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201.
Matthias Dorn Jens Kalmbach Pit Boden Ayla Kruse Chahinez Dab Christian Reber Gereon Niedner-Schatteburg Stefan Lochbrunner Markus Gerhards Michael Seitz Katja Heinze 《Chemical science》2021,12(32):10780
In spite of intense, recent research efforts, luminescent transition metal complexes with Earth-abundant metals are still very rare owing to the small ligand field splitting of 3d transition metal complexes and the resulting non-emissive low-energy metal-centered states. Low-energy excited states decay efficiently non-radiatively, so that near-infrared emissive transition metal complexes with 3d transition metals are even more challenging. We report that the heteroleptic pseudo-octahedral d2-vanadium(iii) complex VCl3(ddpd) (ddpd = N,N′-dimethyl-N,N′-dipyridine-2-yl-pyridine-2,6-diamine) shows near-infrared singlet → triplet spin–flip phosphorescence maxima at 1102, 1219 and 1256 nm with a lifetime of 0.5 μs at room temperature. Band splitting, ligand deuteration, excitation energy and temperature effects on the excited state dynamics will be discussed on slow and fast timescales using Raman, static and time-resolved photoluminescence, step-scan FTIR and fs-UV pump-vis probe spectroscopy as well as photolysis experiments in combination with static quantum chemical calculations. These results inform future design strategies for molecular materials of Earth-abundant metal ions exhibiting spin–flip luminescence and photoinduced metal–ligand bond homolysis.Vanadium is an abundant and cheap metal but near-infrared luminescent vanadium complexes are extremely rare with largely unexplored photophysics and photochemistry. We delineate the photodynamics of VCl3(ddpd) to infer novel design strategies. 相似文献
202.
The equilibrium adsorption of two albumin proteins on a commercial ion exchanger has been studied using a colloidal model. The model accounts for electrostatic and van der Waals forces between proteins and the ion exchanger surface, the energy of interaction between adsorbed proteins, and the contribution of entropy from water-release accompanying protein adsorption. Protein-surface interactions were calculated using methods previously reported in the literature. Lateral interactions between adsorbed proteins were experimentally measured with microcalorimetry. Water-release was estimated by applying the preferential interaction approach to chromatographic retention data. The adsorption of ovalbumin and bovine serum albumin on an anion exchanger at solution pH>pI of protein was measured. The experimental isotherms have been modeled from the linear region to saturation, and the influence of three modulating alkali chlorides on capacity has been evaluated. The heat of adsorption is endothermic for all cases studied, despite the fact that the net charge on the protein is opposite that of the adsorbing surface. Strong repulsive forces between adsorbed proteins underlie the endothermic heat of adsorption, and these forces intensify with protein loading. It was found that the driving force for adsorption is the entropy increase due to the release of water from the protein and adsorbent surfaces. It is shown that the colloidal model predicts protein adsorption capacity in both the linear and non-linear isotherm regions, and can account for the effects of modulating salt. 相似文献
203.
A pressure‐driven flow of elongated bullet‐shaped bubbles in a narrow channel is known as Taylor flow or bubble‐train flow. This process is of relevance in various applications of chemical engineering. In this paper, we describe a typical simplified experimental setting, with surface tension, density and viscosity as prescribed input parameters. We compare a sharp‐interface model based on a moving grid aligned with the bubble boundary (ALE coordinates) and a diffuse‐interface model where the bubble shape is implicitly given by a phase‐field function. Four independent implementations based on the two modeling approaches are introduced and described briefly. Besides the simulation of the bubble shapes, we compare some resulting quantities such as pressure difference and film widths within the implementations and to existing analytical and experimental results. The simulations were conducted in 2D and 3D (rotationally symmetric). Good accordance of the results indicate the applicability and the usability of all approaches. Differences between the models and their implementations are visible but in no contradiction to theoretical results. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
204.
205.
Reaction of N,N-diethyl cinnamyl carbamate with TBDMSC1 yields the mono-silylated carbamate which, on treatment with butyllithium, reacts with various electrophiles to give the corresponding disubstituted carbamates. 相似文献
206.
Neville Davies Doreen Connor Nancy Spencer 《Journal of Applied Mathematics and Decision Sciences》2003,7(2):75-83
In this paper we provide an overview of the international CensusAtSchool project, designed, written and implemented first in the UK from October 2000 - April 2001 for pupils aged 7 -16 in primary and secondary schools. It has been adapted for similar aged school children in South Africa and Australia and was implemented in those countries in July and October 2001, respectively. We present our motivation, aims and objectives for carrying out such a project and show some results of analysis from the returns we have received from all three countries. Key outputs from the project include: worksheets that are suitable for enhancing data handling skills of pupils; a training course that wraps information and communications technology with data handling skills that is suitable to enhance the professional development of teachers; a raised awareness amongst pupils and teachers of the need to properly collect, present and analyze primary data; a contribution to improving the statistical numeracy and thinking skills of both teachers and pupils. 相似文献
207.
Ramaunjan’s tau function, denoted δ (n) is defined by the identity (1) below, wherex represents a complex variable such that |x| < 1. Using properties of t-core partitions, we obtain an alternate proof of the congruence (2) below. 相似文献
208.
209.
Design and optimization for variable rate selective excitation using an analytic RF scaling function
At higher B(0) fields, specific absorption rate (SAR) deposition increases. Due to maximum SAR limitation, slice coverage decreases and/or scan time increases. Conventional selective RF pulses are played out in conjunction with a time independent field gradient. Variable rate selective excitation (VERSE) is a technique that modifies the original RF and gradient waveforms such that slice profile is unchanged. The drawback is that the slice profile for off-resonance spins is distorted. A new VERSE algorithm based on modeling the scaled waveforms as a Fermi function is introduced. It ensures that system related constraints of maximum gradient amplitude and slew rate are not exceeded. The algorithm can be used to preserve the original RF pulse duration while minimizing SAR and peak b1 or to minimize the RF pulse duration. The design is general and can be applied to any symmetrical or asymmetrical RF waveform. The algorithm is demonstrated by using it to (a) minimize the SAR of a linear phase RF pulse, (b) minimize SAR of a hyperbolic secant RF pulse, and (c) minimize the duration of a linear phase RF pulse. Images with a T1-FLAIR (T1 FLuid Attenuated Inversion Recovery) sequence using a conventional and VERSE adiabatic inversion RF pulse are presented. Comparison of images and scan parameters for different anatomies and coils shows increased scan coverage and decreased SAR with the VERSE inversion RF pulse, while image quality is preserved. 相似文献
210.
Ahmad Seyfaee Roberto Moreno-Atanasio Frances Neville 《Colloid and polymer science》2014,292(10):2673-2685
High-resolution dynamic light scattering (DLS), scanning electron microscopy (SEM), time-lapse photography, and attenuated total reflectance Fourier transform infrared spectroscopy were used to analyze the growth kinetics of polyethyleneimine (PEI)-silica particles fabricated from the condensation of hydrolyzed trimethoxymethylsilane (TMOMS) and PEI/phosphate buffer (PEI/PB). Depending on the concentration of hydrolyzed TMOMS and PEI/PB, three stages were identified. We observed the existence of a nucleation time that has never been reported in the literature when TMOMS has been used. During this nucleation time, particles of less than 25 nm were detected using in situ DLS measurements taken every 15 s (high resolution), a DLS time-scale resolution not previously reported. In addition, the length of the nucleation time depended mainly on the PEI/PB concentration, but also TMOMS concentration. The growth stage was evident from the rapid increase of particle size with time. Due to the high resolution of the DLS measurements, a peak could be observed in the particle diameter during particle growth, which corresponds to a secondary population of particles required for the larger particles to further increase in size. Finally, during the equilibrium region, particles reached their maximum diameter that was independent of the concentration of PEI/PB and only changed with concentration of hydrolyzed TMOMS. 相似文献