[2+2] Cycloaddition of the Schrock titanium silylidene and acetylene

Russian Chemical Bulletin - [2+2] Cycloadduct of the titanium silylidene Cp2Ti(thf)=Si[Si3(SiMeBut 2)4] and acetylene was readily prepared, isolated, and characterized by NMR spectroscopy and...     

Electron ionization induced metastable decompositions of isomeric trimethylsilylmethanol, (CH3)3SiCH2OH, and methoxytrimethylsilane, (CH3)3SiOCH3

The metastable decompositions of trimethylsilylmethanol, (CH₃)₃SiCH₂OH (MW: 104, 1) and methoxytrimethylsilane, (CH₃)₃SiOCH₃ (MW: 104, 2) upon electron ionization have been investigated by use of mass-analyzed ion kinetic energy (MIKE) spectroscopy and D labeling. The metastable ions of 1 ^·+ decompose to give the fragment ions m/z 89 (CH ₃ ^· loss) and 73 (^·CH₂OH loss), whereas those of 2 ^·+ only yield the fragment ion m/z 89 (CH ₃ ^· loss). The latter fragment ion is generated by loss of a methyl radical from the trimethylsilyl group via a simple cleavage reaction as shown by D labeling. However, the fragment ions m/z 89 and 73 from 1 ^·+ are generated following an almost statistical exchange of the original methyl and methylene hydrogen atoms in the molecular ion as shown also by D labeling. This exchange indicates a complex rearrangement of the molecular ion of 1 ^·+ prior to metastable decomposition for which as key step a 1,2-trimethylsilyl group migration from carbon to oxygen is suggested. A different behavior is also found between the source-generated m/z 89 ions from 1 ^·+ which decompose in the metastable time region to give ions m/z 61 by loss of ethylene and those from 2 ^·+ which decompose in the metastable region to yield ions m/z 59 by elimination of formaldehyde.     

Synthesis,Characterization, and Crystal Structure of Cyclotrisilene: A Three-Membered Ring Compound with a Si−Si Double Bond

Red-orange crystals of cyclotrisilene 3 were obtained by the reaction of the dibromotrisilane 1 and the tribromodisilane 2 with sodium in toluene [Eq. (1)]. The X-ray crystal structure of 3 shows that the three-membered ring is almost an isosceles triangle and has a twisted Si−Si double bond with a length of 2.138(2) Å.     

A protocol for searching the most probable phase‐retrieved maps in coherent X‐ray diffraction imaging by exploiting the relationship between convergence of the retrieved phase and success of calculation

Coherent X‐ray diffraction imaging (CXDI) is a technique for visualizing the structures of non‐crystalline particles with size in the submicrometer to micrometer range in material sciences and biology. In the structural analysis of CXDI, the electron density map of a specimen particle projected along the direction of the incident X‐rays can be reconstructed only from the diffraction pattern by using phase‐retrieval (PR) algorithms. However, in practice, the reconstruction, relying entirely on the computational procedure, sometimes fails because diffraction patterns miss the data in small‐angle regions owing to the beam stop and saturation of the detector pixels, and are modified by Poisson noise in X‐ray detection. To date, X‐ray free‐electron lasers have allowed us to collect a large number of diffraction patterns within a short period of time. Therefore, the reconstruction of correct electron density maps is the bottleneck for efficiently conducting structure analyses of non‐crystalline particles. To automatically address the correctness of retrieved electron density maps, a data analysis protocol to extract the most probable electron density maps from a set of maps retrieved from 1000 different random seeds for a single diffraction pattern is proposed. Through monitoring the variations of the phase values during PR calculations, the tendency for the PR calculations to succeed when the retrieved phase sets converged on a certain value was found. On the other hand, if the phase set was in persistent variation, the PR calculation tended to fail to yield the correct electron density map. To quantify this tendency, here a figure of merit for the variation of the phase values during PR calculation is introduced. In addition, a PR protocol to evaluate the similarity between a map of the highest figure of merit and other independently reconstructed maps is proposed. The protocol is implemented and practically examined in the structure analyses for diffraction patterns from aggregates of gold colloidal particles. Furthermore, the feasibility of the protocol in the structure analysis of organelles from biological cells is examined.     

Palladium-catalyzed C-H homocoupling of bromothiophene derivatives and synthetic application to well-defined oligothiophenes

Synthesis of oligothiophenes of well-defined structures that possess 2-8 thiophene units is performed with a new synthetic strategy involving C-H homocoupling of bromothiophenes and cross-coupling with organostannanes. Tolerance of the carbon-bromine bond to the palladium-catalyzed C-H homocoupling results in oligothiophenes bearing C-Br bonds at the terminal thiophene rings, which allow further transformation by the catalysis of a transition-metal complex.     

Reconstruction of Scalar Source Intensity Based on Sensor Signal in Turbulent Channel Flow

We consider a turbulent channel flow, where a scalar point source with a time-harmonic intensity releases a substance that can be modeled as a passive scalar. With the source location known, our objective is to estimate the time history of the source intensity based on sensor measurements at different locations downstream of the source by adopting an adjoint approach. It is shown that the proposed algorithm reproduces the original coherent sinusoidal wave of the scalar source accurately from the chaotic scalar signals measured by our sensors. By systematically changing the source-sensor distance and the pulsation frequency of the source, we clarify how these two factors affect the estimation accuracy. The proposed scheme is also applicable to estimation with multiple sensors. We demonstrate that increasing the number of sensors improves the estimation greatly when the scalar is released from a source away from the wall, where large-scale eddies dominate the scalar dispersion. In contrast, the estimation performance remains poor even with multiple sensors when the scalar source is located near the wall, where the source information is quickly lost due to the strong turbulence activity and the scalar diffusion in the near-wall region.     

High-yield boron nitride nanosheets from 'chemical blowing': towards practical applications in polymer composites

An improved 'chemical blowing' route presuming atmospheric-pressure pre-treatment and moderate heating rate of designated precursors was developed to synthesize ultra-thin boron nitride (BN) nanosheets with high yield and large lateral dimensions. The yield reached as high as 40 wt% with respect to raw materials (ammonia borane). The strong oxygen-related ultraviolet luminescence together with a blue emission of these BN nanosheets was then documented and analyzed. This implies potential applications in solid-state lighting, ultraviolet lasing and full-color luminescence. Mechanical strength of different polymeric composites with a small fraction of BN nanosheet fillers was dramatically increased by tens of per cent, while high transparency of composite materials was still maintained in the visible optical range. The increased yield and reduced cost of BN nanosheets should promote their wide practical applications in various composites.