bluuebunny/crossref_metadata_2025_split huggingface dataset:
A Tumor Vascular‐Targeted Interlocking Trimodal Nanosystem That Induces and Exploits Hypoxia
Authors: Luan Xin , Guan Ying‐Yun , Liu Hai‐Jun , Lu Qin , Zhao Mei , Sun Duxin , Lovell Jonathan F. , Sun Peng , Chen Hong‐Zhuan , Fang Chao 
Published: May 2018

AbstractVascular‐targeted photodynamic therapy (VTP) is a recently approved strategy for treating solid tumors. However, the exacerbated hypoxic stress makes tumor eradication challenging with such a single modality approach. Here, a new graphene oxide (GO)‐based nanosystem for rationally designed, interlocking trimodal cancer therapy that enables VTP using photosensitizer verteporfin (VP) (1) with codelivery of banoxantrone dihydrochloride (AQ4N) (2), a hypoxia‐activated prodrug (HAP), and HIF‐1α siRNA (siHIF‐1α) (3) is reported. The VTP‐induced aggravated hypoxia is highly favorable for AQ4N activation into AQ4 (a topoisomerase II inhibitor) for chemotherapy. However, the hypoxia‐induced HIF‐1α acts as a “hidden brake,” through downregulating CYP450 (the dominant HAP‐activating reductases), to substantially hinder AQ4N activation. siHIF‐1α is rationally adopted to suppress the HIF‐1α expression upon hypoxia and further enhance AQ4N activation. This trimodal nanosystem significantly delays the growth of PC‐3 tumors in vivo compared to the control nanoparticles carrying VP, AQ4N, or siHIF‐1α alone or their pairwise combinations. This multimodal nanoparticle design presents, the first example exploiting VTP to actively induce hypoxia for enhanced HAP activation. It is also revealed that HAP activation is still insufficient under hypoxia due to the hidden downregulation of the HAP‐activating reductases (CYP450), and this can be well overcome by GO nanoparticle‐mediated siHIF‐1α intervention.
A Sandwich‐Like Organolead Halide Perovskite Photocathode for Efficient and Durable Photoelectrochemical Hydrogen Evolution in Water
Authors: Zhang Hefeng , Yang Zhou , Yu Wei , Wang Hong , Ma Weiguang , Zong Xu , Li Can 
Published: May 2018

AbstractOrganolead halide perovskite materials have demonstrated great potential in the solar cells field owing to their excellent optoelectronic properties. However, the instability issue of the perovskites impedes the translation of their attractive features for the solar fuel production such as photoelectrochemical H2 production from water splitting. Herein, CH3NH3PbI3 a photocathode with a sandwich‐like structure is fabricated with a general and scalable approach toward addressing this issue. The photocathode exhibits an onset potential at 0.95 V versus reversible hydrogen electrode (RHE) and a photocurrent density of −18 mA cm−2 at 0 V versus RHE with an impressive ideal ratiometric power‐saved efficiency of 7.63%. More impressively, the photocathode retains good stability under 12 h continuous illumination in water at wide pH range. This performance is much superior to that of the best perovskite‐based photoelectrode ever reported.
Light‐Gated Rotation in a Molecular Motor Functionalized with a Dithienylethene Switch
Authors: Roke Diederik , Stuckhardt Constantin , Danowski Wojciech , Wezenberg Sander J. , Feringa Ben L. 
Published: May 2018

AbstractA multiphotochromic hybrid system is presented in which a light‐driven overcrowded alkene‐based molecular rotary motor is connected to a dithienylethene photoswitch. Ring closing of the dithienylethene moiety, using an irradiation wavelength different from the wavelength applied to operate the molecular motor, results in inhibition of the rotary motion as is demonstrated by detailed 1H‐NMR and UV/Vis experiments. For the first time, a light‐gated molecular motor is thus obtained. Furthermore, the excitation wavelength of the molecular motor is red‐shifted from the UV into the visible‐light region upon attachment of the dithienylethene switch.
{Nb288O768(OH)48(CO3)12}: A Macromolecular Polyoxometalate with Close to 300 Niobium Atoms
Authors: Wu Yan‐Lan , Li Xin‐Xiong , Qi Yan‐Jie , Yu Hao , Jin Lu , Zheng Shou‐Tian 
Published: May 2018

AbstractA protein‐sized (ca. 4.2×4.2×3.6 nm3) non‐biologically derived molecule {Nb288O768(OH)48(CO3)12} (Nb288) containing up to 288 niobium atoms has been obtained, which is by far the largest and the highest nuclearity polyoxoniobate (PONb). Particularly, in terms of metal nuclearity number, Nb288 is the second largest cluster so far reported in classic polyoxometalate chemistry (V, Mo, W, Nb, and Ta). Nb288 can be described as a giant windmill‐like cluster aggregate of six nanoscale high‐nuclearity PONb units {Nb47O128(OH)6(CO3)2} (Nb47) joined together by six additional Nb ions. Interestingly, the 47‐nuclearity Nb47 units generated in situ can be isolated and bridged by copper complexes to form an inorganic–organic hybrid three‐dimensional PONb framework, which exhibits effective catalytic activity for hydrolyzing nerve agent simulant of dimethyl methylphosphonate. The unique Nb47 cluster also provides a new type of topology to very limited family of Nb‐O clusters.
Remote Control of Anion–π Catalysis on Fullerene‐Centered Catalytic Triads
Authors: López‐Andarias Javier , Bauzá Antonio , Sakai Naomi , Frontera Antonio , Matile Stefan 
Published: May 2018

AbstractThe design, synthesis and evaluation of catalytic triads composed of a central C60 fullerene with an amine base on one side and polarizability enhancers on the other side are reported. According to an enolate addition benchmark reaction, fullerene–fullerene–amine triads display the highest selectivity in anion–π catalysis observed so far, whereas NDI–fullerene–amine triads are not much better than fullerene–amine controls (NDI=naphthalenediimide). These large differences in activity are in conflict with the small differences in intrinsic π acidity, that is, LUMO energy levels and π holes on the central fullerene. However, they are in agreement with the high polarizability of fullerene–fullerene–amine triads. Activation and deactivation of the fullerene‐centered triads by intercalators and computational data on anion binding further indicate that for functional relevance, intrinsic π acidity is less important than induced π acidity, that is, the size of the oriented macrodipole of polarizable π systems that emerges only in response to the interaction with anions and anionic transition states. The resulting transformation is thus self‐induced, the anionic intermediates and transition states create their own anion–π catalyst.
High Rate of Drug‐Free Remission After Induction Therapy With Golimumab in Early Peripheral Spondyloarthritis
Authors: Carron Philippe , Varkas Gaëlle , Renson Thomas , Colman Roos , Elewaut Dirk , Van den Bosch Filip 
Published: May 2018

ObjectiveNew treatment algorithms using tumor necrosis factor (TNF) blockers in early stages of spondyloarthritis (SpA) induce high rates of clinical remission or low disease activity. It could be anticipated that such early intervention strategies in peripheral SpA may induce drug‐free remission. We undertook this study to evaluate drug‐free clinical remission after induction therapy with golimumab in patients with very early active peripheral SpA, and to identify patient characteristics that predict sustained drug‐free remission.MethodsEligible patients were age ≥18 years and fulfilled the Assessment of SpondyloArthritis international Society criteria for peripheral SpA. All patients had symptom duration of <12 weeks. Sustained clinical remission was defined as the absence of arthritis, enthesitis, and dactylitis at 2 consecutive major visits, after which treatment was withdrawn. Patients were prospectively followed up to assess the rate of sustained drug‐free clinical remission and clinical relapse.ResultsEighty‐two percent of patients (49 of 60) fulfilled sustained clinical remission criteria after a regimen of induction therapy with golimumab. The majority of patients already reached this status at week 24 (n = 30), with an additional 11 and 8 patients at weeks 36 and 48, respectively. All patients had a follow‐up period of at least 18 months after drug withdrawal. Fifty‐three percent of patients (26 of 49) still have drug‐free remission of their disease. Inability to sustain drug‐free remission was associated with the presence of psoriasis and polyarticular disease (swollen joint count >5).ConclusionAnti‐TNF treatment in very early peripheral SpA results in a remarkably high rate of sustained clinical remission. More than 50% of patients continue to have remission of their disease after withdrawal of therapy, which highlights a defined window of opportunity permitting induction of drug‐free remission.
Association of Abnormal Elevations in IFIT3 With Overactive Cyclic GMP‐AMP Synthase/Stimulator of Interferon Genes Signaling in Human Systemic Lupus Erythematosus Monocytes
Authors: Wang Jiehua , Dai Min , Cui Yange , Hou Guojun , Deng Jun , Gao Xin , Liao Zhuojun , Liu Ya , Meng Yao , Wu Lingling , Yao Chao , Wang Yan , Qian Jie , Guo Qiang , Ding Huihua , Qu Bo , Shen Nan 
Published: May 2018

ObjectiveIncreasing evidence indicates that the cyclic GMP‐AMP synthase/stimulator of interferon genes (cGAS/STING) signaling pathway has a critical pathogenic role in systemic lupus erythematosus (SLE). Expression levels of the interferon (IFN)–inducible gene IFIT3 are elevated in SLE patients. However, it is still not clear how IFIT3 contributes to the pathogenesis of SLE. This study was undertaken to investigate the activation of the cGAS/STING signaling pathway in human SLE monocytes, and to determine how elevated expression of IFIT3 could contribute to overactive cGAS/STING signaling in patients with SLE.MethodsMonocytes from SLE patients or healthy controls were examined for activity of the cGAS/STING signaling pathway and expression levels of IFIT3. Correlations between cGAS/STING signaling activity and SLE clinical features were analyzed. Gain‐ or loss‐of‐function experiments were used to determine the role of IFIT3 in cGAS/STING signaling. Coimmunoprecipitation assays were used to identify the interaction between IFIT3 and other proteins.ResultsThe cGAS/STING signaling pathway was found to have enhanced activity in monocytes from SLE patients compared to healthy controls, as indicated by the higher expression of IFNβ downstream. Levels of IFIT3 were significantly elevated in human SLE monocytes, and this was positively correlated with the activity of the cGAS/STING signaling pathway. In vitro, the expression of VACV70‐induced IFNβ was reduced by knockdown of IFIT3, whereas overexpression of IFIT3 produced an opposite effect. Finally, IFIT3 was found to interact with both STING and TANK‐binding kinase 1.ConclusionThese findings suggest that IFIT3 is one of the genes that contributes to the overactive cGAS/STING signaling pathway in human SLE monocytes. IFIT3 may therefore serve as a novel therapeutic target for blocking the production of type I IFN and other proinflammatory cytokines by the cGAS/STING signaling pathway in patients with SLE.
Microbial biosynthesis and in vivo depolymerization of intracellular medium‐chain‐length poly‐3‐hydroxyalkanoates as potential route to platform chemicals
Authors: Anis Siti Nor Syairah , Mohd Annuar Mohd Suffian , Simarani Khanom 
Published: May 2018

AbstractBiosynthesis and in vivo depolymerization of intracellular medium‐chain‐length poly‐3‐hydroxyalkanoates (mcl‐PHA) in Pseudomonas putida Bet001 grown on lauric acid were studied. Highest mcl‐PHA fraction (>50 % of total biomass) and cell concentration (8 g L−1) were obtained at carbon‐to‐nitrogen (C/N) ratio 20, starting cell concentration 1 g L−1, and 48 H fermentation. The mcl‐PHA comprised of 3‐hydroxyhexanoate (C6), 3‐hydroxyoctanote (C8), 3‐hydroxydecanoate (C10), and 3‐hydroxydodecanoate (C12) monomers. In vivo action was studied in a mineral liquid medium without carbon source, and in different buffer solutions with varied pH, molarity, ionic strength, and temperature. The monomer liberation rate reflected the mol percentage distribution of the initial polymer subunit composition. Rate and percentage of in vivo depolymerization were highest in 0.2 M Tris–HCl buffer (pH 9, strength = 0.2 M, 30 °C) at 0.21 g L−1 H−1 and 98.6 ± 1.3 wt%, respectively. There is a congruity vis‐à‐vis to specific buffer type, molarity, pH, ionic strength, and temperature values for superior in vivo depolymerization activities. Direct products from in vivo depolymerization matched the individual monomeric composition of native mcl‐PHA. It points to exo‐type reaction for the in vivo process, and potential biological route to chiral molecules.
Bioenergy from Microalgae – Vision or Reality?
Authors: Hoyer Jan , Cotta Fritz , Diete Anja , Großmann Jochen 
Published: May 2018

AbstractMicroalgae are often heralded as a miracle cure to solve future questions concerning energy and food supply of the world's population. This is due to their vastly superior area productivity compared to terrestrial plants and the feasibility of cultivating them independently of arable land and fresh water. Algal biomass can be used as food and feed as well as a source for a plethora of biofuels and high value products such as nutraceuticals and pharmaceuticals. This review article seeks to shed light on recent advances in microalgal technology and their potential for the production of biofuels.
A Glutathione‐Responsive Short Sequence of Metal–Organic Complex Array
Authors: Bose Purnandhu , Takei Toshiaki , Li Xianglan , Minowa Takashi , Rajmohan Rajamani , Vairaprakash Pothiappan , Tashiro Kentaro 
Published: May 2018

AbstractA short metal–organic complex array (MOCA) containing a sequence of RPtRRu (1Cl) was found to exhibit unique responses to a major biothiol, glutathione (GSH). Upon binding of GSH to 1Cl, the resultant 1:1 complex (1GS) formed nanofibrous assemblies that suggested supramolecular polymerization through the double‐salt‐bridge structure formation. The binding behavior of this MOCA sequence to calf thymus DNA was also dependent on GSH; a larger conformational change of DNA was observed upon binding with 1GS, relative to that with 1Cl.
A Sustainable Method for the Synthesis of Acetic Acid Based on Dehydrogenation of an Ethanol–Water Solution Catalyzed by an Iridium Complex Bearing a Functional Bipyridonate Ligand
Authors: Kuwahara Masato , Nishioka Masaaki , Yoshida Masato , Fujita Ken‐ichi 
Published: May 2018

AbstractAn efficient system for the synthesis of acetic acid via dehydrogenation of an ethanol–water solution using a new iridium catalyst bearing a functional bipyridonate ligand with N,N‐dimethylamino substituents was developed. Quantitative production of acetic acid from an ethanol–water solution was achieved. In addition, recovery and reuse of the catalyst using a simple procedure was also accomplished. Moreover, this catalytic system can be applied in the dehydrogenative transformation of various primary alcohols to the corresponding carboxylic acids.
Facile Synthesis of Nitrogen‐Doped Mesoporous Hollow Carbon Nanospheres for High‐Performance Supercapacitors
Authors: Wang Zhongbing , Qiang Hongwen , Zhu Zihao , Liu Jinpeng , Chen Chunnian , Zhang Dawei 
Published: May 2018

AbstractWe report the facile preparation of nitrogen‐doped mesoporous hollow carbon nanospheres (N‐MHCNS) by directly carbonizing hollow polypyrrole nanospheres that are derived from in situ polymerization. Here, we use a novel soft template (PMMA‐PBMA‐PMAA) as the core. At 700 °C, the obtained N‐MHCNSs (denoted N‐MHCNS700) show superior electrochemical performance. In 1 M HCl electrolyte, N‐MHCNS700 exhibits a capacitance as high as 275.5 F g−1 at a current density of 1 A g−1 and a high rate capability, retaining 54.4 % of the initial capacitance at the current density of 20 A g−1. In addition, the specific capacitance of N‐MHCNS700 is approximately 100 % retained at a current density of 10 A g−1 after 5000 cycles, indicating amazing stable cycling performance. The excellent electrochemical performance can be derived from the amorphous graphitic carbon, hollow nanosphere structure, mesoporous properties, and nitrogen doping effect.
Facile Skeletal Rearrangement of Polycyclic Disilenes with Bicyclo[1.1.1]pentasilanyl Groups
Authors: Yokouchi Yuki , Ishida Shintaro , Iwamoto Takeaki 
Published: May 2018

AbstractThe unexpected formations of fused polycyclic disilenes 2 a and (E),(Z)‐3 b by the reduction of the 1,2‐dibromodisilanes 5 a (R=Me) and 5 b (R=iPr) bearing bicyclo[1.1.1]pentasilanyl (BPS) groups is reported. The disilenes 2 a and (E),(Z)‐3 b were characterized by a combination of NMR spectroscopy and X‐ray diffraction analysis (XRD). The reduction of 5 b in the presence of 2,3‐dimethyl‐1,3‐butadiene provided an ene adduct of the disilene 1 b bearing BPS groups, which suggested that an initial product of the reduction of 5 b was the disilene 1 b. Thermal reactions of 2 a and (E),(Z)‐3 b afforded the highly strained saturated silicon clusters 4 a and 4 b. A computational study suggested that the transformation of 1 to 2, 3, or 4 can involve silyldisilene–disilanylsilylene rearrangement reactions and insertion reactions of a silylene into a Si−Si bond.
One‐Pot Synthesis of CuS Nanoflower‐Decorated Active Carbon Layer for High‐Performance Asymmetric Supercapacitors
Authors: Wang Guoxiang , Zhang Mingyuan , Lu Lu , Xu Hongfeng , Xiao Zuoyi , Liu Sa , Gao Shiping , Yu Zhihui 
Published: May 2018

AbstractCopper sulfide‐active carbon (CuS‐AC) with a three‐dimensional (3D) porous structure is fabricated based on AC‐supported CuS nanosheets by using a solvothermal method and used in a high‐performance asymmetric supercapacitor devices to enhance the specific capacitance, cycling stability, and energy density. The CuS nanosheets form an array on the AC layer, and the two kinds of materials are ideally combined, leading to increased conductivity and enlarged electroactive surface area of the electrode materials. Moreover, the 3D CuS‐AC porous structure exhibited excellent electrochemical energy storage properties with large specific capacitance (247 F g−1 at a current density of 0.5 A g−1), high energy density (24.88 Wh kg−1 at the power density of 800 W kg−1), and good long‐term cycling stability (92% capacitance retention after 5000 cycles). This superior electrochemical performance can be ascribed to the high pseudocapacitance of CuS and large surface area from AC. The experimental results indicate that the hierarchical nanostructure design of CuS grown on AC exhibits considerable potential for supercapacitor applications.
Outstanding Chiroptical Features of Thin Films of Chiral Oligothiophenes
Authors: Albano Gianluigi , Salerno Francesco , Portus Lorenzo , Porzio William , Aronica Laura Antonella , Di Bari Lorenzo 
Published: May 2018

AbstractA chiral benzo[1, 2‐b:4,5‐b′]dithiophene‐based oligothiophene with the very uncommon chiroptical property of signal inversion on sample flipping was recently described. This property is due to the interference between linear dichroism and linear birefringence, called LDLB effect, which is theoretically well understood, but to date very rarely reported in the literature. Samples with very large LDLB effect lead to the unique possibility of discriminating the direction of sample illumination (i. e., from the front or back). This article presents a set of analogue compounds, in which small structural changes are introduced to uncover which factors determine the very large LDLB effect or true circular dichroism connected to supramolecular chirality. It also reveals the impact of the deposition technique, in which spin coating may exert a primary role, and results in films with outstanding chiroptical features. These features are made even more relevant due to the semiconducting properties of oligothiophenes, which are interesting for optical sensing applications.
Highly secure palmprint based biometric template using fuzzy vault
Authors: Sujitha V. , Chitra D. 
Published: May 2018

SummaryBiometric cryptosystem is an integrated system of cryptography with biometric features which is considered to be a promising component of template security. This paper presents a novel method for biometric cryptosystem based on fuzzy vault using palmprint features. Initially, pre‐processing is performed to remove noise in palmprint enrolled image and to pre‐align image automatically. Bottom‐hat filtering is employed for the feature extraction from the palmprint images. A polynomial is evaluated from the secret key and this polynomial is used to generate projections from palmprint features. Fuzzy vault is created by combining projected points with randomly generated dummy or chaff points. During decoding process, matching scores are calculated by comparing the query feature and stored vault. The vault is successfully decoded when the matched scores should be greater than a predefined threshold value. Experiments were conducted on CASIA database. Simulation result demonstrates that the proposed method gives better performance than other methods and improves the robustness against some security attacks.
Optimally bipartitioning sparse matrices with reordering and parallelization
Authors: Mumcuyan Aras , Usta Baran , Kaya Kamer , Yenigün Hüsnü 
Published: May 2018

SummaryA good task‐to‐processor assignment is crucial for parallel efficiency since the communication between the tasks is usually the main bottleneck for scalability. A fundamental approach to solve this problem is modeling the tasks as a hypergraph where the pins correspond to the tasks and the nets represent the communication among them. The vertices in this hypergraph is partitioned into a number of parts, which correspond to processors, in a way that the total number of vertices for each part is balanced and the amount of edges having endpoints in different parts is minimized. Sparse matrix‐vector multiplication is an extensively used kernel in many applications. Recently, a novel, purely combinatorial branch‐and‐bound–based approach has been proposed for sparse‐matrix bipartitioning which can handle hypergraphs that cannot be optimally partitioned by using existing methods due to the problem's complexity. Our work extends the previous study with three ideas. We use 1) matrix ordering techniques to use more information in the earlier branches of the tree, 2) a machine learning approach to choose an ordering based on the matrix features, and 3) a parallelization technique to search an optimal bipartitioning. As our experiments show, these techniques make the bipartitioning process significantly faster.
Template‐Assisted Fabrication of Nanostructured Arrays for Sensing Applications
Authors: Xu Shipu , Lei Yong 
Published: May 2018

AbstractHigh sensitivity imposes strict requirements on a sensing platform, for which nanostructured arrays are promising candidates. The template‐assisted method is an effective strategy to prepare various nanostructured arrays, which are widely developed for different sensing applications. Herein, nanostructured array based sensing platforms prepared from four widely used templates, a colloidal monolayer, anodic aluminum oxide, block copolymer, and a nanoimprint mold, are reviewed. In a series of sensing applications (e.g., biosensing and gas sensing), the resulting nanostructure‐array‐based platforms are high sensitive owing to their advanced morphology features: 1) high‐density alignment of arrayed nanostructures, 2) high surface‐to‐volume ratio, and 3) convex‐rich morphology. In surface‐enhanced Raman spectroscopy (SERS) applications, noble‐metal particle arrays with high‐density alignment produce an enhanced SERS signal owing to a strong concentration of plasmonic resonance on the substrate. To sense biomolecules in solution and gaseous molecules, arrays with a high surface‐to‐volume ratio or convex‐rich morphology can sensitively respond to changes in the environment. Moreover, the nanostructure‐array‐based sensing platforms are divided into three types (0D, 1D, and 3D nanostructured arrays) to demonstrate the morphological origin of the sensing performances.