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1.
The mono- and di-chloroform solvates of [Au2(μ-1,2-bis(diphenylarsino)ethane)2](AsF6)2 undergo single-crystal-to-single-crystal transformations that result in gain (over 12 hours) or slow loss (over five years) of only one chloroform molecule. The change in solvation results in changes in the structure and luminescence of the digold cation. The cation consists of a pair of slightly bent As-Au-As units that are connected through the two bridging dpae ligands and by aurophilic interactions with Au⋅⋅⋅Au contacts of 3.05152(15) Å in the disolvate or 2.9570(5) Å in the monosolvate.  相似文献   
2.
Abstract

The electronic structures of S and Mo as well as the local coordination of Mo are investigated as a function of metal promotion Chevrel-phase (CP) sulfides. We observe the effect of metal promoter-induced electron donation into the stoichiometric range MxMo6S8 (M?=?Fe, Ni, Cu; x?=?0–2) through analysis of X-ray absorption near-edge structure regions. We further observe the effect of this promotion on the bonding environment of Mo6 metal centers through extended X-ray absorption fine structure analysis. We monitor expansion and contraction of Mo6 octahedra with and without metal promotion, as has been predicted by Hückel molecular orbital theory. We further observe a marked tunability in the electronic structure of sulfur upon charge transfer between promoting species and Mo6S8 units. Average Mo6 octahedron Mo–Mo bond contraction from 2.76 Å to as short as 2.69 Å was observed upon incorporation of metal promoters, while intercluster separation displays a pronounced increase for promoter-host lattices compared to un-promoted Mo6S8. To corroborate spectroscopically observed phenomena, we performed computational analyses of spin-polarized densities of state for the CP materials investigated herein, where a detectable increase in sulfur-based frontier orbital population is observed in accordance with experimentally validated orbital filling.  相似文献   
3.
NMR offers many possibilities in chemical analysis, structural investigations, and medical diagnostics. Although it is broadly used, one of NMR spectroscopies main drawbacks is low sensitivity. Hyperpolarization techniques enhance NMR signals by more than four orders of magnitude allowing the design of new contrast agents. Parahydrogen induced polarization that utilizes the para-hydrogen's singlet state to create enhanced signals is of particular interest since it allows to produce molecular imaging agents within seconds. Herein, we present a strategy for signal enhancement of the carbonyl 13C in amino acids by using parahydrogen, as demonstrated for glycine and alanine. Importantly, the hyperpolarization step is carried out in water and chemically unmodified canonical amino acids are obtained. Our approach thus offers a high degree of biocompatibility, which is crucial for further application. The rapid sample hyperpolarization (within seconds) may enable the continuous production of biologically useful probes, such as metabolic contrast agents or probes for structural biology.  相似文献   
4.
本文主要描述小分子在真空紫外波段(VUV,6-20 eV)光解离动力学的最新实验和理论研究进展.得益于基于商业化激光器的真空紫外光源技术,以及离子速度成像、高分辨氢原子-里德堡态标记-飞行时间测量和VUV-VUV泵浦-探测等方法的发展,研究人员现在可以对很多小分子在真空紫外波段的光解离动力学进行量子态到量子态层面的测量和研究,本文重点综述H_2(D_2,HD),CO,N_2,NO,O_2,H_2O(D_2O,HOD),CO_2,N_2O以及一些多原子分子在真空紫外波段光解离动力学的最新研究进展.这些小分子在真空紫外波段的光解离在天体化学以及大气化学中有着非常重要的应用.分子吸收一个VUV光子以后,通常会被直接激发到比较高的电子激发态,解离过程会涉及到多个电子态势能面之间的复杂非绝热相互作用.在实验上对解离截面等参数进行从量子态到量子态层面的精细测量对于深入了解这些复杂的势能面之间的相互作用有非常重要的意义.最近建成的大连相干光源是目前世界上唯一一台在真空紫外波段工作的自由电子激光,具有脉冲能量高、扫描范围宽(50~150 nm)等优越的性能,它的建成必将会大大促进小分子真空紫外光解离研究的发展.  相似文献   
5.
A urease extract prepared by decanting liquid from a suspension of finely ground Citrullus lanatus (watermelon) seeds was characterized and applied to dilute urine samples to demonstrate a low-cost field method to estimate total Kjeldahl nitrogen (TKN) concentrations in human urine. The extract exhibited a Michaelis-Menten constant, Km, of 3.00 mM urea and a specific activity of up to 12.2 U/mg protein at an optimum pH of 8.1. A statistical F-test on 54 samples demonstrated that TKN can be estimated as the total ammonium-nitrogen recovered upon addition of urease in dilute fresh and stale urine samples. The total ammonium-nitrogen in urine samples determined after treatment with watermelon seed urease was consistent with that determined using traditional acid digestion techniques. The extract retained 85% of its initial capacity after three months of refrigeration. The effectiveness of this method to assay nitrogen in unbuffered urine samples will be useful in nitrogen analyses in nutrient recovery and urine or slurry storage contexts. Accordingly, this study is useful in understanding the kinetics of a plant-derived urease acting in dilute urine.  相似文献   
6.
This paper proposes a generalized dynamics model and a leader-follower control architecture for skid-steered tracked vehicles towing polar sleds. The model couples existing formulations in the literature for the powertrain components with the vehicle-terrain interaction to capture the salient features of terrain trafficability and predict the vehicles response. This coupling is essential for making realistic predictions of the vehicles traversing capabilities due to the power-load relationship at the engine output. The objective of the model is to capture adequate fidelity of the powertrain and off-road vehicle dynamics while minimizing the computational cost for model based design of leader-follower control algorithms. The leader-follower control architecture presented proposes maintaining a flexible formation by using a look-ahead technique along with a way point following strategy. Results simulate one leader-follower tractor pair where the leader is forced to take an abrupt turn and experiences large oscillations of its drawbar arm indicating potential payload instability. However, the follower tractor maintains the flexible formation but keeps its payload stable. This highlights the robustness of the proposed approach where the follower vehicle can reject errors in human leader driving.  相似文献   
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Data for optimization problems often comes from (deterministic) forecasts, but it is naïve to consider a forecast as the only future possibility. A more sophisticated approach uses data to generate alternative future scenarios, each with an attached probability. The basic idea is to estimate the distribution of forecast errors and use that to construct the scenarios. Although sampling from the distribution of errors comes immediately to mind, we propose instead to approximate rather than sample. Benchmark studies show that the method we propose works well.  相似文献   
10.
A series of new 1,3‐disiloxanediols has been synthesized, including naphthyl‐substituted and unsymmetrical siloxanes, and demonstrated as a new class of anion‐binding catalysts. In the absence of anions, diffusion‐ordered spectroscopy (DOSY) displays self‐association of 1,3‐disiloxanediols through hydrogen‐bonding interactions. Binding constants determined for 1,3‐disiloxanediol catalysts indicate strong hydrogen‐bonding and anion‐binding abilities with unsymmetrical siloxanes displaying different hydrogen‐bonding abilities for each silanol group.  相似文献   
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