Synthesis and Characterization of 5-Coordinate Tungsten Hydride Anions: [(tBu3SiNH)(tBu3SiN=)2HWR]M

Treatment of (^tBu₃SiNH)(^tBu₃SiN=)₂WH ( 1 -H) with small alkyl anions (RM) afforded tungsten alkyl hydride anions [(^tBu₃SiNH)(^tBu₃SiN=)₂HWR)]M ( 3 -(R)M: R=CH₃, M=Li; R=ⁿBu, M=Li; R=^neoPe, M=Li; R=CH₂Ph (Bn), M=K (two isomers); R=CCH, M=Na; R=CH=CH₂ (Vy), M=Li). The saturated alkyl anions 3 -(R)M ( 3 -(R)M: R=CH₃, M=Li; R=ⁿBu, M=Li; R=^neoPe, M=Li; R=CH₂Ph (Bn), M=K) degraded via apparent 1,2-RH-elimination to produce the known [(^tBu₃SiN=)₃WH]M ( 2 -HM), but the acetylide ( 3 -(C₂H)Na) and vinyl ( 3 -(Vy)Li) anions converted to their hydrogenated isomers, [(^tBu₃SiN=)₃WVy]Na ( 2 -VyNa) and [(^tBu₃SiN=)₃WEt]Li ( 2 -EtLi), respectively. The structure of 3 -(ⁿBu)Li is reported, and a discussion of tungsten-hydride coupling constants in ^tBu₃SiX-ligated (X=O, NH, N) systems is given.     

Transcranial Magnetic Stimulation of the Supplementary Motor Area in the Treatment of Obsessive-Compulsive Disorder: A Multi-Site Study

Recently, strategies beyond pharmacological and psychological treatments have been developed for the management of obsessive-compulsive disorder (OCD). Specifically, repetitive transcranial magnetic stimulation (rTMS) has been employed as an adjunctive treatment in cases of treatment-refractory OCD. Here, we investigate six weeks of low frequency rTMS, applied bilaterally and simultaneously over the sensory motor area, in OCD patients in a randomized, double-blind placebo-controlled clinical trial. Twenty-two participants were randomly enrolled into the treatment (ACTIVE = 10) or placebo (SHAM = 12) groups. At each of seven visits (baseline; day 1 and weeks 2, 4, and 6 of treatment; and two and six weeks after treatment) the Yale-Brown Obsessive Compulsive Scale (Y-BOCS) was administered. At the end of the six weeks of rTMS, patients in the ACTIVE group showed a clinically significant decrease in Y-BOCS scores compared to both the baseline and the SHAM group. This effect was maintained six weeks following the end of rTMS treatment. Therefore, in this sample, rTMS appeared to significantly improve the OCD symptoms of the treated patients beyond the treatment window. More studies need to be conducted to determine the generalizability of these findings and to define the duration of rTMS’ clinical effect on the Y-BOCS. Clinical Trial Registration Number (NCT) at www.clinicaltrials.gov: {"type":"clinical-trial","attrs":{"text":"NCT00616486","term_id":"NCT00616486"}}NCT00616486.     

Hard wood‐composites made of rice straw and recycled polystyrene foam wastes

The submitted work discussed the possibility of using two of the most problematic wastes to formulate an added‐value hard wood‐composite (HWC). The lignocellulosic rice straws (RS) fibers (as reinforced filler) and recycled expanded polystyrene foam (PS) wastes (as dispersed polymer matrix), were used to formulated the hard wood product applying the hot press technique. The air dried RS was added to the molten PS at increasing ratios (30–70% mass:mass), and the reached HWC sheet was subjected to tensile strength, water absorption and acoustic resistance characterizations. Based on the experimental data, it was found that increasing the RS contents accompanied with a diminish in the tensile strength value by about 50% at 70% RS compare to that at 30% RS. To improve the adhesion between the hydrophilic filler RS and the hydrophobic PS matrix, maleated PS graft (PS‐g‐MA) was prepared and added at the expanse of the PS content, to formulate an additional wood‐composite (HWCg) aiming to have better mechanical and dimensional stability features. Results obtained indicated that increasing the coupling agent content, keeping the RS added constant, enhance the tensile strength feature in addition, reduced the water absorption for the final products by more than 45%. The data obtained suggested that, it can create added‐value hard wood composites entirely from the two nominated problematic wastes. In addition to the value gained by the environment, the reached hard wood products record acceptable mechanical characterization, dimensional stability and sound resistance properties that qualified it to replace the natural wood in many daily applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44770.     

Ionomeric polyurethanes of pyridinium type with side azobenzene groups

New polyurethane cationomers synthesized by a two‐step substitution postreaction of urethane hydrogen atoms with nitroazobenzene groups were studied. As a starting polymer, a polyurethane based on poly(tetramethylene oxide)diol, isophorone diisocyanate, and 2,6‐bis(hydroximethyl)pyridine was used. After a preliminary metalation of the above polymer with natrium hydride, by reaction of polyurethane N‐sodate with 4‐nitro‐4′(β–iodoethylurethane)azobenzene, chromophoric groups between 2.85 and 10.53 wt % could be incorporated instead of hydrogen. Such polymers partially functionalized with azobenzene and further quaternized with methyl iodide led to the formation of pyridinium polyurethane cationomers N‐modified with nitroazo groups. The photosensible properties of the azobenzene chromophore in a polymer solution and film state indicated important differences in their photoresponse. In the polymer solution, the trans–cis photoisomerization of the chromophore is accompanied by an irreversible photobleaching effect, while under the same UV irradiation conditions, the ionomeric films exhibited an enhanced photostability. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1240–1247, 2002     

Small amphiphilic organics, coordination extended solids, and constant curvature structures

In this Account, we explore the role constant curvature structures play in amphiphilic small molecule crystals and extended coordination solids. A constant curvature structure is one in which there is a surface or interface that has the same curvature throughout its surface. Simple examples of such structures contain spheres (micelles), columns, or layers. Yet another family are cubic as is found in the gyroid topology. For amphiphilic systems, there are two domains, one generally hydrophobic and the other hydrophilic. We find that the interfaces between these two domains in small molecule structures resemble those in larger scale systems and adopt topologies related to constant curvature structures. The hydrophobic-to-total volume ratio, a molecular parameter, can be used to predict which type of constant curvature structure is adopted. In the case of three coordinate extended solids, constant curvature plays a role both in the extended net topology and in the hydrophobic-to-hydrophilic interface.     

High-throughput approach to the catalytic combustion of diesel soot

A methodology for the evaluation of diesel soot oxidation catalysts by high-throughput (HT) screening was developed. The optimal experimental conditions (soot amount, catalyst/soot ratio, type of contact, composition and flow rate of gas reactants) ensuring a reliable and reproducible detection of light-off temperatures in a 16 parallel channels reactor were set up. The temperature profile measured in the catalyst/soot bed under TPO conditions when the exothermic combustion of soot takes place was shown to provide an accurate measurement of the ignition. Its reproducibility and relevance were checked. The results obtained with a reference noble metal free catalyst (La_0.8Cr_0.8Li_0.2O₃ perovskite) agree very well with literature data. Qualitative mechanistic features could be derived from these experiments, stressing the likely limiting step of oxygen transfer from catalyst surface to soot particulates to ignite the soot combustion. Ceria material was shown to be more appropriate than perovskite one. From an HT screening of a large diverse library (over 100 mixed oxides catalysts) under optimized conditions, about 10 new formulations were found to perform better than selected noble metal free reference materials.     

Modern developments in wind engineering: part 4

This is the fourth in a series of review papers devoted to the state-of-the-art in wind engineering. The first three parts of the series were published in the October 1981 (pp. 233–241 and 242–248) and March 1982 (pp. 66–74) issues of Engineering Structures.     

A survey of APA- and non-APA-approved internship programs.

A survey questionnaire eliciting information on the number of internships offered, average salary of interns, selection criteria, and percentages of work time was sent to 294 American Psychological Association (APA)- and non-APA-approved internship sites. Results of this study and the new criteria for accreditation indicate that students from approved doctoral programs have a definite advantage in the internship marketplace. Sufficient evidence exists, however, to conclude that students from non-APA-approved programs may be encouraged to risk competing for APA-approved internships. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Stabilizing Mean Values and Minimizing Variances of Electronic Systems Performance Criteria

Mathematical statistics are used to design electronic systems in which the effects of the initial variations of the system parameters and the drift of these parameters on the system performance criteria are a minimum. This is accomplished by minimizing the initial variances of the system performance criteria with respect to the initial mean values of the system parameters while constraining the means of these parameters to their required values. In addition, the drift rates of the system parameters are selected in such a manner as to prevent the drift of the mean values of the system performance criteria while reducing the tendencies of the variances of these criteria to increase with time. These techniques were successfully applied to a number of electronic systems, including systems with both active and passive elements, thus illustrating the usefulness of mathematical statistics in the design of mass produced electronic systems.