bluuebunny/crossref_metadata_2025 huggingface dataset:
A Solution‐Processed UV‐Sensitive Photodiode Produced Using a New Silicon Nanocrystal Ink
Authors: Lin Tao , Liu Xin , Zhou Bin , Zhan Zhiyong , Cartwright Alexander N. , Swihart Mark T.
Published: July 2014

This article presents a simple and effective method of functionalizing hydrogen‐terminated silicon (Si) nanocrystals (NCs) to form a high‐quality colloidal Si NC ink with short ligands that allow charge transport in nanocrystal solid films. Si NCs fabricated by laser‐pyrolysis and acid etching are passivated with allyl disulfide via ultraviolet (UV)‐initiated hydrosilylation to form a stable colloidal Si NC ink. Then a Si NC‐based photodiode is directly fabricated in air from this ink. Only a solution‐processed poly(3,4‐ethylenedioxy‐thiophene):poly(styrene sulfonate) (PEDOT: PSS) electron blocking layer and top‐ and bottom‐contacts are needed along with the Si NC layer to construct the device. A Schottky‐junction at the interface between the Si NC absorber layer and aluminum (Al) back electrode drives charge separation in the device under illumination. The unpackaged Si NC‐based photodiode exhibites a peak photoresponse of 0.02 A W−1 to UV light in air, within an order of magnitude of the response of commercially available gallium phosphide (GaP), gallium nitride (GaN), and silicon carbide (SiC) based photodetectors. This provides a new pathway to large‐area, low‐cost solution‐processed UV photodetectors on flexible substrates and demonstrates the potential of this new silicon nanocrystal ink for broader applications in solution‐processed optoelectronics.
Three‐Dimensional Silver Nanoparticle Formation Using Femtosecond Laser Irradiation in Phosphate Glasses: Analogy with Photography
Authors: Marquestaut N. , Petit Y. , Royon A. , Mounaix P. , Cardinal T. , Canioni L.
Published: July 2014

Three‐dimensional patterning of metal–dielectric composites is achieved at the sub‐micrometer scale in glass. A high silver‐content zinc‐phosphate optical transparent glass is structured by means of a near‐infrared femtosecond laser via non‐linear absorption processes. The silver ions embedded in glass photochemically react under controlled laser irradiation, inducing ion clustering and the formation of nucleation centers. A subsequent thermal development causes silver reduction and growth into metallic nanoparticles. A very strong surface plasmon resonance is measured, revealing the very high concentration of metallic particles. The direct laser writing process enables inscriptions of silver nanoparticle domains well below the diffraction limit (∼100 nm). A very detailed parametric study is given, leading to the first thorough understanding of the ultrafast laser‐induced photochemistry in silver‐containing glass materials. These nanostructures are considered promising candidates for the design of highly efficient sensing devices via plasmonics and, beyond that, for photonics and metamaterials applications.
Strongly Coupled Interfaces between a Heterogeneous Carbon Host and a Sulfur‐Containing Guest for Highly Stable Lithium‐Sulfur Batteries: Mechanistic Insight into Capacity Degradation
Authors: Peng Hong‐Jie , Hou Ting‐Zheng , Zhang Qiang , Huang Jia‐Qi , Cheng Xin‐Bing , Guo Meng‐Qing , Yuan Zhe , He Lian‐Yuan , Wei Fei
Published: July 2014

The use of conductive frameworks as the host scaffold to obtain nanostructured sulfur cathodes is an efficient way to increase the sulfur utilization for redox reaction in Li‐S batteries with large discharge capacity and high energy density. However, due to dynamical interfaces driven by phase evolution between the conductive hosts and S‐containing guests during cycling, the cathode still faces poor stability. Herein, the use of O‐/N‐containing nanocarbon as the conductive host sheds a light on the role of the dynamic interface between the carbon host and S‐containing guest for a stable Li‐S cell. The outstanding reversibility and stability of N‐doped C/S cathodes are attributed to the favorable guest‐host interaction at the electron‐modified interface, manifesting as (i) a chemical gradient to adsorb polar polysulfides and (ii) ameliorative deposition and recharging of Li2S on the region of electron‐rich pyridinic N and a graphene domain surrounding quaternary N. Highly reversible, efficient and stable Li storage properties such as mitigated polarization and charge barrier, high capacity of 1370 and 964 mAh g−1 at 0.1 and 1.0 C, respectively, and 70% of capacity retention after 200 cycles are achieved. Mechanistic insight into the capacity fading inspires the rational design on electrodes for high‐performance electrochemical systems.
Heavy Metal Sensing Using Self‐Assembled Nanoparticles at a Liquid–Liquid Interface
Authors: Cecchini Michael P. , Turek Vladimir A. , Demetriadou Angela , Britovsek George , Welton Tom , Kornyshev Alexei A. , Wilton‐Ely James D. E. T. , Edel Joshua B.
Published: July 2014

A novel sensor for the detection of heavy metal ions in solution has been designed. It uses a recently developed new nanoplasmonic platform based on self‐assembled layers of Au nanoparticles (NPs) at a liquid–liquid interface (LLI). This system is shown to be very promising for the detection of trace amounts of analyte molecules through their Raman scattering fingerprints, enhanced by the NPs’ localized plasmonic resonances. For the detection of heavy metals this platform is modified by controlling and optimizing the ligand functionality on the NPs through the use of polyaromatic ligands (PALs). Importantly, the PALs are soluble in the organic phase whilst the NPs and heavy metals are soluble in the aqueous phase; therefore the self‐assembly at the LLI is key to efficient detection. For example, the system described here is able to detect Hg(II) quantities down to 10 pmole levels whilst at the same time differentiating between other heavy metals based on spectral variability. Finally, airborne mercury detection is shown to be possible with a minimally modified platform at the air‐liquid/air‐solid interface, with a clearly resolvable mercury‐positive spectrum being observed within 5 min of exposure.
Equation‐oriented flowsheet simulation and optimization using pseudo‐transient models
Authors: Pattison Richard C. , Baldea Michael
Published: July 2014

Tight integration through material and energy recycling is essential to the energy efficiency and economic viability of process and energy systems. Equation‐oriented (EO) steady‐state process simulation and optimization are key enablers in the optimal design of integrated processes. A new process modeling and simulation concept based on pseudo‐transient continuation is introduced. An algorithm for reformulating the steady‐state models of process unit operations as differential‐algebraic equation systems that are statically equivalent with the original model is presented. These pseudo‐transient models improve the convergence of EO process flowsheet simulations by expanding the convergence basin. This concept is used to build a library of pseudo‐transient models for common process unit operations, and this modeling concept seamlessly integrates with a previously developed time‐relaxation optimization algorithm. Two design case studies are presented to validate the proposed framework. © 2014 American Institute of Chemical Engineers AIChE J 60: 4104–4123, 2014
Do chronic myeloid leukemia patients with late “warning” responses benefit from “watch and wait” or switching therapy to a second generation tyrosine kinase inhibitor?
Authors: García‐Gutiérrez Valentin , Puerta Jose Manuel , Maestro Begoña , Casado Montero Luis Felipe , Muriel Alfonso , Molina Hurtado Jose Ramon , Perez‐Encinas Manuel , Moreno Romero Maria Victoria , Suñol Pere Barba , Sola Garcia Ricardo , De Paz Raquel , Ramirez Sanchez Maria Jose , Osorio Santiago , Mata Vazquez Maria Isabel , Martinez López Joaquin , Sastre Jose Luis , Portero Maria de los Angles , Bautista Guiomar , Duran Nieto Maria Soledad , Giraldo Pilar , Jimenez Jambrina Margarita , Burgaleta Carmen , Ruiz Aredondo Joaquin , Peñarrubia Maria Jesús , Requena Maria José , Fernández Valle María del Carmen , Calle Carmen , Paz Coll Antonio , Hernández‐Rivas Jose Ángel , Franco Osorio Rafael , Cano Pilar , Tallón Pérez David , Fernández de la Mata Margarita , Garrido Pilar López , Steegmann Juan Luis
Published: July 2014

In the latest recommendations for the management of chronic‐phase chronic myeloid leukemia suboptimal responses have been reclassified as “warning responses.” In contrast to previous recommendations current guidance advises close monitoring without changing therapy. We have identified 198 patients treated with first‐line imatinib, with a warning response after 12 months of treatment (patients with a complete cytogenetic response but no major molecular response [MMR]). One hundred and forty‐six patients remained on imatinib, while 52 patients changed treatment to a second generation tyrosine kinase inhibitor (2GTKI). Changing therapy did not correlate with an increase in overall survival or progression‐free survival. Nevertheless, a significant improvement was observed in the probability of a MMR: 24% vs. 42% by 12 months and 43% vs. 64% by 24 months (P = 0.002); as well as the probability of achieving a deep molecular responses (MR4.5): 1% vs. 17% and 7% vs. 23% by 12 and 24 months, respectively (P = <0.001) .The treatment change to 2GTKI remained safe; however, we have observed a 19% of treatment discontinuation due to side effects. We have observed an improvement of molecular responses after changing treatment to 2GTKI in patients with late suboptimal response treated with imatinib first line. However, these benefits were not correlated with an improvement of progression free survival or overall survival. Am. J. Hematol. 89:E206–E211, 2014. © 2014 Wiley Periodicals, Inc.
Risks of a lifetime in construction Part I: Traumatic injuries
Authors: Dong Xiuwen Sue , Ringen Knut , Welch Laura , Dement John
Published: July 2014

Background

Estimates of occupational risk are typically computed on an annual basis. In contrast, this article provides estimates of lifetime risks for fatal and nonfatal injuries among construction workers. A companion paper presents lifetime risks for occupational illnesses.

Methods

Using 2003–2007 data from three large data sources, lifetime risk was computed based on the number of fatal and nonfatal injuries per 100 FTEs for a working lifespan of 45 years.

Results

For a working life in construction, the risk of fatal injuries were approximately one death per 200 FTE, and the leading causes were falls and transportation incidents. For nonfatal injuries resulting in days away from work, the adjusted lifetime risk was approximately 78 per 100 FTEs, and the leading causes were contact with objects/equipment, overexertion, and falls to a lower level.

Conclusions

Lifetime risk estimates help inform both workers and policymakers. Despite improvements over the past decades, risks in construction remain high. Am. J. Ind. Med. 57:973–983, 2014. © 2014 Wiley Periodicals, Inc.
The function of loud calls (Hoot Series) in wild western gorillas (Gorilla gorilla)
Authors: Salmi Roberta , Doran‐Sheehy Diane M.
Published: July 2014

The use of loud vocal signals to reduce distance among separated social partners is well documented in many species; however, the underlying mechanisms by which the reduction of spacing occurs and how they differ across species remain unclear. Western gorillas (Gorilla gorilla) offer an opportunity to investigate these issues because their vocal repertoire includes a loud, long‐distance call (i.e., hoot series) that is potentially used in within‐group communication, whereas mountain gorillas use an identical call exclusively during intergroup encounters. First, we tested whether the hoot series functions as a contact/separation call. Second, we examined which individuals were more likely to reply and which party was more responsible for decreasing distance to identify the underlying mechanisms and cognitive implications of hoot series. We collected behavioral, spatial, and acoustic data on five adult gorillas over 15 months at the Mondika Research Center (Republic of Congo and CAR). Hoot series are individually distinct calls and given by both male and female gorillas when separated from each other. Following hooting, the distance between separated group members decreased significantly; thus we concluded that western gorillas use this call to reestablish group cohesion. The way in which proximity was achieved depended upon listeners replying or not to the caller. Replies may indicate a conflict between callers about intended travel direction, with vocal interchanges serving to negotiate a consensus. Although the acoustic features of vocal signals are highly constrained in closely related species, our results demonstrate that the function and usage of particular calls can be flexible. Am J Phys Anthropol 155:379–391, 2014. © 2014 Wiley Periodicals, Inc.
Catalytic Cleavage of Ether CO Bonds by Pincer Iridium Complexes
Authors: Haibach Michael C. , Lease Nicholas , Goldman Alan S.
Published: July 2014

The development of efficient catalytic methods to cleave the relatively unreactive CO bonds of ethers remains an important challenge in catalysis. Building on our group’s recent work, we report the dehydroaryloxylation of aryl alkyl ethers using pincer iridium catalysts. This method represents a rare fully atom‐economical method for ether CO bond cleavage.
Multiskalenmodellierung biologischer Funktionen: Von Enzymen zu molekularen Maschinen (Nobel‐Aufsatz)
Authors: Warshel Arieh
Published: July 2014

Ein detailliertes Verständnis der Wirkung biologischer Moleküle ist eine Voraussetzung für sinnvolle Fortschritte in der Medizin und verwandten Bereichen. Die Herausforderung besteht darin, aus vorhandenen Strukturinformationen zu einem klaren Verständnis der zugrundeliegenden Funktion des Systems zu gelangen. In Anbetracht der Komplexität von Makromolekülen sind Computersimulationen unentbehrlich, um den Zusammenhang zwischen den molekularen Kräfte und einer bestimmten Funktion zu beschreiben. Allerdings ist es praktisch unmöglich, eine vollständige und zuverlässige quantenmechanische Beschreibung großer molekularer Systeme zu verwenden.[1] Die Lösung für dieses Problem entstand aus der Erkenntnis heraus, dass große Systeme räumlich aufgeteilt werden können, und zwar in einen Teil, der quantenmechanisch beschrieben werden muss (z. B. ein Bereich, in dem Bindungen gebrochen werden), während der Rest des Systems auf einer einfacheren Ebene durch empirische Kraftfelder beschrieben wird. Diese Idee war besonders wirkungsvoll bei der Entwicklung von kombinierten Quantenmechanik/Molekülmechanik(QM/MM)‐Modellen.2 Hierbei zeigte sich, dass das Zusammenspiel zwischen den elektrostatischen Effekten der klassischen und Quantensysteme der Schlüssel für die Beschreibung der Funktionen von Enzymen und anderen Biomolekülen ist. Die Idee der Darstellung komplexer Systeme in unterschiedlichen Auflösungen sowohl auf der Zeit‐ als auch auf der Längenskala hat sich als sehr nützlich bei der Modellierung komplexer Systeme erwiesen. Ausgehend von grobkörnigen (coarse grained, CG) Darstellungen, die sich ursprünglich als sehr wirkungsvoll bei der Simulation der Proteinfaltung erwiesen haben – und die um die Beiträge elektrostatischer Energien erweitert wurden –, gelangte man zu Modellen, die besonders nützlich für die Erforschung der Wirkungsweise molekularer Maschinen sind. Dieser Ansatz der Verwendung mehrerer Skalen (“multiscale modeling”) wird wahrscheinlich eine wichtige Rolle bei der Modellierung noch komplexerer Systeme spielen, einschließlich Zellen und Zellenansammlungen.
Cobalt‐Catalyzed, Aminoquinoline‐Directed C(sp2)H Bond Alkenylation by Alkynes
Authors: Grigorjeva Liene , Daugulis Olafs
Published: July 2014

A method for cobalt‐catalyzed, aminoquinoline‐ and picolinamide‐directed C(sp2)H bond alkenylation by alkynes was developed. The method shows excellent functional‐group tolerance and both internal and terminal alkynes are competent substrates for the coupling. The reaction employs a Co(OAc)2⋅4 H2O catalyst, Mn(OAc)2 co‐catalyst, and oxygen (from air) as a terminal oxidant.
Nanoelectrode for Amperometric Monitoring of Individual Vesicular Exocytosis Inside Single Synapses
Authors: Li Yu‐Tao , Zhang Shu‐Hui , Wang Li , Xiao Rong‐Rong , Liu Wei , Zhang Xin‐Wei , Zhou Zhuan , Amatore Christian , Huang Wei‐Hua
Published: July 2014

Chemical neurotransmission occurs at chemical synapses and endocrine glands, but up to now there was no means for direct monitoring of neurotransmitter exocytosis fluxes and their precise kinetics from inside an individual synapse. The fabrication of a novel finite conical nanoelectrode is reported perfectly suited in size and electrochemical properties for probing amperometrically inside what appears to be single synapses and monitoring individual vesicular exocytotic events in real time. This allowed obtaining direct and important physiological evidences which may yield important and new insights into the nature of synaptic communications.
Towards a Safe Lithium–Sulfur Battery with a Flame‐Inhibiting Electrolyte and a Sulfur‐Based Composite Cathode
Authors: Wang Jiulin , Lin Fengjiao , Jia Hao , Yang Jun , Monroe Charles W. , NuLi Yanna
Published: July 2014

Of the various beyond‐lithium‐ion batteries, lithium–sulfur (Li‐S) batteries were recently reported as possibly being the closest to market. However, its theoretically high energy density makes it potentially hazardous under conditions of abuse. Therefore, addressing the safety issues of Li‐S cells is necessary before they can be used in practical applications. Here, we report a concept to build a safe and highly efficient Li‐S battery with a flame‐inhibiting electrolyte and a sulfur‐based composite cathode. The flame retardant not only makes the carbonates nonflammable but also dramatically enhances the electrochemical performance of the sulfur‐based composite cathode, without an apparent capacity decline over 750 cycles, and with a capacity greater than 800 mA h−1 g−1(sulfur) at a rate of 10 C.
Long‐term stress relaxation behavior of predrawn poly(ethylene terephthalate)
Authors: Hazelwood T. , Jefferson A. D. , Lark R. J. , Gardner D. R.
Published: July 2014

Research has been carried out with the aim of better understanding the relevant properties of materials to be used in a new self‐healing cementitious composite material system. In a previous study, the buildup of stress in a heat‐activated restrained predrawn poly(ethylene terephthalate) (PET) specimen was investigated. In the current study, the long‐term stress relaxation behavior of such a restrained specimen has been explored so that its potential for use in the new material system can be better understood. The work includes an experimental study in which the stress in a number of PET specimens, restrained against longitudinal shrinkage, was measured during the initial heat activation and cooling phases, and then monitored for a further 6 months. These data were used to quantify the stress relaxation of the specimen and to inform the development of a new one‐dimensional numerical model to simulate the thermomechanical behavior of this material. This model is shown to be able to reproduce the observed short‐ and long‐term experimental behavior with good accuracy. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41208.
Magnetic molecularly imprinted polymer nanoparticles coupled with high performance liquid chromatography for solid‐phase extraction of carvedilol in serum samples
Authors: Azodi‐Deilami Saman , Abdouss Majid , Asadi Ebadullah , Hassani Najafabadi Alireza , Sadeghi Sadegh , Farzaneh Sina , Asadi Somayeh
Published: July 2014

Herein, we report a magnetic molecularly imprinted polymers (m‐MIPs) using Fe3O4 as a magnetic component, carvedilol as a template molecule for the solid‐phase extraction (MISPE) as the sample clean‐up technique combined with high‐performance liquid chromatography (HPLC) and for the controlled release of carvedilol at different pH values of 1.0 (simulated gastric fluid), 6.8 (simulated intestinal fluid), and 7.4 (simulated biological fluid). The adsorption kinetics was modeled with the pseudo‐first‐order and pseudo‐second‐order kinetics, and the adsorption isotherms were fitted with Langmuir and Freundlich models. The performance of the m‐MIPs for the controlled release of carvedilol was assessed and results indicated that the magnetic MIPs also have potential applications in controlled drug release. Furthermore, the m‐MIPs were applied to the extraction of carvedilol from human blood plasma samples. Carvedilol can be quantified by this method in the 2–350 μg L−1 concentration range. The limit of detection and limit of quantification in plasma samples are 0.13 and 0.45 μg L−1. The results from HPLC showed good precision (3.5% for 50.0 μg L−1) and recoveries (between 85 and 93) using m‐MIP from human plasma samples. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41209.
Synthesis, helical conformation, and infrared emissivity property study of optically active substituted polyacetylenes derived from serine
Authors: Bu Xiaohai , Zhou Yuming , Zhang Tao , He Man , Wang Yongjuan
Published: July 2014

Serine‐based monosubstituted acetylene monomers were synthesized and polymerized with rhodium zwitterion catalyst in THF to afford optically active polyacetylene derivatives (LPA and DPA) and corresponding racemic polyacetylenes (RPA) with moderate molecular weights in good yields. All of the substituted polyacetylenes (SPA) were characterized by FT‐IR, NMR, GPC, UV‐Vis spectroscopy, circular dichroism (CD) spectroscopy, and TGA. LPA and DPA were soluble in common organic solvents and possessed single‐handed helical conformation according to their intense Cotton effect and large specific rotations, while RPA presented random coiled polymer chain. The characterization results showed that helical structure of these SPAs was stabilized by intra‐ and intermolecular hydrogen bonding between the substituents which played a significant role in creating and maintaining the helix. Further, the infrared emissivity properties of them at wavelength of 8 to 14 μm were investigated at room temperature. Consequently, the LPA and DPA exhibited lower infrared emissivity values than RPA, which came down to 0.632 and 0.616. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 41210.
Ultrasound‐Assisted Synthesis, Anticonvulsant Activity, and Docking Study of Indole‐Appended Thiazolidin‐4‐ones
Authors: Nikalje Anna Pratima G. , Shaikh Sameer I. , Mulay Abhineet , Khan Firoz A. K. , Sangshetti Jaiprakash N. , Shaikh Shoaib
Published: July 2014

Two series of novel indolyl thiazolidin‐4‐one derivatives 4a–j and 5a–j were obtained by an ecofriendly synthetic protocol by treating a mixture of Schiff's bases (0.01 mol) with thioglycolic acid or thiolactic acid (0.01 mol) and anhydrous zinc chloride in catalytic amount in DMF as solvent under ultrasound irradiation, using an ultrasound synthesizer with a synthetic solid probe. The structures of the synthesized compounds were confirmed by IR, 1H NMR, 13C NMR, MS, and elemental analysis. The anticonvulsant activity and neurotoxicity of the newly synthesized compounds were established by MES and sc‐PTZ model and by rotarod test, respectively, in vivo using mouse models. The actophotometer was used for the screening of behavioral activity. The compounds exhibited promising anticonvulsant activity; especially, the compounds showed maximum protection in the MES model at a dose of 100 mg/kg. Further, docking studies of the synthesized compounds were performed against the sodium channel receptor and showed good binding interactions with the receptor. A computational study was carried out to highlight the pharmacophore distance mapping, log p determination, and pharmacokinetic parameters.
Adaptive Dynamic Surface control of An electrohydraulic Actuator with Friction Compensation
Authors: Kheowree Tinnakon , Kuntanapreeda Suwat
Published: July 2014

In this paper, an adaptive nonlinear control scheme with a friction observer for position control of an electrohydraulic actuator is proposed. The observer based on the LuGre friction model is employed to compensate for the friction. Adaptation laws are used to handle parameter uncertainties in the actuator and friction model. The control law including dynamics of the observer is developed through a backstepping‐like dynamic surface control (DSC) technique. Experimental results have illustrated the success of the control scheme. The results also show that the adaptive DSC controller has better tracking performance than an adaptive backstepping and conventional PI controllers.
Almost Sure Exponential Stabilization of a Class of Uncertain Stochastic Systems with Markovian Switching
Authors: Zhu F. , Han Z.
Published: July 2014

This paper is concerned with the almost sure exponential stabilization of a class of uncertain stochastic systems with Markovian switching. A new criterion for testing the stability of such systems is established. The approach is based on stationary distribution theory. A sufficient condition is proposed for the design of robust state‐feedback controllers. An example illustrates the proposed techniques.
Learning rates and their impacts on the optimal capacities and production costs of biorefineries
Authors: Daugaard Tannon , Mutti Lucas A. , Wright Mark M. , Brown Robert C. , Componation Paul
Published: July 2014

Industry statistics indicate that technology‐learning rates can dramatically reduce both feedstock and biofuel production costs. Both the Brazilian sugarcane ethanol and the United States corn ethanol industries exhibit drastic historical cost reductions that can be attributed to learning factors. Thus, the purpose of this paper is to estimate the potential impact of industry learning rates on the emerging advanced biofuel industry in the United States. Results from this study indicate that increasing biorefinery capital and feedstock learning rates could significantly reduce the optimal size and production costs of biorefineries. This analysis compares predictions of learning‐based economies of scale, S‐Curve, and Stanford‐B models. The Stanford‐B model predicts biofuel cost reductions of 55 to 73% compared to base case estimates. For example, optimal costs for Fischer‐Tropsch diesel decrease from $4.42/gallon to $2.00/gallon. The optimal capacities range from small‐scale (grain ethanol and fast pyrolysis) producing 16 million gallons per year to large‐scale gasification facilities with 210 million gallons per year capacity. Sensitivity analysis shows that improving capital and feedstock delivery learning rates has a stronger impact on reducing costs than increasing industry experience suggesting that there is an economic incentive to invest in strategies that increase the learning rate for advanced biofuel production. © 2014 Society of Chemical Industry and John Wiley & Sons, Ltd
A new spectrofluorimetric method for the determination of some tetracyclines based on their interfering effect on resonance fluorescence energy transfer
Authors: Abolhasani Jafar , Farajzadeh Nazli
Published: July 2014

A rapid, simple, inexpensive and highly sensitive spectrofluorimetric method was developed for the determination of trace amounts of some tetracyclines (TCs), namely tetracycline hydrochloride (TCH), oxytetracycline hydrochloride (OTCH) and minocycline hydrochloride (MCH). Binding rhodamine B (RhB) to gold nanoparticles (Au NPs) resulted in quenching of the fluorescence of RhB by a resonance energy transfer (FRET) mechanism, with Au NPs as the energy acceptors. The presence of TCs caused the release of RhB molecules and recovered their fluorescence, and this was used as a basis for the quantitative determination of TCs. The reaction was monitored spectrofluorimetrically by measuring the increase in fluorescence of RhB at 572 nm starting 5 min after mixing the reagents in Tris buffer solution (pH 6.5). The effect of various experimental factors such as buffer type, pH, concentrations of the involved reagents and reaction time were studied to optimize the reaction conditions. Under optimum conditions, the calibration graphs were linear within the ranges 2.08 × 10−9–1.04 × 10−6 mol/L, 2.01 × 10−9–1.00 × 10−6 mol/L and 2.02 × 10−9–1.01 × 10−6 mol/L and detection limits (LODs) of 0.61 × 10−9, 0.32 × 10−9 and 0.66 × 10−9 mol/L were calculated for TCH, OTCH and MCH, respectively, with corresponding percent relative standard deviations (%RSDs) of 1.18, 1.21 and 1.54 (n = 5). The method was successfully applied to the determination of TCs in drinking water, human urine, bovine milk and breast milk samples. Copyright © 2014 John Wiley & Sons, Ltd.
Caution or Warning? A Validity Study of the MAYSI‐2 with Juvenile Offenders
Authors: McCoy Henrika , Vaughn Michael G. , Maynard Brandy R. , Salas‐Wright Christopher P.
Published: July 2014

Given the high prevalence of mental health and substance use disorders in the juvenile justice system and the emphasis on efficient screening and referrals, the current study sought to further validate the use of the Massachusetts Youth Screening Instrument version 2 (MAYSI‐2). Using data from institutionalized delinquents (N = 836) committed to the California Youth Authority, finite mixture modeling was employed to identify distinct latent classes based on MAYSI‐2 scale scores. Identified classes were then compared across a range of covariates, including prior offenses, official records of misconduct, and multiple measures of mental health and psychological well‐being. Findings revealed a three‐class, gradient‐based structure: low distress (n = 380), moderate distress (n = 327), and high distress (n = 129). Overall, the MAYSI‐2 identified juvenile offenders with mental health and substance use issues, but it did not differentiate youths with respect to offending patterns. Copyright © 2014 John Wiley & Sons, Ltd.
The SIMS Screen for Feigned Mental Disorders: the Development of Detection‐based Scales
Authors: Rogers Richard , Robinson Emily V. , Gillard Nathan D.
Published: July 2014

Time‐efficient screens for feigned mental disorders (FMDs) constitute important tools in forensic assessments. The Structured Inventory of Malingered Symptomatology (SIMS) is a 75‐item true–false questionnaire that has been extensively studied as an FMD screen. However, the SIMS scales are not based on established detection strategies, and only its total score is utilized as a feigning screen. This investigation develops two new feigning scales based on well‐established detection‐strategies: rare symptoms (RS) and symptom combinations (SC). They are studied in a between‐subjects simulation design using inpatients with partial‐malingering (i.e., patients with genuine disorders asked to feign greater disabilities) conditions. Subject to future cross‐validation, the SC scale evidenced the highest effect size (d = 2.01) and appeared the most effective at ruling out examinees, who have a high likelihood of genuine responding. Copyright © 2014 John Wiley & Sons, Ltd.
Drug‐eluting stents versus bare metal stents prior to noncardiac surgery
Authors: Bangalore Sripal , Silbaugh Treacy S. , Normand Sharon‐Lise T. , Lovett Ann F. , Welt Frederick G.P. , Resnic Frederic S.
Published: July 2014

Background

The safety of drug‐eluting stents (DES) vs. bare metal stents (BMS) in the perioperative setting, a heightened state of inflammation and thrombosis is not well defined.

Methods

All adults undergoing noncardiac surgical (NCS) procedures within 1 year following percutaneous coronary intervention (PCI) in Massachusetts between April 1, 2004, and September 30, 2007, were identified from an administrative claims database. Patients were divided into those who received BMS vs. DES at index PCI. Primary net clinical outcome was death, myocardial infarction (MI) or bleeding within 30 days of NCS. Primary clinical outcome was 30‐day death or MI.

Results

Among 8,415 (22% BMS) patients that satisfied our inclusion criteria, 1,838 BMS patients were matched with 3,565 DES patients with similar propensity scores. In the DES cohort, the 30‐day primary net clinical outcome rate was lower with longer time from PCI to NCS (P = 0.02) with lowest rates if NCS was performed after 90 days from PCI (event rate 8.57, 7.53, 5.21, and 5.75% for 1–30, 31–90, 91–180, and 181–365 days from PCI to NCS). However, in the BMS cohort, the event rate was uniformly high regardless of the time from PCI to NCS (P = 0.60) (event rate 8.20, 6.56, 8.05, and 8.82% for 1–30, 31–90, 91–180, and 181–365 days from PCI to NCS). There was no significant difference between DES and the BMS group for 30‐day primary net clinical outcome (6.64 vs. 7.89%; P = 0.10), but there was a 26% lower odds of primary clinical outcome (OR = 0.74, 95% CI 0.58–0.94) with DES when compared with BMS, driven mainly by differences in event rates when NCS was performed >90 days post PCI.

Conclusion

DES implantation was not associated with higher adverse events after NCS. Moreover, the incidence of adverse events following NCS was lower when NCS was performed >90 days post‐DES implantation suggesting that it may not be necessary to wait until 12 months post PCI with DES before NCS. © 2014 Wiley Periodicals, Inc.
Rapid Discovery of a Photocatalyst for Air Purification by High‐Throughput Screening
Authors: Sun Song , Zhang Fan , Qi Zeming , Ding Jianjun , Bao Jun , Gao Chen
Published: July 2014

Despite several decades of intensive studies, only a few commercial photocatalysts have been discovered by means of the conventional one‐at‐a‐time synthesis and characterization. Herein, a high‐throughput screening of photocatalysts for air purification using an infrared microscope, equipped with a set of homemade in situ gas reaction cells and a gas dosing system, is described. 1.0 % La3+/0.4 % Nd3+‐TiO2 was rapidly selected as an active photocatalyst for toluene degradation with a mineralization rate of 93.4 % at a humidity level of 70 % in 2 h. The excellent agreement between our combinatorial results and those of the bulk samples confirms the reliability of the developed rapid screening method. In addition, the investigation of the effects of pretreatment with NH3 and H2S on the photocatalytic activity also offers some information about the surface modification for air purification.
Crystallization Kinetics within a Generic Modeling Framework
Authors: Meisler Kresten T. , Solms Nicolas von , Gernaey Krist V. , Gani Rafiqul
Published: July 2014

A new and extended version of a generic modeling framework for analysis and design of crystallization operations is presented. The new features of this framework are described, with focus on development, implementation, identification, and analysis of crystallization kinetic models. Issues related to the modeling of various kinetic phenomena like nucleation, growth, agglomeration, and breakage are discussed in terms of model forms, model parameters, their availability and/or estimation, and their selection and application for specific crystallization operational scenarios under study. The advantages of employing a well‐structured model library for storage, use/reuse, and analysis of the kinetic models are highlighted. Examples illustrating the application of the modeling framework for kinetic model discrimination related to simulation of specific crystallization scenarios and for kinetic model parameter estimation are presented.
Effect of Co‐Grinding on Crystallinity of Clopidogrel Bisulfate
Authors: Mártha Csaba , Jójárt‐Laczkovich Orsolya , Szabó‐Révész Piroska
Published: July 2014

A high energy input during pharmaceutical formulation is capable of decreasing the crystallinity of compounds in the product. The presence of the amorphous form can cause serious problems at any stage of the formulation. Crystallinity changes of a model powder mixture containing clopidogrel bisulfate (CLP) and a colloidal silicon dioxide as additive were investigated during a long‐time co‐grinding process. The crystallinity of CLP was reduced sigmoidally by co‐grinding with longer co‐grinding time. X‐ray powder diffraction and differential scanning calorimetry examinations confirmed that the product had become totally amorphous after four hours of grinding. Thermogravimetric results proved that no major mass reduction happened and FT‐IR changes referred to formulation of a secondary bond between the components.
Determination of Pitzer Parameters for 1‐1 Nitrate and 1‐2 Sulfate Solutions from Freezing Point Data
Authors: Hasan Mehdi , Louhi‐Kultanen Marjatta
Published: July 2014

Freezing point depression (FDP) modeling was performed for selected aqueous nitrate and sulfate salt solutions to evaluate Pitzer ion interaction parameter values at 273.15 K. 1‐1 and 1‐2 electrolyte solutions of NaNO3, KNO3, NH4NO3, Na2SO4, K2SO4, and (NH4)2SO4 were studied. New Pitzer parameter values of β0, β1, and Cϕ were obtained for the studied electrolyte solutions. FDP modeling was also used to determine temperature derivatives of interaction parameters for the Pitzer model for selected salt solutions. Osmotic and activity coefficients using the new parameter values are also presented.
Porous MoO3 Film as a High‐Performance Anode Material for Lithium‐Ion Batteries
Authors: Yu Xiaoyou , Wang Li , Liu Junfeng , Sun Xiaoming
Published: July 2014

A porous MoO3 film is prepared by using a facile hydrothermal route and subsequent calcinations in air. The resulting material has a high capacity (750 mAh g−1 at 1 C), long cycle life (120 cycles with 80 % capacity retention), and high coulombic efficiency as the anode of a lithium‐ion battery.
Channelled Porous TiO2 Synthesized with a Water‐in‐Oil Microemulsion
Authors: Malgras Victor , Jood Priyanka , Sun Ziqi , Dou Shi Xue , Yamauchi Yusuke , Kim Jung Ho
Published: July 2014

Porous titanium dioxide synthesized with a bicontinuous surfactant template is a promising method that leads to a high active surface area electrode. The template used is based on a water/isooctane/dioctyl sodium sulfosuccinate salt together with lecithin. Several parameters were varied during the synthesis to understand and optimize channel formation mechanisms. The material is patterned in stacked conical channels, widening towards the centre of the grains. The active surface area increased by 116 % when the concentration of alkoxide precursors was decreased and increased by 241 % when the template formation temperature was decreased to 10 °C. Increasing the oil phase viscosity tends to widen the pore aperture, thus decreasing the overall active surface area. Changing the phase proportions alters the microemulsion integrity and disrupts channel formation.
Ruthenium‐Catalyzed Cycloadditions of 1‐Haloalkynes with Nitrile Oxides and Organic Azides: Synthesis of 4‐Haloisoxazoles and 5‐Halotriazoles
Authors: Oakdale James S. , Sit Rakesh K. , Fokin Valery V.
Published: July 2014

(Cyclopentadienyl)(cyclooctadiene) ruthenium(II) chloride [CpRuCl(cod)] catalyzes the reaction between nitrile oxides and electronically deficient 1‐choro‐, 1‐bromo‐, and 1‐iodoalkynes leading to 4‐haloisoxazoles. Organic azides are also suitable 1,3‐dipoles, resulting in 5‐halo‐1,2,3‐triazoles. These air‐tolerant reactions can be performed at room temperature with 1.25 equivalents of the respective 1,3‐dipole relative to the alkyne component. Reactive 1‐haloalkynes include propiolic amides, esters, ketones, and phosphonates. Post‐functionalization of the halogenated azole products can be accomplished by using palladium‐catalyzed cross‐coupling reactions and by manipulation of reactive amide groups. The lack of catalysis observed with [Cp*RuCl(cod)] (Cp*=pentamethylcyclopentadienyl) is attributed to steric demands of the Cp* (η5‐C5Me5) ligand in comparison to the parent Cp (η5‐C5H5). This hypothesis is supported by the poor reactivity of [(η5‐C5Me4CF3)RuCl(cod)], which serves as a an isosteric mimic of Cp* and as an isoelectronic analogue of Cp.
Synthesis, Structure, and Reactivity of Diazene Adducts: Isolation of iso‐Diazene Stabilized as a Borane Adduct
Authors: Reiß Fabian , Schulz Axel , Villinger Alexander
Published: July 2014

This work describes the synthesis and full characterization of a series of GaCl3 and B(C6F5)3 adducts of diazenes R1NNR2 (R1=R2=Me3Si, Ph; R1=Me3Si, R2=Ph). Trans‐PhNNPh forms a stable adduct with GaCl3, whereas no adduct, but instead a frustrated Lewis acid–base pair is formed with B(C6F5)3. The cis‐PhNNPh⋅B(C6F5)3 adduct could only be isolated when UV light was used, which triggers the isomerization from trans‐ to cis‐PhNNPh, which provides more space for the bulky borane. Treatment of trans‐PhNNSiMe3 with GaCl3 led to the expected trans‐PhNNSiMe3⋅GaCl3 adduct but the reaction with B(C6F5)3 triggered a 1,2‐Me3Si shift, which resulted in the formation of a highly labile iso‐diazene, Me3Si(Ph)NN; stabilized as a B(C6F5)3 adduct. Trans‐Me3SiNNSiMe3 forms a labile cis‐Me3SiNNSiMe3⋅B(C6F5)3 adduct, which isomerizes to give the transient iso‐diazene species (Me3Si)2NN⋅B(C6F5)3 upon heating. Both iso‐diazene species insert easily into one BC bond of B(C6F5)3 to afford hydrazinoboranes. All new compounds were fully characterized by means of X‐ray crystallography, vibrational spectroscopy, CHN analysis, and NMR spectroscopy. All compounds were further investigated by DFT and the bonding situation was assessed by natural bond orbital (NBO) analysis.
Regioselective Deiodination of Iodothyronamines, Endogenous Thyroid Hormone Derivatives, by Deiodinase Mimics
Authors: Mondal Santanu , Mugesh Govindasamy
Published: July 2014

Iodothyronine deiodinases (IDs) are mammalian selenoenzymes that play an important role in the activation and inactivation£ of thyroid hormones. It is known that iodothyronamines (TnAMs), produced by the decarboxylation of thyroid hormones, act as substrates for deiodinases. To understand whether decarboxylation alters the rate and/or regioselectivity of deiodination by using synthetic deiodinase mimics, we studied the deiodination of different iodothyronamines. The triiodo derivative 3,3′,5‐triiodothyronamine (T3 AM) is deiodinated at the inner ring by naphthyl‐based deiodinase mimics, which is similar to the deiodination of 3,3′,5‐triiodothyronine (T3). However, T3 AM undergoes much slower deiodination than T3. Detailed experimental and theoretical investigations suggest that T3 AM forms a weaker halogen bond with selenium donors than T3. Kinetic studies and single‐crystal X‐ray structures of T3 and T3 AM reveal that intermolecular I⋅⋅⋅I interactions may play an important role in deiodination. The formation of hydrogen‐ and halogen‐bonding assemblies, which leads to the formation of a dimeric species of T3 in solution, facilitates the interactions between the selenium and iodine atoms. In contrast, T3 AM, which does not have I⋅⋅⋅I interactions, undergoes much slower deiodination.
Oxidative Cyclization Reaction of 2‐Aryl‐Substituted Cinnamates To Form Phenanthrene Carboxylates by Using MoCl5
Authors: Wehming Kathrin , Schubert Moritz , Schnakenburg Gregor , Waldvogel Siegfried R.
Published: July 2014

The oxidative cyclization reaction of 2‐aryl cinnamates and derivatives thereof can be easily performed with MoCl5 as the oxidant. This powerful reagent allows oxidative coupling reactions for which other reagents fail. The best results are obtained when the 2‐phenyl substituent of the cinnamate is equipped with two methoxy groups. Even iodo moieties in the bay region of phenanthrene are tolerated under the reaction conditions. If naphthalene moieties are involved, a rearrangement of the skeleton occurs, providing an elegant route to highly functionalized angular arenes. The cyclization is demonstrated for 15 example substrates with isolated yields of up to 99 % for the phenanthrene derivative. The broad scope of the reaction underlines the usefulness of MoCl5 and MoCl5/TiCl4 in the oxidative coupling reaction.
One‐Pot Self‐Templating Synthesis of Pt Hollow Nanostructures and Their Catalytic Properties for CO Oxidation
Authors: Choi Bu‐Seo , Kim Sun Mi , Gong Jintaek , Lee Young Wook , Kang Shin Wook , Lee Hee‐Seung , Park Jeong Young , Han Sang Woo
Published: July 2014

Nanoporous Pt hollow nanostructures with octahedral and hexagonal frame‐like morphologies were prepared by a novel one‐pot self‐templating route with no assistance from a preformed template or shape‐directing agent. The hexagonal frame‐like Pt hollow structures exhibited significantly enhanced catalytic activity toward CO oxidation reaction compared to the octahedral Pt hollow nanostructures due to the higher oxidation state of Pt.
ChemInform Abstract: The Ce2Li0.39Ni1.61Si2 Structure as a New Derivative of the AlB2 Family.
Authors: Stetskiv Andrij , Rozdzynska‐Kielbik Beata , Pavlyuk Volodymyr
Published: July 2014

Ce2Li0.39Ni1.61Si2 is prepared by melting a stoichiometric mixture of the elements and subsequent annealing (Ta crucible, 1.
ChemInform Abstract: A Group‐Subgroup Relationship Between the New Nitride Tellurides of Terbium and Dysprosium with the Composition M4N2Te3.
Authors: Foltin Markus L. , Lissner Falk , Strobel Sabine , Schleid Thomas
Published: July 2014

Tb4N2Te3 (I) and Dy4N2Te3 (II) are prepared by reacting Tb or Dy with NaN3, Te, I2, and NaI as flux (evacuated silica tubes, 950 °C, 7 d).
ChemInform Abstract: Role of Acentric Displacements on the Crystal Structure and Second‐Harmonic Generating Properties of RbPbCO3F and CsPbCO3F.
Authors: Tran T. Thao , Halasyamani P. Shiv , Rondinelli James M.
Published: July 2014

Crystals of the title compounds are solvothermally synthesized by reaction of Pb(OAc)2 and RbF or CsF in a mixture of MeOH and CF3COOH (autoclave, 180 °C, 24 h, 60 and 70% yield for the Rb and Cs compound, resp.).
ChemInform Abstract: Intermetallic Compounds with Multiple Yttrium Sites — An 89Y Solid State NMR Spectroscopic Study.
Authors: Hoeting Christoph , Eckert Hellmut , Haarmann Frank , Poettgen Rainer
Published: July 2014

Y2RuB6 (I), Y2ReB6 (II), Y2RhSi3 (III), YRh2Si (IV), and YPdSi (V) are prepared by arc‐melting of the elements followed by annealing (evacuated silica tubes, 1300 K, 10 d).
ChemInform Abstract: The Photocathodic Properties of a Pb(Zr0.2Ti0.8)O3 Wrapped CaFe2O4 Layer on ITO Coated Quartz for Water Splitting.
Authors: Cheng Xiaorong , Chen Deliang , Dong Wen , Zheng Fengang , Fang Liang , Shen Mingrong
Published: July 2014

Pb(Zr0.2Ti0.8)O3 wrapped CaFe2O4 particles on indium‐tin oxide (ITO) coated quartz is tested as a photocathode for efficient water splitting.
ChemInform Abstract: A New Semiconducting Quaternary Mixed Halogenide: Pentathallium Dimercury Pentabromide Tetraiodide, Tl5Hg2Br5I4.
Authors: Pavlyuk Volodymyr , Dmytriv Grygoriy , Szyrej Malgorzata , Levkovets Sergii , Parasyuk Oleh
Published: July 2014

Tl5Hg2Br5I4 is prepared by fusion of TlBr and HgI2 in a 5:2 molar ratio (evacuated quartz ampoule, 770 K, 6 h, cooling rate of 10 K/h).
ChemInform Abstract: A Synthesis and Crystal Chemical Study of the Fast Ion Conductor Li7—3xGaxLa3Zr2O12 with x = 0.08 to 0.84.
Authors: Rettenwander Daniel , Geiger Charles A. , Tribus Martina , Tropper Peter , Amthauer Georg
Published: July 2014

The series of garnets Li7.08Ga0.06La2.93Zr2.02 O12, Li6.50Ga0.15La2.96Zr2.05 O12, Li6.48Ga0.23La2.93Zr2.04 O12, Li5.93Ga0.36La2.94Zr2.01 O12, Li5.38Ga0.53La2.96Zr2.00 O12, Li4.82Ga0.60La2.96Zr2.02 O12, and Li4.53Ga0.72La2.94Zr1.98 O12 is synthesized by solid state reaction of stoichiometric mixtures of Li2CO3, La2O3, ZrO2, and Ga2O3 (Pt crucible, 1050 °C, 17 h in air).
ChemInform Abstract: Tertiary Thiols from Allylic Thiocarbamates by Tandem Enantioselective [3,3]‐Sigmatropic Rearrangement and Stereospecific Arylation.
Authors: Mingat Gaelle , MacLellan Paul , Laars Marju , Clayden Jonathan
Published: July 2014

Enantiomerically enriched N‐aryl allylic thiocarbamates (II) are obtained via Pd‐catalyzed [3,3]‐sigmatropic rearrangement.
ChemInform Abstract: Copper Nanoparticles from Copper Aluminum Hydrotalcite: An Efficient Catalyst for Acceptor‐ and Oxidant‐Free Dehydrogenation of Amines and Alcohols.
Authors: Damodara Dandu , Arundhathi Racha , Likhar Pravin R.
Published: July 2014

Highly stable nanocopper on alumina is used as recyclable catalyst for the oxidant‐free dehydrogenation of a wide range of amines and alcohols to produce the corresponding dehydrogenation products in good to excellent yields.