Steps along the path to dihydrogen activation at [FeFe] hydrogenase structural models: dependence of the core geometry on electrocatalytic proton reduction

Differences in the rate of electrocatalytic proton reduction by Fe2(mu-PPh2)2(CO)6, DP, and the linked phosphido-bridged analogue Fe2(mu,mu-PPh(CH2)3PPh)(CO)6, 3P, suggest that dihydrogen elimination proceeds through a bridging hydride. The reaction path was examined using electrochemical, spectroscopic, and in silico studies where reduction of 3P gives a moderately stable monoanion [Kdisp(3P-) = 13] and a distorted dianion. The monomeric formulation of 3P- is supported by the form of the IR and EPR spectra. EXAFS analysis of solutions of 3P, 3P-, and 3P2- indicates a large increase in the Fe-Fe separation following reduction (from 2.63 to ca. 3.1-3.55 A). DFT calculations of the 3P, 3P-, 3P2- redox series satisfactorily reproduce the IR spectra in the nu(CO) region and the crystallographic (3P) and EXAFS-derived Fe-Fe distances. Digital simulation of the electrocatalytic response for proton reduction indicates a low rate of dihydrogen evolution from the two-electron, two-proton product of 3P (H23P), with more rapid dihydrogen evolution following further reduction of H23P. Because dihydrogen evolution is not observed upon formation of H2DP, dihydrogen evolution at the two-electron-reduced level does not involve protonation of a hydridic Fe-H ligand. The rates of dihydrogen elimination from H2DP, H23P, and H2Fe2(mu,mu-S(CH2)3S)(CO)6 (H23S) are related to the DFT-calculated H-H distances [H23S (1.880 A) < H23P (2.064 A) < H2DP (3.100 A)], and this suggests a common reaction path for the thiolato- and phosphido-bridged diiron carbonyl compounds.     

Ultra-Compact and Efficient Integrated Multichannel Mode Multiplexer in Silicon for Few-Mode Fibers

Space-division multiplexing (SDM) is one of the key enabling technologies to increase the capacity of fiber communication systems. However, implementing SDM-based systems using multimode fiber has been challenging with the need for compact, low-cost, and scalable mode de/multiplexer (DE/MUX). Here a novel integrated mode MUX for few-mode fibers (FMFs) is presented which can launch up to eight spatial and polarization channels. The new design is composed of a 2D multimode grating coupler (MMGC), highly compact spot size converters (SSCs), and adiabatic directional couplers (ADCs). Eight data lanes in FMFs can be selectively launched with integrated optical phase shifters. Experimental results reveal efficient chip-to-fiber coupling with peak efficiencies of −3.8, −5.5, −3.6, and −4.1 dB for LP₀₁, LP_11a, LP_11b, and LP_21b modes, respectively. Thanks to the use of an integrated subwavelength Mikaelian lens for mode-independent field size conversion with loss ≤−0.25 dB, the total footprint of the MMGC and SSCs is only 35×35 µm². The proposed design shows great potential for densely integrated photonic circuits in future SDM applications.     

Palladium acetate complexes bearing chelating N-heterocyclic carbene (NHC) ligands: Synthesis and catalytic oxidative homocoupling of terminal alkynes

The imidazolium salts 1,1′-dibenzyl-3,3′-propylenediimidazolium dichloride and 1,1′-bis(1-naphthalenemethyl)-3,3′-propylenediimidazolium dichloride have been synthesized and transformed into the corresponding bis(NHC) ligands 1,1′-dibenzyl-3,3′-propylenediimidazol-2-ylidene (L₁) and 1,1′-bis(1-naphthalenemethyl)-3,3′-propylenediimidazol-2-ylidene (L₂) that have been employed to stabilize the Pd^II complexes PdCl₂(κ²-C,C-L₁) (2a) and PdCl₂(κ²-C,C-L₂) (2b). Both latter complexes together with their known homologous counterparts PdCl₂(κ²-C,C-L₃) (1a) (L₃ = 1,1′-dibenzyl-3,3′-ethylenediimidazol-2-ylidene) and PdCl₂(κ²-C,C-L₄) (1b) (L₄ = 1,1′-bis(1-naphthalenemethyl)-3,3′-ethylenediimidazol-2-ylidene) have been straightforwardly converted into the corresponding palladium acetate compounds Pd(κ¹-O-OAc)₂(κ²-C,C-L₃) (3a) (OAc = acetate), Pd(κ¹-O-OAc)₂(κ²-C,C-L₄) (3b), Pd(κ¹-O-OAc)₂(κ²-C,C-L₁) (4a), and Pd(κ¹-O-OAc)₂(κ²-C,C-L₂) (4b). In addition, the phosphanyl-NHC-modified palladium acetate complex Pd(κ¹-O-OAc)₂ (κ²-P,C-L₅) (6) (L₅ = 1-((2-diphenylphosphanyl)methylphenyl)-3-methyl-imidazol-2-ylidene) has been synthesized from corresponding palladium iodide complex PdI₂(κ²-P,C-L₅) (5). The reaction of the former complex with p-toluenesulfonic acid (p-TsOH) gave the corresponding bis-tosylate complex Pd(OTs)₂(κ²-P,C-L₅) (7). All new complexes have been characterized by multinuclear NMR spectroscopy and elemental analyses. In addition the solid-state structures of 1b·DMF, 2b·2DMF, 3a, 3b·DMF, 4a, 4b, and 6·CHCl₃·2H₂O have been determined by single crystal X-ray structure analyses. The palladium acetate complexes 3a/b, 4a/b, and 6 have been employed to catalyze the oxidative homocoupling reaction of terminal alkynes in acetonitrile chemoselectively yielding the corresponding 1,4-di-substituted 1,3-diyne in the presence of p-benzoquinone (BQ). The highest catalytic activity in the presence of BQ has been obtained with 6, while within the series of palladium-bis(NHC) complexes, 4b, featured with a n-propylene-bridge and the bulky N-1-naphthalenemethyl substituents, revealed as the most active compound. Hence, this latter precursor has been employed for analogous coupling reaction carried out in the presence of air pressure instead of BQ, yielding lower substrate conversion when compared to reaction performed in the presence of BQ. The important role of the ancillary ligand acetate in the course of the catalytic coupling reaction has been proved by variable-temperature NMR studies carried out with 6 and 7′ under catalytic reaction conditions.     

Structural variations in novel silver(I) complexes with bitopic pyrazole/n-heterocyclic carbene ligands

The synthesis and structural characterization of several new silver complexes of L (L = a bidendate ligand of pyrazole and N-heterocyclic carbene) are described. The result shows that the choice of counterions, N-substitutions of L, and reaction conditions are crucial which lead to a variety of structural motifs, including novel metallomacrocycles [Ag2(mu-L)2]2+ with or without Ag...Ag close contact, a mononuclear [AgL2]+ complex, and a [LAg(NO3)]n coordination polymer. In particular, the nonbonding Ag...Ag distance and the overall geometry of the metallomacrocycles are controllable with different N-substitutions and counterions. All these complexes have been determined by X-ray diffraction. The solid-state aggregates are retained in solution as supported by the electrospray mass spectroscopic studies.     

Analyses of Stemona alkaloids in Stemona tuberosa by liquid chromatography/tandem mass spectrometry

Alkaloid profiles in Stemona tuberosa were found to be highly variable. Six Stemona alkaloids isolated from the plant were subjected to on-line high-performance liquid chromatography/electrospray ionization mass spectrometry (HPLC/ESI-MS) and tandem mass spectrometry (MS/MS) analyses. Their fragmentation patterns and products were useful for their characterization. The LC/MS fingerprints of these alkaloids, though variable among samples, could provide an overall characterization of the authenticity and quality of this species and help to differentiate it from S. japonica and S. sessilifolia, as all three species are recognized as genuine sources of the herb Radix Stemonae in the Pharmacopoeia of the People's Republic of China.     

Some Evolution Hierarchies Derived from Self-dual Yang-Mills Equations

We develop in this paper a new method to construct two explicit Lie algebras E and F. By using a loop algebra \bar{E} of the Lie algebra E and the reduced self-dual Yang-Mills equations, we obtain an expanding integrable model of the Giachetti-Johnson (GJ) hierarchy whose Hamiltonian structure can
also be derived by using the trace identity. This provides a much simplier construction method in comparing with the tedious variational identity approach. Furthermore, the nonlinear integrable coupling of the GJ hierarchy is readily obtained by introducing the Lie algebra g_N. As an application, we apply the loop algebra \tilde{E} of the Lie algebra E to obtain a kind of expanding integrable model of the Kaup-Newell (KN) hierarchy which, consisting of two arbitrary parametersα andβ, can be reduced to two nonlinear evolution equations. In addition, we use a loop algebra \tilde{F} of the Lie algebra F to obtain an
expanding integrable model of the BT hierarchy whose Hamiltonian structure is the same as using the trace identity. Finally, we deduce five integrable systems in R³ based on the self-dual Yang-Mills equations, which include Poisson structures, irregular lines, and the reduced equations.     

基于影像处理的干涉测量相位重构研究

随着计算机技术和光电成像元件的发展,影像信息处理技术已经在无损检测、医学检测以及干涉测量等领域得到广泛应用。本文主要研究了影像信息在干涉测量领域的波前相位提取方法。干涉条纹图是干涉测量领域中影像信息的载体,在干涉条纹处理方面,针对空域卡雷算法的特点,提出一种基于影像处理的单幅闭合干涉条纹图相位重构新算法。在空域卡雷算法处理方法的基础上,利用迭代修正算法对干涉图相位进行二次逼近,实现了对单幅干涉条纹图的高精度相位重构。Matlab仿真结果表明,迭代修正后的相位残差降低了25.8%,表明该算法在空域卡雷算法的基础上能够有效提高相位重构精度,实现干涉测量领域中影像信息的高精度处理。     

A self consistent normalized calibration protocol for three dimensional magnetic resonance gel dosimetry

In a clinical setting, mixed and inconsistent results have been reported using Magnetic Resonance Relaxation imaging of irradiated aqueous polymeric gels as a three-dimensional dosimeter, for dose verification of conformal radiation therapy. The problems are attributed to the difficulty of identifying an accurate dose calibration protocol for each delivered gel at the radiation site in a clinical setting. While careful calibration is done at the gel manufacturing site in a controlled laboratory setting, there is no guarantee that the dose sensitivity of the gels remains invariant upon delivery, irradiation, magnetic resonance imaging and storage at the clinical site. In this study, we have compared three different dose calibration protocols on aqueous polymeric gels for a variety of irradiation scenarios done in a clinical setting. After acquiring the three-dimensional proton relaxation maps of the irradiated gels, the dose distributions were generated using the off-site manufacturer provided calibration curve (Cal-1), the on-site external tube gel calibration (Cal-2) and the new on-site internal normalized gel calibration (Cal-3) protocols. These experimental dose distributions were compared with the theoretical dose distributions generated by treatment-planning systems. We observed that the experimental dose distributions generated from the Cal-1 and Cal-2 protocols were off by 10% to 40% and up to 200% above the predicted maximum dose, respectively. On the other hand, the experimental dose distributions generated from the Cal-3 protocol matched reasonably well with the theoretical dose distributions to within 10% difference. Our result suggests that an independent on-site normalized internal calibration must be performed for each batch of gel dosimeters at the time of MR relaxation imaging in order to account for the variations in dose sensitivity caused by various uncontrollable conditions in a clinical setting such as oxygen contamination, temperature changes and shelf life of the delivered gel between manufacturing and MR acquisitions.     

Structure selective complexation of cyclodextrins with five polyphenols investigated by capillary electrokinetic chromatography

The complexation of five polyphenols, namely trans‐resveratrol, astilbin, taxifolin, ferulic acid, and syringic acid (guest molecules) with α‐, β‐, and γ‐cyclodextrin (host molecules), was investigated by capillary electrokinetic chromatography. The binding constants were calculated based on the effective electrophoretic mobility change of guests with the addition of cyclodextrins into the background electrolyte. Because of cavity size, cyclodextrins showed structure‐selective complexation property to different guest. The stability of the trans‐resveratrol complexes was in the order of β‐ > α‐ > γ‐cyclodextrin. The cavity size of α‐cyclodextrin was too small for astilbin and taxifolin molecules, and thus they could not form complexes. The molecular size of syringic acid was too big for all cyclodextrins cavity, and no cyclodextrin could form complexes with it. Temperature studies showed that the binding constants decreased with the rise of temperature. Enthalpy and entropy values were calculated and the negative values of these parameters indicated that the complexation process was enthalpy‐controlled. Van der Waals force and release of high‐enthalpy water molecules from the cyclodextrins cavity played important roles in the process.