bluuebunny/crossref_metadata_2025_split huggingface dataset:
Predictors of post‐sentence mental health service use in a population cohort of first‐time adult offenders in Western Australia
Authors: Sodhi‐Berry Nita , Knuiman Matthew , Preen David B. , Alan Janine , Morgan Vera A. 
Published: August 2014

AbstractBackgroundLittle is known about whether or how offenders use mental health services after sentence completion.AimThis study aimed to determine the likelihood of such service use by adult (18–44 years) first‐time offenders up to 5 years after sentence completion and possible predictor variables.MethodsPre‐sentence and post‐sentence mental health service use was obtained from whole‐population linked administrative data on 23,661 adult offenders. Cox proportional hazard models were used to determine which socio‐demographic, offending and pre‐sentence health service variables were associated with such post‐sentence service use.ResultsThe estimated 5‐year probability of any post‐sentence mental health service use was 12% for offenders who had not previously used such services, but still only 42% for those who had. For the latter, best predictors of post‐sentence use were past psychiatric diagnosis and history of self‐harm; history of self‐harm also predicted post‐sentence use among new mental health services users and so also did past physical illness. Indigenous offenders had a greater likelihood of service use for any mental disorder or for substance use disorders than non‐Indigenous offenders, irrespective of pre‐sentence use. Among those with pre‐sentence service contact, imprisoned offenders were less likely to use mental health services after sentence than those under community penalties; in its absence, socio‐economic disadvantage and geographic accessibility were associated with greater likelihood of post‐sentence use.ConclusionsOur findings highlight the discontinuity of mental healthcare for most sentenced offenders, but especially prisoners, and suggest a need for better management strategies for these vulnerable groups with mental disorders. Copyright © 2014 John Wiley & Sons, Ltd.
Synergetic Catalytic Effects in Tri‐Component Mesostructured Ru–Cu–Ce Oxide Nanocomposite in CO Oxidation
Authors: Cui Xiangzhi , Wang Yongxia , Chen Lisong , Shi Jianlin 
Published: August 2014

AbstractThis work focuses on probing the synergetic catalytic effects in mesostructured tri‐component Ru–Cu–Ce oxides in CO oxidation reaction. The crystallized nanocomposites with RuO2 and CuO nanoparticles dispersed homogeneously in the pore network of mesoporous CeO2 were synthesized by the nanocasting replication method. The greatly enhanced catalytic activity was achieved by CuO incorporating in mesoporous CeO2, and further by RuO2 incorporating in the mesostructure of CuO/CeO2. Two types of synergetic catalytic mechanisms have been preliminarily proposed to be copresent in the system: CeO2 activation by CuO through generating oxygen vacancies at CeO2/CuO interface and the CeO2 surface nearby, which consequently activate the oxygen species (O*) and enhance the CO oxidation activity of the bi‐metal CuCe oxide, and the simultaneous adsorption of CO molecules and their activation in parallel on the active surface of RuO2, which results in further elevated catalytic activity.
Catalysis by Dynamically Formed Defects in a Metal–Organic Framework Structure: Knoevenagel Reaction Catalyzed by Copper Benzene‐1,3,5‐tricarboxylate
Authors: Položij Miroslav , Rubeš Miroslav , Čejka Jiří , Nachtigall Petr 
Published: August 2014

AbstractThe high catalytic activity and selectivity of the metal–organic framework (MOF) copper benzene‐1,3,5‐tricarboxylate (CuBTC) that are observed experimentally in the Knoevenagel reaction are explained on the basis of computational investigations by employing a periodic model and density functional theory. Three factors are responsible for the unusually high activity of CuBTC: One, CuBTC can act as a base, and the active methylene reactant is deprotonated, whereas a temporary defect in the framework is formed; two, the thus‐formed defect, a Brønsted acid site, simultaneously activates the aldehyde; three, the reaction takes place on two adjacent Cu2+ sites (Lewis acid sites) that are separated by 8.2 Å. The results reported herein show the great versatility of the CuBTC MOF catalyst, including its amphiphilic character and the concerted effect of nearby framework metal cations.
Electrochemically Controlled One‐Electron Oxidation Coupled to Consecutive Hydrogen Atom Transfer of Caffeine
Authors: Chan Kwok Kiong , Ganguly Rakesh , Li Yongxin , Webster Richard D. 
Published: August 2014

AbstractCaffeine (CAF) undergoes a one‐electron oxidation in acetonitrile to form a cation radical, with variable scan rate CV experiments indicating that the lifetime of the cation radical improves as the trace water content of the solvent is decreased. Electrochemical oxidation (and chemical oxidation with NOSbF6) of CAF in CH3CN leads to the generation of the protonated CAF cation as the long‐term product in high yield, whose structure is confirmed by single‐crystal X‐ray crystallography and NMR spectroscopy. The protonated cation is able to be electrochemically reduced back to CAF under electrolysis conditions. The formation of the protonated cation involves the initial one‐electron oxidation of CAF to form the cation radical, which undergoes a hydrogen atom abstraction reaction. Digital simulations of the CV data show that the rate and equilibrium constants for the hydrogen atom abstraction step are kf=1.0×102 L mol−1 s−1 and Keq=1.0×102.
Vernier‐Templated Synthesis, Crystal Structure, and Supramolecular Chemistry of a 12‐Porphyrin Nanoring
Authors: Kondratuk Dmitry V. , Sprafke Johannes K. , O'Sullivan Melanie C. , Perdigao Luis M. A. , Saywell Alex , Malfois Marc , O'Shea James N. , Beton Peter H. , Thompson Amber L. , Anderson Harry L. 
Published: August 2014

AbstractVernier templating exploits a mismatch between the number of binding sites in a template and a reactant to direct the formation of a product that is large enough to bind several template units. Here, we present a detailed study of the Vernier‐templated synthesis of a 12‐porphyrin nanoring. NMR and small‐angle X‐ray scattering (SAXS) analyses show that Vernier complexes are formed as intermediates in the cyclo‐oligomerization reaction. UV/Vis/NIR titrations show that the three‐component assembly of the 12‐porphyrin nanoring figure‐of‐eight template complex displays high allosteric cooperativity and chelate cooperativity. This nanoring–template 1:2 complex is among the largest synthetic molecules to have been characterized by single‐crystal analysis. It crystallizes as a racemate, with an angle of 27° between the planes of the two template units. The crystal structure reveals many unexpected intramolecular CH⋅⋅⋅N contacts involving the tert‐butyl side chains. Scanning tunneling microscopy (STM) experiments show that molecules of the 12‐porphyrin template complex can remain intact on the gold surface, although the majority of the material unfolds into the free nanoring during electrospray deposition.
One Ligand in Dual Roles: Self‐Assembly of a Bis‐Rhomboidal‐Shaped, Three‐Dimensional Molecular Wheel
Authors: Lu Xiaocun , Li Xiaopeng , Guo Kai , Wang Jing , Huang Mingjun , Wang Jin‐Liang , Xie Ting‐Zheng , Moorefield Charles N. , Cheng Stephen Z. D. , Wesdemiotis Chrys , Newkome George R. 
Published: August 2014

AbstractA facile high yield, self‐assembly process that leads to a terpyridine‐based, three‐dimensional, bis‐rhomboidal‐shaped, molecular wheel is reported. The desired coordination‐driven supramolecular wheel involves eight structurally distorted tristerpyridine (tpy) ligands possessing a 60° angle between the adjacent tpy units and twelve Zn2+ ions. The tpy ligand plays dual roles in the self‐assembly process: two are staggered at 180° to create the internal hub, while six produce the external rim. The wheel can be readily generated by mixing the tpy ligand and Zn2+ in a stoichiometric ratio of 2:3; full characterization is provided by ESI‐MS, NMR spectroscopy, and TEM imaging.
Novel Organocatalytic Activation of Unmodified Morita–Baylis–Hillman Alcohols for the Synthesis of Bicyclic α‐Alkylidene‐Ketones
Authors: Stiller Julian , Kowalczyk Dorota , Jiang Hao , Jørgensen Karl Anker , Albrecht Łukasz 
Published: August 2014

AbstractThe organocatalytic activation of Morita–Baylis–Hillman alcohols via H‐bonding‐iminium‐ion formation is demonstrated for the first time. This activation strategy enables the Morita‐Baylis–Hillman alcohols to undergo a formal SN2′ reaction. In combination with the well‐established enamine reactivity, this creates a new reactivity pattern. The application of this new activation mode for the synthesis of bicyclic α‐alkylidene‐ketones is demonstrated. The developed reaction sequence proceeds efficiently affording nature‐inspired target products with four contiguous stereogenic centers in a highly stereoselective manner.
Impact of Magnesium(II) on Beryllium Fluorides in Solutions Studied by 19F NMR Spectroscopy
Authors: Liu Yixiang , Mao Xian , Liu Maili , Jiang Ling 
Published: August 2014

AbstractBeryllium fluorides are widely used in protein phosphorylation studies to get stable transition state analogs or near attack conformers, which has attracted much attention. BeF3− is one of the optimal phosphoryl (PO3−) analogs for its identical geometry and charge, and Mg2+ naturally participates in the phosphoryl binding in biological systems. In solutions, BeF3− coexists with other beryllium fluorides (BeF42−, BeF2 and BeF+) and magnesium fluorides, and there are equilibriums between these species. In this article, 19F NMR spectroscopy was applied to the investigation of the impact of magnesium(II) on beryllium fluorides. It has been found that when Mg2+ was introduced into the solutions, the chemical shifts, the intensities and the line widths of 19F signals of various beryllium fluoride complexes were changed. After ionic strength correction, these effects were remarkable only for BeF42− and BeF3−, especially BeF42−, when the concentration of the fluoride ion is relatively low. Mechanism of the effects is proposed which involves ion pair formation between Mg2+ and beryllium fluorides.
Chincona Alkaloid‐Catalyzed Enantioselective Trifluoromethylthiolation of Oxindoles
Authors: Yang Tao , Shen Qilong , Lu Long 
Published: August 2014

AbstractAn organocatalytic asymmetric trifluoromethylthiolation of 3‐aryl or 3‐alkyloxindoles employing a trifluoromethyl‐substituted thioperoxide as the electrophilic trifluoromethylthiolating reagent was described. Reactions occurred in good to excellent enantioselectivities to generate oxindoles with a SCF3‐substituted quaternary chiral center.
Aniline Induced Domino Ring Contraction Process on the Rim of an Open‐Cage Fullerene with Carbonyl, Imino and Iactone Moieties
Authors: Liu Shuming , Gan Liangbing 
Published: August 2014

AbstractFunctional groups on the rim of open‐cage fullerenes usually exhibit different reactivity from those in classical organic molecules due to the unique spherical structure of fullerenes. The present work shows a sequence of lactone opening, imino hydrolysis, aminal formation and imine formation processes during the reaction of aniline with the open‐cage compound 1 with functional groups including lactone on the rim of the orifice. Single crystal X‐ray diffraction analysis confirmed the structure of the product.
Bio‐inspired Step‐Economical, Redox‐Economical and Protecting‐Group‐Free Enantioselective Total Syntheses of (−)‐Chaetominine and Analogues
Authors: Luo Shi‐Peng , Peng Qi‐Long , Xu Chu‐Pei , Wang Ai‐E , Huang Pei‐Qiang 
Published: August 2014

AbstractFull details of the enantioselective four‐step and five‐step total syntheses of (−)‐chaetominine from D‐Trp and L‐Trp are described. Featuring an oxidative double cyclization reaction, and tandem C14 epimerization‐lactamization reactions as key steps, the method provides a rapid access to (−)‐chaetominine (6a) and analogues. The total syntheses of (−)‐chaetominine (6a) are so far the most concise and efficient. Through comprehensive investigation, the stereochemical requirements for the double cyclization reaction were revealed, and the confusion regarding physicochemical properties of this natural product was clarified. Moreover, short pathways to complexity generation, a scenarios revealed for the biosynthesis of fungal peptidyl alkaloid multi‐cyclic scaffolds, have been validated through the chemical synthesis. On the basis of these findings, a plausible biosynthetic pathway for (−)‐chaetominine (6a) was suggested.
Cu‐Promoted Oxidative Trifluoromethylation of Terminal Alkynes with Difluoromethylene Phosphobetaine
Authors: Deng Xiaoyun , Lin Jinhong , Zheng Jian , Xiao Jichang 
Published: August 2014

AbstractDifluoromethylene phosphobetaine (Ph3P+CF2CO2−, PDFA), a known difluorocarbene reagent, was found to be able to efficiently trifluoromethylate terminal alkynes in the presence of Cu(I) and potassium fluoride. The transformation proceeded smoothly to afford the corresponding trifluoromethylated acetylenes in moderate yields.
Impact of state‐specific Medicaid reimbursement and eligibility policies on receipt of cancer screening
Authors: Halpern Michael T. , Romaire Melissa A. , Haber Susan G. , Tangka Florence K. , Sabatino Susan A. , Howard David H. 
Published: August 2014

BACKGROUNDAlthough state Medicaid programs cover cancer screening, Medicaid beneficiaries are less likely to be screened for cancer and are more likely to present with tumors of an advanced stage than are those with other insurance. The current study was performed to determine whether state Medicaid eligibility and reimbursement policies affect the receipt of breast, cervical, and colon cancer screening among Medicaid beneficiaries.METHODSCross‐sectional regression analyses of 2007 Medicaid data from 46 states and the District of Columbia were performed to examine associations between state‐specific Medicaid reimbursement/eligibility policies and receipt of cancer screening. The study sample included individuals aged 21 years to 64 years who were enrolled in fee‐for‐service Medicaid for at least 4 months. Subsamples eligible for each screening test were: Papanicolaou test among 2,136,511 patients, mammography among 792,470 patients, colonoscopy among 769,729 patients, and fecal occult blood test among 753,868 patients. State‐specific Medicaid variables included median screening test reimbursement, income/financial asset eligibility requirements, physician copayments, and frequency of eligibility renewal.RESULTSIncreases in screening test reimbursement demonstrated mixed associations (positive and negative) with the likelihood of receiving screening tests among Medicaid beneficiaries. In contrast, increased reimbursements for office visits were found to be positively associated with the odds of receiving all screening tests examined, including colonoscopy (odds ratio [OR], 1.07; 95% confidence interval [95% CI], 1.06‐1.08), fecal occult blood test (OR, 1.09; 95% CI, 1.08‐1.10), Papanicolaou test (OR, 1.02; 95% CI, 1.02‐1.03), and mammography (OR, 1.02; 95% CI, 1.02‐1.03). Effects of other state‐specific Medicaid policies varied across the screening tests examined.CONCLUSIONSIncreased reimbursement for office visits was consistently associated with an increased likelihood of being screened for cancer, and may be an important policy tool for increasing screening among this vulnerable population. Cancer 2014;120:3016–3024. © 2014 American Cancer Society.
Serum‐based miRNAs in the prediction and detection of recurrence in melanoma patients
Authors: Fleming Nathaniel H. , Zhong Judy , da Silva Inês Pires , Vega‐Saenz de Miera Eleazar , Brady Bobbi , Han Sung Won , Hanniford Doug , Wang Jinhua , Shapiro Richard L. , Hernando Eva , Osman Iman 
Published: August 2014

BACKGROUNDIdentification of primary melanoma patients at the highest risk of recurrence remains a critical challenge, and monitoring for recurrent disease is limited to costly imaging studies. We recently reported our array‐based discovery of prognostic serum miRNAs in melanoma. In the current study, we examined the clinical utility of these serum‐based miRNAs for prognosis as well as detection of melanoma recurrence.METHODSSerum levels of 12 miRNAs were tested using qRT‐PCR at diagnosis in 283 melanoma patients (training cohort, n = 201; independent validation, n = 82; median follow‐up, 68.8 months). A refined miRNA signature was chosen and evaluated. We also tested the potential clinical utility of the miRNAs in early detection and monitoring of recurrence using multiple longitudinal samples (pre‐ and postrecurrence) in a subset of 82 patients (n = 225). In addition, we integrated our miRNA signature with publicly available Cancer Genome Atlas data to examine the relevance of these miRNAs to melanoma biology.RESULTSFour miRNAs (miR‐150, miR‐30d, miR‐15b, and miR‐425) in combination with stage separated patients by recurrence‐free survival (RFS) and overall survival (OS) and improved prediction of recurrence over stage alone in both the training and validation cohorts (training RFS and OS, P < .001; validation RFS, P < .001; OS, P = .005). Serum miR‐15b levels significantly increased over time in recurrent patients (P < .001), adjusting for endogenous controls as well as age, sex, and initial stage. In nonrecurrent patients, miR‐15b levels were not significantly changed with time (P =.17).CONCLUSIONSData demonstrate that serum miRNAs can improve melanoma patient stratification over stage and support further testing of miR‐15b to guide patient surveillance. Cancer 2015;121:51–59. © 2014 American Cancer Society.
Morphological parameters able to predict BRAFV600E‐mutated malignancies on thyroid fine‐needle aspiration cytology: Our institutional experience
Authors: Rossi Esther Diana , Bizzarro Tommaso , Martini Maurizio , Capodimonti Sara , Fadda Guido , Larocca Luigi Maria , Schmitt Fernando 
Published: August 2014

BACKGROUNDThe BRAFV600E mutation is the most common diagnostic/prognostic marker in papillary thyroid carcinoma (PTC). Its evaluation is typically performed with DNA‐based techniques; nonetheless, a few articles have recently proposed the morphological prediction of BRAFV600E in histological PTCs. We investigated this morphological parameter in our cytological series.METHODSWe re‐analyzed all 72 cytohistological samples diagnosed as positive for malignancy (favoring PTC) on fine‐needle aspiration cytology from January 2012 to December 2013. We included 22 male patients and 50 female patients. The cytological cases were processed with liquid‐based cytology. We performed molecular analysis and immunocytochemistry for the VE1 BRAFV600E antibody.RESULTSWe reported 47 mutated cases and 25 wild‐type (WT) cases with 100% cytohistological concordance. The cytological evaluations revealed plump cells (abundant eosinophilic cytoplasm and PTC nuclei) in all 47 mutated cases, with only 6 having a focal plump cell component (≤20% cells). Furthermore, 5 of the 25 WT cases showed focal plump cells. A distinctive sickle nuclear shape was found only in the mutated cases. VE1 yielded 100% positivity for all 24 mutated cases that were tested, including 3 cases with focal plump cells.CONCLUSIONSWe demonstrated that the BRAFV600E mutation might be predicted in cytological samples on the basis of some specific morphological features. Although the detection of plump cells (mainly focal) was also observed in WT cases, the detection of sickle‐shaped nuclei provided the highest specificity and sensitivity as a predictive mutational parameter. These morphological features might be a valid tool for selecting cases for molecular analysis. Cancer (Cancer Cytopathol) 2014;122:883–891. © 2014 American Cancer Society.
In Situ Encapsulation of Germanium Clusters in Carbon Nanofibers: High‐Performance Anodes for Lithium‐Ion Batteries
Authors: Wang Wei , Xiao Ying , Wang Xia , Liu Bing , Cao Minhua 
Published: August 2014

AbstractAlloyed anode materials for lithium‐ion batteries (LIBs) usually suffer from considerable capacity losses during charge–discharge process. Herein, in situ‐grown germanium clusters are homogeneously encapsulated into porous nitrogen‐doped carbon nanofibers (N‐CNFs) to form Ge/N‐CNFs hybrids, using a facile electrospinning method followed by thermal treatment. When used as anode in LIBs, the Ge/N‐CNFs hybrids exhibit excellent lithium storage performance in terms of specific capacity, cycling stability, and rate capability. The excellent electrochemical properties can be attributed to the unique structural features: the distribution of the germanium clusters, porous carbon nanofibers, and GeN chemical bonds all contribute to alleviating the large volume changes of germanium during the discharge–charge process, while at same time the unique porous N‐CNFs not only increase the contact area between the electrode and the electrolyte, but also the conductivity of the hybrid.
Multiple Cathodic Reaction Mechanisms in Seawater Cathodic Biofilms Operating in Sediment Microbial Fuel Cells
Authors: Babauta Jerome T. , Hsu Lewis , Atci Erhan , Kagan Jeff , Chadwick Bart , Beyenal Haluk 
Published: August 2014

AbstractIn this study, multiple reaction mechanisms in cathodes of sediment microbial fuel cells (SMFCs) were characterized by using cyclic voltammetry and microelectrode measurements of dissolved oxygen and pH. The cathodes were acclimated in SMFCs with sediment and seawater from San Diego Bay. Two limiting current regions were observed with onset potentials of approximately +400 mVAg/AgCl for limiting current I and −120 mVAg/AgCl for limiting current II. The appearance of two catalytic waves suggests that multiple cathodic reaction mechanisms influence cathodic performance. Microscale oxygen concentration measurements showed a zero surface concentration at the electrode surface for limiting current II but not for limiting current I, which allowed us to distinguish limiting current II as the conventional oxygen reduction reaction and limiting current I as a currently unidentified cathodic reaction mechanism. Microscale pH measurements further confirmed these results.
New Organic Donor–Acceptor–π–Acceptor Sensitizers for Efficient Dye‐Sensitized Solar Cells and Photocatalytic Hydrogen Evolution under Visible‐Light Irradiation
Authors: Li Xing , Cui Shicong , Wang Dan , Zhou Ying , Zhou Hao , Hu Yue , Liu Jin‐gang , Long Yitao , Wu Wenjun , Hua Jianli , Tian He 
Published: August 2014

AbstractTwo organic donor–acceptor–π–acceptor (D‐A‐π‐A) sensitizers (AQ and AP), containing quinoxaline/pyrido[3,4‐b]pyrazine as the auxiliary acceptor, have been. Through fine‐tuning of the auxiliary acceptor, a higher designed and synthesized photoelectric conversion efficiency of 6.02 % for the AQ‐based dye‐sensitized solar cells under standard global AM1.5 solar conditions was achieved. Also, it was found that AQ‐Pt/TiO2 photocatalysts displayed a better rate of H2 evolution under visible‐light irradiation (420 nm<λ<780 nm) because of the stability of the oxidized states and the lower rates of electron recombination. Importantly, sensitizers AQ and AP‐Pt/TiO2 showed strong photocatalytic activity during continuous light soaking for 10 h with methanol as the sacrificial electron donor. Additionally, the processes of their intermolecular electron transfer were further investigated theoretically by using time‐dependent DFT. The calculated results indicate that the auxiliary acceptor plays the role of an electron trap and results in broad spectral responses.