bluuebunny/crossref_metadata_2025_split huggingface dataset:
Base‐Catalyzed Hydrolysis of a RuII–Chloro–dmso Complex and Its Reactivity towards L‐Methionine
Authors: Brindell Małgorzata , Dyduch Karol , Adamowicz Agnieszka , Urbanowicz Elżbieta , Oszajca Maria , Michalak Artur , Stochel Grażyna , van Eldik Rudi 
Published: February 2014

AbstractThe ruthenium(II) complex cis‐[RuCl2(dmso)4] is known for its antiproliferative properties. This has stimulated the discovery of a wide group of new ruthenium complexes considered as potential anticancer drugs. The stability of these ruthenium complexes under physiological conditions and their interaction with protein amino acid residues are particularly important because of their intravenous administration. The studies presented here are devoted to the stability of cis‐[RuCl2(dmso)4] under physiological pH conditions and its reactivity towards L‐methionine. Immediate dissociation of one dmso ligand from the parent complex after dilution in water leads to the formation of fac‐[RuCl2(H2O)(dmso)3], which under basic conditions undergoes stepwise dissociation of chloride ions without further dmso release. The hydrolysis of fac‐[RuCl2(H2O)(dmso)3] at pH 7.4 and also base‐catalyzed hydrolysis were investigated in detail by application of kinetic and spectroscopic (UV/Vis, NMR) measurements. The combined experimental and theoretical study revealed that L‐methionine coordinates to fac‐[RuCl(OH)(H2O)(dmso)3] by substituting a water ligand with simultaneous dmso release. Detailed NMR characterization of the product indicated that methionine coordinates through the NH2 group rather than the thioether moiety. This conclusion was further supported by theoretical calculations with the application of ETS–NOCV analysis.
Quasi‐Planar Organic Synthon and S···X (X = S or H–C) Contacts in Flat Copper Coordination Chains: Syntheses, Structures and Conductive Behaviour
Authors: Zhu Hai‐Bin , Shan Ru‐Yu , Wu Yan‐Fang , Lou Yong‐Bing 
Published: February 2014

AbstractA new organic building block, TEPB, has been synthesized that comprises three 2‐ethylthio‐substituted pyrimidine groups coupled to one central phenyl ring at the 1‐, 3‐ and 5‐positions. TEPB exhibits a quasi‐planar conformation due to its intramolecular C–H···N hydrogen bonds. The assembly of TEPB with CuI and CuCl2 produced two flat coordination chains 1 and 2, both exhibiting similar assembly hierarchies from chain through 2D layer to 3D architecture. It was found that extensive S···S and C–H···S contacts exist in the 2D layers of 1 and 2, respectively. Between the 2D layers of 2, there are O–H···Cl hydrogen‐bonding interactions between water molecules and coordinated Cl atoms that provide a proton‐transfer network. Complex 2 exhibits a smaller optical band gap (1.11 eV) than 1 (1.93 eV), which has been attributed to d‐electron transition in the copper(II) ion. The d.c. conductivities of 1 and 2 at room temperature were measured to be 2.84 × 10–12 and 2.42 × 10–10 S cm–1, respectively. The a.c. conductivity of 2 obtained at room temperature by the complex impedance technique is about 5.90 × 10–9 S cm–1, which can be attributed largely to proton conduction. Moreover, the a.c. conductivity of 2 decreases almost linearly with increasing temperature, presumably as a result of its temperature‐sensitive O–H···Cl hydrogen‐bonding network that allows for proton conduction.
Photo‐Oxidation of Water under Ambient Conditions – The Search for Effective Oxygen‐Evolving Catalysts
Authors: Harriman Anthony 
Published: February 2014

AbstractThis essay is based on research leading to the identification of catalysts capable of the selective oxidation of water to molecular oxygen. The real need for such materials relates to the large‐scale photochemical dissociation of water into its constituent elements, as opposed, for example, to the electrochemical decomposition of water at macroscopic electrodes. Combining the catalyst with the essential components needed for efficacious photochemistry brings special challenges, as does the ultimate need to scale up the system by a massive amount. Nature has developed a highly successful process for O2 evolution under ambient illumination that makes use of a cubane tetramanganese cluster having a closely associated calcium cation in attendance. This catalyst is surprisingly delicate and it is debatable as to whether we could adapt such a system for use with artificial photosystems. Historically the latter have used colloidal metal oxides, and consideration is given here as to which materials might offer the most promising catalytic performance. Moving towards heterogeneous systems has more practical meaning, but the same materials come to mind. Recent attention to cobalt‐based catalysts is highlighted as a possible breakthrough that might lead to interesting electrochemical systems when combined with wind turbines. Molecular catalysts provide interesting opportunities for photochemical O2 evolution but suffer from problems of scale‐up. This field has witnessed the most important progress over the past decade or so but still needs urgent attention if advanced materials are to be identified in a timely manner. Finally, consideration is given to the actual status of the field in specific terms of developing an effective artificial photosynthetic apparatus. Moving progressively from using sacrificial redox agents as a simple means to isolate the oxidative photochemical cycle towards full water cleavage will stimulate the development of demonstration models suitable for public display. The reward should be increased investment.
N‐Heterocyclic Dicarbene Iridium(III) Catalysts Enabling Water Oxidation under Visible Light Irradiation
Authors: Volpe Andrea , Sartorel Andrea , Tubaro Cristina , Meneghini Laura , Di Valentin Marilena , Graiff Claudia , Bonchio Marcella 
Published: February 2014

AbstractInvited for the for the front cover of the Cluster Issue on Water Oxidation Chemistry is the Helios group at the University of Padova, fostering a new research impetus on solar fuels by a collaborative synergy among catalysis, organometallic, mechanistic, and materials science experts. The cover image shows the novel dicarbene iridium(III) complex and oxygen evolution as a result of its catalytic action under visible light irradiation. This is one key goal of the HELIOS strategic project, targeting new molecules and nanomaterials for solar energy schemes, as represented by the fullerene sunflower logo. Dr. Rami Al‐Oweini (ITM‐CNR Postdoctoral Fellow) is acknowledged for his creative design and for putting together the cover illustration.
Cu‐Catalyzed Carbenoid Functionalization of Indoles by Methyl 3,3,3‐Trifluoro‐2‐diazopropionate
Authors: Tsyshchuk Irina E. , Vorobyeva Daria V. , Peregudov Alexander S. , Osipov Sergey N. 
Published: February 2014

AbstractAn efficient protocol for the direct CH‐functionalization of indole and its derivatives has been developed by using Cu(F3‐acac)2‐catalyzed insertion of CF3‐carbene derived from methyl 3,3,3‐trifluoro‐2‐diazopropionate. The reaction proceeds with high regioselectivity within a few minutes under low catalyst loading and allows the introduction of CF3 and carboxylate functions simultaneously into the 3‐ or 2‐position of the indole core. This method can be successfully applied for the synthesis of trifluoromethyl‐containing paullones, which are new members of the known family of potent inhibitors of cyclin‐dependent kinases.
Synthesis of Regioisomeric Pyrido[c]azocanones from Azaindanone Derivatives
Authors: Penning Miriam , Christoffers Jens 
Published: February 2014

AbstractA ring enlargement reaction with methylamine gave new pyrido[2,3‐c]‐, pyrido[3,4‐c]‐ and pyrido[3,2‐c]azocanone derivatives from cyclic β‐oxo esters with a cyclopentapyridine skeleton and a 1,4‐diketone moiety. The starting materials for this ring transformation were either prepared from halogenopyridine carboxylates by Heck reaction and subsequent hydrogenation, or (halogenomethyl)pyridine carboxylates were submitted to SN reaction with diethyl malonate. Both routes were completed by Dieckmann condensation to build the cyclic β‐oxo ester structure and alkylation with phenacylbromide to install the 1,4‐diketone motif.
Cathodic Stripping Determination of Water in Organic Solvents
Authors: Xiao Changlong , Weremfo Alexander , Wan Chenyang , Zhao Chuan 
Published: February 2014

AbstractA cathodic stripping voltammetry (CSV) method has been developed to determine water content in organic solvents based on electrooxidation of a gold electrode in the presence of water to form gold oxides upon anodic polarizations. Following cathodic potential scan, a sharp reductive stripping peak of gold oxides is generated and the magnitude of the peak current is related to the water content in the organic solvents. The method has been applied for determination of water in four commonly used water miscible organic solvents, acetonitrile, tetrahydrofuran, acetone and glacial acetic acid, with limits of detection of 60, 10, 40 and 10 ppm, respectively.
Homonuclear Decoupling of 1H Dipolar Interactions in Solids by means of Heteronuclear Recoupling
Authors: Olsen Gregory L. , Lupulescu Adonis , Dumez Jean‐Nicolas , Emsley Lyndon , Frydman Lucio 
Published: February 2014

AbstractLine narrowing has been traditionally achieved in solid‐state 1H NMR spectroscopy by applying pulse sequences that combine multiple‐pulse operations with magic‐angle spinning (MAS), to effectively average out the dipoledipole homonuclear Hamiltonian. The present study explores a new alternative that departs from the usual concept of directly acting on the strongly coupled spins with radiofrequency pulses; instead, we seek to achieve a net homonuclear dipolar decoupling in solids by exploring the reintroduction of MAS‐averaged heteronuclear dipolar couplings between the 1H nuclei and directly bonded 13C or 15N nuclei. This recouplinganti‐recoupling (RaR) scheme thus relies on the recoupling of the dipolar interaction with heteronuclear spins, which, under fast MAS, will exceed the strength and will not commute with the homonuclear 1H1H coupling one is intending to average out. Subsequent removal (“antiRecoupling”) of these heteronuclear interactions can lead to narrowed 1H resonances, without ever pulsing on the aforementioned channel. The line‐narrowing properties of RaR are illustrated with numerical simulations and with experiments on model organic solids.
An electronic order set for acute myocardial infarction is associated with improved patient outcomes through better adherence to clinical practice guidelines
Authors: Ballesca Manuel A. , LaGuardia Juan Carlos , Lee Philip C. , Hwang Andrew M. , Park David K. , Gardner Marla N. , Turk Benjamin J. , Kipnis Patricia , Escobar Gabriel J. 
Published: February 2014

BACKGROUNDAdherence to evidence‐based recommendations for acute myocardial infarction (AMI) remains unsatisfactory.OBJECTIVEQuantifying association between using an electronic AMI order set (AMI‐OS) and hospital processes and outcomes.DESIGNRetrospective cohort study.SETTINGTwenty‐one community hospitals.PATIENTSA total of 5879 AMI patients were hospitalized between September 28, 2008 and December 31, 2010.MEASUREMENTSWe ascertained whether patients were treated using the AMI‐OS or individual orders (a la carte). Dependent process variables were use of evidence‐based care; outcome variables were mortality and rehospitalization.RESULTSUse of individual and combined therapies improved outcomes (eg, 50% lower odds of 30‐day mortality for patients with ≥3 therapies). The 3531 patients treated using the AMI‐OS were more likely to receive evidence‐based therapies (eg, 50% received 5 different therapies vs 36% a la carte). These patients had lower 30‐day mortality (5.7% vs 8.5%) than the 2348 treated using a la carte orders. Although AMI‐OS patients' predicted mortality risk was lower (3.2%) than that of a la carte patients (4.8%), the association of improved processes and outcomes with the use of the AMI‐OS persisted after risk adjustment. For example, after inverse probability weighting, the relative risk for inpatient mortality in the AMI‐OS group was 0.67 (95% confidence interval: 0.52‐0.86). Inclusion of use of recommended therapies in risk adjustment eliminated the benefit of the AMI‐OS, highlighting its mediating effect on adherence to evidence‐based treatment.CONCLUSIONSUse of an electronic order set is associated with increased adherence to evidence‐based care and better AMI outcomes. Journal of Hospital Medicine 2014;9:155–161. © 2014 Society of Hospital Medicine
Specialties performing paracentesis procedures at university hospitals: Implications for training and certification
Authors: Barsuk Jeffrey H. , Feinglass Joe , Kozmic Sarah E. , Hohmann Samuel F. , Ganger Daniel , Wayne Diane B. 
Published: February 2014

BACKGROUNDParacentesis procedure competency is not required for internal medicine or family medicine board certification, and national data show these procedures are increasingly referred to interventional radiology (IR). However, practice patterns at university hospitals are less clear.OBJECTIVETo evaluate which specialties perform paracentesis procedures at university hospitals, compare characteristics of patients within each specialty, and evaluate length of stay (LOS) and hospital costs.DESIGN, SETTING, PATIENTSObservational administrative database review of patients with liver disease who underwent paracentesis procedures in hospitals participating in the University HealthSystem Consortium (UHC) Database from January 2010 through December 2012. UHC is an alliance of 120 academic medical centers and their 290 affiliated hospitals.EXPOSUREPatients with liver disease who underwent inpatient paracentesis procedures.MEASUREMENTSWe compared characteristics of patients who underwent paracentesis procedures by physician specialty, modeling the effects of patient characteristics on the likelihood of IR referral. We also analyzed LOS and hospital costs among patients with a >20% predicted probability of IR referral.RESULTSThere were 97,577 paracentesis procedures performed during 70,862 hospital stays in 204 hospitals. IR performed 29% of paracenteses versus 49% by medicine and medicine subspecialties including gastroenterology/hepatology. Patients who were female, obese, and those with lower severity of illness were more likely to be referred to IR. Patients with a medicine or gastroenterology/hepatology paracentesis had a similar LOS compared to IR. Hospital costs were an estimated as $1308 less for medicine and $803 less for gastroenterology/hepatology compared to admissions with IR procedures (both P = 0.0001).CONCLUSIONSInternal medicine‐ and family medicine‐trained clinicians frequently perform paracentesis procedures on complex inpatients but are not currently required to be competent in the procedure. Increasing bedside paracentesis procedures may reduce healthcare costs. Journal of Hospital Medicine 2014;9:162–168. © 2014 Society of Hospital Medicine
Patient, hospital, and geographic disparities associated with comanagement during hospitalization for colorectal cancer surgery
Authors: de Vries Simone , Jeffe Donna B. , Pruitt Sandi L. , Davidson Nicholas O. , Schootman Mario 
Published: February 2014

BACKGROUNDComanagement of surgical patients has increased, but information regarding detailed characteristics of patients receiving comanagement during hospitalization for colorectal cancer (CRC) surgery is lacking.OBJECTIVETo examine the use of and characteristics associated with comanagement of patients hospitalized for CRC surgery.DESIGNThis study used a population‐based cross‐sectional design.SETTINGWe used the linked 2000 to 2005 Surveillance, Epidemiology, and End Results and Medicare claims data.PATIENTSWe included 37,065 patients aged 66 years or older, hospitalized for definitive CRC surgery following stage I to III diagnosis.MEASUREMENTSThe outcome of interest was comanagement during hospitalization for CRC surgery, and we examined the association between several patient and hospital characteristics. Comanagement was defined as having a relevant physician (ie, internal medicine hospitalist/generalist) submit a claim for evaluation and management services on 70% or more of the days of hospitalization of the patient.RESULTSDuring hospitalization for CRC surgery, 27.6% of patients were comanaged, but this percentage varied widely across hospitals (from 1.9% to 83.2%). Several patient and hospital characteristics were associated with the use of comanaged care, of which important characteristics included older age at diagnosis, presence of comorbidity, emergency surgery, and hospital volume.CONCLUSIONSExtensive variability existed in comanagement use across patients and hospitals, likely reflecting the lack of evidence for its clinical effectiveness. Journal of Hospital Medicine 2014;9:226–231. © 2014 Society of Hospital Medicine
Internal medicine rounding practices and the accreditation council for graduate medical education core competencies
Authors: Shoeb Marwa , Khanna Raman , Fang Margaret , Sharpe Brad , Finn Kathleen , Ranji Sumant , Monash Brad 
Published: February 2014

BACKGROUNDThe Accreditation Council for Graduate Medical Education (ACGME) has established the requirement for residency programs to assess trainees' competencies in 6 core domains (patient care, medical knowledge, practice‐based learning, interpersonal skills, professionalism, and systems‐based practice). As attending rounds serve as a primary means for educating trainees at academic medical centers, our study aimed to identify current rounding practices and attending physician perceived capacity of different rounding models to promote teaching within the ACGME core competencies.METHODSWe disseminated a 24‐question survey electronically using educational and hospital medicine leadership mailing lists. We assessed attending physician demographics and the frequency with which they used various rounding models, as defined by the location of the discussion of the patient and care plan: bedside rounds (BR), hallway rounds (HR), and card‐flipping rounds (CFR). Using the ACGME framework, we assessed the perceived educational value of each model.RESULTSWe received 153 completed surveys from attending physicians representing 34 institutions. HR was used most frequently for both new and established patients (61% and 43%), followed by CFR for established patients (36%) and BR for new patients (22%). Most attending physicians indicated that BR and HR were superior to CFR in promoting the following ACGME competencies: patient care, systems‐based practice, professionalism, and interpersonal skills.CONCLUSIONSHR is the most commonly employed rounding model. BR and HR are perceived to be valuable for teaching patient care, systems‐based practice, professionalism, and interpersonal skills. CFR remains prevalent despite its perceived inferiority in promoting teaching across most of the ACGME core competencies. Journal of Hospital Medicine 2014;9:239–243. © 2014 Society of Hospital Medicine
Pharmacophore Mapping, In Silico Screening and Molecular Docking to Identify Selective Trypanosoma brucei Pteridine Reductase Inhibitors
Authors: Dube Divya , Sharma Sujata , Singh Tej P. , Kaur Punit 
Published: February 2014

AbstractTrypanosoma brucei Pteridine reductase (TbPTR1) is of vital importance and is an established drug target for dreaded Human African trypanosomiasis (HAT). Pharmacophore perception strategy has been employed to identify key chemical features responsible for the biological activity for TbPTR1. The findings suggest that three different pharmacophore features can be associated with T. brucei anti‐PTR1 activity namely: H‐bond donors (D), Hydrophobic aromatic (H) and Ring aromatic (R). The resulting hypothesis is able to predict the activity of other existing TbPTR1 inhibitors with a correlation coefficient (r) of 0.89. An in silico database screening, based on the best hypothesis, has been used to identify some potential nanomolar range TbPTR1 inhibitors. These compounds were then checked by molecular docking and subjected to ADMET analysis. Further, a detailed comparison of the pharmacophore behavior and differential analysis of binding pockets of T. brucei and L. major was made which revealed subtle differences in terms of their shape and charge properties. This investigation can form the basis for tweaking the specificity of compounds for generating new improved species specific inhibitor molecules for Pteridine reductase in these different parasitic protozoans.
Development of a New Decision Tree to Rapidly Screen Chemical Estrogenic Activities of Xenopus laevis
Authors: Wang Ting , Li Weiying , Zheng Xiaofeng , Lin Zhifen , Kong Deyang 
Published: February 2014

AbstractDuring the last past decades, there is an increasing number of studies about estrogenic activities of the environmental pollutants on amphibians and many determination methods have been proposed. However, these determination methods are time‐consuming and expensive, and a rapid and simple method to screen and test the chemicals for estrogenic activities to amphibians is therefore imperative. Herein is proposed a new decision tree formulated not only with physicochemical parameters but also a biological parameter that was successfully used to screen estrogenic activities of the chemicals on amphibians. The biological parameter, CDOCKER interaction energy (Ebinding) between chemicals and the target proteins was calculated based on the method of molecular docking, and it was used to revise the decision tree formulated by Hong only with physicochemical parameters for screening estrogenic activity of chemicals in rat. According to the correlation between Ebinding of rat and Xenopus laevis, a new decision tree for estrogenic activities in Xenopus laevis is finally proposed. Then it was validated by using the randomly 8 chemicals which can be frequently exposed to Xenopus laevis, and the agreement between the results from the new decision tree and the ones from experiments is generally satisfactory. Consequently, the new decision tree can be used to screen the estrogenic activities of the chemicals, and combinational use of the Ebinding and classical physicochemical parameters can greatly improves Hong’s decision tree.
Scheduling twin robots on a line
Authors: Erdoğan Güneş , Battarra Maria , Laporte Gilbert 
Published: February 2014

AbstractThis article introduces the twin robots scheduling problem (TRSP), in which two robots positioned at the opposite ends of a rail are required to deliver items to positions along the rail, and the objective is to minimize the makespan. A proof of ‐hardness of the TRSP is presented, along with exact and heuristic algorithms. Computational results on challenging instances are provided.Copyright © 2014 Wiley Periodicals, Inc. Naval Research Logistics 61: 119–130, 2014