Geldart B 类颗粒气固流化床内的压力波动特性(英文)

采用多通道压力采集系统测量了Geldart B类颗粒（树脂）矩形流化床(2.000m×0.300m×0.025m)内的压力波动,探索了流化床内的压力波动特征;同时采用标准方差、自相关和互相关函数分析了表观气速和静床高度对压力波动、压力波速度和压力波主频的影响。结果表明,气泡行为（如：气泡的形成、发展、聚并和破碎）是影响流化床内压力波动的主要因素;密相和稀相界面处的压力波动幅值主要由气泡崩塌决定;压力波在流化床内进行传播,并且具有明显的周期性特征;此外,压力波动、压力波速度和压力波主频均与表观气速和静床高度密切相关。     

The serum protein binding of pharmacologically active gallium(III) compounds assessed by hyphenated CE‐MS techniques

Transition metal‐based drugs exhibit high affinity to the soft donors of human serum proteins, especially of the high‐abundance protein HSA and of transferrin (Tf), whereas Ga(III) salts are known to bind to Tf and other iron‐containing metalloproteins, thereby interfering with the iron metabolism. Herein, the utilization of CE‐MS methods for studying the binding behavior of a therapeutic gallium nitrate formulation and the anticancer drug candidate Tris(8‐oxyquinolinato)gallium(III) to Tf and HSA under simulated physiological conditions is described. Both the Ga(III) salt and the complex were found to bind to Tf exclusively in the presence of carbonate, however, at different kinetics and to a different extent. Fe(III) induces the release of the Ga ions due to the higher affinity constant and also prevents the Ga(III) species from accessing the iron‐binding pockets of Tf. In contrast, only low affinity to HSA was observed and even when present at ca. 20‐fold excess, the majority of the Ga was attached to Tf.     

Prediction and analysis of binding affinities for chemically diverse HIV-1 PR inhibitors by the modified SAFE_p approach

One of the biggest challenges in the "in silico" screening of enzyme ligands is to have a protocol that could predict the ligand binding free energies. In our group we have developed a very simple screening function (referred to as solvent accessibility free energy of binding predictor, SAFE_p) which we have applied previously to the study of peptidic HIV-1 protease (HIV-1 PR) inhibitors and later to cyclic urea type HIV-1 PR inhibitors. In this work, we have extended the SAFE_p protocol to a chemically diverse set of HIV-1 PR inhibitors with binding constants that differ by several orders of magnitude. The resulting function is able to reproduce the ranking and in many cases the value of the inhibitor binding affinities for the HIV-1 PR, with accuracy comparable with that of costlier protocols. We also demonstrate that the binding pocket SAFE_p analysis can contribute to the understanding of the physical forces that participate in ligand binding. The analysis tools afforded by our protocol have allowed us to identify an induced fit phenomena mediated by the inhibitor and have demonstrated that larger fragments do not necessarily contribute the most to the binding free energy, an outcome partially brought about by the substantial role the desolvation penalty plays in the energetics of binding. Finally, we have revisited the effect of the Asp dyad protonation state on the predicted binding affinities.     

Regional characteristics of naturally occurring radionuclides in surface sediments of Chinese deserts and the Keum River area of Korea

Naturally occurring radionuclides (NORN) such as ⁴⁰K, ²²⁶Ra and ²³²Th from 44 surface sediment samples collected from four desert regions of Chinese were determined to investigate the regional characteristics of the source areas of Asian dust. The radionuclides for 41 surface sediment samples collected from seven sites of the Keum River area in Korea were also determined to compare the regional characteristics with the Chinese desert area. The specific activities (SA) and the specific activity ratios (SAR) of the radionuclides were investigated for distinguishing the source region of Asian dust. The SA of ²²⁶Ra and ²³²Th as well as the SAR of ²²⁶Ra/⁴⁰K and ²³²Th/⁴⁰K were found to be useful to characterize source area and tracing Asian dust.     

Synthesis,crystal structures,DNA binding and oxidative cleavage studies of copper(II) complexes of N2S2 tetradentate ligands

Two new copper(II) complexes with aminothioether ligands, [Cu(L¹)(ClO₄)](ClO₄) · 0.5H₂O (1) and [Cu(L²)(H₂O)](ClO₄)₂ · H₂O (2) (L¹ = 2-benzyl-1,3-bis(aminoethylthio)propane and L² = 2-(4-butylbenzyl)-1,3-bis(aminoethylthio)propane), have been synthesized and characterized. The single crystal X-ray diffraction analysis reveals that both 1 and 2 adopt distorted square pyramidal geometries. The binding modes of both complexes with calf thymus DNA were investigated by UV–Vis and CD spectroscopies. The results show that both complexes mainly adopt an electrostatic attraction binding mode with DNA and the binding constants are (1.62 ± 0.02) × 10³ and (2.02 ± 0.02) × 10³ M⁻¹, respectively. Both complexes are able to cleave pBR322 plasmid DNA efficiently in the presence of ascorbic acid and the activity of 2 is higher than that of 1. The DNA cleavage by 1 and 2 were inhibited strongly in the presence of DMSO and tert-butyl alcohol, which suggests that hydroxyl radicals are the reactive oxygen species for the cleavage.     

Binding of the Zn2+ ion to ferric uptake regulation protein from E. coli and the competition with Fe2+ binding: a molecular modeling study of the effect on DNA binding and conformational changes of Fur

The three dimensional structure of Ferric uptake regulation protein dimer from E. coli, determined by molecular modeling, was docked on a DNA fragment (iron box) and Zn²⁺ ions were added in two steps. The first step involved the binding of one Zn²⁺ ion to what is known as the zinc site which consists of the residues Cys 92, Cys 95, Asp 137, Asp141, Arg139, Glu 140, His 145 and His 143 with an average metal-Nitrogen distance of 2.5 Å and metal-oxygen distance of 3.1–3.2 Å. The second Zn²⁺ ion is bound to the iron activating site formed from the residues Ile 50, His 71, Asn 72, Gly 97, Asp 105 and Ala 109. The binding of the second Zn²⁺ ion strengthened the binding of the first ion as indicated by the shortening of the zinc-residue distances. Fe²⁺, when added to the complex consisting of 2Zn²⁺/Fur dimer/DNA, replaced the Zn²⁺ ion in the zinc site and when a second Fe²⁺ was added, it replaced the second zinc ion in the iron activating site. The binding of both zinc and iron ions induced a similar change in Fur conformations, but shifted residues closer to DNA in a different manner. This is discussed along with a possible role for the Zn²⁺ ion in the Fur dimer binding of DNA in its repressor activity. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Influence of mesoporous structure type on the controlled delivery of drugs: release of ibuprofen from MCM-48, SBA-15 and functionalized SBA-15

Ordered mesoporous materials exhibit potential features to be used as controlled drug delivery systems, including their wide range of chemical compositions and their outstanding textural and structural properties. Therefore, it is possible to control the drug release kinetics by tailoring such parameters. In this paper, mesoporous materials such as MCM-48 and SBA-15, which present different pore sizes (3.7 and 8.8 nm) and structural characteristics (3D-bicontinuous cubic and 2D-hexagonal, respectively) have been synthesized to evaluate their application as drug delivery system and to determine their influence on release kinetic of ibuprofen. Moreover, a chemical modification of the SBA-15 mesoporous material with octadecyltrimethoxysilane has also been performed to study its influence on the release rate of ibuprofen. The structural characteristics (3D cubic and 2D hexagonal pore system) do not affect the release kinetic profiles of ibuprofen. On the contrary, the pore size affects highly to the release kinetic profiles from first-order kinetic to zero-order kinetic for MCM-48 and SBA-15, respectively. Moreover, the importance of surface functionalization was demonstrate through the very fast delivery of ibuprofen from SBA-15 mesoporous materials functionalized with octadecyl chains.     

Ag nanoparticles deposited onto silica,titania, and zirconia mesoporous films synthesized by sol–gel template method

A variety of Ag nanoparticles/oxide mesoporous films with templated silica, titania, and zirconia was synthesized by sol–gel method at glass, aluminum, and silicon substrates using metal alkoxides (tetraethoxysilane, titanium tetraisopropoxide, and zirconium tetrapropoxide) and AgNO₃ as precursors of oxide films and Ag nanoparticles, respectively, and Pluronic P123 as a template agent. Oxide films alone and Ag/oxide composites were characterized using hexane adsorption, X-ray diffraction (XRD), Raman and ultraviolet (UV)/vis spectroscopies, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) methods. The distribution of Ag nanoparticles within the films, their sizes, intensity, and position of surface plasmon resonance (SPR) absorbance band at λ = 400 nm, as well as the textural and structural characteristics of whole films depend on treatment temperature, types of substrates and oxide matrices, oxide crystallization, and Ag content. Ag nanoparticles form preferably on the outer surface of the films under lower sintering temperatures if the amount of loaded silver is low. Oxide crystallization (e.g., TiO₂) promotes silver embedding into the outer film layer. At higher silver content (≥10 at.%) and higher calcination temperature (873 K), silver nanoparticles could be entrapped more uniformly along the film profile because of more intensive evaporation of silver droplets from the outer surface of the films on heating.     

Apo‐CopC and CopC‐Cu(II) Unfolding Characteristics in GuHCl Solution

The stability of CopC, a copper resistant protein with a Greek β‐barrel motif, in GuHCl solution was investigated by fluorescence spectra. Parameter A, characterizing position and shape of the fluorescence spectra, "phase diagram" method of fluorescence, and cupric binding capacity in GuHCl solution of different concentration showed that the denaturation transition of apo‐CopC and CopC‐Cu(II) might be fitted to a simple two‐state model. According to a two‐state model, the free energy of stabilization for apo‐CopC and CopC‐Cu(II), (17.08±0.35) and (23.81±0.45) kJ·mol^‐1 respectively, was obtained. Copper(II) increased the stability of apo‐CopC. The higher thermodynamics stability of CopC‐Cu(II) was revealed to originate in both the faster folding and the slower unfolding rates by unfolding kinetics.