bluuebunny/crossref_metadata_2025 huggingface dataset:
Structural Modifications in Bilayered Molecular Systems Lead to Predictable Changes in Their Electronic Properties
Authors: Bowers Carleen M. , Zhang Minlu , Lyubarskaya Yekaterina , Toone Eric J. , Tang Ching , Shestopalov Alexander A.
Published: February 2014

This study uses a novel surface engineering approach to demonstrate the influence of organic functional group substitutions on molecular electronic properties. Specifically, bilayered organic monomolecular systems immobilized on an inorganic electrode as the charge‐injecting components of organic electronic devices are compared. Recent literature reports demonstrate that structural modification in functional monolayers have unpredictable effects on their electronic properties. These studies indicate that the structure most certainly plays an important role, but its effect on the molecular resistance is diminished due to differences in other monolayer parameters. It is demonstrated that a separate control over the monolayer geometry and its chemical structure is required in order to observe predictable structure‐property relations. Here, bilayered molecular interfaces, comprising inert and functional layers whose properties can be independently controlled, are formed. It is shown that 1) the charge transfer through the bilayered system is sensitive to small structural molecular changes; 2) that it can be controlled and predicted by controlling the electron‐withdrawing or donating nature of the organic moiety; and 3) that the differences in the charge transfer dynamics of two bilayered systems can be visualized via patterned electroluminescence.
An Efficient Palladium‐Catalyzed Synthesis of Cinnamyl Ethers from Aromatic Halides, Phenols, and Allylic Chloride
Authors: Wang Wei , Zhou Rong , Jiang Zhi‐Jie , Wang Kun , Fu Hai‐Yan , Zheng Xue‐Li , Chen Hua , Li Rui‐Xiang
Published: February 2014

A one‐pot, two‐step catalytic protocol for the preparation of cinnamyl ethers from simple and readily available aryl halides, phenols and allyl chloride is reported for the first time. This simple and highly efficient palladium nanoparticles catalytic system shows good regio‐ and stereoselectivities and affords the desired products in good to high yields (49–85%) from aryl iodides. Furthermore, less reactive aryl bromides can also give the cinnamyl ethers in moderate yields (24–72%).

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Modular Synthesis of Functionalisable Alkoxy‐Tethered N‐Heterocyclic Carbene Ligands and an Active Catalyst for Buchwald–Hartwig Aminations
Authors: Krinsky Jamin L. , Martínez Alberto , Godard Cyril , Castillón Sergio , Claver Carmen
Published: February 2014

Modular syntheses of functionalised, alkoxy‐tethered 1,3‐bis(2,4,6‐trimethylphenyl)imidazolium (IMes⋅H+) and 1,3‐bis(2,6‐diisopropylphenyl)imidazolium (IPr⋅H+) derivatives 1,3‐bis(4‐alkyloxy‐2,4,6‐trimethylphenyl)imidazolium (IXyOR⋅H+) and 1,3‐bis(4‐alkyloxy‐2,6‐diisopropylphenyl)imidazolium (IPrOR⋅H+) are reported. A reliable synthesis of the key starting material 4‐amino‐3,5‐diisopropylphenol is also described. Etherification of hydroxy‐decorated ligand intermediates before formation of the imidazolium core and subsequent modification, or direct etherification of the versatile synthon IPrOH⋅HCl, allowed access to various linker types including triethoxysilyl, primary amino and norbornenyl, which are not accessible by other methods. An IPrOR–palladium(II) complex was prepared, and its catalytic activity was evaluated in challenging Buchwald–Hartwig aminations of aryl chlorides. This precatalyst displayed excellent activity and selectivity under mild reaction conditions, achieving in some cases a 10‐fold improvement in TOF relative to the IPr‐based version. An unexpected activity profile was observed wherein sterically demanding anilines were coupled more easily than those lacking ortho‐substitution.

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Application of “Click” Chemistry to the Construction of Supramolecular Functional Systems
Authors: Xu Liang , Li Yongjun , Li Yuliang
Published: February 2014

The aim of this article is to summarize the recent advances in the synthesis of functional systems based on CuI‐catalyzed azide‐alkyne cycloaddition reaction. This reaction has the ability to exclusively afford 1,4‐disubstituted 1,2,3‐triazoles regioselectively, which have several features. First, such triazoles have a polarized CH bond, which could be used as a H‐bond donor. Second, its atom arrangement and electronic properties are similar to those of a peptide bond, making it a candidate for an amide surrogate. Third, it has three nitrogen atoms, two of which could be used as coordinating sites for metal ions. Based on these features, 1,2,3‐triazoles have potential applications in the construction of supramolecular functional systems. The design and synthesis strategies for anion receptors, bioactive macrocycles, and molecular machines are reviewed here. And in this scope we focus on foldamer‐based receptors, macrocycle‐based receptors, macrocyclic carbohydrates, macrocyclic peptides, catenanes, and rotaxanes.
Increase of high mobility group box chromosomal protein 1 in eosinophilic chronic rhinosinusitis with nasal polyps
Authors: Chen Daishi , Mao Mingfeng , Bellussi Luisa M. , Passali Desiderio , Chen Lei
Published: February 2014

Background

Chronic rhinosinusitis with nasal polyps (CRSwNP) is characterized by eosinophil‐dominant infiltration in Europe and the United States. However, CRSwNP in Asia has shown different immunopathologic features. High‐mobility group protein box 1 (HMGB1) is a DNA‐binding protein that has been suggested to be involved in various chronic inflammatory diseases. The objective of this study is to investigate whether HMGB1 is augmented in the Chinese eosinophilic CRSwNP and if non‐eosinophilic CRSwNP is associated with interleukin 5 (IL‐5), IL‐8, and tumor necrosis factor α (TNF‐α).

Methods

Nasal polyps specimens were collected from 41 patients with CRSwNP (20 eosinophilic and 21 non‐eosinophilic) undergoing functional endoscopic sinus surgery (FESS). Biopsies of uncinate process, and ethmoidal mucosa from 9 non‐CRS patients were used as controls by means of immunohistochemistry (IHC) staining, Western blotting, and quantitative reverse‐transcription polymerase chain reaction (qRT‐PCR).

Results

HMGB1‐positive expression was significantly increased in the epithelium and among the large inflammatory cells infiltration in Eos CRSwNP and non‐Eos CRSwNP as compared with controls (p < 0.001). The HMGB1 protein and messenger RNA (mRNA) levels of HMGB1, IL‐5, IL‐8, and TNF‐α were significantly higher in eosinophilic CRSwNP than those from controls and non‐eosinophilic CRSwNP, but no significant differences in these markers were found between non‐eosinophilic CRSwNP and controls. HMGB1 expression levels correlated significantly and positively with IL‐5, IL‐8, and TNF‐α (rs = 0.665, 0.771, and 0.724, respectively; p < 0.001) and slightly with eosinophil infiltration (rs = 0.149; p = 0.012) and the blood eosinophils count (rs = 0.225; p = 0.001) in all samples.

Conclusion

Upregulation of HMGB1 could be a significant marker typically in eosinophilic CRSwNP and it may also contribute to the pathogenesis of CRSwNP along with IL‐5, IL‐8, and TNF‐α.
Genetics of low spinal muscular atrophy carrier frequency in sub‐Saharan Africa
Authors: Sangaré Modibo , Hendrickson Brant , Sango Hammadoun Ali , Chen Kelian , Nofziger Jonathan , Amara Abdelbasset , Dutra Amalia , Schindler Alice B. , Guindo Aldiouma , Traoré Mahamadou , Harmison George , Pak Evgenia , Yaro Fatoumata N'Go , Bricceno Katherine , Grunseich Christopher , Chen Guibin , Boehm Manfred , Zukosky Kristen , Bocoum Nouhoum , Meilleur Katherine G. , Daou Fatoumata , Bagayogo Koumba , Coulibaly Yaya Ibrahim , Diakité Mahamadou , Fay Michael P. , Lee Hee‐Suk , Saad Ali , Gribaa Moez , Singleton Andrew B. , Maiga Youssoufa , Auh Sungyoung , Landouré Guida , Fairhurst Rick M. , Burnett Barrington G. , Scholl Thomas , Fischbeck Kenneth H.
Published: February 2014

Objective

Spinal muscular atrophy (SMA) is one of the most common severe hereditary diseases of infancy and early childhood in North America, Europe, and Asia. SMA is usually caused by deletions of the survival motor neuron 1 (SMN1) gene. A closely related gene, SMN2, modifies the disease severity. SMA carriers have only 1 copy of SMN1 and are relatively common (1 in 30–50) in populations of European and Asian descent. SMN copy numbers and SMA carrier frequencies have not been reliably estimated in Malians and other sub‐Saharan Africans.

Methods

We used a quantitative polymerase chain reaction assay to determine SMN1 and SMN2 copy numbers in 628 Malians, 120 Nigerians, and 120 Kenyans. We also explored possible mechanisms for SMN1 and SMN2 copy number differences in Malians, and investigated their effects on SMN mRNA and protein levels.

Results

The SMA carrier frequency in Malians is 1 in 209, lower than in Eurasians. Malians and other sub‐Saharan Africans are more likely to have ≥3 copies of SMN1 than Eurasians, and more likely to lack SMN2 than Europeans. There was no evidence of gene conversion, gene locus duplication, or natural selection from malaria resistance to account for the higher SMN1 copy numbers in Malians. High SMN1 copy numbers were not associated with increased SMN mRNA or protein levels in human cell lines.

Interpretation

SMA carrier frequencies are much lower in sub‐Saharan Africans than in Eurasians. This finding is important to consider in SMA genetic counseling in individuals with black African ancestry. Ann Neurol 2014;75:525–532
Mitochondrial DNA and traumatic brain injury
Authors: Bulstrode Harry , Nicoll James A. R. , Hudson Gavin , Chinnery Patrick F. , Di Pietro Valentina , Belli Antonio
Published: February 2014

Objective

Traumatic brain injury (TBI) is a multifactorial pathology with great interindividual variability in response to injury and outcome. Mitochondria contain their own DNA (mtDNA) with genomic variants that have different physiological and pathological characteristics, including susceptibility to neurodegeneration. Given the central role of mitochondria in the pathophysiology of neurological injury, we hypothesized that its genomic variants may account for the variability in outcome following TBI.

Methods

We undertook an analysis of mitochondrial haplogroups in a large, well‐characterized cohort of 1,094 TBI patients. A proportional odds model including age, brain computed tomography characteristics, injury severity, pupillary reactivity, mitochondrial haplogroups, and APOE was applied to Glasgow Outcome Score (GOS) data.

Results

mtDNA had a significant association with 6‐month GOS (p = 0.008). Haplogroup K was significantly associated with favorable outcome (odds ratio = 1.64, 95% confidence interval = 1.08–2.51, p = 0.02). There was also a significant interaction between mitochondrial genome and age (p = 0.002), with a strong protective effect of both haplogroups T (p = 0.015) and K (p = 0.017) with advancing age. We also found a strong interaction between APOE and mitochondrial haplogroups (p = 0.001), indicating a protective effect of haplogroup K in carriers of the APOE ε4 allele.

Interpretation

These findings reveal an interplay between mitochondrial DNA, pathophysiology of TBI, and aging. Haplogroups K and T, which share a common maternal ancestor, are shown as protective in TBI. The data also suggest that the APOE pathways interact with genetically regulated mitochondrial functions in the response to acute injury, as previously reported in Alzheimer disease. Ann Neurol 2014;75:186–195
Characterization of the Simultaneous Decay Kinetics of Metarhodopsin States II and III in Rhodopsin by Solution‐State NMR Spectroscopy
Authors: Stehle Jochen , Silvers Robert , Werner Karla , Chatterjee Deep , Gande Santosh , Scholz Frank , Dutta Arpana , Wachtveitl Josef , Klein‐Seetharaman Judith , Schwalbe Harald
Published: February 2014

The mammalian visual dim‐light photoreceptor rhodopsin is considered a prototype G protein‐coupled receptor. Here, we characterize the kinetics of its light‐activation process. Milligram quantities of α,ε‐15N‐labeled tryptophan rhodopsin were produced in stably transfected HEK293 cells. Assignment of the chemical shifts of the indole signals was achieved by generating the single‐point‐tryptophan to phenylalanine mutants, and the kinetics of each of the five tryptophan residues were recorded. We find kinetic partitioning in rhodopsin decay, including three half‐lives, that reveal two parallel processes subsequent to rhodopsin activation that are related to the photocycle. The meta II and meta III states emerge in parallel with a relative ratio of about 3:1. Transient formation of the meta III state was confirmed by flash photolysis experiments. From analysis of the site‐resolved kinetic data we propose the involvement of the E2‐loop in the formation of the meta III state.
Makrocyclische Peptide mit dem Zielprotein angepassten Kohlenwasserstoffbrücken: Inhibitoren einer pathogenen Protein‐Protein‐Wechselwirkung
Authors: Glas Adrian , Bier David , Hahne Gernot , Rademacher Christoph , Ottmann Christian , Grossmann Tom N.
Published: February 2014

Bioaktive Peptidkonformationen können durch Makrocyclisierung stabilisiert werden, was zu einer Erhöhung der biologischen Aktivität führen kann. Solche makrocyclischen Peptide wurden bereits für die Modulation einer Reihe von biologischen Funktionen, im Besonderen als Inhibitoren von Protein‐Protein‐Interaktionen (PPIs) verwendet. Allerdings handelt es sich bei den meisten Peptid‐abgeleiteten PPI‐Inhibitoren um stabilisierte α‐Helices, wodurch eine Vielzahl von Sekundärstrukturen nicht berücksichtigt wird. Hier präsentieren wir einen rationalen Ansatz zur Stabilisierung von Peptiden mit irregulärer Struktur durch die Einführung einer hydrophoben Kohlenwasserstoffbrücke. Diese Brücke ersetzt dabei Aminosäureseitenketten, welche für die Bindung an das Zielprotein essentiell sind. Die Wechselwirkung wurde im molekularen Detail durch Röntgenstrukturanalyse und isotherme Titrationskalorimetrie untersucht. Als Ergebnis entstanden intramolekular verbrückte Peptide, die die Interaktion zwischen dem humanen Adapterprotein 14‐3‐3 und dem Virulenzfaktor Exoenzym S inhibieren. Da irreguläre Peptidstrukturen vielfach in PPIs vorkommen, bietet unser Ansatz Zugang zu neuen Peptid‐basierten Inhibitoren.
Ligand‐Controlled α‐ and β‐Arylation of Acyclic N‐Boc Amines
Authors: Millet Anthony , Dailler David , Larini Paolo , Baudoin Olivier
Published: February 2014

The palladium‐catalyzed ligand‐controlled arylation of α‐zincated acyclic amines, obtained by directed α‐lithiation and transmetalation, is described. Whereas PtBu3 gave rise to α‐arylated Boc‐protected amines, more flexible N‐phenylazole‐based phosphine ligands induced major β‐arylation through migrative cross‐coupling.
Active palladium catalyst supported by bulky diimine ligand catalyzed Suzuki–Miyauracoupling reaction in water under phosphane‐free and low catalyst loading conditions
Authors: Gholinejad Mohammad , Karimkhani Vahid , Kim Il
Published: February 2014

A new catalytic system based on palladium and bulky diimine ligand for Suzuki–Miyaura coupling reaction of aryl iodides, bromides and chlorides in neat water is described. The desired biphenyl products were obtained in high to excellent yields for aryl iodides and bromides in the presence of low catalyst loading. Air‐stable catalyst has been recycled for the reaction of iodobenzene with phenylboronic acid for five consecutive runs. Copyright © 2014 John Wiley & Sons, Ltd.
Degradation kinetics of photopolymerizable poly(lactic acid) films
Authors: Miller Kent R. , Soucek Mark D.
Published: February 2014

A series of acrylic poly(lactic acid) (PLA) films were produced via photopolymerization. Enzymatic degradation of the films was investigated by submerging or spraying the films with a solution of proteinase K, Chromobacterium viscosum (CvL), Rhizomucor miehei (RmL), or Candida cylindracea (CcL). Degradation was monitored by titration of the carboxylic acid groups, MS, and MS/MS. It was found that the degradation rate of the films was dependent on the water uptake of the film and enzyme solution used. The highest degradation rates, for both systems, were obtained by use of a proteinase K solution. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40475.
Study on antimicrobial potential of neem oil nanoemulsion against Pseudomonas aeruginosa infection in Labeo rohita
Authors: Mishra Prabhakar , R. S Suresh Kumar , Jerobin Jayakumar , Thomas John , Mukherjee Amitava , Chandrasekaran Natarajan
Published: February 2014

Presence of several biochemical constituents in neem makes it an efficient antimicrobial agent for pathogenic diseases. The current investigation was aimed to assess the therapeutic potential of neem nanoemulsion as a control measure for Pseudomonas aeruginosa infection in freshwater fish Labeo rohita. The median lethal concentration (LC50) for the neem oil and neem nanoemulsion was 73.9 and 160.3 mg/L, respectively. The biomarker enzymes of treated fish tissues showed a significant difference in the level of glutathione reductase, catalase, and lipid peroxidation in neem oil‐treated samples than in neem nanoemulsion‐treated samples at P < 0.05. The results were corroborative with histopathology and ultrastructural analysis. The bacterial infection of P. aeruginosa treated using neem nanoemulsion was more effective in both in vitro and in vivo methods. Present findings suggest that neem‐based nanoemulsion has negligible toxicity to Rohu fishes. This makes neem‐based nanoemulsion as an efficient therapeutic agent against P. aeruginosa infection, leading to its possible usage in the aquaculture industry.
Characterization of the 5′ flanking region of lipase gene from Penicillium expansum and its application in molecular breeding
Authors: Zhang Tian , Peng Ying , Yu Qingsheng , Wang Jieliang , Tang Kexuan
Published: February 2014

A major challenge for further promotion of lipase productivity in Penicillium expansum PE‐12 is to find a suitable promoter that can function efficiently in this industrial strain. In this study, the 5′ flanking region of P. expansum lipase (Ppel) containing a putative novel promoter sequence was characterized by fusing to ‐glucuronidase (GUS) and subsequently introducing into P. expansum. As a result, all the transformants showed blue color quickly after incubation in GUS detection buffer, suggesting a strong promoter activity of this fragment. Glucose repression was identified for the promoter, whereas olive oil acted as a positive regulator. Facilitated by this novel promoter, P. expansum PE‐12 was genetically modified, with an improved lipase yield, via a recombinant plasmid with P. expansum lipase gene (PEL) under the control of Ppel promoter and TtrpC terminator. The highest lipase yield among the modified strains could attain 2,100 U/mL, which is more than twofold of the previous industrial strain (900 U/mL). The engineered strain through molecular breeding method as well as this new promoter has great value in lipase industry.
Pavlovian‐conditioned alcohol‐seeking behavior in rats is invigorated by the interaction between discrete and contextual alcohol cues: implications for relapse
Authors: Remedios Jessica , Woods Catherine , Tardif Catherine , Janak Patricia H. , Chaudhri Nadia
Published: February 2014

Introduction

Drug craving can be independently stimulated by cues that are directly associated with drug intake (discrete drug cues), as well as by environmental contexts in which drug use occurs (contextual drug cues). We tested the hypothesis that the context in which a discrete alcohol‐predictive cue is experienced can influence how robustly that cue stimulates alcohol‐seeking behavior.

Methods

Male, Long‐Evans rats received Pavlovian discrimination training (PDT) sessions in which one conditioned stimulus (CS+; 16 trials/session) was paired with ethanol (0.2 mL/CS+) and a second stimulus (CS−; 16 trials/session) was not. PDT occurred in a specific context, and entries into a fluid port where ethanol was delivered were measured during each CS. Next, rats were acclimated to an alternate (nonalcohol) context where cues and ethanol were withheld. Responses to the nonextinguished CS+ and CS− were then tested without ethanol in the alcohol‐associated PDT context, the nonalcohol context or a third, novel context.

Results

Across PDT the CS+ elicited more port entries than the CS−, indicative of Pavlovian discrimination learning. At test, the CS+ elicited more port entries than the CS− in all three contexts: however, alcohol seeking driven by the CS+ was more robust in the alcohol‐associated context. In a separate experiment, extinguishing the context‐alcohol association did not influence subsequent CS+ responding but reduced alcohol seeking during non‐CS+ intervals during a spontaneous recovery test.

Conclusion

These results indicate that alcohol‐seeking behavior driven by a discrete Pavlovian alcohol cue is strongly invigorated by an alcohol context, and suggest that contexts may function as excitatory Pavlovian conditioned stimuli that directly trigger alcohol‐seeking behavior.
The Surprising Features of the TEAD4‐Vgll1 Protein–Protein Interaction
Authors: Mesrouze Yannick , Hau Jean Christophe , Erdmann Dirk , Zimmermann Catherine , Fontana Patrizia , Schmelzle Tobias , Chène Patrick
Published: February 2014

The Hippo signaling pathway, which controls organ size in animals, is altered in various human cancers. The TEAD transcription factors, the most downstream elements in this pathway, are regulated by different cofactors, such as the Vgll (vestigial‐like) proteins. Having studied the interaction between Vgll1‐derived peptides and human TEAD4, we show that, although it lacks a key secondary structure element required for tight binding by two other TEAD cofactors (YAP and TAZ), Vgll1‐derived peptides bind to TEAD with nanomolar affinity. We identify a β‐strand:loop:α‐helix motif as the minimal Vgll binding site. Finally, we reveal an unexpected difference between mouse and human Vgll1‐derived peptides.
Expansion of the polyQ repeats in THAP11 forms intranuclear aggregation and causes cell G0/G1 arrest
Authors: Yin Rong‐Hua , Li Yang , Yang Fan , Zhan Yi‐Qun , Yu Miao , Ge Chang‐Hui , Xu Wang‐Xiang , Tang Liu‐Jun , Wang Xiao‐Hui , Chen Biao , Yang Yang , Li Jian‐Jie , Li Chang‐Yan , Yang Xiao‐Ming
Published: February 2014

Polyglutamine diseases are a group of neurodegenerative disorders caused by expansion of a CAG repeat that encodes polyglutamine in each respective disease gene. The transcription factor THAP11, a member of THAP family, is involved in cell growth, ES cell pluripotency and embryogenesis. Previous studies suggest that THAP11 protein contains a 29‐residue repeat polyglutamine motif and the number of polyglutamine ranges from 20 to 41 in Indian population. We have investigated the CAG numbers at the THAP11 locus in normal individuals and neurodegenerative disease patients of Chinese Han population and a 38Q expansion (THAP11(38Q)) was found in patients. Using fluorescence confocal‐based cell imaging, THAP11(38Q) protein formed intranuclear inclusions easier than THAP11(29Q) in PC12 cells. Enhanced toxicity was investigated in THAP11(38Q)‐expressing cells by growth inhibition and G0/G1 arrest. CREB‐mediated transcription activity was inhibited by THAP11(38Q). The transcription factor, TBP, coactivator CBP, and chaperon protein, HSP70, could be recruited to THAP11(38Q). These results indicate that expansion of the polyglutamine in THAP11 forms intracellular aggregation and is toxic in PC12 cells, suggesting a putative role of THAP11 in polyglutamine disease.
Crucial role of Notch signaling in osteogenic differentiation of periodontal ligament stem cells in osteoporotic rats
Authors: Li Ying , Li SQ , Gao YM , Li Jin , Zhang Bin
Published: February 2014

Estrogen deficiency‐induced osteoporosis typically occurs in postmenopausal women and has been strongly associated with periodontal diseases. Periodontal ligament stem cells (PDLSCs) isolated from the periodontal ligament can differentiate into many types of specialized cells, including osteoblast‐like cells that contribute to periodontal tissue repair. The Notch signaling pathway is highly conserved and associated with self‐renewal potential and cell‐fate determination. Recently, several studies have focused on the relationship between Notch signaling and osteogenic differentiation. However, the precise mechanisms underlying this relationship are largely unknown. We have successfully isolated PDLSCs from both ovariectomized (OVX) and sham‐operated rats. Both the mRNA and protein levels of Notch1 and Jagged1 were upregulated when PDLSCs were cultured in osteogenic induction media. Mineralization assays showed decreased calcium deposits in OVX‐PDLSCs treated with a γ‐secretase inhibitor compared with control cells. Thus Notch signaling is important in maintaining the osteogenic differentiation of PDLSCs in osteoporotic rats, which help in the development of a potential therapeutic strategy for periodontal disease in postmenopausal women.
Prenatal phenotype of Williams–Beuren syndrome and of the reciprocal duplication syndrome
Authors: Marcato Livia , Turolla Licia , Pompilii Eva , Dupont Celine , Gruchy Nicolas , De Toffol Simona , Bracalente Gabriella , Bacrot Severine , Troilo Enzo , Tabet Anne C. , Rossi Sabrina , Delezoïde Anne L. , Baldo Demetrio , Leporrier Nathalie , Maggi Federico , Molin Arnaud , Pilu Gianluigi , Simoni Giuseppe , Vialard Francois , Grati Francesca R.
Published: February 2014

Key Clinical Message

Copy losses/gains of the Williams–Beuren syndrome (WBS) region cause neurodevelopmental disorders with variable expressivity. The WBS prenatal diagnosis cannot be easily performed by ultrasound because only few phenotypic features can be assessed. Three WBS and the first reciprocal duplication prenatal cases are described with a review of the literature.
Solvent‐ and Ligand‐free Diboration of Alkynes and Alkenes Catalyzed by Platinum Nanoparticles on Titania
Authors: Alonso Francisco , Moglie Yanina , Pastor‐Pérez Laura , Sepúlveda‐Escribano Antonio
Published: February 2014

Platinum nanoparticles supported on titania efficiently catalyzed the diboration of alkynes and alkenes under solvent‐ and ligand‐free conditions in air. The cis‐1,2‐diborylalkenes and 1,2‐diborylalkanes were obtained in moderate to excellent yields following, in most cases, a simple filtration workup protocol. The versatility of the cis‐1,2‐diboronvinyl compounds was demonstrated in a series of organic transformations, including the Suzuki–Miyaura cross coupling and the boron–halogen exchange.
Simulation of Membrane Distillation for Purifying Water Containing 1,1,1‐Trichloroethane
Authors: Ghadiri Mehdi , Abkhiz Vahid , Parvini Mehdi , Marjani Azam
Published: February 2014

Vacuum membrane distillation is modeled for the purification of water containing organic matter. The separation medium is a hollow‐fiber membrane contactor that is simplified to a two‐dimensional structure with a single porous membrane wall. The model considers the transport phenomena of a vacuum membrane distillation system in porous media, in which the aqueous volatile organic solution was considered as an incompressible and steady fluid. The numerical simulation of the two‐dimensional model of vacuum membrane distillation for an aqueous solution of 1,1,1‐trichloroethane was established under steady state. The effects of the bulk feed temperature and the feed flow rate on the percentage of 1,1,1‐trichloroethane removal from an aqueous solution are discussed.
Quinoline‐Based p300 Histone Acetyltransferase Inhibitors with Pro‐apoptotic Activity in Human Leukemia U937 Cells
Authors: Lenoci Alessia , Tomassi Stefano , Conte Mariarosaria , Benedetti Rosaria , Rodriguez Veronica , Carradori Simone , Secci Daniela , Castellano Sabrina , Sbardella Gianluca , Filetici Patrizia , Novellino Ettore , Altucci Lucia , Rotili Dante , Mai Antonello
Published: February 2014

Chemical manipulations performed on 2‐methyl‐3‐carbethoxyquinoline (1), a histone acetyltransferase inhibitor previously identified by our research group and active at the sub‐millimolar/millimolar level, led to compounds bearing higher alkyl groups at the C2‐quinoline or additional side chains at the C6‐quinoline positions. Such compounds displayed at least threefold improved inhibitory potency toward p300 protein lysine acetyltransferase activity; some of them decreased histone H3 and H4 acetylation levels in U937 cells and induced high degrees of apoptosis (three compounds >10‐fold higher than compound 1) after treatment of U937 cells.
Homoleptic Copper(I), Silver(I), and Gold(I) Bisphosphine Complexes
Authors: Kaeser Adrien , Moudam Omar , Accorsi Gianluca , Séguy Isabelle , Navarro Jose , Belbakra Abdelhalim , Duhayon Carine , Armaroli Nicola , Delavaux‐Nicot Béatrice , Nierengarten Jean‐François
Published: February 2014

A series of homoleptic copper(I), silver(I), and gold(I) complexes of two bisphosphine ligands {1,2‐bis(diphenylphosphino)benzene, dppb; bis[2‐(diphenylphosphino)phenyl]ether, POP} have been prepared. Whilst all three [M(dppb)2]BF4 complexes are tetracoordinate, this geometry is found only for the silver(I) complex with POP. Instead, [Cu(POP)2]+ and [Au(POP)2]+ adopt a trigonal coordination geometry with an uncoordinated phosphorus atom. A close inspection of the P–M bond lengths reveals an interesting trend. From the copper to silver and gold complexes, a substantial elongation is found. On the other hand, from the silver to gold compounds, a decrease in the M–P bond length is found. Indeed, gold(I) has a smaller van der Waals radius than silver(I) as a result of its peculiar relativistic effects. Electrochemical investigations revealed two oxidation processes for all of the [M(dppb)2]BF4 and [M(POP)2]BF4 complexes. The first oxidation is likely metal‐centered, whereas the second one corresponds to ligand‐centered processes in all cases. The emission properties of these compounds in solution, in frozen rigid matrices at 77 K, and in the solid state at room temperature have been systematically investigated. Although all of them are weak emitters in solution, remarkably high emission quantum yields were found in the solid state, in particular for [Cu(dppb)2]BF4 and [Ag(dppb)2]BF4. Finally, these two compounds were used for the fabrication of light‐emitting devices. Interestingly, both the copper(I) and the silver(I) complex afford quite broad electroluminescence spectra with white light emission.
Elemental Phosphorus and Electromagnetic Radiation
Authors: Serrano‐Ruiz Manuel , Romerosa Antonio , Lorenzo‐Luis Pablo
Published: February 2014

White phosphorus (P4) is a small molecule that is mainly used as a starting material for the large‐scale synthesis of most of the suitable phosphorus derivatives. The process starts with the direct reaction of P4 with Cl2, and the resulting phosphorus chloride is further treated with the adequate organic substrate. This industrial process is very primitive, and for economic and environmental reasons the first oxidation step should be avoided. The observation that the conversion of white P4 to the red allotrope is accelerated by ultraviolet light showed that the P4 molecule is able to be activated by electromagnetic radiation. Metal complexes can also mediate the functionalization of P4. The participation of electromagnetic radiation in the reactions that involve P4 and metal complexes has provided new procedures for obtaining new and interesting compounds that contain phosphorus atoms. Very significant and interesting reviews have summarized, classified and discussed the reactivity of P4 but until now none of them have distilled the relationship between white phosphorus and electromagnetic radiation.
Resorcinarenyl‐Phosphines in Suzuki–Miyaura Cross‐Coupling Reactions of Aryl Chlorides
Authors: Monnereau Laure , El Moll Hani , Sémeril David , Matt Dominique , Toupet Loïc
Published: February 2014

Two phosphines built on a bowl‐shaped resorcin[4]arene skeleton, namely 5‐diphenylphosphanyl‐ and 5‐diisopropylphosphanyl‐4(24),6(10),12(16),18(22)‐tetramethylenedioxy‐2,8,14,20‐tetrapentylresorcin[4]arene, have been synthesised and tested in the Suzuki–Miyaura cross‐coupling reaction of aryl halides. Combining these ligands with [Pd(OAc)2] resulted in highly active catalysts that allowed the formation of o,o′‐biphenyls starting from aryl chlorides. The remarkable activities observed possibly arise from 1) the capacity of the phosphines to operate transiently as P,O chelators, thereby increasing the electron density of the metal, and 2) the ability of the ligands to embed metal–organic units, which, when occurring, makes the ligand considerably bulkier so as to disfavour the coordination of a second phosphine. Both features are known to facilitate the oxidative addition step.
Total Synthesis and Glycosidase Inhibition Studies of (–)‐Gabosine J and Its Derivatives
Authors: Vidyasagar Adiyala , Sureshan Kana M.
Published: February 2014

The total syntheses of (–)‐gabosine J and its two gabosinol derivatives, the reduced forms of (–)‐gabosine J, were achieved by a chiral pool strategy that started from inexpensive and readily available D‐mannitol. The desymmetrization of the C2‐symmetric tri‐O‐isopropylidene mannitol through a H2SO4/silica mediated hydrolysis of one of the two terminal ketals and a ring‐closing methathesis (RCM) of the appropriately protected diene are the key steps in these syntheses. The preparation of (–)‐gabosine J, which involved simple steps as well as inexpensive and readily available reagents and starting material, was completed in 14 steps with an overall yield of 13 %. Similarly, gabosinol J‐α and gabosinol J‐β (two synthetic derivatives of gabosine J) were prepared in 13 steps in an overall yield of 11 and 6 %, respectively. A preliminary investigation into the biological activity of these compounds revealed that (–)‐gabosine J inhibits α‐mannosidase with an IC50 of 260 μM. Its reduced form gabosinol J‐α inhibits β‐galactosidase with an IC50 of 600 μM, and gabosinol J‐β inhibits β‐glucosidase. This is the first synthesis of a gabosine that employs mannitol as the starting material and the first report of the biological activity of gabosine J.
Synthesis of an Oxidation‐Stable Analogue of Cyclic Pyranopterin Monophosphate (cPMP)
Authors: Hilken Stefan , Kaletta Florian , Heinsch Angela , Neudörfl Jörg‐M. , Berkessel Albrecht
Published: February 2014

Molybdenum cofactor (Moco) deficiency is a lethal hereditary metabolic disease. A recently developed therapy requires continuous intravenous supplementation of the biosynthetic Moco precursor cyclic pyranopterin monophosphate (cPMP). The limited stability of the latter natural product, mostly due to oxidative degradation, is problematic for oral administration. Therefore, the synthesis of more stable cPMP analogues is of great interest. In this context and for the first time, the synthesis of a cPMP analogue, in which the oxidation‐labile reduced pterin unit is replaced by a pyrazine moiety, was achieved starting from the chiral pool materials D‐galactose or D‐arabitol. Our synthesis, 13 steps in total, includes the following key transformations: i) pyrazine lithiation, followed by acylation; ii) closure of the pyrane ring by nucleophilic aromatic substitution; and iii) introduction of phosphate.
Comparative chemical sensitivity between marine Australian and Northern Hemisphere ecosystems: Is an uncertainty factor warranted for water-quality–guideline setting?
Authors: Hagen Tarah G. , Douglas Richard W.
Published: February 2014

The lack of Australian species data has pragmatically led to the use of toxicological data from the Northern Hemisphere to develop water-quality guidelines. However, it is unknown whether Australian species and ecosystems are equally as sensitive and if an uncertainty factor is warranted for Australian guideline setting. In the present study, it is hypothesized that an uncertainty factor is not required. This was tested by generating species sensitivity distributions by 2 parametric methods using marine Northern Hemisphere and Australian/New Zealand data. Sufficient acute data were found for only 3 compounds: 4-chlorophenol, phenol, and ammonia. For ammonia and 4-chlorophenol, the 95% species protection levels generated with Australian and Northern Hemisphere data were essentially the same. For phenol, protection levels derived from Australian data were approximately 10-fold higher. Therefore, the derived benchmark concentration from Northern Hemisphere data should be protective. It is tentatively concluded that there is no need for an uncertainty factor when deriving water-quality guidelines for marine Australian ecosystems using Northern Hemisphere data. It is, however, noted that this is based on only 3 compounds. Environ Toxicol Chem 2014;33:1187–1192. © 2014 SETAC
Investigation of the effects of several porosity variation profiles on performance and pollutants emission of the porous media burners
Authors: Mohammadi Iman , Hossainpour Siamak
Published: February 2014

This paper presents results of numerical investigation on the effect of using variable porosity porous media burner on its performance and pollutant emission. A two‐dimensional axisymmetric model for premixed methane/air combustion in porous media has been developed. This code solves the continuity, Navier Stokes, solid and gas energies, and chemical species transport equations using the finite volume method. The pressure and velocity have been coupled with the SIMPLE algorithm. In this paper, the results of applying two different profiles of porosity instead of constant porosity for two zones of burner have been presented. The results showed that by applying porosity variation along the burner, the peak temperature can be decreased about 4.5%, and subsequently, the amount of exhaust pollutants such as NOx can also be decreased while increase in pressure losses along the burner is negligible. In addition, the effects of excess air ratio, volumetric heat transfer coefficient, inlet velocity, chemical kinetics, conductivity coefficient, and wall temperature on the porous media burners with variation of porosity are investigated. Copyright © 2014 John Wiley & Sons, Ltd.
Assessment of the impact of fire retardants on the combustion of natural polymers employing DTG and LOI
Authors: Bakirtzis D. S. , Tsapara V. C. , Kolovos K. G. , Liodakis S. E.
Published: February 2014

Thermal analysis is widely used for the investigation of the thermal decomposition of polymeric/lignocellulosic materials. Differential thermogravimetry (DTG) curves have been used for the assessment of fire retardants employing a mathematical technique, based on the observation that the DTG profile peaks become less pronounced and are shifted to lower temperatures when a fire retardant is added. The efficiency of a fire retardant is proposed to be assessed from a formula comprising of the following: (i) the depth of the main peak; (ii) the main decomposition peak temperature; (iii) the temperature range of the DTG curve; and (iv) the area above the curve. Initially, four well‐known fire retardants have been assessed for their efficiency on a lignocellulosic matrix (Olea europaea). All the results deriving from the mathematical technique have been compared with the mass residue criterion and a limiting oxygen index test (Relative Limiting Oxygen Index). Both are commonly used as reliable tools for the assessment of a fire retardant. Secondly, the impact of fire retardant concentration on efficiency was investigated. In addition, using mathematical routines, an optimum concentration zone was proposed; further, an optimum concentration value (%) has been estimated. Copyright © 2014 John Wiley & Sons, Ltd.
Structure of Polymorphic Stomata in Canella winterena (L.) Geartn. (Canellaceae)
Authors: Mandal Manasi , Mitra Sonia , Maity D.
Published: February 2014

The presence of 10 types of normal stomata along with 4 subtypes, one intermediate type between stephanocytic and hemiparacytic and some abnormal stomatal structures both in the vegetative and floral organs of Canella winterena (L.) Geartn. (Canellaceae) is reported here. The epidermal cells are polygonal, isodiametric in surface view with straight anticlinal walls. The stomata are amphibrachyparacytic, anomocytic, anisocytic, brachyparacytic, brachyparatetracytic, cyclocytic, hemiparacytic, laterocytic, holoparacytic, stephanocytic, one intermediate type between stephanocytic and hemiparacytic, etc. Abnormalities like contiguous stomata, different types of twin stomata and cytoplasmic bridge between adjacent stomata, stomata with single guard cell, single guard cell with pore juxtaposed with normal stoma are also found. The presence of giant stomata is a significant finding. (© 2014 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)
Carbon and oxygen isotopic composition and foraminifers of condensed basal Zechstein (Upper Permian) strata in western Poland: environmental and stratigraphic implications
Authors: Peryt Tadeusz Marek , Hałas Stanisław , Peryt Danuta
Published: February 2014

The basinal facies of the Lopingian Zechstein Limestone in SW Poland consists of thin (often less than 1 m thick) limestones and/or dolomites, often containing the Kupferschiefer (few tens of centimetres thick) at their base, and local thick (up to 90 m) reefal carbonates. The δ13C curve of these basal Zechstein deposits strongly suggests that even when the Kupferschiefer is lacking, the thin (condensed) sequences record the entire interval of the Zechstein prior to the onset of evaporite deposition, in contrast to the thick reef sequences which lack the characteristic δ13C curve for the lowermost part of the Zechstein. The calcite samples show considerable ranges of δ18O values. If the maximum δ18O values are considered to be the closest to the pristine original ones and if δ18Owater value = 0 is assumed, then the calculated range of palaeotemperatures for the Kupferschiefer and Zechstein Limestone calcite ranges from 19 to 34 °C. The faunal restriction, common dwarf foraminifers and the predominance of lagenids in the foraminiferal assemblage indicate continual dysaerobic conditions and possibly elevated salinity of seawater during deposition of thin basinal Zechstein Limestone deposits. The mixing of shallow and deeper waters in the stratified Zechstein Basin caused by upwelling could result in prolific carbonate precipitation in reefs located at the slope of the marginal carbonate platform of the Zechstein Limestone and in isolated reefs related to palaeohighs within the basin; however, there is no isotopic record of eventual upwelling. Copyright © 2014 John Wiley & Sons, Ltd.
Correlation of β‐catenin, but not PIN1 and cyclin D1, overexpression with disease‐free and overall survival in patients with cancer of the parotid gland
Authors: Lill Claudia , Schneider Sven , Seemann Rudolf , Kadletz Lorenz , Aumayr Klaus , Ghanim Bahil , Thurnher Dietmar
Published: February 2014

Background

Malignant tumors of the salivary glands comprise about 3% to 5% of all head and neck carcinomas. The purpose of our study was to find possible predictive and/or prognostic markers for parotid cancer.

Methods

A total of 46 tissue samples of carcinomas of the parotid gland were immunohistochemically stained for ß‐catenin, cyclin D1, and PIN1. The factors were analyzed regarding their prognostic value for disease‐free and overall survival.

Results

An overexpression of the cytoplasmatic ß‐catenin was linked to a statistically significant worse outcome regarding disease‐free (p = .0296) and overall survival (p = .0416). The 5‐year overall survival was 83.9% in patients without and 0% in patients presenting with overexpression of cytoplasmatic ß‐catenin. Additionally, Union Internationale Contre le Cancer (UICC) stage correlated with overall survival (p = .0306) and disease‐free survival (DFS; p = .0473).

Conclusion

Multivariate analysis showed that overexpression of cytoplasmatic ß‐catenin and the UICC stage are 2 independent prognostic markers for survival in patients with parotid cancer. © 2014 Wiley Periodicals, Inc. Head Neck 37: 30–36, 2015
Entrapment in plasma microparticles: A promising strategy for antigen delivery
Authors: Fatima Munazza T. , Ahmad Ejaj , Saleemuddin Mohammed
Published: February 2014

We report the preparation of plasma microparticles (PMPs) from autologous blood plasma for sustained in vivo delivery of the entrapped antigens. The PMPs were prepared by high speed‐stirring of calcium‐enriched plasma, mixed with the antigen to be entrapped, in mineral oil. The preparation of PMPs did not necessitate addition of any external protein/enzyme nor special laboratory setup. Our results suggest that the PMPs release the entrapped invertase in a sustained manner both in vitro and in vivo, especially after crosslinking with glutaraldehyde. The preparations are reasonably stable to proteolysis and constitute strong candidates for eliciting immune response. Induction of humoral immune response by the PMP‐entrapped invertase, as evident from the high antibody titers, was remarkable and comparable with that observed in animals receiving the antigen emulsified with Freund's Complete Adjuvant. Isotypic analysis of antibodies showed a Th1‐biased immune response in animals administered uncrosslinked or crosslinked PMPs‐entrapped invertase, especially after a booster dose. The analysis in animals of the group immunized with adjuvant‐emulsified antigen suggested a combined Th1 and Th2 response. PMP‐entrapment also caused high expression of surface markers (CD80 and CD86) on antigen presenting cells, as well as effector T‐cells surface markers (CD4+ and CD8+) as revealed by FACS. The study suggests that PMPs offer remarkable promise as adjuvant‐free and biocompatible vaccine delivery systems. © 2014 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 102B: 1244–1254, 2014.
In vitro evaluation of photo‐crosslinkable chitosan‐lactide hydrogels for bone tissue engineering
Authors: Kim Sungwoo , Kang Yunqing , Mercado‐Pagán Ángel E. , Maloney William J. , Yang Yunzhi
Published: February 2014

Here we report the development and characterization of novel photo‐crosslinkable chitosan‐lactide (Ch‐LA) hydrogels for bone tissue engineering. We synthesized the hydrogels based on Ch, LA, and methacrylic anhydride (MA), and examined their chemical structures, degradation rates, compressive moduli, and protein release kinetics. We also evaluated the cytotoxicity of the hydrogels and delivery efficacy of bone morphogenetic protein‐2 (BMP‐2) on osteoblast differentiation and mineralization using W‐20‐17 preosteoblast mouse bone marrow stromal cells and C2C12 mouse myoblast cells. NMR and FTIR revealed that the hydrogels were formed via amidation and esterification between Ch and LA, and methacrylation for photo‐crosslinkable networks. Addition of a hydrophobic LA moiety to a hydrophilic Ch chain increased swellability, softness, and degradation rate of the photo‐crosslinkable Ch‐LA hydrogels. Changes in Ch/LA ratio and UV exposure time significantly affected compressive modulus and protein release kinetics. The photo‐crosslinkable Ch‐LA hydrogels were not cytotoxic regardless of the composition and UV crosslinking time. Higher alkaline phosphatase activities of both W‐20‐17 and C2C12 cells were observed in the less‐crosslinked hydrogels at day 5. Mineralization was enhanced by sustained BMP‐2 release from the hydrogels, but was cell type dependent. This photo‐crosslinkable Ch‐LA hydrogel is a promising carrier for growth factors. © 2014 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 102B: 1393–1406, 2014.