bluuebunny/crossref_metadata_2025_split huggingface dataset:
Structural and biophysical characterization of the type VII collagen vWFA2 subdomain leads to identification of two binding sites
Authors: Gebauer Jan M. , Flachsenberg Florian , Windler Cordula , Richer Barbara , Baumann Ulrich , Seeger Karsten 
Published: February 2020

Type VII collagen is an extracellular matrix protein, which is important for skin stability; however, detailed information at the molecular level is scarce. The second vWFA (von Willebrand factor type A) domain of type VII collagen mediates important interactions, and immunization of mice induces skin blistering in certain strains. To understand vWFA2 function and the pathophysiological mechanisms leading to skin blistering, we structurally characterized this domain by X‐ray crystallography and NMR spectroscopy. Cell adhesion assays identified two new interactions: one with β1 integrin via its RGD motif and one with laminin‐332. The latter interaction was confirmed by surface plasmon resonance with a KD of about 1 mm. These data show that vWFA2 has additional functions in the extracellular matrix besides interacting with type I collagen.
Controlled n‐Doping in Air‐Stable CsPbI2Br Perovskite Solar Cells with a Record Efficiency of 16.79%
Authors: Han Yu , Zhao Huan , Duan Chenyang , Yang Shaomin , Yang Zhou , Liu Zhike , Liu Shengzhong (Frank) 
Published: February 2020

AbstractCesium‐based inorganic perovskites, such as CsPbI2Br, are promising candidates for photovoltaic applications owing to their exceptional optoelectronic properties and outstanding thermal stability. However, the power conversion efficiency of CsPbI2Br perovskite solar cells (PSCs) is still lower than those of hybrid PSCs and inorganic CsPbI3 PSCs. In this work, passivation and n‐type doping by adding CaCl2 to CsPbI2Br is demonstrated. The crystallinity of the CsPbI2Br perovskite film is enhanced, and the trap density is suppressed after adding CaCl2. In addition, the Fermi level of the CsPbI2Br is changed by the added CaCl2 to show heavy n‐type doping. As a result, the optimized CsPbI2Br PSC shows a highest open circuit voltage of 1.32 V and a record efficiency of 16.79%. Meanwhile, high air stability is demonstrated for a CsPbI2Br PSC with 90% of the initial efficiency remaining after more than 1000 h aging in air.
Hybridization of Triphenylamine and Salicylaldehyde: A Facile Strategy to Construct Aggregation‐Induced Emission Luminogens with Excited‐State Intramolecular Proton Transfer for Specific Lipid Droplets and Gram‐Positive Bacteria Imaging
Authors: Yin Wei , Li Yue , Li Nan , Yang Weiyao , An Hao , Gao Jinrui , Bi Yu , Zhao Na 
Published: February 2020

AbstractAggregation‐induced emission luminogens (AIEgens) with excited‐state intramolecular proton transfer (ESIPT) process have attracted significant attention in bioimaging applications owing to their high solid‐state emission efficiencies and large Stokes shifts. Herein, a series of simple AIEgens with ESIPT process, referred to as triphenylamine salicylaldehyde (TS) derivatives, are designed and synthesized by a rational hybridization of triphenylamine and salicylaldehyde units as the intramolecular rotor and ESIPT generator, respectively. Owing to the AIE and ESIPT effects, TS derivatives exhibit intense emission and large Stokes shifts (>140 nm) in the aggregated state. By altering the substituents in the triphenylamine units, their solid‐state emission varies from 490 to 590 nm. Owing to their excellent biocompatibilities and suitable lipophilicities, the TS derivatives are able to specifically and rapidly (<5 min) stain the lipid droplets in the cells in a wash‐free manner and successfully image the lipid‐rich tissue in vivo. Moreover, owing to their suitable hydrophilicity, TS and methoxyl substituted TS (TS‐OMe) are shown to stain gram‐positive bacteria with high selectivity.
Super‐Resolution Infrared Imaging of Polymorphic Amyloid Aggregates Directly in Neurons
Authors: Klementieva Oxana , Sandt Christophe , Martinsson Isak , Kansiz Mustafa , Gouras Gunnar K. , Borondics Ferenc 
Published: February 2020

AbstractLoss of memory during Alzheimer's disease (AD), a fatal neurodegenerative disorder, is associated with neuronal loss and the aggregation of amyloid proteins into neurotoxic β‐sheet enriched structures. However, the mechanism of amyloid protein aggregation is still not well understood due to many challenges when studying the endogenous amyloid structures in neurons or in brain tissue. Available methods either require chemical processing of the sample or may affect the amyloid protein structure itself. Therefore, new approaches, which allow studying molecular structures directly in neurons, are urgently needed. A novel approach is tested, based on label‐free optical photothermal infrared super‐resolution microspectroscopy, to study AD‐related amyloid protein aggregation directly in the neuron at sub‐micrometer resolution. Using this approach, amyloid protein aggregates are detected at the subcellular level, along the neurites and strikingly, in dendritic spines, which has not been possible until now. Here, a polymorphic nature of amyloid structures that exist in AD transgenic neurons is reported. Based on the findings of this work, it is suggested that structural polymorphism of amyloid proteins that occur already in neurons may trigger different mechanisms of AD progression.
Deracemisierung durch Photokatalyse mit sichtbarem Licht
Authors: Shi Qinglong , Ye Juntao 
Published: February 2020

AbstractDeracemisierung ist eine ideale, aber anspruchsvolle Strategie, um ein racemisches Gemisch in ein einzelnes Enantiomer umzuwandeln. Aktuelle Studien haben gezeigt, dass Photokatalyse mit sichtbarem Licht verwendet werden kann, um die selektive Deracemisierung von axial‐chiralen Allenen sowie von Cyclopropylchinolonen und cyclischen Harnstoffen mit zentraler Chiralität entweder durch einen Energietransfer oder durch eine Sequenz von Elektronen‐, Protonen‐ und Wasserstoffatomtransfer zu bewirken.
Chemical Synthesis of Interleukin‐2 and Disulfide Stabilizing Analogues
Authors: Murar Claudia E. , Ninomiya Mamiko , Shimura Satomi , Karakus Ufuk , Boyman Onur , Bode Jeffrey W. 
Published: February 2020

AbstractChemical protein synthesis allows the construction of well‐defined structural variations and facilitates the development of deeper understanding of protein structure–function relationships and new protein engineering strategies. Herein, we report the chemical synthesis of interleukin‐2 (IL‐2) variants on a multimilligram scale and the formation of non‐natural disulfide mimetics that improve stability against reduction. The synthesis was accomplished by convergent KAHA ligations; the acidic conditions of KAHA ligation proved to be valuable for the solubilization of the hydrophobic segments of IL‐2. The bioactivity of the synthetic IL‐2 and its analogues were shown to be equipotent to recombinant IL‐2 and exhibit improved stability against reducing agents.
Tumor Microenvironment‐Activated NIR‐II Nanotheranostic System for Precise Diagnosis and Treatment of Peritoneal Metastasis
Authors: Ling Sisi , Yang Xiaohu , Li Chunyan , Zhang Yejun , Yang Hongchao , Chen Guangcun , Wang Qiangbin 
Published: February 2020

AbstractActivatable theranostic systems show potential for improved tumor diagnosis and therapy owing to high detection specificities, effective ablation, and minimal side‐effects. Herein, a tumor microenvironment (TME)‐activated NIR‐II nanotheranostic system (FEAD1) for precise diagnosis and treatment of peritoneal metastases is presented. FEAD1 was fabricated by self‐assembling the peptide Fmoc‐His, mercaptopropionic‐functionalized Ag2S quantum dots (MPA‐Ag2S QDs), the chemodrug doxorubicin (DOX), and NIR absorber A1094 into nanoparticles. We show that in healthy tissue, FEAD1 exists in an NIR‐II fluorescence “off” state, because of Ag2S QDs‐A1094 interactions, while DOX remains in stealth mode. Upon delivery of FEAD1 to the tumor, the acidic TME triggers its disassembly through breakage of the Fmoc‐His metal coordination and DOX hydrophobic interactions. Release of A1094 switches on Ag2S fluorescence, illuminating the tumor, accompanied by burst release of DOX within the tumor tissue, thereby achieving precise tumor theranostics. This TME‐activated theranostic strategy holds great promise for future clinical applications.
Deracemization Enabled by Visible‐Light Photocatalysis
Authors: Shi Qinglong , Ye Juntao 
Published: February 2020

AbstractDeracemization is an ideal but challenging strategy for the conversion of a racemic mixture into a single enantiomer. Recent studies have demonstrated that visible‐light photocatalysis could be utilized to promote selective deracemization of axially chiral allenes as well as cyclopropylquinolones and cyclic ureas with central chirality either through energy transfer or through a sequence of electron, proton, and hydrogen‐atom transfer.
Amide Synthesis by Nickel/Photoredox‐Catalyzed Direct Carbamoylation of (Hetero)Aryl Bromides
Authors: Alandini Nurtalya , Buzzetti Luca , Favi Gianfranco , Schulte Tim , Candish Lisa , Collins Karl D. , Melchiorre Paolo 
Published: February 2020

AbstractHerein, we report a one‐electron strategy for catalytic amide synthesis that enables the direct carbamoylation of (hetero)aryl bromides. This radical cross‐coupling approach, which is based on the combination of nickel and photoredox catalysis, proceeds at ambient temperature and uses readily available dihydropyridines as precursors of carbamoyl radicals. The method's mild reaction conditions make it tolerant of sensitive‐functional‐group‐containing substrates and allow the installation of an amide scaffold within biologically relevant heterocycles. In addition, we installed amide functionalities bearing electron‐poor and sterically hindered amine moieties, which would be difficult to prepare with classical dehydrative condensation methods.
Investigation of ring‐opening polymerization of 5‐[2‐{2‐(2‐methoxyethoxy)ethoxy}‐ethoxymethyl]‐5‐methyl‐1,3‐dioxa‐2‐one by organometallic catalysts
Authors: Chanthaset Nalinthip , Beckerle Klaus , Okuda Jun , Ajiro Hiroharu 
Published: February 2020

ABSTRACTTo develop new polymer‐based materials, the design of aliphatic carbonate has received attention and become a well‐known cyclic monomer. In view of carbonate ring polymer scope, poly(trimethylene carbonate) (PTMC) has been continuously developed for further applications due to its unique degradability. PTMC bearing oligo ethylene glycol units, PTMCM‐MOE3OM, were typically prepared via ring‐opening polymerization (ROP) using amidine‐based catalysts such as 1,8‐diazabicyclo[5.4.0] undec‐7‐ene (DBU) and benzyl alcohol (BnOH) as an initiator. To improve the polymer molecular weight or other properties, several know‐how synthetic catalysts based on organometallic complexes are under consideration as potential catalysts. With the existence of diverse classes of metallic complexes, the inorganic complexes were investigated for their catalytic activity based on tris(dimethylsilyl)amido chelating, bis(phenolate) chelating, and macrocyclic tetradentate (NNNN)‐type cyclen chelating with a metal‐core of tin (II), scandium (III), lutetium (III), and zinc (II). In this study, we found that involving a Zn(II) dimethylcyclen/alkoxide ligand and Mg complexes could accelerate the reaction and finish the polymerization under ambient conditions within 2 hr. Molecular weight reached 11,000 g/mol (40%) and 8,100 g/mol (> 96%). Subsequently, we concluded that Zn and Mg complexes were high reactivity for initiating the ROP of TMCM‐MOE3OM upon steadily degree of polymerization.
Copper‐Catalyzed Enantioselective Synthesis of Oxazolines from Aminotriols via Asymmetric Desymmetrization
Authors: Yamamoto Kosuke , Tsuda Yutaro , Kuriyama Masami , Demizu Yosuke , Onomura Osamu 
Published: February 2020

AbstractA copper‐catalyzed enantioselective transformation of tris(hydroxymethyl)aminomethane‐derived aminotriols was developed to provide multisubstituted oxazolines with a tetrasubstituted carbon center. The present transformation consisted of sequential reactions involving mono‐sulfonylation of aminotriols, subsequent intramolecular cyclization to afford prochiral oxazoline diols, and sulfonylative asymmetric desymmetrization of resultant oxazoline diols. In addition, the kinetic resolution process would be involved in the sulfonylative asymmetric desymmetrization step, which would amplify the enantiopurities of the desired products. Various aminotriols were tolerated in the present reaction, affording the desired oxazolines in good to high yields with excellent enantioselectivities. The synthetic utility of the present reaction was demonstrated by the transformation of the optically active oxazoline into a chiral α‐tertiary amine motif.
3 d Transition Metal‐Catalyzed Hydrogenation of Nitriles and Alkynes
Authors: Sharma Dipesh M. , Punji Benudhar 
Published: February 2020

AbstractSelective hydrogenation of nitriles and alkynes is crucial considering the vast applications of reduced products in industries and in the synthesis of bioactive compounds. Particularly, the late 3d transition metal catalysts (manganese, iron, cobalt, nickel and copper) have shown promising activity for the hydrogenation of nitriles to primary amines, secondary amines and imines. Similarly, semihydrogenation of alkynes to E‐ and Z‐alkenes by 3d metals is adequately successful both via the transfer hydrogenation and by using molecular hydrogen. The emergence of 3d transition metals in the selective synthesis of industrially relevant amines, imines and alkenes makes this protocol more attractive. Herein, we provide a concise overview on the late 3d transition metal‐catalyzed hydrogenation of nitriles to amines and imines as well as semihydrogenation of alkynes to alkenes.
Hexaarylbutadiene: A Versatile Scaffold with Tunable Redox Properties towards Organic Near‐Infrared Electrochromic Material
Authors: Ishigaki Yusuke , Harimoto Takashi , Sugimoto Keisuke , Wu Luyan , Zeng Wenhui , Ye Deju , Suzuki Takanori 
Published: February 2020

AbstractWhen the 1,1,4,4‐tetraanilinobutadiene skeleton is attached with two halogenated aryl units at the 2,3‐positions, they undergo facile two‐electron oxidation to give stable dicationic dyes which exhibit a near‐infrared (NIR) absorption whereas the neutral dienes show only pale color. Therefore, a distinct electrochromic response with an absorption change in the NIR region is achieved, which is attracting considerable recent attention from the viewpoint of bioimaging. Herein, we demonstrate that the redox potentials of the 1,1,4,4‐tetraanilinobutadiene can be precisely controlled by the donating properties of the amino group on the aniline unit as well as the number of halogen atoms on the aryl units at 2,3‐positions on the butadiene. In contrast, the NIR absorption bands mainly depend on the number of halogen atoms irrespective to the donating properties of aniline unit. Thus, the hexaarylbutadiene skeleton is proven to be a versatile scaffold to develop less‐explored organic NIR electrochromic materials, whose redox and spectroscopic properties can be finely tuned by modifying/attaching the proper substituents.
Risk factors and outcomes of chronic opioid use following trauma
Authors: von Oelreich E , Eriksson M , Brattström O , Sjölund K-F , Discacciati A , Larsson E , Oldner A 
Published: February 2020

Abstract

Background
The growing problem of opioid misuse has become a serious crisis in many countries. The role of trauma as a gateway to opioid use is currently not determined. The study was undertaken to assess whether traumatic injury might be associated with chronic opioid use and accompanying increased long-term mortality.

Methods
Injured patients and controls from Sweden were matched for age, sex and municipality. After linkage to Swedish health registers, opioid consumption was assessed before and after trauma. Among injured patients, logistic regression was used to investigate factors associated with chronic opioid use, assessed by at least one written and dispensed prescription in the second quarter after trauma. Cox regression was employed to study excess risk of mortality. In addition, causes of death for postinjury opioid users were explored.

Results
Some 13 309 injured patients and 70 621 controls were analysed. Exposure to trauma was independently associated with chronic opioid use (odds ratio 3·28, 95 per cent c.i. 3·02 to 3·55); this use was associated with age, low level of education, somatic co-morbidity, psychiatric co-morbidity, pretrauma opioid use and severe injury. The adjusted hazard ratio for death from any cause 6–18 months after trauma for chronic opioid users was 1·82 (95 per cent c.i. 1·34 to 2·48). Findings were similar in a subset of injured patients with no pretrauma opioid exposure.

Conclusion
Traumatic injury was associated with chronic opioid use. These patients have an excess risk of death in the 6–18 months after trauma.
Environmental management capabilities for a “circular eco‐innovation”
Authors: Scarpellini Sabina , Valero‐Gil Jesus , Moneva José M. , Andreaus Michele 
Published: February 2020

AbstractAt a micro level, eco‐innovation marks a transition towards a circular economy (CE), and standardised routines and controls are being implemented by businesses to introduce eco‐innovative processes and thus a circular business model. Eco‐innovation applied to a circular model implies changes to companies' environmental management and accounting practices used to manage natural resources. In this context, this study analyses and measures formal and informal environmental management systems, such as certification standards and other management and environmental accounting procedures used in eco‐innovation and the CE within the dynamic capabilities theoretical framework. The study also investigates the cause‐and‐effect relationship between firms' “circular eco‐innovation” and environmental capabilities using partial least squares structural equation modelling and tests it using a sample of Spanish companies. This study offers new knowledge about the interposition of business eco‐innovation and CE‐related activities introduced by firms from the dynamic capabilities perspective.
Topical application of curcumin regulates the angiogenesis in diabetic‐impaired cutaneous wound
Authors: Dehghani Sadegh , Dalirfardouei Razieh , Jafari Najaf Abadi Mohammad Hasan , Ebrahimi Nik Maryam , Jaafari Mahmoud Reza , Mahdipour Elahe 
Published: February 2020

Diabetic wound characterizes with a delayed repair as a result of the lack of neoangiogenesis and the excess of inflammation. Natural products such as curcumin have shown great promises in their regulatory potentials on inflammation and angiogenesis. However, natural agents have several shortages in their bioavailability and stability when used in vivo. In this study, we have evaluated the efficacy of a topical formulation of curcumin in the enhancement of diabetic wound repair. Streptozocin‐induced diabetic mice were wounded, and cream of curcumin (1%) was applied topically to wounds twice daily for different treatment periods. Inflammation, neoangiogenesis, and re‐epithelialization were evaluated in each experimental group. Wounds of animals treated with curcumin showed an enhanced neoangiogenesis. Application of topical curcumin also increased the expression level of RelA as the main subunit of the nuclear factor‐κB (NF‐κB) signalling pathway. However, no significant effects on macrophage polarization and re‐epithelialization were observed in the curcumin‐treated animals. Our study using a higher concentration of curcumin in the form of a topical cream further confirmed the efficacy of curcumin as an angiogenesis‐promoting agent; however, it also conveyed uncertainty over the claimed regulatory effects of curcumin on inflammation.Significance of the studyDiabetes results in several complications such as impaired cutaneous wound repair. Excess of inflammation and lack of angiogenesis are among the main causes of delayed healing in diabetes. Curcumin is famous for its anti‐inflammatory properties. However, when in the body curcumin has shown to have a limited benefit unless in high‐dosage consumes. This is because of its poor absorption from digestive system and its bioavailability. In this study, we have used a topical formulation of curcumin at a relatively high concentration to enhance the healing of a diabetic wound in an animal model of diabetes. We also have studied different cellular and molecular mechanisms by which curcumin may help the wound repair. Our results re‐emphasize the proangiogenic potential of curcumin in diabetic wound environment.
Highly Efficient Oxygen Reduction Reaction Electrocatalysts FeCo−N−C Derived from Two Metallomacrocycles and N‐doped Porous Carbon Materials
Authors: Jin Xinxin , Xie Yan , Wang Lili , Huang Jiahui 
Published: February 2020

AbstractN‐doped porous carbon (NPC) materials are beneficial to anchor desirable active sites for the oxygen reduction reaction (ORR). Herein, FeCo−N−C electrocatalysts with large specific surface areas and 3D interconnected hierarchical porous structures were prepared by pyrolysis of NPC materials with two metallomacrocycles, including iron phthalocyanine (FePc) and vitamin B12 (VB12). The onset potential (Eonset) of FePc(3)VB12(1)/NPC (900) is 0.934 V (vs. RHE), which is larger than that of commercial Pt/C (0.923 V vs. RHE). The half‐wave potential (E1/2) of FePc(3)VB12(1)/NPC (900) is 0.838 V (vs. RHE), which is almost the same with that of Pt/C electrocatalyst (0.839 V vs. RHE). Furthermore, the FePc(3)VB12(1)/NPC (900) also exhibits better durability and methanol tolerance relative to Pt/C in 0.1 M KOH solution. Such outstanding ORR performance is mainly attributed to the high proportion of both pyridinic N and graphitic N in FePc(3)VB12(1)/NPC (900) electrocatalyst.
Effect of Crystal Structures on Electrochemical Performance of Hierarchically Porous CoSe2 Spheres as Anodes for Sodium‐Ion Batteries
Authors: Liu Xin , Xu Guo B. , Cheng Ting T. , Yang Li W. , Cao Jue X. 
Published: February 2020

AbstractMetal selenides with controllable crystal structures and hierarchically porous architectures have recently attracted great attention as the advanced electrode materials for sodium‐ion batteries. In present study, hierarchically porous orthogonal CoSe2 (o‐CoSe2) and cubic CoSe2 (c‐CoSe2) spheres are prepared through a controllable selenization and subsequent annealing strategy. Both types of CoSe2 spheres exhibit superior electrochemical properties resulting from hierarchical architecture, which can alleviate of the structural strain, the accelerated electron transmission and shorten the diffusion pathway of Na+. As anode materials for SIBs, the o‐CoSe2 electrode delivers a higher rate capability of 244 mAh g−1 at 3000 mA g−1 and a better cyclability of 378 mAh g−1 after 100 cycles at 1000 mA g−1 compared to the c‐CoSe2. From detailed microstructure characterization and kinetics behavior analysis, it is revealed that the o‐CoSe2 spheres exhibits larger specific surface, optimized porous nature, higher pseudocapacitive contribution, and more powerful Na+‐ions mobility. Our studies can pave the way for rational design and development of selenides electrode materials in rechargeable batteries.