bluuebunny/crossref_metadata_2025_split huggingface dataset:
Deracemization of Racemic Amines to Enantiopure (R)‐ and (S)‐amines by Biocatalytic Cascade Employing ω‐Transaminase and Amine Dehydrogenase
Authors: Yoon Sanghan , Patil Mahesh D. , Sarak Sharad , Jeon Hyunwoo , Kim Geon‐Hee , Khobragade Taresh P. , Sung Sihyong , Yun Hyungdon 
Published: February 2019

AbstractA one‐pot deracemization strategy for α‐chiral amines is reported involving an enantioselective deamination to the corresponding ketone followed by a stereoselective amination by enantiocomplementary biocatalysts. Notably, this cascade employing a ω‐transaminase and amine dehydrogenase enabled the access to both (R)‐and (S)‐amine products, just by controlling the directions of the reactions catalyzed by them. A wide range of (R)‐and (S)‐amines was obtained with excellent conversions (>80 %) and enantiomeric excess (>99 % ee). Finally, preparative scale syntheses led to obtain enantiopure (R)‐ and (S)‐13 with the isolated yields of 53 and 75 %, respectively.
Utilization of a Hydrogen Source from Renewable Lignocellulosic Biomass for Hydrogenation of Nitroarenes
Authors: Tan Fang‐Fang , Tang Kai‐Li , Zhang Ping , Guo Yan‐Jun , Qu Mengnan , Li Yang 
Published: February 2019

AbstractExploring of hydrogen source from renewable biomass, such as glucose in alkaline solution, for hydrogenation reactions had been studied since 1860s. According to proposed pathway, only small part of hydrogen source in glucose was utilized. Herein, the utilization of a hydrogen source from renewable lignocellulosic biomass, one of the most abundant renewable sources in nature, for a hydrogenation reaction is described. The hydrogenation is demonstrated by reduction of nitroarenes to arylamines in up to 95 % yields. Mechanism studies suggest that the hydrogenation occurs via a hydrogen transformation pathway.
Circularly polarized luminescence of Sm (III) and Eu (III) complexes with chiral ligand (R/S)‐BINAPO
Authors: Cotter Daniel , Dodder Spencer , Klimkowski Valentine J. , Hopkins Todd A. 
Published: February 2019

AbstractLuminescent lanthanide (III) ions have been exploited for circularly polarized luminescence (CPL) for decades. However, very few of these studies have involved chiral samarium (III) complexes. Complexes are prepared by mixing axial chiral ligands (R/S))‐2,2’‐bis(diphenylphosphoryl)‐1,1′‐binaphthyl (BINAPO) with europium and samarium Tris (trifluoromethane sulfonate) (Eu (OTf)3 and Sm (OTf)3). Luminescence‐based titration shows that the complex formed is Ln((R/S)‐BINAPO)2(OTf)3, where Ln = Eu or Sm. The CPL spectra are reported for Eu((R/S)‐BINAPO)2(OTf)3 and Sm((R/S)‐BINAPO)2(OTf)3. The sign of the dissymmetry factors, gem, was dependent upon the chirality of the BINAPO ligand, and the magnitudes were relatively large. Of all of the complexes in this study, Sm((S)‐BINAPO)2(OTf)3 has the largest gem = 0.272, which is one of the largest recorded for a chiral Sm3+ complex. A theoretical three‐dimensional structural model of the complex that is consistent with the experimental observations is developed and refined. This report also shows that (R/S)‐BINAPO are the only reported ligands where gem (Sm3+) > gem (Eu3+).
1‐Hydroxymethyl‐7‐oxabicyclo[2.2.1]hept‐2‐ene skeleton in enantiopure form through enzymatic kinetic resolution
Authors: Reddy U. Chandrasekhar , Manheri Muraleedharan K. 
Published: February 2019

AbstractLipase‐catalysed enantioselective acetylation and deacetylation routes were investigated to prepare 1,5,6‐trisubstituted 7‐oxabicyclo[2.2.1]hept‐2‐ene skeleton in enantio‐pure form. The racemic alcohol (6) used in acetylation reaction was accessed through Diels‐Alder reaction of TBDMS‐protected furfuryl alcohol with maleic anhydride, followed by reduction‐benzylation‐desilylation sequence. After systematic screening of lipases and solvents, Candida antarctica B on acrylic resin in pentane was identified as the best system that gave >98% ee towards the (+) acetate with 40% conversion, in 30 minutes. Absolute stereochemistry of this product was confirmed by X‐ray diffraction analysis of its 3,5‐dinitrobenzoate derivative (9). Enantioselective deacetylation of the racemic acetate of this starting material was then studied with the same set of lipases. After various optimization studies, Candida antarctica B in toluene as the solvent was found to be the most effective that gave 49% conversion with >99% ee towards the (+)‐alcohol (8) at the end of 18 hours.
Androgen deprivation therapy and depression in men with prostate cancer treated with definitive radiation therapy
Authors: Deka Rishi , Rose Brent S. , Bryant Alex K. , Sarkar Reith R. , Nalawade Vinit , McKay Rana , Murphy James D. , Simpson Daniel R. 
Published: February 2019

BackgroundThere is no consensus on the association between the use of androgen deprivation therapy (ADT) and the risk of developing depression. This study investigated the association between ADT use and the development of depression, outpatient psychiatric services, inpatient psychiatric services, and suicide in a homogeneous group of men with prostate cancer (PC) treated with definitive radiation therapy (RT) after controlling for multiple sources of selection bias.MethodsThis was a retrospective, observational cohort study of 39,965 veterans with PC who were treated with definitive RT and were diagnosed by the US Department of Veterans Affairs health care system between January 1, 2001, and October 31, 2015. Exposure was ADT initiation within 1 year of the PC diagnosis. The primary outcome was new development of depression. Secondary outcomes were outpatient psychiatric use, inpatient psychiatric use, and suicide.ResultsDuring follow‐up, 934 patients were newly diagnosed with depression, 7825 patients used outpatient psychiatric services, 358 patients used inpatient psychiatric services, and 54 patients committed suicide. In the multivariable competing risks regression model, ADT was associated with the development of depression (subdistribution hazard ratio [SHR], 1.50; 95% confidence interval [CI], 1.32‐1.71; P < .001). ADT was also associated with outpatient psychiatric utilization (SHR, 1.21; 95% CI, 1.16‐1.27; P < .001). Finally, ADT was not associated with inpatient psychiatric utilization or suicide.ConclusionsAn increase in the risk of depression and the use of outpatient psychiatric services was observed in a large cohort of men with PC who received ADT with definitive RT. These results may provide further evidence for the long‐term risks of ADT for psychiatric health in the treatment of PC.
Construction of Nonmetallic p‐n Heterojunction With Face‐to‐Face Structure for Drastically Enhanced Photocatalytic Performance
Authors: Wang Shuhao , Li Chunmei , Han Juan , Wang Lei , Lu Zhiyuan , Wu Jiacong , Wang Yun 
Published: February 2019

AbstractIt is still a great challenge to exploit high‐efficiency nonmetallic composite photocatalysts by structural design for improving H2 production performance. Here, the nonmetallic p‐n heterojunctions with face‐to‐face structure are prepared via hydrothermal in‐situ polymerization of PEDOT on the surface of g‐C3N4. The face‐to‐face modification of PEDOT on g‐C3N4 not only broadens the response in the visible light region but also increases the electron delocalization of conjugated system, which results in improving the visible light harvest ability and separation efficiency of charge carriers. The obtained PEDOT/g‐C3N4 heterojunctions display the improved H2 production activity, and the optimal H2 production rate reaches up to 3636.6 μmol g−1 h−1 with QE value of 5.6% at 420 nm, which is 5.46 times higher than that of pure g‐C3N4 (665.8 μmol g−1 h−1).
Psychometric properties of the Spanish version of the involvement evaluation questionnaire in caregivers of patients with borderline personality disorders
Authors: Marco José H. , Jorquera Mercedes , Fernandez Irene , Baños Rosa , Guillén Verónica 
Published: February 2019

AbstractThe involvement evaluation questionnaire (IEQ) was created to evaluate the caregiver's experience of burden and the consequences of providing care to people with psychotic disorders. To date, the IEQ has not been validated with caregivers of people diagnosed with borderline personality disorder (BPD). The main objective of the study was to confirm the psychometric properties and factorial structure of the Spanish version of the IEQ in 151 caregivers of people with BPD, with an average age of 54.52 (SD = 9.91). Two models were tested by means of confirmatory factor analysis, following the original factor structure. The Models 1 and 2 displayed adequate fit, with comparative fit index and Tucker‐Lewis index > 0.90 and root‐mean‐square root of approximation < 0.08; however, Model 2 was more parsimonious. The Cronbach's alphas are adequate, ranging from 0.70 to 0.85. The consequences of providing care to people with BPD had a low or moderate association with the Level of Expressed Emotion scores. IEQ scores of caregivers of people diagnosed with BPD with psychiatric comorbidity did not differ from those of caregivers of people diagnosed with BPD without psychiatric comorbidity. The IEQ has adequate psychometric properties and can be utilized to assess burden in caregivers of people with BPD.
Simultaneous Photoelectrocatalytic Water Oxidation and Oxygen Reduction for Solar Electricity Production in Alkaline Solution
Authors: Zhang Bingqing , He Lihue , Yao Tingting , Fan Wenjun , Zhang Xiangtian , Wen Sheng , Shi Jingying , Li Can 
Published: February 2019

AbstractThe photoelectrochemical (PEC) method offers an alternative approach to photovoltaic devices for solar electricity generation. The water oxidation reaction (WOR) on the anode and oxygen reduction reaction (ORR) on the cathode is an ideal design for energy transfer owing to their superiority in terms of cleanliness, eco‐friendliness, and natural abundance. However, solar electricity production based on O2 circulation by a fuel‐free PEC cell is very challenging because it is extremely hard to extract electrons from water molecules owing to the uphill and sluggish WOR together with enormous overpotential for the cathodic ORR. Herein, a PEC cell based on the OH−/O2 redox pair is reported for efficient and sustainable solar electricity production by using two photoelectrodes of TiO2 and polyterthiophene in alkaline electrolyte. This fuel‐free PEC cell delivers an open‐circuit voltage up to 0.90 V and a maximum power density of 222 μW cm−2 with O2‐saturated NaOH electrolyte under AM 1.5 G solar irradiation. A record solar‐to‐electricity conversion efficiency of 0.22 % is achieved in the case of tandem illumination of the two photoelectrodes. In addition, the dual photoelectrode remains robust in accelerated and day–night cycling operation under natural atmosphere for more than a week. This PEC cell is free of fuel, separating membranes, and cocatalyst, which may guide future designs for clean and simple devices for solar energy conversion.
Emotion regulation and cortisol reactivity during a social evaluative stressor: A study of post‐institutionalized youth
Authors: Perry Nicole B. , Donzella Bonny , Parenteau Anna M. , Desjardins Christopher , Gunnar Megan R. 
Published: February 2019

AbstractIn the current study, we compared emotion regulation abilities between post‐institutionalized (PI; N = 124) and never‐institutionalized non‐adopted (NA; N = 172) children and adolescents (7–15 years). We assessed cortisol reactivity and coded emotion regulation during the speech portion of Trier Social Stress Test (TSST‐M). Parents reported on their children's social, academic, and behavioral adjustment. Results suggest that emotion regulation abilities increased with age, but this increase was greater for NA than PI youth. With regard to cortisol, piecewise growth modeling revealed that at higher levels of emotion regulation PI youth had greater baseline values (after a period of time allowing for acclimation to the laboratory) and had steeper recovery slopes than NA youth. There was also a main effect of emotion regulation on the reactivity slope suggesting that for both groups, as emotion regulation increased, the cortisol reactivity slope decreased. Finally, greater emotion regulation predicted fewer internalizing behavior problems for PI youth but not for NA youth.
Immunological and clinical characteristics of latent autoimmune diabetes in the elderly
Authors: Yohena Silvina , Penas‐Steinhardt Alberto , Muller Clara , Faccinetti Natalia I. , Cerrone Gloria E. , Lovecchio Silvia , Ridner Edgardo , Valdez Silvina , Frechtel Gustavo 
Published: February 2019

Background:Latent autoimmune diabetes in adults (LADA) is determined by both a noninsulin‐dependent clinical presentation and an autoimmune pathogenic process. Glutamic acid decarboxylase antibody (GADA) constitutes the most important marker, although IA‐2A and ZnT8A also define LADA presentation. Type 2 diabetes mellitus (T2DM) is the most prevalent type particularly over 65 years old. Studies about autoimmunity in this age group are scarce.Objective:The aim of this work was to determine whether three autoantibodies for diabetes autoimmunity were present in elderly T2DM patients, and to assess the distinctive clinical features of autoantibody‐positive patients.Research Design and Methods:We recruited 153 patients with diabetes with onset of diabetes after 65 years of age and a BMI under 30 kg/m2.Results:The prevalence of at least one of the autoantibodies was 15.68% (24/153). The most prevalent autoantibody was GADA with 8.49% (13/153), followed by ZnT8A with 6.50% (10/153) and IA2A with 1.96% (3/153). The autoimmunity‐positive group presented higher HbA1c (7.01 ± 1.98 vs 6.35 ± 1.01; P = 0.007) and more prevalent insulin therapy (25% vs 10.85%; P = 0.047). GADA‐positive patients with diabetes presented higher FPG (7.79 ± 3.79 mmol/L vs 6.43 ± 1.6 mmol/L; P = 0.014) and insulin therapy more frequently (46% vs 10.71%; p = 0.015). GADA titre levels in the individuals with BMI under 27 kg/m2 were higher (35.00 ± 4.20) than those in the group with BMI over 27 kg/m2 (8.83 ± 3.041; P = 0.0005).Conclusion:Autoantibodies GADA and Znt8A may be useful markers in identifying a subgroup of older patients with a clinical presentation of diabetes which could be characterized as latent autoimmune diabetes in the elderly.
Evolutionary maintenance of genomic diversity within arbuscular mycorrhizal fungi
Authors: Scott Thomas W. , Kiers E. Toby , Cooper Guy A. , dos Santos Miguel , West Stuart A. 
Published: February 2019

AbstractMost organisms are built from a single genome. In striking contrast, arbuscular mycorrhizal fungi appear to maintain genomic variation within an individual fungal network. Arbuscular mycorrhizal fungi dwell in the soil, form mutualistic networks with plants, and bear multiple, potentially genetically diverse nuclei within a network. We explore, from a theoretical perspective, why such genetic diversity might be maintained within individuals. We consider selection acting within and between individual fungal networks. We show that genetic diversity could provide a benefit at the level of the individual, by improving growth in variable environments, and that this can stabilize genetic diversity even in the presence of nuclear conflict. Arbuscular mycorrhizal fungi complicate our understanding of organismality, but our findings offer a way of understanding such biological anomalies.
Ecological evaluation of a marine protected area network: a progressive‐change BACIPS approach
Authors: Thiault L. , Kernaléguen L. , Osenberg C. W. , Lison de Loma T. , Chancerelle Y. , Siu G. , Claudet J. 
Published: February 2019

AbstractMarine protected area (MPA) networks, with varying degrees of protection and use, can be useful tools to achieve both conservation and fisheries management benefits. Assessing whether MPA networks meet their objectives requires data from Before the establishment of the network to better discern natural spatiotemporal variation and preexisting differences from the response to protection. Here, we use a Progressive‐Change BACIPS approach to assess the ecological effects of a network of five fully and three moderately protected MPAs on fish communities in two coral reef habitats (lagoon and fore reef) based on a time series of data collected five times (over three years) Before and 12 times (over nine years) After the network's establishment on the island of Moorea, French Polynesia. At the network scale, on the fore reef, density and biomass of harvested fishes increased by 19.3% and 24.8%, respectively, in protected areas relative to control fished areas. Fully protected areas provided greater ecological benefits than moderately protected areas. In the lagoon, density and biomass of harvested fishes increased, but only the 31% increase in biomass in fully protected MPAs was significant. Non‐harvested fishes did not respond to protection in any of the habitats. We propose that these responses to protection were small, relative to other MPA assessments, due to limited compliance and weak surveillance, although other factors such as the occurrence of a crown‐of‐thorns starfish outbreak and a cyclone after the network was established may also have impeded the ability of the network to provide benefits. Our results highlight the importance of using fully protected MPAs over moderately protected MPAs to achieve conservation objectives, even in complex social–ecological settings, but also stress the need to monitor effects and adapt management based on ongoing assessments.
Conservation planning at the intersection of landscape and climate change: brook trout in the Chesapeake Bay watershed
Authors: Merriam Eric R. , Petty J. Todd , Clingerman Jason 
Published: February 2019

AbstractWe developed a multi‐scale conservation planning framework for brook trout (Salvelinus fontinalis) within the Chesapeake Bay watershed that incorporates both land use and climate stressors. Our specific objectives were to (1) construct a continuous spatial model of brook trout distribution and habitat quality at the stream reach scale; (2) characterize brook trout vulnerability to climate change under a range of future climate scenarios; and (3) identify multi‐scale restoration and protection priorities for brook trout across the Chesapeake Bay watershed. Boosted regression tree analysis predicted brook trout occurrence at the stream reach scale with a high degree of accuracy (CV AUC = 0.92) as a function of both natural (e.g., water temperature and precipitation) and anthropogenic (e.g., agriculture and urban development) landscape and climatic attributes. Current land use activities result in a predicted loss of occurrence in over 11,000 stream segments (40% of suitable habitat) and account for over 15,000 km (45% of current value) of lost functional brook trout fishery value (i.e., length‐weighted occurrence probability) in the Chesapeake Bay watershed. Climate change (increased ambient temperatures and altered precipitation) is projected to result in a loss of occurrence in at least 3000 additional segments (19% of current value) and at least 3000 km of functional fishery value (9% of current value) by 2062. Model outcomes were used to identify low‐ and high‐quality stream segments within relatively intact and degraded sub‐watersheds as restoration and protection priorities, respectively, and conservation priorities were targeted in watersheds with high projected resilience to climate change. Our results suggest that traditional restoration activities, such as habitat enhancement, riparian management, and barrier removal, may be able to recover a substantial amount of brook trout habitat lost to historic landscape change. However, restoration efforts must be designed within the context of expected impacts from climate change or those efforts may not produce long‐term benefits to brook trout in this region.
Thermal disruption of soil bacterial assemblages decreases diversity and assemblage similarity
Authors: Weiser Michael D. , Ning Daliang , Buzzard Vanessa , Michaletz Sean T. , He Zhili , Enquist Brian J. , Waide Robert B. , Zhou Jizhong , Kaspari Michael 
Published: February 2019

AbstractThe metabolic theory of ecology assumes that rates of selection and adaptation for organisms are functions of temperature. Niche theory predicts that strong selection pressure should simplify assemblages as species are extirpated and taxa pre‐adapted for the new environment thrive. Here, we use closed mesocosms to test the prediction that higher temperatures decrease species richness and increase assemblage similarity more and faster than lower temperatures. We incubated two temperate forest soil types at constant temperatures from 10° to 35°, destructively sampling mesocosms at 30, 180, and 440 d. We quantified taxonomic richness and assemblage similarity of soil bacteria using 16S rRNA gene amplicons. As predicted, mesocosms at higher temperatures lost more taxa than those at lower temperature. Contrary to predictions, the simplified assemblages at higher temperatures became less similar to each other over time. After 440 d of incubation, the number of taxa lost was a linear function of the difference between treatment temperature and site mean annual temperature, while assemblage similarity decreased as an accelerating function of this temperature difference.
Differential oviposition and offspring success of gray treefrogs in the presence of an invasive fish
Authors: Smith Geoffrey R. , Harmon Johanna J. 
Published: February 2019

AbstractFemales often decide where to place their eggs or offspring based on the relative risks and benefits of a location. One trade‐off may be between ovipositing with predators and ovipositing with competitors. Many amphibians show risk‐sensitive oviposition and select oviposition sites based on offspring performance. We examined differential oviposition and offspring success by gray treefrogs (Hyla versicolor) in response to the presence of caged or free‐ranging invasive western mosquitofish (Gambusia affinis) using cattletank mesocosms as experimental ponds. Our experiment sought to answer these questions by comparing the number of eggs laid and tadpoles produced among the experimental treatments: (1) Do gray treefrogs exhibit risk‐sensitive oviposition? and (2) What is the relative importance of pre‐colonization and post‐colonization consumptive and trait‐mediated effects of western mosquitofish? Gray treefrogs laid more eggs in control and caged predator mesocosms than in free‐ranging predator mesocosms. At the end of the experiment, there were more tadpoles in control and caged predator mesocosms than in free‐ranging predator mesocosms. Proportional yield was lower in free‐ranging predator mesocosms than control and caged predator mesocosms. Eggs were laid 7–8 d earlier in control mesocosms than caged and free‐ranging predator mesocosms. Western mosquitofish therefore had a negative effect on the successful colonization of experimental ponds by gray treefrogs, most likely through direct physical interactions. Our results also suggest gray treefrogs shift oviposition preferences as the number of conspecifics reaches a threshold where competition risk outweighs predation risk. Western mosquitofish therefore have great potential to affect the distribution of gray treefrogs through pre‐ and post‐colonization effects.