bluuebunny/crossref_metadata_2025 huggingface dataset:
Whole arm deletions of 18p: Medical and developmental effects
Authors: Sebold Courtney , Soileau Bridgette , Heard Patricia , Carter Erika , O'Donnell Louise , Hale Daniel E. , Cody Jannine D.
Published: January 2015

Deletions of the short arm of chromosome 18 have been well‐described in case reports. However, the utility of these descriptions in clinical practice is limited by varied and imprecise breakpoints. As we work to establish genotype–phenotype correlations for 18p‐, it is critical to have accurate and complete clinical descriptions of individuals with differing breakpoints. In addition, the developmental profile of 18p‐ has not been well‐delineated. We undertook a thorough review of the medical histories of 31 individuals with 18p‐ and a breakpoint in the centromeric region. We collected developmental data using mailed surveys and questionnaires. The most common findings included neonatal complications; cardiac anomalies; hypotonia; MRI abnormalities; endocrine dysfunction; strabismus; ptosis; and refractive errors. Less common features included holoprosencephaly and its microforms; hearing loss; and orthopedic anomalies. The developmental effects of the deletion appear to be less severe than reported in the literature, as average IQ scores were in the range of borderline intellectual functioning. Based on responses to standardized questionnaires, it appears this population has marked difficulty with activities of daily living, though several young adults were able to live independent of their parents. This manuscript represents the most comprehensive description of a cohort of 18p‐ individuals with identical breakpoints. Despite identical breakpoints, a great deal of phenotype variability remained among this population, suggesting that many of the genes on 18p‐ cause low‐penetrance phenotypes when present in a hemizygous state. Future efforts will focus on the clinical description of individuals with more distal breakpoints and the identification of critical regions and candidate genes. © 2015 Wiley Periodicals, Inc.
Kontrollierte Freisetzung von verkapselten flüchtigen bioaktiven Verbindungen durch Brechen der Kapselwand als Folge einer lichtinduzierten Gasbildung
Authors: Paret Nicolas , Trachsel Alain , Berthier Damien L. , Herrmann Andreas
Published: January 2015

Die Verkapselung lichtempfindlicher 2‐Oxoacetate in Mikrokapseln mit Kern‐Schale‐Struktur ermöglicht eine lichtinduzierte, kontrollierte Freisetzung biologisch aktiver Substanzen. Durch Bestrahlung mit UVA‐Licht zersetzen sich die verkapselten Oxoacetate und bilden einen Gasüberdruck im Inneren der Kapseln, der die Kapselwand ausdehnt oder zum Bersten bringt. Headspace‐Messungen bestätigten die lichtgesteuerte Bildung von CO und CO2 sowie die erfolgreiche Freisetzung der biologisch aktiven Substanz. Mittels optischer Mikroskopie konnten die Bildung von Gasblasen, das Aufbrechen der Kapselwand sowie das Austreten der verkapselten Ölphase beobachtet werden. Die Effizienz des Freisetzungssystems beruht auf der Struktur und der Menge des im Verhältnis zur Wandstärke verwendeten 2‐Oxoacetats und auf der Intensität des einstrahlenden UVA‐Lichtes.
Intermolecular Enantioselective Dearomatization Reaction of β‐Naphthol Using meso‐Aziridine: A Bifunctional In Situ Generated Magnesium Catalyst
Authors: Yang Dongxu , Wang Linqing , Han Fengxia , Li Dan , Zhao Depeng , Wang Rui
Published: January 2015

A direct, facile, and highly diastereo‐ and enantioselective dearomatization reaction of β‐naphthol derivatives with aziridines has been developed for the first time. A newly designed Box–OH ligand was employed for an in situ generated magnesium catalyst and proved to be efficient. The corresponding dearomatization product was transformed into a polycyclic scaffold and polyhydroxylated compound. 1H NMR studies revealed the activation mode of the dearomatization process of β‐naphthols, and a clear positive nonlinear effect was observed in the reaction, and provides insight into the coordination environment around the MgII center and the possible active species.
Susceptibility of Candida albicans to New Synthetic Sulfone Derivatives
Authors: Staniszewska Monika , Bondaryk Małgorzata , Ochal Zbigniew
Published: January 2015

The influence of halogenated methyl sulfones, i.e. bromodichloromethyl‐4‐chloro‐3‐nitrophenyl sulfone (named halogenated methyl sulfone 1), dichloromethyl‐4‐chloro‐3‐nitrophenyl sulfone (halogenated methyl sulfone 2), and chlorodibromomethyl‐4‐hydrazino‐3‐nitrophenyl sulfone (halogenated methyl sulfone 3), on cell growth inhibition, aspartic protease gene (SAP4–6) expression, adhesion to epithelium, and filamentation was investigated. Antifungal susceptibility of the halogenated methyl sulfones was determined with the M27‐A3 protocol in the range of 16–0.0313 µg/mL. Adherence to Caco‐2 cells was performed in 24‐well plates; relative quantification was normalized against ACT1 in cells after 18 h of growth in YEPD and on Caco‐2 cells. SAP4–6 expression was analyzed using RT‐PCR. Structure–activity relationship studies suggested that halogenated methyl sulfone 1 containing bromodichloromethyl or dichloromethyl function at C‐4 (halogenated methyl sulfone 2) of the phenyl ring showed the best activity (100% cell inhibition at 0.5 µg/mL), while hydrazine at C‐1 (halogenated methyl sulfone 3) reduced the sulfone potential (100% = 4 µg/mL). SAP4–6 were up‐ or down‐regulated depending on the strains’ genetic background and the substitutions on the phenyl ring. Halogenated methyl sulfone 2 repressed germination and affected adherence to epithelium (P ≤ 0.05). The tested halogenated methyl sulfones interfered with the adhesion of Candida albicans cells to the epithelial tissues, without affecting their viability after 90 min of incubation. The mode of action of the halogenated methyl sulfones was attributed to the reduced virulence of C. albicans. SAP5 and SAP6 contribute to halogenated methyl sulfones resistance. Thus, halogenated methyl sulfones can inhibit biofilm formation due to their interference with adherence and with the yeast‐to‐hyphae transition.
Bisphenol A Exposure in Children With Autism Spectrum Disorders
Authors: Stein T. Peter , Schluter Margaret D. , Steer Robert A. , Guo Lining , Ming Xue
Published: January 2015

The etiology of autism spectrum disorders (ASD) is believed to involve genetic and environmental components. This study focused on the plasticizer, Bisphenol‐A (BPA). The major pathway for BPA metabolism and excretion is via glucuronidation. To determine whether there was a relationship between BPA exposure and ASD, urine specimens were collected from 46 children with ASD and 52 controls. Free and total BPA concentrations were determined by mass spectrometry. The fraction glucuronidated was calculated from the difference. A metabolomics study was done to investigate metabolite distribution in the urine. (i) Most of the BPA excreted in the urine was as the glucuronide; (ii) about 20% of the ASD children had BPA levels beyond the 90th percentile (>50 ng/mL) of the frequency distribution for the total sample of 98 children; (iii) Mann–Whitney U tests and multiple regression analyses found significant differences (P < 0.05) between the groups in total and % bound BPA; and (iv) the metabolomics analyses showed the number of absolute partial correlations >|0.30| between metabolite concentrations and total BPA was ∼3 times greater with the ASD group than the controls (P < 0.001), and the number of absolute partial correlations > |0.30| for % bound BPA was ∼15 times higher with ASD (P < 0.001). The results suggest there is an association between BPA and ASD. Autism Res 2015, 8: 272–283. © 2015 International Society for Autism Research, Wiley Periodicals, Inc.
Failure-to-rescue and interprovider comparisons after elective abdominal aortic aneurysm repair
Authors: Sinha S , Ata Ozdemir B , Khalid U , Karthikesalingam A , Poloniecki J D , Thompson M M , Holt P J E
Published: January 2015

Background

The use of postoperative complication rates to derive metrics such as failure-to-rescue (FTR) is of increasing interest in assessing the quality of care. The aim of this study was to quantify FTR rates for elective abdominal aortic aneurysm (AAA) repair in England using administrative data, and to examine its validity against case-note review.

Methods

A retrospective observational study using Hospital Episode Statistics (HES) data was combined with a multicentre audit of data quality. All elective AAA repairs done in England between 2005 and 2010 were identified. Postoperative complications were extracted, FTR rates quantified, and differences in FTR and in-hospital death rates established. A multicentre case-note review was performed to establish the accuracy of coding of complications, and the impact of inaccuracies on FTR rates derived from HES data.

Results

A total of 19 638 elective AAA repairs were identified from HES; the overall mortality rate was 4·6 per cent. Patients with complications (19·2 per cent) were more likely to die than those without complications (odds ratio 12·22, 95 per cent c.i. 10·51 to 14·21; P < 0·001) and had longer hospital stays (P < 0·001). FTR rates correlated strongly with death rates, whereas complication rates did not. On case-note review (661 procedures), 41·5 per cent of patients had a complication recorded in the case notes. There was evidence of systematic under-reporting of complications in HES, leading to an overall misclassification rate of 36·3 (95 per cent c.i. 33·7 to 39·2) per cent (P < 0·001), which was less pronounced for surgical complications (12·6 (11·1 to 13·9) per cent; P <0·001). Despite this, the majority of FTR rates derived from HES were not significantly different from those derived from case-note data.

Conclusion

Postoperative complication and FTR rates after elective AAA repair can be derived from HES data. However, use of the metric for interprovider comparisons should be done cautiously, and only with concurrent case-note validation given the degree of miscoding identified.
Synthesis of Lysozyme–Metallacarborane Conjugates and the Effect of Boron Cluster Modification on Protein Structure and Function
Authors: Kowalski Konrad , Goszczyński Tomasz , Leśnikowski Zbigniew J. , Boratyński Janusz
Published: January 2015

Two complementary methods, “in solution” and “in solid state”, for the synthesis of lysozyme modified with metallacarborane (cobalt bis(dicarbollide), Co(C2B9H11)22−) were developed. As metallacarborane donors, oxonium adducts of cobalt bis(dicarbollide) and 1,4‐dioxane or tetrahydropyran were used. The physicochemical and biochemical properties of the obtained lysozyme–metallacarborane conjugates were studied for changes in secondary and tertiary structure, aggregation behavior, and biological activity. Only minor changes in primary, secondary, and tertiary protein structure were observed, caused by the single substitution of metallacarborane on lysozyme. However, the modification produced significant changes in lysozyme enzymatic activity and a tendency toward time‐ and temperature‐dependent aggregation.
Feasibility and safety of left ventricular endomyocardial biopsy via transradial access: Technique and initial experience
Authors: Schulz Eberhard , Jabs Alexander , Gori Tommaso , Hink Ulrich , Sotiriou Efthymios , Tschöpe Carsten , Schultheiss Heinz‐Peter , Münzel Thomas , Wenzel Philip
Published: January 2015

Background

Endomyocardial biopsy constitutes an essential part of the diagnostic algorithm in patients with heart failure of unknown origin, but usually requires transfemoral access.

Methods and Results

Here, we describe a novel method that allows interventional cardiologists to obtain left ventricular biopsies via transradial access with a 7.5F sheathless multipurpose (MP1.0) guiding catheter. This approach was successfully conducted in 37 consecutive patients at our institution with only one intraprocedural minor complication (ventricular fibrillation during insertion of the guiding catheter).

Conclusions

Transradial access to obtain left ventricular endomyocardial biopsies is a feasible and safe option for experienced radial operators. © 2015 Wiley Periodicals, Inc.
An Alkene‐Promoted Borane‐Catalyzed Highly Stereoselective Hydrogenation of Alkynes to Give Z‐ and E‐Alkenes
Authors: Liu Yongbing , Hu Lianrui , Chen Hui , Du Haifeng
Published: January 2015

The stereoselective hydrogenation of alkynes to alkenes is an extremely useful transformation in synthetic chemistry. Despite numerous reports for the synthesis of Z‐alkenes, the hydrogenation of alkynes to give E‐alkenes is still not well resolved. In particular, selective preparation of both Z‐ and E‐alkenes by the same catalytic hydrogenation system using molecular H2 has rarely been reported. In this paper, a novel strategy of using simple alkenes as promoters for the HB(C6F5)2‐catalyzed metal‐free hydrogenation of alkynes was adopted. Significantly, both Z‐ and E‐alkenes can be furnished by hydrogenation with molecular H2 in high yields with excellent stereoselectivities. Further experimental and theoretical mechanistic studies suggest that interactions between H and F atoms of the alkene promoter, borane intermediate, and H2 play an essential role in promoting the hydrogenolysis reaction.
An Iron‐Catalyzed Cascade Approach to Benzo[b]carbazole Synthesis Followed by 1,4‐Sulfonyl Migration
Authors: Boominathan Siva Senthil Kumar , Senadi Gopal Chandru , Vandavasi Jaya Kishore , Chen Jeff Yi‐Fu , Wang Jeh‐Jeng
Published: January 2015

A simple and straightforward approach was developed to construct 5H‐benzo[b]carbazole derivatives by iron catalysis in a cascade sequence. The notable features of this work include an atom‐economical cascade sequence, unprecedented 1,4‐sulfonyl migration, tolerance of a variety of functional groups, good yields, and an economical catalytic system.
Practical Synthesis of anti‐β‐Hydroxy‐α‐Amino Acids by PdII‐Catalyzed Sequential C(sp3)H Functionalization
Authors: Chen Kai , Zhang Shuo‐Qing , Jiang Huai‐Zhi , Xu Jing‐Wen , Shi Bing‐Feng
Published: January 2015

An improved and practical procedure for the stereoselective synthesis of anti‐β‐hydroxy‐α‐amino acids (anti‐βhAAs), by palladium‐catalyzed sequential C(sp3)H functionalization directed by 8‐aminoquinoline auxiliary, is described. followed by a previously established monoarylation and/or alkylation of the β‐methyl C(sp3)H of alanine derivative, β‐acetoxylation of both alkylic and benzylic methylene C(sp3)H bonds affords various anti‐β‐hydroxy‐α‐amino acid derivatives. As an example, the synthesis of β‐mercapto‐α‐amino acids, which are highly important to the extension of native chemical ligation chemistry beyond cysteine, is described. The synthetic potential of this protocol is further demonstrated by the synthesis of diverse β‐branched α‐amino acids. The observed diastereoselectivities are strongly influenced by electronic effects of aromatic AAs and steric effects of the linear side‐chain AAs, which could be explained by the competition of intramolecular COAc bond reductive elimination from PdIV intermediates vs. intermolecular attack by an external nucleophile (AcO−) in an SN2‐type process.
Fullerene–Ionic‐Liquid Conjugates: A New Class of Hybrid Materials with Unprecedented Properties
Authors: Campisciano Vincenzo , La Parola Valeria , Liotta Leonarda F. , Giacalone Francesco , Gruttadauria Michelangelo
Published: January 2015

A modular approach has been followed for the synthesis of a series of fullerene–ionic‐liquid (IL) hybrids in which the number of IL moieties (two or twelve), anion, and cation have been varied. The combination of C60 and IL give rise to new unique properties in the conjugates such as solubility in water, which was higher than 800 mg mL−1 in several cases. In addition, one of the C60–IL hybrids has been employed for the immobilization of palladium nanoparticles through ion exchange followed by reduction with sodium borohydride. Surprisingly, during the reduction several carbon nanostructures were formed that comprised nano‐onions and nanocages with few‐layer graphene sidewalls, which have been characterized by means of thermogravimetric analysis (TGA), X‐ray photoelectron spectroscopy (XPS), X‐ray diffraction (XRD), scanning electron microscopy/energy‐dispersive X‐ray analysis (SEM‐EDAX), and high‐resolution transmission electron microscopy (HRTEM). Finally, the material thus obtained was successfully applied as catalyst in Suzuki and Mizoroki–Heck reactions in a concentration of just 0.2 mol %. In the former process it was recyclable for five runs with no loss in activity.
An Approach towards Synthesis of Nanoarchitectured LiNi1/3Co1/3Mn1/3O2 Cathode Material for Lithium Ion Batteries
Authors: Hua Weibo , Wang Yanjie , Zhong Yanjun , Wang Guoping , Zhong Benhe , Fang Baizeng , Guo Xiaodong , Liao Shixuan , Wang Haijiang
Published: January 2015

To explore advanced cathode materials for lithium ion batteries (LIBs), a nanoarchitectured LiNi1/3Co1/3Mn1/3O2 (LNCM) material is developed using a modified carbonate coprecipitation method in combination with a vacuum distillation‐crystallisation process. Compared with the LNCM materials produced by a traditional carbonate coprecipitation method, the prepared LNCM material synthesized through this modified method reveals a better hexagonal layered structure, smaller particle sizes (ca. 110.5 nm), and higher specific surface areas. Because of its unique structural characteristics, the as‐prepared LNCM material demonstrates excellent electrochemical properties including high rate capability and good cycleability when it is utilized as a cathode in the lithium ion battery (LIB).
Sensitive Determination of Five Priority Haloacetic Acids by Electromembrane Extraction with Capillary Electrophoresis
Authors: Zhang Xiaoli , Zhang Haitao , Liu Yan , Guo Lin , Ye Jiannong , Chu Qingcui
Published: January 2015

A method for sensitive determination of five priority haloacetic acids in drinking water has been developed for the first time based on electromembrane extraction (EME) prior to CZE with capacitively coupled contactless conductivity detection (CZE‐C4D). The target analytes were extracted from 10 mL of the sample solution (donor phase), through the supported liquid membrane (using a polypropylene membrane supporting 1‐octanol), and into 10 µL of 50 mmol/L NaAc solution (acceptor phase). The extracted solution was directly analyzed by CZE‐C4D without derivatization. Several factors that affect separation, detection and extraction efficiency were investigated. Under the optimum conditions, five haloacetic acids (monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, monobromoacetic acid, and dibromoacetic acid) could be well separated from other components coexisting in water samples within 23 min, exhibiting a linear calibration over two orders of magnitude (r⪖0.9943); the enrichment factors at 430–671 were obtained in a 30 min of extraction, and the limits of detection were in the range of 0.17–0.61 ng/mL. The intraday relative standard deviations for peak areas investigated at 10 ng/mL were between 1.2% and 9.7% for the combined EME‐CZE‐C4D procedure. This approach offers an attractive alternative to the officially proposed method for purified drinking water analysis, which requires derivatization procedure prior to gas chromatography analysis.
Transition Metal Free Chemoselective Reduction of α,β‐Unsaturated Ketones to Saturated Ketones Using Tosyl Hydrazide as a Hydrogen Donor
Authors: Girish Yarabally R , Raghavendra Kanchipura R , Nagaraja Dasappa , Kumar Kothanahally S Sharath , Shashikanth Sheena
Published: January 2015

An efficient, inexpensive and simple method for the reduction of various α,β‐unsaturated ketones to corresponding saturated ketones using tosyl hydrazide as a hydrogen donor in DMF using calcium oxide powder has been reported. A variety of enones underwent reduction without forming undesirable side products. High chemoselectivity, broad functional group tolerance and good yields are the noteworthy features of this protocol.
Interaction of Plasma Proteins with Tri‐quaternary Ammonium Salt Cationic Surfactant Studied by QCM‐D
Authors: Xi Man , Zhang Baoyan
Published: January 2015

A tri‐quaternary ammonium salt cationic surfactant was synthesized. Its structure was confirmed by using Fourier‐transform infrared spectroscopy, 1H nuclear magnetic resonance spectroscopy, and X‐ray photoelectron spectroscopy analyses. Three model surfaces, including Au‐CH3, Au‐OH and Au‐COOH, were fabricated. Adsorptions of surfactant on the three model surfaces and subsequent plasma proteins adsorption were investigated by quartz crystal microbalance with dissipation (QCM‐D). The mass of surfactant on the Au‐COOH surface was the largest, followed by that on the Au‐CH3 surface, and that on the Au‐OH surface. These results suggested that the main driving force of surfactant immobilization was electrostatic interaction followed by hydrophobic interaction. Based on the results obtained, we concluded that the protein mass adsorbed on Au‐CH3‐S, Au‐OH‐S, and Au‐COOH‐S surfaces depended on the protein size and orientation. The mass and thickness of S on the Au‐COOH surface is the largest and the protein adsorption capacity of Au‐COOH‐S surface is inferior to that of Au‐CH3‐S. The Au‐COOH‐S surface could inhibit lysozyme adsorption, maintain the adsorption balance of bovine serum albumin, and induce fibrinogen‐binding protein adsorption.
Highly Enantioselective Direct Asymmetric Aldol Reaction Catalyzed by 4,5‐Methano‐L‐proline
Authors: Zhang Yukun , Zhu Jun , Yu Na , Yu Han
Published: January 2015

The 4,5‐methano‐L‐proline was used as chiral organocatalysts in direct asymmetric aldol reactions. Under the optimal conditions, excellent enantioselectivities (up to 99% ee) were obtained with high chemical yields (up to 95%) for a series of aldehydes using only 5 mol% catalyst loading. To show the practicality of the method, the reaction was tested at a large scale. The reaction was complete in 16 h, and the aldol product was obtained in 86% yield and 93% ee.
Synthesis and Catalytic Activity of a Grubbs‐Hoveyda Pre‐catalyst Having a Trimeric Resting State
Authors: Liu Guiyan , Wu Bin , Wang Jianhui
Published: January 2015

A Grubbs‐Hoveyda pre‐catalyst having a trimeric resting state based on 2,4,6‐trichloro‐1,3,5‐triazine was synthesized and the complex was characterized by NMR, HRMS and elemental analysis. The activity of this complex for ring‐closing metathesis (RCM) was investigated. The catalytic system possesses high catalytic activity for many different olefin substrates.
Non‐parametric generalized linear mixed models in small area estimation
Authors: Torabi Mahmoud , Shokoohi Farhad
Published: January 2015

Mixed models are commonly used for the analysis of small area estimation. In particular, small area estimation has been extensively studied under linear mixed models. Recently, small area estimation under the linear mixed model with penalized spline (P‐spline) regression model, for fixed part of the model, has been proposed. However, in practice there are many situations that we have counts or proportions in small areas; for example a dataset on the number of asthma physician visits in small areas in Manitoba. In particular, the covariates age, genetic, environmental factors, among other covariates seem to predict asthma physician visits, however, these relationships may not be linear (see Section 5). In this paper, small area estimation under generalized linear mixed models using P‐spline regression models is proposed to cover Normal and non‐Normal responses. In particular, the empirical best predictor of small area parameters with corresponding prediction intervals are studied. The performance of the proposed approach is evaluated through simulation studies and also by a real dataset. The Canadian Journal of Statistics 43: 82–96; 2015 © 2015 Statistical Society of Canada
Synthesis and Characterization of Bio‐Inspired Diiron Complexes and Their Catalytic Activity for Direct Hydroxylation of Aromatic Compounds
Authors: Wang Xiao , Zhang Tianyong , Yang Qiusheng , Jiang Shuang , Li Bin
Published: January 2015

Three [FeFe]‐hydrogenase model complexes [(μ‐dmedt){Fe(CO)3}2] [1; dmedt = SCH(CH3)CH(CH3)S], [(μ‐dmedt){Fe(CO)3}{Fe (CO)2PPh3}] (1‐PPh3), and [(μ‐dmest){Fe(CO)3}2] [1‐O; dmest = SCH(CH3)CH(CH3)S(O)], 1‐O were synthesized and characterized. These model complexes, which are generally used as the functional biomimics of the hydrogen‐producing dinuclear active site in [FeFe]‐hydrogenase, were used as efficient catalysts for the selective hydroxylation of aromatic compounds to phenols under mild conditions. Because both the dithiolato‐sulfur site and the Fe–Fe bond in the model complexes were possible active oxidation sites, DFT calculations were used to investigate the oxygenated products, that is, the S‐oxygenated products or the Fe‐oxygenated forms of the model complexes, which may be involved in the catalytic cycle. The experimental and computational results indicate that the thermodynamically favored Fe‐oxygenated intermediates dominate the hydroxylation of the aromatic compounds. A possible mechanism for the hydroxylation is also proposed.
Pyrididine–Carboxylate Ligands as Double‐Bridge Spacers in CuI Metallacycles
Authors: Wu Xialu , Zhang Wenhua , Zhang Xinhai , Ding Nini , Hor T. S. Andy
Published: January 2015

The addition of pyridine‐3‐carboxylic acid (3‐PyCOOH), (E)‐3‐(pyridin‐3‐yl)acrylic acid (3‐PyCH=CHCOOH), or 3‐(pyridin‐4‐yl)benzoic acid (3‐PyPhCOOH) to the Lewis acidic [Cu(dppf)(NCMe)2][BF4]·2MeCN·2H2O [1·2MeCN·2H2O, dppf = 1,1′‐bis(diphenylphosphanyl)ferrocene] in the presence of NEt3 afforded the complexes [Cu2(dppf)2(3‐PyCOO)2]·3CHCl3 (2·3CHCl3), [Cu2(dppf)2(3‐PyCH=CHCOO)2]·CH2Cl2·C6H14 (3·CH2Cl2·C6H14), and [Cu2(dppf)2(3‐PyPhCOO)2]·CH2Cl2 (4·CH2Cl2) with a common metallomacrocycle core and doubly bridging pyridine–carboxylate ligands as spacers. These dinuclear complexes have been structurally characterized by single‐crystal X‐ray crystallography, and their emission activities have been studied.
Photoluminescent One‐Dimensional Coordination Polymers from Suitable Pyridine Antenna and LnCl3 for Visible and Near‐IR Emission
Authors: Matthes Philipp R. , Eyley Jennifer , Klein Johannes H. , Kuzmanoski Ana , Lambert Christoph , Feldmann Claus , Müller‐Buschbaum Klaus
Published: January 2015

The series of one‐dimensional coordination polymers ∞1[LnCl3(bipy)(py)2]·py [bipy = 4,4′‐bipyridine, py = pyridine; Ln = Gd, Tb, Dy, Ho, Er, Yb] as well as ∞1[Lu2Cl5(bipy)2(py)4]∞1[LuCl4(bipy)] were synthesized by the reactions of anhydrous LnCl3 with bipy and py. The formation of extended zigzag chains and saltlike band structures with cationic and anionic strands is observed. Pyridine and 4,4′‐bipyridine ligands serve as suitable antennas for lanthanide‐based luminescence in the visible and near‐infrared range through effective sensitization by the ligands followed by emission through the emissive intra‐4f transitions of the Ln3+ (Tb3+, Dy3+, Er3+, Yb3+) ions. For ∞1[GdCl3(bipy)(py)2]·py, phosphorescence of the coordinated 4,4′‐bipyridine ligand with excitation‐dependent chromaticity leads to ligand‐based emission in the visible range. These processes cannot be observed for the free ligand. The coordination polymers also extend the range of photoluminescence properties of related complexes and metal–organic frameworks (MOFs) and show high efficiency with a quantum yield of 86 % for the Tb3+ compound.
Rhenium(I) Complexes with Alkynylphosphane Ligands: Structural, Photophysical, and Theoretical Studies
Authors: Kondrasenko Ilya , Kisel Kristina S. , Karttunen Antti J. , Jänis Janne , Grachova Elena V. , Tunik Sergey P. , Koshevoy Igor O.
Published: January 2015

A family of mono‐ and bidentate alkynylphosphanes has been used for the preparation of the rhenium(I) phenanthroline complexes [Re(phen)(CO)2(L)2]+ (L = monophosphane), [{Re(phen)(CO)3}2(L)]2+ (L = diphosphane), and [{Re(phen)(CO)2}2(L)2]2+ (L = diphosphane). The dicarbonyl compounds display intense luminescence at 298 K both in solution and in the solid state (Φem ≤ 44 %). The tricarbonyl complexes demonstrate a strong dependence of the emission efficiency on the ancillary ligand L through a pronounced π–π* contribution of the diphosphane to the electronic transitions, as confirmed by TDDFT studies. In the solid state, the complexes [Re(phen)(CO)2(L)2]+ display significant luminescence rigidochromism that is influenced by the structure of the phosphane substituents. The latter provide a means to fine‐tune the photophysical properties of this class of luminophores through variation of the stereochemical characteristics of the ligands that are not directly involved in the electronic transitions.
Size and medium conductivity dependence on dielectrophoretic behaviors of gas core poly‐l‐lysine shell nanoparticles
Authors: Yang Chungja , Wu Chun‐Jen , Ostafin Agnes E. , Thibaudeau Giselle , Minerick Adrienne R.
Published: January 2015

Dynamic (dis)assembly of biocompatible nanoparticles into 3D, packed structures would benefit drug delivery, films, and diagnostics. Dielectrophoretic (DEP) microdevices can rapidly assemble and manipulate polarizable particles within nonuniform electric fields. DEP has primarily discerned micrometer particles since nanoparticles experience smaller forces. This work examines conductivity and size DEP dependencies of previously unexplored spherical core‐shell nanoparticle (CSnp) into 3D particle assemblies. Poly‐l‐lysine shell material was custom synthesized around a gas core to form CSnps. DEP frequencies from 1 kHz to 80 MHz at fixed 5 volts peak‐to‐peak and medium conductivities of 10−5 and 10−3 S/m were tested. DEP responses of ∼220 and ∼400 nm poly‐l‐lysine CSnps were quantified via video intensity densitometry at the microdevice's quadrapole electrode center for negative DEP (nDEP) and adjacent to electrodes for positive DEP. Intensity densitometry was then translated into a relative DEP response curve. An unusual nDEP peak occurred at ∼57 MHz with 25–80 times greater apparent nDEP force. All electrical circuit components were then impedance matched, which changed the observed response to weak positive DEP at low frequencies and consistently weak nDEP from ∼100 kHz to 80 MHz. This impedance‐matched behavior agrees with conventional Clausius–Mossotti DEP signatures taking into account the gas core's contributions to the polarization mechanisms. This work describes a potential pitfall when conducting DEP at higher frequencies in microdevices and concurrently demonstrates nDEP behavior for a chemically and structurally distinct particle system. This work provides insight into organic shell material properties in nanostructures and strategies to facilitate dynamic nanoparticle assemblies.
Electrochemical hematocrit determination in a direct current microfluidic device
Authors: Lee Hwi Yong , Barber Cedrick , Rogers Jessika A. , Minerick Adrienne R.
Published: January 2015

Hematocrit (HCT) tests are widely performed to screen blood donors and to diagnose medical conditions. Current HCT test methods include conventional microhematocrit, Coulter counter, CuSO4 specific gravity, and conductivity‐based point‐of‐care (POC) HCT devices, which can be either expensive, environmentally inadvisable, or complicated. In the present work, we introduce a new and simple microfluidic system for a POC HCT determination. HCT was determined by measuring current responses of blood under 100 V DC for 1 min in a microfluidic device containing a single microchannel with dimensions of 180 μm by 70 μm and 10 mm long. Current responses of red blood cell (RBC) suspensions in PBS or separately plasma at HCT concentrations of 10, 20, 25, 30, 35, 40, 45, 50, 55, 60, and 70 vol% were measured to show feasibility of the microfluidic system for HCT determination. Key parameters affecting current responses included electrolysis bubbles and irreversible RBC adsorption; parameters were optimized via addition of nonionic surfactant Triton X‐100 into sample solution and carbonizing electrode surfaces. The linear trend line of current responses over a range of RBC concentrations were obtained in both PBS and plasma. This work suggested that a simple microfluidic device could be a promising platform for a new POC HCT device.
Determination of pyruvate and lactate as potential biomarkers of embryo viability in assisted reproduction by capillary electrophoresis with contactless conductivity detection
Authors: Mádr Aleš , Celá Andrea , Klejdus Bořivoj , Pelcová Marta , Crha Igor , Žáková Jana , Glatz Zdeněk
Published: January 2015

Human‐assisted reproduction is increasing in importance due to the constantly rising number of couples suffering from infertility issue. A key step in in vitro fertilization is the proper assessment of embryo viability in order to select the embryo with the highest likelihood of resulting in a pregnancy. This study proposes a method based on CE with contactless conductivity detection for the determination of pyruvate and lactate in spent culture media used in human‐assisted reproduction. A fused‐silica capillary of 64.0 cm total length and 50 μm inner diameter was used. The inner capillary wall was modified by the coating of successive layers of the ionic polymers polybrene and dextran sulfate to reverse EOF. The BGE was composed of 10 mM MES/lithium hydroxide, pH 6.50. The sample was injected by pressure 50 mbar for 18 s, separation voltage was set to −24 kV, and capillary temperature to 15°C. The presented method requires only 2 μL of the culture medium, with LODs for pyruvate and lactate of 0.03 and 0.02 μM, respectively. The results demonstrated the method's suitability for the analysis of spent culture media to support embryo viability assessment by light microscopy, providing information about key metabolites of the energy metabolism of a developing embryo.
Combination of IgG N‐glycomics and corresponding transcriptomics data to identify anti‐TNF‐α treatment responders in inflammatory diseases
Authors: Váradi Csaba , Holló Zsolt , Póliska Szilárd , Nagy László , Szekanecz Zoltán , Váncsa Andrea , Palatka Károly , Guttman András
Published: January 2015

Prediction of responsiveness in biological therapies is an important and challenging issue in different diseases. Analyzing glycosylation pattern changes of key serum glycoproteins is one of the possible avenues to follow disease remission. The aim of this study was to investigate the changes of serum IgG glycoforms in Crohn's disease (CD) and rheumatoid arthritis patients in response to antitumor necrosis factor alpha (anti‐TNF‐α) treatment. IgG was isolated from patient serum samples using Protein A affinity pull‐down, followed by the release of N‐glycans with peptide‐N‐glycosidase F. The released glycans were fluorescently tagged with 8‐aminopyrene‐1,3,6‐trisulfonate and analyzed by CGE with laser‐induced fluorescent detection. Significant alterations were detected between responders and nonresponders in both disease groups. In CD patients, disease‐specific alteration was found in response to anti‐TNF‐α therapy, which was also confirmed by transcriptomics data analysis of the corresponding glycosyltransferases and glycosidases.
Cross‐linked aggregation of glutamate decarboxylase to extend its activity range toward alkaline pH
Authors: Dinh Thu Huong , Jang Nan Young , McDonald Karen A , Won Keehoon
Published: January 2015

BACKGROUND

Gamma(γ)‐aminobutyric acid (GABA) is produced through an α‐decarboxylation reaction of L‐monosodium glutamate (MSG) using glutamate decarboxylase (GAD). The pH rise caused by the reaction inactivates the enzyme catalyst, which is active only under acidic conditions, and consequently leads to low reaction conversions. Employment of conventional acids and buffers inevitably forms salts, which result in serious problems in separation and purification of GABA. It is essential to render GAD active even at neutral and alkaline pHs. In the present study, we first apply a cross‐linked aggregation method in order to extend the active range of GAD toward alkaline pH.

RESULTS

GAD from Escherichia coli was prepared as cross‐linked enzyme aggregate (CLEA) in which the enzyme was precipitated using ammonium sulfate (60% saturation) and then cross‐linked with glutaraldehyde (2%) in sodium acetate buffer (0.2 mol L−1, pH 4.6). The cross‐linked aggregation extended an active pH range of GAD from 5.5 up to 8.0; as a result, the reaction conversion of 1 mol L−1 MSG into GABA was improved from 13% to 22%. Moreover, the CLEA of GAD was easily recovered after the reaction and reused retaining >95% of its initial activity during the first four cycles and >60% activity at the 10th cycle.

CONCLUSION

Cross‐linked aggregation could make GAD active even at neutral and alkaline pHs. It is shown to be a useful method capable of facilitating recovery and reuse of the enzyme as well as increasing the reaction conversion by extending the active pH range of GAD. © 2015 Society of Chemical Industry
Lipid degradation and sensory characteristics of ripened sausages packed in modified atmosphere at different carbon dioxide concentrations
Authors: Summo Carmine , Pasqualone Antonella , Paradiso Vito Michele , Centomani Isabella , Centoducati Gerardo , Caponio Francesco
Published: January 2015

BACKGROUND

Conflicting results about the effect of modified atmosphere packaging (MAP) rich in CO2 on the quality of different kinds of meat products are present in the literature. In this study, the degree of lipid degradation and the sensory characteristics of ripened sausages packed in modified atmosphere at three different carbon dioxide (CO2) concentrations were evaluated during 5 months of storage.

RESULTS

The degree of hydrolytic degradation of the lipid fraction was found to decrease with increasing CO2 concentration. Similarly, oxidative phenomena occurred at a lower rate when the CO2 concentration increased. The variations in CO2 concentration influenced the perception of rancid flavor in the examined sausages.

CONCLUSION

An increase in CO2 concentration in MAP slowed down the evolution of lipid oxidation owing to the minor extent of hydrolytic degradation, whose products have pro‐oxidant activity. This effect was more evident in the first 2 months of storage. © 2015 Society of Chemical Industry
Use of switchable hydrophilicity solvents for the homogeneous liquid–liquid microextraction of triazine herbicides from environmental water samples
Authors: Lasarte‐Aragonés Guillermo , Lucena Rafael , Cárdenas Soledad , Valcárcel Miguel
Published: January 2015

A homogeneous liquid–liquid microextraction alternative, based on the use of switchable hydrophilicity solvents, is presented. The extraction technique makes use of 125 μL of a water‐immiscible solvent (N,N‐dimethylcyclohexylamine) that can be solubilized in the aqueous phase in 1:1 ratio using CO2 as a reagent. After the extraction, phase separation is induced by the addition of sodium hydroxide that produces a change on the ionization state of the amine, and centrifugation was not necessary. The extraction technique has been optimized and characterized using the determination of triazine herbicides by gas chromatography with mass spectrometry in water samples. The presence of metallic ions in environmental waters as interferents is easily avoided by the addition of ethylenediaminetetraacetic acid before the microextraction procedure. The proposed method allows the determination of the target analytes at the low microgram per liter range with good precision (relative standard deviation lower than 12.5%).
Do‐It‐Yourself Projects as Path toward Female Empowerment in a Gendered Market Place
Authors: Wolf Marco , Albinsson Pia A. , Becker Cherylynn
Published: January 2015

The role of women as homeowners and heads of households are changing the dynamics in which women engage in do‐it‐yourself (DIY) behavior. Because there is limited extant theory associated with female involvement in DIY behavior, a qualitative study using in‐depth interviews was conducted. Through grounded theory analysis several themes emerged during the coding process, and the themes of empowerment were especially relevant to the informants in this study. Five dimensions of empowerment were identified: empowerment through project initiation, production mastery, adding economic value to goods and services, unleashing creative potential, and empowerment through ownership. The findings show women's involvement in DIY behavior and the consumption of DIY‐related goods is closely tied to the concept of female empowerment.
Consumer–Brand Relationships: A Contrast of Nostalgic and Non‐Nostalgic Brands
Authors: Kessous Aurélie , Roux Elyette , Chandon Jean‐Louis
Published: January 2015

This research examined how consumer–brand relationships change when one contrasts brands perceived as nostalgic with brands perceived as non‐nostalgic. Paired comparisons of brands in six product categories revealed that brand attachment, self‐brand connections, and storytelling, as well as, the propensity to offer the brand as a gift and collect brand‐derived products, depend on the nostalgic status of the brand. On a sample of 606 consumers, the results showed that a brand's nostalgic status has a positive effect on attachment, self‐brand connections, and storytelling. These effects had not previously been considered in nostalgia research. Furthermore, the nostalgic status of a brand has positive effects in terms of intention to purchase the brand as a gift and collect brand‐derived products. Moreover, ANOVA results illustrate that consumer relationships with nostalgic brands are systematically stronger than with non‐nostalgic brands. Finally, results indicated that product category moderates all of the dimensions of brand relationships while gender does not.
Surgical treatment of systemic sclerosis—is it justified to offer peripheral sympathectomy earlier in the disease process?
Authors: Momeni Arash , Sorice Sarah C. , Valenzuela Antonia , Fiorentino David F. , Chung Lorinda , Chang James
Published: January 2015

Purpose

Systemic sclerosis (SSc) is a rare connective tissue disease associated with significant digital vasculopathy. Peripheral sympathectomy is frequently offered late in the disease process after severe digital ischemia has already occurred with patients being symptomatic for numerous years. The purpose of the present study was to analyze the results of peripheral sympathectomy in patients with a confirmed diagnosis of SSc.

Patients and methods

A retrospective analysis of 17 patients (26 hands) who underwent peripheral sympathectomy between January 2003 and September 2013 was performed. Data regarding patient demographics, clinical features, and postoperative outcomes were retrieved. Of note, preoperative pain was present in all patients with a mean duration of 9.6 years prior to peripheral sympathectomy.

Results

Pain improvement/resolution was seen in 24 hands (92.3%). Digital ulcers healed in all patients with only two patients (two hands; 7.7%) requiring surgical intervention for ulcer recurrence 6 months and 4.5 years later. Minor complications were seen in seven hands (26.9%); including infection, wound opening, and stitch abscess, but none required surgical intervention. Seven of eight patients queried would have preferred surgical treatment at an earlier point in the disease process.

Conclusion

Peripheral sympathectomy is a well‐tolerated procedure in patients with SSc and is associated with predictable pain relief and ulcer healing in the majority of patients. In light of these findings it seems prudent to offer surgical treatment not as a last resort but rather earlier in the disease process to decrease the duration that patients suffer pain. © 2015 Wiley Periodicals, Inc. Microsurgery 35:441–446, 2015.
An energy‐momentum method for in‐plane geometrically exact Euler–Bernoulli beam dynamics
Authors: Sansour Carlo , Nguyen Tien Long , Hjiaj Mohammed
Published: January 2015

Nonlinear geometrically exact rod dynamics is of great interest in many areas of engineering. In recent years, the research was focused towards Timoshenko‐type rod theories where shearing is of importance. However, in many general model of mechanisms and spatial deformations, it is desirable to have a displacement‐only formulation, which brings us back to the classical Bernoulli beam. While it is well known for linear analysis, the Bernoulli beam is not as common in geometrically exact models of dynamics, especially when we want to incorporate the rotational inertia into the model. This paper is about the development of an energy‐momentum integration scheme for the geometrically exact Bernoulli‐type rod. We will show that the task is achievable and devise a general framework to do so. Copyright © 2014 John Wiley & Sons, Ltd.
Post‐relapse survival in patients with Ewing sarcoma
Authors: Ferrari Stefano , Luksch Roberto , Hall Kirsten Sundby , Fagioli Franca , Prete Arcangelo , Tamburini Angela , Tienghi Amelia , DiGirolamo Stefania , Paioli Anna , Abate Massimo Eraldo , Podda Marta , Cammelli Silvia , Eriksson Mikael , Brach del Prever Adalberto
Published: January 2015

Background

Post‐relapse survival (PRS) was evaluated in patients with Ewing sarcoma (EWS) enrolled in chemotherapy protocols based on the use of high‐dose chemotherapy with busulfan and melfalan (HDT) as a first‐line consolidation treatment in high‐risk patients.

Procedure

EWS patients enrolled in ISG/SSG III and IV trials who relapsed after complete remission were included in the analysis. At recurrence, chemotherapy based on high‐dose ifosfamide was foreseen, and patients who responded but had not received HDT underwent consolidation therapy with HDT.

Results

Data from 107 EWS patients were included in the analysis. Median time to recurrence (RFI) was 18 months, and 45 (42%) patients had multiple sites of recurrence. Patients who had previously been treated with HDT had a significantly (P = 0.02) shorter RFI and were less likely to achieve a second complete remission (CR2). CR2 status was achieved by 42 (39%) patients. Fifty patients received high‐dose IFO (20 went to consolidation HDT). The 5‐year PRS was 19% (95% CI 11 to 27%). With CR2, the 5‐year PRS was 48% (95% CI 31 to 64%). Without CR2, median time to death was six months (range 1–45 months). According to the multivariate analysis, patients younger than 15 years, recurrence to the lung only, and RFI longer than 24 months significantly influenced the probability of PRS.

Conclusions

Age, pattern of recurrence, RFI, and response to second‐line chemotherapy influence post‐relapse survival in patients with recurrent Ewing sarcoma. No survival advantage was observed from chemotherapy consolidation with HDT. Pediatr Blood Cancer 2015;62:994–999. © 2015 Wiley Periodicals, Inc.