Herein, we describe the structural investigation of one possible uranyl binding site inside a nonstructured protein. This approach couples spectroscopy, thermodynamics, and theoretical calculations (DFT) and studies the interaction of uranyl ions with a phosphopeptide, thus mimicking a possible osteopontin (OPN) hydroxyapatite growth‐inhibition site. Although thermodynamical aspects were investigated by using time‐resolved laser fluorescence spectroscopy (TRLFS) and isothermal titration calorimetry (ITC), structural characterization was performed by extended X‐ray absorption fine structure (EXAFS) at the U LIII‐edge combined with attenuated total reflection Fourier transform infrared (ATR‐FTIR) spectroscopy. From the vibrational and fluorescence spectra, several structural models of a UO22+/peptide complex were developed and subsequently refined by using theoretical calculations to fit the experimental EXAFS obtained. The structural effect of the pH value was also considered under acidic to moderately acidic conditions (pH 1.5–5.5). Most importantly, the uranyl/peptide coordination environment was similar to that of the native protein. 相似文献
The combination of a non‐functionalized constrained bicyclo[2.2.2]octane motif along with urea linkages allowed the formation of a highly rigid 2.512/14 helical system both in solution and the solid state. In this work, we aimed at developing stable and functionalized systems as promising materials for biological applications in investigating the impact of this constrained motif and its configuration on homo and heterochiral mixed‐oligourea helix formation. Di‐, tetra‐, hexa‐, and octa‐oligoureas alternating the highly constrained bicyclic motif of (R) or (S) configuration with acyclic (S)‐β3‐amino acid derivatives were constructed. Circular dichroism (CD), NMR experiments, and the X‐ray crystal structure of the octamer unequivocally proved that the alternating heterochiral R/S sequences form a stable left‐handed 2.5‐helix in contrast to the mixed (S/S)‐oligoureas, which did not adopt any defined secondary structure. We observed that the (?)‐synclinal conformation around the Cα? Cβ bond of the acyclic residues, although sterically less favorable than the (+)‐synclinal conformation, was imposed by the (R)‐bicyclic amino carbamoyl (BAC) residue. This highlighted the strong ability of the BAC residue to drive helical folding in heterochiral compounds. The role of the stereochemistry of the BAC unit was assessed and a model was proposed to explain the misfolding of the S/S sequences. 相似文献
The insertion of an olefin into a preformed metal–carbon bond is a common mechanism for transition‐metal‐catalyzed olefin polymerization. However, in one important industrial catalyst, the Phillips catalyst, a metal–carbon bond is not present in the precatalyst. The Phillips catalyst, CrO3 dispersed on silica, polymerizes ethylene without an activator. Despite 60 years of intensive research, the active sites and the way the first Cr C bond is formed remain unknown. We synthesized well‐defined dinuclear CrII and CrIII sites on silica. Whereas the CrII material was a poor polymerization catalyst, the CrIII material was active. Poisoning studies showed that about 65 % of the CrIII sites were active, a far higher proportion than typically observed for the Phillips catalyst. Examination of the spent catalyst and isotope labeling experiments showed the formation of a Si–(μ‐OH)–CrIII species, consistent with an initiation mechanism involving the heterolytic activation of ethylene at CrIII O bonds. 相似文献
Complexes formed between poly(acrylates) and polyclonal immunoglobulin G (IgG) in its native conformation and after heat stress were characterized using asymmetric flow field-flow fractionation (AF4) coupled with on-line UV-Vis spectroscopy and multi-angle light-scattering detection (MALS). Mixtures of IgG and poly(acrylates) of increasing structural complexity, sodium poly(acrylate) (PAA), a sodium poly(acrylate) bearing at random 3 mol % n-octadecyl groups, and a random copolymer of sodium acrylate (35 mol %), N-n-octylacrylamide (25 mol %) and N-isopropylacrylamide (40 mol %), were fractionated in a sodium phosphate buffer (0.02 M, pH 6.8) in the presence, or not, of 0.1 M NaCl. The AF4 protocol developed allowed the fractionation of solutions containing free poly(acrylates), native IgG monomer and dimer, poly(acrylates)/IgG complexes made up of one IgG molecule and a few polymer chains, and/or larger poly(acrylates)/IgG aggregates. The molar mass and recovery of the soluble analytes were obtained for mixed solutions of poly(acrylates) and native IgG and for the same solutions incubated at 65 °C for 10 min. From the combined AF4 results, we concluded that in solutions of low ionic strength, the presence of PAA increased the recovery ratio of IgG after thermal stress because of the formation of electrostatically-driven PAA/IgG complexes, but PAA had no protective effect in the presence of 0.1 M NaCl. Poly(acrylates) bearing hydrophobic groups significantly increased IgG recovery after stress, independently of NaCl concentration, because of the synergistic effect of hydrophobic and electrostatic interactions. The AF4 results corroborate conclusions drawn from a previous study combining four analytical techniques. This study demonstrates that AF4 is an efficient tool for the analysis of protein formulations subjected to stress, an important achievement given the anticipated important role of proteins in near-future human therapies. ?相似文献
We report the extraordinary performance of carbon‐coated sodium super ion conductor (NASICON)‐type LiTi2(PO4)3 as an ideal host matrix for reversible insertion of both Li and Na ions. The NASICON‐type compound was prepared by means of a Pechini‐type polymerizable complex method and was subsequently carbon coated. Several characterization techniques such as XRD, thermogravimetric analysis (TGA), field‐emission (FE) SEM, TEM, and Raman analysis were used to study the physicochemical properties. Both guest species underwent a two‐phase insertion mechanism during the charge/discharge process that was clearly evidenced from galvanostatic and cyclic voltammetric studies. Unlike that of Li (≈1.5 moles of Li), Na insertion exhibits better reversibility (≈1.59 moles of Na) while experiencing a slightly higher capacity fade (≈8 % higher than Li) and polarization (780 mV) than Li. However, excellent rate capability profiles were noted for Na insertion relative to its counterpart Li. Overall, the Na insertion properties were found to be superior relative to Li insertion, which makes carbon‐coated NASICON‐type LiTi2(PO4)3 hosts attractive for the development of next‐generation batteries. 相似文献
The prospects for using fiber optical parametric amplifiers (OPAs) in optical communication systems are reviewed. Phase‐insensitive amplifiers (PIAs) and phase‐sensitive amplifiers (PSAs) are considered. Low‐penalty amplification at/or near 1 Tb/s has been achieved, for both wavelength‐ and time‐division multiplexed formats. High‐quality mid‐span spectral inversion has been demonstrated at 0.64 Tb/s, avoiding electronic dispersion compensation. All‐optical amplitude regeneration of amplitude‐modulated signals has been performed, while PSAs have been used to demonstrate phase regeneration of phase‐modulated signals. A PSA with 1.1‐dB noise figure has been demonstrated, and preliminary wavelength‐division multiplexing experiments have been performed with PSAs. 512 Gb/s have been transmitted over 6,000 km by periodic phase conjugation. Simulations indicate that PIAs could reach data rate x reach products in excess of 14,000 Tb/s × km in realistic wavelength‐division multiplexed long‐haul networks. Technical challenges remaining to be addressed in order for fiber OPAs to become useful for long‐haul communication networks are discussed.
The toxicity of phosgene (COCl2) combined with its extensive use as a reactant and building block in the chemical industry make its fast and accurate detection a prerequisite. We have developed a carboxylic derivative of 5,6-pinenepyridine which is able to act as colorimetric and fluorimetric sensor for phosgene in air and solution. For the first time, the formation of a pyrido-[2,1-a]isoindolone was used for this purpose. In solution, the sensing reaction is extremely fast (under 5 s), selective and highly sensitive, with a limit of detection (LOD) of 9.7 nM/0.8 ppb. When fixed on a solid support, the sensor is able to detect the presence of gaseous phosgene down to concentrations of 0.1 ppm, one of the lowest values reported to date. 相似文献
Cardamonin is a polyphenolic natural product that has been shown to possess cytotoxic activity against a variety of cancer cell lines. We previously reported the semi-synthesis of a novel Cu (II)–cardamonin complex (19) that demonstrated potent antitumour activity. In this study, we further investigated the bioactivity of 19 against MDA-MB-468 and PANC-1 cancer cells in an attempt to discover an effective treatment for triple-negative breast cancer (TNBC) and pancreatic cancer, respectively. Results revealed that 19 abolished the formation of MDA-MB-468 and PANC-1 colonies, exerted growth-inhibitory activity, and inhibited cancer cell migration. Further mechanistic studies showed that 19 induced DNA damage resulting in gap 2 (G2)/mitosis (M) phase arrest and microtubule network disruption. Moreover, 19 generated reactive oxygen species (ROS) that may contribute to induction of apoptosis, corroborated by activation of caspase-3/7, PARP cleavage, and downregulation of Mcl-1. Complex 19 also decreased the expression levels of p-Akt and p-4EBP1, which indicates that the compound exerts its activity, at least in part, via inhibition of Akt signalling. Furthermore, 19 decreased the expression of c-Myc in PANC-1 cells only, which suggests that it may exert its bioactivity via multiple mechanisms of action. These results demonstrate the potential of 19 as a therapeutic agent for TNBC and pancreatic cancer. 相似文献
Like their owners, dogs and cats are more and more affected by overweight and obesity-related problems and interest in functional pet foods is growing sharply. Through numerous studies, fish protein hydrolysates have proved their worth to prevent and manage obesity-related comorbidities like diabetes. In this work, a human in vitro static simulated gastrointestinal digestion model was adapted to the dog which allowed us to demonstrate the promising effects of a tilapia byproduct hydrolysate on the regulation of food intake and glucose metabolism. Promising effects on intestinal hormones secretion and dipeptidyl peptidase IV (DPP-IV) inhibitory activity were evidenced. We identify new bioactive peptides able to stimulate cholecystokinin (CCK) and glucagon-like peptide 1 (GLP-1) secretions, and to inhibit the DPP-IV activity after a transport study through a Caco-2 cell monolayer. 相似文献