bluuebunny/crossref_metadata_2025 huggingface dataset:
A scalable synthesis of the (S)-4-(tert-butyl)-2-(pyridin-2-yl)-4,5-dihydrooxazole ((S)-t-BuPyOx) ligand
Authors: Shimizu Hideki , Holder Jeffrey C , Stoltz Brian M
Published: August 2013

An efficient method for the synthesis of the (S)-4-(tert-butyl)-2-(pyridin-2-yl)-4,5-dihydrooxazole ((S)-t-BuPyOx) ligand has been developed. Inconsistent yields and tedious purification in known routes to (S)-t-BuPyOx suggested the need for an efficient, dependable, and scalable synthetic route. Furthermore, a route suitable for the synthesis of PyOx derivatives is desirable. Herein, we describe the development of a three-step route from inexpensive and commercially available picolinic acid. This short procedure is amenable to multi-gram scale synthesis and provides the target ligand in 64% overall yield.
Service expectations from high- and low-volume customers in the alcoholic beverage industry
Authors: Beukes Jacques , Prinsloo J.J. , Pelser Theuns G.
Published: August 2013

Orientation: South Africa has a highly competitive alcoholic beverage market. All role players in this market place a huge emphasis on service delivery and customer service.Research purpose: This research study investigated the relationship between the volume a customer buys from an alcoholic beverage supply company and what influence this volume has on their customer service expectations.Motivation for the study: The main purpose of this study was to evaluate what influence the volume an organisation buys from alcoholic beverage suppliers has on their service quality expectations.Research design, approach and method: A non-probability judgement sample method was used, with a sample size of 220 respondents. The questionnaire requested respondents (high- and low-volume) to rank their customer service expectations and opinions with reference to Parasuraman’s service delivery dimensions. Ranking was done using a five-point Likert scale.Main findings: The findings of the study indicated that both the high- and low-volume customers felt that alcoholic beverage supply companies had to deliver on all five service delivery dimensions but failed to do so to full satisfaction.Practical and managerial implications: It is recommended that the alcoholic beverage supply companies should address the problem areas identified in this study to avoid defection of customers.Contribution and value add: This may assist alcoholic beverage supply companies to better understand the customers’ demographic profiles. The study also revealed that the satisfaction level experienced by customers in both sections of the study (high- and low-demand), with a considerable gap between expectations and opinions within the empathy dimension.
Silicone injected cadaveric head for neurosurgical dissection: Prepared from defrosted cadaver
Authors: Limpastan Kriengsak , Vaniyapong Tanat , Watcharasaksilp Wanarak , Norasetthada Thunya
Published: August 2013

Objective: To study and report on an alternative method of preparation of head specimens for neurosurgical dissection using defrosted cadavers. Materials and Methods: Twenty-four head specimens were procured through the Department of Anatomy, received by donation three to seven days after funeral activity. The specimens were sectioned through the neck, and preserved by refrigeration at a temperature of -10°C for a period of one week to three months prior to preparation. The process began with defrosting the frozen head specimens for 48 hours in a refrigerator, in which the temperature was controlled within the range of -2° to -8°C. The great vessels were identified and cannulated. These were then irrigated with tap water until clear, following which colored silicone was injected. The specimens were preserved in 95% ethyl alcohol, and were assessed for quality one week after the preparation process. They were then re-assessed at monthly intervals for 12 months. Results: When compared with specimens prepared from fresh cadavers, our method provided similar quality specimens for dissection. The scalp and muscles of all specimens remained soft. The vasculature was good, and the colored silicone made identification easy. The brain tissues were soft and easily retracted, and still in good condition for dissection after a long preparation period (12 months). Conclusion: The head specimens prepared with this method were of good quality for dissection, and were comparable in quality to those prepared from fresh cadavers as in published methods. We were thus able to provide a suitable substitute to fresh head specimens in situations where access to fresh cadavers is unavailable.
Brain herniation induced by drainage of subdural hematoma in spontaneous intracranial hypotension
Authors: Chotai Silky , Kim Jong-Hyun , Kim Joo Han , Kwon Taek Hyun
Published: August 2013

Spontaneous intracranial hypotension (SIH), typically presents with orthostatic headache, low pressure on lumbar tapping, and diffuse pachymeningeal enhancement on magnetic resonance imaging. SIH is often accompanied by subdural fluid collections, which in most cases responds to conservative treatment or spinal epidural blood patch. Several authors advocate that large subdural hematoma with acute deterioration merits surgical drainage; however, few have reported complications following craniotomy. We describe a complicated case of SIH, which was initially diagnosed as acute subarachnoid hemorrhage with bilateral chronic subdural hematoma (SDH), due to unusual presentation. Burr hole drainage of subdural hematoma was performed due to progressive decrease of consciousness, which then resulted in a huge postoperative epidural hematoma collection. Prompt hematoma evacuation did not restore the patient's consciousness but aggravated downward brain herniation. Trendelenburg position and spinal epidural blood patch achieved a rapid improvement in patient's consciousness. This case indicates that the surgical drainage for chronic SDH in SIH can lead to serious complications and it should be cautiously considered.
Paranoid Ideation and Assessments of Trust
Authors: Kirk Hannah , Gilmour Andrea , Dudley Robert , Riby Deborah M
Published: August 2013

The ability to make accurate social judgements is crucial to effective functioning in society.

Individuals suffering from paranoia are suspicious and mistrustful of others and consequently may have difficulties accurately assessing information about others within their environment.

We investigated the effects of paranoid ideation on evaluations of trustworthiness from unfamiliar faces in a non-clinical sample. Measures of paranoid beliefs about others were used to assess 122 typically developing young adults. Individuals categorised with high paranoid ideation (n = 25) and low paranoid ideation (n = 23) subsequently rated unfamiliar faces that had previously been manipulated to look untrustworthy, of average trust, and trustworthy. Individuals high in paranoid ideation rated faces as significantly less trustworthy than those low in paranoid ideation. Both groups altered their ratings according to the trustworthiness of the face, but those high in paranoia rated all faces as less trustworthy. The findings suggest a bias in social judgements in individuals with high levels of paranoid ideation. They are able to judge faces for trustworthiness but have a bias towards a lower estimation of trust.
Affective Disturbance and Psychopathology: An Emotion Regulation Perspective
Authors: Jazaieri Hooria , Urry Heather L. , Gross James J.
Published: August 2013

It is widely thought that many psychological disorders involve emotion dysregulation. However, it is not yet clear just how many of the disorders presented in the Diagnostic and Statistical Manual of Mental Disorders-IV-Text Revision (DSM-IV-TR) are formally characterized by emotion regulation difficulties and related affective disturbances. To address this issue, we first define emotion, emotion regulation, emotion dysregulation, and affective disturbance. Next, we systematically code the psychological disorders listed in the DSM-IV-TR in terms of the presence or absence of affective disturbance and emotion dysregulation. We then use an emotion regulation perspective to examine affective disturbances in Axis II disorders, with a focus on borderline personality disorder (BPD). Finally, in the last section, we discuss some of the implications of our emotion regulation perspective for clinical assessment and intervention.
Aerosol hygroscopicity derived from size-segregated chemical composition and its parameterization in the North China Plain
Authors: Liu H. J. , Zhao C. S. , Nekat B. , Ma N. , Wiedensohler A. , van Pinxteren D. , Spindler G. , Müller K. , Herrmann H.
Published: August 2013

Abstract. Hygroscopic growth of aerosol particles is of significant importance in quantifying the aerosol radiative effect in the atmosphere. In this study, hygroscopic properties of ambient particles are investigated based on particle chemical composition at a suburban site in the North China Plain during the HaChi campaign (Haze in China) in summer 2009. The size-segregated aerosol particulate mass concentration as well as the particle components such as inorganic ions, organic carbon and water-soluble organic carbon (WSOC) is identified from aerosol particle samples collected with a 10-stage impactor. An iterative algorithm is developed to evaluate the hygroscopicity parameter κ from the measured particle chemical compositions. During the HaChi summer campaign, almost half of the mass concentration of particles between 150 nm and 1 μm is contributed by inorganic species. Organic matter (OM) is abundant in ultrafine particles, and 77% of the particulate mass with diameter (Dp) around 30 nm is composed of OM. A large fraction of coarse particle mass is undetermined and is assumed to be insoluble mineral dust and liquid water. The campaign average size distribution of κ values shows three distinct modes: the less hygroscopic mode (Dp < 150 nm) with κ slightly above 0.2, the highly hygroscopic mode (150 nm 1 μm) with κ about 0.1. The peak of the κ curve appears around 450 nm with a maximum value of 0.35. The derived κ values are consistent with results measured with a High Humidity Tandem Differential Mobility Analyzer within the size range of 50 nm to 250 nm. Inorganics are the predominant species contributing to particle hygroscopicity, especially for particles between 150 nm and 1 μm. For example, NH4NO3, H2SO4, NH4HSO4 and (NH4)2SO4 account for nearly 90% of κ for particles around 900 nm. For ultrafine particles, WSOC plays a critical role in particle hygroscopicity due to the predominant mass fraction of OM in ultrafine particles. 52% of κ is contributed by WSOC for particles around 30 nm. Aerosol particles are more hygroscopic during daytime, which can result from the diurnal evolution of planetary boundary layer, photochemical aging process during daytime and enhanced elemental carbon emission at night. κ is highly correlated with mass fractions of SO42−, NO3− and NH4+ for all sampled particles as well as with the mass fraction of WSOC for particles less than 100 nm. A parameterization scheme of κ is developed using mass fractions of SO42−, NO3−, NH4+ and WSOC due to their high correlations with κ, and κ calculated from parameterization agrees well with κ derived from the particle chemical composition. Further analysis shows that the parameterization scheme is applicable to other aerosol studies in China.
HE4 can Help Discriminate Women with Malignant Ovarian Tumors only if CA125 Levels are Elevated
Authors: Pitta Denise da Rocha , Sarian Luis Otávio , Aparecida Campos Elisabete , Andrade Liliana Lucci De Angelo , Sallum Luis Felipe , Bragança Joana Froes , Campos Camila de Mello , Derchain Sophie
Published: August 2013

Objective

To evaluate the performance of mesothelin, CA125, HE4 and ROMA index in the detection of malignant ovarian tumors.

Study Design

This is a cross-sectional study including 199 women with adnexal masses (67 with malignant tumors and 132 with benign tumors) and 150 healthy women (controls). We used a recursive multivariate partitioning algorithm to assess the contribution of each of the serum markers and the ROMA index to the discrimination of women with malignant tumors. Also, the areas under the ROC curves (AUC) for each of the serum markers and for the ROMA index were compared using the Venkatraman's projection-permutation test.

Results

In the recursive model, CA125 had the best performance in discriminating women with malignant tumors. In women with normal-range CA125 levels, none of the other markers contributed to the discrimination of women with malignant tumors. In women with elevated CA125 levels, elevated HE4 levels were associated with an increased risk of harboring a malignant tumor. The AUC for mesothelin was smaller than that for all the other curves, and both the ROMA index and CA125 had better AUC than HE4.

Conclusion

In women with normal CA125 levels, neither mesothelin nor HE4 contributed to discriminate women with malignant ovarian tumors; however, for women with elevated CA125 levels HE4 may help discriminating those who have a malignant ovarian tumor.
Chronic Wounds: The Persistent Infection Problem
Authors: Davis Nicola
Published: August 2013

Chronic wounds heal poorly and can have a huge impact on a sufferer’s life. They are caused by a number of factors, one of which is the presence of persistent infections. Many standard treatments are unsuccessful at destroying these infections as the bacteria form a biofilm. Biofilms encase the bacteria, preventing immune cells from destroying them. There are multiple bacterial species within a biofilm, sometimes with antibiotics resistance, and which species are present changes over time. The changing, multi-species nature of biofilms can make finding an effective antibiotic treatment difficult. Also, bacteria in biofilms genetically differ from planktonic bacteria, and are often less susceptible to antibiotics. Additionally, biofilms are thought to reduce the access of antibiotics to the bacteria within. These reasons are discussed in further detail in this review, along with some of the reasons why bacteria can prevent wound closure.
Evaluation of Geographic Origin of Torrontés Wines by Chemometrics
Authors: Azcarate Silvana Mariela , Cantarelli Miguel Angel , Marchevsky Eduardo Jorge , Camiña José Manuel
Published: August 2013

This work discusses the determination of the provenance of commercial Torrontés wines from different Argentinean provinces (Mendoza, San Juan, Salta and Rio Negro) by the use of UV-vis spectroscopy and chemometric techniques. In order to find classification models, wines (n = 80) were analyzed using UV-Vis region of the electromagnetic spectrum. Principal component analysis (PCA), linear discriminant analysis (LDA) and partial least squares discriminant analysis (PLS-DA) were used to classify Torrontés wines according to their geographical origin. Classification rates obtained were highly satisfactory. The PLS-DA and LDA calibration models showed that 100% of the Mendoza, San Juan, Salta and Rio Negro Torrontés wine samples had been correctly classified. These results demonstrate the potential use of UV spectroscopy with chemometric data analysis as a method to classify Torrontés wines according to their geographical origin, a procedure which requires low-cost equipment and short-time analysis in comparison with other techniques.
On the Potential Effect of Increased Dietary Intake of Fruits and Vegetables on Biomarkers of Lipid Peroxidation in Type Diabetes Patients
Authors: Pincemail  , N. Paquot  , J. Cillard  , I. Hininger  , L. Iuliano  , M. Cazaubiel  , F. Guéraud  , J.P. Chapelle  , C. Kevers  , C. Charlier  , A. Albert  , J.O. Defraigne
Published: August 2013

The present study was designed to test the hypothesis that an increased consumption of fruits and vegetables up to 600 g per day in type 2 diabetes patients can reduce oxidative damages to lipids. After a clinical examination, 29 type 2 diabetes patients were divided into two groups: the first one did not receive any special instructions about the diet while the second one received fruits and vegetables consumption advices thanks to a picture catalogue describing types of fruits and vegetables as well as quantities to be eaten every day. After two months of intervention, plasma concentrations in vitamin C, b-carotene and polyphenols remained unchanged in both groups when compared to baseline values. No significant decrease in lipid peroxidation as evidenced by nine biomarkers (malonaldehyde as TBAR’s, lipid peroxides, oxidized LDL, antibodies against oxidized LDL, isoprostanes, 7-keto-cholesterol, 7b-hydroxycholesterol, 4-hydroxynonenal metabolite, LDL size) was also noted. In conclusion, our findings confirmed the fact that the effect of high intake of fruits and vegetables on reducing oxidative damage to lipids remains largely controversial even in patients having an oxidative stress profile. Moreover, the present leaves open the question of the most appropriate markers of lipid peroxidation since only small correlations were evidenced between the large battery of tests investigated.
Review on Variants in Genes Associated with Cancer Risk and Red Meat Metabolism
Authors: Samsudin Nurulhafizah , Ramzi Nurul Hanis , Nagaretnam Revathi , Alex Livy
Published: August 2013

With the advent of human genome sequencing project, came the wave of personalized genomics. Scientists have now gone beyond scanning of individual genes and epigenetic variations that might alter an individual’s predisposition to developing complex diseases. Nutritional genomics is a science which is fast catching up. Efforts to explain the diet-gene interactions often recapitulate the effects of genetic makeup in determining the exact fate of the meal we ate last.
Diet-gene interactions play a major role in the metabolism and detoxification of food-derived mutagens and carcinogens. Heterocyclic amines (HCAs), polycyclic aromatic hydrocarbons (PAHs), and N-nitroso compounds (NOCs) are a class of mutagens or carcinogens found in red and processed meat that can lead to various types of cancers. Harboring unfavourable mutations or single nucleotide polymorphisms (SNPs) involved in metabolism of HCAs, PAHs, and NOCs can promote cancers. Increasing risks of several types of cancers, such as cancer of the colorectum, breast, prostate, esophagus, and lung, have been associated with high intake of red and processed meat. We attempt to compile some of the variants based on reports published during the past five years on variations involved in red meat metabolism which aims to provide useful insight in aiding us to regulate our red meat intake to avoid spurring of cancer.
Composition de la famille et risques d’éclatement des familles recomposées : effet réel ou artefact lié au mode de collecte des données ?
Authors: le Bourdais Céline , Lapierre-Adamcyk Évelyne , Heintz-Martin Valerie
Published: August 2013

Ce texte s’intéresse à l’influence que la composition des familles recomposées exerce sur les risques de rupture des couples à partir des informations fournies par les hommes et les femmes interrogés en 2001 dans le cadre de l’Enquête sociale générale (ESG) réalisée par Statistique Canada. Les résultats montrent d’abord une contradiction entre les risques de rupture des familles recomposées avec une belle-mère et avec un beau-père suivant que les réponses des hommes ou des femmes sont utilisées. Après une étude approfondie des données disponibles pour construire les épisodes de vie en famille recomposée, on trouve d’abord que la contradiction ne tient pas uniquement au sexe des répondants, mais également au rôle qu’ils jouent dans la famille recomposée, les risques de rupture étant nettement plus élevés lorsque les épisodes sont rapportés par les parents biologiques. Les auteures montrent que les résultats apparemment contradictoires sont en partie liés à la formulation de certaines questions dans l’ESG et aux difficultés inhérentes aux enquêtes rétrospectives.
Analyse spectromorphologique de La plénitude du vide de Jean-François Laporte
Authors: Palacio-Quintin Cléo
Published: August 2013

Jean-François Laporte est un compositeur inventif pour qui le son est une matière à découvrir et à explorer. Il s’intéresse particulièrement à l’évolution timbrale des sons dans le temps et dans l’espace. Ses démarches de recherche et d’expérimentation sur la matière sonore l’ont mené vers l’invention de nouveaux instruments. La plénitude du vide (2005), commande du quatuor de saxophones Quasar, est composée pour saxophones, orgue à sirènes, trompes-sax, saxophones volants, totem-tu-yos, sub-totems et totems-pompiers. L’oeuvre d’environ 60 minutes présente des textures sonores qui évoluent très lentement et permettent ainsi à l’auditeur de se retrouver dans un état d’écoute contemplative. Une méthode analytique liée à la musique électroacoustique s’est imposée, soit celle de la spectromorphologie, élaborée par Denis Smalley, qui permet de bien définir les mouvements de texture et l’occupation de l’espace spectral. L’analyse de l’oeuvre est réalisée à l’aide de la partition graphique manuscrite du compositeur, de l’enregistrement de la création et d’un sonagramme.
Le choix d’une vie sans enfant à travers le prisme des normes parentales et conjugales
Authors: Debest Charlotte
Published: August 2013

Avec la généralisation de la contraception (principalement féminine) durant la seconde moitié du xxe siècle dans la majorité des pays occidentaux et les avancées scientifiques en matière de procréation médicalement assistée, le concept de famille s’élargit et la dissociation entre conjugalité et parentalité est posée comme une évidence. Or, nous nous interrogerons, dans cet article, au travers d’entretiens sociologiques effectués avec des personnes volontairement sans enfant, sur l’évidence de cette dissociation/conciliation entre vie conjugale et vie parentale. En effet, les personnes volontairement sans enfant mettent en lumière les contradictions entre les conditions normatives du « métier » de parent et celles du « métier » de partenaire amoureux et sexuel.
De la transmission à la construction des savoirs et des pratiques dans les relations
intergénérationnelles de femmes réfugiées au Québec
Authors: Vatz Laaroussi Michèle , Guilbert Lucille , Rachédi Lilyane , Kanouté Fasal , Ansòn Laura , Canales Tania , León Correal Amelia , Presseau Ariane , Thiaw Marie Louise , Zivanovic Sarenac Javorka
Published: August 2013

Parler de familles immigrantes en intervention sociale, c’est souvent parler des
problèmes intergénérationnels et des difficultés d’intégration. À partir d’une recherche
menée auprès de trios de femmes réfugiées au Québec (des grands-mères, des mères et des
filles), ce texte s’intéresse aux processus originaux de circulation des savoirs et de
construction de nouvelles pratiques entre ces générations de femmes. Leurs rapports à
l’autonomie, mais aussi à la famille, au travail, à la santé ou à la collectivité se
transforment et se modulent différemment selon les générations et les événements de leur
trajectoire. Ces échanges intergénérationnels sont importants pour l’insertion des divers
membres des familles immigrantes et il est nécessaire que les intervenants en aient une
compréhension renouvelée.
Video capture on student-owned mobile devices to facilitate psychomotor skills acquisition: A feasibility study
Authors: Hinck Glori , Bergmann Thomas F.
Published: August 2013

Objective

We evaluated the feasibility of using mobile device technology to allow students to record their own psychomotor skills so that these recordings can be used for self-reflection and formative evaluation.

Methods

Students were given the choice of using DVD recorders, zip drive video capture equipment, or their personal mobile phone, device, or digital camera to record specific psychomotor skills. During the last week of the term, they were asked to complete a 9-question survey regarding their recording experience, including details of mobile phone ownership, technology preferences, technical difficulties, and satisfaction with the recording experience and video critique process.

Results

Of those completing the survey, 83% currently owned a mobile phone with video capability. Of the mobile phone owners 62% reported having email capability on their phone and that they could transfer their video recording successfully to their computer, making it available for upload to the learning management system. Viewing the video recording of the psychomotor skill was valuable to 88% of respondents.

Conclusions

Our results suggest that mobile phones are a viable technology to use for the video capture and critique of psychomotor skills, as most students own this technology and their satisfaction with this method is high.
Highly Robust Lithium Ion Battery Anodes from Lignin: An Abundant, Renewable, and Low‐Cost Material
Authors: Tenhaeff Wyatt E. , Rios Orlando , More Karren , McGuire Michael A.
Published: August 2013

The synthesis, processing, and performance of a low‐cost monolithic battery electrode, produced entirely of natural and renewable resources, are reported. This anode material exhibits tunable electrochemical performance suitable for both high power and high energy applications. A synthesis method that directly results in electrically interconnected three‐dimensional architectures is presented, where the carbon framework functions as current collector and lithium insertion material, eliminating the extra mass and expense of inactive materials in conventional designs. Fibrous carbon electrode materials are produced from solvent extracted lignin using scalable melt processing technology and thermal conversion methods. The resulting free‐standing electrodes exhibit comparable electrochemical performance to commercial carbon‐based anodes at a fraction of the materials and processing costs. Compositional and electrochemical characterization shows that carbonized lignin has a disordered nano‐crystalline microstructure. The carbonized mats cycle reversibly in conventional aprotic organic electrolytes with Coulombic efficiencies over 99.9%. Moreover, lignin carbon fibers carbonized at 2000 °C can cycle reversibly in 1 m LiPF6 in propylene carbonate.
Self‐Assembly of Multiple Stacked Nanorings by Vertically Correlated Droplet Epitaxy
Authors: Wu Jiang , Hirono Yusuke , Li Xinlei , Wang Zhiming M. , Lee Jihoon , Benamara Mourad , Luo Siyuan , Mazur Yuriy I. , Kim Eun Soo , Salamo Gregory J.
Published: August 2013

Fabrication of advanced artificial nanomaterials is a long‐term pursuit to fulfill the promises of nanomaterials. In the last ten years, Droplet Epitaxy has been emerging as a versatile fabrication method for various complex nanomaterials, but there is a lack of growth protocol to control the growth vertically. Here we report a vertically correlated Droplet Epitaxy growth method. We find that the nanodroplets form preferable on the preexisting nanorings, which enables fabrication of vertically aligned nanostructures by Droplet Epitaxy. Nucleation thermodynamics and growth kinetics have been proposed to explain the vertically correlated Droplet Epitaxy. Heterojunctions can be realized at nanoscale by the presented method. In addition, the nucleation thermodynamics of nanodroplets observed in this article will allow site‐controlled fabrication of nanostructures.
ortho‐(Dimesitylboryl)phenylphosphines: Positive Boryl Effect in the Palladium‐Catalyzed Suzuki–Miyaura Coupling of 2‐Chloropyridines
Authors: Malacea Raluca , Chahdoura Faouzi , Devillard Marc , Saffon Nathalie , Gómez Montserrat , Bourissou Didier
Published: August 2013

Catalytic systems combining ortho‐(dimesitylboryl)phenylphosphines and palladium precursors have been evaluated in the Suzuki–Miyaura couplings of chloro‐N‐heterocycles, in particular 2‐chloropyridines, with arylboronic acids. The Lewis basic character of the substrates does not interfere with the Lewis acidic site of the ligands, even for a substrate featuring free NH2 groups. The influence of several reaction parameters has been studied and the ortho‐dimesitylboryl moiety was actually found to substantially enhance the catalytic performance. The role of this group has been examined using preformed phosphine‐borane/Pd complexes and the formation of an original phosphine/η4‐boratabutadiene complex has been identified as a possible deactivation pathway. Regioselective coupling of 2,6‐dichloro‐3‐nitropyridine with phosphine‐borane/Pd catalysts has also been explored, and sequential double cross‐couplings were found to give a direct and efficient access to unsymmetrical 2,6‐diarylpyridines.

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Development of a Continuously Operating Process for the Enantioselective Synthesis of a β‐Amino Acid Ester via a Solvent‐Free Chemoenzymatic Reaction Sequence
Authors: Strompen Simon , Weiß Markus , Gröger Harald , Hilterhaus Lutz , Liese Andreas
Published: August 2013

A sequential, chemoenzymatic process for a continuously operating production of the chiral β‐amino acid ester ethyl (S)‐3‐(benzylamino)butanoate was developed. The reactor set‐up combined a plug‐flow reactor for the thermal aza‐Michael addition of benzylamine to trans‐ethyl crotonate coupled to a subsequent packed‐bed reactor for the lipase (Novozym 435)‐catalyzed kinetic resolution of the racemic intermediate product, which was formed in the initial step. The coupled reactors were operated continuously for a time period of 4 days without significant loss of enzyme activity. The target β‐amino acid ester was obtained with 92% conversion in the plug‐flow reactor and 59% conversion in the packed bed reactor at high enantiomeric excess of >98%. A space‐time yield of 0.4 kg L−1 d−1 was calculated for the total reactor system and 1.8 kg L−1 d−1 based solely on the volume of the packed bed reactor. A total turnover number of 158,000 was calculated for the biocatalyst assuming the same deactivation rate as observed in batch experiments. The continuously operating, solvent‐free process thus represents an efficient method for the enantioselective production of a value added (S)‐β‐amino acid ester starting from cheap substrates.

Abbreviations: CALB=Candida antarctica lipase B; CSTR=continuously stirred tank reactor; di=inner diameter [mm]; ee=enantiomeric excess; ε=porosity; kcat,obs=apparent turnover number [h−1]; kdeact=enzyme deactivation constant [h−1]; L=length of reactor [m]; m̄p=average mass of a single particle [g]; N435=Novozym 435 (Candida antarctica lipase B immobilized on acrylic resin); PBR=packed‐bed reactor; PFR=plug‐flow reactor; PTFE=polytetrafluoroethylene; ρbp=bulk particle density [kg m−3]; ρp=density of carrier material [kg m−3]; Q=productivity [kg ${{\rm kg}{{- 1\hfill \atop {\rm N435}\hfill}}}$ d−1]; R=channel radius of curvature [cm]; ttn=total turnover number [mol mol−1]; T=temperature [°C]; τ=residence time [h]; uf=fluid velocity [cm min−1]; $\dot \nu $=volumetric flow rate [mL min−1]; νι=flow rate of substance [mmol min−1]; V=volume [mL]; χi=mole fraction of compound i; Xi=conversion of compound i; STY=space‐time yield [kg L−1 d−1].

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Potassium (E)‐Alkenylaryltrifluoroborates: Orthogonal Functionalization of Haloaryltrifluoroborates via Heck–Mizoroki Reaction
Authors: Song Jung Ho , Kim Taejung , Lee Jae Wook , Moon Soo‐Yeon , Kim Won‐Suk , Ham Jungyeob
Published: August 2013

A series of di‐ or trisubstituted alkene‐containing potassium organotrifluoroborates was prepared from the corresponding haloaryltrifluoroborates via palladium‐catalyzed Heck–Mizoroki reaction with various olefins in good to excellent yields. Furthermore, the Suzuki–Miyaura cross‐coupling reaction of these alkenylaryltrifluoroborates was successfully carried out with aryl and alkenyl bromides using 5 mol% of tetrakis(triphenylphosphine)palladium(0) and 3.0 equiv. of cesium carbonate in aqueous 1,4‐dioxane under microwave irradiation.

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Generation of a Low‐Valent Titanium Species from Titanatrane and its Catalytic Reactions: Radical Ring Opening of Oxetanes
Authors: Takekoshi Naoto , Miyashita Kenji , Shoji Noriaki , Okamoto Sentaro
Published: August 2013

Treatment of a titanatrane complex with trimethylsilyl chloride and magnesium powder in tetrahydrofuran generated a low‐valent titanium species. This species catalyzed the radical ring opening of epoxides and oxetanes to produce the corresponding less substituted alcohols. The reagent also catalyzed the deallylation and depropargylation of allylic and propargylic ethers, respectively, to provide the parent alcohols.

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Atropodiastereoselective CH Olefination of Biphenyl p‐Tolyl Sulfoxides with Acrylates
Authors: Wesch Thomas , Leroux Frédéric R. , Colobert Françoise
Published: August 2013

A stereoselective method for the synthesis of axially chiral biaryl scaffolds by CH bond functionalization was accomplished using chiral sulfoxide both as the directing group enabling the regioselective activation of a CH bond and as the chiral auxiliary generating an asymmetric environment in the coordination sphere of the metal complex. We have demonstrated the directing ability of the p‐tolylsulfinyl group in promoting the Pd(II)‐catalyzed CH olefination of biphenyls.

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The lymphocyte to monocyte ratio improves the IPI‐risk definition of diffuse large B‐cell lymphoma when rituximab is added to chemotherapy
Authors: Rambaldi Alessandro , Boschini Cristina , Gritti Giuseppe , Delaini Federica , Oldani Elena , Rossi Andrea , Barbui Anna Maria , Caracciolo Daniele , Ladetto Marco , Gueli Angela , De Crescenzo Alberto , Passera Roberto , Devizzi Liliana , Patti Caterina , Gianni Alessandro Massimo , Tarella Corrado
Published: August 2013

The peripheral blood lymphocyte to monocyte ratio (LMR) at diagnosis can be clinically relevant in patients with diffuse large B‐cell lymphoma (DLBCL). We reviewed the outcome of 1,057 DLBCL patients followed from 1984 to 2012 at four centers. LMR was analyzed as a clinical biomarker by receiver‐operating characteristic (ROC) analysis and Harrell's C‐statistics. Patients were characterized by a median age of 61 years, International Prognostic Index (IPI) score of >2 in 39%, and were treated with a rituximab‐containing chemotherapy in 66%. LMR proved strongly predictive for survival in patients treated with rituximab‐based programs, but not in those receiving chemotherapy alone. Additionally, an LMR value of ≤2.6 (as determined by ROC analysis) was associated with a worst performance status, a higher lactate dehydrogenase (LDH) level, an advanced clinical stage, and a higher IPI score (P = 0.000). In patients treated with rituximab‐supplemented chemotherapy programs, an LMR value of <2.6 was found in most of the primary refractory patients (75%) which proved as the best cutoff to predict both response and survival (P = 0.018). Finally, multivariate analysis and Harrell's C‐statistics confirmed the IPI‐independent role of LMR on survival (P = 0.0000). In conclusion, LMR is a potent predictor of clinical response and survival in DLBCL treated with rituximab‐containing chemotherapy. Am. J. Hematol. 88:1062–1067, 2013. © 2013 Wiley Periodicals, Inc.
Effects of maya ancestry and environmental variables on knee height and body proportionality in growing individuals in merida, yucatan
Authors: Vázquez‐Vázquez Adriana , Azcorra Hugo , Falfán Ina , Argáeź Jorge , Kantun Diódora , Dickinson Federico
Published: August 2013

Objective

Identify the biological, social, and economic conditions influencing the knee height/stature index (KHSI) in growing individuals of Maya ancestry in the city of Merida, Yucatan, Mexico.

Methods

The hypothesis was that KHSI values would be lower in subjects with two Maya surnames. This was tested by analyzing the effect of a series of environmental, biological, and socioeconomic variables on stature and knee height (KH). Data were collected from 2008 to 2009 from 841 individuals (444 girls), 9 to 17 years of age, in Merida, Yucatan, Mexico. Ancestry was used as a proxy for genetics, and based on number of Maya surnames (2, 1, or none). The KHSI was calculated for all individuals. Multiple regression models were run to identify the variables that best explained variation in stature, KH, and KHSI.

Results

Ancestry negatively (P < 0.05) affected stature, but birth weight, crowding index, and mother's education level (MEL) were more significant (P < 0.01). Ancestry had no effect on KH and KHSI values, but birth weight and MEL had a significant effect. Individuals who had grown up in an adverse environment, in terms of MEL, had higher KHSI values. Apparently, lower leg length was proportionally longer than thigh length in the sample.

Conclusions

Growth measurements were more responsive to the studied environmental variables than to ancestry‐related genetic conditions. Genetic predisposition is, therefore, not the primary cause of short stature in this sample of Yucatec Mayas. Am. J. Hum. Biol., 25:586‐593, 2013. © 2013 Wiley Periodicals, Inc.
Spinal muscular atrophy: Development and implementation of potential treatments
Authors: Arnold W. David , Burghes Arthur H. M.
Published: August 2013

In neurodegenerative disorders, effective treatments are urgently needed, along with methods to determine whether treatment worked. In this review, we discuss the rapid progress in the understanding of recessive proximal spinal muscular atrophy and how this is leading to exciting potential treatments of the disease. Spinal muscular atrophy is caused by loss of the survival motor neuron 1 (SMN1) gene and reduced levels of SMN protein. The critical downstream targets of SMN deficiency that result in motor neuron loss are not known. However, increasing SMN levels has a marked impact in mouse models, and these therapeutics are rapidly moving toward clinical trials. Promising preclinical therapies, the varying degree of impact on the mouse models, and potential measures of treatment effect are reviewed. One key issue discussed is the variable outcome of increasing SMN at different stages of disease progression. Ann Neurol 2013;74:348–362
Nicotinische Acetylcholinrezeptor‐Agonisten: ein Meilenstein für den modernen Pflanzenschutz
Authors: Jeschke Peter , Nauen Ralf , Beck Michael Edmund
Published: August 2013

Die Schädigung von Nutzpflanzen durch wirbellose Schädlinge ist eine große Bedrohung vor dem Hintergrund des kontinuierlich steigenden Nahrungsbedarfs einer wachsenden Weltbevölkerung. Daher sind effiziente Pflanzenschutzmaßnahmen in der breiten Vielfalt der landwirtschaftlichen Produktion von größter Bedeutung für nachhaltige Erträge. Die Entdeckung synthetischer Agonisten, die selektiv an nicotinischen Acetylcholin‐Rezeptoren (nAChR) im Zentralnervensystem von Schadinsekten wirken und als Insektizide Verwendung finden, war ein Meilenstein in der angewandten Pflanzenschutzforschung. Diese Verbindungen läuten wegen ihrer hohen Spezifität am aktiven Zentrum und Vielseitigkeit in der Anwendung eine neue Ära der Bekämpfung einiger der weltweit schwerwiegendsten Schadinsekten ein. Diese Insektizide haben nicht nur Bedeutung als Insektenbekämpfungsmittel in der Landwirtschaft, sie haben auch unsere Kenntnisse über die Biochemie der nicotinischen Acetylcholin‐Rezeptoren von Insekten enorm erweitert. Der globale wirtschaftliche Erfolg der synthetischen nAChR‐Agonisten als Insektizide macht den nicotinischen Acetylcholin‐Rezeptor immer noch zu einem der vielversprechendsten Ziele für die Insektizidforschung.
Development of Structural Complexity by Liquid‐Crystal Self‐assembly
Authors: Tschierske Carsten
Published: August 2013

Since the discovery of the liquid‐crystalline state of matter 125 years ago, this field has developed into a scientific area with many facets. This Review presents recent developments in the molecular design and self‐assembly of liquid crystals. The focus is on new exciting soft‐matter structures distinct from the usually observed nematic, smectic, and columnar phases. These new structures have enhanced complexity, including multicompartment and cellular structures, periodic and quasiperiodic arrays of spheres, and new emergent properties, such as ferroelctricity and spontaneous achiral symmetry‐breaking. Comparisons are made with developments in related fields, such as self‐assembled monolayers, multiblock copolymers, and nanoparticle arrays. Measures of structural complexity used herein are the size of the lattice, the number of distinct compartments, the dimensionality, and the logic depth of the resulting supramolecular structures.
Nicotinic Acetylcholine Receptor Agonists: A Milestone for Modern Crop Protection
Authors: Jeschke Peter , Nauen Ralf , Beck Michael Edmund
Published: August 2013

The destruction of crops by invertebrate pests is a major threat against a background of a continuously rising demand in food supply for a growing world population. Therefore, efficient crop protection measures in a vast range of agricultural settings are of utmost importance to guarantee sustainable yields. The discovery of synthetic agonists selectively addressing the nicotinic acetylcholine receptors (nAChRs), located in the central nervous system of insects, for use as insecticides was a major milestone in applied crop protection research. These compounds, as a result of their high target specificity and versatility in application methods, opened a new innovative era in the control of some of the world′s most devastating insect pests. These insecticides also contributed massively to extending our knowledge of the biochemistry of insect nicotinic acetylcholine receptors. The global economic success of synthetic nAChR agonists as insecticides renders the nicotinic acetylcholine receptor still one of the most attractive target sites for exploration in insecticide discovery.
Property and storage stability of whey protein‐sucrose based safe paper glue
Authors: Wang Guorong , Guo Mingruo
Published: August 2013

Whey is a byproduct of cheese making. Disposal of whey may cause environmental pollutions. Whey protein isolate (WPI) is obtained from whey via ion‐exchange and ultra‐filtration, and contains more than 90% of protein. Most current commercially available paper glue products are made from undegradable synthetic polymers and may be harmful to human. The objective of this study was to develop environmentally friendly and children safe paper glue using WPI and sucrose as major ingredients. Results showed that both desirable bonding strength and viscosity of the safe paper glue were achieved by adding sucrose. The whey protein and sucrose based paper glue had excellent recovered bonding strength (ideal for self‐seal envelopes) and bonding strength to different substrates (paper–paper, paper–wood, paper–plastic, and paper–metal). Shelf life tests indicated that the safe glue was stable with addition of low level of preservative and there were no considerable changes in bonding strength and viscosity during the storage at 23°C or 40°C for up to 1 year. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 39710.
UV‐initiated copolymerization route for facile fabrication of epoxy‐functionalized micro‐zone plates
Authors: Li Li , Bi Xiao‐Dong , Feng Min , Zhu Jia‐Ting
Published: August 2013

Bisphenol A‐based epoxy acrylate (BABEA), a commercial ultraviolet (UV)‐curable material, was introduced as a new manufacturing material for facile fabrication of epoxy‐functionalized micro‐zone plates through UV‐initiated copolymerization using glycidyl methacrylate (GMA) as the functional monomer. The poly (BABEA‐co‐GMA) was highly transparent in visible range while highly opaque when the wavelength is less than 295 nm, and of high replication fidelity. X‐ray photoelectron spectroscope (XPS) results indicated the existence of epoxy groups on the surface of the poly (BABEA‐co‐GMA), which allowed for binding protein through an epoxy‐amino group reaction. A fabrication procedure was proposed for manufacturing BABEA based epoxy‐functionalized micro‐zone plates. The fabrication procedure was very simple; obviating the need of micromachining equipments, wet etching or imprinting techniques. To evaluate the BABEA‐based epoxy‐functionalized micro‐zone plates, α‐fetoprotein (AFP) was immobilized onto the capture zone for chemiluminescent (CL) detection in a noncompetitive immune response format. The proposed AFP immunoaffinity micro‐zone plate was demonstrated as a low cost, flexible, homogeneous, and stable assay for α‐fetoprotein (AFP). © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 39787.
Der Polymethinzustand. III. Mitteilung über allgemeine Zusammenhänge zwischen Farbe und Struktur organischer Verbindungen
Authors: Dahne Siegfried , Leupold Dieter
Published: August 2013

Die vielfältigen Erscheinungen im Bereiche der organischen Verbindungen mit‐Elektronensystemen lassen sich unter der Annahme eines Wechselspiels von drei Grenzzuständen verstehen. Dies sind der aromatische Zustand, gekennzeichnet durch maximalen Bindungsausgleich, gleiche π‐Elektronendichten an allen Atomen und durch hohe Delokalisierungsenergien, der Polyenzustand, gekennzeichnet durch alternierende Bindungsordnungen und gleiche π‐Elektronendichten und der Polymethinzustand, gekennzeichnet durch gleiche

Bindungsordnungen, alternierende π‐Elektronendichten und durch hohe Delokalisierungsenergien. Die Existenz des energetisch ausgezeichneten Polymethinzustandes wird durch einfache quantenmechanische Studien abgeleitet; seine charakteristischen Merkmale werden näher untersucht. Ein wesentliches Kriterium für die Tieffarbigkeit der Polymethine ist die π‐Elektronendichtealternierung im Grundzustand.
Dynamische Theorie der Kristallstrukturanalyse durch Elektronenbeugung im inhomogenen Primärstrahlwellenfeld
Authors: Hegerl R. , Hoppe W.
Published: August 2013

Vor einiger Zeit wurde ein neues Prinzip zur Registrierung der Gesamtinformation (Amplituden und Phasen) in einem Beugungsbild angegeben, welches nicht – wie die Holographie – Interferenzen der Streuwellen mit einer Referenzwelle voraussetzt. Von wesentlicher Bedeutung sind hierbei Interferenzen benachbarter Streuwellen, die entstehen, wenn die Objektfunktion Q(x,y) mit einer verallgemeinerten Primärwellenfunktion p(x,y) multipliziert wird. Im Fourierraum (Beugungsdiagramm) entstehen dabei Faltungen der Fouriertransformierten dieser Funktionen; durch geeignete Formung von p(x,y) läßt sich erreichen, daß die erwähnten, zur Phasenbestimmung ausnutzbaren Interferenzen benachbarter Streustrahlen resultieren. Zum Unterschied zur Holographie soll dieses Verfahren “Ptychographie” (ξ = Falte) genannt werden. Das Verfahren ist für periodische und nichtperiodische Strukturen anwendbar; die einfachsten und übersichtlichsten Beziehungen ergeben sich für Kreuzgitter. In der vorliegenden Arbeit wird die Theorie für Raumgitter mit und ohne Berücksichtigung der dynamischen Theorie erweitert. An einem praktischen Beispiel werden die auftretenden Effekte demonstriert.
Determination of zeranol and its metabolites in bovine muscle and liver by a chemiluminescence enzyme immunoassay: compared to an ultraperformance liquid chromatography tandem mass spectroscopy method
Authors: Haiyang Jiang , Wenjun Wang , Jinghui Zhu , Xiaoqi Tao , Jiancheng Li , Xi Xia , Kai Wen , Fei Xu , Zhaopeng Wang , Min Chen , Xiangmei Li , Xiaoping Wu , Shien Wang , Shuangyang Ding
Published: August 2013

A chemiluminescent enzyme immunoassay (CLEIA) was compared to an ultraperformance liquid chromatography tandem mass spectroscopy (UPLC‐MS/MS) procedure for the analysis of zeranol and its metabolites in bovine tissue samples. Apparent recoveries from fortified samples by both methods were comparable at 0.5–4.0 µg/kg and a significant correlation was obtained. For CLEIA analysis, hapten mimicking the analyte was first synthesized and conjugated with the carrier protein bovine serum albumin as the immunogen to produce monoclonal antibody. The obtained antibody showed extensive cross‐reactivity toward zeranol metabolites (zearalanone). The limit of detection of CLEIA and UPLC‐MS/MS was 0.05 µg/kg and 0.5 µg/kg, respectively. Recoveries of both methods for fortified samples were higher than 75.0% with the coefficient of variation less than 15%. These results indicated that the combination of screening with CLEIA and confirmation with UPLC‐MS/MS for zeranol and its metabolites would be a reliable method for a large number of bovine samples. Copyright © 2013 John Wiley & Sons, Ltd.