bluuebunny/crossref_metadata_2025 huggingface dataset:
Bioactive glass functionalized chondroitin sulfate hydrogel with proangiogenic properties
Authors: Zhang Feng‐Miao , Zhou Lei , Zhou Zheng‐Nan , Dai Cong , Fan Lei , Li Chang‐Hao , Xiao Cai‐Rong , Ning Cheng‐Yun , Liu Yi , Du Jian‐Qiang , Tan Guo‐Xin
Published: August 2019

Blood vessels play an important role in bone defect repair and growth, and a critical challenge of bone defect repair is the promotion of blood vessel formation. Most of the current methods promote vascularization by adding specific growth factors, which are costly and easy to inactivate. In this study, we developed a covalently cross‐linked aminated bioactive glass nanoparticle‐chondroitin sulfate methacrylate (ABGN‐CSMA) organic‐inorganic composite hydrogel with angiogenic properties. The amino groups of the ABGNs form covalent bonds with the carboxyl groups on CSMA. Surface amination modification of BGNs not only improved the dispersion of BGNs in CSMA but also significantly improved the mechanical properties of the composite hydrogel. The largest storage modulus (1200 Pa), the largest loss modulus (560 Pa) and the strongest resistance to deformation of the hydrogel are seen at 10% concentration of ABGNs. Simultaneously, the local pH stability and sustained ion release of the composite hydrogel are conducive to cell adhesion, proliferation, and angiogenesis. This work provides evidence for the development of covalently cross‐linked organic‐inorganic composite hydrogels with angiogenic properties.
Urgent mechanical circulatory support and transcatheter mitral valve repair for refractory hemodynamic compromise
Authors: Rizik David G. , Burke Robert F. , Goldstein James A.
Published: August 2019

Patients presenting with hemodynamic instability attributable to left ventricular systolic dysfunction and concomitant severe mitral regurgitation (MR) are increasingly recognized and pose complex management challenges. Surgical therapy is typically precluded owing to prohibitive mortality. The role of percutaneous mechanical circulatory support in such cases is well established; however, such interventions may be neither sufficient to achieve optimal stability nor prove definitive. The advent of novel catheter‐based mitral repair modalities now offers primary decisive therapeutic intervention. Three cases of cardiogenic shock with severe MR illustrate the salutary hemodynamic and clinical responses to percutaneous mechanical support and valve repair by mitral clip.
Development of a High‐Pressure Reactor Based on Liquid‐Flow Pressurisation to Facilitate Enzymatic Hydroxylation of Gaseous Alkanes
Authors: Ariyasu Shinya , Kodama Yusaku , Kasai Chie , Cong Zhiqi , Stanfield Joshua Kyle , Aiba Yuichiro , Watanabe Yoshihito , Shoji Osami
Published: August 2019

A new type of high‐pressure reactor based on liquid‐flow pressurisation using a HPLC pump has been developed. This high‐pressure reactor allows the easy and safe performance of reactions with gaseous alkanes under high‐pressures up to 10 MPa (100 atm), without the need for high‐pressure gas cylinders. The amount of substrate gas required for a single reaction is very small compared with reactions using a conventional autoclave, which, when using expensive substrate gasses, such as 13C‐labelled ethane, becomes critical. Employing this high‐pressure reactor in conjunction with cytochrome P450BM3 and the assistance of decoy molecules, the direct hydroxylation of gaseous alkanes was drastically improved. At 5 MPa the TOF of propane hydroxylation increased 10‐fold, reaching 2200 min−1. Hydroxylation of ethane was also substantially accelerated at 5 MPa, reaching a TOF of 28 min−1.
Facet‐Dependent Activity of Co3O4 Catalyst for C3H8 Combustion
Authors: Yao Junxuan , Shi Hui , Sun Dekui , Lu Huaiqian , Hou Bo , Jia Litao , Xiao Yong , Li Debao
Published: August 2019

Clarifying the facet‐dependent activity of Co3O4 towards C3H8 combustion is of great importance to have a deep understanding of reaction mechanism and develop highly active Co3O4 based catalysts for light hydrocarbon combustion. In this work, four different Co3O4 nanocatalysts which dominantly exposed {100}, {111}, {110} and {112} facets, respectively, were synthesized via hydrothermal method and further tested in C3H8 combustion. The catalytic activity of different crystal planes varied as the order of {111}>{100}>{110}>{112}. The Co3O4 catalyst with {111} facets exhibited the best catalytic performance with T50 and T90 as low as 209 and 239 °C, respectively. DRIFT and DFT calculations revealed that the facile activation of C−H bond on Co3O4 {111} planes is responsible for the high activity. Moreover, the higher activity of lattice oxygens and easy activation of gas phase oxygen could also contribute to the excellent catalytic performance.
Chemoenzymatic Synthesis of O‐Containing Heterocycles from α‐Diazo Esters
Authors: Mittmann Esther , Hu Yuling , Peschke Theo , Rabe Kersten S. , Niemeyer Christof M. , Bräse Stefan
Published: August 2019

The synergy of biocatalysis and transition metal catalysis is rapidly moving forward, providing increasingly effective workflows in chemical synthesis. Here we present a facile way to prepare synthetically challenging O‐containing heterocycles bearing disubstituted stereogenic centers via catalytic chemoenzymatic transformation of α‐diazo carbonyl compounds. We demonstrate that keto‐α‐diazoesters can be enzymatically reduced to the corresponding alcohols with exquisite enantioselectivity and under retention of the diazo group using the ketoreductases LbADH and Gre2p. To further functionalize the resulting enantiopure (R)‐ and (S)‐hydroxyl α‐diazo esters, a variety of Cu and Rh catalysts were screened for intramolecular ring closure. Six‐ and seven‐membered rings with both, aliphatic and ester substituents, were obtained with up to 93 : 7 diastereomeric ratio and 81 % yield. Up to 98 % enantiomeric excess was obtained for both diastereomers, yielding the thermodynamically less favored α,ω‐trans‐oxepanes as the main products.
Mosaic Red Phosphorus/MoS2 Hybrid as an Anode to Boost Potassium‐Ion Storage
Authors: Gao Yuqing , Ru Qiang , Liu Yang , Cheng Shikun , Wei Li , Ling Francis Chi‐Chung , Chen Fuming , Hou Xianhua
Published: August 2019

Low‐cost, non‐toxic, and abundant red phosphorus (RP) with high gravimetric discharge/charge capacity has been recognized as a promising anode candidate for potassium‐ion batteries (KIBs). However, the large volumetric change, severe agglomeration, and rapid capacity attenuation during discharge/charge cycles are major obstacles for practical applications in potassium‐ion storage. In order to eliminate such intrinsic deficiencies, a mosaic RP/MoS2 hybrid is designed and prepared by using a simple ball‐milling method and subsequently used as an anode for KIBs. The hybrid with a certain ratio of 2 : 1 can achieve a sustainable K+ storage capability (246.6/239.6 mAh g−1 for 100 cycles at 50 mA g−1), considerable long‐cycle performance (120.5/118.0 mAh g−1 at 1000 mA g−1 after 500 cycles), and good rate capability. The cycling performance is attributed to a pseudocapacitive effect, controllable interlayer spacing of MoS2, and enhanced conductivity. In view of the scalable synthesis process and considerable cycling durability, the RP/MoS2 hybrid may shed light on the rational design of novel anode alternatives for KIBs.
Distibanes and Distibenes from Reduction of Sb(NONR)Cl by using MgIReagents
Authors: Schwamm Ryan J. , Coles Martyn P.
Published: August 2019

The bis(amidodimethyl)disiloxane antimony chlorides Sb(NONR)Cl (NONR=[O(SiMe2NR)2]2−; R=tBu, Ph, 2,6‐Me2C6H3=Dmp, 2,6‐iPr2C6H3=Dipp, 2,6‐(CHPh2)2‐4‐tBuC6H2=tBu‐Bhp) are reduced to SbIIand SbIspecies by using MgIreagents, [Mg(BDIR′)]2(BDI=[HC{C(Me)NR′}2]−; R′=2,4,6‐Me3C6H2=Mes, Dipp). Stoichiometric reactions with Sb(NONR)Cl (R=tBu, Ph) form dimeric SbIIstibanes [Sb(NONR)]2, shown crystallographically to contain Sb−Sb single bonds. The analogous distibane with R=Dmp substituents has an exceptionally long Sb−Sb interaction and exhibits spectroscopic and reactivity properties consistent with radical character in solution. When R=Dipp, reductions with MgIreagents directly give distibenes [Sb(μ‐NONDipp)Mg(BDIR′)(THF)n]2(R′=Mes,n=1; R′=Dipp,n=0). Crystallographic analysis shows atrans‐substitution of the Sb=Sb double bond, with bridging NONDipp‐ligands between the SbIand MgIIcentres. An attempt to access the NONPh‐analogue using the same protocol afforded the polystibide cluster Sb8[μ4,η2:2:2:2‐Mg(BDIMes)]4, which co‐crystallized with the ligand transfer product, [Mg(BDIMes)]2(μ‐NONPh).
Synthesis and Application of Ruthenium(II) Alkenyl Complexes with Perylene Fluorophores for the Detection of Toxic Vapours and Gases
Authors: García‐Calvo José , Robson Jonathan A. , Torroba Tomás , Wilton‐Ely James D. E. T.
Published: August 2019

A series of new ruthenium(II) vinyl complexes has been prepared incorporating perylenemonoimide (PMI) units. This fluorogenic moiety was functionalised with terminal alkyne or pyridyl groups, allowing attachment to the metal either as a vinyl ligand or through the pyridyl nitrogen. The inherent low solubility of the perylene compounds was improved through the design of poly‐PEGylated (PEG=polyethylene glycol) units bearing a terminal alkyne or a pyridyl group. By absorbing the compounds on silica, vapours and gases could be detected in the solid state. The reaction of the complexes [Ru(CH=CH‐PerIm)Cl(CO)(py‐3PEG)(PPh3)2] and [Ru(CH=CH‐3PEG)Cl(CO)(py‐PerIm)(PPh3)2] with carbon monoxide, isonitrile or cyanide was found to result in modulation of the fluorescence behaviour. The complexes were observed to display solvatochromic effects and the interaction of the complexes with a wide range of other species was also studied. The study suggests that such complexes have potential for the detection of gases or vapours that are toxic to humans.
π‐Hole Interactions Involving Nitro Aromatic Ligands in Protein Structures
Authors: Bauzá Antonio , Frontera Antonio , Mooibroek Tiddo Jonathan
Published: August 2019

Studying noncanonical intermolecular interactions between a ligand and a protein constitutes an emerging research field. Identifying synthetically accessible molecular fragments that can engage in intermolecular interactions is a key objective in this area. Here, it is shown that so‐called “π‐hole interactions” are present between the nitro moiety in nitro aromatic ligands and lone pairs within protein structures (water and protein carbonyls and sulfurs). Ample structural evidence was found in a PDB analysis and computations reveal interaction energies of about −5 kcal mol−1 for ligand–protein π‐hole interactions. Several examples are highlighted for which a π‐hole interaction is implicated in the superior binding affinity or inhibition of a nitro aromatic ligand versus a similar non‐nitro analogue. The discovery that π‐hole interactions with nitro aromatics are significant within protein structures parallels the finding that halogen bonds are biologically relevant. This has implications for the interpretation of ligand–protein complexation phenomena, for example, involving the more than 50 approved drugs that contain a nitro aromatic moiety.
Light‐Mediated Formal Radical Deoxyfluorination of Tertiary Alcohols through Selective Single‐Electron Oxidation with TEDA2+.
Authors: Aguilar Troyano Francisco José , Ballaschk Frederic , Jaschinski Marcel , Özkaya Yasemin , Gómez‐Suárez Adrián
Published: August 2019

The synthesis of tertiary alkyl fluorides through a formal radical deoxyfluorination process is described herein. This light‐mediated, catalyst‐free methodology is fast and broadly applicable allowing for the preparation of C−F bonds from (hetero)benzylic, propargylic, and non‐activated tertiary alcohol derivatives. Preliminary mechanistic studies support that the key step of the reaction is the single‐electron oxidation of cesium oxalates—which are readily available from the corresponding tertiary alcohols—with in situ generated TEDA2+. (TEDA: N‐(chloromethyl)triethylenediamine), a radical cation derived from Selectfluor®.
Multiscale modelling of mass transfer in gas jets and bubble plumes
Authors: O'Malley Devin J. , Haelssig Jan B.
Published: August 2019

The injection of high‐speed gas streams into liquids is common in many industrial applications, such as sparging in multiphase reactors and contacting in mass transfer devices. Modelling the fluid dynamics and associated heat and mass transfer processes in such a system is complex because it involves many governing scales and drastic changes in physical properties. In this study, one formulation of a multiscale computational fluid dynamics model is proposed to simulate the fluid dynamics and mass transfer in such systems. The model uses volume‐of‐fluid interface capturing in regions where high mesh resolution can be attained and the drift‐flux or mixture model approximation in regions where mesh resolution is too low to directly resolve interface dynamics. The model was developed to provide a tunable, automatic transition between the two modelling approaches for both fluid dynamics and mass transfer predictions. The approach was validated through a comparison with results from two published studies. In the first case, the implementation of the drift‐flux model was validated through the simulation of a dispersed gas bubble plume injected into a cylindrical tank. In the second case, the fluid dynamics and mass transfer predictions were compared to results from an experimental study involving the horizontal injection of air into a rectangular tank filled with water for the application of aeration. The results show that the modelling approach can provide a good prediction of the experimental data using only limited fitting of empirical parameters, making it applicable to a broad range of other applications.
Integrated Target‐Based and Phenotypic Screening Approaches for the Identification of Anti‐Tubercular Agents That Bind to the Mycobacterial Adenylating Enzyme MbtA
Authors: Ferguson Lindsay , Wells Geoff , Bhakta Sanjib , Johnson James , Guzman Junitta , Parish Tanya , Prentice Robin A. , Brucoli Federico
Published: August 2019

Iron is essential for the pathogenicity and virulence of Mycobacterium tuberculosis, which synthesises salicyl‐capped siderophores (mycobactins) to acquire this element from the host. MbtA is the adenylating enzyme that catalyses the initial reaction of mycobactin biosynthesis and is solely expressed by mycobacteria. A 3200‐member library comprised of lead‐like, structurally diverse compounds was screened against M. tuberculosis for whole‐cell inhibitory activity. A set of 846 compounds that inhibited the tubercle bacilli growth were then tested for their ability to bind to MbtA using a fluorescence‐based thermal shift assay and NMR‐based Water‐LOGSY and saturation transfer difference (STD) experiments. We identified an attractive hit molecule, 5‐hydroxyindol‐3‐ethylamino‐(2‐nitro‐4‐trifluoromethyl)benzene (5), that bound with high affinity to MbtA and produced a MIC90 value of 13 μm. The ligand was docked into the MbtA crystal structure and displayed an excellent fit within the MbtA active pocket, adopting a binding mode different from that of the established MbtA inhibitor Sal‐AMS.
Development and validation of an individualized risk prediction model for oropharynx cancer in the US population
Authors: Tota Joseph E. , Gillison Maura L. , Katki Hormuzd A. , Kahle Lisa , Pickard Robert K. , Xiao Weihong , Jiang Bo , Graubard Barry I. , Chaturvedi Anil K.
Published: August 2019

Background

The incidence of oropharynx cancers has increased substantially in the United States. However, risk stratification tools for the identification of high‐risk individuals do not exist. In this study, an individualized risk prediction model was developed and validated for oropharynx cancers in the US population.

Methods

A synthetic, US population–based case‐control study was conducted. Oropharynx cancer cases diagnosed at Ohio State University (n = 241) were propensity‐weighted to represent oropharynx cancers occurring annually in the United States during 2009‐2014 (n = 12,656). Controls (n = 9327) included participants in the National Health and Nutrition Examination Survey (2009‐2014) and represented the annual US population aged 30 to 69 years (n = 154,532,508). The individualized 1‐year absolute risk of oropharynx cancer was estimated with weighted logistic regression.

Results

The risk prediction model included age, sex, race, smoking, alcohol use, lifetime sexual partners, and oral oncogenic human papillomavirus (HPV) status. The model had good discrimination and calibration in split‐sample validation (area under the curve [AUC], 0.94; 95% confidence interval [CI], 0.92‐0.97; observed/expected [O/E], 1.01; 95% CI, 0.70‐1.32) and external validation (AUC, 0.87; 95% CI, 0.84‐0.90; O/E, 1.08; 95% CI, 0.77‐1.39). In the US population, 1‐year predicted risks of oropharynx cancer were highest for older individuals (21.1/100,000 for 65‐ to 69‐year‐olds), men (13.9/100,000), whites (10.4/100,000), smokers (18.0/100,000 for >20 pack‐years), heavy alcohol users (18.4/100,000), and those with prevalent oral oncogenic HPV (140.4/100,000). The risk prediction model provided substantial risk stratification, with approximately 77% of all oropharynx cancers and approximately 99% of HPV‐positive oropharynx cancers occurring in the 10% of the US population with the highest model‐predicted risk.

Conclusions

This risk prediction model will enable the efficient design of studies to address the outstanding questions pertaining to the natural history, screening, and secondary prevention of oropharynx cancers.
Agrin plays a major role in the coalescence of the aquaporin‐4 clusters induced by gamma‐1‐containing laminin
Authors: Noël Geoffroy , Tham Daniel Kai Long , MacVicar Brian A. , Moukhles Hakima
Published: August 2019

The basement membrane that seperates the endothelial cells and astrocytic endfeet that comprise the blood–brain barrier is rich in collagen, laminin, agrin, and perlecan. Previous studies have demonstrated that the proper recruitment of the water‐permeable channel aquaporin‐4 (AQP4) to astrocytic endfeet is dependent on interactions between laminin and the receptor dystroglycan. In this study, we conducted a deeper investigation into how the basement membrane might further regulate the expression, localization, and function of AQP4, using primary astrocytes as a model system. We found that treating these cells with laminin causes endogenous agrin to localize to the cell surface, where it co‐clusters with β‐dystroglycan (β‐DG). Conversely, agrin sliencing profoundly disrupts β‐DG clustering. As in the case of laminin111, Matrigel™, a complete basement membrane analog, also causes the clustering of AQP4 and β‐DG. This clustering, whether induced by laminin111 or Matrigel™ is inhibited when the astrocytes are first incubated with an antibody against the γ1 subunit of laminin, suggesting that the latter is crucial to the process. Finally, we showed that laminin111 appears to negatively regulate AQP4‐mediated water transport in astrocytes, suppressing the cell swelling that occurs following a hypoosmotic challenge. This suppression is abolished if DG expression is silenced, again demonstrating the central role of this receptor in relaying the effects of laminin.
PPy‐Derived Sandwich‐Structured Hollow Carbon Fiber Anchoring Sn4P3 as Anode Materials with Improved Na+ Storage
Authors: Wei Minghui , Wang Yarong , Li Cong , Jin Chao , Sui Jing , Yang Ruizhi
Published: August 2019

Sn4P3 has been considered as one of the promising anode materials for sodium ion batteries (SIBs) due to its high reversible capacity and low redox potential. However, the large volume expansion and Sn aggregation during the sodiation‐desodiation process result in the poor cycle stability, limiting its commercial use. Herein, a sandwich‐structured hollow carbon fiber anchoring Sn4P3 quantum dots (C@Sn4P3@HCF) is synthesized by carbon coating, carbonization/reduction and phosphorization with PPy hollow fiber as a template. Benefitting from the unique sandwiched architecture as well as the synergistic effect between Sn4P3 and N‐doped hollow carbon fiber, C@Sn4P3@HCF hybrids deliver a high initial discharge capacity of 631 mAh g−1 at 100 mA g−1, excellent rate capability (205 mAh g−1 at 50 mA g−1, 108 mAh g−1 at 1500 mA g−1) and ultrastable capacity retention of >103 mAh g−1 with a coulombic efficiency of 99.4% over 1000 cycles at 300 mA g−1. Hence, C@Sn4P3@HCF hybrids show great potential as an alternative anode material for next‐generation SIBs.
Highly Tunable Growth and Etching of Silica Shells on Surfactant‐Free Gold Nanostars
Authors: Atta Supriya , Rangan Sylvie , Fabris Laura
Published: August 2019

Herein, we report an efficient method to coat gold nanostars with a silica shell of variable thickness and then tunably etch it by using a mild silica etching reagent, NaBH4. This method generates a novel type of nanostar coating in which silica only covers the core, leaving the tips variably exposed.
Selective Preparation of 4‐Alkylphenol from Lignin‐Derived Phenols and Raw Biomass over Magnetic Co–Fe@N‐Doped Carbon Catalysts
Authors: Liu Xiaohao , Wang Chenguang , Zhang Ying , Qiao Yan , Pan Yang , Ma Longlong
Published: August 2019

Lignin valorization to produce high‐value chemicals selectively is an enormous challenge in biorefinery. In this study, 4‐alkylphenol, formed by breaking the robust Caryl−OCH3 bonds solely with the retention of other structures in lignin‐derived methoxylalkylphenols, was produced selectively over a Co1–Fe0.1@NC catalyst from real lignin oil as feedstock, which was obtained by a “lignin‐first” strategy from either birch or cornstalk. A yield of 64.7 or 88.3 mol % of 4‐propylphenol was obtained if birch lignin oil or eugenol was used as the substrate, respectively. The catalysts were characterized by using methods that include Brunauer–Emmett–Teller measurements, XRD, X‐ray photoelectron spectroscopy, high‐resolution transmission electron microscopy, high‐angle annular dark‐field scanning transmission electron microscopy, energy‐dispersive X‐ray spectroscopy, and temperature‐programmed desorption with synchrotron vacuum ultraviolet photoionization mass spectrometry. The results of catalyst characterization and comparison experiments indicated that CoNx was the main active phase for demethoxylation and hydrogenation, and the incorporation of Fe weakens the adsorption of 4‐propylphenol to the catalyst, which inhibits the excessive hydrogenation of 4‐propylphenol. This work shows the potential to produce high‐value‐added 4‐alkylphenol from renewable raw biomass.
Iodine‐Deficient BiO1.2I0.6 Coupling with Bi2O3 for Degradation of Volatile Organic Compounds under Simulated Sunlight Irradiation
Authors: Wang Shaomang , Guan Yuan , Zeng Ruiheng , Zhang Zhijun , Liu Liang , Li Zhongyu , An Wen , Fu Yang
Published: August 2019

A photocatalyst with a high separation efficiency of carriers is crucial for the photocatalytic efficient decomposition of volatile organic compounds (VOCs). In this work, a new iodine‐deficient BiO1.2I0.6/Bi2O3 photocatalyst was developed through a solvothermal approach coupled with thermal decomposition. The 2 wt % BiO1.2I0.6/Bi2O3 sample demonstrated optimal photocatalytic activity for the degradation of toluene, achieving a 55.1 % mineralization ratio under 8 h of irradiation, which was 14.9 and 2.1 times higher than those of BiO1.2I0.6 and Bi2O3, respectively. Compared with BiO1.2I0.6 and Bi2O3, 2 wt % BiO1.2I0.6/Bi2O3 exhibited the weakest fluorescence band, highest photocurrent density, and lowest impedance; thus suggesting that Bi2O3 compounded by 2 wt % BiO1.2I0.6 distinctly promoted the separation efficiency of carriers. The hydroxyl radical (.OH) was the main active species, apart from holes, for the photocatalytic degradation of toluene.
Enhanced CO2 Capture and Hydrogen Purification by Hydroxy Metal–Organic Framework/Polyimide Mixed Matrix Membranes
Authors: Ma Canghai , Urban Jeffrey J.
Published: August 2019

Membrane separation technology provides substantial savings in energy and cost for molecular separations in chemical industry, ideally complementing conventional thermally driven separation approaches. However, current membranes are subject to limitations, primarily lying in the Robeson permeability–selectivity upper bound limits. In this study, hydroxy metal‐organic framework (MOF)/polyimide mixed‐matrix membranes are found to enable high separation performance for applications including CO2 capture and hydrogen purification while offering enhanced compatibility with state‐of‐the‐art membrane‐manufacturing processes. The mixed‐matrix membranes exceed the present Robeson upper bounds with H2 and CO2 permeabilities of 907 and 650 Barrers, respectively and H2/CH4 and CO2/CH4 selectivities of 45 and 32, respectively. The unparalleled performance results from intimate interactions at the boundary of the hydroxy MOFs and carboxylic polymers through strong hydrogen bonds. The principle of design opens the door to highly permeable membranes with synergistic compatibility with established membrane manufacturing platforms for energy‐efficient molecular separations.
Evaluation of impurities and dissolution profiles of illegal antimicrobial drugs encountered in Belgium
Authors: Tie Yaxin , van Loock Kevin , Deconinck Eric , Adams Erwin
Published: August 2019

Substandard and falsified (SF) antimicrobials are gaining popularity in both developing and developed countries, posing a growing threat to public health. In general, the evaluation of SF antimicrobial drugs mainly focuses on the identification and quantification of the pharmaceutical active ingredients, ignoring other parameters of drug quality control. This study performed an in‐depth characterization and hazard identification of suspected SF antimicrobial medicinal products encountered in Belgium. In this comprehensive evaluation, impurity tests and dissolution studies were carried out. The dissolution profiles of illegal SF antimicrobials were mathematically compared to their genuine counterparts using the f1 and f2‐factor.

The results indicated that 17 out of 57 illegal samples contained higher than permitted amounts of impurities and clearly demonstrated low equivalences of dissolution profiles between SF antimicrobials and genuine products. The variations between tablets at the different time points of the dissolution curves were also higher for the SF medicines. Moreover, 11 out of 19 illegal samples failed to meet the dissolution criteria prescribed by the United States Pharmacopeia. As impurities may induce adverse reactions and improper dissolution patterns may be the cause of insufficient drug efficacy, aggravation of illness and even promotion of antimicrobial resistance can be expected.
Terrestrial contributions to Afrotropical aquatic food webs: The Congo River case
Authors: Soto David X. , Decru Eva , Snoeks Jos , Verheyen Erik , Van de Walle Lora , Bamps Jolien , Mambo Taylor , Bouillon Steven
Published: August 2019

Understanding the degree to which aquatic and terrestrial primary production fuel tropical aquatic food webs remains poorly understood, and quantifying the relative contributions of autochthonous and allochthonous inputs is methodologically challenging. Carbon and nitrogen stable isotope ratios (δ13C, δ15N) can provide valuable insights about contributions of terrestrial resources and trophic position, respectively, but this approach has caveats when applied in typical complex natural food webs.

Here, we used a combination of C, N, and H (δ2H) stable isotope measurements and Bayesian mixing models to estimate the contribution of terrestrial (allochthonous) and aquatic (autochthonous) inputs to fish and invertebrate communities in the Congo River (and some tributaries).

Overall, our results show that we gained power to distinguish sources by using a multiple tracer approach and we were able to discriminate aquatic versus terrestrial sources (esp. including hydrogen isotopes). Fish δ2H values were clearly correlated with their food preferences and revealed a high level of variation in the degree of allochthony in these tropical aquatic communities.

At the community level, it is clear that terrestrial C3 plants are an important source fueling the Congo River food web. However, in order to better constrain source contribution in these complex environments will require more robust constraints on stable isotope values of algal and methane‐derived C sources.
Imidazole‐Bridged Tetrameric Group(IV) Heteroleptic Complexes from the Spontaneous Metal‐Ligand Assembly of a Potentially N4‐Tetradentate Ligand
Authors: Luconi Lapo , Tuci Giulia , Yakhvarov Dmitry , Poli Giovanni , Rossin Andrea , Khusnuriyalova Aliya , Giambastiani Giuliano
Published: August 2019

The imidazole‐containing N4‐tetradentate ligand N‐(2‐(1H‐imidazol‐2‐yl)‐3‐(pyridin‐2‐yl)propyl)‐2,6‐diisopropylaniline (L2H) and its N‐benzyl‐protected variant (L2Bn) at the imidazole fragment have been synthesized and fully characterized. Both molecules contain an unresolved Csp3 stereogenic center. The coordination behavior of the newly prepared ligands towards group IV metal ions (MIV = Zr, Hf) has been examined through multinuclear 1H and 13C{1H} NMR spectroscopy and selected single‐crystal X‐ray structural analyses. The ability of the imidazole fragment to enter the metal coordination sphere as a neutral or a monoanionic system has also been investigated, unveiling quite original coordination modes as well as unexpected molecular architectures. When one N imidazole atom is blocked by a benzyl protecting group (L2Bn), the ligand reaction with MIV(NMe2)4 (MIV = Zr, Hf) as metal precursor gives rise to discrete monometallic tris(dimethylamido) 5‐coordinated compounds of general formula L2BnM(NMe2)3. The ligand chelates the metal ion as a bidentate monoanionic κ2{N–,N} system through the imidazole moiety and the anilido N donor while an uncoordinated picolyl arm dangles away from the metal center. Upon coordination to the metal ion, the unprotected L2H undergoes a unique self‐assembly of the chiral racemic ligand to generate an achiral tetrameric network featuring a regularly alternating (R*,S*,R*,S*) configuration around the 6‐coordinated metal centers. The resulting bis(dimethylamido) tetrameric architectures of formula [L2HM(NMe2)2]4 named “poker complexes” contain the imidazole fragment of each ligand bridging two adjacent MIV ions in a µ‐κ{N}:κ{N–} coordination hapticity. At the same time, the picolyl fragments of each chelating L2H ligand “sting” a neighboring metal center as unconventional scorpion's tails that impose further rigidity to the tetrameric structure.
Synthesis and Anticancer Activity of Structure Simplified Naturally Inspired Dimeric Chromenone Derivatives
Authors: Ali Rameez , Guan Yong , Leveille Alexandria N. , Vaughn Elizabeth , Parelkar Sangram , Thompson Paul R. , Mattson Anita E.
Published: August 2019

Select dimeric chromenones exhibit low micromolar cytotoxicity toward lymphoma and leukemia cell lines, L5178Y and HL60, respectively. The bioactive dimeric chromenones were identified from a focused library of structurally simplified derivatives of naturally occurring dimeric chromenones and tetrahydroxanthones that was prepared as part of this study. The simple dimeric chromenone scaffolds contain no stereogenic centers, are easily synthesized, and may be utilized as lead compounds in cancer research and drug discovery.
Construction of α‐(Hetero)aryl Ethenesulfonyl Fluorides for SuFEx Click Chemistry
Authors: Leng Jing , Alharbi Njud S. , Qin Hua‐Li
Published: August 2019

The construction of α‐(hetero)aryl ethenesulfonyl fluorides was achieved via a Pd‐catalyzed Suzuki coupling of arylboronic acids with 1‐bromoethene‐1‐sulfonyl fluoride (1‐Br‐ESF). The novel α‐aryl ethenesulfonyl fluorides were found to be another selectively addressable bis‐electrophile for wide diversification through SuFEx click chemistry, or Michael addition with excellent chemical discrimination.
C3‐Alkenylation between Pyrroles and Aldehydes Mediated by a Brønsted Acid and a Brønsted Base
Authors: Sahu Samrat , Roy Avijit , Gorai Mahadeb , Guria Sudip , Sudan Maji Modhu
Published: August 2019

A transition‐metal‐free, redox‐neutral, organocatalytic C3‐alkenylation of pyrroles is reported. Readily available aldehydes were employed as alkenylating agent and the reaction tolerates several key functional groups. The E‐alkenylated products were isolated in moderate to exclusive selectivity. A one‐pot two‐fold alkenylation strategy is also developed for further downstream modifications. To show the applicability, synthetically challenging indolylpyrrole derivatives were synthesized using Cadogan cyclization.
N,N′‐Disubstituted Barbituric Acid: A Versatile and Modular Multifunctional Platform for Obtaining β‐C‐Glycoconjugates from Unprotected Carbohydrates in Water
Authors: Portier François , Solier Justine , Halila Sami
Published: August 2019

Direct access to non‐hydrolyzable glycoconjugates is highly mandatory for stabilizing their intrinsic biological or physical‐chemistry properties in the surrounding environment. Here, a simple and versatile approach for the preparation of multifunctional clickable β‐C‐glycoconjugates has been developed. Readily accessible N,N′‐disubstituted barbituric acids have been synthesized and ligated in water to the reducing end of unprotected carbohydrates via Knoevenagel condensation. Additionally, divalent glycoclusters have been built from bis‐urea backbones and showed ability to interact with a model lectin, the peanut agglutinin. This concept can be readily adapted for the preparation of other C‐glycoconjugates applicable in diverse area of glycosciences.
Date Pit Carbon Dots Induce Acidic Inhibition of Peroxidase and Disrupt DNA Repair in Antibacteria Resistance
Authors: Nurkesh Ayan A. , Sun Qinglei , Fan Haiyan , Dukenbayev Kanat , Tsoy Andrey , Altaikyzy Akerke , Wang Kunjie , Xie Yingqiu
Published: August 2019

Carbon nanodots (C‐dots) are emerging as a new type of promising agent in anticancer, imaging, and new energy. Reports as well as the previous research indicate that certain C‐dots can enhance targeted cancer therapy. However, in‐depth mechanisms for such anticancer effect remain unclear. In this work, treatment provided by the date pit‐derived C‐dots, exhibits significant DNA damage; Annexin V/7‐AAD‐mediated apoptosis, and G2/M cell cycle arrest in prostate cancer cells. The application of C‐dots to the cell generally leads to acidulation of the cell medium, cooperated with membrane compact. The date pit‐derived C‐dots are observed inhibiting the horseradish peroxidase. Moreover, the C‐dots disrupt likely through nucleotide excision DNA repair at low dose during DNA ligation step suggesting the antimicrobial effect and targeting Pim‐1, EGFR, mTOR, and DNA damage pathways in cancer cells. For the first time the detailed and novel mechanisms underlying the C‐dots, derived from the date‐pit, as an efficient, low‐cost, and green nanomaterial are reveled for cancer therapy and anti‐infection.
Monocarboxylate transporter 1 in Schwann cells contributes to maintenance of sensory nerve myelination during aging
Authors: Jha Mithilesh Kumar , Lee Youngjin , Russell Katelyn A. , Yang Fang , Dastgheyb Raha M. , Deme Pragney , Ament Xanthe H. , Chen Weiran , Liu Ying , Guan Yun , Polydefkis Michael J. , Hoke Ahmet , Haughey Norman J. , Rothstein Jeffrey D. , Morrison Brett M.
Published: August 2019

Schwann cell (SC)‐specific monocarboxylate transporter 1 (MCT1) knockout mice were generated by mating MCT1
f/f mice with myelin protein zero (P0)‐Cre mice. P0‐Cre+/−, MCT1
f/f mice have no detectable early developmental defects, but develop hypomyelination and reduced conduction velocity in sensory, but not motor, peripheral nerves during maturation and aging. Furthermore, reduced mechanical sensitivity is evident in aged P0‐Cre+/−, MCT1
f/f mice. MCT1 deletion in SCs impairs both their glycolytic and mitochondrial functions, leading to altered lipid metabolism of triacylglycerides, diacylglycerides, and sphingomyelin, decreased expression of myelin‐associated glycoprotein, and increased expression of c‐Jun and p75‐neurotrophin receptor, suggesting a regression of SCs to a less mature developmental state. Taken together, our results define the contribution of SC MCT1 to both SC metabolism and peripheral nerve maturation and aging.
Trajectories of neuropsychiatric symptoms over time in healthy volunteers and risk of MCI and dementia
Authors: Leoutsakos Jeannie‐Marie S. , Wise Elizabeth A. , Lyketsos Constantine G. , Smith Gwenn S.
Published: August 2019

Objectives

To identify subtypes of neuropsychiatric symptom (NPS) course among cognitively normal individuals and to assess the association between these subtypes and hazard of later mild cognitive impairment (MCI) or dementia diagnosis.

Methods

We modeled neuropsychiatric inventory questionnaire (NPI‐Q) scores from 4184 volunteers over approximately 4 years using growth mixture models, generating latent classes of trajectory. We then fit Cox proportional hazard models to determine if membership in trajectory classes was associated with increased hazard of diagnosis of MCI or dementia.

Results

We identified four trajectory classes: the majority of the sample (65%) would be expected to belong to a class with consistently low or zero NPS. The next most prevalent class, (16%) showed a decrease over time in NPI‐Q total score but, compared with the majority class had an almost threefold increase in hazard of MCI or dementia (HR: 2.92; 95% CI: 1.82‐4.68). Another class (14%) showed an increase in NPS over time and was also associated with greater hazard of MCI or dementia (HR: 3.96; CI: 2.61‐6.03). The smallest class (5%) had high and fluctuating NPI‐Q total scores and had the greatest hazard (HR: 4.57; CI: 2.72‐7.63).

Conclusion

We have demonstrated that it is possible to identify meaningful groups of NPS trajectories and that trajectory of NPS can convey information beyond a single cross‐sectional measure. While even those whose NPS improved were at increased hazard of MCI or dementia, hazard increased as a function of the severity of the NPS trajectory.
Improvements of building envelope using passive cooling techniques to reduce the cooling load in hot‐dry regions
Authors: Hussein Mustafa K.
Published: August 2019

In developed countries, the buildings are responsible for massive energy consumption. When the construction is based on the use of nonsustainable methods, the buildings were dependent on the active systems, for ensuring a maximal indoor comfort. This has increased energy consumption and related greenhouse gas emissions. In this study, a reduction technique of cooling load and power consumption in buildings is proposed. This technique involves the combination of three passive cooling techniques, thermal insulation, phase change materials (PCMs), and electrochromic double glazing. These techniques are applied through simulation software “DesignBuilder” to a building envelope model in various areas like walls, roofs, and glazing. For this purpose, a standard building model is compared with 16 other cases that incorporated the passive cooling techniques for determining the effectiveness of the proposed method. The results show that a combination of PCMs, thermal insulation, and double glazing can reduce the cooling load from 70.37 to 50.53 kW and the energy consumption from 1.51 to 0.90 kWh/m
2.
Neutrophil‐to‐lymphocyte ratio and risk of lung cancer mortality in a low‐risk population: A cohort study
Authors: Kang Jihoon , Chang Yoosoo , Ahn Jiin , Oh Sukjoong , Koo Dong‐Hoe , Lee Yun‐Gyoo , Shin Hocheol , Ryu Seungho
Published: August 2019

Neutrophil‐to‐lymphocyte ratio (NLR) is associated with poor prognosis in patients with lung cancer, but the predictive role of NLR on the risk of developing lung cancer is unknown. We investigated the association between NLR and lung cancer mortality in lung cancer‐free adults. A cohort study was performed with 527,124 Korean adults who were free of lung cancer and were followed for up to 16 years. Vital status and lung cancer‐related deaths were ascertained through national death records. Hazard ratios (HRs) and 95% confidence intervals (CIs) for lung cancer mortality were estimated using a Cox proportional hazards model. During 4,567,495.8 person‐years of follow‐up, 574 lung cancer deaths were identified. A higher NLR was positively associated with lung cancer mortality. The multivariable‐adjusted HR (95% CI) for lung cancer mortality comparing quintiles 2, 3, 4 and 5 of NLR to the lowest quintile were 1.26 (0.96–1.67), 1.23 (0.93–1.63), 1.33 (1.01–1.75) and 1.47 (1.13–1.92), respectively. The highest risk of lung cancer mortality was also observed in the highest NLR quintile among never‐smokers and low‐risk individuals after adjusting for lung function and other possible confounders. Platelet‐to‐lymphocyte ratio showed an inverse J‐shaped association with lung cancer mortality in men but the trends in women, low‐risk individuals or never‐smokers were neither linear nor U‐shaped. In this large cohort of young and middle‐aged individuals, NLR was independently associated with increased risk of lung cancer mortality in low‐risk individuals, indicating a role of systemic inflammation in lung cancer mortality in our study population.
What influences a bank's decision to go public?
Authors: Sermpinis Georgios , Tsoukas Serafeim , Zhang Ping
Published: August 2019

A bank's decision to go public by issuing an Initial Public Offering (IPO) transforms its operations and capital structure. Much of the empirical investigation in this area focuses on the determinants of the IPO decision, applying accounting ratios and other publicly available information in nonlinear models. We mark a break with this literature by offering methodological extensions and an extensive and updated U.S. dataset to predict bank IPOs. Combining the least absolute shrinkage and selection operator with a Cox proportional hazard, we uncover value in several financial factors as well as market‐driven and macroeconomic variables in predicting a bank's decision to go public. Importantly, we document a significant improvement in the model's predictive ability compared with standard frameworks used in the literature. Finally, we show that the sensitivity of a bank's IPO to financial characteristics is higher during periods of global financial crisis than in calmer times.
The “Longing for Interpersonal Touch Picture Questionnaire”: Development of a new measurement for touch perception
Authors: Beßler Ria , Bendas Johanna , Sailer Uta , Croy Ilona
Published: August 2019

Touch is a crucial factor of physiological and psychological health in humans. A lack of touch in contrast is associated with adverse implications on mental health. A new “Longing for Interpersonal Touch Picture Questionnaire (LITPQ)” was developed and tested for its concurrent, predictive, discriminant and face validity as well as its relation to psychological distress. Six different types of touch were depicted and touch frequency and touch wish concerning different interaction partners assessed. A sample of 110 participants aged 18–56 years completed the LITPQ as well as an existing touch deprivation questionnaire and a questionnaire on mental health. Frequency and wish for touch were higher for close interaction partners than for strangers. For 72.7% of the participants, their touch wish exceeded the reported touch frequency. The LITPQ correlated moderately with the existing questionnaire for touch deprivation and was independent of relationship status or gender but positively correlated with depressiveness, anxiety and somatization. Measuring longing for touch is a very complex task considering the many aspects of subjective touch perception and confounds in the method of self‐report of touch. In our view, the LITPQ provides promising insights into this matter.
Space‐confined microwave synthesis of ternary‐layered BiOCl crystals with high‐performance ultraviolet photodetection
Authors: Kang Lixing , Yu Xuechao , Zhao Xiaoxu , Ouyang Qingling , Di Jun , Xu Manzhang , Tian Dan , Gan Weiliang , Ang Calvin C. I. , Ning Shoucong , Fu Qundong , Zhou Jiadong , Kutty R. G. , Deng Ya , Song Pin , Zeng Qingsheng , Pennycook Stephen J. , Shen Jun , Yong Ken‐T. , Liu Zheng
Published: August 2019

In recent years, two‐dimensional (2D) ternary materials have attracted wide attention due to their novel properties which can be achieved by regulating their chemical composition with a very great degree of freedom and adjustable space. However, as for the precise synthesis of 2D ternary materials, great challenges still lie ahead that hinder their further development. In this work, we demonstrated a simple and reliable approach to synthesize 2D ternary‐layered BiOCl crystals through a microwave‐assisted space‐confined process in a short time (<3 minutes). Their ultraviolet (UV) detection performance was analyzed systematically. The photodetectors based on the as‐obtained BiOCl platelets demonstrate high sensitivity to 266‐nm laser illumination. The responsivity is calculated to be ∼8 A/W and the response time is up to be ∼18 ps. On the other hand, the device is quite stable after being exposed in the ambient air within 3 weeks and the response is almost unchanged during the measurement. The facile and fast synthesis of single crystalline BiOCl platelets and its high sensitivity to UV light irradiation indicate the potential optoelectronic applications of 2D BiOCl photodetectors.

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Skin and subcutaneous fat morphology alterations under the LED or laser treatment in rats in vivo
Authors: Yanina Irina Y. , Navolokin Nikita A. , Bucharskaya Alla B. , Мaslyakova Galina N. , Tuchin Valery V.
Published: August 2019

The main objective of this work is to quantify the impact of photodynamic/photothermal treatment by using visible LED and NIR laser irradiation through the skin of subcutaneous fat in vivo followed up by tissue sampling and histology. The optical method may provide reduction of regional or site‐specific accumulations of abdominal or subcutaneous adipose tissue precisely and least‐invasively by inducing cell apoptosis and controlled necrosis of fat tissue. As photodynamic/photothermal adipose tissue sensitizers Brilliant Green (BG) or Indocyanine Green (ICG) dyes were injected subcutaneously in rats. The CW LED device (625 nm) or CW diode laser (808 nm) were used as light sources, respectively. Biopsies of skin together with subcutaneous tissues were taken for histology. The combined action BG‐staining and LED‐irradiation (BG + LED) or ICG‐staining and NIR‐laser irradiation (ICG + NIR) causes pronounced signs of damage of adipose tissue characterized by a strong stretching, thinning, folding and undulating of cell membranes and appearance of necrotic areas. As a posttreatment after 14 days only connective tissue was observed at the site of necrotic areas. The data obtained are important for safe light treatment of site‐specific fat accumulations, including cellulite. This work provides a basis for the development of fat lipolysis technologies and to move them to clinical applications. Schematics of animal experiment.