Boronate Ligands in Materials: Determining Their Local Environment by Using a Combination of IR/Solid‐State NMR Spectroscopies and DFT Calculations

Boronic acids (R‐B(OH)₂) are a family of molecules that have found a large number of applications in materials science. In contrast, boronate anions (R‐B(OH)₃^?) have hardly been used so far for the preparation of novel materials. Here, a new crystalline phase involving a boronate ligand is described, Ca[C₄H₉‐B(OH)₃]₂, which is then used as a basis for the establishment of the spectroscopic signatures of boronates in the solid state. The phase was characterized by IR and multinuclear solid‐state NMR spectroscopy (¹H, ¹³C, ¹¹B and ⁴³Ca), and then modeled by periodic DFT calculations. Anharmonic OH vibration frequencies were calculated as well as NMR parameters (by using the Gauge Including Projector Augmented Wave—GIPAW—method). These data allow relationships between the geometry around the OH groups in boronates and the IR and ¹H NMR spectroscopic data to be established, which will be key to the future interpretation of the spectra of more complex organic–inorganic materials containing boronate building blocks.     

氨三乙酸、缬氨酸、亮氨酸的三元过渡金属配合物：合成和生物学应用

以氨三乙酸HNTA2-为主要配体,缬氨酸(valine)或亮氨酸(leucine)为次要配体在微酸性介质中合成了Ni(Ⅱ),Cu(Ⅱ),and Zn(Ⅱ)的三元配合物。用元素分析、热分析、FTIR,UV-Vis分光光度法,磁性测量和质谱法表征了合成的三元配合物。结果表明,三元配合物可在金属(M):氨三乙酸(HNTA)∶缬氨酸(valine)或亮氨酸(leucine)=1∶1∶1时制得,其分子结构为[M(HNTA)(valine)(H2O)2].1.5H2O and[M(HNTA)(leucine)(H2O)2].1.5H2O(其中M=Ni(Ⅱ)or Cu(Ⅱ))和H2[Zn(NTA)(valine)(H2O)]H2O。标题三元过渡金属配合物为八面体对称构型。同时研究了该三元配合物对大肠杆菌,金黄色葡萄球菌,白色念珠菌,黄曲霉菌(菌株从开罗大学理学院微分析中心获得)的抗菌活性。根据推荐的知名方法用标准的抗菌和抗真菌剂进行体外测试(in vitro)以评估我们的新制备的配合物对细菌和真菌物种的生长抑制活性。     

Base mediated synthesis of α-aminated aroyl/acetylnaphthalenes through [4+2] annulations

We have developed a base promoted simple, efficient and alternative approach for the synthesis of 4-amino-3-aroyl//heteroaroyl/acetyl-2-methylsulfanyl-naphthalene-1-carbonitriles by reaction of easily accessible 3,3-bis(methylthio)-1-aryl/heteroaryl/acetylprop-2-en-1-one and 2-cyanomethyl-benzonitrile. Reaction of 1-(2-halo/methoxy-phenyl)-3,3-bis(methylthio)prop-2-en-1-one and 2-cyanomethyl-benzonitrile under basic conditions also afforded 6-(methylthio)-7-oxo-7,12-dihydrobenzo[c]acridine-5-carbonitrile along with usual product. Structure of the synthesized product has been confirmed by single X-ray crystallography.     

Cooperative Q‐learning techniques for distributed online power allocation in femtocell networks

In this paper, we address the problem of distributed interference management of femtocells that share the same frequency band with macrocells using distributed multi‐agent Q‐learning. We formulate and solve two problems representing two different Q‐learning algorithms, namely, femto‐based distributed and sub‐carrier‐based distributed power controls using Q‐learning (FBDPC‐Q and SBDPC‐Q). FBDPC‐Q is a multi‐agent algorithm that works on a global basis, for example, deals with the aggregate macrocell and femtocell capacities. Its complexity increases exponentially with the number of sub‐carriers in the system. Also, it does not take into consideration the sub‐carrier macrocell capacity as a constraint. To overcome these problems, SBDPC‐Q is proposed, which is a multi‐agent algorithm that works on a sub‐carrier basis, for example, sub‐carrier macrocell and femtocell capacities. Each of FBDPC‐Q and SBDPC‐Q works in three different learning paradigms: independent (IL), cooperative (CL), and weighted cooperative (WCL). IL is considered the simplest form for applying Q‐learning in multi‐agent scenarios, where all the femtocells learn independently. CL and WCL are the proposed schemes in which femtocells share partial information during the learning process in order to strike a balance between practical relevance and performance. We prove the convergence of the CL paradigm when used in the FBDPC‐Q algorithm. We show via simulations that the CL paradigm outperforms the IL paradigm in terms of the aggregate femtocell capacity, especially in networks with large number of femtocells and large number of power levels. In addition, we propose WCL to address the CL limitations. Finally, we evaluate the robustness and scalability of both FBDPC‐Q and SBDPC‐Q, against several typical dynamics of plausible wireless scenarios (fading, path loss, random activity of femtocells, etc.). We show that the CL paradigm is the most scalable to large number of femtocells and robust to the network dynamics compared with the IL and WCL paradigms. Copyright © 2014 John Wiley & Sons, Ltd.     

Effect of moisture content on the 222Rn mass exhalation rates for different grain-size samples of red brick and cement mortar used in Qena city,Egypt

Journal of Radioanalytical and Nuclear Chemistry - Four different grain size fractions (0.2–0.5, 0.5–1, 1–1.8, 1.8–2 mm) of red brick and cement mortar samples at...     

Phenylpropanoids from Tanacetum baltistanicum with Nematocidal and Insecticidal Activities

Chemistry of Natural Compounds - One new and seven known secondary metabolites 1–8 were isolated, and the nematocidal and insecticidal activities of major compounds from Tanacetum...     

Reactive sensing capability towards the working electrical and chemical conditions of poly (aniline –co–o-toluidine) copolymers

Conducting polymers are considered as reactive gels which can sense the working ambient through their unique electrochemical reaction. Copolymers of aniline with o-toluidine for three different monomer compositions were synthesized chemically and were characterized using FTIR and UV-Vis spectroscopy, SEM, TGA, and cyclic voltammetry. The electrochemical reactive sensing characteristics with respect to the electrical and chemical working conditions of the copolymers were verified and compared through Chronopotentiometric responses in aqueous solutions of HCl by changing the reaction variables: applied current and chemical environment (electrolyte concentration) at a fixed constant charge. The consumed electrical energy during the electrochemical reaction of the copolymers varies linearly with the driving current and follows a logarithmic dependence on the electrolyte concentration. The consumed electrical energy during the reaction was found to act as the sensing parameter. At the same experimental condition, the sensitivity was associated with the conductivity of the copolymers. The highly conducting composition gives the highest sensitivity. These experimental results were fitted with the theoretical equation.

     

Dewatering of cellulose nanofibrils using ultrasound

Although cellulose nanomaterials have promising properties and performance in a wide application space, one hinderance to their wide scale industrial application has been associated with their economics of dewatering and drying and the ability to redisperse them back into suspension without introducing agglomerates or lose of yield. The present work investigates the dewatering of aqueous suspensions of cellulose nanofibrils (CNFs) using ultrasound as a potentially low-cost, non-thermal, and scalable alternative to traditional heat-based drying methods such as spray drying. Specifically, we use vibrating mesh transducers to develop a direct-contact mode ultrasonic dewatering platform to remove water from CNF suspensions in a continuous manner. We demonstrate that the degree of dewatering is modulated by the number of transducers, their spatial configuration, and the flow rate of the CNF suspension. Water removal of up to 72 wt.% is achieved, corresponding to a final CNF concentration of 11 wt.% in 30 min using a two-transducer configuration. To evaluate the redispersibility of the dewatered CNF material, we use a microscopic analysis to quantify the morphology of the redispersed CNF suspension. By developing a custom software pipeline to automate image analysis, we compare the histograms of the dimensions of the redispersed dewatered fibrils with the original CNF samples and observe no significant difference, suggesting that no agglomeration is induced due to ultrasonic dewatering. We also perform SEM analysis to evaluate the nanoscale morphology of these fibrils showing a width range of 20 nm–4 um. We estimate that this ultrasound dewatering technique is also energy-efficient, consuming up to 36% less energy than the enthalpy of evaporation per kilogram of water. Together with the inexpensive cost of transducers (<?$1), the potential for scaling up in parallel flow configurations, and excellent redispersion of the dewatered CNFs, our work offers a proof-of-concept of a sustainable CNF dewatering system, that addresses the shortcomings of existing techniques.

     

Defects-engineered tailoring of tri-doped interlinked metal-free bifunctional catalyst with lower gibbs free energy of OER/HER intermediates for overall water splitting

Controllable tailoring of metal-free/carbon-based nanostructures tends an encouraging way to enhance the bifunctional activity of electrodes, but a great challenge owing to the sluggish kinetics of oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Herein, a facile tempted-defects assisted fractionation strategy is presented to synthesize N, S, and O tri-doped metal-free catalyst (DE-TDAP). Due to this effective tempted-defects and heteroatoms interlinking in DE-TDAP, it delivers the lowest overpotential toward both the OER (346 mV) and HER (154 mV) at 10 mA cm^?2. Remarkably, the DE-TDAP-electrode carries only a cell voltage of 1.81 V at 10 mA cm^?2 for overall water splitting and long-term stability. Considerably, the density functional theory (DFT) calculation exposes that the tailored-defects in tri-doped interlinking could enhance bifunctional catalytic performance devising from lower Gibbs free energy of OER/HER intermediates on active sites. This struggle henceforth provides a perceptive understanding of the synergetic principles of heteroatom-interlinking-tailoring nanostructures in water splitting.     

An updated review of nanofluids in various heat transfer devices

Journal of Thermal Analysis and Calorimetry - The field of nanofluids has received interesting attention since the concept of dispersing nanoscaled particles into a fluid was first introduced in...