bluuebunny/crossref_metadata_2025 huggingface dataset:
Biosynthetic Origin of the Antibiotic Cyclocarbamate Brabantamide A (SB‐253514) in Plant‐Associated Pseudomonas.
Authors: Schmidt Yvonne , van der Voort Menno , Crüsemann Max , Piel Jörn , Josten Michaele , Sahl Hans‐Georg , Miess Henrike , Raaijmakers Jos M. , Gross Harald
Published: January 2014

Within the framework of our genome‐based program to discover new antibiotic lipopeptides from Pseudomonads, brabantamides A–C were isolated from plant‐associated Pseudomonas sp. SH‐C52. Brabantamides A–C displayed moderate to high in vitro activities against Gram‐positive bacterial pathogens. Their shared structure is unique in that they contain a 5,5‐bicyclic carbamate scaffold. Here, the biosynthesis of brabantamide A (SB‐253514) was studied by a combination of bioinformatics, feeding experiments with isotopically labelled precursors and in vivo and in vitro functional analysis of enzymes encoded in the biosynthetic pathway. The studies resulted in the deduction of all biosynthetic building blocks of brabantamide A and revealed an unusual feature of this metabolite: its biosynthesis occurs via an initially formed linear di‐lipopeptide that is subsequently rearranged by a novel FAD‐dependent Baeyer–Villiger monooxygenase.
ChemInform Abstract: β‐Technetium Dichloride: Solid‐State Modulated Structure, Electronic Structure, and Physical Properties.
Authors: Sattelberger Alfred P. , et al. et al.
Published: January 2014

β‐TcCl2 is synthesized by reaction of Tc metal and Cl2 in a sealed Pyrex tube at 450 °C for 24 h, and characterized by single crystal XRD, magnetic susceptibility, band gap, and charge transport measurements, and DFT calculations.
ChemInform Abstract: Electronic and Ionic Conductivity in Alkaline Earth Diazenides MAEN2 (MAE: Ca, Sr, Ba) and in Li2N2.
Authors: Schneider Sebastian B. , Mangstl Martin , Friederichs Gina M. , Frankovsky Rainer , Schmedt auf der Guenne Joern , Schnick Wolfgang
Published: January 2014

6Li2N2, nondoped Li2N2 (I), SrN2 (II), and BaN2 (III) are prepared from their respective azides by high pressure isostatic hot pressing (multianvil press, 9 GPa for (I) and (II), 3 GPa for (III), 750—850 K, 15—50 min).
ChemInform Abstract: A Rapid Microwave‐Assisted Solvothermal Approach to Lower‐Valent Transition Metal Oxides.
Authors: Moorhead‐Rosenberg Zachary , Harrison Katharine L. , Turner Travis , Manthiram Arumugam
Published: January 2014

Binary oxides such as V4O9, Mn3O4 or MnO, CoO, and Cu2O are prepared within a short reaction time of 30 min by reduction of V2O5, MnO2, Co3O4, or CuO with tetraethylene glycol under microwave irradiation at <300 °C.
ChemInform Abstract: Hydrothermal Preparation, Structure and Characterizations of Noncentrosymmetric LiZnO(IO3).
Authors: Gao Jianhua , Li Shuai , Li Jian , Sanjeewa Liurukara Duminda
Published: January 2014

The new title compound is hydrothermally prepared from aqueous mixtures of ZnO, Li2CO3, and HIO3 (autoclave, 200 °C, 7 d, 80% yield).
ChemInform Abstract: Crystal Structures and Properties of Europium Aluminum Oxynitride Eu2AlO3.75N0.1 and Europium Aluminum Oxide EuAl2O4.
Authors: Tezuka Keitaro , Tokuhara Yoshimi , Wakeshima Makoto , Shan Yue Jin , Imoto Hideo , Hinatsu Yukio
Published: January 2014

Eu2AlO3.75N0.1 (I) and EuAl2O4 (II) are synthesized by reaction of Eu2O3, AlN, and Al2O3 with Eu/Al ratios of 2:1 and 1:2, respectively (silica tubes, 1200 °C, 10 h).
ChemInform Abstract: Y2MoSe3O12 and Y2MoTe3O12: Solid‐State Synthesis, Structure Determination, and Characterization of Two New Quaternary Mixed Metal Oxides Containing Asymmetric Coordination Environment.
Authors: Bang Seong‐eun , Pan Zhi , Kim Yeong Hun , Lee Dong Woo , Ok Kang Min
Published: January 2014

Y2MoSe3O12 (I) and Y2MoTe3O12 (II) are prepared by solid state reactions of stoichiometric amounts of Y2O3, MoO3, and SeO2 or TeO2 (evacuated silica tubes, 700 resp.
ChemInform Abstract: Arylations of Substituted Enamides by Aryl Iodides: Regio‐ and Stereoselective Synthesis of (Z)‐β‐Amido‐β‐Arylacrylates.
Authors: Gou Quan , Deng Bin , Zhang Hongbin , Qin Jun
Published: January 2014

The use of the unusual catalyst system PdCl2(cod)/Ag3PO4 and the assistance of a directing carbonyl group allow the highly regio‐ and stereoselective reaction of enamides with aryl iodides to give the corresponding (Z)‐products.
ChemInform Abstract: Free‐Amine Directed Arylation of Biaryl‐2‐amines with Aryl Iodides by Palladium Catalysis.
Authors: Liang Zunjun , Feng Ruokun , Yin Hong , Zhang Yuhong
Published: January 2014

The title method allows the synthesis of ortho‐monoarylated or diarylated biaryl‐2‐amines with exclusive regioselectivity.
ChemInform Abstract: Diaminophosphine Oxide Ligand Enabled Asymmetric Nickel‐Catalyzed Hydrocarbamoylations of Alkenes.
Authors: Donets Pavel A. , Cramer Nicolai
Published: January 2014

The novel chiral diaminophosphine oxide ligand SPO is used in a catalytic system in combination with nickel(0) and trimethylaluminum to activate formamide C—H bonds under mild conditions providing pyrrolidones via intramolecular hydrocarbamoylation.
ChemInform Abstract: Pd(II)‐Catalyzed Intramolecular 1,2‐Aminoalkylation of Conjugated 1,3‐Dienes for the Synthesis of Pyrrolizidines.
Authors: Xing Dong , Yang Dan
Published: January 2014

A palladium(II)‐catalyzed tandem cyclization reaction involving an intramolecular 1,2‐aminoalkylation of N‐4,6‐dienyl β‐keto amides is developed.
ChemInform Abstract: Synthesis of New Pyrazole‐1,2,3‐triazole Dyads.
Authors: Ferreira Joana P. A. , Silva Vera L. M. , Elguero Jose , Silva Artur M. S.
Published: January 2014

Upon reaction with hydrazine hydrate, previously described chromon‐2‐yl‐1H‐1,2,3‐triazoles (I) afford title compounds (II).
ChemInform Abstract: β‐Lactam‐Synthon‐Interceded Synthesis of Isatin—Imidazolidine‐2‐thione Conjugates with Structural Validation Using Molecular Dynamic Simulations and Cytotoxic Evaluation.
Authors: Nisha Nisha , Singh Parvesh , Hendricks Denver T. , Bisetty Krishna , Kumar Vipan
Published: January 2014

The anion derived from isatins (I) reacts with isocyanates (II) to form imidazolidine‐2‐thiones (III), some of which show significant cytotoxic activity against the oesophageal cancer cell line WHCO1.
ChemInform Abstract: Efficient Multicomponent Synthesis of Mono‐, Bis‐, Tris‐1,2,3‐triazoles Supported by Hydroxybenzene Scaffolds.
Authors: Mendoza‐Espinosa Daniel , Negron‐Silva Guillermo E. , Lomas‐Romero Leticia , Gutierrez‐Carrillo Atilano , Soto‐Castro Delia
Published: January 2014

Starting from mono‐, di‐, and tripropargyloxybenzenes the synthesis of the title species is achieved via 1,3‐dipolar cycloaddition reaction with sodium azide and benzyl halides.
ChemInform Abstract: Copper‐Catalyzed Tandem Azide—Alkyne Cycloaddition, Ullmann Type C—N Coupling, and Intramolecular Direct Arylation.
Authors: Pericherla Kasiviswanadharaju , Jha Amitabh , Khungar Bharti , Kumar Anil
Published: January 2014

Novel triazole‐fused heterocycles are regioselectively obtained via a ligand‐free copper‐catalyzed tandem azide—alkyne cycloaddition (CuAAC), Ullmann‐type C—N coupling reaction and subsequent intramolecular C—C bond formation by C—H functionalization.
ChemInform Abstract: Catalytic Asymmetric Construction of Chiral Hydropyridazines via Conjugate Addition of N‐Monosubstituted Hydrazones to Enones.
Authors: Wu Wenbin , Yuan Xiaoqian , Hu Juan , Wu Xinxin , Wei Yuan , Liu Zunwu , Lu Junzhu , Ye Jinxing
Published: January 2014

The first examples of a highly enantioselective formal diaza‐ene reaction between N‐monosubstituted hydrazones and enones are reported.
ChemInform Abstract: Synthesis of 3‐Tetrazolylmethyl‐azepino[4,5‐b]indol‐4‐ones in Two Reaction Steps: (Ugi‐Azide/N‐Acylation/SN2)/Free Radical Cyclization and Docking Studies to a 5‐Ht6 Model.
Authors: Gordillo‐Cruz Raul E. , Renteria‐Gomez Angel , Islas‐Jacome Alejandro , Cortes‐Garcia Carlos J. , Diaz‐Cervantes Erik , Robles Juvencio , Gamez‐Montano Rocio
Published: January 2014

Nine novel 3‐tetrazolylmethyl‐azepinoindolones (VII) are synthesized starting from tryptamine (I) and evaluated for their interactions with the 5‐Ht6 protein.
ChemInform Abstract: Broensted Base Catalyzed [2,3]‐Wittig/Phospha‐Brook Tandem Rearrangement Sequence.
Authors: Kondoh Azusa , Terada Masahiro
Published: January 2014

The reaction products can be easily transformed into structurally diverse building blocks.
ChemInform Abstract: Discovery and Biological Activity of New Chondramides from Chondromyces sp.
Authors: Herrmann Jennifer , Huettel Stephan , Mueller Rolf
Published: January 2014

Over 30 new Chondramine derivatives are isolated and identified from Chrondromyces sp.
ChemInform Abstract: Biomimetic Synthesis of ent‐(—)‐Azonazine and Stereoochemical Reassignment of Natural Product.
Authors: Zhao Ji‐Chen , Yu Shun‐Ming , Liu Yun , Yao Zhu‐Jun
Published: January 2014

The first total synthesis of ent‐(‐)‐azonazine (I) is accomplished using a hypervalent iodine‐mediated biomimetic oxidative cyclization to construct the highly strained core (not shown).
ChemInform Abstract: Antiviral Spirooliganones A (I) and B (II) with Unprecedented Skeletons from the Roots of Illicium oligandrum.
Authors: Yu Shi‐Shan , et al. et al.
Published: January 2014

The two isolated compounds show obvious activities against coxsackie virus B3 and influenza virus A, whereas spirooliganone B is the more potent one (IC50 3.70‐5.05 μM).
ChemInform Abstract: Cucurbit[n]uril‐Based Coordination Chemistry: From Simple Coordination Complexes to Novel Poly‐Dimensional Coordination Polymers
Authors: Tao Zhu , et al. et al.
Published: January 2014

Review: 130 refs.
ChemInform Abstract: Reaction of Diazo Compounds with Organoboron Compounds
Authors: Li Huan , Zhang Yan , Wang Jianbo
Published: January 2014

Review: 58 refs.
ChemInform Abstract: Profound Methyl Effects in Drug Discovery and a Call for New C—H Methylation Reactions
Authors: Schoenherr Heike , Cernak Tim
Published: January 2014

Review: <100 refs.
ChemInform Abstract: Expanding the Scope of Metathesis: A Survey of Polyfunctional, Single‐Site Supported Tungsten Systems for Hydrocarbon Valorization
Authors: Popoff Nicolas , Mazoyer Etienne , Pelletier Jeremie , Gauvin Regis M. , Taoufik Mostafa
Published: January 2014

Review: 122 refs.
ChemInform Abstract: Tunable Assembly of Amphiphilic Rod‐Coil Block Copolymers in Solution
Authors: Zhang Jie , Chen Xiao‐Fang , Wei Hai‐Bing , Wan Xin‐Hua
Published: January 2014

Review: valuable contribution in the past six years on the self‐assembly behavior of rod‐coil block copolymers; 239 refs.
ChemInform Abstract: Polymer‐ and Ionic Liquid‐Containing Palladium: Recoverable Soluble Cross‐Coupling Catalysts
Authors: Navalon Sergio , Alvaro Mercedes , Garcia Hermenegildo
Published: January 2014

Review: <150 refs.
ChemInform Abstract: Sol—Gel Microencapsulation of Odorants and Flavors: Opening the Route to Sustainable Fragrances and Aromas
Authors: Ciriminna Rosaria , Pagliaro Mario
Published: January 2014

Review: 43 refs.
ChemInform Abstract: Supramolecular Chemistry and Chemical Warfare Agents: From Fundamentals of Recognition to Catalysis and Sensing
Authors: Sambrook M. R. , Notman S.
Published: January 2014

Review: 47 refs.
Structural Basis for the Inhibition of AKR1B10 by Caffeic Acid Phenethyl Ester (CAPE)
Authors: Zhang Liping , Zhang Hong , Zheng Xuehua , Zhao Yining , Chen Shangke , Chen Yunyun , Zhang Renwei , Li Qing , Hu Xiaopeng
Published: January 2014

Caffeic acid phenethyl ester (CAPE), the major bioactive component of honeybee propolis, is a potent selective inhibitor of aldo‐keto reductase family member 1B10 (AKR1B10), and a number of derivatives hold promise as potential anticancer agents. However, sequence homology between AKR1B10 and other members of the superfamily, including critical phase I metabolizing enzymes, has resulted in a concern over the selectivity of any potential therapeutic agent. To elucidate the binding mode of CAPE with AKR1B10 and to provide a tool for future in silico efforts towards identifying selective inhibitors, the crystal structure of AKR1B10 in complex with CAPE was determined. The observed interactions provide an explanation for the selectivity exhibited by CAPE for AKR1B10, and could be used to guide further derivative design.
Comparative effectiveness of upfront treatment strategies in elderly women with ovarian cancer
Authors: Wright Jason D. , Ananth Cande V. , Tsui Jennifer , Glied Sherry A. , Burke William M. , Lu Yu‐Shiang , Neugut Alfred I. , Herzog Thomas J. , Hershman Dawn L.
Published: January 2014

BACKGROUND

Observational studies comparing neoadjuvant chemotherapy to primary surgery for advanced‐stage ovarian cancer are limited by strong selection bias. Multiple methods were used to control for confounding and selection bias to estimate the effect of primary treatment on survival for ovarian cancer.

METHODS

The Surveillance, Epidemiology, and End Results (SEER)‐Medicare database was used to identify women ≥ 65 years of age with stage II‐IV epithelial ovarian cancer who survived > 6 months from the date of diagnosis and received treatment from 1991 through 2007. Traditional regression analysis, propensity score‐based analysis, and an instrumental variable analysis (IVA) using geographic location as an instrument were used to compare survival between neoadjuvant chemotherapy and primary surgery.

RESULTS

A total of 9587 patients with stage II‐IV ovarian cancer were identified. Use of primary surgery decreased from 63.2% in 1991 to 49.5% by 2007, whereas primary chemotherapy increased from 19.7% in 1991 to 31.8% in 2007 (P < .0001). In the observational cohort survival (hazard ratio [HR] = 1.27; 95% confidence interval [CI] = 1.19−1.35) was inferior for patients treated with neoadjuvant chemotherapy; both median survival (15.8 versus 28.8 months) and 2‐year survival (36% versus 56%) were lower in the neoadjuvant chemotherapy group compared to those who underwent surgery. In the IVA, primary treatment had minimal effect on overall survival (HR = 1.04; 95% CI = 0.67−1.60). The median survival for patients with a value of the instrument less than the median (24.0 months, 95% CI = 23.0−25.0) and greater than or equal to median value of the IV (24.0 months, 95% CI = 23.0−26.0) were similar.

CONCLUSIONS

Use of neoadjuvant therapy has increased over time. Survival with neoadjuvant chemotherapy did not differ significantly from primary surgery in elderly women in the United States. Cancer 2014;120:1246–1254. © 2014 American Cancer Society.
Cost‐effectiveness of a standard intervention versus a navigated intervention on colorectal cancer screening use in primary care
Authors: Lairson David R. , DiCarlo Melissa , Deshmuk Ashish A. , Fagan Heather B. , Sifri Randa , Katurakes Nora , Cocroft James , Sendecki Jocelyn , Swan Heidi , Vernon Sally W. , Myers Ronald E.
Published: January 2014

BACKGROUND

Colorectal cancer (CRC) screening is cost‐effective but underused. The objective of this study was to determine the cost‐effectiveness of a mailed standard intervention (SI) and tailored navigation interventions (TNIs) to increase CRC screening use in the context of a randomized trial among primary care patients.

METHODS

Participants (n = 945) were randomized either to a usual care control group (n = 317), to an SI group (n = 316), or to a TNI group (n = 312). The SI group was sent both colonoscopy instructionsandstool blood tests irrespective of baseline preference. TNI group participants were sent instructions for scheduling a colonoscopy, a stool blood test, or both based on their test preference, as determined at baseline; then, they received a navigation telephone call. Activity cost estimation was used to determine the cost of each intervention and to compute incremental cost‐effectiveness ratios. Statistical uncertainty within the base case was assessed with 95% confidence intervals derived from net benefit regression analysis. The effects of uncertain parameters, such as the cost of planning, training, and involvement of those receiving “investigator salaries,” were assessed with sensitivity analyses.

RESULTS

Program costs of the SI were $167 per participant. The average cost of the TNI was $289 per participant.

CONCLUSIONS

The TNI was more effective than the SI but substantially increased the cost per additional individual screened. Decision‐makers need to consider cost structure, level of planning, and training required to implement these 2 intervention strategies and their willingness to pay for additional individuals screened to determine whether a tailored navigation would be justified and feasible.Cancer2014;120:1042–1049. ©2013 American Cancer Society.
Anatomy of the auditory thalamocortical system in the mongolian gerbil: Nuclear origins and cortical field‐, layer‐, and frequency‐specificities
Authors: Saldeitis Katja , Happel Max F.K. , Ohl Frank W. , Scheich Henning , Budinger Eike
Published: January 2014

Knowledge of the anatomical organization of the auditory thalamocortical (TC) system is fundamental for the understanding of auditory information processing in the brain. In the Mongolian gerbil (Meriones unguiculatus), a valuable model species in auditory research, the detailed anatomy of this system has not yet been worked out in detail. Here, we investigated the projections from the three subnuclei of the medial geniculate body (MGB), namely, its ventral (MGv), dorsal (MGd), and medial (MGm) divisions, as well as from several of their subdivisions (MGv: pars lateralis [LV], pars ovoidea [OV], rostral pole [RP]; MGd: deep dorsal nucleus [DD]), to the auditory cortex (AC) by stereotaxic pressure injections and electrophysiologically guided iontophoretic injections of the anterograde tract tracer biocytin. Our data reveal highly specific features of the TC connections regarding their nuclear origin in the subdivisions of the MGB and their termination patterns in the auditory cortical fields and layers. In addition to tonotopically organized projections, primarily of the LV, OV, and DD to the AC, a large number of axons diverge across the tonotopic gradient. These originate mainly from the RP, MGd (proper), and MGm. In particular, neurons of the MGm project in a columnar fashion to several auditory fields, forming small‐ and medium‐sized boutons, and also hitherto unknown giant terminals. The distinctive layer‐specific distribution of axonal endings within the AC indicates that each of the TC connectivity systems has a specific function in auditory cortical processing. J. Comp. Neurol. 522:2397–2430, 2014. © 2014 Wiley Periodicals, Inc.
Parvalbumin and calbindin expression in parallel thalamocortical pathways in a gleaning bat, Antrozous pallidus
Authors: del Campo Heather Martin , Measor Kevin , Razak Khaleel A.
Published: January 2014

The pallid bat (Antrozous pallidus) listens to prey‐generated noise to localize and hunt terrestrial prey while reserving echolocation to avoid obstacles. The thalamocortical connections in the pallid bat are organized as parallel pathways that may serve echolocation and prey localization behaviors. Thalamic inputs to the cortical echolocation call‐ and noise‐selective regions originate primarily in the suprageniculate nucleus (SG) and ventral division of medial geniculate body (MGBv), respectively. Here we examined the distribution of parvalbumin (PV) and calbindin (CB) expression in cortical regions and thalamic nuclei of these pathways. Electrophysiology was used to identify cortical regions selective for echolocation calls and noise. Immunohistochemistry was used to stain for PV and CB in the auditory cortex and MGB. A higher percentage (relative to Nissl‐stained cells) of PV+ cells compared with CB+ cells was found in both echolocation call‐ and noise‐selective regions. This was due to differences in cortical layers V–VI, but not layers I–IV. In the MGB, CB+ cells were present across all divisions of the MGB, with a higher percentage in the MGBv than the SG. Perhaps the most surprising result was the virtual absence of PV staining in the MGBv. PV staining was present only in the SG. Even in the SG, the staining was mostly diffuse in the neuropil. These data support the notion that calcium binding proteins are differentially distributed in different processing streams. Our comparative data, however, do not support a general mammalian pattern of PV/CB staining that distinguishes lemniscal and nonlemniscal pathways. J. Comp. Neurol. 522:2431–2445, 2014. © 2014 Wiley Periodicals, Inc.
Nonlinear finite element simulations of injuries with free boundaries: Application to surgical wounds
Authors: Valero C. , Javierre E. , García‐Aznar J. M. , Gómez‐Benito M. J.
Published: January 2014

Wound healing is a process driven by biochemical and mechanical variables in which a new tissue is synthesised to recover original tissue functionality. Wound morphology plays a crucial role in this process, as the skin behaviour is not uniform along different directions. In this work, we simulate the contraction of surgical wounds, which can be characterised as elongated and deep wounds. Because of the regularity of this morphology, we approximate the evolution of the wound through its cross section, adopting a plane strain hypothesis. This simplification reduces the complexity of the computational problem; while allows for a thorough analysis of the role of wound depth in the healing process, an aspect of medical and computational relevance that has not yet been addressed. To reproduce wound contraction, we consider the role of fibroblasts, myofibroblasts, collagen and a generic growth factor. The contraction phenomenon is driven by cell‐generated forces. We postulate that these forces are adjusted to the mechanical environment of the tissue where cells are embedded through a mechanosensing and mechanotransduction mechanism. To solve the nonlinear problem, we use the finite element method (FEM) and an updated Lagrangian approach to represent the change in the geometry. To elucidate the role of wound depth and width on the contraction pattern and evolution of the involved species, we analyse different wound geometries with the same wound area. We find that deeper wounds contract less and reach a maximum contraction rate earlier than superficial wounds. Copyright © 2014 John Wiley & Sons, Ltd.
Palladium‐Based Anion‐Exchange Membrane Fuel Cell Using KOH‐Doped Polybenzimidazole as the Electrolyte
Authors: Fujigaya Tsuyohiko , Kim ChaeRin , Matsumoto Kazuya , Nakashima Naotoshi
Published: January 2014

The development of a low‐cost and high‐performance fuel cell is a strong social demand. Anion‐exchange membrane fuel cells (AEMFCs) have recently emerged as an alternative technology to conventional fuel cells that use a proton‐exchange membrane as they enable the use of cheaper metals than platinum. An AEMFC exhibiting a maximum power density of 241 mW cm−2 based on a palladium‐based electrocatalyst has been developed. The polybenzimidazole‐wrapped carbon nanotubes were used to anchor the palladium nanoparticles, and the material was doped using KOH to form an ideal triple‐phase boundary structure around the palladium. The observed maximum power density is the highest among previously reported AEMFCs using palladium as the metal catalyst.
Scaling in structural complexity
Authors: De Biagi Valerio , Chiaia Bernardino
Published: January 2014

Structural complexity has been shown to be a measure of the variety of load paths in structures with high degree of static indeterminacy, for example, frames. The variations of the value of complexity parameters across different structures have been investigated in previous researches. Herein, the effects of scaling on load distribution and on geometry of the structural scheme are outlined. A scale invariance is shown for load magnitude. Complexity variation is outlined for geometric similar structures, depending essentially on the consistency of the load set. A transition in the behavior of the structural scheme under loads is recorded in case of similar structures from small to large scales. The results are discussed. © 2014 Wiley Periodicals, Inc. Complexity 20: 57–63, 2014
MyD88 signalling in myeloid cells is sufficient to prevent chronic mycobacterial infection
Authors: Berod Luciana , Stüve Philipp , Swallow Maxine , Arnold‐Schrauf Catharina , Kruse Friederike , Gentilini Maria V. , Freitag Jenny , Holzmann Bernhard , Sparwasser Tim
Published: January 2014

Tuberculosis is a chronic infectious disease caused by Mycobacterium tuberculosis that is responsible for almost 1.5 million deaths per year. Sensing of mycobacteria by the host's immune system relies on different families of receptors present on innate immune cells. Amongst them, several members of the TLR family are involved in the activation of immune cells by mycobacteria, yet the in vivo contribution of individual TLRs to the protective immune response remains controversial. On the contrary, MyD88, the adaptor molecule for most TLRs, plays a non‐redundant role in the protection against tuberculosis and mice with a complete germline deletion of MyD88 succumb very early to infection. MyD88 is expressed in both immune and non‐immune cells, but it is not clear whether control of mycobacteria requires ubiquitous or cell‐type specific MyD88 expression. Therefore, using novel conditional switch‐on mouse models, we aimed to investigate the importance of MyD88 signalling in DCs and macrophages for the induction of protective effector mechanisms against mycobacterial infection. We conclude that specific reactivation of MyD88 signalling in CD11c‐ or lysozyme M‐expressing myeloid cells during Mycobacterium bovis Bacille Calmette‐Guerin infection is sufficient to restore systemic and local inflammatory cytokine production and to control pathogen burden.
From I‐Ligated and I‐Doped to O‐Ligated Hafnium(IV) Phthalocyaninate(2–) Complexes
Authors: Janczak Jan , Kubiak Ryszard
Published: January 2014

Treatment of HfPcI2·Pht (Pc = C32H16N82–; Pht = phthalonitrile) or bromide analogue HfPcBr2·Pht with acetylacetone (acacH) led to the formation of a HfPc(acac)2 complex that, depending on the crystallization conditions, crystallized with solvent acacH molecules to form mono‐ and disolvate crystals: HfPc(acac)2·acacH (1) and HfPc(acac)2·2acacH (2). Treatment of the partially oxidized iodine sandwich‐type hafnium(IV) diphthalocyanine HfPc2(I3)2/3, in which two of three HfPc2 units are a one‐electron‐oxidized [HfPc2]+ unit with a π‐radical character, with benzonitrile (BN) or 4‐methylpyridine (4‐Mepy) under ambient conditions led to the formation of μ2(O,OH)(C6H5COO)(HfPc)2 (3), which is bridged by O2– and OH– and stapled together by deprotonated benzoic acid complex, and μ2(O,OH)(C5H4NCOO)(HfPc)2 (4), which is bridged by O2– and OH– and stapled by deprotonated isonicotinic acid. Complexes 1–4 were structurally characterized by X‐ray single‐crystal analysis. In these complexes, the eight or seven coordination number of the closed‐shell (d0) Hf4+ cation is saturated by four isoindole nitrogen atoms of the phthalocyaninate macrocycle and by four oxygen atoms in 1 and in 2 or three oxygen atoms in 3 and 4. Interaction of the Hf4+ cation with the isoindole nitrogen atoms of Pc macrocycle led to the distortion of the aromatic Pc macrocycle to the flattened crown, with the Hf4+ cation about 1.2 Å out of the N4‐isoindole plane of the Pc macrocycle. The complexes were also characterized by UV/Vis spectroscopy.
Lanthanide Complexes with Heteroditopic Ligands as Fluorescent Zinc Sensors
Authors: Roger Mélissa , Regueiro‐Figueroa Martín , Ben Azzeddine Chams , Patinec Véronique , Bonnet Célia S. , Platas‐Iglesias Carlos , Tripier Raphaël
Published: January 2014

We report the synthesis of two ligands containing a DO3A unit (H3DO3A = 1,4,7,10‐tetraazacyclododecane‐1,4,7‐triacetic acid) linked to a triazacyclononane (TACN) moiety by a 2,6‐dimethylpyridine spacer designed to form stable Ln3+ complexes in solution that respond to the presence of Zn2+ ions. The Eu3+ and Gd3+ complexes have been characterized by using a combination of experimental and theoretical techniques that include absorption and emission electronic spectroscopy, NMR spectroscopy, 1H relaxometry, and DFT calculations. The Ln3+ ions are eight‐coordinated by the ligand, which binds to the metal ion through the seven donor atoms of the DO3A unit and the nitrogen atom of the pyridyl linker. Luminescence lifetime measurements recorded from solutions of the Eu3+ complexes in H2O and D2O and relaxometric measurements point to the absence of inner‐sphere water molecules. The addition of Zn2+ causes important changes in the absorption spectra of the complexes that evidence the formation of both 1:1 and 2:1 (Ln3+/Zn2+) complex species. However, the emission lifetimes of the Eu3+ complexes and relaxivity experience weak changes, thus indicating that Zn2+ addition does not significantly affect the number of coordinated water molecules. The Gd3+ complexes show a weak emission band at 325 nm, the intensity of which dramatically increases in the presence of Zn2+. However, the “turn‐on” behaviour induced by Zn2+ is not observed for other metal cations such as Ca2+, Mg2+ or Cu2+. DFT calculations indicate that a photoinduced electron‐transfer (PET) process is responsible for the quenching of the luminescence in the absence of Zn2+.
Unique Deca‐ and Tetranuclear Halocuprate(I) Clusters of a Clamplike Ligand: Isolation, Structure, and Luminescence Properties
Authors: Li Li , Li Hai‐Yan , Ren Zhi‐Gang , Lang Jian‐Ping
Published: January 2014

The reaction of 3‐aminopyridine with formaldehyde afforded a clamplike ligand, 3,7‐di(3‐pyridyl)‐1,5‐dioxa‐3,7‐diazacyclooctane (L). The diffusion of a CH2Cl2 solution of L into an MeCN solution of CuX produced one decanuclear cluster [Cu10Cl10(L)4] (1) and two tetranuclear clusters [Cu4X4(L)2(MeCN)2] [X = Br (2), I (3)]. Compound 1 possesses a unique [Cu10Cl10] cluster core consisting of two stairlike [Cu5Cl5] fragments that share two μ6‐Cl and two μ‐Cl atoms. Compounds 2 and 3 have a stairlike [Cu4X4] cluster core that is anchored by two L ligands. The trans configuration of the two pyridyl groups of the free L ligand was converted into the cis configuration of the two pyridyl groups of each bridging L ligand in 1–3. The photoluminescence properties of 1–3 in the solid state were also investigated.
Polyoxometalate Multi‐Electron‐Transfer Catalytic Systems for Water Splitting
Authors: Sumliner Jordan M. , Lv Hongjin , Fielden John , Geletii Yurii V. , Hill Craig L.
Published: January 2014

The viable production of solar fuels requires a visible‐light‐absorbing unit, a H2O (or CO2) reduction catalyst (WRC), and a water oxidation catalyst (WOC) that work in tandem to split water or reduce CO2 with H2O rapidly, selectively, and for long periods of time. Most catalysts and photosensitizers developed to date for these triadic systems are oxidatively, thermally, and/or hydrolytically unstable. Polyoxometalates (POMs) constitute a huge class of complexes with extensively tunable properties that are oxidatively, thermally, and (over wide and adjustable pH ranges) hydrolytically stable. POMs are some of the fastest and most stable WOCs to date under optimal conditions. This Microreview updates the very active POM WOC field; it reports the application of POMs as WRCs and initial self‐assembling metal oxide semiconductor–photosensitizer–POM catalyst triad photoanodes. The complexities of investigating these POM systems, including but not limited to the study of POM‐hydrated metal‐ion–metal‐oxide speciation processes, are outlined. The achievements and challenges in POM WOC, WRC, and triad research are outlined.
Oxo‐Rhenium(V) Complexes Containing Heterocyclic Ligands as Catalysts for the Reduction of Sulfoxides
Authors: Sousa Sara C. A. , Bernardo Joana R. , Wolff Mariusz , Machura Barbara , Fernandes Ana C.
Published: January 2014

This work reports the catalytic activity of a large variety of oxo‐rhenium(V) complexes (1 mol‐%) containing the ligands 2‐(2‐hydroxy‐5‐methylphenyl)benzotriazole (Hhmpbta), 2‐(2‐hydroxyphenyl)benzothiazole (Hhpbt), 2‐(2‐hydroxyphenyl)benzoxazole (Hhpbo), and 2‐(2‐hydroxyphenyl)‐1H‐benzimidazole (Hhpbi) in the deoxygenation of sulfoxides with silanes or boranes as the reducing agents. In general, all of the complexes are excellent catalysts, although the PhSiH3/[ReOBr2(hmpbta)(PPh3)] and pinacolborane/[ReOBr2(hmpbta)(PPh3)] systems are the most efficient for the reduction of aromatic and aliphatic sulfoxides and tolerate different functional groups.
Removal of arsenic (III) and arsenic (V) using copper exchange zeolite‐a
Authors: Pillewan Pradnya , Mukherjee Shrabanti , Meher Alok Kumar , Rayalu Sadhana , Bansiwal Amit
Published: January 2014

In this work, modification of zeolite‐A was performed by ion exchange method using copper salts and the copper exchanged zeolite (CEZ) was used for removal of Arsenic (III) and Arsenic (V) from water. The adsorption capacity of zeolite‐A was significantly improved after modification by copper. CEZ removes more than 98% of both As (III) and As (V) from monocomponent solutions. The material was characterized by powder X‐ray diffraction (XRD) and scanning electron microscopy (SEM). XRD pattern shows loss in crystalline structure after copper incorporation which is evident from the decrease in intensity of characteristic peaks of zeolite‐A. SEM images shows that cubical morphology characteristic of zeolite‐A has been distorted after copper incorporation. Various isotherm and kinetic models were used to determine adsorption and kinetic parameters and to delineate the probable mechanism of adsorption. The data revealed that adsorption of arsenic on CEZ followed Langmuir model with maximum sorption capacity of 1.37 and 1.48 mg/g at 30°C for As (III) and As (V), respectively. CEZ effectively removes arsenic from water at wide pH range of 3–10 and in the presence of interfering ions namely phosphate, sulfate, nitrate, carbonate, and bicarbonate which is evident from tap water study. CEZ appears to be a promising adsorbent for removing arsenic from water. The water quality after treatment with CEZ also confirms that it is safe for drinking purpose and within the permissible limits as per World Health Organization guideline values and Indian drinking water standards. © 2014 American Institute of Chemical Engineers Environ Prog, 33: 1274–1282, 2014
Developmental toxicity of treated municipal wastewater effluent on Bombina orientalis (Amphibia: Anura) embryos
Authors: Park Chan Jin , Ahn Hyo Min , Cho Seong Chan , Kim Tae-Hoon , Oh Jong-Min , Ahn Hong Kyu , Chun Seung-Hoon , Gye Myung Chan
Published: January 2014

Amphibian populations have been decreasing in urban freshwater systems in Korea. To elucidate the biological safety of treated wastewater effluent (TWE) in the Tancheon basin, the capital area of Korea, a 7-d–exposure Bombina orientalis embryo developmental toxicity assay was examined during the breeding season. In March, there were no significant differences in embryonic survival or malformation among the water samples. In July, following monsoon precipitation, embryonic lethality in TWE was significantly higher than in the upstream water sample. Malformation in TWE and TWE-mixed waters was significantly higher than in the control and upstream water samples. Tail muscle height of tadpoles also significantly decreased in TWE and TWE-mixed waters. Heavy metals were not detected in any samples. Total nitrogen, total phosphorous, and chemical oxygen demand in TWE markedly increased together with a decrease in dissolved oxygen in July. The increase in organic and inorganic loading following precipitation could have made TWE and TWE-mixed water not suitable for embryonic development. Though being managed based on physicochemical criteria, the water quality of TWE may not be sufficient to assure normal development of amphibian embryos. An amphibian developmental toxicity assay would be helpful for the water-quality management of TWE and urban freshwater systems in Korea. Environ Toxicol Chem 2014;33:954–961. © 2014 SETAC
Arecoline stimulated early growth response‐1 production in human buccal fibroblasts: Suppression by epigallocatechin‐3‐gallate
Authors: Hsieh Yu‐Ping , Chen Hsin‐Ming , Chang Jenny Zwei‐Chieng , Chiang Chun‐Pin , Deng Yi‐Ting , Kuo Mark Yen‐Ping
Published: January 2014

Background

Early growth response‐1 (Egr‐1) protein plays an important role in many human fibrotic diseases. Areca nut chewing is the most important risk factor of oral submucous fibrosis (OSF).

Methods

Egr‐1 protein expression in OSF was examined using antibody to Egr‐1. Arecoline‐induced Egr‐1 expression and its signaling pathways were assessed by Western blot analyses in human buccal mucosal fibroblasts (BMFs).

Results

Elevated Egr‐1 staining was observed in epithelial cells, fibroblast, and inflammatory cells in 7 of 10 OSF cases. Arecoline, a main alkaloid found in the areca nut, stimulated Egr‐1 synthesis in BMFs. Pretreatment with antioxidant N‐acetyl‐L‐cysteine, c‐Jun NH2‐terminal kinase inhibitor SP600125, and extracellular signal‐regulated kinase inhibitor PD98059 significantly reduced arecoline‐induced Egr‐1 synthesis. Epigallocatechin‐3‐gallate (EGCG) inhibited arecoline‐induced Egr‐1 synthesis and collagen gel contraction in a dose‐responsive manner.

Conclusion

Constitutive Egr‐1 expression during areca nut chewing may play a role in the pathogenesis of OSF. EGCG could be a good candidate for prevention or treatment of OSF. © 2014 Wiley Periodicals, Inc. Head Neck 37: 493–497, 2015
New Dammarane‐Type Saponins from the Roots of Panax notoginseng
Authors: Qiu Li , Jiao Yang , Huang Gui‐Kun , Xie Ji‐Zhao , Miao Jian‐Hua , Yao Xin‐Sheng
Published: January 2014

Three new dammarane‐type triterpenoid saponins, 1–3, were isolated and identified as (20S)‐20‐O‐[β‐D‐xylopyranosyl‐(1→6)‐β‐D‐glucopyranosyl‐(1→6)‐β‐D‐glucopyranosyl]dammar‐24‐ene‐3β,6α,12β, 20‐tetrol (1), (20S)‐6‐O‐[(E)‐but‐2‐enoyl‐(1→6)‐β‐D‐glucopyranosyl]dammar‐24‐ene‐3β,6α,12β,20‐tetrol (2), and (20S)‐6‐O‐[β‐D‐xylopyranosyl‐(1→2)‐β‐D‐xylopyranosyl]dammar‐24‐ene‐3β,6α,12β,20‐tetrol (3) from the roots of Panax notoginseng (Burkill) F.H.Chen (Araliaceae). Their structures were elucidated on the basis of spectroscopic analyses, including 1D‐ and 2D‐NMR techniques and HR‐ESI‐MS, as well as by acidic hydrolysis.
Enterolactone concentrations and prognosis after postmenopausal breast cancer: Assessment of effect modification and meta‐analysis
Authors: Seibold Petra , Vrieling Alina , Johnson Theron S. , Buck Katharina , Behrens Sabine , Kaaks Rudolf , Linseisen Jakob , Obi Nadia , Heinz Judith , Flesch‐Janys Dieter , Chang‐Claude Jenny
Published: January 2014

We previously reported that high concentrations of enterolactone, a lignan metabolite, are associated with lower mortality in 1,140 breast cancer patients from Germany. Using an extended set of 2,182 patients aged 50–74 years at diagnosis (2001–2005) and prospectively followed up until 2009, we investigated whether the association with mortality differs by lifestyle factors and tumor characteristics. Hazard ratios (HR) and 95% confidence intervals (CI) were estimated using multivariable Cox regression. Potential differential effects by tumor characteristics and lifestyle factors were assessed and a meta‐analysis of five studies addressing lignan exposure and breast cancer prognosis was performed to summarize evidence. Median enterolactone concentrations were 17.4 (±30.5 standard deviation) and 22.9 nmol L−1 (±44.8), respectively, for 269 deceased and 1,913 patients still alive. High enterolactone concentrations were significantly associated with lower all‐cause mortality (per 10 nmol L−1: HR 0.94, 95% CI 0.90–0.98), breast cancer‐specific mortality (HR 0.94, 0.89–0.99), and distant disease‐free survival (HR 0.94, 0.90–0.98). Associations were found for stage 0–IIIA but not for stage IIIB–IV disease (phet = 0.01) and were stronger in patients with BMI <25 kg m−2 than those with BMI ≥25 (phet = 0.04). In patients with healthy lifestyle (BMI <25, nonsmoker, physically active), the inverse association with all‐cause mortality was still apparent (HR 0.92, 0.85–0.99). The meta‐analysis yielded significant associations both for all‐cause (HR 0.57, 0.42–0.78) and breast cancer‐specific mortality (HR 0.54, 0.39–0.75). Our findings show that high lignan exposure is associated with reduced mortality in breast cancer patients. The inverse association observed in this study cannot be entirely explained by a healthy lifestyle.
Endocrine Effects of Marijuana
Authors: Brown Todd T. , Dobs Adrian S.
Published: January 2014

In the 35 years since the active compound of marijuana Δ9‐tetrahydrocannabinol, was isolated, the psychological and physiological impact of marijuana use has been actively investigated. Animal models have demonstrated that cannabinoid administration acutely alters multiple hormonal systems, including the suppression of the gonadal steroids, growth hormone, prolactin, and thyroid hormone and the activation of the hypothalamic‐pituitary‐adrenal axis. These effects are mediated by binding to the endogenous cannabinoid receptor in or near the hypothalamus. Despite these findings in animals, the effects in humans have been inconsistent, and discrepancies are likely due in part to the development of tolerance. The long‐term consequences of marijuana use in humans on endocrine systems remain unclear.
A national comparison of burnout and work‐life balance among internal medicine hospitalists and outpatient general internists
Authors: Roberts Daniel L. , Shanafelt Tait D. , Dyrbye Liselotte N. , West Colin P.
Published: January 2014

BACKGROUND

General internists suffer higher rates of burnout and lower satisfaction with work‐life balance than most specialties, but the impact of inpatient vs outpatient practice location is unclear.

METHODS

Physicians in the American Medical Association Physician Masterfile were previously surveyed about burnout, depression, suicidal ideation, quality of life, fatigue, work‐life balance, career plans, and health behaviors. We extracted and compared data for these variables for the 130 internal medicine hospitalists and 448 outpatient general internists who participated. Analyses were adjusted for age, sex, hours worked, and practice setting.

RESULTS

There were 52.3% of the hospitalists and 54.5% of the outpatient internists affected by burnout (P = 0.86). High scores on the emotional exhaustion subscale (43.8% vs 48.1%, P = 0.71) and on the depersonalization subscale (42.3% vs 32.7%, P = 0.17) were common but similar in frequency in the 2 groups. Hospitalists were more likely to score low on the personal accomplishment subscale (20.3% vs 9.6%, P = 0.04). There were no differences in symptoms of depression (40.3% for hospitalists vs 40.0% for outpatient internists, P = 0.73) or recent suicidality (9.2% vs 5.8%, P = 0.15). Rates of reported recent work‐home conflict were similar (48.4% vs 41.3%, P = 0.64), but hospitalists were more likely to agree that their work schedule leaves enough time for their personal life and family (50.0% vs 42.0%, P = 0.007).

CONCLUSIONS

Burnout was common among both hospitalists and outpatient general internists, although hospitalists were more satisfied with work‐life balance. A better understanding of the causes of distress and identification of solutions for all internists is needed. Journal of Hospital Medicine 2014;9:176–181. © 2014 Society of Hospital Medicine
Intra‐articular injection of rhFGF‐18 improves the healing in microfracture treated chondral defects in an ovine model
Authors: Power Jonathon , Hernandez Paula , Guehring Hans , Getgood Alan , Henson Frances
Published: January 2014

Microfracture is a common cartilage repair procedure. Strategies to improve healing post‐microfracture include the use of growth factors to enhance hyaline cartilage production. This study investigates the effect of intra‐articular recombinant human fibroblastic growth factor 18 (rhFHF18) on the healing of a chondral defect treated with microfracture in an ovine model. Chondral defects (8 mm diameter) were created in the medial femoral condyle of 80 sheep (n = 16/treatment group). Defects were treated with microfracture alone or microfracture + intra‐articular rhFGF‐18 (administered either as one or two cycles of 3× weekly injections). Outcome measures included mechanical testing, macroscopic International Cartilage Repair Society repair score, modified O'Driscoll histology score, qualitative histology, and immunohistochemistry for types I, II, and VI collagen. In treated animals, there was a statistically significant improvement in ICRS tissue repair score and tissue infill score, in the modified O'Driscoll score between control and 1 cycle of rhFGF‐18 at 6 m, and in the cartilage repair score and structural characteristic score between the control and both rhFGF‐18 groups at 6 m. There was no evidence of degeneration of adjacent cartilage in the rhFGF‐18 treated cartilage. The increase in hyaline cartilage‐like tissue formed in the microfracture + rhFGF‐18 treated groups indicates that rhFGF‐18 potentiates the formation of hyaline cartilage repair following microfracture. © 2014 Orthopaedic Research Society. Published by Wiley Periodicals, Inc. J Orthop Res 32:669–676, 2014.
A non‐destructive approach for doping profiles characterization by micro‐Raman spectroscopy: the case of B‐implanted Ge
Authors: Sanson A. , Napolitani E. , Carnera A. , Impellizzeri G. , Giarola M. , Mariotto G.
Published: January 2014

B‐implanted Ge samples have been investigated by micro‐Raman spectroscopy under different excitation wavelengths, with the aim of gaining insights about the B distribution at different depths beneath the sample surface. The intensities, observed under the different excitation wavelengths, of the B–Ge Raman peak at about 545 cm−1, which is due to the local vibrational mode of the substitutional B atoms in the Ge matrix, have been used to calibrate the optical absorption lengths in B‐implanted Ge. Then, by using these calibrated values, a very sharp correlation between the spectral features of the Ge–Ge Raman peak at ~300 cm−1 and the content of substitutional B atoms has been derived. Accordingly, a non‐destructive approach, based on micro‐Raman spectroscopy under different excitation wavelengths, is presented to estimate, at least at the lowest depths, the carrier concentration profiles from the spectral features of the Ge–Ge Raman peak. Copyright © 2014 John Wiley & Sons, Ltd.
Shear Reversible Cell/Microsphere Aggregate as an Injectable for Tissue Regeneration
Authors: Woo Eunkyeong , Park Honghyun , Lee Kuen Yong
Published: January 2014

Injectable delivery systems have been widely used in tissue engineering as they can deliver cells into the body in a minimally invasive manner. In this study, it is hypothesized that microspheres with a similar size of cells could effectively form a shear reversible aggregate in the presence of cells and the aggregate could be useful to engineer tissues. Alginate microspheres are prepared by an emulsion method, followed by modification with a peptide containing the arginine‐glycine‐aspartic acid (RGD) sequence. RGD‐modified alginate microspheres form an aggregate in the presence of chondrocytes, and the aggregation behavior is shear reversible. This cell/microsphere aggregate is useful to deliver chondrocytes into an animal model using a syringe, and effectively regenerates cartilage tissues in vivo.