bluuebunny/crossref_metadata_2025 huggingface dataset:
Collecting duct of Bellini renal carcinoma with psoas muscle recurrence: A case report and review of literature
Authors: Chua Michael Erlano , Olondriz Karen , Maniwa Michael , Mendoza Jonathan , Castillo Josefino
Published: March 2014

Collecting duct carcinoma (CDC) is a rare type of renal carcinoma with an aggressive course and poor treatment response. Up to date, there are only few reports of CDC, which may be due to unrecognized or unfamiliarity of its features and characteristics. We report a case of CDC in a 63-year-old male who initially presented with localized disease, and developed psoas muscle metastasis 15 months after partial nephrectomy with good surgical margins. No guidelines currently exist for the management of CDC; however, aggressiveness of the disease warrants close surveillance and consideration of adjuvant therapy even in patients with localized tumours. We postulate that CDC in its localized stage can be managed by partial nephrectomy, while preserving renal function; however, it is also important to consider a good oncologic outcome by administering adjuvant therapy, such as chemotherapy, and targeted therapy for a better prognostic outcome.
Trudności diagnostyczne w rozpoznaniu ziarnicy złośliwej śródpiersia u młodego mężczyzny—Opis przypadku
Authors: Bubel Adam , Rogoziński Paweł , Wandzel Piotr , Bruliński Krzysztof
Published: March 2014

Chłoniaki to nowotwory z limfocytów i ich komórek prekursorowych. Rozwijają się w węzłach chłonnych lub w tkance limfatycznej pozawęzłowej, często lokalizując się w klatce piersiowej. Autorzy opisują przypadek młodego mężczyzny, którego przyjęto na oddział torakochirurgii z powodu guza śródpiersia przedniego z naciekiem podstawy szyi. Przeprowadzone wstępne badania diagnostyczne dały mylne rozpoznanie promienicy. Brak postępu w leczeniu oraz wystąpienie stanu zagrożenia życia spowodowały wdrożenie agresywniejszych metod diagnostycznych. W pobranych podczas torakotomii wycinkach rozpoznano ostatecznie chłoniaka Hodgkina o typie nodular sclerosis. Guzy śródpiersia mogą powodować trudności diagnostyczne, dlatego w celu uniknięcia pomyłki klasyczne badania histologiczne preparatów należy uzupełnić o celowane testy immunohistochemiczne.
Czy istnieje związek między nadciśnieniem indukowanym ciążą a obturacyjnym bezdechem sennym? Opis przypadku
Authors: Gruca-Stryjak Karolina , Cofta Szczepan , Wysocka Ewa , Banaszewski Jacek , Bręborowicz Grzegorz
Published: March 2014

W pracy przeanalizowano przypadek kobiety w ciąży bliźniaczej powikłanej stanem przedrzucawkowym i zaburzeniami oddychania podczas snu. Pacjentka została przyjęta do szpitala z powodu nadciśnienia tętniczego, białkomoczu oraz narastających obrzęków. Wyniki badań laboratoryjnych ujawniły białkomocz oraz zmniejszenie stężenia białka całkowitego w surowicy krwi. Rozpoznano łagodną postać stanu przedrzucawkowego. Z uwagi na zaobserwowaną nasiloną senność dzienną, głośne chrapanie i przerwy w oddychaniu podczas snu wykonano u pacjentki badanie polisomnograficzne, podczas którego obserwowano liczne epizody bezdechów obturacyjnych i spłyconego oddychania podczas snu. Wartość wskaźnika AHI (apnea-hypopnea index) wynosiła 82.1 z licznymi epizodami desaturacji osiągającymi najniższą wartość 82%. Rozpoznano ciężką postać obturacyjnego bezdechu sennego i włączono leczenie za pomocą protezy powietrznej (CPAP). Zastosowanie CPAP pozwoliło na zmniejszenie wskaźnika AHI do 1.2 oraz lepszą kontrolę ciśnienia tętniczego. Między 33. a 35. tygodniem ciąży pacjentka stosowała CPAP. W 35. tygodniu ciąży z uwagi na wystąpienie objawów zagrożenia życia pierwszego bliźniaka w zapisie kardiotokograficznym ukończono ciążę cięciem cesarskim. Urodziły się dwa noworodki płci męskiej w stanie dobrym. W okresie połogu pacjentka zaprzestała stosowania CPAP. Obserwowano wzrost wskaźnika AHI do 45.3 oraz wzrost wartości ciśnienia tętniczego do najwyższej wartości 180/100 mm Hg. Pacjentka w stanie ogólnym dobrym w 7. dobie połogu została zwolniona do domu z zaleceniami dalszej diagnostyki i leczenia w poradni zaburzeń snu. Podsumowując, należy stwierdzić że, zaburzenia snu wywierają niekorzystny wpływ na zdrowie matki i płodu, na nastrój i jakość życia ciężarnej. Udowodniono, że istnieje wiele zależności między snem a zdrowiem. Zaburzenia snu wraz z zaburzeniami oddychania podczas snu przyczyniają się do rozwoju wielu różnych chorób ogólnych bądź też pogarszają ich przebieg. A choroby te z drugiej strony negatywnie wpływają na jakość snu. Podstawowe znaczenie ma leczenie schorzenia podstawowego, lecz towarzyszące mu zaburzenia snu także wymagają terapii.
Société de l’information et infobésité : perceptions et représentations croisées
Authors: Reibel Marie , Desrochers Nadine
Published: March 2014

Cette étude qualitative de contenu vise à interroger les concepts de société de l’information et d’infobésité auprès d’un petit groupe d’étudiants par l’entremise d’un questionnaire en ligne. Des représentations artistiques de ces concepts ont été présentées aux répondants afin d’évaluer leurs perceptions. Les résultats obtenus mettent l’accent sur la valeur de l’information, une forte présence de la communauté et révèlent également un rapport au temps singulier. Les données ont été analysées à la lumière d’un cadre conceptuel comprenant quatre auteurs : Daniel Bell, Manuel Castells, Roland Barthes et Lev Manovich.
Adolescent HIV disclosure in Zambia: barriers, facilitators and outcomes
Authors: Mburu Gitau , Hodgson Ian , Kalibala Sam , Haamujompa Choolwe , Cataldo Fabian , Lowenthal Elizabeth D , Ross David
Published: March 2014

Introduction

As adolescents living with HIV gain autonomy over their self‐care and begin to engage in sexual relationships, their experiences of being informed about their HIV status and of telling others about their HIV status may affect their ability to cope with having the disease.

Methods

In 2010, we conducted a qualitative study among adolescents aged 10–19 living with HIV in Zambia, and with their parents and health care providers. Through interviews and focus group discussions, we explored the disclosure of HIV status to adolescents living with HIV; adolescents’ disclosure of their status to others; and the impact of both forms of disclosure on adolescents.

Results

Our study identified three main barriers to disclosure of HIV status: local norms that deter parents from communicating with their children about sexuality; fear of HIV stigma; and an underlying presumption that adolescents would not understand the consequences of a HIV diagnosis on their lives and relationships. With regard to adolescents’ disclosure of their HIV status to their sexual partners, our study identified fear of rejection as a common barrier. In rare cases, open family conversations about HIV helped adolescents come to terms with a HIV diagnosis. Findings indicated that disclosure had various outcomes at the individual and interpersonal levels. At the individual level, some adolescents described being anxious, depressed and blaming themselves after being told they had HIV. At the interpersonal level, disclosure created opportunities for adolescents to access adherence support and other forms of psychosocial support from family members and peers. At the same time, it occasionally strained adolescents’ sexual relationships, although it did not always lead to rejection.

Conclusions

There is a need for public health interventions that guide adolescents living with HIV, their parents and families through the disclosure process. Such interventions should help parents to assess and understand the evolving cognitive capacity and maturity of their adolescents in order to determine the appropriate time to inform them of their HIV‐positive status. Such interventions should also mitigate the risk of HIV stigma, as well as local norms that may prevent discussions of sexuality within families. Adolescents who have been informed of their HIV status should be provided with on‐going support to prevent disclosure from negatively affecting their psychological and sexual wellbeing. Further research is needed to explore the potential role of trusted family members in contributing to the disclosure process.
Extracellular matrix signatures of human mammary carcinoma identify novel metastasis promoters
Authors: Naba Alexandra , Clauser Karl R , Lamar John M , Carr Steven A , Hynes Richard O
Published: March 2014

The extracellular matrix (ECM) is a major component of tumors and a significant contributor to cancer progression. In this study, we use proteomics to investigate the ECM of human mammary carcinoma xenografts and show that primary tumors of differing metastatic potential differ in ECM composition. Both tumor cells and stromal cells contribute to the tumor matrix and tumors of differing metastatic ability differ in both tumor- and stroma-derived ECM components. We define ECM signatures of poorly and highly metastatic mammary carcinomas and these signatures reveal up-regulation of signaling pathways including TGFβ and VEGF. We further demonstrate that several proteins characteristic of highly metastatic tumors (LTBP3, SNED1, EGLN1, and S100A2) play causal roles in metastasis, albeit at different steps. Finally we show that high expression of LTBP3 and SNED1 correlates with poor outcome for ER−/PR−breast cancer patients. This study thus identifies novel biomarkers that may serve as prognostic and diagnostic tools.
Evidence of deflected super‐Alfvénic electron jet in a reconnection region with weak guide field
Authors: Zhou Meng , Deng Xiaohua , Tang Rongxin , Pang Ye , Xu Xiaojun , Yuan Zhigang , Huang Shiyong
Published: March 2014

Recent numerical simulations demonstrated that electron diffusion region develops into two‐scale structure, i.e., the inner electron diffusion region and the outer electron diffusion region. The outer diffusion region is manifested as super‐Alfvénic electron jet embedded in central current sheet. However, the electron jets are deflected from neutral sheet with a weak guide field. In this paper we present the in situ evidence of deflected super‐Alfvénic electron jet in a reconnection region with a weak guide field in the Earth's magnetotail. The electron‐scale jet was detected at about 37 ion inertial lengths from the X line. There was a strong electric field at the jet. The strong electric field at the jet was primarily balanced by Hall electric field, as the intense current was mainly carried by magnetized electrons. Another event in the magnetosheath also supports our conclusion that guide field deflects the electron jet away the neutral sheet.
Bayesian inversion for the filtered flow at the Earth's core‐mantle boundary
Authors: Baerenzung Julien , Holschneider Matthias , Lesur Vincent
Published: March 2014

The inverse problem of determining the flow at the Earth's core‐mantle boundary according to an outer core magnetic field and secular variation model has been investigated through a Bayesian formalism. To circumvent the issue arising from the truncated nature of the available fields, we combined two modeling methods. In the first step, we applied a filter on the magnetic field to isolate its large scales by reducing the energy contained in its small scales, we then derived the dynamical equation, referred as filtered frozen flux equation, describing the spatiotemporal evolution of the filtered part of the field. In the second step, we proposed a statistical parametrization of the filtered magnetic field in order to account for both its remaining unresolved scales and its large‐scale uncertainties. These two modeling techniques were then included in the Bayesian formulation of the inverse problem. To explore the complex posterior distribution of the velocity field resulting from this development, we numerically implemented an algorithm based on Markov chain Monte Carlo methods. After evaluating our approach on synthetic data and comparing it to previously introduced methods, we applied it to a magnetic field model derived from satellite data for the single epoch 2005.0. We could confirm the existence of specific features already observed in previous studies. In particular, we retrieved the planetary scale eccentric gyre characteristic of flow evaluated under the compressible quasi‐geostrophy assumption although this hypothesis was not considered in our study. In addition, through the sampling of the velocity field posterior distribution, we could evaluate the reliability, at any spatial location and at any scale, of the flow we calculated. The flow uncertainties we determined are nevertheless conditioned by the choice of the prior constraints we applied to the velocity field.
Cloud‐precipitation‐radiation‐dynamics interaction in global climate models: A snow and radiation interaction sensitivity experiment
Authors: Li J.‐L. F. , Lee W.‐L. , Waliser D. E. , David Neelin J. , Stachnik Justin P. , Lee Tong
Published: March 2014

Conventional global climate models (GCMs) often consider radiation interactions only with small‐particle/suspended cloud mass, ignoring large‐particle/falling and convective core cloud mass. We characterize the radiation and atmospheric circulation impacts of frozen precipitating hydrometeors (i.e., snow), using the National Center for Atmospheric Research coupled GCM, by conducting sensitivity experiments that turn off the radiation interaction with snow. The changes associated with the exclusion of precipitating hydrometeors exhibit a number differences consistent with biases in CMIP3 and CMIP5 (Coupled Model Intercomparison Project Phase 3 and Phase 5), including more outgoing longwave flux at the top of atmosphere and downward shortwave flux at the surface in the heavily precipitating regions. Neglecting the radiation interaction of snow increases the net radiative cooling near the cloud top with the resulting increased instability triggering more convection in the heavily precipitating regions of the tropics. In addition, the increased differential vertical heating leads to a weakening of the low‐level mean flow and an apparent low‐level eastward advection from the warm pool resulting in moisture convergence south of the Intertropical Convergence Zone and north of the South Pacific Convergence Zone (SPCZ). This westerly bias, with effective warm and moist air transport, might be a contributing factor in the model's northeastward overextension of the SPCZ and the concomitant changes in sea surface temperatures, upward motion, and precipitation. Broader dynamical impacts include a stronger local meridional overturning circulation over the middle and east Pacific and commensurate changes in low and upper level winds, large‐scale ascending motion, with a notable similarity to the systematic bias in this region in CMIP5 upper level zonal winds.
Energy Survey Activities off Atlantic Coast Get Green Light From Obama Administration
Authors: Showstack Randy
Published: March 2014

The 27 February release of an environmental review of geological and geophysical (G&G) survey activities off the mid‐ and South Atlantic outer continental shelf is a key step toward potentially opening the area to oil and gas exploration, according to industry and environmental groups. That is a prospect industry groups favor and environmental groups say will harm marine life.
Polymer‐Supported Electron‐Rich Oxime Palladacycle as an Efficient Heterogeneous Catalyst for the Suzuki Coupling Reaction
Authors: Cho Hong‐Jun , Jung Sungwon , Kong Saerom , Park Sung‐Jun , Lee Sang‐Myung , Lee Yoon‐Sik
Published: March 2014

Various electron‐rich oxime palladacycle resins designed as heterogeneous catalysts were employed for the Suzuki coupling reaction of aryl halides with arylboronic acids. The electron‐richness of the oxime ligand was controlled by the substituted alkoxy groups. Evaluation based on the electronic effect of the catalysts revealed that the alkoxy‐substituted oxime palladacycle resins showed better catalytic activity than palladated Kaiser oxime resin in the Suzuki coupling reactions and that the catalytic activity of oxime palladacycle resins increased as the electron‐richness of oxime ligand increased. The most electron‐rich oxime palladacycle resin exhibited an excellent catalytic performance for the synthesis of both biaryl and heterobiaryl compounds, despite its heterogeneous system. As a practical application of the catalyst, a valsartan precursor was synthesized in high yield under mild conditions. The electron‐rich oxime resin could also be reused for up to 5 cycles while maintaining good catalytic activity in the Suzuki coupling reaction.

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Adhesive Catalyst Immobilization of Palladium Nanoparticles on Cotton and Filter Paper: Applications to Reusable Catalysts for Sequential Catalytic Reactions
Authors: Nishikata Takashi , Tsutsumi Hironori , Gao Lei , Kojima Keisuke , Chikama Katsumi , Nagashima Hideo
Published: March 2014

Palladium nanoparticles dispersed in ammonium salts of hyperbranched polystyrenes are adhesively immobilized on the surface of cotton or filter papers by simply heating with dicarboxylic acids or halide anions. The resulting Pd@cotton and Pd@filter paper behave as reusable catalysts; in particular, Pd@filter paper is useful as catalyst for application to sequential cross‐coupling and hydrogenation reactions to produce several different products with just one piece of the paper catalyst.

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Sodium Nitrite‐Catalyzed Aerobic Oxidative Csp2Csp3 Coupling: Direct Construction of the 4‐Aryldihydroisoquinolinone Moiety
Authors: Su Bo , Deng Meng , Wang Qingmin
Published: March 2014

A bioinspired approach for the construction of the 4‐aryldihydroisoquinolinone moiety via direct oxidative Csp2Csp3 coupling has been developed, which uses inexpensive sodium nitrite as catalyst and environmentally benign oxygen in the air as terminal oxidant.

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New Palladium‐Catalyzed Domino Reaction with Intramolecular Ring Closure of an N‐(2‐Chloro‐3‐heteroaryl)arylamide: First Synthesis of Oxazolo[4,5‐b]pyrazines
Authors: Demmer Charles S. , Hansen Jacob C. , Kehler Jan , Bunch Lennart
Published: March 2014

The synthesis of novel planar heterocycles is at the heart of basic research as such scaffolds constitute key building blocks in important diverse areas of research: drug discovery, material sciences, and pesticides. The well‐known benzoxazole is often contained in drug candidates but tweaking its lipophilicity and target interaction points are often desired. In this respect, the oxazolo[4,5‐b]pyrazine is an attractive heterocyclic scaffold as it possesses increased water solubility as well as two additional hydrogen bonding acceptors. We here report a new Pd(II)‐catalyzed domino reaction comprising the first Pd(II)‐assisted intramolecular cyclization of an N‐(2‐chloro‐3‐heteroaryl)arylamide and validate its value by application to the first synthesis of 2‐substituted oxazolo[4,5‐b]pyrazines. We demonstrate that a bidentate phosphorus ligand as well as the presence of an aromatic nitrogen atom is required for the domino reaction to proceed. The robustness of the methodology is confirmed by the synthesis of 23 2‐substituted oxazolo[4,5‐b]pyrazine analogues in good‐to‐high yields and containing both electron‐withdrawing as well as electron‐donating substituents on the reacting arylamide.

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Nickel‐Catalyzed Regio‐ and Stereoselective Reductive Coupling of Oxa‐ and Azabicyclic Alkenes with Enones and Electron‐Rich Alkynes
Authors: Mannathan Subramaniyan , Cheng Chien‐Hong
Published: March 2014

A nickel‐catalyzed regio‐ and stereoselective reductive coupling of oxa‐ and azabicyclic alkenes with activated alkenes and electron‐rich alkynes is described. Thus, 7‐oxabenzonorbornadienes underwent reductive coupling with various vinyl ketones such as ethyl, methyl, propyl and α‐methyl‐substituted vinyl ketones, in the presence of a nickel(II) iodide (NiI2), zinc (Zn), and water catalyst system in acetonitrile at 50 °C for 14 h to afford 2‐alkylnaphthalenes in good to excellent yields. Under similar reaction conditions, 7‐azabenzonorbornadiene derivatives provided cis‐2‐alkyl‐1,2‐dihydronaphthalene derivatives in high yields. On the other hand, the nickel(II) iodide, tris(4‐fluorophenyl)phoshine [P(4‐FC6H4)3] and zinc catalyst system successfully catalyzed the reductive coupling reaction of electron‐rich alkynes, with 7‐aza‐ and 7‐oxabenzonorbornadienes to give cis‐2‐alkenyl‐1,2‐dihydronaphthalene derivatives in good to excellent yields. In the reaction, a mild reducing agent (zinc) and simple hydrogen source (water) were used.

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Reversible P(III)/P(V) Redox: Catalytic Aza‐Wittig Reaction for the Synthesis of 4(3H)‐Quinazolinones and the Natural Product Vasicinone
Authors: Wang Long , Wang Ying , Chen Min , Ding Ming‐Wu
Published: March 2014

The catalytic aza‐Wittig reaction based on a phosphine/phosphine oxide catalytic cycle is reported. The by‐product triphenylphosphine oxide (Ph3PO) was reducedin situto triphenylphosphine (Ph3P) with good chemselectivity so that the aza‐Wittig reaction can be accomplished by using merely a catalytic amount of triphenylphosphine. The reaction has been demonstrated in an efficient synthesis of 4(3H)‐quinazolinones and the natural product (S)‐vasicinone in high yields, by using a catalytic amount of triphenylphosphine (5%) and the tetramethyldisiloxane/titanium tetraisopropoxide [TMDS/Ti(O‐i‐Pr)4] reductant system (81–95% yields and >99%ee).

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National surveillance for hemophilia inhibitors in the United States: Summary report of an expert meeting
Authors: Soucie J. Michael , Miller Connie H. , Kelly Fiona M. , Aschman Diane , DiMichele Donna , Konkle Barbara A. , Kulkarni Roshni , Monahan Paul E. ,   the CDC Inhibitor Surveillance Working Group
Published: March 2014

On March 12, 2012, the Centers for Disease Control and Prevention (CDC) held a meeting of its partners in hemophilia treatment, community‐based organizations, industry, and government to review data and discuss implementation issues relevant to planned United States (U.S.) national inhibitor surveillance. Issues discussed included the current status of inhibitor surveillance in the United Kingdom (UK) and the US, the results of a US inhibitor surveillance feasibility study, proposed national surveillance schemes, laboratory testing and reporting issues and potential opportunities for future inhibitor‐related research. It was concluded that implementation of a national program of inhibitor surveillance using standardized testing through an established public health registry along with patient and care provider education and targeted research provide the best opportunity to inform efforts to develop and evaluate effective prevention strategies.Am. J. Hematol. 89:621–625, 2014. © 2014 Wiley Periodicals, Inc.
Does affective organizational commitment and experience of meaning at work predict risk of disability pensioning? An analysis of register‐based outcomes using pooled data on 40,554 observations in four occupational groups
Authors: Clausen Thomas , Burr Hermann , Borg Vilhelm
Published: March 2014

Background

The aim of this study is to investigate whether experience of meaning at work (MAW) and affective organizational commitment (AOC) predict risk of disability pensioning in four occupational groups.

Methods

Survey data from 40,554 individuals were fitted to a national register (DREAM) containing information on payments of disability pension. Using multi‐adjusted Cox‐regression, observations were followed in the DREAM‐register to assess risk of disability pensioning.

Results

Low levels of MAW significantly increased risk of disability pensioning during follow‐up referencing high levels of MAW. Respondents with medium levels of AOC had a significantly reduced risk of disability pensioning, when compared to respondents with high levels of AOC. Furthermore, results indicate an interaction effect between AOC and MAW in predicting risk of disability pension.

Conclusions

AOC and MAW are significantly associated with risk of disability pensioning. Promoting MAW and managing AOC in contemporary workplaces may contribute towards reducing risk of disability pensioning. Am. J. Ind. Med. 57:709–717, 2014. © 2014 Wiley Periodicals, Inc.
Leading the way to genomic medicine
Authors: Manolio Teri A. , Green Eric D.
Published: March 2014

The National Human Genome Research Institute, in close collaboration with its research community, is pursuing an ambitious research agenda to facilitate and promote the implementation of genomics in clinical care. Since 2011, research programs utilizing next‐generation sequencing in the management of cancer and other multigenic conditions, workup of undiagnosed conditions, and evaluation of disorders of the newborn period have been initiated, along with projects identifying clinically actionable variants and exploring the ethical and social implications of reporting these findings. Several genomic medicine symposia and other consultations have helped to shape these research initiatives and develop educational materials for physicians and others working to implement the use of genomic findings in clinical care. These efforts provide a valuable complement to the highly successful basic genomics research enterprise that has at last enabled the transition of genomics from the bench to the bedside. © 2014 Wiley Periodicals, Inc.
PG4KDS: A model for the clinical implementation of pre‐emptive pharmacogenetics
Authors: Hoffman James M. , Haidar Cyrine E. , Wilkinson Mark R. , Crews Kristine R. , Baker Donald K. , Kornegay Nancy M. , Yang Wenjian , Pui Ching‐Hon , Reiss Ulrike M. , Gaur Aditya H. , Howard Scott C. , Evans William E. , Broeckel Ulrich , Relling Mary V.
Published: March 2014

Pharmacogenetics is frequently cited as an area for initial focus of the clinical implementation of genomics. Through the PG4KDS protocol, St. Jude Children's Research Hospital pre‐emptively genotypes patients for 230 genes using the Affymetrix Drug Metabolizing Enzymes and Transporters (DMET) Plus array supplemented with a CYP2D6 copy number assay. The PG4KDS protocol provides a rational, stepwise process for implementing gene/drug pairs, organizing data, and obtaining consent from patients and families. Through August 2013, 1,559 patients have been enrolled, and four gene tests have been released into the electronic health record (EHR) for clinical implementation: TPMT, CYP2D6, SLCO1B1, and CYP2C19. These genes are coupled to 12 high‐risk drugs. Of the 1,016 patients with genotype test results available, 78% of them had at least one high‐risk (i.e., actionable) genotype result placed in their EHR. Each diplotype result released to the EHR is coupled with an interpretive consult that is created in a concise, standardized format. To support‐gene based prescribing at the point of care, 55 interruptive clinical decision support (CDS) alerts were developed. Patients are informed of their genotyping result and its relevance to their medication use through a letter. Key elements necessary for our successful implementation have included strong institutional support, a knowledgeable clinical laboratory, a process to manage any incidental findings, a strategy to educate clinicians and patients, a process to return results, and extensive use of informatics, especially CDS. Our approach to pre‐emptive clinical pharmacogenetics has proven feasible, clinically useful, and scalable. © 2014 Wiley Periodicals, Inc.
Copper(I) Iodide Catalyzed Aerobic Oxidative CN and CS bond formations through CH Activation: Synthesis of Functionalized Imidazo[1,2‐a]pyridines
Authors: Mohan Darapaneni Chandra , Rao Sadu Nageswara , Ravi Chitrakar , Adimurthy Subbarayappa
Published: March 2014

Copper(I) iodide catalyzed oxidative synthesis of imidazo[1,2‐a]pyridines through CH activation of methyl ketones in water is reported. One‐pot, three‐component coupling reactions for the synthesis of sulfenylimidazo [1,2‐a]pyridines have also been developed from readily available methyl ketones, amino pyridines, and diphenyl disulphide.
Repairing the Thiol‐Ene Coupling Reaction
Authors: Povie Guillaume , Tran Anh‐Tuan , Bonnaffé David , Habegger Jacqueline , Hu Zhaoyu , Le Narvor Christine , Renaud Philippe
Published: March 2014

Thiol‐ene coupling (TEC) reactions emerged as one of the most useful processes for coupling different molecular units under reaction mild conditions. However, TEC reactions involving weak CH bonds (allylic and benzylic fragments) are difficult to run and often low yielding. Mechanistic studies demonstrate that hydrogen‐atom transfer processes at allylic and benzylic positions are responsible for the lack of efficiency of the radical‐chain process. These competing reactions cannot be prevented, but reported herein is a method to repair the chain process by running the reaction in the presence of triethylborane and catechol. Under these reaction conditions, a unique repair mechanism leads to an efficient chain reaction, which is demonstrated with a broad range of anomeric O‐allyl sugar derivatives including mono‐, di‐, and tetrasaccharides bearing various functionalities and protecting groups.
Genetically Encoding Photoswitchable Click Amino Acids in Escherichia coli and Mammalian Cells
Authors: Hoppmann Christian , Lacey Vanessa K. , Louie Gordon V. , Wei Jing , Noel Joseph P. , Wang Lei
Published: March 2014

The ability to reversibly control protein structure and function with light would offer high spatiotemporal resolution for investigating biological processes. To confer photoresponsiveness on general proteins, we genetically incorporated a set of photoswitchable click amino acids (PSCaas), which contain both a reversible photoswitch and an additional click functional group for further modifications. Orthogonal tRNA‐synthetases were evolved to genetically encode PSCaas bearing azobenzene with an alkene, keto, or benzyl chloride group in E. coli and in mammalian cells. After incorporation into calmodulin, the benzyl chloride PSCaa spontaneously generated a covalent protein bridge by reacting with a nearby cysteine residue through proximity‐enabled bioreactivity. The resultant azobenzene bridge isomerized in response to light, thereby changing the conformation of calmodulin. These genetically encodable PSCaas will prove valuable for engineering photoswitchable bridges into proteins for reversible optogenetic regulation.
The Isolation and Characterization of a Rhodacycle Intermediate Implicated in Metal‐Catalyzed Reactions of Alkylidenecyclopropanes
Authors: Inglesby Phillip A. , Bacsa John , Negru Daniela E. , Evans P. Andrew
Published: March 2014

The isolation and characterization of a rhodacycle intermediate implicated in rhodium‐catalyzed reactions of alkylidenecyclopropanes (ACPs) is described. The structure of the metallacycle was unambiguously determined by X‐ray crystallography and is catalytically competent in the rhodium‐catalyzed carbocyclization and ene‐cycloisomerization reactions of ACPs. This work represents a rare example of the isolation of a metallacycle in a metal‐catalyzed higher‐order carbocyclization reaction and thereby provides important insight into the ligand requirements for the insertion of π‐components. Furthermore, it serves as a convenient synthon for the development of challenging higher‐order carbocyclization reactions, as exemplified by the reaction with an activated allene.
Self‐assembled Dynamic 3D Fingerprints in Liquid‐Crystal Coatings Towards Controllable Friction and Adhesion
Authors: Liu Danqing , Broer Dirk J.
Published: March 2014

Chiral‐nematic polymer network coatings form a “fingerprint” texture through self‐assembly. For this purpose the molecular helix of the coating is oriented parallel to the substrate. The coating has a flat surface but when actuated by light in the presence of a copolymerized azobenzene compound, 3D fingerprint structures appear in the coating. The helix forms protrusions at the positions where the molecules are aligned parallel to the surface and withdraws at the positions where the orientation is perpendicular. This process proceeds rapidly and is reversible, that is, the fingerprint‐shaped protrusions disappear when the light is switched off. The texture in the on‐state resembles that of a human fingerprint and is used to manipulate the gripping friction of a robotic finger. The friction coefficient drops by a factor of four to five when the fingerprint switched on because of reduced surface contacts.
Oxidative Cross‐Coupling of Allenyl Ketones and Organoboronic Acids: Expeditious Synthesis of Highly Substituted Furans
Authors: Xia Ying , Xia Yamu , Ge Rui , Liu Zhen , Xiao Qing , Zhang Yan , Wang Jianbo
Published: March 2014

Allenyl ketones are employed as coupling partners in palladium‐catalyzed oxidative cross‐coupling reactions with organoboronic acids. This reaction constitutes an efficient methodology for the synthesis of highly substituted furan derivatives. Palladium‐carbene migratory insertion is proposed as the key step in this transformation.
Aerobic Damage to [FeFe]‐Hydrogenases: Activation Barriers for the Chemical Attachment of O2
Authors: Kubas Adam , De Sancho David , Best Robert B. , Blumberger Jochen
Published: March 2014

[FeFe]‐hydrogenases are the best natural hydrogen‐producing enzymes but their biotechnological exploitation is hampered by their extreme oxygen sensitivity. The free energy profile for the chemical attachment of O2 to the enzyme active site was investigated by using a range‐separated density functional re‐parametrized to reproduce high‐level ab initio data. An activation free‐energy barrier of 13 kcal mol−1 was obtained for chemical bond formation between the di‐iron active site and O2, a value in good agreement with experimental inactivation rates. The oxygen binding can be viewed as an inner‐sphere electron‐transfer process that is strongly influenced by Coulombic interactions with the proximal cubane cluster and the protein environment. The implications of these results for future mutation studies with the aim of increasing the oxygen tolerance of this enzyme are discussed.
Rheological properties of citrus pectin dispersions and its blends with polyquaternium‐7 and colloidal particles
Authors: Martinez Renata Miliani , Shimojo Andréa Arruda Martins , Santana Maria Helena Andrade
Published: March 2014

This article reports on the rheological behavior of a 5% (w/w) citrus pectin (CP) dispersion, its blends with polyquaternium‐7 (PQ) and also with 200 nm nanoparticles (NP) and 1.8 µm microparticles (MP) of CP. The viscous (G″) and elastic (G′) moduli of the CP dispersion were similar, whereas G′ was higher than G″ for PQ. The 1:20 (w/w) blend of CP and PQ enhanced the viscoelastic profile of CP and also decreased its cross‐over frequency. NP and MP were equally effective in enhancing the viscoelastic properties of CP. The best viscoelastic behavior was obtained with 1:20:0.4 (w/w) CP:PQ:(NP or MP) composition. The association of CP with PQ and/or MP or NP tended to change the behavior of CP and PQ dispersions from pseudoplastic to Newtonian. Cox‐Merz superposition was observed for CP:PQ and CP:(MP or NP). These findings contribute for modulation of the rheological properties of CP dispersions for specific applications. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40583.
Carbon fibers derived from UV‐assisted stabilization of wet‐spun polyacrylonitrile fibers
Authors: Morales Marlon S. , Ogale Amod A.
Published: March 2014

A rapid, dual‐stabilization route for the production of carbon fibers from polyacrylonitrile (PAN) precursor fibers is reported. A photoinitiator, 4,4′‐bis(diethylamino)benzophenone, was added to PAN solution before the fiber wet‐spinning step. After a short UV treatment that induced cyclization and crosslinking at a lower temperature, precursor fibers could be rapidly thermo‐oxidatively stabilized and successfully carbonized. Scanning electron microscopy micrographs show no deterioration of the microstructure or hollow‐core formation in the fibers due to UV treatment or presence of photoinitiator. Fast‐thermally stabilized pure PAN‐based carbon fibers show hollow‐core fiber defects due to inadequate thermal stabilization, but such defects were not observed in carbon fibers derived from fast‐thermally stabilized fibers that contained photoinitiator and were UV treated. Tensile testing results confirm that fibers containing 1 wt % photoinitiator and UV treated for 5 min display higher tensile modulus than all other sets of thermally stabilized and carbonized fibers. Wide‐angle X‐ray diffraction results show a higher development of the aromatic structure and molecular orientation in thermally stabilized fibers. No significant increase in interplanar spacing or decrease in crystals size were observed within the UV‐stabilized carbon fibers containing photoinitiator, but such fibers retain a higher extent of molecular orientation when compared with control fibers. These results establish for the first time, the positive effect of the external addition of photoinitiator and UV treatment on the properties of the PAN‐based fibers, and may be used to reduce the precursor stabilization time for faster carbon fiber production rate. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40623.
Cytocompatible and regenerable antimicrobial cellulose modified by N‐halamine triazine ring
Authors: Ma Kaikai , Xie Zhiwei , Jiang Qianyuan , Li Jing , Li Rong , Ren Xuehong , Huang Tung‐Shi , Zhang Ke‐Qin
Published: March 2014

This study reports the formation of cyanuric chloride hydrolysate and its attachment onto cellulose fibers though covalent bonding. The hydrolysis product, 2,4‐dichloro‐6‐hydroxy‐1,3,5‐triazine, is prepared in water solution at ambient temperature, and directly used as a treatment solution for the treatment of cotton fabrics without any prior work‐up. The triazine treated fabrics are rendered antimicrobial through exposure to chlorine bleach. The oxidative chlorine bonded to the triazine‐treated cotton is very stable and regenerable to standard washing tests and UVA irradiation test. The N‐halamine modified cotton fabrics demonstrate excellent antimicrobial efficacy against Staphylococcus aureus ATCC 6538 and Escherichia coli O157:H7 ATCC 43895 with 7‐logs reductions within the contact time of 10 and 5 min, respectively. In addition, the results of in vitro cell viability test suggested that the N‐halamine modified fabrics have excellent cytocompatibility to mammalian cells. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40627.
A Fluorescent Polymeric Quantum Dot/Aptamer Superstructure and Its Application for Imaging of Cancer Cells
Authors: Jie Guifen , Zhao Yanbin , Qin Yingqiang
Published: March 2014

In this work, a novel polymeric quantum dot/aptamer superstructure with a highly intense fluorescence was fabricated by a molecular engineering strategy and successfully applied to fluorescence imaging of cancer cells. The polymeric superstructure, which is composed of both multiple cell‐based aptamers and a high ratio of quantum dot (QD)‐labeled DNA, exploits the target recognition capability of the aptamer, an enhanced cell internalization through multivalent effects, and cellular disruption by the polymeric conjugate. Importantly, the polymeric superstructure exhibits an increasingly enhanced fluorescence with recording time and is thus suitable for long‐term fluorescent cellular imaging. The unique and excellent fluorescence property of the QD superstructure paves the way for developing polymeric QD superstructures that hold promise for applications such as in vivo imaging.
Role of trace elements (Zn, Sr, Fe) in bone development: Energy dispersive X‐ray fluorescence study of rat bone and tooth tissue
Authors: Maciejewska Karina , Drzazga Zofia , Kaszuba Michał
Published: March 2014

Osteoporosis is one of the most common debilitating disease around the world and it is more and more established among young people. There are well known recommendations for nutrition of newborns and children concerning adequate calcium and vitamin D intake in order to maintain proper bone density. Nevertheless, important role in structure and function of a healthy bone tissue is played by an integration between all constituents including elements other than Ca, like trace elements, which control vital processes in bone tissue. It is important from scientific point of view as well as prevention of bone diseases, to monitor the mineralization process considering changes of the concentration of minerals during first stage of bone formation. This work presents studies of trace element (zinc, strontium, and iron) concentration in bones and teeth of Wistar rats at the age of 7, 14, and 28 days. Energy dispersive X‐ray fluorescence (EDXRF) was used to examine mandibles, skulls, femurs, tibiae, and incisors. The quantitative analysis was performed using fundamental parameters method (FP). Zn and Sr concentrations were highest for the youngest individuals and decreased with age of rats, while Fe content was stable in bone matrix for most studied bones. Our results reveal the necessity of monitoring concentration of not only major, but also minor elements, because the trace elements play special role in the first period of bone development. © 2014 BioFactors, 40(4):425–435, 2014
Defined Conjugation of Glycans to the Lysines of CRM197 Guided by their Reactivity Mapping
Authors: Crotti Stefano , Zhai Huili , Zhou Jing , Allan Martin , Proietti Daniela , Pansegrau Werner , Hu Qi‐Ying , Berti Francesco , Adamo Roberto
Published: March 2014

Systematic characterisation of the reactivity of the lysine moieties in CRM197 towards N‐hydroxysuccinimide linkers bearing alkynes or azides is described. This involves two‐step conjugation of various glycans to CRM197 by click chemistry in a well‐defined manner. By semiquantitative LC‐MS/MS analysis of proteolytic digests of the conjugates formed, the reactivity of lysine residues in the protein was mapped and ranked. Computational analysis of the solvent accessibility of each lysine residue (based on the CRM197 crystal structure) established a correlation between reactivity and surface exposure. By this approach, conjugation involving lysine residues (normally a random process) can be controlled. It enables the preparation of lysine‐mediated glycoconjugates with improved batch‐to‐batch reproducibility, thereby producing neo‐glycoconjugates with more‐consistent biological activity.
Rapid Total Synthesis of DARPin pE59 and Barnase
Authors: Mong Surin K. , Vinogradov Alexander A. , Simon Mark D. , Pentelute Bradley L.
Published: March 2014

We report the convergent total synthesis of two proteins: DARPin pE59 and Bacillus amyloliquefaciens RNase (Barnase). Leveraging our recently developed fast‐flow peptide‐synthesis platform, we rapidly explored numerous conditions for the assembly of long polypeptides, and were able to mitigate common side reactions, including deletion and aspartimide products. We report general strategies for improving the synthetic quality of difficult peptide sequences with our system. High‐quality protein fragments produced under optimal synthetic conditions were subjected to convergent native chemical ligation, which afforded native full‐length proteins after a final desulfurization step. Both DARPin and Barnase were folded and found to be as active as their recombinant analogues.
Regiocontroled Palladium‐Catalysed Direct Arylation at Carbon C2 of Benzofurans using Benzenesulfonyl Chlorides as the Coupling Partners
Authors: Loukotova Lenka , Yuan Kedong , Doucet Henri
Published: March 2014

The regioselective palladium‐catalysed direct arylation of benzofurans with aryl halides is a challenging reaction because carbons C2 and C3 display similar reactivity. Such couplings generally lead to mixtures of C2 and C3 arylation products together with C2,C3 diarylation products. We found that the use of benzenesulfonyl chlorides instead of aryl halides as the coupling partner allows for controlling the regioselectivity of the palladium‐catalysed arylation of benzofurans in favour of carbon C2. This method tolerates a variety of substituents on the benzenesulfonyl derivative.
Platinum–Rhenium Synergy on Reducible Oxide Supports in Aqueous‐Phase Glycerol Reforming
Authors: Ciftci Aysegul , Eren Seda , Ligthart D. A. J. Michel , Hensen Emiel J. M.
Published: March 2014

A significant support effect was observed for the aqueous‐phase reforming (APR) of glycerol over a series of Pt‐ and PtRe‐loaded ceria‐, ceria–zirconia‐, zirconia‐, and titania‐supported catalysts. Glycerol conversion rates decreased in the order Pt/TiO2>Pt/ZrO2>Pt/CeZrO2>Pt/CeO2. Upon addition of Re, APR activities of all the Pt catalysts increased. Re promotion for glycerol APR was strongest for PtRe/CeO2. Pt/CeO2 was least active because of the incomplete reduction of Pt. Pt was more easily reduced in PtRe/CeO2 because of the strong Pt–Re interaction. On comparison with previous data on Pt/C and PtRe/C, the oxide‐supported catalysts were more active in the WGS reaction, with the titania‐supported catalyst as the most active, which was a result of the activation of water on the titania support. The acidity of these groups also resulted in increased CO cleavage rates of Pt/TiO2 relative to the rates of Pt/C in APR. A more detailed comparison of Pt(Re)/C and Pt(Re)/TiO2 is made. Monitoring acetaldehyde decomposition to determine the rate of CC bond cleavage evidenced a strong promoting effect of Re on the supported Pt catalysts. All catalysts produced carbon monoxide, methane, and ethanol during acetaldehyde decomposition; notably, Pt(Re)/TiO2 also formed products such as ethylene, ethane, propylene, and propane, indicative of a mechanism also involving ethanol dehydration and olefin coupling to CHx surface intermediates derived from acetaldehyde. The activity in overall glycerol conversion in APR decreased in the order PtRe/C>PtRe/TiO2>Pt/TiO2>Pt/C.
Manganese‐Corrole Complexes as Versatile Catalysts for the Ring‐Opening Homo‐ and Co‐Polymerization of Epoxide
Authors: Robert Carine , Ohkawara Takahiro , Nozaki Kyoko
Published: March 2014

Manganese‐corrole complexes in combination with a co‐catalyst [PPN]X ([PPN]+=bis(triphenylphosphoranylidene)iminium) were found to be new versatile catalysts for the polymerization of epoxides, copolymerization of epoxides with CO2, and copolymerization of epoxides with cyclic anhydrides affording a wide range of polymeric materials. This work should allow the synthesis of new types of improved innovative (co)polymers with original properties and would clearly increase the number of applications for polyesters, polycarbonates, and polyethers.
Ruthenium/Imidazolylphosphine Catalysis: Hydrogenation of Aliphatic and Aromatic Nitriles to Form Amines
Authors: Werkmeister Svenja , Junge Kathrin , Wendt Bianca , Spannenberg Anke , Jiao Haijun , Bornschein Christoph , Beller Matthias
Published: March 2014

A convenient and efficient catalyst system for the hydrogenation of aliphatic nitriles towards the corresponding primary amines in high to excellent yields is presented. In addition, aromatic nitriles are reduced smoothly, too. The use of low catalyst loadings and molecular hydrogen make this protocol an attractive methodology.