bluuebunny/crossref_metadata_2025 huggingface dataset:
Microsomal protein per gram of liver (MPPGL) in paediatric biliary atresia patients
Authors: De Bock Lies , Boussery Koen , De Bruyne Ruth , Van Winckel Myriam , Stephenne Xavier , Sokal Etienne , Van Bocxlaer Jan
Published: March 2014

The microsomal protein per gram of liver (MPPGL) is an important scaling factor in the in vitro–in vivo extrapolation of metabolic data obtained in liver microsomes. This study aimed to determine the MPPGL in four biliary atresia patients (0.6–1.6 years old) undergoing liver transplantation, as it is known that the MPPGL is affected by age and possibly by liver disease. Due to the presence of bilirubin in the homogenates and microsomes, the NADPH‐cytochrome reductase activity was used to determine the recovery factor, rather than methods using the dithionite difference spectrum. A mean value of 18.73 (± 2.82) mg/g (geometric mean ± SD, n = 4) was observed, which is lower than the expected MPPGL based on the age of the patients (26.60 ± 0.40 mg/g). This suggests a decreased amount of microsomal protein in the livers of biliary atresia patients. Moreover, no differences in MPPGL between different zones of the liver could be detected. Copyright © 2014 John Wiley & Sons, Ltd.
Candidate gene associations with mood disorder, cognitive vulnerability, and fronto‐limbic volumes
Authors: Frazier Thomas W. , Youngstrom Eric A. , Frankel Brian A. , Zunta‐Soares Giovana B. , Sanches Marsal , Escamilla Michael , Nielsen David A. , Soares Jair C.
Published: March 2014

Background

Four of the most consistently replicated variants associated with mood disorder occur in genes important for synaptic function:ANK3(rs10994336),BDNF(rs6265),CACNA1C(rs1006737), andDGKH(rs1170191).

Aims

The present study examined associations between these candidates, mood disorder diagnoses, cognition, and fronto‐limbic regions implicated in affect regulation.

Methods and materials

Participants included 128 individuals with bipolar disorder (33% male, Mean age = 38.5), 48 with major depressive disorder (29% male, Mean age = 40.4), and 149 healthy controls (35% male, Mean age = 36.5). Genotypes were determined by 5′‐fluorogenic exonuclease assays (TaqMan®). Fronto‐limbic volumes were obtained from high resolution brain images using Freesurfer. Chi‐square analyses, bivariate correlations, and mediational models examined relationships between genetic variants, mood diagnoses, cognitive measures, and brain volumes.

Results

Carriers of the minorBDNFandANK3alleles showed nonsignificant trends toward protective association in controls relative to mood disorder patients (P = 0.047).CACNA1Cminor allele carriers had larger bilateral caudate, insula, globus pallidus, frontal pole, and nucleus accumbens volumes (smallestr = 0.13,P = 0.043), and increasedIQ(r = 0.18,P < 0.001).CACNA1Cassociations with brain volumes andIQwere independent; larger fronto‐limbic volumes did not mediate increasedIQ. Other candidate variants were not significantly associated with diagnoses, cognition, or fronto‐limbic volumes.

Discussion and conclusions

CACNA1Cmay be associated with biological systems altered in mood disorder. Increases in fronto‐limbic volumes and cognitive ability associated withCACNA1Cminor allele genotypes are congruent with findings in healthy samples and may be a marker for increased risk for neuropsychiatric phenotypes. Even larger multimodal studies are needed to quantify the magnitude and specificity of genetic‐imaging‐cognition‐symptom relationships.
Nerve entrapment syndromes in musicians
Authors: Wilson Robert J. , Watson Jeffry T. , Lee Donald H.
Published: March 2014

Nerve entrapment syndromes are common in instrumental musicians. Carpal tunnel syndrome, ulnar neuropathy at the elbow, and thoracic outlet syndrome appear to be the most common. While electrodiagnostic studies may confirm the diagnosis of nerve entrapment, they may be falsely normal in musicians. Non‐operative treatment with instrument and technique modification may help. Involvement with the musician's teacher to implement appropriate treatment is recommended. Outcomes for both non‐operative and operative treatment for various nerve entrapment syndromes have yielded mostly good to excellent results, similar to the general population. Clin. Anat. 27:861–865, 2014. © 2014 Wiley Periodicals, Inc.
An Azide‐Modified Nucleoside for Metabolic Labeling of DNA
Authors: Neef Anne B. , Luedtke Nathan W.
Published: March 2014

Metabolic incorporation of azido nucleoside analogues into living cells can enable sensitive detection of DNA replication through copper(I)‐catalyzed azide–alkyne cycloaddition (CuAAC) and strain‐promoted azide–alkyne cycloaddition (SPAAC) “click” reactions. One major limitation to this approach is the poor chemical stability of nucleoside derivatives containing an aryl azide group. For example, 5‐azido‐2′‐deoxyuridine (AdU) exhibits a 4 h half‐life in water, and it gives little or no detectable labeling of cellular DNA. In contrast, the benzylic azide 5‐(azidomethyl)‐2′‐deoxyuridine (AmdU) is stable in solution at 37 °C, and it gives robust labeling of cellular DNA upon addition of fluorescent alkyne derivatives. In addition to providing the first examples of metabolic incorporation into and imaging of azide groups in cellular DNA, these results highlight the general importance of assessing azide group stability in bioorthogonal chemical reporter strategies.
Facile Synthesis of Au/g‐C3N4 Nanocomposites: An Inorganic/Organic Hybrid Plasmonic Photocatalyst with Enhanced Hydrogen Gas Evolution Under Visible‐Light Irradiation
Authors: Samanta Subhajyoti , Martha Satyabadi , Parida Kulamani
Published: March 2014

Noble‐metal Au nanoparticles deposited on graphitic carbon nitride polymer (g‐C3N4) photocatalyst by a facile deposition–precipitation method exhibited high photocatalytic activity for hydrogen gas production under visible‐light irradiation. The Au/g‐C3N4 nanocomposite plasmonic photocatalysts were characterized by X‐ray diffraction spectroscopy, diffuse reflectance UV/Vis spectroscopy, FTIR spectroscopy, field‐emission scanning electron microscopy, high‐resolution transmission electron microscopy, selected‐area electron diffraction, X‐ray photoelectron spectroscopy, photoluminescence spectroscopy, and photoelectrochemical measurements. We studied the effect of Au deposition on the photocatalytic activity of g‐C3N4 by investigation of optical, electronic, and electrical properties. Enhanced photocatalytic activity of Au/g‐C3N4 naocomposite for hydrogen production was attributed to the synergic mechanism operating between the conduction band minimum of g‐C3N4 and the plasmonic band of Au nanoparticles including high optical absorption, uniform distribution, and nanoscale particle size of gold. The mechanism of te photocatalytic activity of the nanocomposite photocatalyst is discussed in detail. Deposition of Au nanoparticles on g‐C3N4 was optimized and it was found that 1 wt % Au‐loaded g‐C3N4 composite plasmonic photocatalyst generated a photocurrent density of 49 mA cm−2 and produced a hydrogen gas amount of 532 μmol under visible light, which were more than 3000 times higher and 23 times higher, respectively, than the values of neat g‐C3N4.
Partial least squares discriminant analysis: taking the magic away
Authors: Brereton Richard G. , Lloyd Gavin R.
Published: March 2014

Partial least squares discriminant analysis (PLS‐DA) has been available for nearly 20 years yet is poorly understood by most users. By simple examples, it is shown graphically and algebraically that for two equal class sizes, PLS‐DA using one partial least squares (PLS) component provides equivalent classification results to Euclidean distance to centroids, and by using all nonzero components to linear discriminant analysis. Extensions where there are unequal class sizes and more than two classes are discussed including common pitfalls and dilemmas. Finally, the problems of overfitting and PLS scores plots are discussed. It is concluded that for classification purposes, PLS‐DA has no significant advantages over traditional procedures and is an algorithm full of dangers. It should not be viewed as a single integrated method but as step in a full classification procedure. However, despite these limitations, PLS‐DA can provide good insight into the causes of discrimination via weights and loadings, which gives it a unique role in exploratory data analysis, for example in metabolomics via visualisation of significant variables such as metabolites or spectroscopic peaks. Copyright © 2014 John Wiley & Sons, Ltd.
Conformational Analysis of a 20‐Membered Cyclic Peptide Disulfide from Conus virgo with a WPW Segment: Evidence for an Aromatic–Proline Sandwich
Authors: Sonti Rajesh , Rao K. N. Shashanka , Chidanand Sudarshan , Gowd Konkallu Hanumae , Raghothama Srinivasarao , Balaram Padmanabhan
Published: March 2014

A novel peptide containing a single disulfide bond, CIWPWC (Vi804), has been isolated and characterised from the venom of the marine cone snail, Conus virgo. A precursor polypeptide sequence derived from complementary DNA, corresponding to the M‐superfamily conotoxins, has been identified. The identity of the synthetic and natural peptide sequence has been established. A detailed analysis of the conformation in solution is reported for Vi804 and a synthetic analogue, CIDWPWC (DW3‐Vi804), in order to establish the structure of the novel WPW motif, which occurs in the context of a 20‐membered macrocyclic disulfide. Vi804 exists exclusively in the cis W3P4 conformer in water and methanol, whereas DW3‐Vi804 occurs exclusively as the trans conformer. NMR spectra revealed a W3P4 type VI β turn in Vi804 and a type II′ β turn in the analogue peptide, DW3‐Vi804. The extremely high‐field chemical shifts of the proline ring protons, together with specific nuclear Overhauser effects, are used to establish a conformation in which the proline ring is sandwiched between the flanking Trp residues, which emphasises a stabilising role for the aromatic–proline interactions, mediated predominantly by dispersion forces.
Highly Efficient Direct Aerobic Oxidative Esterification of Cinnamyl Alcohol with Alkyl Alcohols Catalysed by Gold Nanoparticles Incarcerated in a Nanoporous Polymer Matrix: A Tool for Investigating the Role of the Polymer Host
Authors: Buonerba Antonio , Noschese Annarita , Grassi Alfonso
Published: March 2014

The selective aerobic oxidation of cinnamyl alcohol to cinnamaldehyde, as well as direct oxidative esterification of this alcohol with primary and secondary aliphatic alcohols, were achieved with high chemoselectivity by using gold nanoparticles supported in a nanoporous semicrystalline multi‐block copolymer matrix, which consisted of syndiotactic polystyrene‐co‐cis‐1,4‐polybutadiene. The cascade reaction that leads to the alkyl cinnamates occurs through two oxidation steps: the selective oxidation of cinnamyl alcohol to cinnamaldehyde, followed by oxidation of the hemiacetal that results from the base‐catalysed reaction of cinnamaldehyde with an aliphatic alcohol. The rate constants for the two steps were evaluated in the temperature range 10–45 °C. The cinnamyl alcohol oxidation is faster than the oxidative esterification of cinnamaldehyde with methanol, ethanol, 2‐propanol, 1‐butanol, 1‐hexanol or 1‐octanol. The rate constants of the latter reaction are pseudo‐zero order with respect to the aliphatic alcohol and decrease as the bulkiness of the alcohol is increased. The activation energy (Ea) for the two oxidation steps was calculated for esterification of cinnamyl alcohol with 1‐butanol (Ea=57.8±11.5 and 62.7±16.7 kJ mol−1 for the first and second step, respectively). The oxidative esterification of cinnamyl alcohol with 2‐phenylethanol follows pseudo‐first‐order kinetics with respect to 2‐phenylethanol and is faster than observed for other alcohols because of fast diffusion of the aromatic alcohol in the crystalline phase of the support. The kinetic investigation allowed us to assess the role of the polymer support in the determination of both high activity and selectivity in the title reaction.
Noble Metals Can Have Different Effects on Photocatalysis Over Metal–Organic Frameworks (MOFs): A Case Study on M/NH2‐MIL‐125(Ti) (M=Pt and Au)
Authors: Sun Dengrong , Liu Wenjun , Fu Yanghe , Fang Zhenxing , Sun Fangxiang , Fu Xianzhi , Zhang Yongfan , Li Zhaohui
Published: March 2014

M‐doped NH2‐MIL‐125(Ti) (M=Pt and Au) were prepared by using the wetness impregnation method followed by a treatment with H2 flow. The resultant samples were characterized by powder X‐ray diffraction (XRD), X‐ray photoelectron spectroscopy (XPS), X‐ray absorption fine structure (XAFS) analyses, N2‐sorption BET surface area, and UV/Vis diffuse reflectance spectroscopy (DRS). The photocatalytic reaction carried out in saturated CO2 with triethanolamine (TEOA) as sacrificial agent under visible‐light irradiations showed that the noble metal‐doping on NH2‐MIL‐125(Ti) promoted the photocatalytic hydrogen evolution. Unlike that over pure NH2‐MIL‐125(Ti), in which only formate was produced, both hydrogen and formate were formed over Pt‐ and Au‐loaded NH2‐MIL‐125(Ti). However, Pt and Au have different effects on the photocatalytic performance for formate production. Compared with pure NH2‐MIL‐125(Ti), Pt/NH2‐MIL‐125(Ti) showed an enhanced activity for photocatalytic formate formation, whereas Au has a negative effect on this reaction. To elucidate the origin of the different photocatalytic performance, electron spin resonance (ESR) analyses and density functional theory (DFT) calculations were carried out over M/NH2‐MIL‐125(Ti).The photocatalytic mechanisms over M/NH2‐MIL‐125(Ti) (M=Pt and Au) were proposed. For the first time, the hydrogen spillover from the noble metal Pt to the framework of NH2‐MIL‐125(Ti) and its promoting effect on the photocatalytic CO2 reduction is revealed. The elucidation of the mechanism on the photocatalysis over M/NH2‐MIL‐125(Ti) can provide some guidance in the development of new photocatalysts based on MOF materials. This study also demonstrates the potential of using noble metal‐doped MOFs in photocatalytic reactions involving hydrogen as a reactant, like hydrogenation reactions.
A Remarkable Solvent Effect on the Nuclearity of Neutral Titanium(IV)‐Based Helicate Assemblies
Authors: Weekes David Michael , Diebold Carine , Mobian Pierre , Huguenard Clarisse , Allouche Lionel , Henry Marc
Published: March 2014

The spontaneous self‐assembly of a neutral circular trinuclear TiIV‐based helicate is described through the reaction of titanium(IV) isopropoxide with a rationally designed tetraphenolic ligand. The trimeric ring helicate was obtained after diffusion of n‐pentane into a solution with dichloromethane. The circular helicate has been characterized by using single‐crystal X‐ray diffraction study, 13C CP‐MAS NMR and 1H NMR DOSY solution spectroscopic, and positive electrospray ionization mass‐spectrometric analysis. These analytical data were compared with those obtained from a previously reported double‐stranded helicate that crystallizes in toluene. The trimeric ring was unstable in a pure solution with dichloromethane and transformed into the double‐stranded helicate. Thermodynamic analysis by means of the PACHA software revealed that formation of the double‐stranded helicates was characterized by ΔH(toluene)=−30 kJ mol−1 and ΔS(toluene)=+357 J K−1 mol−1, whereas these values were ΔH(CH2Cl2)=−75 kJ mol−1 and ΔS(CH2Cl2)=−37 J K−1 mol−1 for the ring helicate. The transformation of the ring helicate into the double‐stranded helicate was a strongly endothermic process characterized by ΔH(CH2Cl2)=+127 kJ mol−1 and ΔH(n‐pentane)=+644 kJ mol−1 associated with a large positive entropy change ΔS=+1115 J K−1⋅mol−1. Consequently, the instability of the ring helicate in pure dichloromethane was attributed to the rather high dielectric constant and dipole moment of dichloromethane relative to n‐pentane. Suggestions for increasing the stability of the ring helicate are given.
Silver‐Free Two‐Component Approach in Gold Catalysis: Activation of [LAuCl] Complexes with Derivatives of Copper, Zinc, Indium, Bismuth, and Other Lewis Acids
Authors: Fang Weizhen , Presset Marc , Guérinot Amandine , Bour Christophe , Bezzenine‐Lafollée Sophie , Gandon Vincent
Published: March 2014

Complexes of type [LAuCl] (L=phosphine, phosphite, NHC and others) are widely employed in homogeneous catalysis, however, they are usually inactive as such and must be used jointly with a halide scavenger. To date, this role has mostly been entrusted to silver salts (AgSbF6, AgPF6, AgBF4, AgOTf, etc.). However, silver salts can be the source of deactivation processes or side reactions, so it is sometimes advisable to use silver‐free cationic gold complexes, which can be difficult to synthesize and to handle compared with the more robust chloride. We show in this study that various Lewis acids of the transition and main group metal families are expedient substitutes to silver salts. We have tested CuI, CuII, ZnII, InIII, SiIV, BiIII, and other salts in a variety of typical AuI‐catalyzed transformations, and the results have revealed that [LAuCl] can form active species in their presence.
Cyclometalated Iridium(III) Bipyridyl–Phenylenediamine Complexes with Multicolor Phosphorescence: Synthesis, Electrochemistry, Photophysics, and Intracellular Nitric Oxide Sensing
Authors: Law Wendell Ho‐Tin , Leung Kam‐Keung , Lee Lawrence Cho‐Cheung , Poon Che‐Shan , Liu Hua‐Wei , Lo Kenneth Kam‐Wing
Published: March 2014

We present a new class of phosphorescent cyclometalated iridium(III) bipyridyl–phenylenediamine complexes [Ir(N^C)2(bpy‐DA)](PF6) (bpy‐DA=4‐(N‐(2‐amino‐5‐methoxyphenyl)aminomethyl)‐4′‐methyl‐2,2′‐bipyridine; HN^C=2‐(2,4‐difluorophenyl)pyridine (Hdfppy) (1 a), 2‐phenylpyridine (Hppy) (2 a), 2‐phenylquinoline (Hpq) (3 a), 2‐phenylcinchoninic acid methyl ester (Hpqe) (4 a)) and their triazole counterparts [Ir(N^C)2(bpy‐T)](PF6) (bpy‐T=4‐((6‐methoxybenzotriazol‐1‐yl)methyl)‐4′‐methyl‐2,2′‐bipyridine; HN^C=Hdfppy (1 b), Hppy (2 b), Hpq (3 b), Hpqe (4 b)). Upon photoexcitation, the diamine complexes exhibited fairly weak green to red phosphorescence under ambient conditions whereas the triazole derivatives emitted strongly. The photophysical properties of complexes 2 a and 2 b have been studied in more detail. Upon protonation, the diamine complex 2 a displayed increased emission intensity, but the emission properties of its triazole counterpart complex 2 b were independent on the pH value of the solution. Also, complex 2 a was found to be readily converted into complex 2 b upon reaction with NO under aerated conditions, resulting in substantial emission enhancement of the solution. The reaction was highly specific toward NO over other reactive oxygen and nitrogen species (RONS) as revealed by spectroscopic analyses. The lipophilicity and cellular uptake efficiency of the diamine complexes have been examined and correlated to their molecular structures. Also, cell‐based assays showed that these complexes were noncytotoxic toward human cervix epithelioid carcinoma (HeLa) cells (at 10 μM, 4 h, percentage survival ≈80–95 %). Additionally, the diamine complexes have been used to visualize intracellular NO generated both exogenously in HeLa cells and endogenously in RAW 264.7 murine macrophages by laser‐scanning confocal microscopy.
State‐of‐the‐science of patient navigation as a strategy for enhancing minority clinical trial accrual
Authors: Ghebre Rahel G. , Jones Lovell A. , Wenzel Jennifer A. , Martin Michelle Y. , Durant Raegan W. , Ford Jean G.
Published: March 2014

BACKGROUND

Patient navigation programs are emerging that aim to address disparities in clinical trial participation among medically underserved populations, including racial/ethnic minorities. However, there is a lack of consensus on the role of patient navigators within the clinical trial process as well as outcome measures to evaluate program effectiveness.

METHODS

A review of the literature was conducted of PubMed, Medline, CINHAL, and other sources to identify qualitative and quantitative studies on patient navigation in clinical trials. The search yielded 212 studies, of which only 12 were eligible for this review.

RESULTS

The eligible studies reported on the development of programs for patient navigation in cancer clinical trials, including training and implementation among African Americans, American Indians, and Native Hawaiians. A low rate of clinical trial refusal (range, 4%‐6%) was reported among patients enrolled in patient navigation programs. However, few studies reported on the efficacy of patient navigation in increasing clinical treatment trial enrollment.

CONCLUSIONS

Outcome measures are proposed to assist in developing and evaluating the efficacy and/or effectiveness of patient navigation programs that aim to increase participation in cancer clinical trials. Future research is needed to evaluate the efficacy of patient navigators in addressing barriers to clinical trial participation and increasing enrollment among medically underserved cancer patients. Cancer 2014;120(7 suppl):1122–30. © 2014 American Cancer Society.
Fishing for myelodysplastic syndromes finds uncaptured cases by state cancer registries: Need for more resources
Authors: Cogle Christopher R.
Published: March 2014

There is a high number of uncaptured cases with myelodysplastic syndromes (MDS) by population‐based cancer registries. A novel method of capture‐recapture was used to identify uncaptured MDS cases.
A formal analysis of authentication protocols for mobile devices in next generation networks
Authors: Aiash Mahdi
Published: March 2014

Next Generation Networks comprise a wide variety of access technologies such as 2G/3G, WLAN as well as the Long‐Term Evolution (LTE) networks. In this environment, mobile devices are expected to store sensitive data and represent users to access the underlying networks and connect to a wide variety of sensitive servers. It is crucial, in this sense, for end users to trust their mobile devices and for all transactions using them to be secure. Therefore, a number of communication frameworks in Next Generation Networks have been working on designing device authentication protocols that achieve mutual authentication between users and mobile terminals. This paper analyses some of these protocols and introduces two new device authentication protocols, verifies them using formal methods approach and discusses how they achieved desired security proprieties. The performance analysis highlights another advantage of the proposed protocols. Copyright © 2014 John Wiley & Sons, Ltd.
Framework Stability and Brønsted Acidity of Isomorphously Substituted Interlayer‐Expanded Zeolite COE‐4: A Density Functional Theory Study
Authors: Li Haichao , Zhou Danhong , Tian Dongxu , Shi Chuan , Müller Ulrich , Feyen Mathias , Yilmaz Bilge , Gies Hermann , Xiao Feng‐Shou , De Vos Dirk , Yokoi Toshiyuki , Tatsumi Takashi , Bao Xinhe , Zhang Weiping
Published: March 2014

COE‐4 zeolites possess a unique two‐dimensional ten‐ring pore structure with the Si(OH)2 hydroxyl groups attached to the linker position between the ferrierite‐type layers, which has been demonstrated through the interlayer‐expansion approach in our previous work (H. Gies et al. Chem. Mater.­ 2012, 24, 1536). Herein, density functional theory is used to study the framework stability and Brønsted acidity of the zeolite T‐COE‐4, in which the tetravalent Si is isomorphously substituted by a trivalent Fe, B, Ga, or Al heteroatom at the linker position. The influences of substitution energy and equilibrium geometry parameters on the stability of T‐COE‐4 are investigated in detail. The relative acid strength of the linker position is revealed by the proton affinity, charge analysis, and NH3 adsorption. It is found that the range of the 〈T‐O‐Si〉 angles is widened to maintain the stability of isomorphously substituted T‐COE‐4 zeolites. The smaller the 〈O1‐T‐O2〉 bond angle is, the more difficult is to form the regular tetrahedral unit. Thus, the substitution energies at the linker positions increase in the following sequence: Al‐COE‐4 < Ga‐COE‐4 < Fe‐COE‐4 < B‐COE‐4. The adsorption of NH3 as a probe molecule indicates that the acidity can affect the hydrogen‐bonding interaction between (NH⋅⋅⋅O2) and (N⋅⋅⋅HO2). The relative Brønsted‐acid strength of the interlayer‐expanded T‐COE‐4 zeolite decreases in the order of Al‐COE‐4 > Ga‐COE‐4 > Fe‐COE‐4 > B‐COE‐4. These findings may be helpful for the structural design and functional modification of interlayer‐expanded zeolites.
Photocatalytic Carboxylation of Organic Substrates with Carbon Dioxide at Zinc Sulfide with Deposited Ruthenium Nanoparticles
Authors: Baran Tomasz , Dibenedetto Angela , Aresta Michele , Kruczała Krzysztof , Macyk Wojciech
Published: March 2014

Photocatalytic carboxylation of acetylacetone with carbon dioxide has been performed by using ZnS‐based photocatalysts. The formation of two isomeric carboxylic acids, as proven by IR and 13C NMR spectroscopy, was observed. The reaction yield was enhanced after deposition of ruthenium nanoparticles on ZnS. The reaction encompasses ruthenium‐mediated one‐electron reduction of CO2 to CO2.− with electrons from the conduction band of ZnS and one‐hole oxidation of acetylacetone to the relevant radical. Coupling of photogenerated radicals leads to the formation of carboxylic acids. Generation of CO2.− has been confirmed by spin‐trapping EPR measurements. The process described herein may find applications for the solar‐light‐driven green synthesis of Cn+1 carboxylic compounds from Cn substrates by utilising carbon dioxide.
Synthesis of MoSe2/Reduced graphene oxide composites with improved tribological properties for oil‐based additives
Authors: Li Hongping , Chen Lin , Zhang Yi , Ji Xiaorui , Chen Shuai , Song Haojie , Li Changsheng , Tang Hua
Published: March 2014

In this work, we developed a facile and effective hydrothermal method synthesis of MoSe2 nanoflowers on reduced graphene oxide (RGO) sheets. The as‐prepared MoSe2/reduced graphene oxide (MoSe2/RGO) composites are characterized by X‐ray diffractometer (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results indicated that MoSe2 nanoflowers were successfully deposited on RGO nanosheets to form a well interconnected hybrid structure. The tribological properties of MoSe2/RGO composites as lubricating oil additive were investigated by a UMT‐2 ball‐on‐plate friction and wear tester. By the addition of MoSe2/RGO composites in paraffin oil, the antiwear ability was improved and the friction coefficient was decreased. The based oil with MoSe2/RGO composites showed better tribological properties than the oil with MoSe2 and pure oil. The good friction and wear properties of MoSe2/RGO composites as additives were attributed to the formation of a thin physical tribofilm on the substrate.
Recent Advances in Carbon Dioxide Capture, Fixation, and Activation by using N‐Heterocyclic Carbenes
Authors: Yang Longhua , Wang Hongming
Published: March 2014

In the last two decades, CO2 emission has caused a lot of environmental problems. To mitigate the concentration of CO2 in the atmosphere, various strategies have been implemented, one of which is the use of N‐heterocyclic carbenes (NHCs) and related complexes to accomplish the capture, fixation, and activation of CO2 effectively. In this review, we summarize CO2 capture, fixation, and activation by utilizing NHCs and related complexes; homogeneous reactions and their reaction mechanisms are discussed. Free NHCs and NHC salts can capture CO2 in both direct and indirect ways to form imidazolium carboxylates, and they can also catalyze the reaction of aromatic aldehydes with CO2 to form carboxylic acids and derivatives. Moreover, associated with transition metals (TMs), NHCs can form NHC–TM complexes to transform CO2 into industrial acid or esters. Non‐metal–NHC complexes can also catalyze the reactions of silicon and boron complexes with CO2. In addition, catalytic cycloaddition of epoxides with CO2 is another effective function of NHC complexes, and NHC ionic liquids perform excellently in this aspect.
Entropically Favored Adsorption of Cellulosic Molecules onto Carbon Materials through Hydrophobic Functionalities
Authors: Yabushita Mizuho , Kobayashi Hirokazu , Hasegawa Jun‐ya , Hara Kenji , Fukuoka Atsushi
Published: March 2014

Carbon‐based materials have attracted interest as high‐performance catalysts for the aqueous‐phase conversion of cellulose. The adsorption of β‐glucans plays a crucial role in the catalytic performance of carbons, although the primary driving force and details of the adsorption process remain unclear. This study demonstrates that adsorption occurs at hydrophobic sites on the carbon surface and that hydrophilic groups are not involved. Analysis of adsorption temperature dependence also reveals that the entropy change associated with adsorption is positive. Our results indicate that adsorption occurs by entropically driven hydrophobic interactions in addition to CH–π hydrogen bonding. These same CH–π hydrogen bonds are also confirmed by DFT calculations. The adsorption of β‐glucans on carbons is significantly stronger than the affinity between β‐glucans. The adsorption equilibrium constants of β‐glucans on carbons increase exponentially with increasing degrees of polymerization, which supports the theory of strong interactions between the carbon and the long β‐glucans found in cellulose.
Switching to multiple daily injection therapy with glulisine improves glycaemic control, vascular damage and treatment satisfaction in basal insulin glargine‐injected diabetic patients
Authors: Yanagisawa Katsuyuki , Ashihara Junya , Obara Shinji , Wada Norio , Takeuchi Masayoshi , Nishino Yuri , Maeda Sayaka , Ishibashi Yuji , Yamagishi Sho‐ichi
Published: March 2014

Background

Basal and bolus insulin therapy is required for strict blood control in diabetic patients, which could lead to prevention of vascular complications in diabetes. However, the optimal combination regimen is not well established.

Methods

Fifty‐nine diabetic patients (49 type 1 and 10 type 2; 52.9 ± 13.3 years old) whose blood glucose levels were uncontrolled (HbA1c > 6.2%) by combination treatment of basal insulin glargine with multiple daily pre‐meal injections of bolus short‐acting insulin [aspart (n = 19), lispro (n = 37) and regular human insulin (n = 3)] for at least 8 weeks were enrolled in this study. We examined whether glycaemic control and vascular injury were improved by replacement of short‐acting insulin with glulisine. Patient satisfaction was assessed with Diabetes Treatment Satisfaction Questionnaire.

Results

Although bolus and basal insulin doses were almost unchanged before and after replacement therapy, switching to glulisine insulin for 24 weeks significantly decreased level of HbA1c, advanced glycation end products (AGEs), soluble receptor for AGEs (sRAGE), monocyte chemoattractant protein‐1 (MCP‐1) and urinary albumin excretion. In multiple stepwise regression analysis, change in MCP‐1 values from baseline (ΔMCP‐1) was a sole determinant of log urinary albumin excretion. ΔAGEs and ΔsRAGE were independently correlated with each other. The relationship between ΔMCP‐1 and ΔsRAGE was marginally significant (p = 0.05). Replacement of short‐acting insulin by glulisine significantly increased Diabetes Treatment Satisfaction Questionnaire scores.

Conclusions

Our present study suggests that combination therapy of glargine with multiple daily pre‐meal injections of glulisine might show superior efficacy in controlling blood glucose, preventing vascular damage and improving treatment satisfaction in diabetic patients. Copyright © 2014 John Wiley & Sons, Ltd.
Lixisenatide treatment improves glycaemic control in Asian patients with type 2 diabetes mellitus inadequately controlled on metformin with or without sulfonylurea: a randomized, double‐blind, placebo‐controlled, 24‐week trial (GetGoal‐M‐Asia)
Authors: Yu Pan Chang , Han Ping , Liu Xiaoming , Yan Shengli , Feng Ping , Zhou Zhiguang , Lv Xiaofeng , Tian Hui , Jin Kui Yang , Su Benli , Shang Shuhua , Niemoeller Elisabeth
Published: March 2014

Background

This study assessed the efficacy and safety of the once‐daily glucagon‐like peptide‐1 receptor agonist, lixisenatide, in Asian patients with type 2 diabetes mellitus inadequately controlled on metformin ± sulfonylurea.

Methods

In this 24‐week, double‐blind, placebo‐controlled, multinational study, patients were randomized to lixisenatide 20 µg once daily or placebo. The primary endpoint was absolute change in glycated haemoglobin (HbA1c) from baseline to week 24.

Results

A total of 391 patients were randomized. Lixisenatide significantly reduced HbA1c levels compared with placebo (LS mean difference: −0.36%, p = 0.0004). A significantly higher proportion of lixisenatide‐treated patients achieved HbA1c targets of <7% (p = 0.003) and ≤6.5% (p = 0.001) versus placebo. Lixisenatide was associated with a statistically significant reduction in 2‐h postprandial plasma glucose after a standardized breakfast versus placebo (LS mean difference: −4.28 mmol/L, p < 0.0001) and a significant reduction in fasting plasma glucose (p = 0.0109). There was no difference in weight loss versus placebo, with a modest reduction in body weight reported for both groups (lixisenatide: −1.50 kg, placebo: −1.24 kg; p = 0.296). The incidence of treatment‐emergent adverse events (TEAEs) was 64.3% with lixisenatide versus 47.4% with placebo, with serious TEAEs reported in 1.5% versus 2.1% of patients, respectively. The most common TEAE in the lixisenatide group was nausea (16.3% vs 2.6% with placebo). The incidence of symptomatic hypoglycaemia was 5.6% with lixisenatide treatment and 2.6% with placebo (p = 0.1321), with no severe symptomatic hypoglycaemia events reported.

Conclusions

In Asian patients with type 2 diabetes mellitus insufficiently controlled on metformin ± sulfonylurea, lixisenatide significantly improved glycaemic control and was well tolerated during the 24‐week study. © 2014 The Authors. Diabetes/Metabolism Research and Reviews published by John Wiley & Sons, Ltd.
Quantitative analysis reveals dominance of gliogenesis over neurogenesis in an adult brainstem oscillator
Authors: Sîrbulescu Ruxandra F. , Ilieş Iulian , Zupanc Günther K.H.
Published: March 2014

Neural stem/progenitor cells in the neurogenic niches of the adult brain are widely assumed to give rise predominantly to neurons, rather than glia. Here, we performed a quantitative analysis of the resident neural progenitors and their progeny in the adult pacemaker nucleus (Pn) of the weakly electric fishApteronotus leptorhynchus. Approximately 15% of all cells in this brainstem nucleus are radial glia‐like neural stem/progenitor cells. They are distributed uniformly within the tissue and are characterized by the expression of Sox2 and Meis 1/2/3. Approximately 2–3% of them are mitotically active, as indicated by expression of proliferating cell nuclear antigen. Labeling of proliferating cells with a single pulse of BrdU, followed by chases of up to 100 days, revealed that new cells are generated uniformly throughout the nucleus and do not undergo substantial migration. New cells differentiate into S100+ astrocytes and Hu C/D+ small interneurons at a ratio of 4:1, reflecting the proportions of the total glia and neurons in this brain region. The continuous addition of new cells leads to a diffuse growth of the Pn, which doubles in volume and total cell number over the first 2 years following sexual maturation of the fish. However, the number of pacemaker and relay cells, which constitute the oscillatory neural network, remains constant throughout adult life. We hypothesize that the dominance of gliogenesis is an adaptation to the high‐frequency firing of the oscillatory neurons in this nucleus. © 2014 Wiley Periodicals, Inc. Develop Neurobiol 74: 934–952, 2014
Renal denervation and heart failure
Authors: Böhm Michael , Ewen Sebastian , Kindermann Ingrid , Linz Dominik , Ukena Christian , Mahfoud Felix
Published: March 2014

Renal denervation has been developed in order to lower systolic blood pressure in resistant hypertension by a reduction in renal afferent and efferent sympathetic nerve activity. In heart failure sympathetic activation, in particular, renal norepinephrine release is closely associated with morbidity and mortality. Initial studies have shown that renal denervation is able to reduce not only blood pressure but also heart rate, and is associated with a reduction in myocardial hypertrophy, improved glucose tolerance, and ameliorated microalbuminuria. Since some experimental and observational data suggest an antiarrhythmic effect, it is possible that renal denervation might also play a therapeutic role in arrhythmias often occurring in chronic heart failure. The first proof‐of‐concept studies are planned to evaluate the clinical effect of this pathophysiologically plausible method, which might be able to change clinical practice.
The additive burden of iron deficiency in the cardiorenal–anaemia axis: scope of a problem and its consequences
Authors: Klip IJsbrand T. , Jankowska Ewa A. , Enjuanes Cristina , Voors Adriaan A. , Banasiak Waldemar , Bruguera Jordi , Rozentryt Piotr , Polonski Lech , van Veldhuisen Dirk J. , Ponikowski Piotr , Comin‐Colet Josep , van der Meer Peter
Published: March 2014

Aims

Iron deficiency (ID), anaemia, and chronic kidney disease (CKD) are common co‐morbidities in chronic heart failure (CHF) and all independent predictors of unfavourable outcome. The combination of anaemia and CKD in CHF has been described as the cardiorenal–anaemia syndrome. However, the role of ID within this complex interplay of co‐existing pathologies is unclear.

Methods and results

We studied the clinical correlates of ID (defined as ferritin <100 µg/L or 100–299 µg/L in combination with a transferrin saturation <20%, anaemia) and renal dysfunction (defined as estimated glomerular filtration rate <60 mL/min/1.73 m2) and their prognostic implications in an international pooled cohort, comprising 1506 patients with CHF. Mean age was 64 ± 13 years, 74.2% were male, and 47.3% were in NYHA functional class III. The presence of ID, anaemia, CKD, or a combination of these co‐morbidities was observed in 69.3% of the patients. During a median (Q1–Q3) follow‐up of 1.92 years (1.18–3.26 years), 440 patients (29.2%) died. Eight‐year survival rates decreased significantly from 58.0% for no co‐morbidities to 44.6, 33.0, and 18.4%, for one, two, or three co‐morbidities, respectively (P < 0.001). Multivariate hazard models revealed ID to be the key determinant of prognosis, either individually (P = 0.04) or in combination with either anaemia (P = 0.006), CKD (P = 0.03), or both (P = 0.02).

Conclusions

Iron deficiency frequently overlaps with anaemia and/or CKD in CHF. The presence of ID amplifies mortality risk, either alone or in combination with anaemia, CKD, or both, making it a potential viable therapeutic target.
Synthesis of Unexpected Bifunctionalized Thiazoles by Nucleophilic Attack on Allenyl Isothiocyanate
Authors: Jawabrah Al‐Hourani Baker , Richter Frank , Vrobel Kai , Banert Klaus , Korb Marcus , Rüffer Tobias , Walfort Bernhard , Lang Heinrich
Published: March 2014

Treatment of allenyl isothiocyanate with a variety of nucleophiles leads to 5‐methylthiazoles with a functional group at the 2‐position. The same pattern of reactivity is also seen with N‐aminophthalimide. In the presence of azide salt, hydrazoic acid, or N,N‐disubstituted hydroxylamines, however, allenyl isothiocyanate is converted into bifunctionalized thiazoles. We explain the formation of these products by nucleophilic addition at the isothiocyanato moiety followed by ring closure and an N–N or N–O cleavage reaction to generate short‐lived 2‐imino‐5‐methylidenethiazole or 5‐methylidenethiazol‐2‐one. Such intermediates are trapped by addition reactions to give the final heterocyclic compounds. In the case of N,N‐disubstituted hydroxylamines, the primary addition products with allenyl isothiocyanate can be detected as unstable intermediates by IR and NMR spectroscopy.
Dynamic Double Kinetic Resolution of Amines and Alcohols under the Cocatalysis of Raney Nickel/Candida antarctica Lipase B: From Concept to Application
Authors: Xia Bo , Cheng Guilin , Lin Xianfu , Wu Qi
Published: March 2014

Herein, we have established a dynamic double kinetic resolution (DDKR) strategy under the co‐catalysis of Raney nickel and Candida antarctica lipase B (CAL‐B) for the one‐pot simultaneous resolution of primary amines and secondary alcohols (or esters). The DDKR strategy was successfully applied to the resolution of a series of racemic amines and secondary alcohols (or esters) as well as mexiletine, an important antiarrhythmic agent. The catalysts could be recycled and reused several times with the same high activity. Scale‐up experiments were also successful. As a more atom‐economical and efficient process than traditional simple kinetic resolutions, the DDKR strategy can be widely used to prepare optically pure amines and alcohols.
A Bioanode Using Thermostable Alcohol Dehydrogenase for an Ethanol Biofuel Cell Operating at High Temperatures
Authors: Kontani Aya , Masuda Miyuki , Matsumura Hirotoshi , Nakamura Nobuhumi , Yohda Masafumi , Ohno Hiroyuki
Published: March 2014

To extend the range of biofuel cell applications, we wish to increase their maximum operational temperatures. Using a thermostable alcohol dehydrogenase as a biocatalyst, we prepared an enzyme‐immobilized bioanode that can operate at high temperatures. The catalytic current for ethanol oxidation was increased using this electrode at temperatures up to 80 °C.
Tubular and Microcylindrical Platinum Electrodes for Amperometric Detection of Aminobiphenyls and Aminonaphthalenes in HPLC
Authors: Zavazalova Jaroslava , Dejmkova Hana , Barek Jiri , Peckova Karolina
Published: March 2014

Platinum electrodes in microcylindrical and tubular arrangements were compared as working electrodes for amperometric detection of 2‐aminobiphenyl, 4‐aminobiphenyl, 1‐aminonaphthalene, and 2‐aminonaphthalene in HPLC. Factors influencing separation efficiency are favourable for microcylindrical arrangement while tubular arrangement exhibits higher sensitivities and lower limits of detection. These are in the range of 0.0078–0.027 µmol L−1 for tubular, and 0.11–0.42 µmol L−1 for microcylindrical arrangement. Further, a new method with nanomolar detection limits was proposed for determination of tested compounds in urine using solid phase extraction for preliminary separation and preconcentration of the analytes.
Promotion Effect of Bismuth on Nickel Electrodeposition and Its Electrocatalysis to Glucose Oxidation
Authors: Wu Jiuyang , Miao Yuqing , Liang Xiaocai , Yang Zhuoyuan , Yang Yang , Ouyang Ruizhuo
Published: March 2014

Metallic Bi and Ni were co‐deposited onto the surface of glass carbon electrode (GCE) from the electrolyte solution containing their respective nitrate to fabricate a Bi/Ni alloy modified GCE (Bi/Ni‐GCE). The purpose is to study the influence of Bi3+ on the deposition of Ni and that of deposited Bi on the electrocatalytic performance of Ni to glucose in alkali solution. The results show that both redox signal of Ni(OH)2/NiOOH and Ni(OH)2/NiOOH mediated electrocatalysis to glucose is remarkably increased in the presence of Bi. It seems that there is a synergistic effect between Bi and Ni on each other’s redox electrochemistry. It’s possible that the firstly deposited Bi on GCE surface helps to the following nucleation and growth of Ni, leading to the deposition of more metallic Ni on GCE surface. An extremely attractive feature of Bi/Ni‐GCE is reflected by the fast response time to the electrocatalytic oxidation of glucose. The electrode nearly responses immediately after glucose is added and it reaches a steady‐state level within only 2 seconds, demonstrating a good electrocatalytic property of Bi/Ni‐GCE. The calibration plot is linear over the wide concentration range of 0–5.8 mM with a sensitivity of 33.96 µA/mM and a correlation coefficient of 0.9985. The detection limit of the glucose was found to be 0.59 µM at a signal‐to‐noise ratio of 3. The fabricated Bi/Ni‐GCE was successfully employed to analyze the glucose level in blood samples, exhibiting high accuracy, strong resistance against inference and good reliability in the practical applications.
Design and Fabrication of an All‐Solid‐State Thin‐Film Li‐Ion Microbattery with Amorphous TiO2 as the Anode
Authors: Feng Jinkui , Yan Binggong , Lai Man O. , Li Lu
Published: March 2014

We have fabricated an all‐solid‐state thin film microbattery by using reactive radio frequency (RF) magnetron sputtering of the positive LiNi1/3Mn1/3Co1/3O2 (LNMC) electrode at an elevated temperature, amorphous Li3+xPO4−xNx (LiPON) electrolyte at room temperature, and in situ deposition of an amorphous titania (TiO2) film below 200 °C. Electrochemical measurement of the TiO2 half‐cell reveals a first discharge capacity of 102 μAh cm−2 μm−1 with 86 % capacity retention after 100 cycles. A capacity of 58 μAh cm−2 μm−1 from the LNMC thin film electrode can be achieved. The initial capacity of the TiO2/LiPON/LNMC full‐cell is as high as 52 μAh cm−2 μm−1 and 90 % capacity is retained after 400 cycles.
Determination of Minimum Miscibility Pressure of Crude Oil–CO2 System by Oil Swelling/Extraction Test
Authors: Abedini Ali , Mosavat Nader , Torabi Farshid
Published: March 2014

The minimum miscibility pressure (MMP) of crude oil–CO2 systems was determined through analyzing the experimental data of swelling/extraction tests. First, the oil swelling factor (SF) as a result of CO2 dissolution in a crude oil sample was determined at four different temperatures in the range of T=21–40 °C. In addition, three sets of swelling/extraction data of previous studies were collected and included so that more conclusive and satisfactory results can be obtained. The results demonstrated that the oil swelling factor increases with the equilibrium pressure (Peq), reaches the maximum value at light hydrocarbon extraction pressure (Pext), and then reduces with further increase in equilibrium pressure. It was found that the reduction behavior of oil swelling factor occurs in two distinct regions. In the upper extraction phase (UEP), the oil swelling factor decreased sharply at pressures just over extraction pressure and then declined gradually in what is called the lower extraction phase (LEP). Finally, the MMP of the crude oil–CO2 system at a specific temperature was estimated by finding the intersection of the linear regression correlation corresponding to each of the aforementioned regions (i.e., UEP and LEP). The crude oil–CO2 MMP was also determined by employing the vanishing interfacial tension (VIT) technique and a series of CO2 injection tests. Comparing the MMP values of the crude oil–CO2 systems determined by three methods revealed that the MMP values estimated by swelling/extraction data are in approximate agreement with those determined by the two other methods.
Physically motivated scale interaction parameterization in reduced rank quadratic nonlinear dynamic spatio‐temporal models
Authors: Gladish D.W. , Wikle C.K.
Published: March 2014

Many environmental spatio‐temporal processes are best characterized by nonlinear dynamical evolution. Recently, it has been shown that general quadratic nonlinear models provide a very flexible class of parametric models for such processes. However, such models have a very large potential parameter space that must be reduced for most practical applications, even when one considers a reduced rank state process. We provide a parameterization for such models, which is motivated by physical arguments of wave mode interactions in which medium scales influence the evolution of large‐scale modes. This parameterization has the potential to improve forecasts in addition to reducing the parameter space. The methodology is illustrated on real‐world forecasting problems associated with Pacific sea surface temperature anomalies and mid‐latitude sea level pressure. Copyright © 2014 John Wiley & Sons, Ltd.