bluuebunny/crossref_metadata_2025_split huggingface dataset:
Conductive Two‐Dimensional Phthalocyanine‐based Metal–Organic Framework Nanosheets for Efficient Electroreduction of CO2
Authors: Yi Jun‐Dong , Si Duan‐Hui , Xie Ruikuan , Yin Qi , Zhang Meng‐Di , Wu Qiao , Chai Guo‐Liang , Huang Yuan‐Biao , Cao Rong 
Published: May 2021

AbstractThe electrocatalytic conversion of CO2 into value‐added chemicals is a promising approach to realize a carbon‐energy balance. However, low current density still limits the application of the CO2 electroreduction reaction (CO2RR). Metal–organic frameworks (MOFs) are one class of promising alternatives for the CO2RR due to their periodically arranged isolated metal active sites. However, the poor conductivity of traditional MOFs usually results in a low current density in CO2RR. We have prepared conductive two‐dimensional (2D) phthalocyanine‐based MOF (NiPc‐NiO4) nanosheets linked by nickel‐catecholate, which can be employed as highly efficient electrocatalysts for the CO2RR to CO. The obtained NiPc‐NiO4 has a good conductivity and exhibited a very high selectivity of 98.4 % toward CO production and a large CO partial current density of 34.5 mA cm−2, outperforming the reported MOF catalysts. This work highlights the potential of conductive crystalline frameworks in electrocatalysis.
Selective Separation of Hexachloroplatinate(IV) Dianions Based on Exo‐Binding with Cucurbit[6]uril
Authors: Wu Huang , Wang Yu , Jones Leighton O. , Liu Wenqi , Zhang Long , Song Bo , Chen Xiao‐Yang , Stern Charlotte L. , Schatz George C. , Stoddart J. Fraser 
Published: May 2021

AbstractThe recognition and separation of anions attracts attention from chemists, materials scientists, and engineers. Employing exo‐binding of artificial macrocycles to selectively recognize anions remains a challenge in supramolecular chemistry. We report the instantaneous co‐crystallization and concomitant co‐precipitation between [PtCl6]2−dianions and cucurbit[6]uril, which relies on the selective recognition of these dianions through noncovalent bonding interactions on the outer surface of cucurbit[6]uril. The selective [PtCl6]2−dianion recognition is driven by weak [Pt−Cl⋅⋅⋅H−C] hydrogen bonding and [Pt−Cl⋅⋅⋅C=O] ion–dipole interactions. The synthetic protocol is highly selective. Recognition is not observed in combinations between cucurbit[6]uril and six other Pt‐ and Pd‐ or Rh‐based chloride anions. We also demonstrated that cucurbit[6]uril is able to separate selectively [PtCl6]2−dianions from a mixture of [PtCl6]2−, [PdCl4]2−, and [RhCl6]3−anions. This protocol could be exploited to recover platinum from spent vehicular three‐way catalytic converters and other platinum‐bearing metal waste.
Clinical risk prediction models and informative cluster size: Assessing the performance of a suicide risk prediction algorithm
Authors: Coley Rebecca Yates , Walker Rod L. , Cruz Maricela , Simon Gregory E. , Shortreed Susan M. 
Published: May 2021

AbstractClinical visit data are clustered within people, which complicates prediction modeling. Cluster size is often informative because people receiving more care are less healthy and at higher risk of poor outcomes. We used data from seven health systems on 1,518,968 outpatient mental health visits from January 1, 2012 to June 30, 2015 to predict suicide attempt within 90 days. We evaluated true performance of prediction models using a prospective validation set of 4,286,495 visits from October 1, 2015 to September 30, 2017. We examined dividing clustered data on the person or visit level for model training and cross‐validation and considered a within cluster resampling approach for model estimation. We evaluated optimism by comparing estimated performance from a left‐out testing dataset to performance in the prospective dataset. We used two prediction methods, logistic regression with least absolute shrinkage and selection operator (LASSO) and random forest. The random forest model using a visit‐level split for model training and testing was optimistic; it overestimated discrimination (area under the curve, AUC = 0.95 in testing versus 0.84 in prospective validation) and classification accuracy (sensitivity = 0.48 in testing versus 0.19 in prospective validation, 95th percentile cut‐off). Logistic regression and random forest models using a person‐level split performed well, accurately estimating prospective discrimination and classification: estimated AUCs ranged from 0.85 to 0.87 in testing versus 0.85 in prospective validation, and sensitivity ranged from 0.15 to 0.20 in testing versus 0.17 to 0.19 in prospective validation. Within cluster resampling did not improve performance. We recommend dividing clustered data on the person level, rather than visit level, to ensure strong performance in prospective use and accurate estimation of future performance at the time of model development.
Measuring resting cerebral haemodynamics using MRI arterial spin labelling and transcranial Doppler ultrasound: Comparison in younger and older adults
Authors: Burley Claire V. , Francis Susan T. , Whittaker Anna C. , Mullinger Karen J. , Lucas Samuel J.E. 
Published: May 2021

AbstractIntroductionResting cerebral blood flow (CBF) and perfusion measures have been used to determine brain health. Studies showing variation in resting CBF with age and fitness level using different imaging approaches have produced mixed findings. We assess the degree to which resting CBF measures through transcranial Doppler (TCD) and arterial spin labeling (ASL) MRI provide complementary information in older and younger, fit and unfit cohorts.MethodsThirty‐five healthy volunteers (20 younger: 24 ± 7y; 15 older: 66 ± 7y) completed two experimental sessions (TCD/MRI). Aging and fitness effects within and between imaging modalities were assessed.ResultsMiddle cerebral artery blood velocity (MCAv, TCD) was lower and transit time (MRI) slower in older compared with younger participants (p < .05). The younger group had higher gray matter cerebral perfusion (MRI) than the older group, albeit not significantly (p = .13). Surprisingly, fitness effects in the younger group (decrease/increase in MCAv/transit time with fitness, respectively) opposed the older group (increase/decrease in MCAv/transit time). Whole cohort transit times correlated with MCAv (r=−0.63; p < .05), whereas tissue perfusion did not correlate with TCD measures.ConclusionTCD and MRI modalities provide complementary resting CBF measures, with similar effects across the whole cohort and between subgroups (age/fitness) if metrics are comparable (e.g., velocity [TCD] versus transit time [MRI]).
Association between homocysteine and white matter hyperintensities in rural‐dwelling Chinese people with asymptomatic intracranial arterial stenosis: A population‐based study
Authors: Wang Xiang , Yin Hao , Ji Xiaokang , Sang Shaowei , Shao Sai , Wang Guangbin , Lv Ming , Xue Fuzhong , Du Yifeng , Sun Qinjian 
Published: May 2021

AbstractPurposeAlthough homocysteine (Hcy) has been proven to be associated with the incidence of white matter hyperintensities (WMH) in patients with stroke, this association remains unclear in participants with asymptomatic intracranial arterial stenosis (aICAS). This study aimed to investigate the association of Hcy with WMH in participants with aICAS.Materials and methodsThis was a cross‐sectional study based on the Kongcun Town Study. Participants diagnosed with aICAS by magnetic resonance angiography in the Kongcun Town Study were enrolled in this study. Data on demographics, lifestyle, medical histories, and Hcy levels were collected via interviews, clinical examinations, and laboratory tests. The volume of WMH was calculated using the lesion segmentation tool system for the Statistical Parametric Mapping package based on magnetic resonance imaging. The association between Hcy and WMH volume was analyzed using linear and logistic regression analyses.ResultsA total of 137 aICAS participants were enrolled in the present study. Hcy was associated with the incidence of severe WMH (4th quartile, ≥4.20 ml) after adjustment for certain covariates [Hcy as a continuous variable, odds ratio (95% confidence interval) (OR (95% CI)): 1.09 (1.00, 1.19), p = .047; as a categorical variable (Hcy ≥15 μmol/L), OR (95% CI): 3.74 (1.37, 10.19), p = .010)]. After stratification according to the degree of aICAS, this relationship remained significant only in the moderate‐to‐severe stenosis group (stenosis ≥50%). (Hcy as continuous variable, OR (95% CI): 1.14 (1.02, 1.27), p = .025; as a categorical variable (Hcy ≥15 μmol/L), OR (95% CI): 5.59 (1.40, 15.25), p = .015).ConclusionSerum Hcy concentration may be positively associated with the volume of WMH in rural‐dwelling Chinese people with moderate‐to‐severe (stenosis ≥50%) aICAS.
Toward a method for evaluating court actor influences on plea negotiations: A preliminary exploration of public defenders
Authors: Metcalfe Christi 
Published: May 2021

AbstractPlea negotiations remain difficult to study, partly because their informality implicates workgroup‐related factors within decision‐making. In quantitative analyses, these factors are impossible to measure using the case‐level data alone. The current study proposes a combined method using survey data and administrative case data as a means of contextualizing the plea process from the standpoint of workgroup members and quantifying workgroup characteristics that can be used as variables in models predicting actual plea outcomes. A preliminary exploration of this kind is conducted with public defenders. The survey data revealed that public defenders thought pleas were necessary to manage caseloads and resources, but also felt the benefits to defendants outweighed the drawbacks. In a descriptive analysis linking survey‐ and case‐level data, the percent of charge reductions among plea cases varied substantively based on both workgroup relationship characteristics and ideologies of the public defenders. Directions for future research adopting this type of approach are discussed.
Caged Cumate Enables Proximity‐Dependent Control Over Gene Expression
Authors: Love Anna C. , Tran Sabrina H. , Prescher Jennifer A. 
Published: May 2021

AbstractCell‐cell interactions underlie diverse physiological processes yet remain challenging to examine with conventional imaging tools. Here we report a novel strategy to illuminate cell proximity using transcriptional activators. We repurposed cumate, a small molecule inducer of gene expression, by caging its key carboxylate group with a nitrile. Nitrilase‐expressing activator cells released the cage, liberating cumate for consumption by reporter cells. Reporter cells comprising a cumate‐responsive switch expressed a target gene when in close proximity to the activator cells. Overall, this strategy provides a versatile platform to image and potentially manipulate cellular interactions over time.
Co‐Oxidative Transformation of Piperine to Piperonal and 3,4‐Methylenedioxycinnamaldehyde by a Lipoxygenase from Pleurotus sapidus
Authors: Krahe Nina‐Katharina , Berger Ralf G. , Kahlert Lukas , Ersoy Franziska 
Published: May 2021

AbstractThe valuable aroma compound piperonal with its vanilla‐like olfactory properties is of high interest for the fragrance and flavor industry. A lipoxygenase (LOXPsa1) of the basidiomycete Pleurotus sapidus was identified to convert piperine, the abundant pungent principle of black pepper (Piper nigrum), to piperonal and a second volatile product, 3,4‐methylenedioxycinnamaldehyde, with a vanilla‐like odor through an alkene cleavage. The reaction principle was co‐oxidation, as proven by its dependence on the presence of linoleic or α‐linolenic acid, common substrates of lipoxygenases. Optimization of the reaction conditions (substrate concentrations, reaction temperature and time) led to a 24‐fold and 15‐fold increase of the piperonal and 3,4‐methylenedioxycinnamaldehyde concentration using the recombinant enzyme. Monokaryotic strains showed different concentrations of and ratios between the two reaction products.
Simple Plug‐In Synthetic Step for the Synthesis of (−)‐Camphor from Renewable Starting Materials
Authors: Calderini Elia , Drienovská Ivana , Myrtollari Kamela , Pressnig Michaela , Sieber Volker , Schwab Helmut , Hofer Michael , Kourist Robert 
Published: May 2021

AbstractRacemic camphor and isoborneol are readily available as industrial side products, whereas (1R)‐camphor is available from natural sources. Optically pure (1S)‐camphor, however, is much more difficult to obtain. The synthesis of racemic camphor from α‐pinene proceeds via an intermediary racemic isobornyl ester, which is then hydrolyzed and oxidized to give camphor. We reasoned that enantioselective hydrolysis of isobornyl esters would give facile access to optically pure isoborneol and camphor isomers, respectively. While screening of a set of commercial lipases and esterases in the kinetic resolution of racemic monoterpenols did not lead to the identification of any enantioselective enzymes, the cephalosporin Esterase B from Burkholderia gladioli (EstB) and Esterase C (EstC) from Rhodococcus rhodochrous showed outstanding enantioselectivity (E>100) towards the butyryl esters of isoborneol, borneol and fenchol. The enantioselectivity was higher with increasing chain length of the acyl moiety of the substrate. The kinetic resolution of isobornyl butyrate can be easily integrated into the production of camphor from α‐pinene and thus allows the facile synthesis of optically pure monoterpenols from a renewable side‐product.
Misplaced enthusiasm with neglect of Human Rights ‐ Beneficence is not enough
Authors: Gunn John 
Published: May 2021

AbstractBackgroundOak Ridge, a unit for "criminally insane" male patients at Penetanguishene in Ontario, Canada opened in1965 and provided an experimental system of treatment whereby patients looked after other in a strictly controlled and harsh environment. It closed in 1983.AimsThis article draws attention to the unethical treatments used.MethodSome of the treatments are described, as is, briefly, the recent civil lawsuit in Ontario which concerned 28 ex‐patients in a class action suit against the province and the two doctors overseeing the experimental project.ResultThe judge severely criticised the experimental treatment and awarded damages to all of the 28 plaintiffs.ConclusionThe vivid story leads to a number of important principles which are enumerated at the head of the article.
Heavy‐Atom‐Free Bay‐Substituted Perylene Diimide Donor‐Acceptor Photosensitizers
Authors: Deckers Jasper , Cardeynaels Tom , Lutsen Laurence , Champagne Benoît , Maes Wouter 
Published: May 2021

AbstractPerylene diimide (PDI) dyes are extensively investigated because of their favorable photophysical characteristics for a wide range of organic material applications. Fine‐tuning of the optoelectronic properties is readily achieved by functionalization of the electron‐deficient PDI scaffold. Here, we present four new donor‐acceptor type dyads, wherein the electron donor units – benzo[1,2‐b : 4,5‐b’]dithiophene, 9,9‐dimethyl‐9,10‐dihydroacridine, dithieno[3,2‐b : 2’,3’‐d]pyrrole, and triphenylamine‐are attached to the bay‐positions of the PDI acceptor. Intersystem crossing occurs for these systems upon photoexcitation, without the aid of heavy atoms, resulting in singlet oxygen quantum yields up to 80 % in toluene solution. Furthermore, this feature is retained when the system is directly irradiated with energy corresponding to the intramolecular charge‐transfer absorption band (at 639 nm). Geometrical optimization and (time‐dependent) density functional theory calculations afford more insights into the requirements for intersystem crossing such as spin‐orbit coupling, dihedral angles, the involvement of charge‐transfer states, and energy level alignment.
High‐Throughput NanoString Analysis of Oncogenic Human Papillomavirus and Tumor Microenvironment Transcription in Head and Neck Squamous Cell Carcinoma
Authors: Stepp Wesley H. 
Published: May 2021

AbstractHuman papillomaviruses (HPVs), specifically high‐risk HPVs, are responsible for up to 3% of all cancers in women and up to 2% of all cancers in men. They have been identified as the etiological agent of cervical cancer and have been increasingly found to be the driver behind head and neck cancers of the oropharynx. A system in which we can simultaneously observe transcriptional changes to both a host's tumor microenvironment and its associated oncogenic driver (e.g., HPV) would be highly valuable for understanding HPV's role in tumorigenesis. This article describes a detailed methodology for utilizing high‐throughput RNA analysis to study viral transcription in formalin‐fixed, paraffin‐embedded clinical tumor samples. Although our lab utilizes these methods for the study of head and neck cancer, the principles contained within are widely applicable to all fields of HPV study. © 2021 Wiley Periodicals LLC.Basic Protocol: HPV16 transcript analysis using NanoStringSupport Protocol 1: Preparation of RNA from formalin‐fixed, paraffin‐embedded slidesSupport Protocol 2: Preparation of RNA from cell lysatesSupport Protocol 3: Fluorometric RNA concentration and RNA integrity analysisSupport Protocol 4: Determination of input RNA based on DV300 calculation
A Case Study to Address: “Is Your Pulsed Laser Deposition Chamber Clean?”
Authors: Dumen Manish , Kaur Ripudaman , Goyal Saveena , Tomar Ruchi , Wadehra Neha , Chakraverty Suvankar 
Published: May 2021

AbstractPulsed laser deposition (PLD) is one of the important techniques for the growth of oxide thin films, interfaces, and superlattices. It can also be utilized to implement diverse combinatorial approaches. Thin film growth using PLD hinges on various parameters that decide the composition, structure, quality, and finally the physical properties of the films, interfaces, and superlattices. In this paper it is demonstrated how the growth conditions inside the chamber during the growth can be judged from outside by combining in situ and ex situ techniques. An example of the growth of LaVO3‐SrTiO3 interface is given to elucidate the effect of repetitive growth on the chamber condition and hence on the reproducibility of the physical properties of the samples. The experiments suggest noticeable change in transport properties with successive deposition processes.
Controlling Void Space in Crumpled Graphene‐Encapsulated Silicon Anodes using Sacrificial Polystyrene Nanoparticles
Authors: She Zimin , Uceda Marianna , Pope Michael A. 
Published: May 2021

AbstractSilicon anodes have a theoretical capacity of 3590 mAh g−1 (for Li15Si4, at room temperature), which is tenfold higher than the graphite anodes used in current Li‐ion batteries. This, and silicon's natural abundance, makes it one of the most promising materials for next‐generation batteries. Encapsulating silicon nanoparticles (Si NPs) in a crumpled graphene shell by spray drying or spray pyrolysis are promising and scalable methods to produce core–shell structures, which buffer the extreme volume change (>300 vol %) caused by (de)lithiaton of silicon. However, capillary forces cause the graphene‐based materials to tightly wrap around Si NP clusters, and there is little control over the void space required to further improve cycle life. Herein, a simple strategy is developed to engineer void‐space within the core by incorporating varying amounts of similarly sized polystyrene (PS) nanospheres in the spray drier feed mixture. The PS completely decomposes during thermal reduction of the graphene oxide shell and results in Si cores of varying porosity. The best performance is achieved at a 1 : 1 ratio (PS/Si), leading to high capacities of 1638, 1468, and 1179 mAh g−1Si+rGO at 0.1, 1, and 4 A g−1, respectively. Moreover, at 1 A g−1, the capacity retention is 80.6 % after 200 cycles. At a practical active material loading of 2.4 mg cm−2, the electrodes achieve an areal capacity of 2.26 mAh cm−2 at 1 A g−1.
Acid Hydrotropic Fractionation of Lignocelluloses for Sustainable Biorefinery: Advantages, Opportunities, and Research Needs
Authors: Zhu Junyong , Chen Liheng , Cai Cheng 
Published: May 2021

AbstractThis Minireview provides a comprehensive discussion on the potential of using acid hydrotropes for sustainably fractionating lignocelluloses for biorefinery applications. Acid hydrotropes are a class of acids that have hydrotrope properties toward lignin, which helps to solubilize lignin in aqueous systems. With the capability of cleaving ether and ester bonds and even lignin‐carbohydrate complex (LCC) linkages, these acid hydrotropes can therefore isolate lignin embedded in the plant biomass cell wall and subsequently solubilize the isolated lignin in aqueous systems. Performances of two acid hydrotropes, that is, an aromatic sulfonic acid [p‐toluenesulfonic acid (p‐TsOH)] and a dicarboxylic acid [maleic acid (MA)], in terms of delignification and dissolution of hemicelluloses, and reducing lignin condensation, were evaluated and compared. The advantages of lignin esterification by MA for producing cellulosic sugars through enzymatic hydrolysis and lignin‐containing cellulose nanofibrils (LCNFs) through mechanical fibrillation from the fractionated water insoluble solids (WIS), and for obtaining less condensed lignin with light color, were demonstrated. The excellent enzymatic digestibility of maleic acid hydrotropic fractionation WISs was also demonstrated by comparing with WISs from other fractionation processes. The recyclability and reusability of acid hydrotropes were also reviewed. Finally, perspectives on future research needs to address key technical issues for commercialization were also provided.
Development and evaluation of an automated palpebral fissure length measurement method and implementation system
Authors: Arisaka Naoya , Mamorita Noritaka , Inaoka Hidenori 
Published: May 2021

AbstractEyelid dysfunction results in symptoms of ptosis and eyelid retraction. Indicators of eyelid function include the corneal reflection distance at the eyelid margin and eyelid fissure (PF). There is currently no system in Japan that automatically measures the PF, which is a comprehensive measure of eyelid function. We devised a method to measure PF automatically from frontal images using ArUco markers and facial landmark estimation, and developed an implementation of the method using OpenCV and dlib. The system was shown to be significantly smaller than the digital calipers.
Influence of external mass transfer and support resistances for hydrogen permeation through composite palladium membranes
Authors: Arzani Fernanda A. , Ribeiro Neto Altamirando C. , Terra Natália M. , Cardoso Vicelma L. , Reis Miria H. M. 
Published: May 2021

AbstractPalladium membranes represent a suitable alternative to obtain high purity hydrogen for industrial applications. The modeling of hydrogen permeation through composite membranes is important to understand gas separation systems. Here, experimental and calculated hydrogen flux data through composite palladium/alumina membranes were compared. A dense palladium film of 2.4 μm thick was deposited on a porous support and the produced composite membrane presented infinite hydrogen/nitrogen selectivity. Experimental molecular hydrogen flux at 100 kPa and 723 K was 0.1015 ± 0.0009 mol m−2 s−1. Calculated molecular hydrogen fluxes with the conventional permeation model, without considering external mass transfer and support resistances, were at least 5.7 times greater than experimental data. However, calculated hydrogen flux was only 6.7% lower than the experimental flux at 100 kPa and 723 K when external mass transfer and support resistances were included in the conventional permeation model. Thus, external mass transfer resistances and the permeation through the porous support should be considered for a suitable description of hydrogen fluxes through composite palladium membranes.