bluuebunny/crossref_metadata_2025 huggingface dataset:
A Temporary Barrier Effect of the Alloy Layer During Selenization: Tailoring the Thickness of MoSe2 for Efficient Cu2ZnSnSe4 Solar Cells
Authors: Li Jianjun , Zhang Yi , Zhao Wei , Nam Dahyun , Cheong Hyeonsik , Wu Li , Zhou Zhiqiang , Sun Yun
Published: February 2015

The influence of a prealloying process on the formation of MoSe2 and thus on the performance of Cu2ZnSnSe4 (CZTSe) solar cells is investigated using sputtering deposition and post‐annealing approaches. The dense alloy layer, which is made by a low‐temperature prealloying process, acts as a temporary Se diffusion barrier during a subsequent high‐temperature selenization process. The formation of thick interfacial MoSe2 can be suppressed effectively by this temporary barrier, cooperating with subsequent quick formation of compact CZTSe layer. The thickness of interfacial MoSe2 layer in CZTSe solar cells can be tailored by adjusting the preannealing process during selenization. As a consequence, the series resistance of CZTSe solar cells is reduced to a low level (≈0.6 Ω cm2), and the performance of CZTSe solar cells is improved significantly. A CZTSe solar cell with efficiency of 8.7% is fabricated.
Analysis of slot coating flow under tilted die
Authors: Lee Semi , Nam Jaewook
Published: February 2015

Slot coating is a high precision coating method, where the film thickness is controlled by the flow rate fed to the die and the production speed. The range of desirable operating conditions for uniform coating is limited by the shape and locations of upstream and downstream menisci, which are controlled by the pressure gradient within the coating flow. The gradient can be controlled by the shape and orientation of the slot coating die, that is, die configuration. Here, the tilted die, the so‐called angle‐of‐attack configuration is considered. The configuration is similar to underbite and overbite configurations, but it has a sloped die lip due to tilting. Coating flows with such a configuration are examined by computer‐aided analysis using the Galerkin/finite element method. Using steady‐state analysis, the effect of the angle of attack on the upstream meniscus location is discussed. In transient analysis, the amplitude of the thickness variation is predicted under different types of disturbances, namely flow rate and gap oscillations. The analysis shows that die lip configurations affect the thickness uniformity under periodic disturbances. The effect of die tilting can be similar to or different from the underbite/overbite configurations, depending on the type of oscillation. During the analysis, the flow rate apportioning inside the coating flow and decomposing thickness variations into two separating oscillations are useful in understanding the results is found. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1745–1758, 2015
Ultrathin Alternating Copolymer Nanotubes with Readily Tunable Surface Functionalities
Authors: Chen Jianxin , Yu Chunyang , Shi Zengqian , Yu Songrui , Lu Zhongyuan , Jiang Wengfeng , Zhang Meng , He Wei , Zhou Yongfeng , Yan Deyue
Published: February 2015

Well‐defined ultrathin nanotubes (30 nm in diameter and of micrometer‐scale length) were generated through the self‐assembly of a novel alternative copolymer synthesized using an epoxy–thiol click‐chemistry reaction. The self‐assembly mechanism was investigated both by experiments and using dissipative particle dynamics (DPD) simulations. The obtained nanotubes can be readily functionalized with carboxy groups, amino groups, peptides, or other groups by simple modular click copolymerization.
Black Phosphorus Quantum Dots
Authors: Zhang Xiao , Xie Haiming , Liu Zhengdong , Tan Chaoliang , Luo Zhimin , Li Hai , Lin Jiadan , Sun Liqun , Chen Wei , Xu Zhichuan , Xie Linghai , Huang Wei , Zhang Hua
Published: February 2015

As a unique two‐dimensional nanomaterial, layered black phosphorus (BP) nanosheets have shown promising applications in electronics. Although mechanical exfoliation was successfully used to prepare BP nanosheets, it is still a challenge to produce novel BP nanostructures in high yield. A facile top‐down approach for preparation of black phosphorus quantum dots (BPQDs) in solution is presented. The obtained BPQDs have a lateral size of 4.9±1.6 nm and thickness of 1.9±0.9 nm (ca. 4±2 layers). As a proof‐of‐concept application, by using BPQDs mixed with polyvinylpyrrolidone as the active layer, a flexible memory device was successfully fabricated that exhibits a nonvolatile rewritable memory effect with a high ON/OFF current ratio and good stability.
Ausdehnung des Enzym‐Universums: Zugang zu nicht‐natürlichen Reaktionen durch mechanismusgeleitete, gerichtete Evolution
Authors: Renata Hans , Wang Z. Jane , Arnold Frances H.
Published: February 2015

Hohe Selektivitäten und ausgezeichnete Kontrolle des Reaktionsverlaufs regen Chemiker dazu an, in der organischen Synthese Biokatalysatoren einzusetzen. Viele nützliche Reaktionen sind auf diese Weise jedoch nicht zugänglich, weil sie im Repertoire der Natur nicht vorkommen. In diesem Aufsatz werden wir einen evolutiven Ansatz zur Entwicklung von Enzymen beschreiben, die solche nicht‐natürlichen Reaktionen katalysieren. Wir beginnen mit Beispielen dafür, wie die Natur neue katalytische Funktionen entdeckt hat und wie solche evolutiven Fortschritte im Labor nachvollzogen wurden, indem man von existierenden Enzymen ausging. Wir untersuchen dann nicht‐natürliche Enzymaktivitäten, die für die chemische Synthese entdeckt und verwendet wurden, wobei wir uns auf Reaktionen ohne natürliches Pendant konzentrieren. Wir zeigen Beispiele, wie nicht‐natürliche Aktivitäten durch gerichtete Evolution verbessert wurden, indem der Prozess nachgeahmt wurde, mit dem die Natur neue Katalysatoren erzeugt. Zum Schluss beschreiben wir noch Entdeckungen nicht‐natürlicher katalytischer Funktionen, die künftig Chancen auf eine Ausdehnung des enzymatischen Universums bieten können.
Sulfur Cathodes Based on Conductive MXene Nanosheets for High‐Performance Lithium–Sulfur Batteries
Authors: Liang Xiao , Garsuch Arnd , Nazar Linda F.
Published: February 2015

Lithium–sulfur batteries are amongst the most promising candidates to satisfy emerging energy‐storage demands. Suppression of the polysulfide shuttle while maintaining high sulfur content is the main challenge that faces their practical development. Here, we report that 2D early‐transition‐metal carbide conductive MXene phases—reported to be impressive supercapacitor materials—also perform as excellent sulfur battery hosts owing to their inherently high underlying metallic conductivity and self‐functionalized surfaces. We show that 70 wt % S/Ti2C composites exhibit stable long‐term cycling performance because of strong interaction of the polysulfide species with the surface Ti atoms, demonstrated by X‐ray photoelectron spectroscopy studies. The cathodes show excellent cycling performance with specific capacity close to 1200 mA h g−1 at a five‐hour charge/discharge (C/5) current rate. Capacity retention of 80 % is achieved over 400 cycles at a two‐hour charge/discharge (C/2) current rate.
Chemical‐Reaction‐Induced Hot Electron Flows on Platinum Colloid Nanoparticles under Hydrogen Oxidation: Impact of Nanoparticle Size
Authors: Lee Hyosun , Nedrygailov Ievgen I. , Lee Changhwan , Somorjai Gabor A. , Park Jeong Young
Published: February 2015

Generation of hot electron flows and the catalytic activity of Pt nanoparticles (NPs) with different sizes were investigated using catalytic nanodiodes. We show that smaller Pt NPs lead to higher chemicurrent yield, which is associated with the shorter travel length for the hot electrons, compared with their inelastic mean free path. We also show the impact of capping on charge carrier transfer between Pt NPs and their support.
Expanding the Enzyme Universe: Accessing Non‐Natural Reactions by Mechanism‐Guided Directed Evolution
Authors: Renata Hans , Wang Z. Jane , Arnold Frances H.
Published: February 2015

High selectivity and exquisite control over the outcome of reactions entice chemists to use biocatalysts in organic synthesis. However, many useful reactions are not accessible because they are not in nature’s known repertoire. In this Review, we outline an evolutionary approach to engineering enzymes to catalyze reactions not found in nature. We begin with examples of how nature has discovered new catalytic functions and how such evolutionary progression has been recapitulated in the laboratory starting from extant enzymes. We then examine non‐native enzyme activities that have been exploited for chemical synthesis, with an emphasis on reactions that do not have natural counterparts. Non‐natural activities can be improved by directed evolution, thus mimicking the process used by nature to create new catalysts. Finally, we describe the discovery of non‐native catalytic functions that may provide future opportunities for the expansion of the enzyme universe.
CuSbS2‐Sensitized Inorganic–Organic Heterojunction Solar Cells Fabricated Using a Metal–Thiourea Complex Solution
Authors: Choi Yong Chan , Yeom Eun Joo , Ahn Tae Kyu , Seok Sang Il
Published: February 2015

The device performance of sensitizer‐architecture solar cells based on a CuSbS2 light sensitizer is presented. The device consists of F‐doped SnO2 substrate/TiO2 blocking layer/mesoporous TiO2/CuSbS2/hole‐transporting material/Au electrode. The CuSbS2 was deposited by repeated cycles of spin coating of a Cu‐Sb‐thiourea complex solution and thermal decomposition, followed by annealing in Ar at 500 °C. Poly(2,6‐(4,4‐bis‐(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b;3,4‐b′]dithiophene)‐alt‐4,7(2,1,3‐benzothiadiazole)) (PCPDTBT) was used as the hole‐transporting material. The best‐performing cell exhibited a 3.1 % device efficiency, with a short‐circuit current density of 21.5 mA cm−2, an open‐circuit voltage of 304 mV, and a fill factor of 46.8 %.
Ligand‐Promoted Oxidative Cross‐Coupling of Aryl Boronic Acids and Aryl Silanes by Palladium Catalysis
Authors: Yu Jingxun , Liu Jun , Shi Guangfa , Shao Changdong , Zhang Yanghui
Published: February 2015

The first cross‐coupling reaction between aryl silanes and aryl boronic acids is described. This transformation represents one of the very few examples of coupling reactions between two nucleophilic organometallic reagents and provides a new method for the formation of biaryl compounds. The successful development of this reaction was enabled by the use of commercially available 2,2′‐bis(diphenylphosphino)‐1,1′‐binaphthyl (BINAP) as the ligand. A small amount of BINAP (3 mol %) was sufficient to suppress the formation of the homocoupling products, and the reaction yielded the cross‐coupling products with high selectivity under mild conditions, even when the ratio of the two coupling partners was 1:1.
Novel organosilicon dendrons as effective linkers for biomolecules binding on a glass surface
Authors: Hreczycho Grzegorz , Frydrych‐Tomczak Emilia , Sterzynska Karolina , Budna Joanna , Malinska Agnieszka , Maciejewski Hieronim , Zabel Maciej
Published: February 2015

A new, flexible and selective protocol for the synthesis of new organofunctional silicon dendrons of the general formula EtOSi(CH2CH2SiMe2CH2CH2SiMe2R)3 (where R is an amine or epoxy substituent) has been developed. The title compounds have been efficiently obtained via Karstedt platinum‐catalysed hydrosilylation and linked to a glass surface. Modified solid supports are successfully applied in immobilization of proteins, especially monoclonal antibodies against a wide range of antigens. Copyright © 2015 John Wiley & Sons, Ltd.
Cycloaddition of epoxide and CO2 to cyclic carbonate catalyzed by VO(IV) porphyrin
Authors: Bai Dongsheng , Zhang Zhiyong , Wang Guangjian , Ma Fang
Published: February 2015

The cycloaddition of epoxide and CO2 to synthesize cyclic carbonate catalyzed by VO(IV) porphyrin was achieved under 1.4 MPa at 150°C. The effects of reaction temperature, time, CO2 pressure, co‐catalyst and porphyrin framework were investigated. The catalytic results showed that moderate to high yields of cyclic carbonates were obtained under the optimal reaction conditions. Copyright © 2015 John Wiley & Sons, Ltd.
Gelation and crosslinking characteristics of photopolymerized poly(ethylene glycol) hydrogels
Authors: Hwang Ji Won , Noh Seung Man , Kim Bumsang , Jung Hyun Wook
Published: February 2015

The gelation and crosslinking features of poly(ethylene glycol) (PEG) hydrogels were scrutinized through the UV polymerization processes of poly(ethylene glycol) methacrylate (PEGMA) and poly(ethylene glycol) dimethacrylate (PEGDMA) mixtures. The real‐time evolutions of the elastic moduli of the prepolymerized mixtures with different crosslinking ratios of PEGMA and PEGDMA and the photoinitiator concentrations were measured during photopolymerization. The rheological properties were compared with other properties of the PEG hydrogels, including the relative changes in the CC amounts in the mixtures before and after UV irradiation, water swelling ratio, gel fraction, mesh size, and mechanical hardness. As the portion of PEGDMA as a crosslinker increased, the final elastic modulus and gel fraction increased, whereas the swelling ratio and scratch penetration depth at the hydrogel film surface decreased because of the formation of compact networks inside the hydrogels. These results indicate that there was a good correlation between the rheological analysis for predicting the crosslinking transition during photopolymerization and the macroscopic properties of the crosslinked hydrogels. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41939.
In Situ Chemical Oxidative Polymerization Preparation of Poly(3,4‐ethylenedioxythiophene)/Graphene Nanocomposites with Enhanced Thermoelectric Performance
Authors: Xu Kongli , Chen Guangming , Qiu Dong
Published: February 2015

Three different in situ chemical oxidative polymerization routes, that is, (A) spin‐coating and subsequent liquid layer polymerization, (B) spin‐coating followed by vapor phase polymerization, and (C) in situ polymerization and then post‐treatment by immersion in ethylene glycol (EG), have been developed to achieve poly(3,4‐ethylenedioxythiophene)/reduced graphene oxide (PEDOT/rGO) nanocomposites. As demonstrated by scanning electron microscopic and energy‐dispersive X‐ray spectroscopic techniques, PEDOT has been successfully coated on the surface of the rGO nanosheets by each of the three preparation routes. Importantly, all of the nanocomposites display a greatly enhanced thermoelectric performance (power factors) relative to those of the corresponding neat PEDOT.
‘Time‐free’ preventive maintenance of systems with structures described by signatures
Authors: Finkelstein Maxim , Gertsbakh Ilya
Published: February 2015

A new approach to optimal maintenance of multicomponent systems (networks) is suggested. It is applied to systems subject to external shock processes. Signatures are used for description of systems structures and for dealing with the corresponding optimal maintenance problems. The number of shocks experienced by a system defines a discrete parameter for minimization of the long‐run costs per unit of time and is viewed as an alternative scale. The optimal preventive maintenance is performed either after the shock with the obtained optimal number or the corrective maintenance (replacement) of the whole failed system occurs, whichever comes first. A numerical example is considered and the comparison with the age‐based preventive maintenance is performed. Copyright © 2015 John Wiley & Sons, Ltd.
Association of cerebral white matter lesions with cognitive function and mood in Japanese elderly people: a population‐based study
Authors: Yamawaki Mika , Wada‐Isoe Kenji , Yamamoto Mikie , Nakashita Satoko , Uemura Yusuke , Takahashi Yoshimitsu , Nakayama Takeo , Nakashima Kenji
Published: February 2015

Background

To determine the relationships between regional white matter lesions (WMLs), lifestyle factors, and cognitive, motor function and mood.

Methods

A comprehensive evaluation, including brain MRI, blood tests, the Unified Parkinson's Disease Rating Scale, the Mini Mental State Examination, and the Geriatric Depression Scale, was performed for people aged 65 years or older living in Ama‐cho on October 1, 2009. Participants were classified by severity of periventricular hyperintensities (PVH) and deep white matter hyperintensities (DWMH) using the Fazekas score.

Results

Of 900 eligible participants, 688 (76.4%) were enrolled, including 303 men. Significant predictors of severe PVH were older age, lower low‐density lipoprotein cholesterol (LDL‐C) levels, elevated blood pressure (BP), cerebral infarction, and no current alcohol use. Significant predictors of severe DWMH were older age, lower 1,5‐anhydroglucitol (1,5‐AG) levels, elevated BP, cerebral infarction, and no current alcohol use. Higher cognitive function was associated with younger age, female sex, mild DWMH, more years of education, and higher high‐density lipoprotein cholesterol levels. Depressive symptoms were associated with lower 1,5‐AG levels, lower LDL‐C levels, moderate to severe PVH, and no current alcohol use.

Conclusions

White matter lesions in elderly people were related to hypertension and impaired glucose tolerance. The severity of WMLs was associated with cognitive function and mood.
Application of fluorescence melting curve analysis for dual DNA detection using single peptide nucleic acid probe
Authors: Ahn Jeong Jin , Lee Seung Yong , Hong Ji Young , Kim Youngjoo , Kim Gi Won , Hwang Seung Yong
Published: February 2015

Peptide nucleic acid (PNA) is an artificially synthesized polymer. PNA oligomers show greater specificity in binding to complementary DNAs. Using this PNA, fluorescence melting curve analysis (FMCA) for dual detection was established. Genomic DNA of Mycoplasma fermentans and Mycoplasma hyorhinis was used as a template DNA model. By using one PNA probe, M. fermentans and M. hyorhinis could be detected and distinguished simultaneously in a single tube. The developed PNA probe is a dual‐labeled probe with fluorescence and quencher dye. The PNA probe perfectly matches the M. fermentans 16s rRNA gene, with a melting temperature of 72°C. On the other hand, the developed PNA probe resulted in a mismatch with the 16s rRNA gene of M. hyorhinis, with a melting temperature of 44–45°C. The melting temperature of M. hyorhinis was 27–28°C lower than that of M. fermentans. Due to PNA's high specificity, this larger melting temperature gap is easy to create. FMCA using PNA offers an alternative method for specific DNA detection. © 2015 American Institute of Chemical Engineers Biotechnol. Prog., 31:730–735, 2015
Challenges with afucosylation content in antibody‐based drugs: Guidance provided by mathematical modeling
Authors: Zhan Peter L. , Chung John D.
Published: February 2015

The theory of competitive ligand–receptor binding has been used to analyze the effect of afucosylation‐based antibody heterogeneity on Fc‐FcγRIIIa ligand–receptor binding activity. In vitro activity is found to represent a linear combination of the component antibody activities, weighted by the relative concentrations of the different afucosylated antibody forms. An analysis of ELISA binding activity data has allowed for the dissection of the activity contributions of the different afucosylated antibodies, revealing that the heterogeneous afucosylated antibody exhibits greater activity, on a per mole basis, when compared to the homogeneous afucosylated antibody. The ratio of the afucosylated antibody equilibrium dissociation constants is computed to be KAF/KA ≈ 0.6–0.9, where KAF and KA denote the dissociation equilibrium constant of the heterogeneous and the homogeneous afucosylated antibodies, respectively. Our analysis also reveals that, in general, activity scales quadratically with the afucosylated glycan content of a sample. Linear activity–afucosylated glycan fraction correlations reported in the literature are shown to represent specific cases of this general scaling and result from oversimplifying the underlying antibody concentration distributions. The implications of our findings for drug development are also discussed. © 2015 American Institute of Chemical Engineers Biotechnol. Prog., 31:775–782, 2015
Psychology Without Psy Professionals: Exploring an Unemployed Centre Families Project as a Mental Health Resource
Authors: Walker Carl , Hanna Paul , Hart Angie
Published: February 2015

The activities and technologies of the psychology (Psy) disciplines, in the process of privileging professional understandings of distress, could be seen to be potentially facilitating corrosion in the capacity of the lay public to understand and ameliorate their distress. This paper draws on the experiences of people who use an Unemployed Centre Families Project in the South of England to provide an example of community mental health work that does not draw on the dominant discourses, institutions or practitioners of the Psy sciences. Through interviews with centre users, staff and volunteers, a picture emerges of a community space that provides a variety of services, projects and opportunities that have a very considerable positive impact on the mental well‐being of the centre users. This picture highlights non‐medical intersubjective processes that offer possibilities for recoveries from mental distress but that are often neglected and subordinated in the professional worlds of Psy and psychiatry. Such centres facilitate social networks and practical help, and transitions in identity can be beneficial for those experiencing mental distress. In so doing, they make prominent some of the key limitations of biomedical approaches to recovery. Copyright © 2015 John Wiley & Sons, Ltd.
Vignettes of DES failure
Authors: Gilchrist Ian C.
Published: February 2015

Key Points

Clinical and angiographic patterns of restenosis after DES vary as a function of time since stent placement

Acute coronary syndromes and myocardial infarction can be a late (>36 months) manifestation of DES failure with a poor prognosis

The role of extended antiplatelet therapy is unclear, but this continued hazard should encourage evidence‐based practice to optimize long‐term outcomes
Aerobic Oxidative Esterification of Benzyl Alcohol and Acetaldehyde over Gold Supported on Nanostructured Ceria–Alumina Mixed Oxides
Authors: Smolentseva Elena , Costa Vinícius V. , Cotta Rafaela F. , Simakova Olga , Beloshapkin Sergey , Gusevskaya Elena V. , Simakov Andrey
Published: February 2015

Au nanoparticles supported on nanostructured ceria‐alumina mixed oxides (10 and 30 wt % ceria) were prepared by a deposition–precipitation method. Their properties were studied by N2 adsorption, XRD, TEM, X‐ray photoelectron spectroscopy, and UV/Vis spectroscopy under temperature‐programmed reduction or oxidation. The materials catalyzed the liquid‐phase aerobic oxidative esterification of benzyl alcohol and benzaldehyde effectively and showed a much better performance than Au supported on the individual oxides. The reactions occurred with high turnover numbers (up to 19 000) in methanol solutions in the absence of any auxiliary base and gave mainly methyl benzoate. The strong synergetic effect of ceria and alumina can be explained by the enhanced oxygen storage capacity of the materials prepared from mixed oxides compared to that of pure alumina and ceria. The order of the catalytic activity (Au/Al2O3<Au/CeO2<Au/Ce(10)‐Al<Au/Ce(30)‐Al) correlated well with the oxygen activation capacity of the materials.
Simulation of a Lignite‐Based Polygeneration System Coproducing Electricity and Tar with Carbon Capture
Authors: Guo Zhihang , Wang Qinhui , Fang Mengxiang , Luo Zhongyang , Cen Kefa
Published: February 2015

Lignite‐based polygeneration systems for coproducing tar and electricity with and without carbon capture and storage (CCS) were proposed and simulated. Predried lignite was pyrolyzed into coal gas, tar, and char. Coal gas was fired in a gas turbine after the cleanup process, while char was combusted in circulating fluidized‐bed (CFB) boilers. The polygeneration plant without CCS turned out to be more efficient than the conventional CFB power plant, suggesting that the former is a promising and efficient option to utilize lignite resources. Moreover, the performance and emissions of polygeneration plants with and without CCS were compared. It was shown that the more CO2 is captured, the larger energy penalty it will cost. Therefore, a trade‐off should be made between low emissions and high efficiency.
Cross‐Talk Between the Octarepeat Domain and the Fifth Binding Site of Prion Protein Driven by the Interaction of Copper(II) with the N‐terminus
Authors: Di Natale Giuseppe , Turi Ildikó , Pappalardo Giuseppe , Sóvágó Imre , Rizzarelli Enrico
Published: February 2015

Prion diseases are a group of neurodegenerative diseases based on the conformational conversion of the normal form of the prion protein (PrPC) to the disease‐related scrapie isoform (PrPSc). Copper(II) coordination to PrPC has attracted considerable interest for almost 20 years, mainly due to the possibility that such an interaction would be an important event for the physiological function of PrPC. In this work, we report the copper(II) coordination features of the peptide fragment Ac(PEG11)3PrP(60‐114) [Ac=acetyl] as a model for the whole N‐terminus of the PrPC metal‐binding domain. We studied the complexation properties of the peptide by means of potentiometric, UV/Vis, circular dichroism and electrospray ionisation mass spectrometry techniques. The results revealed that the preferred histidyl binding sites largely depend on the pH and copper(II)/peptide ratio. Formation of macrochelate species occurs up to a 2:1 metal/peptide ratio in the physiological pH range and simultaneously involves the histidyl residues present both inside and outside the octarepeat domain. However, at increased copper(II)/peptide ratios amide‐bound species form, especially within the octarepeat domain. On the contrary, at basic pH the amide‐bound species predominate at any copper/peptide ratio and are formed preferably with the binding sites of His96 and His111, which is similar to the metal‐binding‐affinity order observed in our previous studies.
An Efficient Nanoparticle‐Supported and Magnetically Recoverable Copper(I) Catalyst for Synthesis of Furans from Ene‐yne‐ketone
Authors: Liu Yi , Liu Zhan , Cui Yingde
Published: February 2015

A magnetic nano‐supported Cu(I) catalyst was prepared and showed high activity for cyclization of ene‐yne‐ketone to synthesize furans. The catalyst was easily recovered from the reaction by using external magnets and reused 8 times without significant loss of its catalytic activity.
Acceptor‐Donor‐Acceptor Type Small Molecular Low Band Gap Organic Semiconductors Containing 2‐Dicyanomethylen‐3‐cyano‐4,5,5‐trimethyl‐dihydrofuran
Authors: Chen Sanlong , Qiao Xiaolan , Li Heping , Li Hongxiang
Published: February 2015

Acceptor‐donor‐acceptor type compounds W1–W3 were designed and synthesized. These compounds had the same donor moiety of 2,6‐di(thiophen‐2‐yl)dithieno[3,2‐b:2′,3′‐d]thiophene and different acceptor groups of 2‐dicyanomethylen‐3‐cyano‐4,5,5‐trimethyl‐2,5‐dihydrofuran (TCF), dicyanovinyl (DCV) and 3‐ethyl‐2‐thioxothiazolidin‐4‐one. Experimental results showed all compounds had high thermal stability and strong absorption in the visible light region. Among them, compound W1 with TCF as acceptor group displayed the lowest LUMO energy level of −3.74 eV and the smallest HOMO‐LUMO band gap of 1.74 eV, suggesting the potential applications of TCF unit in low band gap organic semiconductors.
Pillar[n]arenes and Other Cavitands: Aspects of Complex Thermodynamics
Authors: Park Chiyoung , Kim Kyoung Taek
Published: February 2015

Novel cavitands, the pillar[n]arenes, have captivated the attention of supramolecular chemists since the first reported synthesis of pillar[5]arene displaying binding capability to guest molecules. Recently, pillar[n]arenes and their functionalized pillar[n]arenes have been applied in many different areas, from supramolecular chemistry to materials science. Pillar[n]arenes have symmetric pillar shapes, and consist of n hydroquinone units bridged by methylene groups, which link the 2‐ and 5‐positions of the hydroquinone units. The inner surface of the cavity of pillar[n]arenes is π‐electron‐rich, thus providing a favorable environment for guest molecules bearing electron withdrawing groups. Despite the extensive efforts, however, the complex thermodynamics of pillar[n]arenes have not been systematically investigated to date. This review outlines the range and perspectives of the thermodynamic characteristics of pillar[n]arenes in comparison with other successful cavitands, such as cyclodextrins and cucurbit[n]urils.
Late Percutaneous Coronary Intervention Prevents Left Ventricular Remodeling and Improves Clinical Outcomes in Patients With ST‐Elevation Myocardial Infarction
Authors: Fan Yan , Bai Xiaojun , Chen Yuewu , Shen Guidong , Lu Qun , Wan Zhaofei , Zhou Dong , Shen Yuan , Ma Aiqun
Published: February 2015

Background

The optimal strategy for treating late presenters of ST‐elevation myocardial infarction (STEMI) remains uncertain.

Hypothesis

percutaneous coronary intervention (PCI) has a favorable effect on left ventricular (LV) remodeling and clinical outcomes in late presenters of STEMI.

Methods

Patients with STEMI who were hospitalized between 2009 and 2011 at 7 PCI‐capable hospitals in China were selected. Cardiac characteristics were reassessed by echocardiography between August 2013 and January 2014. The clinical endpoints were evaluated during a median follow‐up period of 36 months.

Results

1090 patients who either underwent late PCI (n = 786) or received standard medical therapy alone (n = 304) was analyzed. Left ventricular remodeling was more pronounced in the conservative‐treatment group. Logistic regression revealed that late PCI was independently and negatively correlated with LV remodeling (odds ratio: 0.356, 95% confidence interval [CI]: 0.251‐0.505, P < 0.001). Kaplan‐Meier analysis showed the lower risks of major adverse cardiovascular events (MACE), all‐cause death, and rehospitalization for heart failure in the late‐PCI group. Multivariate Cox regression revealed that late PCI was significantly associated with lower risks for MACE, all‐cause death, and rehospitalization for heart failure both in all patients (hazard ratio [HR]: 0.507, 95% CI: 0.412‐0.625, P < 0.001; HR: 0.419, 95% CI: 0.314‐0.559, P < 0.001; and HR: 0.583, 95% CI: 0.379‐0.896, P = 0.014, respectively) and in the matched patients (HR: 0.466, 95% CI: 0.358‐0.607, P < 0.001; HR: 0.398, 95% CI: 0.277‐0.571, P < 0.001; and HR: 0.498, 95% CI: 0.283‐0.878, P = 0.016, respectively) by propensity‐score analysis.

Conclusions

Late‐PCI strategy prevents LV remodeling and improves clinical outcomes in STEMI patients compared with conservative strategies.
The past, present, and future of cancer incidence in the United States: 1975 through 2020
Authors: Weir Hannah K. , Thompson Trevor D. , Soman Ashwini , Møller Bjørn , Leadbetter Steven
Published: February 2015

BACKGROUND

The overall age‐standardized cancer incidence rate continues to decline whereas the number of cases diagnosed each year increases. Predicting cancer incidence can help to anticipate future resource needs, evaluate primary prevention strategies, and inform research.

METHODS

Surveillance, Epidemiology, and End Results data were used to estimate the number of cancers (all sites) resulting from changes in population risk, age, and size. The authors projected to 2020 nationwide age‐standardized incidence rates and cases (including the top 23 cancers).

RESULTS

Since 1975, incident cases increased among white individuals, primarily caused by an aging white population, and among black individuals, primarily caused by an increasing black population. Between 2010 and 2020, it is expected that overall incidence rates (proxy for risk) will decrease slightly among black men and stabilize in other groups. By 2020, the authors predict annual cancer cases (all races, all sites) to increase among men by 24.1% (−3.2% risk and 27.3% age/growth) to >1 million cases, and by 20.6% among women (1.2% risk and 19.4% age/growth) to >900,000 cases. The largest increases are expected for melanoma (white individuals); cancers of the prostate, kidney, liver, and urinary bladder in males; and the lung, breast, uterus, and thyroid in females.

CONCLUSIONS

Overall, the authors predict cancer incidence rates/risk to stabilize for the majority of the population; however, they expect the number of cancer cases to increase by >20%. A greater emphasis on primary prevention and early detection is needed to counter the effect of an aging and growing population on the burden of cancer. Cancer 2015;121:1827–1837. © 2015 American Cancer Society.
Unrelated cord blood compared with haploidentical grafts in patients with hematological malignancies
Authors: El‐Cheikh Jean , Crocchiolo Roberto , Furst Sabine , Bramanti Stefania , Sarina Barbara , Granata Angela , Vai Andrea , Lemarie Claude , Faucher Catherine , Mohty Bilal , Harbi Samia , Bouabdallah Reda , Vey Norbert , Santoro Armando , Chabannon Christian , Castagna Luca , Blaise Didier
Published: February 2015

BACKGROUND

Alternative donors, such as unrelated umbilical cord blood (UCB) and related haploidentical (haplo) donors, are more and more frequently searched for and used for patients who are candidates for allogeneic hematopoietic stem cell transplantation but are without a suitable related or unrelated donor. The aim of the current retrospective study was to compare the outcome of patients after haplo and UCB grafts prepared using a nonmyeloablative conditioning regimen.

METHODS

A total of 150 adult patients with high‐risk hematologic diseases who underwent allogeneic hematopoietic stem cell transplantation from alternative donors at 2 centers (Paoli‐Calmettes Institute [Marseille, France] and Humanitas Cancer Center [Milan, Italy]) were analyzed. Sixty‐nine patients had haplo donors and 81 patients had UCB donors.

RESULTS

The cumulative incidence of nonrecurrence mortality at 1 year was 23% in the UCB group versus 17% in the haplo group (P = .39). The incidence of grade 2 to 4 acute graft‐versus‐host disease and extensive chronic graft‐versus‐host disease in the UCB group versus the haplo group was 52% versus 29% (P = .05) and 12% versus 6% (P<.0001), respectively. The overall survival rate at 2 years was 45% in the UCB group (95% confidence interval [95% CI], 34%‐56%) versus 69% in the haplo group (95% CI, 58%‐80%) (P = .10). The progression‐free survival rate at 2 years was 36% in the UCB group (95% CI, 25%‐47%) versus 65% in the haplo group (95% CI, 53%‐77%) (P = .01).

CONCLUSIONS

The results of the current study suggest that for patients with high‐risk hematological diseases without a related or unrelated donor, haploidentical transplants are a promising alternative option that deserves further investigation. Cancer 2015;121:1809–1816. © 2015 American Cancer Society.
The gyri of the octopus vertical lobe have distinct neurochemical identities
Authors: Shigeno Shuichi , Ragsdale Clifton W.
Published: February 2015

The cephalopod vertical lobe is the largest learning and memory structure known in invertebrate nervous systems. It is part of the visual learning circuit of the central brain, which also includes the superior frontal and subvertical lobes. Despite the well‐established functional importance of this system, little is known about neuropil organization of these structures and there is to date no evidence that the five longitudinal gyri of the vertical lobe, perhaps the most distinctive morphological feature of the octopus brain, differ in their connections or molecular identities. We studied the histochemical organization of these structures in hatchling and adult Octopus bimaculoides brains with immunostaining for serotonin, octopus gonadotropin‐releasing hormone (oGNRH), and octopressin‐neurophysin (OP‐NP). Our major finding is that the five lobules forming the vertical lobe gyri have distinct neurochemical signatures. This is most prominent in the hatchling brain, where the median and mediolateral lobules are enriched in OP‐NP fibers, the lateral lobule is marked by oGNRH innervation, and serotonin immunostaining heavily labels the median and lateral lobules. A major source of input to the vertical lobe is the superior frontal lobe, which is dominated by a neuropil of interweaving fiber bundles. We have found that this neuropil also has an intrinsic neurochemical organization: it is partitioned into territories alternately enriched or impoverished in oGNRH‐containing fascicles. Our findings establish that the constituent lobes of the octopus superior frontal–vertical system have an intricate internal anatomy, one likely to reflect the presence of functional subsystems within cephalopod learning circuitry. J. Comp. Neurol. 523:1297–1317, 2015. © 2015 Wiley Periodicals, Inc.
Mechanistic Studies on the Cascade Conversion of 1,3‐Dihydroxyacetone and Formaldehyde into α‐Hydroxy‐γ‐butyrolactone
Authors: Yamaguchi Sho , Matsuo Takeaki , Motokura Ken , Sakamoto Yasuharu , Miyaji Akimitsu , Baba Toshihide
Published: February 2015

The chemical synthesis of commercially and industrially important products from biomass‐derived sugars is absolutely vital to establish biomass utilization as a sustainable alternative source of chemical starting materials. α‐Hydroxy‐γ‐butyrolactone is a useful synthetic intermediate in pharmaceutical chemistry, and so novel biomass‐related routes for its production may help to validate this eco‐friendly methodology. Herein, we report the specific catalytic activity of homogeneous tin halides to convert the biomass‐derived triose sugar 1,3‐dihydroxyacetone and formaldehyde into α‐hydroxy‐γ‐butyrolactone. A detailed screening of catalysts showed the suitability of tin catalysts for this reaction system, and isotope experiments using [D2]paraformaldehyde, substrate screening, and time profile measurements allowed us to propose a detailed reaction pathway. In addition, to elucidate the activated species in this cascade reaction, the effect of additional water and the influence of additional Brønsted acids on the reaction preferences for the formation of α‐hydroxy‐γ‐butyrolactone, lactic acid, and vinyl glycolate were investigated. The active form of the Sn catalyst was investigated by 119Sn NMR spectroscopy.
The role of cell adhesion molecules in visual circuit formation: From neurite outgrowth to maps and synaptic specificity
Authors: Missaire Mégane , Hindges Robert
Published: February 2015

The formation of visual circuitry is a multistep process that involves cell–cell interactions based on a range of molecular mechanisms. The correct implementation of individual events, including axon outgrowth and guidance, the formation of the topographic map, or the synaptic targeting of specific cellular subtypes, are prerequisites for a fully functional visual system that is able to appropriately process the information captured by the eyes. Cell adhesion molecules (CAMs) with their adhesive properties and their high functional diversity have been identified as key actors in several of these fundamental processes. Because of their growth‐promoting properties, CAMs play an important role in neuritogenesis. Furthermore, they are necessary to control additional neurite development, regulating dendritic spacing and axon pathfinding. Finally, trans‐synaptic interactions of CAMs ensure cell type‐specific connectivity as a basis for the establishment of circuits processing distinct visual features. Recent discoveries implicating CAMs in novel mechanisms have led to a better general understanding of neural circuit formation, but also revealed an increasing complexity of their function. This review aims at describing the different levels of action for CAMs to shape neural connectivity, with a special focus on the visual system. © 2015 Wiley Periodicals, Inc. Develop Neurobiol 75: 569–583, 2015
Proliferation following tetraploidization regulates the size and number of erythrocytes in the blood flow during medaka development, as revealed by the abnormal karyotype of erythrocytes in the medaka TFDP1 mutant
Authors: Taimatsu Kiyohito , Takubo Keiyo , Maruyama Kouichi , Suda Toshio , Kudo Akira
Published: February 2015

Background: For the delivery of oxygen, the correct size/number of erythrocytes is required for proper blood flow. Results: By combined analyses of wild‐type (WT) medaka and the kyoho (kyo) mutant, we found proliferation‐mediated adaptation for size/number of erythrocytes in the blood flow during medaka development. Before the start of heart beating in the WT medaka, the karyotype of erythrocytes was 2N‐4N. After the start of blood flow, the karyotype changed to 4N‐8N with tetraploidization, and the cell size became larger. After the start of intersegmental and pharyngeal blood flow, the erythrocytes became smaller. The medaka mutant kyo showed erythrocytes of large size, and positional cloning of kyo demonstrated the candidate gene TFDP1, indicating higher polyploidization due to arrest in S‐phase in erythrocytes of the kyo mutant. Conclusions: From our findings, we uncovered a previously unrecognized system for the regulation of the size/number in the blood flow:proliferation of erythrocytes following tetraploidization during embryonic development. Developmental Dynamics 244:651–668, 2015. © 2015 Wiley Periodicals, Inc.
Interactive effect of warming, nitrogen and phosphorus limitation on phytoplankton cell size
Authors: Peter Kalista Higini , Sommer Ulrich
Published: February 2015

Cell size is one of the ecologically most important traits of phytoplankton. The cell size variation is frequently related to temperature and nutrient limitation. In order to disentangle the role of both factors, an experiment was conducted to determine the possible interactions of these factors. Baltic Sea water containing the natural plankton community was used. We performed a factorial combined experiment of temperature, type of nutrient limitation (N vs. P), and strength of nutrient limitation. The type of nutrient limitation was manipulated by altering the N:P ratio of the medium (balanced, N and P limitation) and strength by the dilution rate (0% and 50%) of the semicontinuous cultures. The negative effect of temperature on cell size was strongest under N limitation, intermediate under P limitation, and weakest when N and P were supplied at balanced ratios. However, temperature also influenced the intensity of nutrient imitation, because at higher temperature there was a tendency for dissolved nutrient concentrations to be lower, while the C:N or C:P ratio being higher…higher at identical dilution rates and medium composition. Analyzing the response of cell size to C:N ratios (as index of N limitation) and C:P ratios (as index of P limitation) indicated a clear dominance of the nutrient effect over the direct temperature effect, although the temperature effect was also significant.
Fundamental Aspects of Rare Earth Oxides Affecting Direct NO Decomposition Catalysis
Authors: Tsujimoto Soichiro , Masui Toshiyuki , Imanaka Nobuhito
Published: February 2015

The basic aspects of rare earth oxides (REOs) that affect their capacity for direct NO decomposition catalysis were investigated. A correlation between crystal structure and catalytic activity was found, which is related to the NO adsorption ability of the REOs. The crystal structure was the most important factor affecting direct NO decomposition over REOs, since the adsorption of NO was significantly dependent on the coordination environments of the rare earth cations within each crystal lattice. Among the REOs, cubic C‐type oxides showed higher NO decomposition activities than those of the others. Within a series of C‐type cubic REOs, the activity was typically dominated by the density of the surface basic sites, and the effects of particle morphology and lattice parameters were small.
A Eu‐Doped Y‐Based Luminescent Metal–Organic Framework as a Highly Efficient Sensor for Nitroaromatic Explosives
Authors: Singha Debal Kanti , Majee Prakash , Mondal Sudip Kumar , Mahata Partha
Published: February 2015

By an isomorphous substitution strategy, a three‐dimensional metal–organic framework (MOF), [Y1.8Eu0.2(PDA)3(H2O)1]·2H2O (1; PDA = 1,4‐phenylenediacetate), has been synthesized by solvent‐assisted liquid grinding and direct heating. Dehydrated 1 (1′) shows strong red photoluminescence through the antenna effect upon excitation at 240 nm. The red emissive property was used for the visual detection of nitroaromatic explosives in acetonitrile through luminescence quenching. Importantly, 1′ exhibited high sensitivity towards the sensing of 2,4,6‐trinitrophenol (TNP), 1,3‐dinitrobenzene (DNB), 2,4‐dinitrotoluene (DNT), 4‐nitrotoluene (NT), and nitrobenzene (NB) at very low concentrations (0 to 20 μM). The estimated KSV (quenching constant based on linear Stern–Volmer plots) values are in the range 15.9 × 104–1.1 × 104 M–1, which are amongst the highest values known for nitroaromatic‐sensing materials. For 1′, sensing of TNP down to 23 ppb has been achieved.
Complexation of Tetrakis(acetato)chloridodiruthenium with Naphthyridine‐2,7‐dicarboxylate – Characterization and Catalytic Activity
Authors: Lee Chia‐Han , Wu Cai‐Ling , Hua Shao‐An , Liu Yi‐Hung , Peng Shie‐Ming , Liu Shiuh‐Tzung
Published: February 2015

The reaction of calcium naphthyridine‐2,7‐dicarboxylate (Cadcnp) with Ru2(OAc)4Cl in water resulted in the formation of Ca[Ru2(dcnp)(OAc)3]2 (3). X‐ray crystal structural analysis of 3 confirmed its molecular structure and showed that the calcium ion binds to the lateral carboxylate groups of four neighboring anionic units of [Ru2(dcnp)(μ‐OAc)3] and two acetone molecules to form a two‐dimensional framework. The RuII–RuII valence state of the diruthenium core was supported by superconducting quantum interference device (SQUID) magnetometry [μeff (300 K) = 2.77 μB]. Complex 3 appears to be an efficient catalyst for the oxidative cleavage of olefins in aqueous media under mild conditions. Typically, the reaction of pulegone with NaIO4 in water catalyzed by 3 (1 mol‐%) at 45 °C afforded 3‐methyladipic acid quantitatively.