bluuebunny/crossref_metadata_2025 huggingface dataset:
Training Teachers on Facilitative Interaction with Learners
Authors: Ромашина  , Romashina Svetlana
Published: March 2014

The paper concerns implications and substance of how

to develop teacher’s facilitative interaction skills, based on techniques,

designed for subject of education developing. Specifics of

education-oriented facilitation and the role of a teacher in the

process of interaction with learners are emphasized.
Learning to Use Students’ Scholarship Support Efficiently
Authors: Артемьева  , Artemyeva Svetlana , Шишов  , Shishov Cergey , Гринько  , Grinko V.
Published: March 2014

The paper discusses several aspects of constructing a

model of monitoring effectiveness of scholarship funds use in

institutions of higher education. The authors consider prospects

to train to-be members of Scholarship commissions in legal issues

to get them prepared to use scholarship provision mechanism as

a leverage for motivating students to improve the quality of learning.
Pedagogical Conditions for Developing Structural Components of Students’ Genealogical Culture
Authors: Извеков  , Izvekov Igor
Published: March 2014

The paper discussed how to optimize moral and spiritual

upbringing of competent to-be specialists in the student

environment. The potential of genealogy (family) as a means of

character education, yet-uninvolved by the educational system,

is considered. According to the author’s viewpoint, this potential

helps to nurture morality and spirituality through scientifically

grounded study of the family history in the context of National

History. The author also explores the teaching aid and educational

program named «A History of Family in the National

History: genealogy in the higher school educational process»

published by INFRA-M publishing house (2013).
A Serendipitous Field Test against the Cellar Fungus Coniophora olivacea
Authors: Morris Paul Ian , Dale Angela , Ingram Janet Kathleen
Published: March 2014

A weather-protected aboveground field test was established at Kincardine, Ontario, Canada, to assess the performance against termites of two formulations of carbon-based preservative in Pacific silver fir (Abies amabilis) and white spruce (Picea glauca). A naturally durable untreated reference species was also included. The boards were visually inspected for decay and termite attack after 6 years. Termite attack was negligible, but the test material was challenged by Coniophora olivacea, a soil-inhabiting, strand-forming, brown-rot fungus. While decay was well advanced in some untreated controls and western red cedar (Thuja plicata) reference samples, treated samples that had been similarly challenged remained in excellent condition.
Peer-Mentored Preparedness (PM-Prep): A New Disaster Preparedness Program for Adults Living Independently in the Community
Authors: Eisenman David Paul , Bazzano Alicia , Koniak-Griffin Deborah , Tseng Chi-hong , Lewis Mary-Ann , Lamb Kerry , Lehrer Danise
Published: March 2014

The authors studied a health promotion program called PM-Prep (Peer-Mentored Prep), which was designed to improve disaster preparedness among adults living independently in the community. PM-Prep consists of four 2-hour classes co-taught by a health educator and peer-mentors. Adults were randomly assigned to an experimental arm or a wait-list control arm. Earthquake safety knowledge and preparedness supplies were assessed prior to the intervention and at 1 month after the intervention (N  =  82). Adults in the experimental arm significantly increased preparedness by 19 percentage points, from 56% to 75% completed (p < .0001), and improved their knowledge by 8 percentage points, from 79% to 87% correct (p  =  .001). This is the first peer-mentored, targeted, and tailored disaster preparedness program tested with this population.
Lessons Learned From Our Elders: How to Study Polypharmacy in Populations With Intellectual and Developmental Disabilities
Authors: Stortz Jessica N. , Lake Johanna K. , Cobigo Virginie , Ouellette-Kuntz Hélène M. J. , Lunsky Yona
Published: March 2014

Polypharmacy is the concurrent use of multiple medications, including both psychotropic and non-psychotropic drugs. Although it may sometimes be clinically indicated, polypharmacy can have a number of negative consequences, including medication nonadherence, adverse drug reactions, and undesirable drug–drug interactions. The objective of this paper was to gain a better understanding of how to study polypharmacy among people with intellectual and developmental disabilities (IDD). To do this, we reviewed literature on polypharmacy among the elderly and people with IDD to inform future research approaches and methods on polypharmacy in people with IDD. Results identified significant variability in methods used to study polypharmacy, including definitions of polypharmacy, samples studied, analytic strategies, and variables included in the analyses. Four valuable methodological lessons to strengthen future polypharmacy research in individuals with IDD emerged. These included the use of consistent definitions of polypharmacy, the implementation of population-based sampling strategies, the development of clinical guidelines, and the importance of studying associated variables.
CURRENT WAYS TO HARVEST ENERGY USING A COMPUTER MOUSE
Authors: Horvat Frantisek , Cekan Michal , Soltes Lukas , Biath Peter , Hucko Branislav , Jedinak Igor
Published: March 2014

This paper deals with the idea of an energy harvesting (EH) system that uses the mechanical energy from finger presses on the buttons of a computer mouse by means of a piezomaterial (PVF2). The piezomaterial is placed in the mouse at the interface between the button and the body. This paper reviews the parameters of the PVF2 piezomaterial and tests their possible implementation into EH systems utilizing these types of mechanical interactions. The paper tests the viability of two EH concepts: a battery management system, and a semi-autonomous system. A statistical estimate of the button operations is performed for various computer activities, showing that an average of up to 3300 mouse clicks per hour was produced for gaming applications, representing a tip frequency of 0.91 Hz on the PVF2 member. This frequency is tested on the PVF2 system, and an assessment of the two EH systems is reviewed. The results show that fully autonomous systems are not suitable for capturing low-frequency mechanical interactions, due to the parameters of current piezomaterials, and the resulting very long startup phase. However, a hybrid EH system which uses available power to initiate the circuit and eliminate the startup phase may be explored for future studies.
DESIGN THEORY FOR THE PRESSING CHAMBER IN THE SOLID BIOFUEL PRODUCTION PROCESS
Authors: Kováčová Monika , Matúš Miloš , Križan Peter , Beniak Juraj
Published: March 2014

The quality of a high-grade solid biofuel depends on many factors, which can be divided into three main groups - material, technological and structural. The main focus of this paper is on observing the influence of structural parameters in the biomass densification process. The main goal is to model various options for the geometry of the pressing chamber and the influence of these structural parameters on the quality of the briquettes. We will provide a mathematical description of the whole physical process of densifying a particular material and extruding it through a cylindrical chamber and through a conical chamber. We have used basic mathematical models to represent the pressure process based on the geometry of the chamber. In this paper we try to find the optimized parameters for the geometry of the chamber in order to achieve high briquette quality with minimal energy input. All these mathematical models allow us to optimize the energy input of the process, to control the final quality of the briquettes and to reduce wear to the chamber. The practical results show that reducing the diameter and the length of the chamber, and the angle of the cone, has a strong influence on the compaction process and, consequently, on the quality of the briquettes. The geometric shape of the chamber also has significant influence on its wear. We will try to offer a more precise explanation of the connections between structural parameters, geometrical shapes and the pressing process. The theory described here can help us to understand the whole process and influence every structural parameter in it.
ANALYSIS OF PARAMETERS AFFECTING THE QUALITY OF A CUTTING MACHINE
Authors: Onderová Iveta , Šooš Lubomír
Published: March 2014

The quality of cutting machines is affected by several factors that can be directly or indirectly influenced by manufacturers, technicians and users of machine tools. The most critical qualitative evaluation parameters of machine tools include accuracy and stability. Investigations of accuracy and repeatable positioning accuracy were essential for the research presented in this paper. The aim was to develop and experimentally verify the design of a methodology for cutting centers aimed at achieving the desired working precision. Before working on the topic described here, it was necessary to make several scientific analyses, which are summarized in this paper. We can build on the initial working hypothesis that by improving the technological parameters (e.g. by increasing the working speed of the machine, or by improving the precision of the positioning) the quality of the cutting machine will also be improved. For the purposes of our study, several investigated parameters were set affecting positioning accuracy, such as rigidity, positioning speed, etc. First, the stiffness of the portal structure of the cutting machine was analyzed. FEM analysis was used to investigate several alternative structures of the cutting machine, and also an innovative solution for beam mounting. The second step was to integrate two types of drives into the design of the cutting machine. The first drive is a classic rack and pinion drive for cutting machines. To increase (improve) the working speed of the machine, linear motors were designed as an alternative drive. The portal of the cutting machine was designed for a working speed of 260mmin−1 and acceleration of 25 m. s−2. The third step was based on the results of the analysis. In collaboration with Microstep, an experimental cutting machine in a portal version was produced using linear synchronous motors driving the portal on both sides, and with direct linear metering of its position. In the fourth step, an experiment was designed and conducted to explore the positioning accuracy and the repeatable positioning accuracy.
NOx PREDICTION FOR FBC BOILERS USING EMPIRICAL MODELS
Authors: Štefanica Jiří , Hrdlička Jan
Published: March 2014

Reliable prediction of NOx emissions can provide useful information for boiler design and fuel selection. Recently used kinetic prediction models for FBC boilers are overly complex and require large computing capacity. Even so, there are many uncertainties in the case of FBC boilers. An empirical modeling approach for NOx prediction has been used exclusively for PCC boilers. No reference is available for modifying this method for FBC conditions. This paper presents possible advantages of empirical modeling based prediction of NOx emissions for FBC boilers, together with a discussion of its limitations. Empirical models are reviewed, and are applied to operation data from FBC boilers used for combusting Czech lignite coal or coal-biomass mixtures. Modifications to the model are proposed in accordance with theoretical knowledge and prediction accuracy.
SPECIFIC EMISSIONS FROM BIOMASS COMBUSTION
Authors: Skopec Pavel , Hrdlička Jan , Kaválek Michal
Published: March 2014

This paper deals with determining the specific emissions from the combustion of two kinds of biomass fuels in a small-scale boiler. The tested fuels were pellets made of wood and pellets made of rape plant straw. In order to evaluate the specific emissions, several combustion experiments were carried out using a commercial 25 kW pellet-fired boiler. The specific emissions of CO, SO2 and NOx were evaluated in relation to a unit of burned fuel, a unit of calorific value and a unit of produced heat. The specific emissions were compared with some data acquired from the reference literature, with relatively different results. The differences depend mainly on the procedure used for determining the values, and references provide no information about this. Although some of our experimental results may fit with one of the reference sources, they do not fit with the other. The reliability of the references is therefore disputable.
Os estudantes de engenharia e as suas intenções empreendedoras
Authors: Vieira Filipa Dionísio , Rodrigues Cristina Santos
Published: March 2014

No ambiente atual a promoção do empreendedorismo é uma oportunidade chave, e o ensino da engenharia tem reconhecido a sua relevância ao incluir nos seus currículos disciplinas básicas relacionadas com as áreas financeiras. Na situação econômica atual, fornecer ao futuro engenheiro conceitos e técnicas, que lhe permita passar do conhecimento para a ação, é indispensável para melhorar a compreensão do valor do empreendedorismo como uma alternativa de empregabilidade em detrimento de outras opções. O objetivo deste trabalho é o de apresentar os resultados preliminares da pesquisa ENGEmpreende desenvolvida para analisar as atitudes percebidas e os valores associados ao empreendedorismo por parte dos estudantes de engenharia. A amostra envolveu 387 estudantes dos cursos de engenharia da Universidade do Minho, em Portugal. Os estudantes de engenharia portugueses revelaram que têm uma boa opinião sobre o empreendedorismo. Este estudo também mostrou que a predisposição empreendedora dos estudantes inquiridos tem relações de dependência com o gênero, o conceito sobre empreendedorismo e o comportamento empreendedor. Os resultados sobre a imagem percebida do empresário sugerem que os estudantes reconhecem que o empreendedor tem uma imagem positiva na sociedade, mas têm dúvidas sobre o que é melhor: ser empresário ou ser um empregado numa grande empresa. Como barreiras, os estudantes de engenharia apresentam uma dificuldade em encontrar uma ideia de negócio ou  como obter acesso a capitais de investimento através de empréstimos bancários. As capacidades e competências percebidas dos estudantes sugerem uma elevada adaptabilidade, confiança, confiança técnica e orientação para os resultados. Pretende-se com os resultados obtidos, por meio do questionário ENGEmpreende, contribuir para o tema de intenções empreendedoras de estudantes de engenharia, a fim de identificar as atitudes empreendedoras, predisposição para o autoemprego, imagem empresarial, obstáculos que interferem ao espírito empresarial, conhecimento sobre os riscos e confiança técnica.
PRINCÍPIOS ÉTICOS EM VIGOTSKI: PERSPECTIVAS PARA A PSICOLOGIA E A EDUCAÇÃO
Authors: Delari Junior Achilles
Published: March 2014

Este texto explora criticamente princípios éticos pertinentes à psicologia de Vigotski, nem sempre explicitados por outros estudiosos, procurando esboçar suas consequências para a prática social do psicólogo e do educador, de modo reflexivo e não normativo. Na primeira seção, explicita-se que o valor fundamental para a perspectiva histórico-cultural é a própria humanidade. Contudo, não se trata de um humanismo ingênuo, nem liberal, mas crítico de raiz marxista. No interior deste “humanismo crítico”, detalham-se os conceitos de “superação”, “colaboração” e “emancipação”, como busca de salto para o “reino da liberdade”. Na segunda seção, são abordadas contradições enfrentadas por trabalhadores da psicologia e da educação que tentem pautar suas práticas em tais valores morais. Alia-se a necessidade de ver a realidade de modo crítico com a de entendê-la em sua historicidade, portanto, no caráter dinâmico e conflitivo das lutas que constituem a sociedade e nossos papéis dentro dela. Na terceira seção, coloca-se o “método construtivo” [konstruktivnii metod] como um elo entre os princípios antes discutidos e a prática social do psicólogo e do educador, na constituição da sua personalidade e a de seus interlocutores. Finalmente, como desafio e pedido de réplica, problematizam-se as possibilidades de superação da hipocrisia da ética burguesa, com base no princípio da organização coletiva classista radical.http://dx.doi.org/10.14572/nuances.v24i1.2153
EDUCAÇÃO E TRABALHO NA PERSPECTIVA DE EGRESSOS DO ENSINO MÉDIO E ESTUDANTES UNIVERSITÁRIOS
Authors: Bernardim Márcio Luiz
Published: March 2014

Este artigo discute a transição do Ensino Médio para o Ensino Superior, valendo-se de um conjunto de investigações realizadas com alunos do Ensino Médio, da Educação de Jovens e Adultos (EJA) e universitários, além de utilizar estatísticas oficiais sobre o ensino médio e o ensino superior no Brasil. Tomando o Ensino Médio como etapa da educação escolar básica que visa preparar para o trabalho e para o prosseguimento dos estudos, e o ensino superior como espaço possível de continuidade da formação de jovens e adultos trabalhadores, este artigo apresenta e analisa a importância atribuída pelos alunos à educação escolar. O tratamento estatístico dos microdados do vestibular de uma instituição pública paranaense proporcionou a apuração de indicadores do aproveitamento de cada um dos grupos de egressos do ensino médio nesse processo, de acordo com a natureza da escola frequentada (pública x privada) e da faixa etária dos candidatos. A pesquisa com universitários de último ano de curso permitiu detectar o tipo de escola frequentada no Ensino Médio, a importância atribuída ao curso escolhido e as perspectivas quanto ao futuro educacional e laboral. Ao final, a análise e discussão dos dados permitiu concluir que: a escola continua desempenhando um papel importante na vida dos jovens; a educação escolar representa um novo ânimo na vida dos adultos que ficaram historicamente marginalizados das oportunidades educacionais; embora os egressos da EJA manifestem interesse de ingressar na universidade, poucos são os que se inscrevem e, dentre os que o fazem, menos ainda os que obtêm êxito; que as chances de aprovação são maiores entre os que tentam ingresso logo ao término do Ensino Médio.http://dx.doi.org/10.14572/nuances.v24i1.2168
Ecstasy use and serotonin syndrome: a neglected danger to adolescents and young adults prescribed selective serotonin reuptake inhibitors
Authors: Dobry Yuriy , Rice Timothy , Sher Leo
Published: March 2014

Background: At present, there are scarce clinical and basic lab data concerning the risk of acute serotonin toxicity from selective serotonin reuptake inhibitors (SSRIs) and 3,4-methylenedioxymethamphetamine (MDMA, ecstasy) co-administration. The health care community can strongly benefit from efforts to address the high risks associated with serotonin syndrome from this specific drug combination.

Objective: The aim of this work is to review the risk of serotonin syndrome in adolescents and young adults prescribed with SSRIs and are concurrently using ecstasy.

Data sources: An electronic search of the major behavioral science bibliographic databases (Pubmed, PsycINFO, Medline) was conducted to retrieve peer-reviewed articles, which detail the clinical characteristics, biological mechanisms and social implications of SSRIs, MDMA, and their potential synergism in causing serotonin syndrome in the pediatric and young adult population. Search terms included “serotonin syndrome”, “ecstasy”, “MDMA”, “pediatric”, and “SSRI”. Additional references were incorporated from the bibliographies of these retrieved articles.

Results: MDMA, in combination with the widely-prescribed SSRI antidepressant class, can lead to rapid, synergistic rise of serotonin (5-HT) concentration in the central nervous system, leading to the acute medical emergency known as serotonin syndrome. This review addresses such complication through an exploration of the theoretical mechanisms and clinical manifestations of this life-threatening pharmacological interaction.

Conclusion: The increasing incidences of recreational ecstasy use and SSRI pharmacotherapy among multiple psychiatric disorders in the adolescent population have made this an overlooked yet increasingly relevant danger, which poses a threat to public health. This can be curbed through further research, as well as greater health care provision and attention from a regulatory body owing.
Dating violence and suicidal behavior in adolescents
Authors: Holmes Kristin , Sher Leo
Published: March 2014

The aim of this paper is to assess the possible consequences of adolescent physical, emotional and sexual dating violence through a review of the literature on the topic. An electronic search of major biomedical bibliographic databases (Pubmed, ISI, PsycINFO) was used to retrieve articles providing information on the prevalence rates, risk factors, associated consequences and possible preventive measures for adolescent dating violence across different populations. Currently, there have been few longitudinal studies conducted to identify potential risk factors for entering a violent dating relationship in adolescence. Risky behaviors such as early sexual intercourse may predispose someone for victimization. Dating violence itself is also a predictor of future dating violence. Adolescent dating violence was associated with an increase in other violence-related behaviors, substance use, depression, poorer educational outcomes, posttraumatic stress, unhealthy weight control and risky sexual behavior. The association between adolescent dating violence and an increase in suicidal behavior is a major public health concern. Future research should focus on longitudinal studies so that a causal relationship between dating violence and suicidality may be better understood.
Security analysis of Modified Rivest Scheme
Authors: Haridas Deepthi , Venkataraman Sarma , Varadan Geeta
Published: March 2014

The Modified Rivest Scheme (MRS) is an additive homomorphic
scheme recently used in many applications which demands third party processing of encrypted data. The present study carries out a comprehensive security analysis of MRS. We work out an attack from the category of known plaintext, chosen plaintext, chosen ciphertext where the adversary is having with him the pair of plaintext and its corresponding ciphertext. It is demonstrated that in such a scenario the adversary can compute the private key of the legitimate node causing threat to the security of the entire system. The novelty of the present study lies in the fact that any attack from the above mentioned category could be mounted on MRS (which is not being attacked so far), irrespective of the fact whether the modulus of the underlying MRS is kept private or made public.
Electrochromic and unique chiroptical properties of helically deformed tetraarylquinodimethanes generated from less-hindered dicationic precursors upon reduction
Authors: Suzuki Takanori , Sakano Yuto , Iwai Tomohiro , Iwashita Shinichi , Miura Youhei , Katoono Ryo , Kawai Hidetoshi , Fujiwara Kenshu , Tsuji Yasushi , Fukushima Takanori
Published: March 2014

Electron-donating 1,1,4,4-tetraarylbutadiene is a representative electrochromic dye, and the same chromophore can be found in 9,10-bis(diarylmethylene)-9,10-dihydrophenanthrene (dibenzo-oQD) albeit in a fixed s-cis geometry. Unlike thermodynamically unstable 7,7,8,8-tetraaryl-o-quinodimethane, spontaneous electrocyclization is prohibited by dibenzo-annulation. Several derivatives of dibenzo-oQD were successfully generated despite highly strained geometry caused by steric hindrance between the bulky diarylmethylene units. Their precursors are phenanthrene-9,10-diyl bis(diarylmethylium) dyes (PDM2+) stabilized by four electron-donating alkoxy groups. The redox pairs of dibenzo-oQD/PDM2+ exhibit vivid change in color upon redox interconversion (electrochromism). Both dibenzo-oQD and PDM2+ adopt a helical conformation, whose configuration is unstable. When a chiral alkoxy substituent is attached on each of the aryl groups, the point chirality is successfully transmitted to helicity of PDM2+. Resulting diastereomeric biasing is the key for dibenzo-oQD/PDM2+ to exhibit the two-way-output response (e.g., UV–vis and CD). In addition, much more strained quinodimethane derivatives, 1,2-bis(diarylmethylene)acenaphthene and 1,16-diaryldibenzo[b,n]perylene, were also generated from the dicationic precursors, demonstrating that the reductive transformation can serve as a useful protocol to generate severely deformed π-conjugated systems.
Synthesis, properties, and performance of nanostructured metal oxides for supercapacitors
Authors: Dubal Deepak P. , Holze Rudolf
Published: March 2014

Beyond activated carbon and other forms of high-surface area carbon operating solely as double layer storage materials in capacitors of high capacitance commonly somewhat imprecisely called supercapacitors other electrode materials storing electric charge by reversible and fast superficial redox processes are studied as active masses. The resulting devices combining double layer and Faradaic process-based charge storage – commonly called hybrid ones – show significantly higher capacitances at only marginally diminished power capability. Among the suggested materials metal oxides feature most prominently. Their formation, characterization and properties together with the performance of prepared devices are reviewed here.
Assessment of international reference materials for isotope-ratio analysis (IUPAC Technical Report)
Authors: Brand Willi A. , Coplen Tyler B. , Vogl Jochen , Rosner Martin , Prohaska Thomas
Published: March 2014

Since the early 1950s, the number of international measurement standards for anchoring stable isotope delta scales has mushroomed from 3 to more than 30, expanding to more than 25 chemical elements. With the development of new instrumentation, along with new and improved measurement procedures for studying naturally occurring isotopic abundance variations in natural and technical samples, the number of internationally distributed, secondary isotopic reference materials with a specified delta value has blossomed in the last six decades to more than 150 materials. More than half of these isotopic reference materials were produced for isotope-delta measurements of seven elements: H, Li, B, C, N, O, and S. The number of isotopic reference materials for other, heavier elements has grown considerably over the last decade. Nevertheless, even primary international measurement standards for isotope-delta measurements are still needed for some elements, including Mg, Fe, Te, Sb, Mo, and Ge. It is recommended that authors publish the delta values of internationally distributed, secondary isotopic reference materials that were used for anchoring their measurement results to the respective primary stable isotope scale.
Supramolecular control of electronic properties in aromatic materials
Authors: Chen Yan-Fang , Dubacheva Galina V. , Tseng Kuo-Pi , Raffy Guillaume , Guerzo André Del , Hirsch Lionel , Shyue Jing-Jong , Wong Ken-Tsung , Bassani Dario M.
Published: March 2014

The use of supramolecular interactions for controlling the electronic and photophysical properties of organic π-conjugated materials is described. This leads to materials presenting unique properties, such as light-induced switching of polarization (photopolism), or the spontaneous formation of highly luminescent vesicles. In another approach, reversible covalent bonds are used to prepare densely packed fullerene monolayers whose conductivity could be probed using conducting AFM.
Soybean hulls residue adsorbent for rapid removal of lead ions
Authors: Wei Xuling , Li Hui-Ru , Wang Li , He Yu-Feng , Wang Rong-Min
Published: March 2014

Soybean hulls residue (SHR) is a kind of typical biocompatible and edible natural polymer with containing cellulose, glycoprotein and lignin. In this paper, SHR is extracted by simple method and characterized by FTIR, XRD, SEM, elemental and XPS analysis. Then, this natural polymer adsorbent is applied to remove Pb(II), and main factors on Pb(II) removal by SHR are investigated in details, such as initial concentration of lead, pH value, SHR dosage, oscillating time and temperature. It shows that the removal rate of Pb(II) quickly increases more than 90% within the first 5 min, and the removal rate get to 99% within 20 min. The isotherm, kinetic models and thermodynamic parameters are applied to test the experimental data, respectively. It indicates that Pb(II) adsorption on SHR is an endothermic and spontaneous process. The adsorption mechanism has also been investigated. In summary, SHR exhibits excellent adsorption ability for removing Pb(II), which could be used as a fast edible antidote in emergency, especially in cases of mass poisoning by lead.
Metal-catalyzed synthesis of heterocycles bearing a trifluoromethyl group
Authors: Sodeoka Mikiko , Egami Hiromichi
Published: March 2014

The trifluoromethyl group has unique functional properties and is widely used not only in organic chemistry, but also in pharmaceutical and agrochemical science. Here we describe trifluoromethylation reactions of indoles and alkenes using Togni’s reagent. These reactions provide useful trifluoromethylated organic compounds, including heterocycles, with high efficiency.
Synthesis of tetraazatetracenes and -pentacenes: role of the substituents for their stability
Authors: Märken Michaela , Lindner Benjamin D. , Appleton Anthony L. , Rominger Frank , Bunz Uwe H.F.
Published: March 2014

We report the synthesis of a series of novel tetraazaacene derivatives and compare their stability with respect to size, oxidation potential and position of the TIPS-ethynyl groups. The latter has the most pronounced effects on the stability. In case of azatetracenes where TIPS-alkynes are either attached laterally or in theperi-positions, the former ones dimerized while the latter are stable. Attempts to expand this concept to the corresponding tetrakis-peri-substituted heptacenes led to the isolation of the dimerized butterfly product.
Synthetic and structural considerations on highly curved bowl-shaped fragments of fullerenes
Authors: Wu Yao-Ting , Wu Tsun-Cheng , Chen Min-Kuan , Hsin Hsin-Ju
Published: March 2014

Numerous highly curved fragments of C60 and unique subunits of C70 were synthesized under mild conditions using metal-catalyzed protocols. According to X-ray crystallographic analyses, highly curved fragments of C60 have a maximum π-orbital axis vector (POAV) pyramidalization angle of up to 12.9 °, whereas distinctive fragments of C70, analogous to the tube portion of the rugby-shaped buckyball, are less curved. Among the eight buckybowls studied herein, five form polar crystals. Depending on the molecular geometry, the inversion dynamics of buckybowls involves either a planar or an S-shaped (non-planar) transition structure.
Nanomaterials engineering and applications in catalysis
Authors: Zhang Qiao , Yin Yadong
Published: March 2014

Heterogeneous catalysis utilizing metal particles plays an essential role in the industrial applications. Design and fabrication of highly active catalysts in an efficient and cost-effective way is thus an important topic. The emergence of nanotechnology provides an excellent opportunity for developing new catalysts. In this critical review, we present our efforts and perspective on the recent advances in engineering nanomaterials for catalysis, including synthesis, stabilization, and catalytic applications of nanoparticles. We first briefly summarize the advanced colloidal synthesis of metal nanoparticles using Ag nanoplates as the model system, and then discuss the strategies for stabilization of metal nanoparticles using both chemical and physical approaches. And finally, for practical applications, we have designed and synthesized a highly efficient, stable, and cost-effective TiO2-based photocatalyst by combining both non-metal doping and noble metal decoration.
Emulsion-templated macroporous polymer/polymer composites with switchable stiffness
Authors: Jiang Qixiang , Menner Angelika , Bismarck Alexander
Published: March 2014

Emulsion templates containing monomers in both emulsion phases were used to manufacture polystyrene-co-divinylbenzene based polymerized high internal phase emulsions (polyHIPEs) which have been reinforced by poly(methacrylic acid) (polyMAA) and poly(dimethyl aminoethyl methacrylate) (polyDMAEMA). The morphology of the hydrogel-filled polyHIPEs is affected by the hydrogels synthesized in the aqueous emulsion phase. The pore structure of polyMAA-filled polyHIPEs is highly interconnected indicating the formation of a methacrylic acid-co-styrene copolymer at the oil/water interface of the emulsion templates during synthesis. However, polyDMAEMA-filled polyHIPEs are predominately closed celled and the pore walls are covered by grafted hydrogel. The ability of the hydrogel-filled polyHIPEs to absorb water decreased with increasing crosslinking density of the hydrogels. The dry hydrogel reinforced the polyHIPE scaffolds possessed higher elastic moduli and crush strengths than the control polyHIPEs. The reinforcing ability of the dry hydrogels was further enhanced by increasing their degree of crosslinking. However, the reinforcement could be “switched off” simply by hydrating the hydrogels. The switchable mechanical properties of the hydrogel-filled polyHIPEs could potentially be utilized in smart humidity sensor technology.
Reentrant condensation, liquid–liquid phase separation and crystallization in protein solutions induced by multivalent metal ions
Authors: Zhang Fajun , Roosen-Runge Felix , Sauter Andrea , Wolf Marcell , Jacobs Robert M. J. , Schreiber Frank
Published: March 2014

We briefly summarize the recent progress in tuning protein interactions as well as phase behavior in protein solutions using multivalent metal ions. We focus on the influence of control parameters and the mechanism of reentrant condensation, the metastable liquid–liquid phase separation and classical vs. non-classical pathways of protein crystallization.
Cobalt-catalyzed directed alkylation of arenes with primary and secondary alkyl halides
Authors: Yoshikai Naohiko , Gao Ke
Published: March 2014

A cobalt–N-heterocyclic carbene catalyst allows ortho-alkylation of aromatic imines with unactivated primary and secondary alkyl chlorides and bromides under room-temperature conditions. The scope of the reaction encompasses or complements that of cobalt-catalyzed ortho-alkylation reactions with olefins as alkylating agents that we developed previously. Stereochemical outcomes of secondary alkylation reactions suggest that the reaction involves single-electron transfer from a cobalt species to the alkyl halide to generate the corresponding alkyl radical. A cycloalkylated product obtained by this method can be transformed into unique spirocycles through manipulation of the directing group and the cycloalkyl groups.
Challenges to large molecular encapsulation
Authors: Fujita Daishi
Published: March 2014

One-to-one capture and confinement of a molecule within a finely designed synthetic scaffold is a highly topical field of research that aims to control the functions, properties, and stabilities of trapped molecules. In this account, a brief history of molecular encapsulation, for the design and synthesis of suitable molecular cages for large molecules, summarizes the daunting synthetic challenge associated with increasing molecular weight, and the attendant challenge to encapsulate macromolecules like proteins by synthetic hosts. Recent approaches toward the overall objective of large molecular encapsulation are discussed, and a personal account is given of the design and assembly of an advanced scaffolding system, which offers the promise of unprecedented progress toward this goal.
Thiolate-protected Au38(SR)24 nanocluster: size-focusing synthesis, structure determination, intrinsic chirality, and beyond
Authors: Qian Huifeng
Published: March 2014

Thiolate-protected Au nanoclusters with core diameters smaller than 2 nm have captured considerable attention in recent years due to their diverse applications ranging from biological labeling to photovoltaics and catalysis. This new class of nanomaterials exhibits discrete electronic structure and molecular-like properties, such as HOMO-LUMO electronic transition, intrinsic magnetism, chiroptical properties, and enhanced catalytic properties. This review focuses on the research into thiolate-protected Au38(SR)24 – one of the most representative nanoclusters, including its identification, size-focusing synthesis, structure determination, and intrinsic chirality. The properties of two size-adjacent Au nanoclusters [Au40(SR)24 and Au36(SR)24] are also discussed. The experimental and theoretical methodologies developed in studies of the Au38(SR)24 model nanocluster open up new opportunities in the synthesis and properties investigation of other atomically precise Au
n
(SR)
m
nanoclusters.
Hybrid material design for energy applications: impact of graphene and carbon nanotubes
Authors: Wang Hailiang
Published: March 2014

This article reviews the origin and progress of inorganic/nanocarbon hybrid material research in my Ph.D. career. Building chemical bonds between inorganic active materials and nanocarbon substrates is the key to controlled hybrid material synthesis that allows for controlling the size and morphology of the materials and enhancing electron transport within the electrodes. Our inorganic/nanocarbon hybrid materials manifest superior electrochemical performance for asymmetrical supercapacitors, ultrafast nickel-iron batteries, lithium ion batteries, lithium-sulfur batteries, and electrocatalysis of oxygen reduction and evolution reactions. X-ray absorption near edge structure (XANES) spectroscopy has been utilized to characterize the chemical bonding and charge transfer at the interface of inorganic nanocrystals and nanocarbon substrates. Probing the physical and chemical states of the hybrid materials under electrochemical reaction conditions is an important future direction in this area.
Enthalpies of solution, limiting solubilities, and partial molar heat capacities of n-alcohols in water and in trehalose crowded media
Authors: Bai Guangyue , Nunes Sandra C.C. , Rocha Marisa A.A. , Santos Luís M.N.B.F. , Eusébio M. Ermelinda S. , Moreno M. João , Bastos Margarida
Published: March 2014

The enthalpies of solution of alcohols were determined by calorimetry in HEPES and (HEPES + trehalose) at 298.15 K. The used methodology and experiment’s design allowed us to extract from a single titration experiment the enthalpy of solution (Δsol
H
m), the limiting solubility of the alcohol in each aqueous media, and an estimation of the enthalpy of solution of water in the alcohol phase. From these values the changes in Gibbs energy (Δsol
G
m) and in entropy (Δsol
S
m) of solution were derived. A decrease in solubility for 1-butanol and 1-pentanol in the crowded media (HEPES + trehalose) was observed which is driven by a significant decrease in the favorable enthalpy of solution. The partial molar heat capacity, in each media was determined in our heat capacity drop calorimeter, also at 298.15 K. A significant decrease of the partial molar heat capacity was observed for both alcohols in (HEPES + trehalose), which together with the obtained decrease in favorable Δsol
H
m, is consistent with a decrease in hydrophobic solvation, as a result of a decrease in free solvent availability induced by the trehalose. Finally, we tentatively predict that in the aqueous media of the crowded solutions that characterize cells and biological fluids, solutes with low aqueous solubility will be more soluble, whereas the solubility of highly polar solutes will be reduced.
Optimization of superamphiphobic layers based on candle soot
Authors: Paven Maxime , Papadopoulos Periklis , Mammen Lena , Deng Xu , Sachdev Hermann , Vollmer Doris , Butt Hans-Jürgen
Published: March 2014

Liquid repellent layers can be fabricated by coating a fractal-like layer of candle soot particles with a silicon oxide layer, combusting the soot at 600 °C and subsequently silanizing with perfluoroalkylsilanes. Drops of different liquids deposited on these so called “superamphiphobic” layers easily roll off thanks to the low liquid-solid adhesion. The lower value of the surface tension of liquids that can be repelled depends on details of the processing. Here, we analyze the influence of the soot deposition duration and height with respect to the flame on the structure and wetting properties of the superamphiphobic layer. The mean diameter of the soot particles depends on the distance from the wick. Close to the wick, the average diameter of the particles varies between 30 and 50 nm as demonstrated by scanning electron microscopy (SEM). Close to the top of the flame, the particles size decreases to 10–20 nm. By measuring the mass of superamphiphobic layers and their thickness by laser scanning confocal microscopy (LSCM) in reflection mode, we could determine that the average porosity is 0.91. The height-dependent structural differences affect the apparent contact and roll-off angles. Lowest contact angles are measured when soot is deposited close to the wick due to wax that is not completely burnt, smearing out the required overhanging structures. The small particle size close to the top of the flame also reduces contact angles, again due to decreasing size of overhangs. Sooting in the middle of the flame led to optimal liquid repellency. Furthermore, for sooting times longer than 45 s the properties of the layer did not change with sooting time, verifying the self-similarity of the layer.
Kinetic studies on cyclopalladation in palladium(II) complexes containing an indole moiety
Authors: Iwatsuki Satoshi , Suzuki Takuya , Tanooka Syogo , Yajima Tatsuo , Shimazaki Yuichi
Published: March 2014

Various Pd–C complexes have been developed to date, affording deep insights into the reaction intermediates in useful catalytic reactions in organic syntheses. Cyclopalladation is one of the most famous Pd–C bond formation reactions to generate the palladacycles. Indole is an electron-rich aromatic ring involved in the side chain of an essential amino acid, tryptophan (Trp), and Trp and its derivatives are important in biological systems, such as electron transfer in protein, cofactors for conversion of biological molecules and so on. Pd catalysts are also useful for syntheses of such indole derivatives, and the mechanisms are considered to be through the Pd–C intermediates. However, the detailed properties and formation mechanisms of Pd–indole species are still unclear. With these points in mind, we focus on Pd(II)–indole-C2 carbon bond formations using various Pd(II) complexes having an indole moiety, especially on the recent studies on the kinetic analyses for these cyclopalladation reactions and their detailed mechanisms.
Properties of the one-electron oxidized copper(II) salen-type complexes: relationship between electronic structures and reactivities
Authors: Shimazaki Yuichi
Published: March 2014

The Cu(II)-phenoxyl radical formed during the catalytic cycle of galactose oxidase (GO) attracted much attention, and the structures and properties of a number of metal-phenoxyl radical complexes have been studied. Some of the functional model systems of GO reported previously have shown that the Cu complexes oxidize primary alcohols to aldehydes and that the Cu(II)-phenoxyl radical species is formed in the catalytic cycle. Many Cu(II)-phenoxyl radical species have been produced by one-electron oxidation of the Cu(II)-phenolate complexes. On the other hand, one-electron oxidation of a Cu(II)-phenolate complex has the possibility to give different electronic structures, one of which is the Cu(III)-phenolate. From these points of view, this micro review is focused on the one-electron oxidized square-planar Cu(II) complexes of the salen-type ligands. Introduction of substituents into the phenolate moieties and conversion from a 5- to a 6-membered chelate backbone alter the electronic structure of the one-electron oxidized Cu(II) complexes and give rise to a different reactivity of benzyl alcohol oxidation. The relationship between the electronic structure and the reactivity is herein discussed.
Effective interaction between small unilamellar vesicles as probed by coarse-grained molecular dynamics simulations
Authors: Shinoda Wataru , Klein Michael L.
Published: March 2014

A series of molecular dynamics (MD) simulations has been undertaken to investigate the effective interaction between vesicles including PC (phosphatidylcholine) and PE (phosphatidylethanolamine) lipids using the Shinoda–DeVane–Klein coarse-grained force field. No signatures of fusion were detected during MD simulations employing two apposed unilamellar vesicles, each composed of 1512 lipid molecules. Association free energy of the two stable vesicles depends on the lipid composition. The two PC vesicles exhibit a purely repulsive interaction with each other, whereas two PE vesicles show a free energy gain at the contact. A mixed PC/PE (1:1) vesicle shows a higher flexibility having a lower energy barrier on the deformation, which is caused by lipid sorting within each leaflet of the membranes. With a preformed channel or stalk between proximal membranes, PE molecules contribute to stabilize the stalk. The results suggest that the lipid components forming the membrane with a negative spontaneous curvature contribute to stabilize the stalk between two vesicles in contact.
Definition of the transfer coefficient in electrochemistry (IUPAC Recommendations 2014)
Authors: Guidelli Rolando , Compton Richard G. , Feliu Juan M. , Gileadi Eliezer , Lipkowski Jacek , Schmickler Wolfgang , Trasatti Sergio
Published: March 2014

The transfer coefficient α is a quantity that is commonly employed in the kinetic investigation of electrode processes. An unambiguous definition of the transfer coefficient, independent of any mechanistic consideration and exclusively based on experimental data, is proposed. The cathodic transfer coefficient α
c is defined as –(RT/F)(dln|j
c|/dE), where j
c is the cathodic current density corrected for any changes in the reactant concentration on the electrode surface with respect to its bulk value, E is the applied electric potential, and R, T, and F have their usual significance. The anodic transfer coefficient α
a is defined similarly, by simply replacing j
c with the anodic current density and the minus sign with the plus sign. This recommendation aims at clarifying and improving the definition of the transfer coefficient reported in the 3rd edition of the IUPAC Green Book.
Solvation of a sponge-like geometry
Authors: Evans Myfanwy E. , Roth Roland
Published: March 2014

Periodic entanglements of filaments and networks, which resemble sponge-like materials, are often found as self-assembled materials. The interaction between the geometry of the assembly and a solvent in its interstices can dictate the geometric configuration of the structure as well as influence macroscopic properties such as swelling and mechanics. In this paper, we show the calculation of the solvation free energy as a function of the solute–solvent interaction from hydrophilic to hydrophobic, for a candidate entanglement of filaments. We do this using the morphometric approach to solvation free energy, a method that disentangles geometric properties from thermodynamic coefficients, which we compute via density functional theory.
Organometallic catalysis for applications in radical chemistry and asymmetric synthesis
Authors: Aubert Corinne , Barbazanges Marion , Jutand Anny , Kyne Sara H. , Ollivier Cyril , Fensterbank Louis
Published: March 2014

Two organometallic catalysis studies are presented. The first one deals with the development of a new catalytic agent based on the mixture of a hydride and an iron salt to trigger efficient radical cyclization processes. In a second line of research, we have shown that the use of chiral anions can outperform chiral ligands in a carbocyclization reaction and a [2 + 2 + 2] cycloaddition.
Activation of stable σ-bonds for organic synthesis
Authors: Hiyama Tamejiro
Published: March 2014

Since the conference on Organometallic Chemisrty Directed Towards Organic Synthesis (OMCOS) started in 1981, the author has been involved in the invention of novel synthetic reactions for C–C bond formation, taking advantage of organometallic reagents and catalysis. Herein is described a guideline story of how it is done.