Mass Spectrometric Identification of [4Fe–4S](NO)x Intermediates of Nitric Oxide Sensing by Regulatory Iron–Sulfur Cluster Proteins

Nitric oxide (NO) can function as both a cytotoxin and a signalling molecule. In both cases, reaction with iron–sulfur (Fe–S) cluster proteins plays an important role because Fe–S clusters are reactive towards NO and so are a primary site of general NO-induced damage (toxicity). This sensitivity to nitrosylation is harnessed in the growing group of regulatory proteins that function in sensing of NO via an Fe–S cluster. Although information about the products of cluster nitrosylation is now emerging, detection and identification of intermediates remains a major challenge, due to their transient nature and the difficulty in distinguishing spectroscopically similar iron-NO species. Here we report studies of the NO-sensing Fe–S cluster regulators NsrR and WhiD using non-denaturing mass spectrometry, in which non-covalent interactions between the protein and Fe/S/NO species are preserved. The data provide remarkable insight into the nitrosylation reactions, permitting identification, for the first time, of protein-bound mono-, di- and tetranitrosyl [4Fe–4S] cluster complexes ([4Fe–4S](NO), [4Fe–4S])(NO)₂ and [4Fe–4S](NO)₄) as intermediates along pathways to formation of product Roussin's red ester (RRE) and Roussin's black salt (RBS)-like species. The data allow the nitrosylation mechanisms of NsrR and WhiD to be elucidated and clearly distinguished.     

Synthesis and characterisation of low density porous polymers by reversible addition-fragmentation chain transfer (RAFT)

PolyHIPE foams with densities of 0.05–0.1 g cm^?3 have been prepared by the polymerisation of the continuous phase of high internal phase emulsions (HIPEs). The internal aqueous phase in HIPE occupies more than 74 % of the total volume, which leads to highly porous and open-cell morphologies. In this paper a method of preparing polyHIPE foams by using reversible addition-fragmentation chain transfer (RAFT) polymerisation has been investigated. Polystyrene-co-polymethyl methacrylate (PS-co-PMMA) has been studied and by using a variety of characterisation methods, it was possible to compare the polyHIPEs prepared by the conventional free radical polymerisation (FRP) to those by RAFT polymerisation. Scanning electron microscopy images have confirmed the presence of a cellular polyHIPE structure. PS-co-PMMA polyHIPEs made by RAFT have significantly narrower molecular weight distribution with values for the polydispersity index (PDI) for PS-co-PMMA between 1.46 and 2.08 compared to 4.68 observed by FRP. The effects of different concentrations of the RAFT agent on structure, glass transition temperature (T _g) and PDI of PS-co-PMMA polyHIPE foams are presented.     

On time regularity and related conditions for power-bounded operators

Let T be a bounded linear operator in a complex Banach space.Our main result gives various characterizations of the condition:T is power-bounded and an estimate ||(I – T)Tⁿ || cn^–1/2 holds for all positive integers n. In particular, this conditionholds if and only if T = β S + (1 – β)I, forsome β (0, 1) and some power-bounded operator S; or ifand only if T is power-bounded and the discrete semigroup (Tⁿ)is dominated by the continuous semigroup (e^{– t(I –T)})_{t 0} in a natural sense. As a consequence of our main results,for 1/2 < 1 we characterize the condition that T is power-boundedand ||(I – T)Tⁿ || c n^– for all n, in terms ofestimates on the semigroup e^{–t(I – T)}.     

Divisors in residue classes, constructively

Let be integers satisfying , , , and let . Lenstra showed that the number of integer divisors of equivalent to is upper bounded by . We re-examine this problem, showing how to explicitly construct all such divisors, and incidentally improve this bound to .

     

Synthesis, characterization, and DFT/TD-DFT calculations of highly phosphorescent blue light-emitting anionic iridium complexes

Highly phosphorescent blue-light-emitting anionic iridium complexes (C4H9)4N[Ir(2-phenylpyridine)2(CN)2] (1), (C4H9)4N[Ir(2-phenyl-4-dimethylaminopyridine)2(CN)2] (2), (C4H9)4N[Ir(2-(2,4-difluorophenyl)-pyridine)2(CN)2] (3), (C4H9)4N[Ir(2-(2,4-difluorophenyl)-4-dimethylaminopyridine)2(CN)2] (4), and (C4H9)4N[Ir(2-(3,5-difluorophenyl)-4-dimethylaminopyridine)2(CN)2] (5) were synthesized and characterized using NMR, UV-vis absorption, and emission spectroscopy and electrochemical methods. In these complexes color and quantum yield tuning aspects are demonstrated by modulating the ligands with substituting donor and acceptor groups on both the pyridine and phenyl moieties of 2-phenylpyridine. Complexes 1-5 display intense photoluminescence maxima in the blue region of the visible spectrum and exhibit very high phosphorescence quantum yields, in the range of 50-80%, with excited-state lifetimes of 1-4 micros in acetonitrile solution at 298 K. DFT and time dependent-DFT calculations were performed on the ground and excited states of the investigated complexes to provide insight into the structural, electronic, and optical properties of these systems.     

Efficient Blue‐Colored Solid‐State Dye‐Sensitized Solar Cells: Enhanced Charge Collection by Using an in Situ Photoelectrochemically Generated Conducting Polymer Hole Conductor

A high power conversion efficiency (PCE) of 5.5 % was achieved by efficiently incorporating a diketopyrrolopyrrole‐based dye with a conducting polymer poly(3,4‐ethylenediothiophene) (PEDOT) hole‐transporting material (HTM) that was formed in situ, compared with a PCE of 2.9 % for small molecular spiro‐OMeTAD‐based solid‐state dye solar cells (sDSCs). The high PCE for PEDOT‐based sDSCs is mainly attributed to the significantly enhanced charge‐collection efficiency, as a result of the three‐order‐of‐magnitude higher hole conductivity (0.53 S cm^?1) compared with that of the widely used low molecular weight HTM spiro‐OMeTAD (3.5×10^?4 S cm^?1).     

Nitrosylation of Nitric‐Oxide‐Sensing Regulatory Proteins Containing [4Fe‐4S] Clusters Gives Rise to Multiple Iron–Nitrosyl Complexes

The reaction of protein‐bound iron–sulfur (Fe‐S) clusters with nitric oxide (NO) plays key roles in NO‐mediated toxicity and signaling. Elucidation of the mechanism of the reaction of NO with DNA regulatory proteins that contain Fe‐S clusters has been hampered by a lack of information about the nature of the iron‐nitrosyl products formed. Herein, we report nuclear resonance vibrational spectroscopy (NRVS) and density functional theory (DFT) calculations that identify NO reaction products in WhiD and NsrR, regulatory proteins that use a [4Fe‐4S] cluster to sense NO. This work reveals that nitrosylation yields multiple products structurally related to Roussin's Red Ester (RRE, [Fe₂(NO)₄(Cys)₂]) and Roussin's Black Salt (RBS, [Fe₄(NO)₇S₃]. In the latter case, the absence of ³²S/³⁴S shifts in the Fe?S region of the NRVS spectra suggest that a new species, Roussin's Black Ester (RBE), may be formed, in which one or more of the sulfide ligands is replaced by Cys thiolates.     

QSAR modeling using automatically updating correction libraries: application to a human plasma protein binding model

It is assumed that compounds occupying the same region of model space will be subject to similar errors in prediction, and hence, where these errors are known, they can be applied to predictions. Thus, any available measured data can be used to refine predictions of query compounds. This study describes the application of a correction library to a human plasma protein binding model. Compounds that have been measured since the model was built are entered into the library to improve predictions of current compounds. Time-series simulations were conducted to measure the time dependence of the correction library. This study demonstrates significant improvements in predictions where a library is applied, compared with both a static model and an updating model that includes recently measured data.     

Time Regularity for Random Walks on Locally Compact Groups

Let G be a compactly generated, locally compact group, and let T be the operator of convolution with a probability measure μ on G. Our main results give sufficient conditions on μ for the operator T to be analytic in L ^p (G), 1 < p < ∞, where analyticity means that one has an estimate of form for all n = 1, 2, ... in L ^p operator norm. Counterexamples show that analyticity may not hold if some of the conditions are not satisfied.