene galactaramide) produced from ethylenediamine was water soluble ([Table 1](#ijms-20-03660-t001){ref-type="table"}). *meso*-Galactaric acid has a highly symmetric structure in which the carbon chain extends in a zigzag, bearing alternating hydroxy groups as confirmed by crystallography \[[@B63-ijms-20-03660]\]. Through these hydroxy groups, *meso*-galactaric acids can interact via intermolecular hydrogen bonding \[[@B63-ijms-20-03660]\]. In the case of [d]{.smallcaps}-glucaric acid, which is asymmetric, the 1,3-steric repulsions between the hydroxy groups at the C2 and C4 positions result in a bent molecular structure rather than an extended-zigzag structure \[[@B64-ijms-20-03660]\]. Kiely et al. reported that the stereochemical differences between hexaric acids were responsible for the differences in the physical properties between the polyamides \[[@B31-ijms-20-03660]\]. Because the galactaric acid moiety is extended, poly(alkylene galactaramide)s readily become linear. The adoption of a linear structure could increase both the hydrogen bonding between the galactaric acid moieties and the van der Waals forces derived from alignment of the alkylenediamine moieties. In contrast, poly(alkylene [d]{.smallcaps}-glucaramide)s tend to form a bent structure because the [d]{.smallcaps}-glucaric acid moiety is bent, preventing attractive forces from developing between the polymers. The authors concluded that the differences in interchain attraction underlay the differences in melting points and water solubility between these compounds. Poly(alkylene [d]{.smallcaps}-mannaramide)s have head-to-tail type stereoregularity because of the hydroxy groups bound symmetrically along the carbon chain of [d]{.smallcaps}-mannaric acid moiety. Because the 1,3-steric repulsions are not present in [d]{.smallcaps}-mannaric acid, the authors assumed that the acid tends to form extended-zigzag structures, resulting in melting points and water solubility similar to those of poly(alkylene galactaramide)s. Polymer syntheses that take advantage of physical property differences derived from the different stereochemical properties of aldaric acids have been reported. For example, a polymer derived from [d]{.smallcaps}-glucaric acid has an amorphous nature because the attractive interactions between the polymers are weak, which is advantageous for synthesizing materials that have good film-forming and adhesive properties \[[@B30-ijms-20-03660]\]. The nature of *meso*-galactaric acid-derived polymers, which tend to form linear structures, was used to improve the thermophysical properties of polyanhydrides \[[@B42-ijms-20-03660]\]. Henkensmeier et al. reported that they were able to change the physical properties of a polymer by combining [d]{.smallcaps}-glucaric acid and *meso*-galactaric acid; their method allowed for precisely adjusting the glass transition temperatures of silicone surfactants \[[@B34-ijms-20-03660]\].

3.2. Application of Hexaric Acid Polymers: An Example {#sec3dot2-ijms-20-03660}
-----------------------------------------------------

Applications of synthetic polymers, including as drug delivery carriers, have been reported. Liu and Reineke et al. reported polyamides composed of hexaric acid moieties and secondary amines as the repeating units that could replace viruses as nucleic acid medicine carriers ([Figure 3](#ijms-20-03660-f003){ref-type="fig"}E--G) \[[@B35-ijms-20-03660]\]. Conventionally, polyethylene imines (PEIs) and chitosan have been studied as substitutes for viruses. The PEIs used in this study showed high gene-transport efficiencies in almost all cell lines used in the study, and chitosan displayed no cytotoxicity. However, each polymer also had a drawback: longer PEIs showed strong cytotoxicities, and chitosan had an inferior transport efficiency. The synthesized polyamides in this study had an abundance of secondary amines and hydroxy groups, and showed both good biocompatibilities and high transport efficiencies. Similar to PEI and chitosan, the synthesized polyamides formed viral-like electrostatic complexes with plasmid DNA (pDNA), termed polyplexes, which were taken up through the endocytotic pathway and dissociated within the endosome. The stereochemistry between the hexaric acid moiety and the number of amines in the repeating units greatly changed the binding affinity to pDNA, its volume in the binding complex, and its transportation efficiency into cells. The polymers derived from *meso*-galactaric acid showed higher transport efficiencies than those derived from [d]{.smallcaps}-glucaric acid or [d]{.smallcaps}-mannaric acid.

3.3. Macromolecules {#sec3dot3-ijms-20-03660}
-------------------

Macromolecules derived from hexaric acids have also been studied for use in drug delivery systems \[[@B50-ijms-20-03660],[@B51-ijms-20-03660]\]. Gu et al. synthesized amphiphilic macromolecules by bonding the hydroxy groups and a terminal carboxylic group of the hexaric acids, commencing with *meso*-galactaric acid, to alkyl chains and poly(ethylene glycol)s, respectively ([Figure 4](#ijms-20-03660-f004){ref-type="fig"}) \[[@B51-ijms-20-03660]\].

The resulting amphiphilic macromolecules, which showed low critical micelle concentrations, were studied for use as drug carriers for hydrophobic anticancer agents and gene therapy agents. Furthermore, these amphiphilic macromolecules were found to treat atherosclerosis by preventing macrophage intake of oxidized low-density lipoproteins.

3.4. Chelating Agents, Coordination Polymers and Metal--Organic Frameworks {#sec3dot4-ijms-20-03660}
--------------------------------------------------------------------------

Complexation of the carboxyl and hydroxy groups of hexaric acids with metals has been used in applied research. For example, such products have been investigated for use as agents to remove metals from polluted environments and incinerator plants, as corrosion inhibitors, and as Ca-sequestering agents, several of which have been commercialized \[[@B6-ijms-20-03660]\]. The chelation ability of hexaric acids was exploited for the synthesis of coordination polymers and metal--organic frameworks (MOFs). Abrahams et al. synthesized coordination polymers derived from hexaric acids and metals. For example, they used [d]{.smallcaps}-glucaric acid and Zn to form a coordination polymer with two types of isolated, parallel channels, one of which was hydrophilic and the other hydrophobic \[[@B44-ijms-20-03660]\]. The hydroxy groups of [d]{.smallcaps}-glucaric acid were exposed in the hydrophilic channels, while the hydrophobic channels had C-H bonds along the channel wall. Water molecules were in both channels, especially in the hydrophilic channel where they were hydrogen bonded. The water molecules in the hydrophobic channels were easily exchanged for azobenzene, I~2~, elemental sulfur, hydrocarbons, CCl~4~ and CI~4~. This material was expected to be applicable to the simultaneous introduction of two different species into the different channels.

Wong et al. synthesized a porous structure from *meso*-galactaric acid and terbium that could detect guest molecules ([Figure 5](#ijms-20-03660-f005){ref-type="fig"}) \[[@B46-ijms-20-03660]\]. This structure formed a two-dimensional networked complex that created vertical one-dimensional channels when stacked in layers. Crystallography of this MOF revealed that the layers were connected through hydrogen bonding via water molecules; however, heating removed the water molecules without destroying the structure. In aqueous solutions, this MOF could remove I^−^, Br^−^, Cl^−^, F^−^, CN^−^, and CO~3~^2−^ and small amounts of SO~4~^2−^ and PO~4~^3−^. These anions were assumed to be removed by forming hydrogen bonds with the *meso*-galactaric acid moieties. The fluorescent properties of terbium, a lanthanide element, were successfully utilized to monitor the intake of anions into the MOF. Desorption of the anions from the MOF was confirmed by placing the absorbed complexes in pure water.

3.5. Other Platform Chemicals {#sec3dot5-ijms-20-03660}
-----------------------------

Hexaric acids have also been studied for use as the starting materials for other platform chemicals \[[@B54-ijms-20-03660],[@B55-ijms-20-03660],[@B56-ijms-20-03660],[@B57-ijms-20-03660],[@B58-ijms-20-03660],[@B59-ijms-20-03660],[@B60-ijms-20-03660],[@B61-ijms-20-03660],[@B62-ijms-20-03660]\], including adipic acid \[[@B59-ijms-20-03660],[@B60-ijms-20-03660],[@B61-ijms-20-03660],[@B62-ijms-20-03660]\], furan dicarboxylic acid (an alternative to terephthalic acid) \[[@B57-ijms-20-03660]\], and pyrrole \[[@B55-ijms-20-03660]\].

Li et al. reported the highly efficient conversion of *meso*-galactaric acid, via muconic acid, into adipic acid through an oxorhenium-complex-catalyzed deoxydehydration (DODH) reaction and following a Pt/C-catalyzed transfer hydrogenation \[[@B59-ijms-20-03660]\]. Ionic liquid was integrated as a reaction medium into this DODH reaction in another paper \[[@B61-ijms-20-03660]\]. The use of ionic liquid enabled an efficient separation of muconic acid by simple decantation. The recovered ionic liquid, which contained an expensive Re catalyst, was used up to four times without much of a decrease in yields. [d]{.smallcaps}-Glucaric acid can also be a starting compound for adipic acid. Recently, a catalyst system that provided adipate esters from [d]{.smallcaps}-glucaric acid in a single operation was reported, in which hydrogen was used as a terminal reductant \[[@B62-ijms-20-03660]\].

According to the report by Thiyagarajan et al. \[[@B58-ijms-20-03660]\], although the first report of furan-2,5-dicarboxylic acid from *meso*-galactaric acid was published in 1876, little attention has been paid to this route because isolated yields were moderate and *meso*-galactaric acid was not readily available. In terms of the availability of hexaric acids including *meso*-galactaric acid, it will be improved by the research mentioned in following sections. As for synthesis of furan-2,5-dicarboxylic acid from *meso*-galactaric acid, some works were reported. For example, one-step synthesis of dibutyl furandicarboxylates from *meso*-galactaric acid and 1-butanol, in the presence of sulfuric acid, was reported \[[@B57-ijms-20-03660]\]. In this paper, the diester of furan-2,5-dicarboxylic acid was synthesized because it can be distilled or recrystallized by the use of existing solvents and can be polymerized directly using diols.

4. Hexaric Acid Production Using Inorganic Catalysts {#sec4-ijms-20-03660}
====================================================

The earliest attempts of hexaric acid preparation were reported in the late 1800s (oxidation of carbohydrates with HNO~3~, of which the reaction origin could be traced back to lactose oxidation by Liebig and is still used today \[[@B65-ijms-20-03660],[@B66-ijms-20-03660]\]). However, the yields using this method are limited to approximately 40% because of side reactions. Moreover, this method results in the excessive production of nitrogen oxide gas because of the rapid and highly exothermic nature of the oxidation reaction. These drawbacks have prevented the mass production of hexaric acids using this method \[[@B67-ijms-20-03660],[@B68-ijms-20-03660]\]. Kiely's group have improved [d]{.smallcaps}-glucaric and [d]{.smallcaps}-mannaric acid production via nitric acid oxidation to solve these problems, enabling industrial mass production of these hexaric acids ([Figure 6](#ijms-20-03660-f006){ref-type="fig"}) \[[@B67-ijms-20-03660],[@B69-ijms-20-03660]\].

In their studies, the amount, rate, and temperature of the [d]{.smallcaps}-glucose and [d]{.smallcaps}-mannose additions were controlled by a computer to prevent rapid temperature increases caused by the oxidation of the saccharides by nitric acid and the resulting generation of large amounts of nitrogen dioxide and other gases. Relatively low reaction temperatures (25--40 °C) were accomplished. Furthermore, a positive oxygen pressure on the reaction system generated nitric dioxide from nitric monoxide, and the dissolution of the dioxide into water reproduced nitric acid, enabling reproduction and recycling of the nitric acid ([Figure 7](#ijms-20-03660-f007){ref-type="fig"}). The removal of nitric acid from the reaction mixture was also improved.

To date, nitric acid has been removed by evaporation by heating under reduced pressure. However, complete removal is difficult because nitric acid and water form a negative azeotrope. Moreover, the relatively severe conditions used in this method allow for further oxidation reactions to occur in an uncontrolled manner. Therefore, nitric acid removal by nanofiltration and diffusion dialysis was also investigated in Kiely's study. Selective nitric acid removal was achieved by both methods. However, because the addition of a large amount of water and pH adjustment was necessary, nanofiltration was not practical. Diffusion dialysis required neither the addition of water, the adjustment of pH, nor large amounts of energy for nitric acid removal. Further recycling of the removed nitric acid was easy. However, a problem remains in that the removed nitric acid solution contains a large amount of the products. Moreover, the yield of the reaction was not improved, remaining at 45% for [d]{.smallcaps}-glucaric acid. In addition to nitric acid oxidation, the production of hexaric acids by oxidation with bromine and manganese(III) sulfate has been reported \[[@B70-ijms-20-03660],[@B71-ijms-20-03660],[@B72-ijms-20-03660],[@B73-ijms-20-03660]\]. Recently, ozonic oxidation has been proposed to solve several of the problems of conventional conversions, including their high environmental burden, byproduct generation, slow reaction rates, and high costs \[[@B74-ijms-20-03660],[@B75-ijms-20-03660]\].

In addition to the use of strong oxidants, catalytic oxidation with transition metals has been explored. The Pt-catalyzed production of a hexaric acid, [d]{.smallcaps}-mannaric acid, was reported in 1938 \[[@B76-ijms-20-03660]\]. Production of hexaric acids catalyzed by metals has been of industrial interest since the 1940s \[[@B77-ijms-20-03660],[@B78-ijms-20-03660],[@B79-ijms-20-03660],[@B80-ijms-20-03660],[@B81-ijms-20-03660]\]. Following these antecedent works, several studies have been reported \[[@B68-ijms-20-03660],[@B82-ijms-20-03660],[@B83-ijms-20-03660],[@B84-ijms-20-03660],[@B85-ijms-20-03660],[@B86-ijms-20-03660],[@B87-ijms-20-03660],[@B88-ijms-20-03660],[@B89-ijms-20-03660],[@B90-ijms-20-03660],[@B91-ijms-20-03660],[@B92-ijms-20-03660],[@B93-ijms-20-03660],[@B94-ijms-20-03660],[@B95-ijms-20-03660],[@B96-ijms-20-03660],[@B97-ijms-20-03660],[@B98-ijms-20-03660]\]. Although Pt \[[@B76-ijms-20-03660],[@B82-ijms-20-03660],[@B83-ijms-20-03660],[@B84-ijms-20-03660],[@B91-ijms-20-03660],[@B92-ijms-20-03660],[@B97-ijms-20-03660]\] and Au \[[@B68-ijms-20-03660],[@B84-ijms-20-03660],[@B85-ijms-20-03660],[@B86-ijms-20-03660],[@B89-ijms-20-03660],[@B94-ijms-20-03660],[@B95-ijms-20-03660],[@B96-ijms-20-03660]\] have been used as catalysts frequently, other elements like Ti \[[@B87-ijms-20-03660],[@B88-ijms-20-03660]\], Mn \[[@B90-ijms-20-03660]\], Fe \[[@B98-ijms-20-03660]\], Mo \[[@B93-ijms-20-03660]\], and Pd \[[@B91-ijms-20-03660],[@B99-ijms-20-03660]\] can also be incorporated in catalyst composites. Aldohexoses \[[@B84-ijms-20-03660],[@B85-ijms-20-03660],[@B86-ijms-20-03660],[@B87-ijms-20-03660],[@B88-ijms-20-03660],[@B90-ijms-20-03660],[@B91-ijms-20-03660],[@B92-ijms-20-03660],[@B93-ijms-20-03660],[@B94-ijms-20-03660],[@B95-ijms-20-03660],[@B97-ijms-20-03660],[@B98-ijms-20-03660]\], aldohexonic acids \[[@B82-ijms-20-03660],[@B83-ijms-20-03660],[@B84-ijms-20-03660]\], and hexuronic acid \[[@B68-ijms-20-03660],[@B89-ijms-20-03660],[@B96-ijms-20-03660]\], in addition to the corresponding sugar alcohol \[[@B76-ijms-20-03660],[@B85-ijms-20-03660]\], can be starting compounds for the metal-catalyzed production of hexaric acids. In addition to the use of oxidants like H~2~O~2~ and O~2~, electrochemical \[[@B85-ijms-20-03660],[@B90-ijms-20-03660]\] and photochemical \[[@B87-ijms-20-03660],[@B88-ijms-20-03660]\] oxidation of the substrates has been examined. Recently, catalysis under autogenous pH conditions has attracted attention, although alkaline conditions were favored for some traditional efficient catalysis reactions \[[@B95-ijms-20-03660],[@B96-ijms-20-03660],[@B97-ijms-20-03660]\].

Hexaric acid separation from the reaction mixture was based on various methodologies, including precipitation by lowering the pH and the use of ion exchange resins \[[@B67-ijms-20-03660],[@B69-ijms-20-03660],[@B100-ijms-20-03660]\]. For example, [d]{.smallcaps}-glucarate was isolated by pH change (basification of the reaction mixture to pH 9.5, which was followed by acidification to pH 3--4 \[[@B67-ijms-20-03660]\]). *meso*-Galactarate was also separated from the culture supernatant by acid precipitation, where 97% recovery was achieved with 97.5% purity at pH 6.5 \[[@B100-ijms-20-03660]\]. [d]{.smallcaps}-Glucarate and [d]{.smallcaps}-mannarate were separated from each reaction mixture by ion exchange resins following their analyses \[[@B67-ijms-20-03660],[@B69-ijms-20-03660]\].

5. Hexaric Acid Production Using Biocatalysts {#sec5-ijms-20-03660}
=============================================

Hexaric acid production using biocatalysts has also been studied. Biocatalysts, which are regenerable, enable environmentally friendly hexaric acid production. Furthermore, the substrate and reaction specificity of biocatalysts commonly omit the need for strict purification processes to extract the saccharides from the biomass \[[@B6-ijms-20-03660]\].

Although a variety of dehydrogenases and oxidases are known to oxidize hexoses at the C1 position, few reports describe direct enzymatic oxidation of hexoses at the C6 position, such as eukaryotic and bacterial organisms that use uridine diphosphate (UDP)- and guanosine diphosphate (GDP)-bound hexoses as substrates to oxidize the C6 position. The products of these reactions are UDP- and GDP-uronic acids, which serve as the starting compounds for synthesizing polysaccharides, ascorbic acid, and other biomolecules \[[@B6-ijms-20-03660],[@B101-ijms-20-03660],[@B102-ijms-20-03660],[@B103-ijms-20-03660],[@B104-ijms-20-03660],[@B105-ijms-20-03660]\].

Because direct oxidation of hexose at the C6 position is difficult, combinations of biocatalysts have been used to produce hexuronic acids. For instance, Moon et al. reported a method for the production of [d]{.smallcaps}-glucaric acid using genetically modified *Escherichia coli* (*E. coli,* [Figure 8](#ijms-20-03660-f008){ref-type="fig"}) \[[@B106-ijms-20-03660]\]. In recombinant *E.* *coli*, phosphotransferase activity produces [d]{.smallcaps}-glucose-6-phosphate, which is then converted by *myo*-inositol-1-phosphate synthase into *myo*-inositol-1-phosphate. A phosphatase then converts the *myo*-inositol-1-phosphate into *myo*-inositol, which is then converted to [d]{.smallcaps}-glucuronic acid (the hexuronic acid of [d]{.smallcaps}-glucose) by *myo*-inositol oxidase. Moon's report also describes the production of [d]{.smallcaps}-glucaric acid from the oxidation of [d]{.smallcaps}-glucuronic acid by nicotinamide adenine dinucleotide (NAD)-dependent uronate dehydrogenase (UDH). Because the yield of this reaction was low, improvements in the production system have been made \[[@B107-ijms-20-03660],[@B108-ijms-20-03660],[@B109-ijms-20-03660],[@B110-ijms-20-03660],[@B111-ijms-20-03660],[@B112-ijms-20-03660]\]. Galactose oxidase is an uncommon enzyme that can oxidize hexoses at the C6 position. For example, [d]{.smallcaps}-galactose oxidation catalyzed by this enzyme produces [d]{.smallcaps}-galactohexodialdose \[[@B113-ijms-20-03660],[@B114-ijms-20-03660]\]. The enzymatic oxidation of [d]{.smallcaps}-galactohexodialdose cannot produce hexuronic acid or hexaric acid because bicyclic structures are formed; however, the oxidation of dialdose by sodium chlorite is reported to produce [d]{.smallcaps}-galacturonic acid, the hexuronic acid of [d]{.smallcaps}-galactose \[[@B115-ijms-20-03660]\]. Recently, a mutation in this enzyme, changing its structure, was reported to enable glucose oxidation at the C6 position \[[@B107-ijms-20-03660],[@B116-ijms-20-03660],[@B117-ijms-20-03660]\].

As described above, UDP- and GDP-uronic acids have been utilized to synthesize polysaccharides in vivo; thus, hexuronic acids are abundant in nature as the main component of polysaccharides \[[@B6-ijms-20-03660],[@B101-ijms-20-03660],[@B102-ijms-20-03660],[@B103-ijms-20-03660],[@B104-ijms-20-03660],[@B105-ijms-20-03660]\]. For example, [d]{.smallcaps}-galacturonic acid can be derived from pectin \[[@B118-ijms-20-03660],[@B119-ijms-20-03660],[@B120-ijms-20-03660],[@B121-ijms-20-03660]\]. Alginic acid hydrolysis produces [d]{.smallcaps}-mannuronic acid and [l]{.smallcaps}-guluronic acid, the hexuronic acids of [d]{.smallcaps}-mannose and [l]{.smallcaps}-gulose, respectively \[[@B122-ijms-20-03660],[@B123-ijms-20-03660],[@B124-ijms-20-03660],[@B125-ijms-20-03660],[@B126-ijms-20-03660],[@B127-ijms-20-03660]\]. [d]{.smallcaps}-Glucuronic acid can be obtained from hemicellulose \[[@B128-ijms-20-03660],[@B129-ijms-20-03660]\]. [d]{.smallcaps}-Glucuronic acid can also be obtained as a monomer from ulvan \[[@B123-ijms-20-03660],[@B130-ijms-20-03660]\]. Therefore, some studies have used hexuronic acids derived from polysaccharides, which are not used as food, as the starting compounds for hexaric acids.

Mojzita et al. reported the production of *meso*-galactaric acid from [d]{.smallcaps}-galacturonic acid using recombinant microorganisms in which the gene for UDH had been introduced \[[@B100-ijms-20-03660]\]. Many microorganisms that live on putrid plants have enzymatic pathways that catabolize [d]{.smallcaps}-galacturonic acid. Eukaryotic microorganisms use a reduction pathway that starts with the reduction of [d]{.smallcaps}-galacturonic acid into [l]{.smallcaps}-galactonic acid, catalyzed by [d]{.smallcaps}-galacturonic acid reductase, while bacteria use an oxidative pathway that first produces *meso*-galactaric acid in a reaction catalyzed by UDH. In their study, Mojzita et al. eliminated the gene for [d]{.smallcaps}-galacturonic acid reductase in two eukaryotic microorganisms, *Aspergillus niger* (*A. niger*) and *Hypocrea jecorina* (*H. jecorina*), and introduced the gene for UDH, which was derived from the bacterium *Agrobacterium tumefaciens* (*A. tumefaciens*). Neither strain with a single-gene deletion of the reductase grew on medium in which [d]{.smallcaps}-galacturonic acid was the sole carbon source. In contrast, *meso*-galactaric acid production in both strains was confirmed when deletion of the reductase was accompanied by introduction of the dehydrogenase ([Figure 9](#ijms-20-03660-f009){ref-type="fig"}). Because the amount of *meso*-galactaric acid obtained was small in the case of *A. niger*, it is assumed that *A. niger* metabolizes *meso*-galactaric acid derived from [d]{.smallcaps}-galacturonic acid. Although a high yield of *meso*-galactaric acid was achieved with *H. jecorina*, the addition of [d]{.smallcaps}-glucose as an energy source was necessary because [d]{.smallcaps}-galacturonic acid cannot be used as the sole carbon source. Furthermore, the addition of [d]{.smallcaps}-glucose was found to decrease the yield of *meso*-galactaric acid. The fermentation method used to produce *meso*-galactaric acid has been improved \[[@B131-ijms-20-03660],[@B132-ijms-20-03660],[@B133-ijms-20-03660],[@B134-ijms-20-03660],[@B135-ijms-20-03660],[@B136-ijms-20-03660]\].

When chemicals are produced through an oxidative reaction, the electrons obtained from the substrate are usually transferred to electron accepters, such as O~2~. However, an enzymatic anode in a biofuel cell can serve as an electron acceptor. Enzymatic oxidative conversion on the anode can be combined with O~2~ reduction on the cathode to generate electricity. That is, the simultaneous production of chemicals and electricity is possible through oxidative conversion within enzymatic biofuel cells. This method reduces the energy required for producing chemicals and can even generate energy for other uses. The concept of a system that co-produces platform chemicals and electrical energy from biomass by demonstrating the simultaneous production of a hexaric acid and electrical energy using an enzymatic biofuel cell has been proposed \[[@B137-ijms-20-03660],[@B138-ijms-20-03660],[@B139-ijms-20-03660]\]. The electrochemical oxidation of [d]{.smallcaps}-galacturonic acid and the production of *meso*-galactaric acid by a pyrroloquinoline quinone-dependent glucose dehydrogenase (PQQ-GDH)-modified electrode was confirmed \[[@B137-ijms-20-03660],[@B139-ijms-20-03660]\]. The electrode was used as the anode in a biofuel cell with a bilirubin oxidase (BOD) cathode \[[@B139-ijms-20-03660]\] ([Figure 10](#ijms-20-03660-f010){ref-type="fig"}). The cell generated electricity by using [d]{.smallcaps}-galacturonic acid and the hydrolysate of pectic acid as a fuel. This simultaneous production mechanism is applicable to other chemicals. We confirmed the oxidation of [d]{.smallcaps}-glucuronate and [d]{.smallcaps}-mannuronate, both catalyzed by PQQ-GDH, and the oxidation of [l]{.smallcaps}-guluronate, catalyzed by the PQQ domain of pyranose dehydrogenase from *Coprinopsis cinerea* (DH~PDH~) \[[@B138-ijms-20-03660],[@B139-ijms-20-03660]\]. According to NMR measurements, the production of [d]{.smallcaps}-glucarate from the oxidation of [d]{.smallcaps}-glucuronate and [l]{.smallcaps}-guluronate and the production of [d]{.smallcaps}-mannarate from the [d]{.smallcaps}-mannuronate oxidation were confirmed. DH~PDH~ is also suitable for use as an anode catalyst. These combinations of enzymes and chemicals are applicable to simultaneous production systems.

6. Conclusions {#sec6-ijms-20-03660}
==============

Hexaric acids are sugar acids that can be produced from biomass. Due to their stereochemical diversity, chelation abilities, and high solubility in water, numerous applications have been developed. These applications include their use as chelating agents and corrosion inhibitors and as precursors for various polymers, coordination polymers, macromolecules, cross-linkers in hydrogels, and medicines. The conventional production of hexaric acids is conducted by the oxidation of saccharides with nitric acids. To overcome the problems derived from the use of nitric acids, in addition to improving the nitric acid oxidation process, green chemical methods have been developed to produce hexaric acids. Transition metal catalysts and modified microorganisms have been utilized to produce hexaric acids from hexuronic acids under mild conditions. Quite recently, the production of hexuronic acids using high-frequency ultrasound irradiation without a catalyst has been reported \[[@B140-ijms-20-03660]\]. In addition, the production of hexuronic acids by using metal catalysts has been developed \[[@B141-ijms-20-03660]\]. Combining these technologies with the aforementioned technologies, the production of hexaric acids can be improved. Furthermore, hexaric acid was produced directly from aldohexoses by using modified microorganisms. The oxidation reaction of aldohexoses using enzymes is considered to have an advantage in terms of stereoselectivity. In the future, processes for producing hexaric acids using a biocatalyst including enzymes could be constructed.

R.S. and N.N. wrote and edited the manuscript.

This research was partially funded by a Grant-in-Aid for JSPS Fellows (Grant No. 16J07225 to R.S.).

The authors declare no conflict of interest.

DOE

The US Department of Energy

PEIs

Polyethylene imines

MOF

Metal--organic framework

UDP

Uridine diphosphate

GDP

Guanosine diphosphate

UDH

Uronate dehydrogenase

PQQ

Pyrroloquinolone quinone

GDH

Glucose dehydrogenase

BOD

Bilirubin oxidase

DH

PDH

PQQ domain of pyranose dehydrogenase from

Coprinopsis cinerea

![Structures of aldose and its acids.](ijms-20-03660-g001){#ijms-20-03660-f001}

![Structures of hexaric acids.](ijms-20-03660-g002){#ijms-20-03660-f002}

![Schematic depiction of the syntheses of poly(alkylene galactaramide)s (**A**), poly(alkylene [d]{.smallcaps}-glucaramide)s (**B**), and poly(alkylene [d]{.smallcaps}-mannaramide)s (**C**) from their corresponding monomers and alkylenediamines \[[@B31-ijms-20-03660]\] and the syntheses of poly([d]{.smallcaps}-gulcaramidoamine)s (**D**), poly(galactaramidoamine)s (**E**), and poly([d]{.smallcaps}-mannaramidoamine)s (**F**) from their corresponding monomers and secondary amines \[[@B35-ijms-20-03660]\].](ijms-20-03660-g003){#ijms-20-03660-f003}

![Sugar-based amphiphilic polymers (SBAPs) for biomedical applications \[[@B51-ijms-20-03660]\]. oxLDL = oxidized low-density lipoproteins.](ijms-20-03660-g004){#ijms-20-03660-f004}

![Crystal structure of the neutral metal--organic framework (MOF) (Tb(galactarate)~1.5~(H~2~O)~2~)·5H~2~O shown in a ball-and-stick representation, with the Tb(III) ions in a space-filling model. Water molecules in the channels have been omitted for clarity, and atoms are color coded as follows: C = black; H = white; O = red; Tb = turquoise \[[@B48-ijms-20-03660]\].](ijms-20-03660-g005){#ijms-20-03660-f005}

![The nitric oxidation of (**A**) [d]{.smallcaps}-glucose and (**B**) [d]{.smallcaps}-mannose \[[@B67-ijms-20-03660],[@B69-ijms-20-03660]\].](ijms-20-03660-g006){#ijms-20-03660-f006}

![Common NO and NO~2~ reactions in water/O~2~ proposed in a previous report \[[@B69-ijms-20-03660]\].](ijms-20-03660-g007){#ijms-20-03660-f007}

![Designed pathway for the production of [d]{.smallcaps}-glucaric acid in *E. coli.* PTS = phosphoenolpyruvate-dependent phosphotransferase system; phosphatase = SuhB, an endogenous *E. coli* enzyme; PEP = phosphoenolpyruvate; MIOX = *myo*-inositol oxygenase; Udh = uronate dehydrogenase; \[[@B106-ijms-20-03660]\].](ijms-20-03660-g008){#ijms-20-03660-f008}

![Engineering of the [d]{.smallcaps}-galacturonic acid pathway in fungi. Deletion of the gene encoding [d]{.smallcaps}-galacturonate reductase resulted in strains unable to utilize [d]{.smallcaps}-galacturonic acid as a carbon source. The expression of the bacterial *udh* gene, encoding an nicotinamide adenine dinucleotide (NAD)-dependent UDH ([d]{.smallcaps}-galacturonic acid dehydrogenase), resulted in fungal strains that were able to oxidize [d]{.smallcaps}-galacturonic acid to *meso*-galactaric acid. UDH forms a galactaro-lactone that spontaneously hydrolyzes \[[@B100-ijms-20-03660]\].](ijms-20-03660-g009){#ijms-20-03660-f009}

![Schematic description of an enzymatic biofuel cell that simultaneously produces *meso*-galactaric acid and electricity from pectin extracted from biomass. PQQ-GHD = pyrroloquinoline quinone-dependent glucose dehydrogenase; BOD = bilirubin oxidase.](ijms-20-03660-g010){#ijms-20-03660-f010}

ijms-20-03660-t001_Table 1

######

Isolated yields, melting points, and water solubility of poly(alkylene hexaramide)s \[[@B31-ijms-20-03660]\]. The original tables have been combined into this table.

  Polymers                                            Yield   mp (°C) ^a^   Water Solubility ^b^   *M~n~* ^c^
  --------------------------------------------------- ------- ------------- ---------------------- ------------
  Poly(ethylene [d]{.smallcaps}-glucaramide)          93.3    185           Yes                    2036
  Poly(tetramethylene [d]{.smallcaps}-glucaramide)    88.3    192--195      Yes                    2725
  Poly(hexamethylene [d]{.smallcaps}-glucaramide)     89.4    192--194      No                     2552
  Poly(octamethylene [d]{.smallcaps}-glucaramide)     86.8    195--200      No                     3562
  Poly(decamethylene [d]{.smallcaps}-glucaramide)     89.8    200--205      No                     3218
  Poly(dodecamethylene [d]{.smallcaps}-glucaramide)   93.9    200--205      No                     2730
  Poly(ethylene galactaramide)                        90.1    205           VS                     702
  Poly(tetramethylene galactaramide)                  82.1    230           SS                     1179
  Poly(hexamethylene galactaramide)                   85.2    228           NS                     2320
  Poly(octamethylene galactaramide)                   79.4    230           NS                     4920
  Poly(decamethylene galactaramide)                   82.2    230           NS                     2560
  Poly(dodecamethylene galactaramide)                 87.4    225           NS                     2356
  Poly(ethylene [d]{.smallcaps}-mannaramide)          72      180--206      VS                     1410
  Poly(tetramethylene [d]{.smallcaps}-mannaramide)    77      194--201      VS                     1249
  Poly(hexamethylene [d]{.smallcaps}-mannaramide)     68      205--210      NS                     1247

^a^ All polymers decomposed upon melting. mp = melting point. ^b^ VS = very soluble; SS = slightly soluble; NS = not soluble. ^c^ *M~n~* = number average molecular weight.


Lindaweni Fanetri

Lindaweni Fanetri (born 18 January 1990 in Jakarta) is a female former Indonesian badminton player. She played in women's singles. Fanetri is from PB. Suryanaga, a badminton club from Surabaya, the same club with the likes of Sony Dwi Kuncoro, Alvent Yulianto, and Ryan Agung Saputra. She won a bronze medal at 2015 BWF World Championship after losing to Saina Nehwal in the semifinals. In her quarterfinals match she was down 14–20 in the second game after losing the first game against Tai-Tzu ying of Chinese Taipei. But Lindaweni saved 6 match points and eventually took the second game, 22–20. She won the decider third game to ensure her place in the semifinals.

Achievements

BWF World Championships
 2015 BWF World Championships at the Istora Senayan in Jakarta, Indonesia

{| style='font-size: 90%; text-align: center;' class='wikitable'
!colspan=5 style="background:#CC9966;"|2015 BWF World Championships – Women's Singles
|-
!|Round
!|Opponent
!|Score
!|Result
|-
|style="text-align:left; background:white"|1st
|align="left"| Soraya De Visch Eijbergen
|align="left"|21–13, 21–15
|align="center"|Win
|-
|style="text-align:left; background:white"|2nd
|align="left"| Minatsu Mitani [13]
|align="left"|19–21, 21–14, 21–11
|align="center"|Win
|-
|style="text-align:left; background:white"|3rd
|align="left"| Ratchanok Intanon [5]
|align="left"|24–26, 21–10, 5–8 retired
|align="center"|Win
|-
|style="text-align:left; background:white"|QF|align="left"| Tai Tzu-ying [4]
|align="left"|14–21, 22–20, 21–12
|align="center"|Win
|-
|style="text-align:left; background:white"|SF|align="left"| Saina Nehwal [2]
|align="left"|17–21, 17–21
|style="text-align:left; background:white"| Bronze
|-
|}

 BWF Grand Prix (1 title, 2 runners-up)
The BWF Grand Prix has two level such as BWF Grand Prix and Grand Prix Gold. It is a series of badminton tournaments, sanctioned by Badminton World Federation (BWF) since 2007.

 BWF Grand Prix tournament
 BWF Grand Prix Gold tournament

Participation at Indonesian team
 3 times at Uber Cup (2010, 2012, 2014)
 4 times at Sudirman Cup (2009, 2011, 2013, 2015)

Performance timeline
Indonesian team
 Junior level Senior levelIndividual competitions
 Senior level''

Record against top ranked players
Record against World Superseries finalists, World Championships semifinalists, and Olympic quarterfinalists, as well as all Olympic opponents.

  Jiang Yanjiao 0–1
  Li Xuerui 1–5
  Sun Yu 0–1
  Wang Shixian 0–3
  Wang Yihan 1–4
  Yao Xue 0–1
  Cheng Shao-chieh 1–0
  Tai Tzu-ying 2–1
  Tine Baun 0–1
  Juliane Schenk 0–2
  Yip Pui Yin 1–1
  Zhou Mi 0–1
  P. V. Sindhu 2–8
  Saina Nehwal 1–3
  Eriko Hirose 2–1
  Minatsu Mitani 3–2
  Nozomi Okuhara 2–3
  Sayaka Sato 0–2
  Shizuka Uchida 1–0
  Yui Hashimoto 1–0
  Bae Youn-joo 0–3
  Sung Ji-hyun 1–5
  Wong Mew Choo 0–2
  Carolina Marin 2–2
  Porntip Buranaprasertsuk 1–4
  Ratchanok Inthanon 1–4

References

External links

Category:Indonesian female badminton players
Category:Sportspeople from Jakarta
Category:1990 births
Category:Living people
Category:Badminton players at the 2016 Summer Olympics
Category:Olympic badminton players of Indonesia
Category:Badminton players at the 2010 Asian Games
Category:Badminton players at the 2014 Asian Games
Category:Asian Games bronze medalists for Indonesia
Category:Asian Games medalists in badminton
Category:Medalists at the 2010 Asian Games
Category:Competitors at the 2009 Southeast Asian Games
Category:Competitors at the 2011 Southeast Asian Games
Category:Competitors at the 2015 Southeast Asian Games
Category:Southeast Asian Games silver medalists for Indonesia
Category:Southeast Asian Games bronze medalists for Indonesia
Category:Southeast Asian Games medalists in badminton


J-A23003-15

NON-PRECEDENTIAL DECISION - SEE SUPERIOR COURT I.O.P. 65.37

COMMONWEALTH OF PENNSYLVANIA,            :      IN THE SUPERIOR COURT OF
                                         :            PENNSYLVANIA
                 Appellee                :
                                         :
           v.                            :
                                         :
KATELYN WEBSTER,                         :
                                         :
                 Appellant               :           No. 729 WDA 2014

      Appeal from the Judgment of Sentence entered on May 1, 2014
           in the Court of Common Pleas of Allegheny County,
              Criminal Division, No. CP-02-CR-0005521-2013

BEFORE: GANTMAN, P.J., LAZARUS and MUSMANNO, JJ.

MEMORANDUM BY MUSMANNO, J.:                  FILED NOVEMBER 25, 2015

     Katelyn Webster (“Webster”) appeals the judgment of sentence

imposed following her guilty plea to one count each of perjury and false

swearing.1 See 18 Pa.C.S.A. §§ 4902(a), 4903(a). We affirm the judgment

of sentence.

     The trial court set forth the relevant factual and procedural history in

its Opinion, which we incorporate herein by reference.      See Trial Court

Opinion, 12/9/14, at 1-3.

     On appeal, Webster raises the following questions for our review:

     1. Whether the trial court erred by denying [Webster’s] request
        to transfer the case to the juvenile division?

     2. [Whether] the trial court erred by sentencing [Webster] in the
        aggravated range without providing sufficient reasons[?]

1
 Webster also pled guilty to false reports; however, that charge was later
withdrawn by the Commonwealth prior to sentencing.
J-A23003-15

Brief for Appellant at 2, 17 (capitalization omitted, issues renumbered).

        Webster contends that the trial court erred by denying her Motion to

transfer the case to the juvenile division when (1) she was under 21 at the

time of her prosecution; and (2) she committed a “delinquent act” prior to

reaching the age of 18.      Id. at 8.     Webster asserts that the course of

conduct that formed the basis for the charges against her began when she

was a juvenile.    Id.   Webster points out that she was charged with false

reports, perjury and false swearing, and claims that each of the charges

related to her fabricated allegations of rape against M.F. Id. at 10. Webster

argues that the false reports charge pertains to her initial fabricated

allegation, which was made when she was 17 years old. Id. at 11. Webster

claims that, because M.F.’s preliminary hearing was postponed to a date

after Webster turned 18 years old, the charges of perjury and false swearing

stem from the false testimony that she provided after she turned 18 years

old. Id. Webster contends that, because she committed a delinquent act

before she turned 18, her case should have been transferred to the juvenile

division by operation of law.    Id.     Webster asserts that the spirit of the

Juvenile Act2 requires her case to be transferred to the juvenile division, as

the Act favors adjudication of cases through the juvenile division as opposed

to the criminal division, and because she was amenable to rehabilitation

through the juvenile division. Id. at 12, 14.

2
    See 42 Pa.C.S.A. § 6301, et seq.

                                  -2-
J-A23003-15

      In its Opinion, the trial court addressed Webster’s first claim, and

determined that it lacks merit.     See Trial Court Opinion, 12/9/14, at 3-5.

We concur with the reasoning of the trial court, and affirm on this basis as to

this issue. See id.

      In her second issue, Webster contends that the trial court erred by

sentencing her in the aggravated range without providing sufficient reasons.

Brief for Appellant at 17.        Webster asserts the trial court based its

aggravated sentence primarily on the impact to the victim, M.F. Id. at 19.

Webster claims that, although she presented evidence of her need of intense

treatment and therapy, “the trial court’s reasoning for the aggravated

sentence is nearly void of any reference thereto.” Id. Webster argues that

her psychological issues, coupled with her immaturity and young age,

weighed against an aggravated sentence, even in light of the severe

consequences suffered by the victim. Id.

      Webster’s second claim challenges the discretionary aspects of her

sentence.   “Challenges to the discretionary aspects of sentencing do not

entitle an appellant to review as of right.” Commonwealth v. Moury, 992

A.2d 162, 170 (Pa. Super. 2010).          Prior to reaching the merits of a

discretionary sentencing issue,

      [this Court conducts] a four part analysis to determine: (1)
      whether appellant has filed a timely notice of appeal, see
      Pa.R.A.P. 902 and 903; (2) whether the issue was properly
      preserved at sentencing or in a motion to reconsider and modify
      sentence, see Pa.R.Crim.P. [720]; (3) whether appellant’s brief
      has a fatal defect, [see] Pa.R.A.P. 2119(f); and (4) whether

                                   -3-
J-A23003-15

      there is a substantial question that the sentence appealed from
      is not appropriate under the Sentencing Code, [see] 42
      Pa.C.S.A. § 9781(b).

Moury, 992 A.2d at 170 (citation omitted). When an appellant challenges

the discretionary aspects of her sentence, we must consider her brief on this

issue as a petition for permission to appeal.    Commonwealth v. Yanoff,

690 A.2d 260, 267 (Pa. Super. 1997); see also Commonwealth v.

Tuladziecki, 522 A.2d 17, 18 (Pa. 1987); 42 Pa.C.S.A. § 9781(b).

      In the instant case, Webster filed a timely Notice of Appeal, preserved

her claims in a timely post-sentence Motion, and included in her appellate

brief a separate Rule 2119(f) statement.        As such, she is in technical

compliance with the requirements to challenge the discretionary aspects of a

sentence.   Commonwealth v. Rhoades, 8 A.3d 912, 916 (Pa. Super.

2010). Thus, we will proceed to determine whether Webster has presented

a substantial question for our review.

      An allegation that a sentencing court failed to consider or did not

adequately consider certain mitigating factors does not raise a substantial

question that the sentence was inappropriate.       See Commonwealth v.

Lewis, 911 A.2d 558, 567 (Pa. Super. 2006). Thus, we decline to address

Webster’s claims that the trial court failed to adequately consider her

psychological issues, immaturity and young age.

      However, a claim that a sentencing court failed to state adequate

reasons on the record for the sentence imposed has been held to raise a

                                  -4-
J-A23003-15

substantial question. See Commonwealth v. Krysiak, 535 A.2d 165, 168

(Pa. Super. 1987). Thus, we will address Webster’s claim in this regard.

      The trial court addressed Webster’s second claim, and determined that

it lacks merit.   See Trial Court Opinion, 12/9/14, at 5-8; see also N.T.

(Post-Sentence Motion), 5/1/14, at 51-55; N.T. (Sentencing), 3/27/14, at

40-44. We concur with the reasoning of the trial court, and affirm on this

basis as to this issue. See Trial Court Opinion, 12/9/14, at 5-8.

      Judgment of sentence affirmed.

Judgment Entered.

Joseph D. Seletyn, Esq.
Prothonotary

Date: 11/25/2015

                                 -5-
                                                                           Circulated 11/06/2015 02:35 PM

       IN THE COURT OF CO:MMON PLEAS OF ALLEGHENY COUNTY, PENNSYLVANIA
                                      CRIMINAL DIVISION                                c\".'-             ".'-;;:::..
                                                                                ,..:;
                                                                            ••              -v:              .s::"
                                                                            -;:.- c• -\                       c
                                                                             ~~o
                                                                             ··-;) . ..-          -{"'.
                                                                                i;3_,
                                                                                \,,
                                                                                '-:c ~·-
                                                                                o0
                                                                                r-r'\ ~
                                                                                ._, Y'                                '
                                                                                ..D
                                                                                ~re.
COMMONWEALTH OF PENNSYL V ANJA                       )                              c,O~
                                                                                OL
                                                                                c. -- ?},
                                                     )                                 ;t: cJ) ff\
       vs.                                           ) CC No. 2013-05521                A()Cl
                                                                                ..L.. :t:~
                                                     )                                   -0
                                                                                "?      JP
                                                                                0
KATELYN WEBSTER,                                     )
                                                     )
               Defendant.                            )

                                      OPINION
                                                     )
                                                                       ORIGINAL
                                                                           Criminal Oivisfon
                                                                       Dept. of Court Records
                                                                       Allegheny County, PA.
Mariani, J.

       This is a direct appeal wherein the defendant appeals the Judgment of Sentence of

Septe_mber 23, 2013, which became final when this Court denied defendant's Motion for

Reconsideration on May 1, 2014.         Defendant filed a timely Notice of Appeal and

Concise Statement of Matters Complained of on Appeal Pursuant to Pa.R.A.P. 1925(b)

alleging that this Court erred by not transferring this case to the Juvenile Division of the

Court of Common Pleas after defendant's guilty plea and that the sentence imposed in

this case was manifestly excessive.

       On September 23, 2013, the defendant entered a general plea of guilty to the

information filed in this case charging false reports, perjury and false swearing. After the

guilty plea, on October 3, 2013, the defendant filed a motion to transfer her case to the

Juvenile Division of the Court of Common Pleas due to the fact that the false reports

offense to which she pied guilty occurred when the defendant was 17 years old.                                 The

Commonwealth of Pennsylvania objected to the motion and sought to withdraw that lone

                                                                                l)
                                                                               Circulated 11/06/2015 02:35 PM

count.   A sentencing proceeding occurred on March 27, 2014. During sentencing, this

Court granted the Commonwealth's              request to withdraw the false reports count.               This

Court then sentenced the defendant to a term of imprisonment of not less than one year

less one day to not more than 2 years less 2 days, followed by 3 years of probation. This

Court also ordered restitution in the amount of $15,000.

         The facts of the underlying case are as follows:

The defendant was born on July 15, 1994.                    On June 3, 2012, detectives from the

Allegheny County Police Department               were dispatched to Washington Hospital for a

report of a sexual assault.          The defendant, who was then 17 years old, reported to

detectives that she had been raped by the victim in this case.1                 The victim was arrested

and charged with rape. The defendant turned 18 years old on July 15, 2012. On August

6, 2012, a preliminary was held and the defendant testified under oath that the victim

raped her, touched her breasts and buttocks and physically assaulted her in the parking lot

of a local swimming pool.           All charges were held for court and an additional charge of

unlawful restraint was added by the Commonwealth.

         The victim's criminal trial was scheduled for March 20, 2013. Prior to the trial,

two witnesses came forward and advised law enforcement that the defendant had asked

them to lie and tell people that they were with the defendant at the pool on June 3, 2012.

Initially, the witnesses did not understand why they were being asked to lie. However,

when they learned that the defendant claimed she was the victim of a sexual assault on

1
  This Court will not identify the alleged victim by name due to the sensitive nature of the false and
inflammatory allegations made against him.

                                                      2
                        ,·
                        L                                                   Circulated 11/06/2015 02:35 PM

that date, they decided to come forward. These witnesses advised that the defendant was

with them on June 2, 2012 and June 3, 2012. They had been at a club, Club Zoo, and

spent the night at another individual's house.     While the defendant was at the other

individual's house on June 3, 2012, she voluntarily had sexual intercourse with a young

male, not the victim, and she sustained "sucker bites" during the interlude. On March 16,

2013, detectives interviewed the defendant about this information.           Although the

defendant initially persisted in making the false accusations against the victim, eventually

the defendant admitted that she had never been sexually assaulted by the victim. She

acknowledged that she fabricated the story about the victim so that she would not get into

trouble with her father because of the "sucker bites" she received while having voluntary

sexual intercourse with another young male.

       As a result of the false claims made by the defendant, the victim was arrested at

the home he shared with his parents at 2:00 a.m.        Despite having just had shoulder

surgery, he was placed in handcuffs and transported to the Allegheny County Jail.         He

was incarcerated there for three nights prior to being released on house arrest. He was

required to live with his grandparents in Allegheny County due to the fact that his parents

resided in Washington County. As a result of his arrest, he lost his job. According to the

victim, the arrest ruined his life for nine months. His family incurred expenses in the

amount of $34,295.30 in helping to prepare for their son's defense.

       Defendant first claims that this Court erred by not transferring her case to juvenile

court. The trial record clearly establishes that the defendant pled guilty to three offenses

                                              3
                                                                               Circulated 11/06/2015 02:35 PM

in this case, one of which occurred when she was a juvenile, or a "child" pursuant to 42

Pa.C.S.A. §6302 and 42 Pa.C.S.A. §6322, and two of which clearly occurred when she

was an adult.    As the record reflects, this Court believed that it had no option but to grant

the Commonwealth's        motion because it did not believe that an offense charging the

defendant with making false reports at a time when she was a juvenile was properly

before the Criminal Division of the Court of Common Pleas.2 See §6321(a)(3)(providing

that a proceeding for a delinquent act committed by a minor should be commenced by the

filing of a petition pursuant to the Juvenile Act). That count having been removed from

this case, all that remained for disposition were two counts which were alleged to have

occurred when the defendant was an adult.

        This Court is not aware of, and the defendant did not supply, any legal authority

permitting this Court to transfer two adult convictions to the Juvenile Division of the

Court of Common Pleas for disposition.           The Juvenile Act, as set forth in 42 Pa.C.S.A.

§6322, provides:

                   (a) GENERAL RULE.-- Except as provided in 75 Pa.C.S.
                 § 6303 (relating to rights and liabilities of minors) or in the
                 event the child is charged with murder or any of the
                 offenses excluded by paragraph (2)(ii) or (iii) of the
                 definition of "DELINQUENT ACT" in section 6302
                 (relating to definitions) or has been found guilty in a
                 criminal proceeding, if it appears to the court in a criminal
                 proceeding that the defendant is a child, this chapter shall
                 immediately become applicable, and the court shall
                 forthwith halt further criminal proceedings, and, where
                 appropriate, transfer the case to the division or a judge of
                 the court assigned to conduct juvenile hearings, together
                 with a copy of the accusatory pleading and other papers,

2
 The defendant does not claim on appeal that this Court erred by granting the Commonwealth's motion to
withdraw that count.

                                                   4
                                                                           Circulated 11/06/2015 02:35 PM

               documents, and transcripts of testimony relating to the case.
               If it appears to the court in a criminal proceeding charging
               murder or any of the offenses excluded by paragraph (2)(ii)
               or (iii) of the definition of "DELINQUENT ACT" in
               section 6302, that the defendant is a child, the case may
               similarly be transferred and the provisions of this chapter
               applied. In determining whether to transfer a case charging
               murder or any of the offenses excluded from the definition
               of "DELINQUENT ACT" in section 6302, the child shall
               be required to establish by a preponderance of the evidence
               that the transfer will serve the public interest. In
               determining whether the child has so established that the
               transfer will serve the public interest, the court shall
               consider the factors contained in section 6355(a)(4)(iii)
               (relating to transfer to criminal proceedings).

In this case, the defendant was not a "child", as that term is defined in 42 Pa.C.S.A.

§6302 and used in 42 Pa.C.S.A. §6322, at the time she committed the offenses of perjury

and false swearing. She was 18 years old. There is no authority to transfer a case of an

adult to juvenile court for disposition.    According to the plain letter of the law, this

claim fails.

        Defendant next claims that this Court erred by sentencing the defendant in the

aggravated range of the sentencing guidelines because it failed to provide sufficient

reasons for the sentence. For the following reasons, this appeal lacks merit.

        A sentencing judge is given a great deal of discretion in the determination of a

sentence, and that sentence will not be disturbed on appeal unless the sentencing court

manifestly abused its discretion." Commonwealth v. Boyer, 856 A2d 149, 153 (Pa.

Super. 2004), citing Commonwealth v. Kenner, 784 A.2d 808, 811 (Pa.Super. 2001)

                                             5
                                                                              Circulated 11/06/2015 02:35 PM

appeal denied, 568 Pa. 695, 796 A.2d 979 (2002); 42 Pa.C.S.A. §9721.             An abuse of

discretion is not a mere error of judgment; it involves bias, partiality, prejudice, ill-will,

or manifest unreasonableness.       See Commonwealth v. Flores, 921 A.2d 517, 525

(Pa.Super. 2007), citing Commonwealth v. Busanet, 817 A.2d 1060, 1076 (Pa. 2002).

          Furthermore, the "[s]entencing court has broad discretion in choosing the range of

permissible confinements which best suits a particular defendant and the circumstances

surrounding his crime." Boyer, supra, quoting Commonwealth v. Moore, 617 A.2d 8, 12

(1992).      Discretion is limited, however, by 42 Pa.C.S.A. §9721(b), which provides that

a sentencing court must formulate a sentence individualized to that particular case and

that particular defendant. Section 9721(b) provides.. "[t]he court shall follow the general

principle that the sentence imposed should call for confinement that is consistent with the

protection of the public, the gravity of the offense, as it relates to the impact on the life of

the victim and on the community, and the rehabilitative needs of the defendant . . .. "

Boyer, supra at 153, citing 42 Pa.C.S.A. §9721(b). Furthermore,

                 In imposing sentence, the trial court is required to consider
                 the particular circumstances of the offense and the character
                 of the defendant. The trial court should refer to the
                 defendant's prior criminal record, age, personal
                 characteristics, and potential for rehabilitation. However,
                 where the sentencing judge had the benefit of a presentence
                 investigative report, it will be presumed that he or she was
                 aware of the relevant information regarding the defendant's
                 character and weighed those considerations along with
                 mitigating statutory factors.

Boyer, supra at 154, citing Commonwealth v. Bums, 765 A.2d 1144, 1150-1151 (Pa.Super.

2000) (citations omitted).

                                               6
                                                                               Circulated 11/06/2015 02:35 PM

      In fashioning an appropriate sentence, courts must be mindful that the sentencing

guidelines "have no binding effect, in that they do not predominate over individualized

sentencing factors and that they include standardized recommendations, rather than

mandates, for a particular sentence." Commonwealth v. Walls, 592 Pa. 557, 567, 926 A.2d

957, 964 (2007).       A sentencing court is, therefore, permitted to impose a sentence

outside the recommended guidelines. If it does so, however, it "must provide a written

statement setting forth the reasons for the deviation .... " Id., 926 A.2d at 963.

        A sentencing judge can satisfy the requirement of placing reasons for a particular

sentence on the record by indicating that he or she has been informed by the pre-

sentencing report; thus properly considering and weighing all relevant factors. Boyer,

supra, citing Burns, supra, citing Commonwealth v. Egan, 451 Pa.Super. 219, 679 A.2d

237 (1996).

        The record in this case supports the sentence imposed by this Court. Contrary to

the allegations made by the defendant, the sentencing record reflects that this Court did

consider the presentence report and it set forth a number of reasons explaining its

sentence. This Court noted that the original false allegation of rape was made by the

defendant in June, 2012. After she became an adult, she took an oath to tell the truth and

persisted in her pattern of lies and deceit by testifying falsely during a preliminary

hearing that the victim raped her. She enlisted two friends to lie on her behalf to

perpetuate the very serious lies. This Court noted at sentencing that it viewed the harm

                                               7
                        I,_   .
                                                                          Circulated 11/06/2015 02:35 PM

caused to the victim in this case by the false allegations of rape was "about as high a

level" of a false accusation that could be made. The false allegation led people to believe

that the victim abused the defendant in a "very, very nasty way that requires a hands-on

violation of somebody else's person, a nasty, nasty accusation, and it does go to the issue

of victim impact." This Court considered that the defendant attempted to enlist others to

go along with her lies and only admitted to her false allegations after those witnesses

came forward. In this Court's estimation, the defendant would have followed through on

the false allegations had her lies not been exposed.            This Court considered the

presentence report which noted that the victim was rousted at his home at 2:00 a.m. when

he was arrested. He was handcuffed despite having recently undergone shoulder surgery.

He was housed in the Allegheny County Jail for three days and was subjected to house

arrest. For almost a year, he lived with the emotional impact of being falsely accused of

rape and facing the real possibility of receiving a stiff prison sentence. He lost his job

and friends.    Based on the circumstances of this case, the sentence imposed on this

defendant, which was a county sentence, was hardly excessive and this Court provided

ample reasons for it on the record.

       For the foregoing reasons, the Judgment of Sentence should be affirmed.

                                                By the Court:

Date:~~~                          ?, 2()/   f

                                                8


from django.utils import timezone

def update_last_login(sender, request, user, **kwargs):
    user.last_login = timezone.now()
    user.last_login_ip = request.META.get("REMOTE_ADDR", None)
    user.save(update_fields=['last_login', 'last_login_ip'])

def update_joined(sender, request, user, **kwargs):
    user.ip_joined = request.META.get("REMOTE_ADDR", None)
    user.save(update_fields=['ip_joined'])


Texas Tech Quick Hits

 Texas Tech is looking for its first win in Austin since 1996, when the Red Raiders defeated the Longhorns, 75-58, en route to its Southwest Conference championship. Texas Tech has lost 16 in a row against Texas at the Frank Erwin Center.

 This is the 130th meeting between the two schools, with Texas leading the series, 77-52. Texas has won 15 of the last 16 meetings with Texas Tech.

 Texas Tech just ran the gauntlet of five straight game against RPI Top 50 teams - Baylor (45), Kansas (3), Oklahoma (21), Oklahoma State (38) and Iowa State (37).

 Texas Tech snapped a four-game losing streak with a 56-51 win over Iowa State on Wednesday.

 Texas Tech is looking to win three Big 12 games for the first time since 2011. The Red Raiders have a winning record through 17 games (9-8) for the first time since the 2009-10 season.

 Texas Tech finished the non-conference portion of its schedule 7-4. It was the longest homestand in program history at 11 games.

 Texas Tech is averaging 70.2 possessions per game and 0.97 points per possession, while Texas is averaging 70.3 possessions and 0.91 points per possession. Last season, Texas Tech averaged 0.92 points per possession.

 Jaye Crockett is the nation's top Sixth Man in the Power Six conferences in terms of rebounding (8.0 rebounds) and second in scoring (13.1 points). Crockett has led the team in scoring 11 times this season.

 Since Dusty Hannahs moved into the starting rotation, he has gone from 3.6 points per game off the bench to 9.1 points per game in his nine starts.

 Josh Gray is second in the Big 12 and 58th nationally in steals (2.0), while averaging 9.5 points and 2.6 assists per game.

 Dejan Kravic recorded his third 20-point game of the season against Oklahoma after connecting on 8 of 10 from the field and 4 of 7 from the line. He is adding 9.7 points, 5.4 rebounds and 1.4 blocks.

 Texas Tech is 6-0 when Jordan Tolbert recorded eight or more rebounds in a game.


JOINT MEDIA RELEASE -- Three agencies join forces to address disparity in numbers of Native children in state care

(Anchorage, AK)— An Alaska tribe, a tribal organization and the state’s child protection agency have formed an unprecedented partnership to provide help and resources for Alaska Native families and children before they come in contact with the child protection system, and to preserve families so Alaska Native children won’t ever have to come into state care.

Alaska Native children in Anchorage are 14 times more likely than non-Native children to be involved with the state’s child protection agency, according to statistics compiled by the Alaska Department of Health and Social Services. The statistics show that more than 60 percent of children currently in the legal custody of the state and placed in out-of-home care are Alaska Native children, despite being about 10 percent of the area’s total child population.

To combat this disparity, the state’s Office of Children’s Services, Cook Inlet Tribal Council (CITC), and the Native Village of Eklutna have partnered to create an Alaska Native Family Preservation Unit. The unit will share authority and decision making, working exclusively with Alaska Native families. It expects to serve 180 families its first year, and 240 for each of the following four years.

Cook Inlet Tribal Council, on behalf of the partnership, sought funding through a grant from the U.S. Department of Health and Human Services in the amount of $2.5 million over five years. The funding was successfully secured this month, and now the work begins to hire workers from each of the organizations. Ideally, the Alaska Native Family Preservation Unit will begin working — and preserving families — early in 2008.

The unit will consist of six workers — two each from the Office of Children’s Services, Cook Inlet Tribal Council and the Native Village of Eklutna — plus a supervisor. The goal will be to provide early intervention services for those Alaska Native families most at risk for further involvement with the child protection system — before out-of-home placement is necessary.

James LaBelle Jr., Child Welfare Liaison for Cook Inlet Tribal Council, states the unit will fill an important gap in current services, by providing culturally-grounded interventions to address the myriad causes of children coming into state care. Interventions include screening for substance abuse, linking to behavioral health providers, family counseling, developmental assessments, as well as home and community-based support.

“Not a lot of work is done at the outset with families when they are first seen in the system, when the level of need does not warrant out-of-home care,” LaBelle said. “Unfortunately, when they come back through the system, the needs are often greater.”

This level of collaboration between state and tribal entities may be unique in the country, according to the team that originated the idea.

“This is going to be a model of collaboration,” said Travis Erickson, Children’s Services Manager. “It’s not being done anywhere else that we know of.”


Still, Tribune has nearly $4 billion in debt and interest
payments due by the end of 2009, according to Gimme Credit
analyst Dave Novosel, making it all but certain that the
company will be forced to sell more marquee properties and make
deeper cost cuts to avoid violating debt covenants.

"Tribune is a big microcosm of issues across the industry,
and Sam Zell made an unfortunate bet, if you will, jumping into
a business he knew nothing about," said veteran newspaper
analyst Miles Groves.

Zell, a Chicago real estate tycoon, took Tribune private
last year in an $8.2 billion leveraged buyout that restructured
the publisher of the Los Angeles Times as an employee-owned
company, saddling it with more than $10 billion in debt.

As recently as December, at the time of the deal's closing,
Zell was pledging to keep Tribune intact, except for the Cubs.

A major asset sale would be seen not only as a failure for
the man who dubs himself "The Grave Dancer" for coaxing big
profits from distressed businesses, but also as a warning to
other would-be saviors of the troubled newspaper industry.

Reached at a real estate conference in New York on
Thursday, Zell, Tribune's chief executive, declined to comment.
He plans to hold a conference call with lenders on April 17.

So far, Zell has shared few of his plans to turn around the
business. He portrays himself as a roll-up-the-sleeves change
agent, using profanity and humor to boost morale.

One YouTube video of Zell swearing at an Orlando Sentinel
photographer has cemented his reputation for tough, blunt talk.

That may not be enough.

Analysts say Newsday could fetch up to $600 million, while
the Cubs and related properties could fetch $1 billion.

According to data from Reuters Loan Pricing Corp, Tribune
needs to repay at least $1.6 billion of its loan facilities in
2008 and 2009.

But Gimme Credit's Novosel has slightly higher numbers
after factoring in amortization payments.

Novosel estimates that Tribune has to make $1 billion in
debt and amortization payments in 2008, and has another $850
million in debt and amortization payments that will mature in
2009.

Tribune also faces nearly $2 billion in combined interest
expenses for 2008 and 2009, he said.

That could be covered by anticipated free cash flow, unless
the newspaper industry sinks further amid the weak U.S. economy
and the recession in advertising spending.

So far, the outlook is grim. Goldman Sachs analyst Peter
Appert said he expected first quarter newspaper ad revenue to
decline by 10 percent. "Managements will find it nearly
impossible to fully offset this level of revenue decline with
cost cutting," he said.

The declines in the industry and the company, unforeseen by
the deal's architects last year, have narrowed what analysts
have said is Zell's already slim margin of error.

Tribune's previous management, who negotiated the deal, had
overestimated 2007's anticipated cash flow by about 20 percent,
according to a source familiar with Tribune's finances before
it went private. "They were very aggressive," the source said.

In February, Tribune's own Baltimore Sun reported that Zell
told Sun employees that an unexpected 16 to 18 percent decline
in Tribune's newspaper revenue -- worse than the projected 2 to
3 percent fall -- could force it to sell more assets.

DEBT COVENANTS

Tribune has an existing bank facility that could cover $260
million of $1 billion debt obligations this year, said Fitch
analyst Mike Simonton.

But Novosel said that was a stop-gap measure. "Tribune
could tap credit lines, but this could impair cash needed for
operations, so it is only a temporary solution," he said.

Tribune's lackluster results at the beginning of the year
prompted Standard & Poor's to lower its corporate credit rating
on March 17 to "B-" from "B" with a negative outlook.

"To date we have not seen them or anyone turn the corner so
to speak," Fitch's Simonton said. "There is no real evidence
from even the best cost cutters in the industry, they
(publishers) can offset these revenue declines."

If ad revenues keep falling, Tribune could drift perilously
close to violating covenants on its senior secured debt. These
require the ratio of the company's debt to the trailing four
quarters of EBITDA (earnings before interest, tax, depreciation
and amortization) to not exceed 9 to 1.

Fitch estimated the company was at 8 to 1 at the end of
2007. By the first quarter of 2009, that covenant tightens to
8.75 to 1, "further pressuring flexibility around the
covenants," Fitch said of Tribune on March 24.

As recently as February, Zell said the company expected to
meet those conditions.

As for what Tribune could sell, its 31 percent stake in the
Food Network is a candidate, but it is a bad time to go to
market. Hot cable networks generally sell for 14 times cash
flow valuation, according to SNL Kagan analyst Derek Baine, but
the current market commands a multiple of 11 to 12 times.

Thus, Tribune's stake in the Food Network would yield $775
million to $1 billion based on estimates from Goldman Sachs and
Gimme Credit.

Tribune also owns a stable of local television stations and
well known, but financially strapped newspapers like the LA
Times and Chicago Tribune, as well as stakes in companies
including jobs network Careerbuilder.com.

Zell wouldn't talk about Tribune at the real estate
conference on Thursday. But he did acknowledge the state of the
business, joking to the audience that going from property to
newspapers was like "going from leprosy to cancer."

BATON ROUGE, La. U.S. President-elect Donald Trump on Friday said that China and other countries often devalue their currencies as the U.S. economy improves, vowing to combat currency manipulation and the dumping of foreign products into U.S. markets below cost.

Reuters is the news and media division of Thomson Reuters. Thomson Reuters is the world's largest international multimedia news agency, providing investing news, world news, business news, technology news, headline news, small business news, news alerts, personal finance, stock market, and mutual funds information available on Reuters.com, video, mobile, and interactive television platforms. Learn more about Thomson Reuters products:


1. Field of the Invention
The present invention broadly relates to the measurement of transient pore water pressure in soils and more particularly, is concerned with a system for measuring dynamic pore pressure which utilizes a unique probe assembly and two-stage technique for emplacement thereof.
2. Description of the Prior Art
Despite significant advances in recent years toward understanding the behavior of soils under dynamic or shock loading conditions, relatively little is known of the way in which transient pore water pressures affect the response of saturate soils. Much effort has been devoted to the development and refinement of instrumentation for measurement of stresses and motions in soils subjected to loading; however, in contrast, there appears to be a marked absence of work in the area of transient pore water pressure measurement.
There are some difficult problems associated with measurement of the transient behavior of pore water pressure, particularly when the disturbance is blast induced. First, blast or shock generated pressure pulses require a significantly faster responding instrument than that required in conventional piezometer applications. Next, a large dynamic range of response is required since peak pressures at the start of the loading are typically very large compared to the pressures remaining behind the blast wave. Furthermore, peak amplitudes of blast induced pressures are often difficult to predict. Finally, placement of the probe is critical because soil disturbance due to the placement can significantly affect the measurement.
With respect to the last-mentioned problem, the distribution of dynamic pore pressure in a soil mass resulting from a disturbance or fluctuation is critically dependent upon local permeability. Disturbance or remoulding of the soil due to placement of instrumentation is therefore an important consideration. In a saturated soil the lumped effective bulk modulus (a critical factor affecting propagation velocity and attenuation of dynamic disturbances) is high. If, during placement, a piezometer introduces any voids of air, a massive local reduction of this parameter can be created. The effect of such a disturbance vanishes rapidly with increasing distance from the inclusion and invariably the total soil mass system will not realize the effect. However, the piezometer at the center of the disturbed zone will register an unrepresentative dynamic pressure history.
In view of the above-described problems associated with the measurement of transient behavior of pore water pressure, the need exists for a measurement device small in size and having a fast response time, but rugged enough to survive emplacement and subsequent operating conditions.


Social media have become crucial tools for political activists and protest movements, providing another channel for promoting messages and garnering support. Twitter, in particular, has been identified as a noteworthy medium for protests in countries including Iran and Egypt to receive global attention. The Occupy movement, originating with protests in, and the physical occupation of, Wall Street, and inspiring similar demonstrations in other U.S. cities and around the world, has been intrinsically linked with social media through location–specific hashtags: #ows for Occupy Wall Street, #occupysf for San Francisco, and so on. While the individual protests have a specific geographical focus–highlighted by the physical occupation of parks, buildings, and other urban areas — Twitter provides a means for these different movements to be linked and promoted through tweets containing multiple hashtags. It also serves as a channel for tactical communications during actions and as a space in which movement debates take place.

This paper examines Twitter’s use within the Occupy Oakland movement. We use a mixture of ethnographic research through interviews with activists and participant observation of the movements’ activities, and a dataset of public tweets containing the #oo hashtag from early 2012. This research methodology allows us to develop a more accurate and nuanced understanding of how movement activists use Twitter by cross–checking trends in the online data with observations and activists’ own reported use of Twitter. We also study the connections between a geographically focused movement such as Occupy Oakland and related, but physically distant, protests taking place concurrently in other cities. This study forms part of a wider research project, Mapping Movements, exploring the politics of place, investigating how social movements are composed and sustained, and the uses of online communication within these movements.

In October, Dr. Tim Highfield and I will be presenting some of our Occupy Oakland research at the Internet Research 13.0 Conference. We’ve started putting together the paper over the last few weeks (which means that my Tumblr is currently full of useful quotations I’ve found along the way), and have been enjoying the process tremendously. In coming weeks I’ll be sending drafts to interviewees who said they were interested in seeing the project develop to get their feedback, and hopefully within a few months Tim and I will have the full article to share. The abstract for the presentation (co-written with Tim) is here:

#oo activism: Uses of Twitter within the Occupy Oakland movement

Social media have become crucial tools for political activists and protest movements, providing another channel for promoting messages and garnering support. Twitter, in particular, has been identified as a noteworthy medium for protests in countries including Iran and Egypt to receive global attention (Gaffney, 2010; Lotan, Ananny, Gaffney, & boyd, 2011). The Occupy movement, originating with protests in, and the physical occupation of, Wall Street and inspiring similar demonstrations in other U.S. cities and around the world, has been intrinsically linked with social media through location-specific hashtags: #ows for Occupy Wall Street, #occupysf for San Francisco, and so on. While the individual protests have a specific geographical focus – highlighted by the physical occupation of parks, buildings, and other urban areas – Twitter provides a means for these different movements to be linked and promoted through tweets containing multiple hashtags. It also serves as a channel for tactical communications during actions and as a space in which movement debates take place.

In this paper, we undertake a preliminary study of Twitter’s use within the Occupy Oakland movement. We analyse a dataset of public tweets published between 29 January and 15 February 2012 containing the #oo hashtag to identify the ways in which social media are employed within the movement, from promoting events to broadcasting live from marches and meetings. This timeframe is particularly noteworthy because it covers the aftermath of the Move In Day action, an attempt to take over a disused building and turn it into a social centre. The failure of this action in the face of police repression led to intense debate within the movement about strategies and tactics, as well as between participants and observers in Oakland and elsewhere. There were also a number of follow-up actions organised, including solidarity actions for the 409 people arrested at Move In Day. Much of this debate and organising took place on Twitter and was tagged with the #oo hashtag. While this is not the only hashtag used for this specific movement (#occupyoakland is also featured in tweets), #oo’s length makes it a popular choice for protesters faced with only 140 characters with which to write their tweets.

Our analysis of the content of #oo tweets examines how Twitter is used within the movement; as, variably, a means of organisation, communication, broadcasting, or debate, for example. As part of this study, we evaluate how Twitter activity corresponds with events such as rallies, arrests, and meetings, and determine the presence of any sub-groups of Twitter users within the movement focused on particular activities, such as livestreaming and the controversial weekly anti-police rallies. Using methods developed specifically for processing Twitter datasets (Bruns, 2011), we also examine the hashtags, @replies and mentions, and retweets included in the gathered tweets to identify any links with other #occupy movements and movements around the world (including those in Egypt and Syria), and the relationship between Occupy Oakland and local institutions and places. This step allows us to study the connections between a geographically-focused movement such as Occupy Oakland and related, but physically distant, protests taking place concurrently in other cities.

This preliminary study forms part of a wider project exploring the politics of place, investigating how social movements are composed and sustained. In addition to movement-specific data collected from sites such as Twitter, the project also draws on ethnographic research through interviews with activists, and participant observation of the movements’ activities. This research methodology allows us to develop a more accurate and nuanced understanding of how movement activists use Twitter by cross-checking trends in the online data with observations and activists’ own reported use of Twitter.


Q:

Cassandra one to one relationship

I have a SQL table with the following structure -
Ticket_info
ticket_num int
region     text
division   text
error_count text
PRIMAR KEY (ticket_num,region)

As the ticket db could grow large we are planning to store in cassandra.
The only issue is that the user can query on any of the fields shown above.
I'm planning to denormalize the data as such -
Ticket_info_region
ticket_num int
region     text
PRIMAR KEY (ticket_num,region)

Ticket_info_division
ticket_num int
division     text
PRIMAR KEY (ticket_num,division)

Ticket_info_error_count
ticket_num int
error_count     text
PRIMAR KEY (ticket_num,error_count)

With the above structure I see 2 issues.

Should I manually merge the results if the user gives multiple conditions?
With multiple tables how can I maintain the data integrity. For ex:- after I insert into the region table, if the division table fails, I will have integrity issues.

A:

Do not use cassandra to query all the tables together. If such a condition is necessary use cassandra integrated with solr/elasticsearch. There is a solr implementation available from Datastax.
Use Batch updates for atomic updates. This will ensure that all of your updates are performed and in case of failure, nothing is updated.


Intratumoral echo-guided injection of interleukin-2 and lymphokine-activated killer cells in hepatocellular carcinoma.
Interleukin-2 has proved to be effective for the intralesional treatment of tumors of the bladder. There are examples in literature of hepatocellular carcinoma (HCC) treatment with lymphokine-activated killer (LAK) cells infused in the hepatic artery. We decided to check the effects of echo-guided intralesional injection of these cells in this disease. We treated 5 patients with inoperable hepatocellular carcinoma, following cirrhosis; in 4 cases the mass had a diameter less than 3 cm (small HCC) while in the remaining case it measured 7 cm. Tumor size remained unchanged in 3 of the 4 small HCC, and increased only slightly in the other (over a period of 10 months). This would appear to indicate that treatment halted neoplasm growth or at least slowed it down. The echo pattern of the lesions changed, with a constant reduction in echogenicity. Finally, in multiple control biopsies, fibrosis, present in only one case before treatment, was found fairly constantly after treatment. There were no significant side effects, apart from slight water retention in one patient. On the basis of our preliminary results, we consider it worthwhile continuing this study to establish the most suitable IL-2 doses and analyze in more detail the modifications induced in the neoplasm.


Ask HN: How to Cure Burn Out? - HNLurker2
======
planetzero
Well, if you are still doing what caused you to burn out, you won't be cured.
If it's a job that won't stop the death march projects..you will need to quit.

------
msadowski
What worked for me was quitting and starting working as a freelancer. I'm not
sure there is a burnout scale but I'd say I was around 7/10 I felt quite
miserable at work. I don't think I was fully depressed but I knew that if I
didn't change anything then I'd have issues.

Before I quit I did one solid project on UpWork and had about 6 months of
runway funds saved and I was very lucky that my girlfriend would support me if
things went south. My plan was to quit, try to find more projects and worst
case start job hunting after 6 months.

Things worked out really well, I'm approaching year 2 as a solo consultant and
I'm loving my job. When I think of my burnout times I realized much later on
how risky my approach was and in normal circumstances I wouldn't do it.

I would advise to only follow my approach if you have a solid plan or
circumstances that make it a low risk. Remember that your well being is most
important. If you can be happier in a job that pays less money then it might
be worth it!

------
factorialboy
Diet. Exercise. Music. Yoga. And doing something different.


Lack of secondary suppressor response in enhanced allografted rats with endogenous suppressor activity in spleen and diminished cytotoxic T cell response.
In order to better understand the mechanisms of alloimmunization occurring in transplantation, we studied the immune response of an inbred rat strain (WF) to varied presentation of alloantigens (LEW). Hyperimmunized rats acutely reject transplanted allografts and demonstrate direct cytotoxic activity, as well as an expanded potential to generate cytotoxic and suppressor cell activity. In contrast, passively and actively enhanced animals, which exhibit allograft tolerance, demonstrate endogenous suppressor cell activity and significantly reduced potential to generate cytotoxic and suppressor cell activity. Thus, the method of immunization of the same responder strain animals with identical alloantigens will determine whether rejection or tolerance is evidenced following transplantation. The suppressor T cell activity demonstrated in the enhanced animals appears to regulate the immune response by reducing cell proliferation when challenged with alloantigen. However, when restimulated in vitro with donor cells, splenic suppressor activity declines--i.e., there is not a secondary suppressor response.