bluuebunny/crossref_metadata_2025 huggingface dataset:
Optical Patterning of Sol–Gel Silica Coatings
Authors: Desbœufs Nicolas , Vu Anh‐Duc , Lahlil Khalid , Lassailly Yves , Martinelli Lucio , Boilot Jean‐Pierre , Peretti Jacques , Gacoin Thierry
Published: November 2015

Azobenzene molecules are well known for their photoswitching properties. When incorporated into a polymer film, push−pull azobenzene derivatives such as the DR1 (Dispersed Red 1) confer to the film some remarkable photomechanical properties, allowing for the direct optical inscription of relief patterns. While mainly investigated in the case of organic polymers such as poly(methyl methacrylate) (PMMA), it was shown some years ago that similar photoinduced deformation phenomena could occur in materials using sol‐gel silica as a host matrix. In the present study, the process is revisited, showing that photopatterning can be drastically improved through a careful control of the rheology of the sol‐gel film. Increase in the photoinscribed relief pattern amplitude by up to a factor of three to four is thus achieved. In the second step, it is also shown that sol‐gel silica matrix offers the possibility of removing all organic compounds from the film after photostructuration, without any relaxation of the patterns. This opens the way toward the use of sol‐gel azo/silica films for the elaboration of micro and nanostructured transparent silica coatings that could be used for many applications among which there is light extraction management in light emitting devices.
Body proportions in children with Kabuki syndrome
Authors: Penders Bas , Schott Nina , Gerver Willem‐Jan M. , Stumpel Constance T. R. M.
Published: November 2015

Facial characteristics, short stature, and skeletal anomalies have been described for the clinical diagnosis of Kabuki Syndrome (KS) in children. However, no studies have investigated body proportions in KS. Knowledge of body proportions in KS may contribute to better insight into the growth pattern and characterization of this genetic disorder. Therefore we compared body proportions of children with KS to normally proportioned controls to investigate if atypical body proportions are part of this genetic disorder. This study was designed and conducted within the setting of the Maastricht University Medical Centre (MUMC+), the official Dutch expert center for Kabuki syndrome. We conducted a cross‐sectional study in 32 children (11 children with KS and 21 controls). Body proportions were determined by means of photogrammetric anthropometry, measurements based on digital photography. Body proportions, quantified as body ratios, differ significantly in children with KS from normally proportioned children. Children with KS have larger heads and longer arms proportional to their trunks and have been found to have longer upper arms proportional to their tibia length and feet. Based on deviations in body proportions it was shown possible to discern children with KS from normally proportioned controls. © 2015 Wiley Periodicals, Inc.
Struktur der Dioxygenase AsqJ: mechanistische Einblicke in die Eintopf‐Mehrstufen‐Biosynthese eines Chinolonantibiotikums
Authors: Bräuer Alois , Beck Philipp , Hintermann Lukas , Groll Michael
Published: November 2015

Für die Biosynthese von Naturstoffen sind Multi‐Enzymkaskaden verantwortlich, die generell eine Inspirationsquelle für Synthesechemiker darstellen. Die FeII/α‐Ketoglutarat‐abhängige Dioxygenase AsqJ aus Aspergillus nidulans ist außergewöhnlich, da sie stereoselektiv sowohl eine Desaturierung als auch Epoxidierung eines Benzodiazepindions katalysiert. Interessanterweise löst das enzymatisch gebildete, gespannte Spiro‐Epoxid die enzymunabhängige Umlagerung des 6,7‐Bicyclus zum 6,6‐Chinolongerüst des Alkaloids 4′‐Methoxyviridicatin aus. Verschiedene Kristallstrukturen des Proteins in Ab‐ und Anwesenheit synthetisierter Substrate, Substratanaloga und Zwischenprodukte erlaubten uns, die einzelnen Stufen der Reaktionssequenz dieser einzigartigen Dioxygenase nachzuahmen und zu hinterleuchten.
Precrystalline Aggregates Enable Control over Organic Crystallization in Solution
Authors: Shahar Chen , Dutta Sounak , Weissman Haim , Shimon Linda J. W. , Ott Holger , Rybtchinski Boris
Published: November 2015

Understanding and controlling organic crystallization in solution is a long‐standing challenge. Herein, we show that crystallization of an aromatic amphiphile based on perylene diimide in aqueous media involves initially formed amorphous spherical aggregates that evolve into the crystalline phase. The initial appearance of the crystalline order is always confined to the spherical aggregates that are precursors for crystalline evolution. The change in the solvation of the prenucleation phase drives the crystallization process towards crystals that exhibit very different structure and photofunction. The initial molecular structure and subsequent crystal evolution can be regulated by tuning the hydrophobicity at various stages of crystallization, affording dissimilar crystalline products or hindering crystallization. Thus, the key role of the precrystalline states in organic crystal evolution enables a new strategy to control crystallization by precrystalline state manipulation.
A Highly Reactive Seven‐Coordinate Osmium(V) Oxo Complex: [OsV(O)(qpy)(pic)Cl]2+
Authors: Liu Yingying , Ng Siu‐Mui , Lam William W. Y. , Yiu Shek‐Man , Lau Tai‐Chu
Published: November 2015

Seven‐coordinate ruthenium oxo species have been proposed as active intermediates in catalytic water oxidation by a number of highly active ruthenium catalysts, however such species have yet to be isolated. Reported herein is the first example of a seven‐coordinate group 8 metal‐oxo species, [OsV(O)(qpy)(pic)Cl]2+ (qpy=2,2′:6′,2′′:6′′,2′′′‐quaterpyridine, pic=4‐picoline). The X‐ray crystal structure of this complex shows that it has a distorted pentagonal bipyramidal geometry with an OsO distance of 1.7375 Å. This oxo species undergoes facile O‐atom and H‐atom‐transfer reactions with various organic substrates. Notably it can abstract H atoms from alkylaromatics with CH bond dissociation energy as high as 90 kcal mol−1. This work suggests that highly active oxidants may be designed based on group 8 seven‐coordinate metal oxo species.
Radical [1,3] Rearrangements of Breslow Intermediates
Authors: Alwarsh Sefat , Xu Yi , Qian Steven Y. , McIntosh Matthias C.
Published: November 2015

Breslow intermediates that bear radical‐stabilizing N substituents, such as benzyl, cinnamyl, and diarylmethyl, undergo facile homolytic CN bond scission under mild conditions to give products of formal [1,3] rearrangement rather than benzoin condensation. EPR experiments and computational analysis support a radical‐based mechanism. Implications for thiamine‐based enzymes are discussed.
A Peptidyl‐Transesterifying Type I Thioesterase in Salinamide Biosynthesis
Authors: Ray Lauren , Yamanaka Kazuya , Moore Bradley S.
Published: November 2015

Salinamide A belongs to a rare class of bicyclic depsipeptide antibiotics in which the installation of a (4‐methylhexa‐2,4‐dienoyl)glycine handle across a hexadepsipeptide core contributes to its chemical complexity and biological properties. Herein, we report the genetic and biochemical basis for salinamide construction in the marine bacterium Streptomyces sp. CNB‐091, which involves a novel intermolecular transesterification reaction catalyzed by a type I thioesterase. Heterologous expression studies revealed the central role of the nonribosomal peptide synthetase Sln9 in constructing and installing the distinctive acylglycine “basket handle” of salinamide. Biochemical characterization of the Sln9 thioesterase domain established that transesterification of the serine residue of desmethylsalinamide E with acylated glycyl thioesters yields desmethylsalinamide C.
Obesity and the Relative Risk of Knee Replacement Surgery in Patients With Knee Osteoarthritis: A Prospective Cohort Study
Authors: Leyland Kirsten M. , Judge Andrew , Javaid M. Kassim , Diez‐Perez Adolfo , Carr Andrew , Cooper Cyrus , Arden Nigel K. , Prieto‐Alhambra Daniel
Published: November 2015

Objective

It is unclear what impact obesity has on the progression of knee osteoarthritis (OA) from diagnosis to knee replacement surgery. This study was undertaken to examine the relative risk of knee replacement surgery in overweight and obese patients who were newly diagnosed as having knee OA in a community setting.

Methods

Subjects were selected from the Information System for Development of Primary Care Research database, which compiles comprehensive clinical information collected by health care professionals for >5.5 million people in Catalonia, Spain (80% of the population). Patients newly diagnosed as having knee OA in primary care between 2006 and 2011 were included. Knee replacement was ascertained using International Classification of Diseases, Ninth Revision, Clinical Modification codes from linked hospital admissions data. Multivariable Cox regression models were fitted for knee replacement according to body mass index (BMI), and were adjusted for relevant confounders. Population proportional attributable risk was calculated.

Results

A total of 105,189 participants were followed up for a median of 2.6 years (interquartile range 1.3–4.2). Of these patients, 7,512 (7.1%) underwent knee replacement. Adjusted hazard ratios and 95% confidence intervals (95% CIs) for knee replacement for the World Health Organization BMI categories were 1.41 (95% CI 1.27–1.57) for overweight, 1.97 (95% CI 1.78–2.18) for obese I, 2.39 (95% CI 2.15–2.67) for obese II, and 2.67 (95% CI 2.34–3.04) for obese III compared to normal weight. The effect of BMI on risk of knee replacement was stronger among younger participants. The population attributable risk of obesity for knee OA–related knee replacement was 31.0%.

Conclusion

Overweight and obese patients are at >40% and 100% increased risk of knee replacement surgery, respectively, compared to patients with normal weight. This association is even stronger in younger patients. Weight reduction strategies could potentially reduce the need for knee replacement surgery by 31% among patients with knee OA.
Association of Joint Inflammation With Pain Sensitization in Knee Osteoarthritis: The Multicenter Osteoarthritis Study
Authors: Neogi Tuhina , Guermazi Ali , Roemer Frank , Nevitt Michael C. , Scholz Joachim , Arendt‐Nielsen Lars , Woolf Clifford , Niu Jingbo , Bradley Laurence A. , Quinn Emily , Frey Law Laura
Published: November 2015

Objective

Pain sensitization is associated with pain severity in knee osteoarthritis (OA), but its cause in humans is not well understood. We examined whether inflammation, assessed as synovitis and effusion on magnetic resonance imaging (MRI), or mechanical load, assessed as bone marrow lesions (BMLs), was associated with sensitization in knee OA.

Methods

Subjects in the Multicenter Osteoarthritis Study, a National Institutes of Health–funded cohort of persons with or at risk of knee OA, underwent radiography and MRI of the knee, and standardized quantitative sensory testing (temporal summation and pressure pain threshold [PPT]) of the wrist and patellae at baseline and 2 years later. We examined the relation of synovitis, effusion, and BMLs to temporal summation and PPT cross‐sectionally and longitudinally.

Results

There were 1,111 subjects in the study sample (mean age 67 years, mean body mass index 30 kg/m2, 62% female). Synovitis was associated with a significant decrease in PPT at the patella (i.e., more sensitized) over 2 years (adjusted β −0.30 [95% confidence interval (95% CI) −0.52, −0.08]). Effusion was similarly associated with a decrease in PPT at the wrist (adjusted β −0.24 [95% CI −0.41, −0.08]) and with risk of incident temporal summation at the patella (adjusted OR 1.54 [95% CI 1.01, 2.36]). BMLs were not associated with either quantitative sensory testing measure.

Conclusion

Inflammation, as evidenced by synovitis or effusion, is associated with pain sensitization in knee OA. In contrast, BMLs do not appear to contribute to sensitization in knee OA. Early targeting of inflammation is a reasonable strategy to test for prevention of sensitization and through this, reduction of pain severity, in knee OA.
Derivation and External Validation of a Prediction Rule for Five‐Year Mortality in Patients With Early Diffuse Cutaneous Systemic Sclerosis
Authors: Domsic Robyn T. , Nihtyanova Svetlana I. , Wisniewski Stephen R. , Fine Michael J. , Lucas Mary , Kwoh C. Kent , Denton Christopher P. , Medsger Thomas A.
Published: November 2015

Objective

Although diffuse cutaneous systemic sclerosis (dcSSc) is associated with a reduction in life expectancy, there are no validated prognostic models for determining 5‐year mortality in patients with dcSSc. The objective of this study was to derive and validate a rule for predicting 5‐year mortality in patients with early dcSSc.

Methods

We studied an inception cohort of 388 US Caucasian patients with early dcSSc (<2 years from the appearance of the first symptom). Predefined baseline variables were analyzed in a stepwise logistic regression model in order to identify factors independently associated with 5‐year all‐cause mortality. We rounded the beta weights to the nearest integer and summed the points assigned to each variable in order to stratify patients into low‐risk (<0 points), moderate‐risk (1–2 points), and high‐risk (≥3 points) groups. We then applied this rule to an external validation cohort of 144 Caucasian patients with early dcSSc from the Royal Free Hospital cohort and compared stratum‐specific 5‐year mortality.

Results

Six independent predictors (rounded beta weight) comprised the model: age at first visit (points allotted: −1, 0, or 1), male sex (points allotted: 0 or 1), tendon friction rubs (points allotted: 0 or 1), gastrointestinal involvement (points allotted: 0 or 1), RNA polymerase III antibodies (points allotted: 0 or 1), and anemia (points allotted: 0 or 1). The 3‐level risk stratification model performed well, with no significant differences between the US derivation cohort and the UK validation cohort.

Conclusion

We derived and externally validated, in US and UK cohorts, an easy‐to‐use 6‐variable prediction rule that assigns low‐risk, moderate‐risk, and high‐risk categories for 5‐year mortality in patients with early dcSSc. Only history, physical examination, and basic laboratory assessments are required.
When Is Osteonecrosis Not Osteonecrosis?: Adjudication of Reported Serious Adverse Joint Events in the Tanezumab Clinical Development Program
Authors: Hochberg Marc C. , Tive Leslie A. , Abramson Steven B. , Vignon Eric , Verburg Kenneth M. , West Christine R. , Smith Michael D. , Hungerford David S.
Published: November 2015

Objective

Tanezumab, a monoclonal antibody against nerve growth factor, has demonstrated efficacy in clinical trials of chronic pain in osteoarthritis (OA) and chronic low back pain. Unexpected adverse events (AEs) described as osteonecrosis (ON) occurred during tanezumab development, leading the US Food and Drug Administration to impose a partial clinical hold for all indications except cancer pain. A blinded Adjudication Committee (AC) including orthopedic surgeons, rheumatologists, and an orthopedic pathologist reviewed and adjudicated joint‐related AEs in the tanezumab clinical program.

Methods

The AC adjudicated all reported cases of ON as well as cases of total joint replacements (TJRs) not reported as ON for which radiographs obtained within 9 months of the surgery were available. The AC prespecified categories for joint safety events including primary ON, worsening OA (rapid progression of OA [RPOA], normal progression of OA, insufficient information to distinguish between rapid and normal progression of OA), other, or insufficient information to distinguish between primary ON and worsening OA or another diagnosis.

Results

The AC reviewed events in 249 of 386 patients with an investigator‐reported AE of ON and/or a TJR. Two events were adjudicated as primary ON, 200 events were adjudicated as worsening OA (68 of which were classified as RPOA), 29 events had another diagnosis, 11 had insufficient information to distinguish primary ON from worsening OA, and 7 did not have committee member consensus.

Conclusion

Despite initial reports, tanezumab treatment was not associated with an increase in ON but was associated with an increase in RPOA. Higher doses of tanezumab, tanezumab administered with nonsteroidal antiinflammatory drugs, and preexisting subchondral insufficiency fractures were risk factors for RPOA in this cohort.
Global Output‐Feedback Stabilization for Stochastic Nonlinear Systems with Function Control Coefficients
Authors: Jin Shaoli , Liu Yungang , Man Yongchao
Published: November 2015

This paper investigates the global output‐feedback stabilization for a class of stochastic nonlinear systems with function control coefficients. Notably, the systems in question possess control coefficients that are functions of output, rather than constants; hence, they are different from the existing literature on stochastic stabilization. To solve the control problem, an appropriate reduced‐order observer is introduced to reconstruct the unmeasured system states before a smooth output‐feedback controller is designed using the backstepping method, which guarantees that the closed‐loop system is globally asymptotically stable in probability. This paper combines the related results in the deterministic and stochastic setting and gives the first treatment on the global output‐feedback stabilization for the stochastic nonlinear systems with function control coefficients. A simulation example is given also to illustrate the effectiveness of the proposed approach.
Action Dynamics in Intertemporal Choice Reveal Different Facets of Decision Process
Authors: Cheng Jiuqing , González‐Vallejo Claudia
Published: November 2015

Two experiments were conducted to examine decision process in intertemporal choice with spatial and temporal action dynamic measures generated from cursor movement. The effects of the context valence (gain and loss) and magnitude of the payoffs (small and large) were investigated. Other factors examined were differences between decisions made at versus away from the indifference point and response variability dependent on what was selected (delayed versus non‐delayed/less‐delayed payoff). Using principal components analysis, decision process is described with three orthogonal components. General decision difficulty is encompassed by two components: (1) Conflict, depicted by Idle time and deviations from a direct choice path, and (2) decision uncertainty or Wavering, described by left‐right directional flips. A general Locomotion factor was also present. In Experiment 1, Conflict was best at capturing the gain/loss and magnitude context effects. Greater Conflict was observed in the loss context and the small magnitude condition. When choices were closer to the indifference point, Wavering was most salient. In Experiment 2, when selecting larger, delayed payoffs, both Conflict and Wavering increased suggesting that controlling the temptation of selecting the sooner, smaller reward entails effort. By analyzing trajectories, the study advances knowledge of the construct validity of different action dynamic measures and supports the distinction of decision uncertainty and decision conflict. Copyright © 2015 John Wiley & Sons, Ltd.
The (In)visibility of Psychodiagnosticians' Expertise
Authors: Schulte‐Mecklenbeck Michael , Spaanjaars Nanon L. , Witteman Cilia L. M.
Published: November 2015

This study investigates decision making in mental health care. Specifically, it compares the diagnostic decision outcomes (i.e., the quality of diagnoses) and the diagnostic decision process (i.e., pre‐decisional information acquisition patterns) of novice and experienced clinical psychologists. Participants' eye movements were recorded while they completed diagnostic tasks, classifying mental disorders. In line with previous research, our findings indicate that diagnosticians' performance is not related to their clinical experience. Eye‐tracking data provide corroborative evidence for this result from the process perspective: experience does not predict changes in cue inspection patterns. For future research into expertise in this domain, it is advisable to track individual differences between clinicians rather than study differences on the group level. Copyright © 2015 John Wiley & Sons, Ltd.
Which one of the two common reporter systems is more suitable for chemiluminescent enzyme immunoassay: alkaline phosphatase or horseradish peroxidase?
Authors: Yu Songcheng , Yu Fei , Liu Lie , Zhang Hongquan , Zhang Zhenzhong , Qu Lingbo , Wu Yongjun
Published: November 2015

Alkaline phosphatase and horseradish peroxidase are the most commonly used reporter systems in chemiluminescent enzyme immunoassay (CLEIA). Which one, therefore, would be better when establishing a CLEIA method for a new target substance? There was no standard answer. In this study, both reporters were compared systematically including luminescence kinetics, conjugation methods, optimal condition and detection performance, using two common drugs, SD‐methoxy‐pyrimidine and enrofloxacin, as determination objects. The results revealed that there was much difference between the luminescence kinetics of the two systems. However, there was little difference between these systems when detecting the same substance, including in optimal conditions and determination of performance. Both reporters were suitable for establishing chemiluminescent enzyme immunoassays. Therefore, the choice of alkaline phosphatase or horseradish peroxidase as the reporter system in chemiluminescent enzyme immunoassays depends on availability. Conversely, these two report systems could be applied in simultaneous analysis of multicomponents due to their different optical behaviors and similar performances. But attention should be paid to conjugation method and coating buffer, which affected the luminescent intensity of different determination targets. Copyright © 2015 John Wiley & Sons, Ltd.
A ‘turn‐on’ fluorescent chemosensor for quantification of serum albumin in aqueous solution at neutral pH
Authors: Li Yuanyuan , Li Kai , He Juan
Published: November 2015

A fluorescent chemosensor 1 (4‐diethylamino‐2′‐hydroxychalcone) for detecting serum albumin with long‐wavelength emission, good selectivity and facile synthesis was reported. Upon the addition of bovine serum albumin (BSA) to an aqueous solution of 1 at neutral pH, a ‘turn‐on’ fluorescence response was observed at 596 nm based on a hydrophobic binding mode between 1 and BSA. A linear range of 0.10–1.00 mg/mL and a detection limit of 9.1 µg/mL for BSA were obtained, respectively. Moreover, 1 was successfully applied to detect BSA in real bovine serum samples with satisfied recovery and accuracy, which suggested that 1 could serve as a valid and effective fluorescent chemosensor for quantification of BSA. Copyright © 2015 John Wiley & Sons, Ltd.
Theoretical and experimental investigation of doping M in ZnSe (M = Cd, Mn, Ag, Cu) clusters: optical and bonding characteristics
Authors: Xu Shuhong , Xu Xiaojing , Wang Chunlei , Zhao Zengxia , Wang Zhuyuan , Cui Yiping
Published: November 2015

The optical and bonding characteristics of doping ZnSe quantum dots (QDs) were investigated. Cd‐, Mn‐, Ag‐ and Cu‐doped ZnSe were synthesized in aqueous solution. Theoretically, the intensity of the Cd–Se bond was similar to that of the Zn–Se bond, which illustrates that Cd can be doped into ZnSe materials at any ratio. We found that Mn–Se bonding was stronger than Zn–Se bonding. Ag‐doped ZnSe nanoclusters show the same bonding and configuration as Cu‐doped ZnSe. Moreover, Cd can be doped into ZnSe using both the substitution‐ and vacancy‐doping method. For Mn‐doped ZnSe clusters, small amounts of Mn impurity lead to stronger bonding with Se, but larger amounts of Mn impurity led to the formation of a Mn–Mn metal bond. The theoretical results show that it is difficult to form a vacancy‐doping cluster for Mn‐doped ZnSe materials. In experiments, the absorption and photoluminescence (PL) spectral wavelengths of Mn‐doped ZnSe nanocrystals were the same as those of pure ZnSe nanocrystals, showing that the Mn impurity is not doped into ZnSe nanocrystals. Ag‐ and Cu‐doped ZnSe nanocrystals have the same PL characteristics. The doping of an impurity is related to the solubility product, and not the bonding intensity. Copyright © 2015 John Wiley & Sons, Ltd.
Light‐Stable Silver N‐Heterocyclic Carbene Catalysts for the Alkynylation of Ketones in Air
Authors: Lazreg Faïma , Lesieur Mathieu , Samson Andrew J. , Cazin Catherine S. J.
Published: November 2015

N‐Heterocyclic carbene (NHC) silver(I) complexes were employed efficiently in the alkynylation of ketones. These cationic complexes were highly active and efficient under mild conditions and in air without the need for an additive. The mechanism of this transformation was investigated. Experiments suggest that the formation of a silver acetylide key intermediate and the release of one ligand from the silver centre enable the transformation.
Artificial Photosynthesis at Dynamic Self‐Assembled Interfaces in Water
Authors: Hansen Malte , Troppmann Stefan , König Burkhard
Published: November 2015

Artificial photosynthesis is one of the big scientific challenges of today. Self‐assembled dynamic interfaces, such as vesicles or micelles, have been used as microreactors to mimic biological photosynthesis. These aggregates can help to overcome typical problems of homogeneous photocatalytic water splitting. Microheterogeneous environments organize catalyst–photosensitizer assemblies at the interface in close proximity and thus enhance intermolecular interactions. Thereby vesicles and micelles may promote photoinitiated charge separation and suppress back electron transfer. The dynamic self‐assembled interfaces solubilize non‐polar compounds and protect sensitive catalytic units and intermediates against degradation. In addition, vesicles provide compartmentation that was used to separate different redox environments needed for an overall water splitting system. This Minireview provides an overview of the applications of micellar and vesicular microheterogeneous systems for solar energy conversion by photosensitized water oxidation and hydrogen generation.
Fabrication of Fe‐Doped LiCoO2 Sandwich‐Like Nanocomposites as Excellent Performance Cathode Materials for Lithium‐Ion Batteries
Authors: Liu Li , Zhang Huijuan , Yang Jiao , Mu Yanping , Wang Yu
Published: November 2015

In this article, the two‐layer sandwiched graphene@LiFe0.2Co0.8O2 nanoparticles (SG@LFCO) have been prepared and investigated as high‐rate and long‐life cathode materials for rechargeable lithium‐ion batteries. The materials possess a high‐surface area (267.1 m2 g−1) and lots of void spaces. By combining various favorable conditions, such as Fe doping, coating graphene, and designing novel morphology, the as‐prepared materials deliver a specific capacity of 115 mAh g−1 at 10 C. At the 0.1 C cycling rate, the capacity retention of 97.2 % is sustained after 250 cycles and a coulombic efficiency of around 97.6 % is obtained.
ChemInform Abstract: Luminescence Properties of Dysprosium Doped Calcium Magnesium Silicate Phosphor by Solid State Reaction Method.
Authors: Sahu Ishwar Prasad , Chandrakar Priya , Baghel R.n. , Bisen D.p. , Brahme Nameeta , Tamrakar Raunak Kumar
Published: November 2015

CaMgSi2O6:Dy3+ white light emitting phosphor is prepared by firing a stoichiometric mixture of CaCO3, MgO, SiO2, and Dy2O3 in air (alumina crucible, 1050 °C, 3 h).
ChemInform Abstract: White Light Emission from Ca9Bi(PO4)7:Dy3+ Single‐Phase Phosphors for Light‐Emitting Diodes.
Authors: Zhang Z. W. , Song A. J. , Yue Y. , Zhong H. , Zhang X. Y. , Ma M. Z. , Liu R. P.
Published: November 2015

Ca9Bi1‐x(PO4)7:xDy3+ (x = 0.02—1) is prepared by solid state reaction of stoichiometric mixtures of CaCO3, (NH4)2HPO4, Bi2O3, and Dy2O3 in air (1.
ChemInform Abstract: Magnetic Properties and Electronic Structure of Manganese‐Based Blue Pigments: A High‐Frequency and ‐Field EPR Study.
Authors: Krzystek J. , Telser Joshua , Li Jun , Subramanian M. A.
Published: November 2015

Solid solutions of YIn1‐xMnxO3 (0.02 < x < 0.25) are prepared according to the literature.
ChemInform Abstract: Li5Cr9Ti4O24: A New Anode Material for Lithium‐Ion Batteries.
Authors: Lin Chunfu , Deng Shengjue , Shen Hong , Wang Guizhen , Li Yanfang , Yu Lei , Lin Shiwei , Li Jianbao , Lu Li
Published: November 2015

The theoretical capacity of Li4Ti5O12 is increased by combining Ti3+/Ti4+ and Cr2+/Cr3+ redox couples.
ChemInform Abstract: Synthesis and Crystal Structure Determination of YCo1‐xFexO3 (x = 0, 0.33, 0.5, 0.67 and 1) Perovskites.
Authors: Dimitrovska‐Lazova S. , Aleksovska S. , Tzvetkov P.
Published: November 2015

The title compounds are prepared by a solution combustion method from solutions of Y(NO3)3, Co(NO3)2, and Fe(NO3)3 in a small amount of water.
ChemInform Abstract: Rhodium‐Catalyzed Hydroaminomethylation of Cyclopentadiene.
Authors: Behr Arno , Levikov Denys , Nuerenberg Edward
Published: November 2015

Saturated C6‐cyclopentylmethyl amines are obtained in a single step using the homogeneous catalyst Rh(II) octanoate dimer without additional phosphorus ligands under mild reaction conditions.
ChemInform Abstract: On the Understanding of BF3·Et2O‐Promoted Intra‐ and Intermolecular Amination and Oxygenation of Unfunctionalized Olefins.
Authors: Yang Chun‐Hua , Fan Wen‐Wen , Liu Gong‐Qing , Duan Lili , Li Lin , Li Yue‐Ming
Published: November 2015

BF3.Et2O is effective for both intra‐ and intermolecular hydroamination as well as for lactonization and esterification reactions of unactivated C=C double bonds.
ChemInform Abstract: CF3‐Carbenoid C—H Functionalization of (Hetero)arenes under Chelation‐Controlled RhIII Catalysis.
Authors: Iagafarova Irina E. , Vorobyeva Daria V. , Peregudov Alexander S. , Osipov Sergey N.
Published: November 2015

An efficient method for the Rh(III)‐catalyzed CF3‐carbenoid C—H functionalization of benzenes and indoles bearing a directing group is presented.
ChemInform Abstract: Scope and Limitation of the Microwave‐Assisted Catalytic Wittig Reaction.
Authors: Hoffmann Marcel , Deshmukh Sunetra , Werner Thomas
Published: November 2015

The effect of various reaction parameters, silanes as reducing agents, masked bases as well as the substrate scope of the title reaction are studied in detail.
ChemInform Abstract: Ligand‐Free Pd‐Catalyzed Double Carbonylation of Aryl Iodides with Amines to α‐Ketoamides under Atmospheric Pressure of Carbon Monoxide and at Room Temperature.
Authors: Du Hongyan , Ruan Qing , Qi Minghao , Han Wei
Published: November 2015

In situ generation of Pd nanoparticles in PEG‐400 is the key to the first general, ligand‐ and additive‐free protocol for double carbonylation of aryl iodides in the presence of amines to furnish α‐ketoamides.
ChemInform Abstract: Aerobic Copper‐Catalyzed O‐Methylation with Methylboronic Acid.
Authors: Jacobson Clare E. , Martinez‐Munoz Noelia , Gorin David J.
Published: November 2015

The oxidative coupling of alkylboronic acids with oxygen nucleophiles offers a strategy for replacing toxic, electrophilic alkylating reagents but, O‐alkylation with boronic acids is rare.
ChemInform Abstract: The Dual Reactivity of 5‐S/5‐O‐Phenyl‐1,4,2‐oxathiazoles: A Fragmentation Pathway That Affords Nitriles in the Presence of Water.
Authors: Lim Yi Wee , Hewitt Russell J. , Burkett Brendan A.
Published: November 2015

The role of water in the ring‐opening rearrangement of substituted 1,4,2‐oxathiazoles towards nitriles is examined.
ChemInform Abstract: Iridium‐Catalyzed Regioselective Decarboxylative Allylation of β‐Ketoacids: Efficient Construction of γ,δ‐Unsaturated Ketones.
Authors: Chen Shu‐Jie , Lu Guo‐Ping , Cai Chun
Published: November 2015

The presented approach allows direct usage of allylic alcohols as starting material without prior activation.
ChemInform Abstract: One‐Pot Relay Reduction—Isomerization of β‐Trifluoromethylated‐α,β‐unsaturated Ketones to Chiral β‐Trifluoromethylated Saturated Ketones over Combined Catalysts in Aqueous Medium.
Authors: Xia Xuelin , Wu Meng , Jin Ronghua , Cheng Tanyu , Liu Guohua
Published: November 2015

A newly synthesized chiral ruthenium catalyst is applied in the reduction‐isomerization reaction sequence to yield chiral β‐trifluoromethylated ketones is described.
ChemInform Abstract: Direct Thiolation of Methoxybenzenes with Thiols under Metal‐Free Conditions by Iodine Catalysis.
Authors: Yan Kelu , Yang Daoshan , Sun Pengfei , Wei Wei , Liu Yao , Li Guoqing , Lu Shenglei , Wang Hua
Published: November 2015

Optimized conditions allow the direct thiolation of various methoxybenzenes, aniline (IVc) and heteroaromatic compounds.
ChemInform Abstract: Pd(OAc)2 in WERSA: A Novel Green Catalytic System for Suzuki—Miyaura Cross‐Coupling Reactions at Room Temperature.
Authors: Boruah Preeti Rekha , Ali Abdul Aziz , Chetia Mitali , Saikia Bishwajit , Sarma Diganta
Published: November 2015

Palladium‐catalyzed Suzuki—Miyaura cross‐coupling reactions are performed in the presence of water extract of rice straw ash (WERSA) which is obtained by burning rice straw to ashes.
ChemInform Abstract: Noncovalent Catalysis of Glucose‐Containing Imidazolium Salt in Solvent‐Free One‐Pot Synthesis of ortho‐Aminocarbonitriles.
Authors: Zhang Li‐zhuo , Wan Yu , Zhang Xiao‐xiao , Cui Hao , Zou Huan , Zhou Qiu‐ju , Wu Hui
Published: November 2015

Glucose‐containing imidazolium salt (GIM) efficiently catalyzes the four component condensation of cyclohexanone, aldehydes, and malononitrile to produce the title compounds (IV) in good yields.
ChemInform Abstract: Direct Access to Functionalized 4‐Nitromethyl‐chromenes via a Domino Reaction under Catalyst‐Free Conditions.
Authors: Xu Wengang , Li Qingcui , Wang Wangwang , Zheng Hua , Zhang Fanglin , Hu Yunxing
Published: November 2015

The catalyst‐free reaction of α,β‐unsaturated ketones with a nitroalkane (II,IV) yields 4‐nitromethyl‐chromenes of type (III) or (V).
ChemInform Abstract: Organocatalytic, Enantioselective Synthesis of 1‐ and 3‐Substituted Isochromans via Intramolecular Oxa‐Michael Reaction of Alkoxyboronate: Synthesis of (+)‐Sonepiprazole.
Authors: Ravindra Barnala , Maity Sanjay , Das Braja Gopal , Ghorai Prasanta
Published: November 2015

A new and practical route to enantioenriched substituted isochroman derivatives is developed and successfully applied to the enantioselective synthesis of the dopamine receptor antagonist sonepiprazole (XI).
ChemInform Abstract: Efficient One Pot Multi‐Component Domino Aldol Condensation—Michael Addition—Suzuki Coupling Reaction for the Highly Functionalized Quinolines.
Authors: Ubba Eethamukkala , Kumar Y. Suneel , Dasaradhan C. , Khan Fazlur‐Rahman Nawaz , Jeong Euh Duck , Chung Eun Hyuk
Published: November 2015

The title sequence allows the synthesis of highly functionalized quinolines via three‐ component reaction of 2‐chloro‐3‐formylquinolines, acetophenones, and boronic acids.
ChemInform Abstract: Construction of Pyrrolophenanthridinone Scaffolds Mediated by Samarium(II) Diiodide and Access to Natural Product Synthesis.
Authors: Suzuki Kenji , Iwasaki Hiroki , Domasu Reika , Hitotsuyanagi Naho , Wakizaka Yuka , Tominaga Mao , Kojima Naoto , Ozeki Minoru , Yamashita Masayuki
Published: November 2015

A facile methodology for the construction of pyrrolophenanthridinone derivatives via a SmI2‐mediated reductive cyclization is developed and applied to the concise synthesis of the natural product anhydrolycorinone (IV).
ChemInform Abstract: Nitronium Salts as Novel Reagents for the Heterocyclization of gem‐Bromofluorocyclopropanes into Pyrimidine Derivatives.
Authors: Sedenkova Kseniya N. , Averina Elena B. , Grishin Yuri K. , Bacunov Aleksandr B. , Troyanov Sergey I. , Morozov Igor V. , Deeva Evgeniya B. , Merkulova Anna V. , Kuznetsova Tamara S. , Zefirov Nikolay S.
Published: November 2015

Nitronium triflate, either preformed or generated in situ from nitric and triflic acid, reacts with cyclopropane (I) and nitriles to give pyrimidine N‐oxides.
ChemInform Abstract: Optimization of Reaction and Substrate Activation in the Stereoselective Cross‐Coupling of Chiral 3,3‐Diboronyl Amides.
Authors: Lee Jack Chang Hung , Sun Ho‐Yan , Hall Dennis G.
Published: November 2015

Substrate (I) which bears a Weinreb amide undergoes a direct coupling of the Bpin moiety with inversion of the stereochemistry.
ChemInform Abstract: Diterpene Glycosides from the Dry Fronds of Conyza japonica.
Authors: Hu Jiang , Song Yan , Li Hui , Mao Xia , Shi Xiaodong , Liu Zhiming
Published: November 2015

Three new labdane diterpene glycosides (Ia,b) and (II) are isolated together with their already known aglycone.
ChemInform Abstract: Preparation of 2,3‐Unsaturated Pseudoglycosides with Ferrier Rearrangement Promoted by Tm(OTf)3 as a Highly Efficient Catalyst.
Authors: Chen Peiran , Bi Bin
Published: November 2015

Tm(OTf)3 is shown to be a highly efficient catalyst for the preparation of various 2,3‐unsaturated glycosides in Ferrier rearrangement reactions.
ChemInform Abstract: Structure and Order in CoPt‐Type Nanoalloys: From Thin Films to Supported Clusters
Authors: Andreazza Pascal , Pierron‐Bohnes Veronique , Tournus Florent , Andreazza‐Vignolle Caroline , Dupuis Veronique
Published: November 2015

Review: 442 refs.
ChemInform Abstract: Charge Rearrangement in Magnetite: from Magnetic Field Induced Easy Axis Switching to Femtoseconds Electronic Processes
Authors: Kakol Z. , Kozlowski A. , Kolodziej T. , Przewoznik J.
Published: November 2015

Review: 34 refs.
ChemInform Abstract: Transformations of Functional Groups Attached to Cyclopentadienyl or Related Ligands in Group 4 Metal Complexes
Authors: Pinkas Jiri , Lamac Martin
Published: November 2015

Review: 282 refs.
ChemInform Abstract: Stereodivergent Asymmetric Reactions Catalyzed by Brucine Diol
Authors: Kim Hun Young , Oh Kyungsoo
Published: November 2015

Review: [29 refs.
ChemInform Abstract: Stereoselective Formation of Amines by Nucleophilic Addition to Azomethine Derivatives
Authors: Charette Andre B. , Lindsay Vincent
Published: November 2015

Review: 247 refs.
ChemInform Abstract: Recent Achievements in Organic Trithiocarbonates Synthesis
Authors: Kazemi Mosstafa , Shiri Lotfi , Kohzadi Homa
Published: November 2015

Review: 55 refs.
ChemInform Abstract: Peptide δ‐Turn: Literature Survey and Recent Progress
Authors: Toniolo Claudio , Crisma Marco , Moretto Alessandro , Peggion Cristina , Formaggio Fernando , Aleman Carlos , Cativiela Carlos , Ramakrishnan Chandrasekharan , Balaram Padmanabhan
Published: November 2015

Review: 88 refs.
ChemInform Abstract: A New Class of PN3‐Pincer Ligands for Metal‐Ligand Cooperative Catalysis
Authors: Li Huaifeng , Zheng Bin , Huang Kuo‐Wei
Published: November 2015

Review: 107 refs.
ChemInform Abstract: Application of Sugars in Stereoselective Synthesis. What Is Interesting About Sucrose?
Authors: Jarosz S.
Published: November 2015

Review: 74 refs.
ChemInform Abstract: High‐Efficiency Silicon Solar Cells: A Review
Authors: Lee Youngseok , Park Cheolmin , Balaji Nagarajan , Lee Youn‐Jung , Dao Vinh Ai
Published: November 2015

Review: 99 refs.
ChemInform Abstract: Process Intensification Tools in the Small‐Scale Pharmaceutical Manufacturing of Small Molecules
Authors: Mitic Aleksandar , Gernaey Krist V.
Published: November 2015

Review: 143 refs.
ChemInform Abstract: Printing Peptide Arrays with a Complementary Metal Oxide Semiconductor Chip
Authors: Loeffler Felix F. , Cheng Yun‐Chien , Muenster Bastian , Striffler Jakob , Liu Fanny C. , Ralf Bischoff F. , Doersam Edgar , Breitling Frank , Nesterov‐Mueller Alexander
Published: November 2015

Review: 41 refs.
Clinical Practice Patterns in Constrictive Pericarditis Patients With Heart Failure: A Retrospective Cohort Study Using a National Inpatient Database in Japan
Authors: Isogai Toshiaki , Yasunaga Hideo , Matsui Hiroki , Tanaka Hiroyuki , Hisagi Motoyuki , Fushimi Kiyohide
Published: November 2015

Background

Previous studies on constrictive pericarditis (CP) mainly concerned patients undergoing pericardiectomy. The reported perioperative mortality of CP patients remained high. Data on medically treated CP patients without pericardiectomy have been scarce.

Hypothesis

Constrictive pericarditis patients with more comorbidities are less likely to undergo pericardiectomy.

Methods

Using the Diagnosis Procedure Combination database from 2007 to 2013, we retrospectively identified CP patients admitted with heart failure of New York Heart Association (NYHA) class II to IV. We compared clinical characteristics between patients treated with and without pericardiectomy. A multivariable logistic regression analysis was performed to assess the factors associated with likelihood of undergoing pericardiectomy.

Results

Of 855 eligible patients, 164 (19.2%) underwent pericardiectomy (surgery group) and 691 (80.8%) did not (no‐surgery group). The surgery group was younger (mean age, 65.0 years vs 70.3 years; P < 0.001) and more often male (81.7% vs 72.2%; P = 0.013) than the no‐surgery group. No significant difference was seen in NYHA class and Barthel Index between the groups, whereas the surgery group had a lower Charlson Comorbidity Index (CCI). Older age, female sex, and higher CCI were significantly associated with a lower likelihood of undergoing pericardiectomy. In the surgery group, 30‐day postoperative mortality was significantly higher in patients who underwent cardiopulmonary bypass than in those who did not (11.3% vs 2.9%; P = 0.030).

Conclusions

Patients' backgrounds were associated with the likelihood of undergoing pericardiectomy. Conservative medical therapy may be acceptable in CP patients with severe background and high preoperative need for cardiopulmonary bypass.
Stereoselective Modulation of P‐Glycoprotein by Chiral Small Molecules
Authors: Carocci Alessia , Catalano Alessia , Turi Francesco , Lovece Angelo , Cavalluzzi Maria M. , Bruno Claudio , Colabufo Nicola A. , Contino Marialessandra , Perrone Maria G. , Franchini Carlo , Lentini Giovanni
Published: November 2015

Inhibition of drug efflux pumps such as P‐glycoprotein (P‐gp) is an approach toward combating multidrug resistance, which is a significant hurdle in current cancer treatments. To address this, N‐substituted aryloxymethyl pyrrolidines were designed and synthesized in their homochiral forms in order to investigate the stereochemical requirements for the binding site of P‐gp. Our study provides evidence that the chiral property of molecules could be a strategy for improving the capacity for interacting with P‐gp, as the most active compounds of the series stereoselectively modulated this efflux pump. The naphthalene‐1‐yl analogue (R)‐2‐[(2,3‐dichlorophenoxy)methyl]‐1‐(naphthalen‐1‐ylmethyl)pyrrolidine) [(R)‐7 a] emerged foremost for its potency and stereoselectivity toward P‐gp, with the S enantiomer being nearly inactive. The modulation of P‐gp by (R)‐7 a involved consumption of ATP, thus demonstrating that the compound behaves as a P‐gp substrate.
Benzoxazepines Achieve Potent Suppression of IL‐17 Release in Human T‐Helper 17 (TH17) Cells through an Induced‐Fit Binding Mode to the Nuclear Receptor RORγ
Authors: Olsson Roine I. , Xue Yafeng , von Berg Stefan , Aagaard Anna , McPheat Jane , Hansson Eva L. , Bernström Jenny , Hansson Pia , Jirholt Johan , Grindebacke Hanna , Leffler Agnes , Chen Rongfeng , Xiong Yao , Ge Hongbin , Hansson Thomas G. , Narjes Frank
Published: November 2015

RORγt, an isoform of the retinoic acid‐related orphan receptor gamma (RORc, RORγ), has been identified as the master regulator of T‐helper 17 (TH17) cell function and development, making it an attractive target for the treatment of autoimmune diseases. Validation for this target comes from antibodies targeting interleukin‐17 (IL‐17), the signature cytokine produced by TH17 cells, which have shown impressive results in clinical trials. Through focused screening of our compound collection, we identified a series of N‐sulfonylated benzoxazepines, which displayed micromolar affinity for the RORγ ligand‐binding domain (LBD) in a radioligand binding assay. Optimization of these initial hits resulted in potent binders, which dose‐dependently decreased the ability of the RORγ‐LBD to interact with a peptide derived from steroid receptor coactivator 1, and inhibited the release of IL‐17 secretion from isolated and cultured human TH17 cells with nanomolar potency. A cocrystal structure of inverse agonist 15 (2‐chloro‐6‐fluoro‐N‐(4‐{[3‐(trifluoromethyl)phenyl]sulfonyl}‐2,3,4,5‐tetrahydro‐1,4‐benzoxazepin‐7‐yl)benzamide) bound to the RORγ‐LBD illustrated that both hydrophobic interactions, leading to an induced fit around the substituted benzamide moiety of 15, as well as a hydrogen bond from the amide NH to His479 seemed to be important for the mechanism of action. This structure is compared with the structure of agonist 25 (N‐(2‐fluorophenyl)‐4‐[(4‐fluorophenyl)sulfonyl]‐2,3,4,5‐tetrahydro‐1,4‐benzoxazepin‐6‐amine ) and structures of other known RORγ modulators.
Identification of para‐Substituted Benzoic Acid Derivatives as Potent Inhibitors of the Protein Phosphatase Slingshot
Authors: Li Kang‐shuai , Xiao Peng , Zhang Dao‐lai , Hou Xu‐Ben , Ge Lin , Yang Du‐xiao , Liu Hong‐da , He Dong‐fang , Chen Xu , Han Ke‐rui , Song Xiao‐yuan , Yu Xiao , Fang Hao , Sun Jin‐peng
Published: November 2015

Slingshot proteins form a small group of dual‐specific phosphatases that modulate cytoskeleton dynamics through dephosphorylation of cofilin and Lim kinases (LIMK). Small chemical compounds with Slingshot‐inhibiting activities have therapeutic potential against cancers or infectious diseases. However, only a few Slingshot inhibitors have been investigated and reported, and their cellular activities have not been examined. In this study, we identified two rhodanine‐scaffold‐based para‐substituted benzoic acid derivatives as competitive Slingshot inhibitors. The top compound, (Z)‐4‐((4‐((4‐oxo‐2‐thioxo‐3‐(o‐tolyl)thiazolidin‐5‐ylidene)methyl)phenoxy)methyl)benzoic acid (D3) had an inhibition constant (Ki) of around 4 μm and displayed selectivity over a panel of other phosphatases. Moreover, compound D3 inhibited cell migration and cofilin dephosphorylation after nerve growth factor (NGF) or angiotensin II stimulation. Therefore, our newly identified Slingshot inhibitors provide a starting point for developing Slingshot‐targeted therapies.
Combined Use of Oligopeptides, Fragment Libraries, and Natural Compounds: A Comprehensive Approach To Sample the Druggability of Vascular Endothelial Growth Factor
Authors: Bayó‐Puxan Núria , Rodríguez‐Mias Ricard , Goldflam Michael , Kotev Martin , Ciudad Sonia , Hipolito Christopher J. , Varese Monica , Suga Hiroaki , Campos‐Olivas Ramón , Barril Xavier , Guallar Víctor , Teixidó Meritxell , García Jesús , Giralt Ernest
Published: November 2015

The modulation of protein–protein interactions (PPIs) is emerging as a highly promising tool to fight diseases. However, whereas an increasing number of compounds are able to disrupt peptide‐mediated PPIs efficiently, the inhibition of domain–domain PPIs appears to be much more challenging. Herein, we report our results related to the interaction between vascular endothelial growth factor (VEGF) and its receptor (VEGFR). The VEGF–VEGFR interaction is a typical domain–domain PPI that is highly relevant for the treatment of cancer and some retinopathies. Our final goal was to identify ligands able to bind VEGF at the region used by the growth factor to interact with its receptor. We undertook an extensive study, combining a variety of experimental approaches, including NMR‐spectroscopy‐based screening of small organic fragments, peptide libraries, and medicinal plant extracts. The key feature of the successful ligands that emerged from this study was their capacity to expose hydrophobic functional groups able to interact with the hydrophobic hot spots at the interacting VEGF surface patch.