bluuebunny/crossref_metadata_2025 huggingface dataset:
Ionizable Amino‐Polyesters Synthesized via Ring Opening Polymerization of Tertiary Amino‐Alcohols for Tissue Selective mRNA Delivery
Authors: Kowalski Piotr S. , Capasso Palmiero Umberto , Huang Yuxuan , Rudra Arnab , Langer Robert , Anderson Daniel G.
Published: July 2018

The utility of messenger RNA (mRNA) as a therapy is gaining a broad interest due to its potential for addressing a wide range of diseases, while effective delivery of mRNA molecules to various tissues still poses a challenge. This study reports on the design and characterization of new ionizable amino‐polyesters (APEs), synthesized via ring opening polymerization (ROP) of lactones with tertiary amino‐alcohols that enable tissue and cell type selective delivery of mRNA. With a diverse library of APEs formulated into lipid nanoparticles (LNP), structure‐activity parameters crucial for efficient transfection are established and APE‐LNPs are identified that can preferentially home to and elicit effective mRNA expression with low in vivo toxicity in lung endothelium, liver hepatocytes, and splenic antigen presenting cells, including APE‐LNP demonstrating nearly tenfold more potent systemic mRNA delivery to the lungs than vivo‐jetPEI. Adopting tertiary amino‐alcohols to initiate ROP of lactones allows to control polymer molecular weight and obtain amino‐polyesters with narrow molecular weight distribution, exhibiting batch‐to‐batch consistency. All of which highlight the potential for clinical translation of APEs for systemic mRNA delivery and demonstrate the importance of employing controlled polymerization in the design of new polymeric nanomaterials to improve in vivo nucleic acid delivery.
Spinel Structural Disorder Influences Solar‐Water‐Splitting Performance of ZnFe2O4 Nanorod Photoanodes
Authors: Zhu Xiaodi , Guijarro Néstor , Liu Yongpeng , Schouwink Pascal , Wells Rebekah A. , Le Formal Florian , Sun Song , Gao Chen , Sivula Kevin
Published: July 2018

Zinc spinel ferrite, ZnFe2O4 (ZFO), is an emerging photoanode material for photoelectrochemical (PEC) solar fuel production. However, a lack of fundamental insight into the factors limiting the photocurrent has prevented substantial advance in its performance. Herein, it is found that ZFO nanorod array photoelectrodes with varying crystallinity exhibit vastly different PEC properties. Using a sacrificial hole scavenger (H2O2), spatially defined carrier generation, and electrochemical impedance spectroscopy, it is shown that ZFO with a relatively poor crystallinity but a higher spinel inversion degree (due to cation disorder) exhibits superior photogenerated charge separation efficiency and improved majority charge carrier transport compared to ZFO with higher crystallinity and a lower inversion degree. Conversely, the latter condition leads to better charge injection efficiency. Optimization of these factors, and the addition of a nickel–iron oxide cocatalyst overlayer, leads to a new benchmark solar photocurrent for ZFO of 1.0 mA cm−2 at 1.23 V versus reversible hydrogen electrode (RHE) and 1.7 mA cm−2 at 1.6 V versus RHE. Importantly, the observed correlation between the cation disorder and the PEC performance represents a new insight into the factors important to the PEC performance of the spinel ferrites and suggests a path to further improvement.
Free‐Standing 2D Hexagonal Aluminum Nitride Dielectric Crystals for High‐Performance Organic Field‐Effect Transistors
Authors: Yang Fangxu , Jin Lei , Sun Lingjie , Ren Xiaochen , Duan Xiaoli , Cheng Hongjuan , Xu Yongkuan , Zhang Xiaotao , Lai Zhanping , Chen Wei , Dong Huanli , Hu Wenping
Published: July 2018

The existence of defects and traps in a transistor plays an adverse role on efficient charge transport. In response to this challenge, extensive research has been conducted on semiconductor crystalline materials in the past decades. However, the development of dielectric crystals for transistors is still in its infancy due to the lack of appropriate dielectric crystalline materials and, most importantly, the crystal morphology required by the gate dielectric layer, which is also crucial for the construction of high‐performance transistor as it can greatly improve the interfacial quality of carrier transport path. Here, a new type of dielectric crystal of hexagonal aluminum nitride (AlN) with the desired 2D morphology of combing thin thickness with large lateral dimension is synthesized. Such a suitable morphology in combination with the outstanding dielectric properties of AlN makes it promising as a gate dielectric for transistors. Furthermore, ultrathin 2,6‐diphenylanthracene molecular crystals with only a few molecular layers can be prepared on AlN crystal via van der Waals epitaxy. As a result, this all‐crystalline system incorporating dielectric and semiconductor crystals greatly enhances the overall performance of a transistor, indicating the importance of minimizing defects and preparing high‐quality semiconductor/dielectric interface in a transistor configuration.
Phase Modulation of (1T‐2H)‐MoSe2/TiC‐C Shell/Core Arrays via Nitrogen Doping for Highly Efficient Hydrogen Evolution Reaction
Authors: Deng Shengjue , Yang Fan , Zhang Qinghua , Zhong Yu , Zeng Yinxiang , Lin Shiwei , Wang Xiuli , Lu Xihong , Wang Cai‐Zhuang , Gu Lin , Xia Xinhui , Tu Jiangping
Published: July 2018

Tailoring molybdenum selenide electrocatalysts with tunable phase and morphology is of great importance for advancement of hydrogen evolution reaction (HER). In this work, phase‐ and morphology‐modulated N‐doped MoSe2/TiC‐C shell/core arrays through a facile hydrothermal and postannealing treatment strategy are reported. Highly conductive TiC‐C nanorod arrays serve as the backbone for MoSe2 nanosheets to form high‐quality MoSe2/TiC‐C shell/core arrays. Impressively, continuous phase modulation of MoSe2 is realized on the MoSe2/TiC‐C arrays. Except for the pure 1T‐MoSe2 and 2H‐MoSe2, mixed (1T‐2H)‐MoSe2 nanosheets are achieved in the N‐MoSe2 by N doping and demonstrated by spherical aberration electron microscope. Plausible mechanism of phase transformation and different doping sites of N atom are proposed via theoretical calculation. The much smaller energy barrier, longer HSe bond length, and diminished bandgap endow N‐MoSe2/TiC‐C arrays with substantially superior HER performance compared to 1T and 2H phase counterparts. Impressively, the designed N‐MoSe2/TiC‐C arrays exhibit a low overpotential of 137 mV at a large current density of 100 mA cm−2, and a small Tafel slope of 32 mV dec−1. Our results pave the way to unravel the enhancement mechanism of HER on 2D transition metal dichalcogenides by N doping.
In Situ Formed Protective Barrier Enabled by Sulfur@Titanium Carbide (MXene) Ink for Achieving High‐Capacity, Long Lifetime Li‐S Batteries
Authors: Tang Huan , Li Wenlong , Pan Limei , Cullen Conor P. , Liu Yu , Pakdel Amir , Long Donghui , Yang Jian , McEvoy Niall , Duesberg Georg S. , Nicolosi Valeria , Zhang Chuanfang (John)
Published: July 2018

Sulfur (S) is an attractive cathode material with advantages including high theoretical capacity and low cost. However, issues such as the lithium polysulfide shuttle effect and its insulating properties greatly limit the future applications of lithium‐sulfur (Li‐S) batteries. Here, a viscous aqueous ink with nanoscale S uniformly decorated on the polar, metallically conductive titanium carbide MXene nanosheets (S@Ti3C2Tx) is reported to address these issues. Importantly, it is observed that the conductive Ti3C2Tx mediator efficiently chemisorbs the soluble polysulfides and converts them into thiosulfate/sulfate. The in situ formed sulfate complex layer acts as a thick protective barrier, which significantly retards the shuttling of polysulfides upon cycling and improves the sulfur utilization. Consequently, the binder‐free, robust, highly electrically conductive composite film exhibits outstanding electrochemical performance, including high capacities (1244–1350 mAh g‐1), excellent rate handling, and impressive cycling stability (0.035–0.048% capacity loss per cycle), surpassing the best MXene‐S batteries known. The fabrication of a pouch cell based on the freestanding S@Ti3C2Tx film is also reported. The prototype device showcases high capacities and excellent mechanical flexibility. Considering the broad family of MXenes and their unique roles in immobilizing the polysulfides, various S@MXene composites can be similarly fabricated with promising Li+ storage capability and long lifetime performance.
Stack the Bowls: Tailoring the Electronic Structure of Corannulene‐Integrated Crystalline Materials
Authors: Rice Allison M. , Dolgopolova Ekaterina A. , Yarbrough Brandon J. , Leith Gabrielle A. , Martin Corey R. , Stephenson Kenneth S. , Heugh Rebecca A. , Brandt Amy J. , Chen Donna A. , Karakalos Stavros G. , Smith Mark D. , Hatzell Kelsey B. , Pellechia Perry J. , Garashchuk Sophya , Shustova Natalia B.
Published: July 2018

We report the first examples of purely organic donor–acceptor materials with integrated π‐bowls (πBs) that combine not only crystallinity and high surface areas but also exhibit tunable electronic properties, resulting in a four‐orders‐of‐magnitude conductivity enhancement in comparison with the parent framework. In addition to the first report of alkyne–azide cycloaddition utilized for corannulene immobilization in the solid state, we also probed the charge transfer rate within the Marcus theory as a function of mutual πB orientation for the first time, as well as shed light on the density of states near the Fermi edge. These studies could foreshadow new avenues for πB utilization for the development of optoelectronic devices or a route for highly efficient porous electrodes.
Tunable Water‐Soluble Supramolecular Polymers by Visible‐Light‐Regulated Host–Guest Interactions
Authors: Jin Ting‐Ting , Zhou Xiao‐He , Yin Yong‐Fei , Zhan Tian‐Guang , Cui Jiecheng , Liu Li‐Juan , Kong Li‐Chun , Zhang Kang‐Da
Published: July 2018

The development of artificial self‐assembling systems with dynamic photo‐regulation features in aqueous solutions has drawn great attention owing to the potential applications in fabricating elaborate biological materials. Here we demonstrate the fabrication of water‐soluble cucurbit[8]uril (CB[8])‐mediated supramolecular polymers by connecting the fluorinated azobenzene (FAB) containing monomers through host‐enhanced heteroternary π–π stacking interactions. Benefiting from the unique visible‐light‐induced E→Z photoisomerization of the FAB photochromophores, the encapsulation behaviors between the CB[8] macrocycle and the monomers could be regulated upon visible light irradiation, resulting in the depolymerization of such CB[8]‐mediated supramolecular polymers.
Validation of an LC‐MS/MS method for simultaneous determination of icotinib and its four major circulating metabolites in human plasma and its application in a pharmacokinetic study
Authors: Xiao Ying , Maiolino Piera , Yan Jin‐Hua , Ma Jie , Li Jin , Chen Li
Published: July 2018

In this study, a simple and sensitive LC‐MS/MS method was developed and validated for simultaneous determination of icotinib and its four circulating metabolites in human plasma. The analytes were extracted with acetonitrile and separated on a C18 column using 2 mm ammonium acetate containing 0.2% formic acid and acetonitrile as mobile phase. The analytes were introduced into the mass spectrometer via an electrospray ionization source operated in positive ion mode. Precursor‐to‐product transitions were optimized to be m/z 392.2 → 304.1 for icotinib, m/z 424.1 → 278.2 for M1 and M2, m/z 408.2 → 320.1 for M3, m/z 410.2 → 322.1 for M4 and m/z 394.4 → 278.1 for IS. The assay showed good linearity over the concentration ranges of 0.1–600 ng/mL for icotinib and 0.1–200 ng/mL for metabolites, with correlation coefficients >0.994 (r > 0.994). The LLOQ was 0.1 ng/mL for each analyte. The intra‐ and inter‐day precisions (RSD) were ≤12.98% while the accuracy (RE) ranged from −8.76 to 12.01%. No significant matrix effect was observed. The validated method was successfully applied for the pharmacokinetic study of icotinib and its four circulating metabolites in human plasma after oral administration of icotinib at a single dose of 125 mg.
Comparative study of chemical composition and active components against α‐glucosidase of various medicinal parts of Morus alba L.
Authors: Chen Zhiyong , Du Xia , Yang Yuanyuan , Cui Xiaomin , Zhang Zijia , Li Ye
Published: July 2018

Morus alba L has long been used as fodder and as a traditional medicine. The different parts of M. alba (Cortex Mori, Ramulus Mori, Folium Mori and Fructus Mori) have different bioactivities; however, most current evidence is focused on anti‐diabetic properties. In spite of their widespread use, few studies have compared the chemical composition and activity against α‐glucosidase of the various medicinal parts of M. alba. In this study, we developed an HPLC method for simultaneous quality control and discrimination of Cortex Mori, Ramulus Mori, Folium Mori and Fructus Mori using 13 marker compounds. We found that quercetin, morin, kuwanon G, sanggenon C, morusin, mulberroside A and rutin were chemically distinct among the various medicinal parts of M. alba. A spectrum–effect relationship method was established to compare α‐glucosidase inhibitory activity of various batches of samples to determine the activity of the primary active components against α‐glucosidase. Taken together with molecular docking data, we found that prenylated flavonoids (morin, sanggenon C, kuwanon G and morusin), flavonols (kaempferol, quercetin, rutin and isoquercitrin) and alkaloids (1‐deoxynojirimycin) were small molecule α‐glucosidase inhibitory ingredients. In conclusion, we laid a solid foundation for effective substance identification in various parts of M. alba, and simultaneously provided a basis for their quality control.
Core‐Shell Structured NiCo2O4@FeOOH Nanowire Arrays as Bifunctional Electrocatalysts for Efficient Overall Water Splitting
Authors: Li Man , Tao Leiming , Xiao Xin , Lv Xiaowei , Jiang Xingxing , Wang Mingkui , Peng Zhangquan , Shen Yan
Published: July 2018

Exploring earth‐abundant and high‐performance catalysts for water‐splitting is extremely crucial to produce clean hydrogen fuel. In this work, FeOOH was electrodeposited on NiCo2O4 nanowire to form a three dimensional (3D) core‐shell structure on Ni foam (NiCo2O4@FeOOH/NF) as bifunctional catalyst for overall water splitting. To control the thickness of FeOOH shell layer by optimizing electrodeposition time, the NiCo2O4@FeOOH/NF(500s) with FeOOH layer of ∼7 nm thickness exhibits excellent catalytic activity and stability for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline solution. Moreover, in a two‐electrode water splitting system, extremely small potential of 1.52 V can be achieved for NiCo2O4@FeOOH/NF(500s), giving a current density of 10 mA cm−2. Detailed investigation reveals that the thickness of FeOOH layer, strong electronic interaction at the interface between NiCo2O4 and FeOOH play critical role in the excellent catalytic property.
Multiple Multicomponent Reactions: Unexplored Substrates, Selective Processes, and Versatile Chemotypes in Biomedicine
Authors: Ghashghaei Ouldouz , Caputo Samantha , Sintes Miquel , Revés Marc , Kielland Nicola , Estarellas Carolina , Luque F. Javier , Aviñó Anna , Eritja Ramón , Serna‐Gallego Ana , Marrugal‐Lorenzo José Antonio , Pachón Jerónimo , Sánchez‐Céspedes Javier , Treadwell Ryan , de Moliner Fabio , Vendrell Marc , Lavilla Rodolfo
Published: July 2018

Multiple multicomponent reactions rapidly assemble complex structures. Despite being very productive, the lack of selectivity and the reduced number of viable transformations restrict their general application in synthesis. Hereby, we describe a rationale for a selective version of these processes based in the preferential generation of intermediates which are less reactive than the initial substrates. In this way, applying the Groebke–Blackburn–Bienaymé reaction on a range of α‐polyamino‐polyazines, we prepared a family compact heterocyclic scaffolds with relevant applications in medicinal and biological chemistry (live cell imaging probes, selective binders for DNA quadruplexes, and antiviral agents against human adenoviruses). The approach has general character and yields complex molecular targets in a selective, tunable and direct manner.
Functional Control of Peptide Amphiphile Assemblies via Modulation of Internal Cohesion and Surface Chemistry Switch
Authors: Lu Sheng , Cui Weijia , Li Jason , Sheng Yuebiao , Chen Pu
Published: July 2018

Understanding the impacts of the internal cohesion and surface chemistry of supramolecular systems on the collective behaviors in the contacts between the systems and biomolecules can greatly expand the functional diversity and adaptivity of supramolecular nanostructures. Here we show how the tuned molecular interactions modulate the morphologies and internal cohesion of peptide amphiphile (PA) self‐assemblies and their resultant functions. Circular dichroism spectroscopy, fluorescence probing, atomic force and electron microscopy, along with molecular dynamics simulations, revealed that the PA self‐assembly formed compact long fibers when surface charge repulsion was screened, but formed loose short fibers or micelle‐like assemblies when hydrogen bonding was disrupted or hydrophobic core was enhanced. More importantly, depending on the strength of the phospholipid affinity for the cationic segment of the PA, the same internal cohesion of PA nanostructures can lead to either cell death or cell survival, providing unique insights into the design of supramolecular materials.
Long‐term outcomes of partial prostate treatment with magnetic resonance imaging‐guided brachytherapy for patients with favorable‐risk prostate cancer
Authors: King Martin T. , Nguyen Paul L. , Boldbaatar Ninjin , Tempany Clare M. , Cormack Robert A. , Beard Clair J. , Hurwitz Mark D. , Suh W. Warren , D'Amico Anthony V. , Orio Peter F.
Published: July 2018

BACKGROUND

Partial prostate treatment has emerged as a potential method for treating patients with favorable‐risk prostate cancer while minimizing toxicity. The authors previously demonstrated poor rates of biochemical disease control for patients with National Comprehensive Cancer Network (NCCN) intermediate‐risk disease using partial gland treatment with brachytherapy. The objective of the current study was to estimate the rates of distant metastasis and prostate cancer‐specific mortality (PCSM) for this cohort.

METHODS

Between 1997 and 2007, a total of 354 men with clinical T1c disease, a prostate‐specific antigen (PSA) level < 15 ng/mL, and Gleason grade ≤3 + 4 prostate cancer underwent partial prostate treatment with brachytherapy to the peripheral zone under 0.5‐Tesla magnetic resonance guidance. The cumulative incidences of metastasis and PCSM for the NCCN very low‐risk, low‐risk, and intermediate‐risk groups were estimated. Fine and Gray competing risk regression was used to evaluate clinical factors associated with time to metastasis.

RESULTS

A total of 22 patients developed metastases at a median of 11.0 years (interquartile range, 6.9‐13.9 years). The 12‐year metastasis rates for patients with very low‐risk, low‐risk, and intermediate‐risk disease were 0.8% (95% confidence interval [95% CI], 0.1%‐4.4%), 8.7% (95% CI, 3.4%‐17.2%), and 15.7% (95% CI, 5.7%‐30.2%), respectively, and the 12‐year PCSM estimates were 1.6% (95% CI, 0.1%‐7.6%), 1.4% (95% CI, 0.1%‐6.8%), and 8.2% (95% CI, 1.9%‐20.7%), respectively. On multivariate analysis, NCCN risk category (low risk: hazard ratio, 6.34 [95% CI, 1.18‐34.06; P = .03] and intermediate risk: hazard ratio, 6.98 [95% CI, 1.23‐39.73; P = .03]) was found to be significantly associated with the time to metastasis.

CONCLUSIONS

Partial prostate treatment with brachytherapy may be associated with higher rates of distant metastasis and PCSM for patients with intermediate‐risk disease after long‐term follow‐up. Treatment of less than the full gland may not be appropriate for this cohort.
Effect of exercise on metabolic syndrome in black women by family history and predicted risk of breast cancer: The FIERCE Study
Authors: Dash Chiranjeev , Taylor Teletia R. , Makambi Kepher H. , Hicks Jennifer , Hagberg James M. , Adams‐Campbell Lucile L.
Published: July 2018

Background

This study examined the effects of supervised and home‐based exercise interventions on changes in metabolic syndrome (MetS) according to breast cancer risk (high vs low) in black women enrolled in the Focused Intervention on Exercise to Reduce Cancer (FIERCE) trial.

Methods

Postmenopausal, obese, metabolically unhealthy black women, 45 to 65 years old, were randomized to supervised aerobic exercise (73 women), home‐based walking‐based exercise (69 women), or a control arm (71 women). Participants in the exercise arms underwent a 6‐month intervention with study assessments conducted at the baseline and 6 months. The primary outcome measure was MetS (fasting glucose, waist circumference, blood pressure, serum triglycerides, and high‐density lipoprotein [HDL]). The intervention effects on MetS, stratified by breast cancer risk as measured by the family history of breast cancer and model‐based projected breast cancer risk, were examined with intent‐to‐treat analyses using generalized estimating equation models.

Results

Among women with a family history of breast cancer, the exercise arms had lower mean MetS z scores, which suggested an improvement in the metabolic profile, than controls at 6 months (controls, + 0.55; home‐based arm, –0.97, P < .01; supervised arm, –0.89, P < .01). Stratified analyses by projected breast cancer risk suggested similar but statistically nonsignificant findings, with those at high risk having more favorable changes in the MetS z score in the exercise arms versus the control arm. These changes were primarily attributable to changes in blood pressure, triglycerides, and HDL.

Conclusions

Short‐term aerobic activity regimens may improve the metabolic profile and thereby reduce breast cancer risk in obese, metabolically unhealthy black women at high risk for cancer. © 2018 American Cancer Society.
Gut microbiota‐immune‐brain interactions in chemotherapy‐associated behavioral comorbidities
Authors: Jordan Kelley R. , Loman Brett R. , Bailey Michael T. , Pyter Leah M.
Published: July 2018

Increasing scientific attention is focused on the gut‐brain axis, including the ability of the gastrointestinal (GI) tract to modulate central nervous system function. Changes in the intestinal microbiome can influence affective‐like behavior, cognitive performance, fatigue, and sleep in rodents and humans. Patients with cancer who are receiving chemotherapy experience similar negative behavioral changes and concurrent GI symptoms. These chemotherapy comorbidities can be long‐lasting and may reduce patients' quality of life and motivation to comply with treatment. This review summarizes the clinical and preclinical evidence supporting a role for the intestinal microbiome in mediating behavioral comorbidities through peripheral immune activation in patients with cancer who are receiving chemotherapy. In addition, evidence suggesting that targeted modification of the intestinal microbiome during cancer treatment could ameliorate associated behavioral comorbidities is reviewed.
Thermodynamic Limit for Directed Polymers and Stationary Solutions of the Burgers Equation
Authors: Bakhtin Yuri , Li Liying
Published: July 2018

The first goal of this paper is to prove multiple asymptotic results for a time‐discrete and space‐continuous polymer model of a random walk in a random potential. These results include: existence of deterministic free energy density in the infinite‐volume limit for every fixed asymptotic slope, concentration inequalities for free energy implying a bound on its fluctuation exponent, and straightness estimates implying a bound on the transversal fluctuation exponent. The culmination of this program is almost sure existence and uniqueness of polymer measures on one‐sided infinite paths with given endpoint and slope, and interpretation of these infinite‐volume Gibbs measures as thermodynamic limits. Moreover, we prove that marginals of polymer measures with the same slope and different endpoints are asymptotic to each other.

The second goal of the paper is to develop ergodic theory of the Burgers equation with positive viscosity and random kick forcing on the real line without any compactness assumptions. Namely, we prove a one force–one solution principle, using the infinite‐volume polymer measures to construct a family of stationary global solutions for this system, and proving that each of those solutions is a one‐point pullback attractor on the initial conditions with the same spatial average. This provides a natural extension of the same program realized for the inviscid Burgers equation with the help of action minimizers that can be viewed as zero temperature limits of polymer measures. © 2018 Wiley Periodicals, Inc.
β‐Cyclodextrin as a Precursor to Holey C‐Doped g‐C3N4 Nanosheets for Photocatalytic Hydrogen Generation
Authors: Da Silva Eliana S. , Moura Nuno M. M. , Coutinho Ana , Dražić Goran , Teixeira Bruno M. S. , Sobolev Nikolai A. , Silva Cláudia G. , Neves M. Graça P. M. S. , Prieto Manuel , Faria Joaquim L.
Published: July 2018

A green, template‐free and easy‐to‐implement strategy was developed to access holey g‐C3N4 (GCN) nanosheets doped with carbon. The protocol involves heating dicyandiamide with β‐cyclodextrin (βCD) prior to polymerization. The local symmetry of the GCN skeleton is broken, yielding CxGCN (x corresponds to the initial amount of βCD used) with pores and a distorted structure. The electronic, emission, optical and textural properties of the best‐performing material, C2GCN, were significantly modified as compared to bulk GCN. The spectroscopic and luminescent features of C2GCN show the characteristic π–π* electronic transition of GCN, accompanied by much stronger n–π* electronic transitions owing to the porous and distorted network. These new electronic transitions, along with the presence of additional carbon synergistically contributed to enhanced visible light absorption and restrained recombination of electron–hole pairs. Steady‐state and time‐resolved photoluminescence showed an effective quench of the fluorescence emission, accompanied by a decrease of fluorescence lifetime of C2GCN (2.20 ns) in comparison with GCN (5.85 ns), owing to the delocalization of electron and holes to new recombination centers. The photocatalytic activity of C2GCN was attributed to efficient charge carrier separation and improved visible‐light absorbing ability. As result, C2GCN exhibited ∼5 times higher photocatalytic H2 generation under visible light than bulk GCN.
A Cobalt‐Based Metal–Organic Framework as Cocatalyst on BiVO4 Photoanode for Enhanced Photoelectrochemical Water Oxidation
Authors: Zhang Wang , Li Rui , Zhao Xin , Chen Zhong , Law Adrian Wing‐Keung , Zhou Kun
Published: July 2018

A metal–organic framework (MOF)‐modified bismuth vanadate (BiVO4) photoanode is fabricated by an ultrathin sheet‐induced growth strategy, where ultrathin cobalt oxide sheets act as a metal source for the in situ synthesis of Co‐based MOF poly[Co2(benzimidazole)4] (denoted [Co2(bim)4]) nanoparticles on the surface of BiVO4. [Co2(bim)4] with small particle size and high dispersion can serve as a promising cocatalyst to accept holes transferred from BiVO4 and boost surface reaction kinetics for photoelectrochemical (PEC) water oxidation. The photocurrent density of a [Co2(bim)4]‐modified BiVO4 photoanode can achieve 3.1 mA cm−2 under AM 1.5G illumination at 1.23 V versus the reversible hydrogen electrode (RHE), which is better than those of pristine and cobalt‐based inorganic materials‐modified BiVO4 photoanodes. [Co2(bim)4], with porosity and abundant metal sites, exhibits a high surface charge‐separation efficiency (83 % at 1.2 V versus RHE), leading to the enhanced PEC activity. This work will bring new insight into the development of MOF materials as competent cocatalysts for PEC water splitting applications.
Tin(IV) Porphyrins Containing β‐Substituted Bromines: Synthesis, Conformations, Electrochemistry and Photophysical Evaluation
Authors: Ravikumar Murugan , Kathiravan Arunkumar , Neels Antonia , Mothi Ebrahim M.
Published: July 2018

Tin(IV) porphyrins containing bromine atoms at 2,3,12,13 β‐pyrrole positions are synthesised using four different bisaxial ligands; namely, chloro 2, hydroxo 3, phenolato 4 and 4‐nitrophenolato 5. The compounds are characterised using 1H NMR spectroscopy, ESI‐MS and elemental analysis. Despite steric loading at the β‐pyrrole positions, the X‐ray diffraction crystal structure analysis of 4 reveals a planar macrocyclic conformation. However, the structure of 5 shows a nonplanar conformation, with a predominant out‐of‐plane wave distortion mode. Normal‐coordinate structural decomposition (NSD) analysis, as well as analysis of the Sn–N distances, shows that the relief of steric strain in 4 is through in‐plane core elongation, while in 5, both in‐plane and out‐of‐plane distortions are evident. The effect of the highly charged central metal ion, SnIV, together with β‐bromine atoms and different axial ligands on the photophysical and electrochemical redox properties of the porphyrin π‐ring system, is studied with UV/Vis, fluorescence and transient‐absorption spectroscopy. Photophysical studies disclose redshifted absorption bands and reduced fluorescence quantum yield, as a result of the presence of bromine atoms. Cyclic voltammetric measurements indicate that the porphyrin π system becomes much easier to reduce. Preliminary experiments on the singlet‐oxygen‐generation efficiency reveal the role of the axial ligands in tuning such properties.
The Conformation of the Mannopyranosyl Phosphate Repeating Unit of the Capsular Polysaccharide of Neisseria meningitidis Serogroup A and Its Carba‐Mimetic
Authors: Calloni Ilaria , Unione Luca , Jiménez‐Osés Gonzalo , Corzana Francisco , Del Bino Linda , Corrado Alessio , Pitirollo Olimpia , Colombo Cinzia , Lay Luigi , Adamo Roberto , Jiménez‐Barbero Jesús
Published: July 2018

Neisseria meningitidis serogroup A (MenA) is an aerobic diplococcal Gram‐negative bacterium responsible for epidemic meningitis disease. Its capsular polysaccharide (CPS) has been identified as the primary virulence factor of MenA. This polysaccharide suffers from chemical lability in water. Thus, the design and synthesis of novel and hydrolytically stable structural analogues of MenA CPS may provide additional tools for the development of therapies against this disease. In this context, the structural features of the natural phosphorylated monomer have been analyzed and compared to those of its carba‐analogue, where the endocyclic oxygen has been replaced by a methylene moiety. The lowest energy geometries of the different molecules have been calculated using a combination of quantum mechanical techniques and molecular dynamics simulations. The predicted results have been compared and validated using NMR experiments. The results indicate that the more stable designed glycomimetics may adopt the conformation adopted by the natural monomer, although they display a wider flexibility around the torsional degrees of freedom.
Hummingbirds and bumble bees exposed to neonicotinoid and organophosphate insecticides in the Fraser Valley, British Columbia, Canada
Authors: Bishop Christine A. , Moran Alison J. , Toshack Michelle C. , Elle Elizabeth , Maisonneuve France , Elliott John E.
Published: July 2018

To measure exposure to neonicotinoid and other pesticides in avian pollinators, we made novel use of cloacal fluid and fecal pellets from rufous (Selasphorus rufus) and Anna's (Calypte anna) hummingbirds living near blueberry fields in the Fraser River Valley and Vancouver Island, British Columbia, Canada. To examine on-farm exposure to pesticides in invertebrate pollinators, we also collected bumble bees native to Canada (Bombus mixtus, Bombus flavifrons, and Bombus melanopygus), their pollen, and blueberry leaves and flowers from within conventionally sprayed and organic blueberry farms. By sites and sample type, the results reported in the present study represent pooled samples (n = 1). In 2015 to 2016, the combined concentration of the neonicotinoid insecticides imidacloprid, thiamethoxam, and clothianidin detected in hummingbird cloacal fluid from sites near conventionally sprayed blueberry fields was 3.63 ng/mL (ppb). Among the 18 compounds measured in fecal pellets, including one neonicotinoid (imidacloprid), only piperonyl butoxide was detected (1.47–5.96 ng/g). Piperonyl butoxide is a cytochrome P450 inhibitor applied with some insecticides to increase their toxic efficacy. Only diazinon was detected in bumble bees (0.197 ng/g), whereas diazinon (1.54–1.7 ng/g) and imidacloprid (up to 18.4 ng/g) were detected in pollen collected from bumble bees including the bees from organic sites located near conventionally sprayed blueberry farms. Imidacloprid was also detected at 5.16 ng/g in blueberry flowers collected 1 yr post spray from 1 of 6 conventionally sprayed blueberry farms. Environ Toxicol Chem 2018;37:2143–2152. © 2018 SETAC

Abstract
Striatal subdivisions that coherently interact with multiple cerebrocortical networks
Authors: Ogawa Akitoshi , Osada Takahiro , Tanaka Masaki , Hori Masaaki , Aoki Shigeki , Nikolaidis Aki , Milham Michael P. , Konishi Seiki
Published: July 2018

The striatum constitutes the cortical‐basal ganglia loop and receives input from the cerebral cortex. Previous MRI studies have parcellated the human striatum using clustering analyses of structural/functional connectivity with the cerebral cortex. However, it is currently unclear how the striatal regions functionally interact with the cerebral cortex to organize cortical functions in the temporal domain. In the present human functional MRI study, the striatum was parcellated using boundary mapping analyses to reveal the fine architecture of the striatum by focusing on local gradient of functional connectivity. Boundary mapping analyses revealed approximately 100 subdivisions of the striatum. Many of the striatal subdivisions were functionally connected with specific combinations of cerebrocortical functional networks, such as somato‐motor (SM) and ventral attention (VA) networks. Time‐resolved functional connectivity analyses further revealed coherent interactions of multiple connectivities between each striatal subdivision and the cerebrocortical networks (i.e., a striatal subdivision‐SM connectivity and the same striatal subdivision‐VA connectivity). These results suggest that the striatum contains a large number of subdivisions that mediate functional coupling between specific combinations of cerebrocortical networks.
Disrupted neural variability during propofol‐induced sedation and unconsciousness
Authors: Huang Zirui , Zhang Jun , Wu Jinsong , Liu Xiaoge , Xu Jianghui , Zhang Jianfeng , Qin Pengmin , Dai Rui , Yang Zhong , Mao Ying , Hudetz Anthony G. , Northoff Georg
Published: July 2018

Variability quenching is a widespread neural phenomenon in which trial‐to‐trial variability (TTV) of neural activity is reduced by repeated presentations of a sensory stimulus. However, its neural mechanism and functional significance remain poorly understood. Recurrent network dynamics are suggested as a candidate mechanism of TTV, and they play a key role in consciousness. We thus asked whether the variability‐quenching phenomenon is related to the level of consciousness. We hypothesized that TTV reduction would be compromised during reduced level of consciousness by propofol anesthetics. We recorded functional magnetic resonance imaging signals of resting‐state and stimulus‐induced activities in three conditions: wakefulness, sedation, and unconsciousness (i.e., deep anesthesia). We measured the average (trial‐to‐trial mean, TTM) and variability (TTV) of auditory stimulus‐induced activity under the three conditions. We also examined another form of neural variability (temporal variability, TV), which quantifies the overall dynamic range of ongoing neural activity across time, during both the resting‐state and the task. We found that (a) TTM deceased gradually from wakefulness through sedation to anesthesia, (b) stimulus‐induced TTV reduction normally seen during wakefulness was abolished during both sedation and anesthesia, and (c) TV increased in the task state as compared to resting‐state during both wakefulness and sedation, but not anesthesia. Together, our results reveal distinct effects of propofol on the two forms of neural variability (TTV and TV). They imply that the anesthetic disrupts recurrent network dynamics, thus prevents the stabilization of cortical activity states. These findings shed new light on the temporal dynamics of neuronal variability and its alteration during anesthetic‐induced unconsciousness.
Multispectral optoacoustic tomography of systemic sclerosis
Authors: Masthoff Max , Helfen Anne , Claussen Jing , Roll Wolfgang , Karlas Angelos , Becker Heidemarie , Gabriëls Gert , Riess Jan , Heindel Walter , Schäfers Michael , Ntziachristos Vasilis , Eisenblätter Michel , Gerth Ulrich , Wildgruber Moritz
Published: July 2018

The study aimed to evaluate the clinical feasibility of hybrid ultrasound/multispectral optoacoustic tomography (MSOT) for assessing microvascular dysfunction in systemic sclerosis (SSc). A handheld US/MSOT imaging system was applied for imaging patients diagnosed with SSc (n = 7) and healthy volunteers (n = 8). Semiquantitative MSOT values for deoxygenated (HbR), oxygenated (HbO2) and total haemoglobin (HbT) were analysed for subcutaneous finger tissue of both hands (8 fingers per subject, 120 fingers in total) and used to assess disease activity (progressive vs stable). Grouped data were compared by one‐way nested analysis of variance, Tukey post‐hoc test as well as student's t test were used for statistical analysis.Subcutaneous finger tissue of patients with SSc provided significantly lower MSOT values for HbO2 (26.16 ± 0.71 vs 38.2 ± 1.54, P = .023) and HbT (55.92 ± 1.62 vs 72.46 ± 1.90, P = .018) compared to healthy volunteers. Patients with progressive SSc had significantly lower MSOT values compared to patients with stable disease and healthy volunteers.This pilot study shows the feasibility of MSOT imaging to resolve microvascular dysfunction in SSc as a marker of disease activity. By providing biological tissue properties not revealed by other imaging modalities, MSOT might help to grade SSc non‐invasively and monitor early therapy response.
Intermolecular amination of allylic and benzylic alcohols leads to effective inhibitions of acetylcholinesterase enzyme and carbonic anhydrase I and II isoenzymes
Authors: Atmaca Ufuk , Yıldırım Alper , Taslimi Parham , Çelik Seda Tuncel , Gülçin İlhami , Supuran Claudiu T. , Çelik Murat
Published: July 2018

In this study, we aimed to determine the inhibition effects of novel synthesized sulfamates (2a–g), sulfonamides (3b–f), carbonyl sulfonamides (3h and i), and carbonyl sulfamates (4h and 4i), which were tested against two human cytosolic carbonic anhydrase I and II isozymes (hCA I and II) and acetylcholinesterase (AChE) enzyme. For inhibition properties of allylic sulfamates, the half maximal inhibitory concentration (IC50) and inhibition constant (Ki) were calculated for each novel compounds. The allylic sulfamates showed that Ki values are in the range of 187.33–510.31 pM for hCA I, 104.22–290.09 pM against hCA II, and 12.73–103.63 pM against AChE. The results demonstrated that all newly synthesized compounds had shown effective inhibition against hCA I and II isoenzymes and AChE enzyme.
Clinical relevance of copeptin plasma levels as a biomarker of disease severity and mortality in critically ill patients
Authors: Koch Alexander , Yagmur Eray , Hoss Alexander , Buendgens Lukas , Herbers Ulf , Weiskirchen Ralf , Koek Ger H. , Trautwein Christian , Tacke Frank
Published: July 2018

Background

Copeptin, also termed C‐terminal pre‐pro‐vasopressin or CTproAVP, mirrors endogenous vasopressin (anti‐diuretic hormone, ADH) activity and might thereby serve as a biomarker reflecting the biological stress level. We therefore hypothesized that copeptin plasma concentrations are associated with disease severity in critically ill patients and could predict mortality.

Methods

We analyzed plasma copeptin levels in a prospective, single‐center, observational study comprising 218 critically ill patients at admission to the medical intensive care unit (ICU). Mortality was assessed during a 2‐year observational follow‐up period.

Results

Copeptin plasma levels were significantly elevated in critically ill patients (n = 218) at ICU admission, as compared with 66 healthy controls. Neither sepsis as the cause of critical illness nor pre‐existing metabolic disorders (type 2 diabetes, obesity) were found to influence copeptin levels. On the contrary, plasma copeptin was closely associated with disease severity (eg APACHE‐II score) and correlated with biomarkers of inflammation, renal failure, metabolism, vascular tone, and tissue perfusion. Elevated copeptin levels at ICU admission predicted short‐term and long‐term mortality.

Conclusions

Copeptin plasma concentrations are significantly elevated in critically ill patients, correlate with disease severity and predict ICU and long‐term outcome. Thus, copeptin could be a promising tool for prognostication and management of critically ill patients.
Synthesis and Reactions of Some New Quinazoline Derivatives for In Vitro Evaluation as Anticancer and Antimicrobial Agents
Authors: Gouhar Rasha S. , Kamel Mohsen M.
Published: July 2018

A novel series of N,O,S heterocyclic compounds incorporated at position‐3 of a quinazolin‐4(3H)‐one moiety were synthesized through a p‐phenloxy binding including oxadiazolethione pyridazinetrione, thiazolidinedione, benzothiazindione, and quinazolinedione. New carbamates, urea derivatives, and Mannich bases were also prepared for the purpose of in vitro anticancer cell lines evaluation and cytotoxic activity. The key intermediate 2‐(4‐chlorophenyl)‐3‐(4‐hydroxyphenyl)quinazolin‐4(3H)‐one was prepared from the reaction of 4H‐benzo [d][3,1]oxazin‐4‐one and a nitrogenous nucleophilic compound, 4‐aminophenol. Some of the newly synthesized compounds showed significant cytotoxic activity.
Volatile, phenolic, and sensory profiles of in‐amphorae Chardonnay wine by mass spectrometry and chemometric analysis
Authors: Rossetti Fabrizio , Merkyte Vakare , Longo Edoardo , Pavlic Branimir , Jourdes Michael , Teissedre Pierre‐Louis , Boselli Emanuele
Published: July 2018

The sensory properties, the phenolic composition, and the volatile profile of Chardonnay wine made in amphorae were compared with the wine obtained in large wooden barrels (2000 L) and small toasted barrels (225 L). Hierarchical cluster analysis and principal component analysis built on the phenolics and volatiles variables allowed to group effectively the samples according to the winemaking material used. In‐amphorae wines showed more abundant catechin and caffeic acid and less abundant caftaric acid and trans‐coutaric acid. Condensation reactions proceeded in the wood containers leading to esterification of organic acids with ethanol and alcohols, whereas in‐amphorae wines were characterized by a higher content of free phenolic acids and higher volatile alcohols. Among the volatile compounds, ramified ethyl esters contributed mostly in samples made in small toasted barrels, whereas nonbranched ethyl esters contributed more for the samples made in large wooden tanks; higher alcohols contributed more for the in‐amphorae wine. The sensory analysis showed negligible differences induced by the in‐amphorae vinification with respect to the wooden one. Four variables could distinguish wines made in‐amphorae compared with the other containers: solvent and acetone (SA), astringent/pungency (AP), fruity (FR), and color intensity (CI). The overall approach proposed here is promising for future developments of innovative types of Chardonnay wine blends.
A case of ventricular ectopy eliminated by catheter ablation: Diversity of the potentials on the left coronary cusp
Authors: Kajiyama Takatsugu , Hachiya Hitoshi , Iesaka Yoshito
Published: July 2018

An 18‐year‐old man without organic heart disease underwent catheter ablation for frequent monomorphic ventricular ectopic beats(VEBs). The origin of the VEB was presumed located on the left coronary cusp(LCC) regarding his electrocardiography. Local activation in the right ventricular outflow tract was not so early. On the LCC, four different prepotentials were obtained by slight relocation of the catheter. Finally, on the site with positive discrete prepotential recorded on the distal electrodes, an application of radiofrequency current immediately eliminated the VEB. Although LCC is considered as a small structure, detailed mapping may be important to find the most optimal ablation site.
Precipitation changes in the Qilian Mountains associated with the shifts of regional atmospheric water vapour during 1960–2014
Authors: Wang Xuejia , Pang Guojin , Yang Meixue , Wan Guoning , Liu Zhaochen
Published: July 2018

Precipitation plays an essential role in hydrological cycle, water resource availability, and ecological economics sustainable development both within the Qilian Mountains (QM) and its surrounding. On the basis of meteorological station records and reanalysis data sets, we investigate the variations of precipitation in the QM during 1960–2014 and their connection to the shifts of regional atmospheric water vapour. Results show that precipitation in the QM as a whole has experienced pronounced wetting at an annual rate of 6.95 mm/decade. Significant (at 95% confidence level) precipitation increase mainly occurs in JJA (June–August) and slightly in DJF (December–February). The evident increase of precipitation appears in the mid‐east of the QM. Furthermore, the increasing rates of annual, JJA, and SON (September–November) precipitation increase with elevation, indicating obvious elevation‐dependent precipitation increase in the QM. The atmospheric precipitable water (PW) for annual, JJA, and SON time series over the targeted region generally shows significant increasing trends, especially during 1979–2014. The meridional and zonal water vapour budgets positively and negatively contribute to the regional net water vapour budget, respectively. Moreover, we demonstrate that the zonal water vapour budgets are strongly intensified and meanwhile the meridional ones except in transitional seasons are weakened. Thus, regional net water vapour budgets for annual and seasonal time series are increased. All in all, the shifts of the regional atmospheric water vapour, such as the increases of PW and water vapour budget (referring to the zonal and regional net water vapour budgets), agree with the result that the QM precipitation increases from 1960 to 2014, which suggests the QM wetting trend is in connection with the changes of the atmospheric water vapour.
Evaluation of Spanish Versions of Subjective Well‐Being Measures With Latinx College Students
Authors: VELA JAVIER CAVAZOS , KARAMAN MEHMET A. , AGUILAR ALMA , RIGUENES ROBERTO , SALDANA KARLA
Published: July 2018

The authors administered Spanish versions of 2 measures of subjective well‐being to Latinx college students. Results of a confirmatory factor analysis support the reliability and validity of the Satisfaction With Life and Subjective Happiness scales. Psychometric properties and implications for humanistic counselors are discussed.
A note on sequences witnessing singularity, following Magidor and Sinapova
Authors: Gitik Moti
Published: July 2018

We address some questions raised in the paper by Magidor and Sinapova. An application to weak form of normality for strongly compact is given.