bluuebunny/crossref_metadata_2025 huggingface dataset:
Well‐Defined, Nanometer‐Sized LiH Cluster Compounds Stabilized by Pyrazolate Ligands
Authors: Stasch Andreas
Published: January 2014

The assembly of well‐defined large cluster compounds of ionic light metal hydrides is a synthetic challenge and of importance for synthesis, catalysis, and hydrogen storage. The synthesis and characterization of a series of neutral and anionic pyrazolate‐stabilized lithium hydride clusters with inorganic cores in the nanometer region is now reported. These complexes were prepared in a bottom‐up approach using alkyl lithium and lithium pyrazolate mixtures with silanes in hydrocarbon solutions. Structural characterization using synchrotron radiation revealed isolated cubic clusters that contain up to 37 Li+ cations and 26 H− ions. Substituted pyrazolate ligands were found to occupy all corners and some edges for the anionic positions.
Dinuclear Ruthenium(II) Complexes as Two‐Photon, Time‐Resolved Emission Microscopy Probes for Cellular DNA
Authors: Baggaley Elizabeth , Gill Martin R. , Green Nicola H. , Turton David , Sazanovich Igor V. , Botchway Stanley W. , Smythe Carl , Haycock John W. , Weinstein Julia A. , Thomas Jim A.
Published: January 2014

The first transition‐metal complex‐based two‐photon absorbing luminescence lifetime probes for cellular DNA are presented. This allows cell imaging of DNA free from endogenous fluorophores and potentially facilitates deep tissue imaging. In this initial study, ruthenium(II) luminophores are used as phosphorescent lifetime imaging microscopy (PLIM) probes for nuclear DNA in both live and fixed cells. The DNA‐bound probes display characteristic emission lifetimes of more than 160 ns, while shorter‐lived cytoplasmic emission is also observed. These timescales are orders of magnitude longer than conventional FLIM, leading to previously unattainable levels of sensitivity, and autofluorescence‐free imaging.
Reversible Single‐Crystal‐to‐Single‐Crystal Photochemical Formation and Thermal Cleavage of a Cyclobutane Ring
Authors: Kole Goutam Kumar , Kojima Tatsuhiro , Kawano Masaki , Vittal Jagadese J.
Published: January 2014

A [2+2] cycloaddition reaction has been observed in a number of solids. The cyclobutane ring in a photodimerized material can be cleaved into olefins by UV light and heat. The high thermal stability of the metal–organic salt K2SDC (H2SDC=4,4’‐stilbenedicarboxylic acid) has been successfully utilized to investigate the reversible cleavage of a cyclobutane ring. The two polymorphs of K2SDC undergo reversible cyclobutane formation by UV light and cleavage by heat in cycles. Of these, one polymorph retains its single‐crystal nature during the reversible processes. Polymorphs are known to show different physical properties and chemical reactivities. This work reveals that the retention of single‐crystal nature is strongly associated with the packing of molecules, which is controlled by kinetics and thermodynamics. The photoemissive nature of the products makes this as a promising material for photoswitches and optical data storage devices.
Test‐Strip‐Based Fluorometric Detection of Fluoride in Aqueous Media with a BODIPY‐Linked Hydrogen‐Bonding Receptor
Authors: Ashokkumar Pichandi , Weißhoff Hardy , Kraus Werner , Rurack Knut
Published: January 2014

The measurement of biologically relevant anions, such as fluoride, is an important task in analytical chemistry, in particular, for dental health and osteoporosis. Although a large number of fluoride probes are known, the applicability under relevant conditions is limited to a few examples. To improve this situation, BODIPY‐amidothiourea dyes with varying hydrogen‐bond donating strengths were developed, the most H‐acidic of which (1 c) could detect F− from an inorganic source (NaF) in 50 % aqueous solution (DMSO/water 1:1, v/v) with 0.01 ppm sensitivity through selective fluorescence quenching by a photoinduced electron‐transfer (PET) process. Use of the probe and a reference dye with a test‐strip assay and a portable and rapidly recording lateral‐flow fluorescence reader made determination of F− in neat aqueous solutions, such as spiked water samples and toothpaste extracts, possible in a self‐referenced manner, achieving a detection limit of 0.2 ppm.
Allylic Functionalization of Unactivated Olefins with Grignard Reagents
Authors: Bao Hongli , Bayeh Liela , Tambar Uttam K.
Published: January 2014

New advances in the functionalization of unactivated olefins with carbon nucleophiles have provided more efficient and practical approaches to convert inexpensive starting materials into valuable products. Recent examples have been reported with stabilized carbon nucleophiles, tethered carbon nucleophiles, diazoesters, and trifluoromethane donors. A general method for functionalizing olefins with aromatic, aliphatic, and vinyl Grignard reagents was developed. In a one‐pot process, olefins are oxidized by a commercially available reagent to allylic electrophiles, which undergo selective copper‐catalyzed allylic alkylation with Grignard reagents. Products are formed in high yield and with high regioselectivity. This was utilized to synthesize a series of skipped dienes, a class of compounds that are prevalent in natural products and are difficult to synthesize by known allylic alkylation methods.
Preparations and properties of a high performance semicrystalline copolyimide and composites reinforced with glass fiber
Authors: Wang Wei , Zhou Hongwei , Chen Dongfeng , Wu Meimei , Liu Yuntao , Chen Chunhai
Published: January 2014

A semicrystalline copolyimide derived from 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (s‐BPDA), 1,3‐bis‐(4‐aminophenoxy)benzene (TPER), and 4,4′‐oxydianiline (4,4′‐ODA), end capped with phthalic anhydride (PA), was synthesized. Glass fiber reinforced composite was also prepared by impregnating powdery glass fiber with poly(amic acid) followed by solution imidization techniques. This copolyimide displayed a glass transition temperature of 202°C and a melting temperature of 373°C by differential scanning colorimeter (DSC). Crystallization and melting behaviors were investigated under nonisothermal and isothermal crystallization conditions. Double exothermic peaks were found by DSC when the copolyimide was cooled from the melt and multiple melting behaviors can be observed after the coployimide had been isothermally crystallized at different temperatures. Mechanical properties were investigated by dynamical mechanical analysis (DMA) and tensile experiments. The samples were cured at different temperatures and then tested at different temperatures. Results indicated that the copolyimide and the composite showed excellent mechanical properties. Additionally, this copolyimide also showed lower melt viscosity by rheological analysis. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40345.
Ultrafine cellulose triacetate mats electrospun by using co‐solvent of DMSO/chloroform system
Authors: Lan Tian , Shao Zi‐Qiang , Wang Wen‐Jun , Wang Fei‐Jun , Zhang Da‐Lun , Wang Jian‐Quan , Liu Yan‐Hua , Kong Lin‐Lin
Published: January 2014

Cellulose triacetate (CTA) nanofiber nonwoven mats were continuously electrospun by using mixed solvent of DMSO/chloroform system. The size and morphology of CTA nanofibers were investigated. It was found that CTA fibers with diameters in the range of 98 nm–1.81 μm were obtained from 8 wt % CTA solutions in 1 : 1, 3 : 2, 2 : 1, 3 : 1, 5 : 1 and 7 : 1 (v/v) DMSO/chloroform. The average diameter of CTA nanofiber was decreased and size distribution was narrowed with increasing the DMSO content in the mixed solvent. Smooth and uniform nanofibers with mean diameters of about 260 nm could be obtained from a solution of CTA in the binary system DMSO/chloroform 5 : 1(v/v) at a polymer concentration of 8 wt %. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40373.
Ab initio emulsion RAFT polymerization of vinylidene chloride mediated by amphiphilic macro‐RAFT agents
Authors: Yang Jie , Bao Yongzhong , Pan Pengju
Published: January 2014

An amphiphilic copolymer poly(acrylic acid)‐block‐poly(styrene) (PAA‐b‐PS) with a trithiocarbonate reactive group was used in the ab initio reversible addition‐fragmentation chain transfer (RAFT) emulsion polymerization of vinylidene chloride (VDC). The fast polymerization and high conversion were achieved. The parameters for a good control over the formation of well‐defined PAA‐b‐PS‐b‐PVDC amphiphilic block copolymers and self‐stabilized latexes were identified. To improve the emulsion stability and prevent the desorption of water‐soluble initiating radicals, the acid groups of PAA‐b‐PS were neutralized by NaOH at the later stage of polymerization. The PAA‐b‐PS‐b‐PVDC block copolymer with a high molar mass of 30 kg mol−1 and the stable latex with 30 wt % solid content was obtained. The kinetics of RAFT emulsion copolymerization of VDC in a living manner was first investigated. The as‐prepared PAA‐b‐PS‐b‐PVDC latex particles were further used as seeds in the emulsion polymerization of styrene, enabling the preparation of novel PAA‐b‐PS‐b‐PVDC‐b‐PS tetra‐block copolymers with a molar mass of 76 kg mol−1 and a relatively low molecular weight distribution of 1.6. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40391.
Spray‐drying microencapsulation of β‐carotene by soy protein isolate and/or OSA‐modified starch
Authors: Deng Xi‐Xiang , Chen Zhong , Huang Qiang , Fu Xiong , Tang Chuan‐He
Published: January 2014

Microencapsulation is an effective strategy to improve the storage stability of β‐carotene. This article investigated the potential and effectiveness of soy protein isolate (SPI) and octenylsuccinic anhydride‐modified starch (MS), alone or in combination (1:1, w/w), to encapsulate β‐carotene by spray drying. The results indicated that the microcapsule with MS exhibited much lower encapsulation efficiency (NE) and poorer dissolution behavior, but much better redispersion behavior, than that with SPI or its blends with MS. The NE was basically unaffected by total solid content (TC) or core/wall ratio; increasing the TC impaired the dissolution and/or redispersion behavior. The dispersion behavior was closely associated with the morphology of the microcapsules. The encapsulated β‐carotene suffered a progressive loss upon storage under high humid or temperature environment, but it exhibited extraordinary stability at low temperatures (e.g., 4°C). The β‐carotene degradation was independent of sunlight. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40399.
Study of polyarylene ether nitrile terminated with phthalonitrile/hybrid Fe3O4 nanospheres composites by orthogonal experiments
Authors: Tong Lifen , Liu Mengdie , Long Ya , Liu Xiaobo
Published: January 2014

A novel series of composites of polyarylene ether nitrile terminated with phthalonitrile (PEN‐t‐Ph) filled with hybrid Fe3O4 nanospheres (h‐Fe3O4) was prepared via in situ composition. Based on the cross‐linking interactions between the phthalonitrile at the end of PEN‐t‐Ph molecular chains and the phthalonitrile on the surface of h‐Fe3O4 particles to form phthalocyanine ring, it was shown that the PEN‐t‐Ph/h‐Fe3O4 system had superior interfacial compatibility and the h‐Fe3O4 particles were locked in the matrix resin. These results had been confirmed by scanning electron microscope analysis. By orthogonal experiments and statistic analysis, the optimal conditions of cure temperature, type of h‐Fe3O4 and content of h‐Fe3O4 had been determined. Meanwhile, the results of range analysis and variance analysis indicated that the cure temperature had great effects on the thermal properties. Thermal studies revealed that the glass transition temperature of PEN‐t‐Ph/h‐Fe3O4 cured at 320°C was 214.7°C, increased by about 40°C compared to the PEN‐t‐Ph/h‐Fe3O4 without heat treatment, and the temperature corresponding to the weight loss of 5 wt % was increased by about 20°C. Mechanical measurements indicated that PEN‐t‐Ph/h‐Fe3O4 cured at 320°C possesses excellent mechanical properties with tensile strength of 93.33 MPa and tensile modulus of 2414.05 MPa, 9.91 MPa, 355.76 MPa higher than pure PEN‐t‐Ph film cured at 320°C, and 13.26 MPa, 397.90 MPa higher than PEN‐t‐Ph/h‐Fe3O4 without heat treatment. Most importantly, the presence of h‐Fe3O4 particles endows PEN‐t‐Ph/h‐Fe3O4 system with good magnetic property. Thus, PEN‐t‐Ph/h‐Fe3O4 cured at 320°C may have potential applications in field of magnetic materials. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40418.
Self‐Assembly of Chiral Propeller‐like Supermolecules with Unusual “Sergeants‐and‐Soldiers” and “Majority‐Rules” Effects
Authors: Nie Bo , Zhan Tian‐Guang , Zhou Tian‐You , Xiao Ze‐Yun , Jiang Guo‐Fang , Zhao Xin
Published: January 2014

Chiral amplification is an interesting phenomenon in supramolecular chemistry mainly observed in complicated systems in which cooperative effect dominate. Herein, chiral, supramolecular, propeller‐like architectures have been constructed through coassembly of an achiral disk‐shaped molecule and chiral amino acid derivatives driven by intermolecular hydrogen bonding. Both the “sergeants‐and‐soldiers” principle and “majority‐rules” effect are applicable in these discrete four‐component supermolecules, which are the simplest supramolecular system ever reported that exhibit chiral amplification.
Finite‐Horizon ε‐Optimal Tracking Control of Discrete‐Time Linear Systems Using Iterative Approximate Dynamic Programming
Authors: Tan Fuxiao , Luo Bin , Guan Xinping
Published: January 2014

In this paper, we propose a finite‐horizon neuro‐optimal tracking control strategy for a class of discrete‐time linear systems. In applying the iterative approximate dynamic programming (ADP) algorithm to determine the optimal tracking control law for linear systems, we need finite iterations to obtain the result in practical applications, instead of infinite iterations. An ε‐error bound is introduced into the ADP algorithm to determine the number of iteration steps. The approximation optimal tracking control law will approach the solution of the Hamilton‐Jacobi‐Bellman (HJB) equation through a self‐adaptive iteration within the given value of ε‐error bound. ε error bound is used to stop the iteration process. So, we can obtain the ε‐approximation tracking control law in a finite number of iterations. Nevertheless, different ε will produce different control performances. Furthermore, we will find an optimal ε error bound, which can obtain optimal performance of the ADP algorithm on the basis of the controlled system tracking the desired trajectory. One example is included to complete the ADP algorithm under different error bounds. From the simulation results, we can find the optimal ε error bound. Finally, the simulation validates the efficiency of the proposed algorithm.
Robust Stability and Stabilization of Positive Interval Systems Subject to Actuator Saturation
Authors: Zhang Ji‐Shi , Deng Zeguan , Wang Yan‐Wu
Published: January 2014

This paper addresses the stabilization problem for a class of uncertain positive linear systems (PLSs) in the presence of saturating actuators. The objective is to obtain sufficient conditions for the robust stability of PLSs and to design robust state feedback control laws such that the closed‐loop uncertain system is asymptotically stable and positive at the origin with a large domain of attraction. Several sufficient conditions for robust stabilization and positivity are derived via the Lyapunov function approach and convex analysis method for both the discrete‐time and the continuous‐time cases, respectively. The state feedback controller design and the estimation of the domain of attraction are presented by solving a convex optimization problem with linear matrix inequalities (LMIs) constraints. A numerical example is given to show the effectiveness of the proposed methods.
Tensor Product Model Transformation Based Control and Synchronization of a Class of Fractional‐Order Chaotic Systems
Authors: Kuntanapreeda Suwat
Published: January 2014

Fractional‐order chaotic systems are the complex systems that involve non‐integer order derivatives. In this paper, tensor product (TP) model transformation‐based controller design for control and synchronization of a class of the fractional‐order chaotic systems is investigated. We propose a novel linear matrix inequality (LMI)‐based stabilization condition for fractional‐order TP models with a controller derived via a parallel distributed compensation (PDC) structure. In the controller design, the controlled system first is transformed into a convex state‐space TP model using the TP model transformation. Based on the transformed TP model, the controller is determined by solving the proposed LMI condition. To the best of our knowledge, this is the first investigation of TP model transformation based design in fractional‐order systems. Several illustrative examples are given to demonstrate the convenience of the proposed LMI condition and the effectiveness of the controller design.
Drama and learning science: an empty space?
Authors: Braund Martin
Published: January 2014

Constructivist teaching methods such as using drama have been promoted as productive ways of learning, especially in science. Specifically, role plays, using given roles or simulated and improvised enactments, are claimed to improve learning of concepts, understanding the nature of science and appreciation of science's relationship with society (Ødegaard 2001, Unpublished Dr. scient., Dissertation, University of Oslo). So far, theorisation of drama in learning, at least in science, has been lacking and no attempt has been made to integrate drama theory in science education with that of theatre. This article draws on Peter Brook's notion of the theatre as the ‘empty space’ (Brook 1968, The empty space, Harmondsworth, Penguin Books) to provide a new theoretical model acting as a lens through which drama activities used to teach science can be better understood and researched. An example of a physical role play is used to ground the theory. The paper concludes by suggesting areas for further research.
Chiral separability of boron cluster species studied by screening approaches utilizing polysaccharide‐based chiral stationary phases
Authors: Mangelings D. , Vander Heyden Y. , Vespalec R.
Published: January 2014

In this study, the screening steps of chiral separation strategies with polysaccharide‐based chiral stationary phases were applied on boron cluster compounds in normal‐phase liquid chromatography (NPLC) and polar organic solvents chromatography (POSC). Since the screening steps were initially developed to analyze organic compounds, their applicability for boron clusters was investigated. Overall, the screening steps in NPLC were applicable for the separation of zwitterions, while for anions mostly no elution was observed. A hypothesis for the latter behavior is precipitation of anions in the nonpolar mobile phases. Ten out of 11 compounds could be partially or baseline separated on the NPLC screening systems. In POSC, all zwitterions were separated on at least one of the screening systems, with an overall lower retention as in NPLC. Anions were detected but not separated in the majority of the experiments. Also their retention on the chiral stationary phases was very limited. This study showed that the chiral discrimination potential of chemically modified polysaccharides is meaningful for chiral separations of structurally chiral boron cluster species, but needs further systematic research, in which recognition mechanisms should be further explored. In addition, some unusual peaks also indicated that conditions with a high separation efficiency must first be searched for some of the tested systems. Copyright © 2014 John Wiley & Sons, Ltd.
A geometric approach to animating thin surface features in smoothed particle hydrodynamics water
Authors: Jang Taekwon , Noh Junyong
Published: January 2014

We propose a geometric approach to animating thin surface features of smoothed particle hydrodynamics‐based water. Explicit interparticle connections are created among smoothed particle hydrodynamics particles to approximate the geometries of thin surfaces while addressing the issue of unresolved surface areas. The deformations measured on the connections actuate the animations of the surfaces by disconnecting the stretched and bent connections. The reconstruction of thin surfaces and the accuracy of the animation are improved by adding auxiliary particles over the connections via Poisson‐disk sampling. Copyright © 2014 John Wiley & Sons, Ltd.
Incidence of acute kidney injury following cardiac catheterization prior to cardiopulmonary bypass in children
Authors: Huggins Nicholas , Nugent Alan , Modem Vinai , Rodriguez Joseph S. , Forbess Joseph , Scott William , Dimas V. Vivian
Published: January 2014

Objectives

To determine whether contrast administration was a risk factor for development of acute kidney injury (AKI) in cyanotic congenital heart disease (CHD) patients undergoing cardiopulmonary bypass (CPB).

Background

AKI following CPB or contrast administration is well described. In previous studies, administration of contrast prior to CPB has been shown to increase the risk of AKI. Chronic cyanosis leads to glomerular damage and dysfunction, thus potentially placing this population at increased risk of developing AKI following contrast administration prior to CPB.

Methods

One hundred twenty‐two patients with cyanotic CHD undergoing preoperative cardiac catheterization (PCC) and subsequent CPB at Children's Medical Center of Dallas from January 1, 2007 until November 30, 2010 were identified, looking specifically at bi‐directional Glenn (BDG) anastomoses and Fontan procedures. One hundred thirteen patients undergoing PCC ≤ 48 hr prior to and > 5 days prior to CPB were included. Occurrence of AKI following CPB was the primary outcome variable.

Results

Logistic regression analysis revealed pre‐catheterization serum creatinine was a risk factor for post‐CPB AKI (P < 0.001) in both Fontan and BDG patients. All other variables were not significantly associated with the development of AKI in either BDG or Fontan patients. Length of stay (hospital or ICU) was not different among the groups regardless of the occurrence of AKI.

Conclusions

In this study of cyanotic CHD patients, contrast administration within 48 hr prior to CPB was not an additional risk factor for the development of AKI. © 2014 Wiley Periodicals, Inc.
Tip of iceberg: when unusual vision complaints with a normal examination prompt a closer look
Authors: Weiss Kathleen D. , Chang Ta C. , Cavuoto Kara M.
Published: January 2014

Key Clinical Message

Nonorganic vision loss (NOVL) is a relatively common condition in pediatric patients. Prompt diagnosis can prevent costly, time‐consuming, and frustrating workups. It is valuable for general practitioners and specialists alike to include NOVL in their differential when evaluating patients with visual complaints that are inconsistent with normal examination findings.
On the Catalysis of the Cycloisomerization of 1,6‐Dienes with Tin(IV) Salts: The Important Role of a Water Molecule
Authors: Nava Paola , Carissan Yannick , Drujon Jean , Grau Fanny , Godeau Julien , Antoniotti Sylvain , Duñach Elisabet , Humbel Stéphane
Published: January 2014

A diene cycloisomerisation reaction catalysed by tin(IV) triflimidate is studied by using DFT computations. It is proposed that the mechanism does not involve the direct addition of the tin(IV) cation to a double bond because the catalyst regeneration step would be energetically unfeasible. We show that a water molecule may play a decisive role to enable the smooth completion of the catalytic cycle. The proposed active catalyst is thus a hydrated triflimidate salt. The hydrolysis and hydration energies are computed for three ligands of SnL4, L=triflate (OTf), triflimidate (NTf2) and a chlorosulfonate model (OSO2Cl). The diastereoselectivity observed in the cycloisomerisation is discussed in light of the transition‐state geometries. The hypothesis of hidden Brønsted acid catalysis is discussed and ruled out on the basis of new experimental results.
Paradigm Shift from Alkaline (Earth) Metals to Early Transition Metals in Fluoroorganometal Chemistry: Perfluoroalkyl Titanocene(III) Reagents Prepared via Not Titanocene(II) but Titanocene(III) Species
Authors: Fujiu Motohiro , Hashimoto Ryota , Nakamura Yuzo , Aikawa Kohsuke , Ito Shigekazu , Mikami Koichi
Published: January 2014

Perfluoroalkyl (RF) titanocene reagents [Cp2TiIIIRF] synthesized via [Cp2TiIIICl] rather than [Cp2TiII] show new types of perfluoroalkylation reactions. The [Cp2TiIIIRF] reagents exhibit a wide variety of reactivity with carbonyl compounds including esters and nitriles, and selectivities far higher than those reported for conventional RFLi and RFMgX reagents.
A Stable Microporous Mixed‐Metal Metal–Organic Framework with Highly Active Cu2+ Sites for Efficient Cross‐Dehydrogenative Coupling Reactions
Authors: Yang Xiu‐Li , Zou Chao , He Yabing , Zhao Min , Chen Banglin , Xiang Shengchang , O'Keeffe Michael , Wu Chuan‐De
Published: January 2014

Two metalloporphyrin octacarboxylates were used to link copper(II) nodes for the formation of two novel porous mixed‐metal metal–organic frameworks (M′MOFs) containing nanopore cages (2.1 nm in diameter) or nanotubular channels (1.5 nm in diameter). The highly active Cu2+ sites on the nanotubular surfaces of the stable porous M′MOF ZJU‐22, stabilized by three‐connected nets, lead to the superior catalytic activity for the cross‐dehydrogenative coupling (CDC) reaction.
Binary Pd–Polyoxometalates and Isolation of a Ternary Pd–V–Polyoxomolybdate Active Species for Selective Aerobic Oxidation of Alcohols
Authors: Huang Xianqiang , Zhang Xiaomei , Zhang Dan , Yang Song , Feng Xiao , Li Jikun , Lin Zhengguo , Cao Jie , Pan Ran , Chi Yingnan , Wang Bo , Hu Changwen
Published: January 2014

Binary Pd–polyoxometalates [Pd(dpa)2]3[PW12O40]2⋅12 DMSO (2), [Pd(dpa)2]3[PMo12O40]2⋅12 DMSO⋅2 H2O (3), and [Pd(dpa)(DMSO)2]2[HPMo10V2O40]⋅4 DMSO (4) were synthesized by reaction of [Pd(dpa)(OAc)2]⋅2 H2O (1; dpa=2,2′‐dipyridylamine) with three Keggin‐type polyoxometalates and fully characterized by single‐crystal and powder XRD analyses, IR spectroscopy, and elemental analyses. The synthesis is facile and straightforward, and the complicated ligand‐modification procedure often used in the traditional charge‐transfer method can be omitted. In 2–4, Pd complexes and polyoxometalate anions are coupled through electrostatic interaction. Compound 4 is more active than the other three compounds in the selective aerobic oxidation of alcohols at ambient pressure. Interestingly, during catalytic recycling of compound 4, unprecedented ternary Pd–V–polyoxometalate [Pd(dpa)2{VO(DMSO)5}2][PMo12O40]2⋅4 DMSO (5), which was captured and characterized by single‐crystal XRD, proved to be the true active species and showed high catalytic activity for the selective aerobic oxidation of aromatic alcohols (98.1–99.8 % conversion, 91.5–99.1 % selectivity). Moreover, on the basis of control experiments and EPR and UV/Vis spectra, a plausible reaction mechanism for the oxidation of alcohols catalyzed by 5 was proposed.
Enantioselective Continuous‐Flow Production of 3‐Indolylmethanamines Mediated by an Immobilized Phosphoric Acid Catalyst
Authors: Osorio‐Planes Laura , Rodríguez‐Escrich Carles , Pericàs Miquel A.
Published: January 2014

A polystyrene‐supported 1,1’‐bi‐2‐naphthol derived phosphoric acid has been synthesized and applied in the enantioselective Friedel–Crafts reaction of indoles and sulfonylimines. The immobilized catalyst was highly active and selective, and gave rise to a broad range of 3‐indolylmethanamines (19 examples) in high yields and excellent enantioselectivities (up to 98 % enantiomeric excess) after short reaction times under very convenient reaction conditions (RT in dichloromethane). Moreover, repeated recycling (14 cycles) was possible with no substantial loss in catalytic performance and the system could be adapted to a continuous‐flow operation (6 h). Finally, the applicability of the system was further confirmed by rapid access to a library of compounds with three points of diversity in a single continuous‐flow experiment that involved sequential pumping of different substrate combinations.
Surface Chemistry on Small Ruthenium Nanoparticles: Evidence for Site Selective Reactions and Influence of Ligands
Authors: Novio Fernando , Monahan Daniele , Coppel Yannick , Antorrena Guillermo , Lecante Pierre , Philippot Karine , Chaudret Bruno
Published: January 2014

The reactivity of two classes of ruthenium nanoparticles (Ru NPs) of small size, either sterically stabilized by a polymer (polyvinylpyrrolidone, PVP) or electronically stabilized by a ligand (bisdiphenylphosphinobutane, dppb) was tested towards standard reactions, namely CO oxidation, CO2 reduction and styrene hydrogenation. The aim of the work was to identify the sites of reactivity on the nanoparticles and to study how the presence of ancillary ligands can influence the course of these catalytic reactions by using NMR and IR spectroscopies. It was found that CO oxidation proceeds at room temperature (RT) on Ru NPs but that the system deactivates rapidly in the absence of ligands because of the formation of RuO2. In the presence of ligands, the reaction involves exclusively the bridging CO groups and no bulk oxidation is observed at RT under catalytic conditions. The reverse reaction, CO2 reduction, is achieved at 120 °C in the presence of H2 and leads to CO, which coordinates exclusively in a bridging mode, hence evidencing the competition between hydrides and CO for coordination on Ru NPs. The effect of ligands localized on the surface is also evidenced in catalytic reactions. Thus, styrene is slowly hydrogenated at RT by the two systems Ru/PVP and Ru/dppb, first into ethylbenzene and then into ethylcyclohexane. Selectively poisoning the nanoparticles with bridging CO groups leads to catalysts that are only able to reduce the vinyl group of styrene whereas a full poisoning with both terminal and bridging CO groups leads to inactive catalysts. These results are interpreted in terms of location of the ligands on the particles surface, and evidence site selectivity for both CO oxidation and arene hydrogenation.
The First Europium(III) β‐Diketonate Complex Functionalized Polyhedral Oligomeric Silsesquioxane
Authors: Chen Xiaofan , Zhang Panning , Wang Tianren , Li Huanrong
Published: January 2014

The first europium(III) β‐diketonate complex functionalized polyhedral oligomeric silsesquioxane (POSS) has been obtained by immobilization of such a complex at a silicon vertex of the POSS cage through the complexation of Eu3+ ions with thenoyltrifluoroacetone‐functionalized POSS. The new molecular hybrid material is liquid at room temperature, and shows bright‐red emission when irradiated with UV light due to energy transfer from the thenoyltrifluoroacetone ligand to the coordinated Eu3+ ions. Thermal analysis has revealed a significant improvement in the thermal stability of the material compared with tris(2‐thenoyltrifluoroacetonate)europium(III) dihydrate, [Eu(TTA)3]⋅2 H2O. In the context of recent advances in printable electronic technology, this novel luminescent organic liquid with the characteristic emission of Eu3+ may potentially be useful in the development of next‐generation organic devices such as flexible displays.
Ruthenium‐Catalyzed Synthesis of Indoles from Anilines and Epoxides
Authors: Peña‐López Miguel , Neumann Helfried , Beller Matthias
Published: January 2014

A general synthetic route to indoles from readily available anilines and epoxides by using ruthenium catalysis is described. This straightforward transformation allows a variety of indoles to be obtained in good yields by using [Ru3(CO)12]/1,1′‐bis(diphenylphosphino)ferrocene as the catalytic system. Water and hydrogen are formed as the only stoichiometric by‐products, making this process highly atom efficient.
ChemInform Abstract: Synthesis, Structures, Optical Properties and Electronic Structures of Two Mixed Metal Borates MBaB5O9 (M: Na, K).
Authors: Yu Hongwei , Pan Shilie , Wu Hongping , Su Xin , Yang Zhihua
Published: January 2014

Polycrystalline NaBaB5O9 (I) and KBaB5O9 (II) are prepared by solid state reaction of stoichiometric amounts of NaNO3 or KNO3, Ba(NO3)2, and H3BO3 (Pt crucible, 650 °C, 2 d).
ChemInform Abstract: NdNiMg5, a New Magnesium‐Rich Phase with an Unusual Structural Type.
Authors: Ourane Bassem , Gaudin Etienne , Zouari Ridha , Couillaud Samuel , Bobet Jean‐Louis
Published: January 2014

NdNiMg5 is identified during a study of the Mg‐rich part of the Mg—Nd—Ni system and can be synthesized by melting of the elements (sealed tantalum tube, 973 K, 10 d).
ChemInform Abstract: Yb5Ga2Sb6: A Mixed Valent and Narrow‐Band Gap Material in the RE5M2X6 Family.
Authors: Subbarao Udumula , Sarkar Sumanta , Gudelli Vijay Kumar , Kanchana V. , Vaitheeswaran G. , Peter Sebastian C.
Published: January 2014

Yb5Ga2Sb6 is synthesized by the metal flux technique with excess Ga as flux (alumina crucible, 1123 K, 3 d) followed by centrifugal separation of surplus Ga at 673 K.
ChemInform Abstract: Structure and Magnetic Properties of the α‐NaFeO2‐Type Honeycomb Compound Na3Ni2BiO6.
Authors: Seibel Elizabeth M. , Roudebush J. H. , Wu Hui , Huang Qingzhen , Ali Mazhar N. , Ji Huiwen , Cava R. J.
Published: January 2014

Layered polycrystalline Na3Ni2BiO6 is prepared by firing stoichiometric amounts of Na2CO3, NaBiO3, and NiO with a 3% excess of Na for compensating volatilization losses (alumina boat, 700 °C, 8 h, flowing O2).
ChemInform Abstract: New Two‐Dimensional Niobium and Vanadium Carbides as Promising Materials for Li‐Ion Batteries.
Authors: Naguib Michael , Halim Joseph , Lu Jun , Cook Kevin M. , Hultman Lars , Gogotsi Yury , Barsoum Michel W.
Published: January 2014

New two‐dimensional niobium and vanadium carbide phases are prepared by treating Nb2AlC and V2AlC in aqueous HF at room temperature for 90 h.
ChemInform Abstract: High‐Performance Silicon Photoanodes Passivated with Ultrathin Nickel Films for Water Oxidation.
Authors: Kenney Michael J. , Gong Ming , Li Yanguang , Wu Justin Z. , Feng Ju , Lanza Mario , Dai Hongjie
Published: January 2014

Deposition of a thin nickel film (approximately 2 nm thick) on n‐type silicon with its native oxide yields a high‐performance metal‐insulator‐semiconductor photoanode for photoelectrochemical water oxidation in both aqueous KOH (pH 14) and aqueous borate buffer (pH 9.5) solutions.
ChemInform Abstract: Selective Preparation of Bi2O3 Visible Light‐Driven Photocatalyst by Dispersant and Calcination.
Authors: Cheng Lijun , Kang Yong
Published: January 2014

Bi2O3 is precipitated by addition of NaOH to an aqueous HNO3 solution of Bi(NO3)3 containing PEG as dispersant followed by drying and optimized calcination.
ChemInform Abstract: High‐Pressure Syntheses and Characterization of the Rare‐Earth Fluoride Borates RE2(BO3)F3 (RE: Tb, Dy, Ho).
Authors: Hinteregger Ernst , Enders Michael , Pitscheider Almut , Wurst Klaus , Heymann Gunter , Huppertz Hubert
Published: January 2014

The new title compounds are prepared under high‐pressure/high‐temperature conditions from Ln2O3 (Ln: Tb, Dy, Ho), LnF3, and B2O3 (multianvil press, BN crucible, 900—1200 °C, 1.5—3 GPa).
ChemInform Abstract: Synthesis, Characterization, and Properties of the First Indium Borogermanate Incorporating and Organic Amine Ligand: InBGe2O6(OH)2(CH3CH (NH2)CH2NH2)·2H2O.
Authors: Wang Chih‐Min , Chiu Cheng‐Wei , Lin Hsiu‐Mei , Lii Kwang‐Hwa
Published: January 2014

The title compound is solvothermally synthesized from a mixture of In(NO3)2, GeO2, H3BO3, 1,2‐diaminopropane, and HF in H2O/pyridine (autoclave, 170 °C, 10 d).
ChemInform Abstract: SrGe2B2O8 and Sr3Ge2B6O16: Novel Strontium Borogermanates with Three‐Dimensional and Layered Anionic Architectures.
Authors: Hao Yu‐Cheng , Hu Chun‐Li , Xu Xiang , Kong Fang , Mao Jiang‐Gao
Published: January 2014

SrGe2B2O8 (I) and Sr3Ge2B6O16 (II) are synthesized by solid state reaction of stoichiometric mixtures of SrCO3, GeO2, and H3BO3 (Pt crucible, 900 °C, 3 d).
ChemInform Abstract: A New Mixed Metal Borate of BaPb[B5O9(OH)]·H2O with Acentric Structure.
Authors: Wu Han‐Qing , He Huan , Yang Bai‐Fei , Yang Guo‐Yu
Published: January 2014

The new title compound is hydrothermally synthesized from a mixture of H3BO3, Pb(OAc)2, Ba(OH)2, and H2O (autoclave, 200 °C, 6 d, 78% yield).
ChemInform Abstract: Mono‐ and Di‐Lanthanide Derivatives of 22‐Tungsto‐2‐antimonate(III), [Ln(H2O)4Sb2W21O72 (OH)]10‐ and [Ln2 (H2O)8Sb2W20O70] 8‐.
Authors: Ismail Amal H. , Bassil Bassem S. , Roemer Isabella , Kortz Ulrich
Published: January 2014

The structures of the mono‐ and di‐lanthanoid polyoxotungstate derivatives are determined by single crystal XRD.
ChemInform Abstract: Enzymatic Kinetic Resolution and Racemization of 2‐(Tetramethylpiperidine‐1‐oxyl)ethanols.
Authors: Prechter Agnes , Heinrich Markus R.
Published: January 2014

It is found that title compounds can be resolved effectively using Candida antarctica lipase B.
ChemInform Abstract: Synthesis of Some New Oxazolinyl/Thiazolinyl/Imidazolinyl‐benzoxazoles, ‐benzothiazoles and ‐benzimidazoles
Authors: Seenaiah D. , Venkatesh B. C. , Padmaja A. , Padmavathi V.
Published: January 2014

via Sm(III)‐catalyzed cyclocondensation reactions of the corresponding heterocyclic sulfonylacetic acid ester (I) with 2‐aminoethanol, 2‐aminoethanethiol or ethylenediamine, respectively
ChemInform Abstract: Palladium(II)‐Catalyzed Sequential C—Cl Bond Formation: A Novel and Efficient Method for Direct α,α‐Dichlorination of β‐Dicarbonyl Compounds.
Authors: Liu Weibing , Tan Liquan , Zhou Peng , Chen Cui , Zhang Qing
Published: January 2014

Reaction conditions are optimized for the selective α,α‐dichlorination of N‐substituted acetoacetamides and the process is investigated with a series of related substrates.
ChemInform Abstract: Nickel‐Catalyzed ortho‐Selective Hydrodefluorination of N‐Containing Heterocycle‐Polyfluoroarenes.
Authors: He Yi , Chen Zhao , He Chun‐Yang , Zhang Xingang
Published: January 2014

Nickel‐catalyzed, chelation‐assisted, ortho‐selective mono hydrodefluorination of pyridyl or quinolyl substituted polyfluoroarenes is developed using triorganylsilanes as hydrogen source.
ChemInform Abstract: Selective Reduction of Carboxylic Acids to Aldehydes Through Manganese Catalyzed Hydrosilylation.
Authors: Zheng Jianxia , Chevance Soizic , Darcel Christophe , Sortais Jean‐Baptiste
Published: January 2014

A simple method is elaborated for the manganese‐catalyzed hydrosilylation of carboxylic acids under UV irradiation.
ChemInform Abstract: Ruthenium‐Catalyzed Olefin Metathesis Accelerated by the Steric Effect of the Backbone Substituent in Cyclic (Alkyl)(amino) Carbenes.
Authors: Zhang Jun , Song Shangfei , Wang Xiao , Jiao Jiajun , Shi Min
Published: January 2014

The metathesis catalyst shows very high activity and selectivity towards the ring closing metathesis of (I), as well as in the ethenolysis of methyl oleate (III) compared to readily available Grubbs‐Hoveyda catalysts.
ChemInform Abstract: Phosphorus(V)‐Catalyzed Deoxydichlorination Reactions of Aldehydes.
Authors: An Jie , Tang Xiaoping , Moore Joshua , Lewis William , Denton Ross M.
Published: January 2014

The conversion of aldehydes into geminal dichlorides proceeds via a phosphorus(V)‐catalysis manifold in which phosphine oxide turnover is induced by using oxalyl chloride as a consumable reagent.
ChemInform Abstract: A Selective Transformation of Enals into Chiral γ‐Amino Alcohols.
Authors: Calow Adam D. J. , Batsanov Andrei S. , Pujol Alba , Sole Cristina , Fernandez Elena , Whiting Andrew
Published: January 2014

The key feature of this enantioselective route for the one‐pot conversion of enals to γ‐amino alcohols is an in situ imine formation using a sterically demanding amine to ensure complete selectivity in the subsequent β‐boration step.
ChemInform Abstract: Nucleophilic Trifluoromethylthiolation of Allylic Bromides: A Facile Preparation of Allylic Trifluoromethyl Thioethers.
Authors: Tan Jianwei , Zhang Guoting , Ou Yangli , Yuan Yaofeng , Weng Zhiqiang
Published: January 2014

A nucleophilic trifluoromethylthiolation of allyl bromides and an allyl chloride is described using (bipy)CuSCF3 as the reagent.
ChemInform Abstract: L‐Lysine/Imidazole‐Catalyzed Multicomponent Cascade Reaction: Facile Synthesis of C5‐Substituted 3‐Methylcyclohex‐2‐enones.
Authors: Xiang Ziwei , Liu Zhiqiang , Liang Yiru , Wu Qi , Lin Xianfu
Published: January 2014

Yields of these reactions are determined by HPLC‐analysis.
ChemInform Abstract: Synthesis of a New Urea Derivative: A Dual‐Functional Organocatalyst for Knoevenagel Condensation in Water.
Authors: Le Wen‐Jun , Lu Hong‐Fei , Zhou Jun‐Tao , Cheng He‐Long , Gao Yu‐Hua
Published: January 2014

The phenylalanine—urea compound (I) is synthesized and utilized as catalyst for Knoevenagel condensations under mild conditions.
ChemInform Abstract: Selective Reduction of Nitroarenes with Molybdenum Disulfide.
Authors: Huang Lei , Luo Pingfei , Xiong Man , Chen Rizhi , Wang Yong , Xing Weihong , Huang Jun
Published: January 2014

The catalyst is recyclable several times without loss of activity.
ChemInform Abstract: Heterogeneous Palladium‐Catalyzed Synthesis of Aromatic Ethers by Solvent‐Free Dehydrogenative Aromatization: Mechanism, Scope, and Limitations under Aerobic and Non‐aerobic Conditions.
Authors: Sutter Marc , Lafon Romain , Raoul Yann , Metay Estelle , Lemaire Marc
Published: January 2014

The present method is a safe and straightforward alternative to existing methods for C—O bond formation.
ChemInform Abstract: Eco‐Friendly and Economic Method for Knoevenagel Condensation by Employing Natural Catalyst.
Authors: Patil Suresh S. , Jadhav Swati D. , Deshmukh M. B.
Published: January 2014

An extract of pineapple juice (pH 3.7) is successfully used as acid catalyst for the Knoevenagel condensation of aldehydes with malononitrile (12 examples).
ChemInform Abstract: One‐Step Synthesis of Unsymmetrical Sulfides Bearing Hexafluorocumyl Moiety.
Authors: Zajac Adrian , Drabowicz Jozef
Published: January 2014

Title compounds (III) are conveniently prepared starting from commercially available alcohol (I).
ChemInform Abstract: Highly Stereoselective and One‐Pot Synthesis of Tetra‐Substituted Monofluoroalkenes with Aldehydes and Fluorobis(phenylsulfonyl)methane.
Authors: Shen Xiao , Ni Chuanfa , Hu Jinbo
Published: January 2014

A highly stereoselective method for the synthesis of tetrasubstituted (Z)‐monofluoroalkenes is developed.
ChemInform Abstract: Iron‐Catalyzed Homocoupling of Aryl Halides and Derivatives in the Presence of Alkyllithiums.
Authors: Toummini Dounia , Ouazzani Fouad , Taillefer Marc
Published: January 2014

The efficient title reaction proceeds under very mild conditions.
ChemInform Abstract: Indium(III) Catalyzed Direct sp3—sp C—C Bond Formation from Alcohols and Terminal Alkynes.
Authors: Nan Guangming , Zhou Jun
Published: January 2014

The method presented here does not require any ligand, base or additive and tolerates a variety of aromatic and aliphatic alkynes as well as alcohols including benzylic, allylic, and propargylic ones.
ChemInform Abstract: Efficient Synthesis of Trifluoromethylated Cyclopentadienes/Fulvenes/Norbornenes from Divinyl Ketones.
Authors: Liu Xiao , Xu Xianxiu , Pan Ling , Zhang Qian , Liu Qun
Published: January 2014

A series of trifluoromethylated 1,3‐dien‐3‐ols (IV) are synthesized by regiospecific addition of the Ruppert—Prakash reagent to divinyl ketones (I) and transformed into trifluoromethylated cyclopentadienes (V), norbornenes (VII), and fulvenes (IX).
ChemInform Abstract: Copper‐Catalyzed Direct N‐Arylation of Naphthalimides Using Diaryliodonium Salts.
Authors: Mao Song , Guo Fenglou , Li Juan , Geng Xu , Yu Jianjun , Han Jianwei , Wang Limin
Published: January 2014

The new convenient method uses diaryliodonium salts as efficient, mild and selective arylating agents.
ChemInform Abstract: Highly Sterically Hindered Binaphthalene‐Based Monophosphane Ligands: Synthesis and Application in Stereoselective Suzuki—Miyaura Reactions.
Authors: Meskova Michaela , Putala Martin
Published: January 2014

Novel sterically hindered binaphthyl based monophosphanes are developed and ligand BNP is successfully applied for the stereoselective preparation of axially chiral biaryls (III) and (V).
ChemInform Abstract: Rhodium‐Catalyzed Direct Annulation of Aldehydes with Alkynes Leading to Indenones: Proceeding Through in situ Directing Group Formation and Removal.
Authors: Chen Shuyou , Yu Jintao , Jiang Yan , Chen Fan , Cheng Jiang
Published: January 2014

The reaction proceeds via installation of an intermediary acetylhydrazone as ortho‐directing group.
ChemInform Abstract: Absolute Asymmetric Synthesis of Enantiopure Organozinc Reagents, Followed by Highly Enantioselective Chlorination.
Authors: Olsson Susanne , Lennartson Anders , Haakansson Mikael
Published: January 2014

A spontaneous asymmetric resolution during the recrystallization of compound (IV) is described.
ChemInform Abstract: Synthesis of Fluorenone and Anthraquinone Derivatives from Aryl‐ and Aroyl‐Substituted Propiolates.
Authors: Puenner Florian , Schieven Justin , Hilt Gerhard
Published: January 2014

Compound (VIIc) is only obtained in traces contaminated with compound (XII).
ChemInform Abstract: An Innovative Protocol for the Synthesis of 3‐(Pyridin‐2‐yl)‐5‐sec‐aminobiphenyl‐4‐carbontriles and 9,10‐Dihydro‐3‐(pyridine‐2‐yl)‐1‐sec‐aminophenanthrene‐2‐carbonitriles.
Authors: Patil Umesh D. , Mahulikar Pramod P.
Published: January 2014

12 Title compounds of type (III), (V), or (VII) are prepared by a ring transformation reaction via a two‐carbon insertion from 2‐acetylpyridine (II).
ChemInform Abstract: Design, Synthesis and Antitubercular Evaluation of Novel 2‐Substituted‐3H‐benzofuro Benzofurans via Palladium—Copper Catalyzed Sonogashira Coupling Reaction.
Authors: Yempala Thirumal , Sridevi Jonnalagadda Padma , Yogeeswari Perumal , Sriram Darmarajan , Kantevari Srinivas
Published: January 2014

Compound (Ve) is found to exhibit the best in vitro anti‐mycobacterial activity against Mycobacterium tuberculosis H37Rv with lower cytotoxicity and good therapeutic index.
ChemInform Abstract: Asymmetric Michael‐Aldol Tandem Reaction of 2‐Substituted Benzofuran‐3‐ones and Enones: A Facile Synthesis of Griseofulvin Analogues.
Authors: Dong Nan , Li Xin , Wang Feng , Cheng Jin‐Pei
Published: January 2014

This reaction sequence yields the spiro‐products with adjacent quaternary and tertiary stereocenters with excellent enantioselectivities.
ChemInform Abstract: Pd‐Catalyzed Oxidative Cross‐Coupling Between Two Electron Rich Heteroarenes.
Authors: He Chun‐Yang , Wang Zhen , Wu Cai‐Zhi , Qing Feng‐Ling , Zhang Xingang
Published: January 2014

The title reaction of two heteroaromatic cross‐coupling partners with similar structures and electronic properties under mild conditions is achieved.
ChemInform Abstract: Dual Selectivity: Electrophile and Nucleophile Selective Cross‐Coupling Reactions on a Single Aromatic Substrate.
Authors: Heinrich Annika C. J. , Thiedemann Birk , Gates Paul J. , Staubitz Anne
Published: January 2014

The first microwave assisted very high selective one‐pot Stille cross‐coupling of aromatic compounds yields bifunctional products.
ChemInform Abstract: Synthesis of Hexahydroisoindole‐3a‐carboxylates by IMDA Reaction of Morita—Baylis—Hillman Adduct‐Derived Dienes Bearing a Z‐Alkenyl Tether.
Authors: Kim Ko Hoon , Lee Sangku , Lee Junseong , Go Min Jeong , Kim Jae Nyoung
Published: January 2014

An intramolecular Diels—Alder (IMDA) reaction of Morita—Baylis—Hillman adduct‐derived dienes bearing a Z‐alkenyl dienophile tether affords hexahydroisoindole‐3a‐carboxylates in excellent yields and stereoselectivity.
ChemInform Abstract: A Convenient Approach to the Design and Synthesis of Indolo[3,2‐c]coumarins via the Microwave‐Assisted Cadogan Reaction.
Authors: Irgashev Roman A. , Karmatsky Arseny A. , Slepukhin Pavel A. , Rusinov Gennady L. , Charushin Valery N.
Published: January 2014

Microwave‐assisted Cadogan reaction of easily accessible 3‐(4,5‐dimethoxy‐2‐nitrophenyl)coumarins affords the corresponding indolo[3,2‐c]coumarins.