荧光光谱法研究蒜头果蛋白与金属离子的相互作用

蒜头果蛋白(malanin)是从云南、广西特有植物蒜头果中分离纯化出的一种新的、具有抗肿瘤活性的糖蛋白。用荧光光谱法研究了Cu2+,Ag+和Ca2+对malanin和apo-malanin溶液(经EDTA透析脱去金属离子后的脱金属蛋白)荧光强度的影响。结果表明,Cu2+对malanin和apo-malanin荧光均有明显的静态猝灭现象,其离解常数K_d分别为2.37×10-4和2.66×10-4 mol·L-1;Ag+对malanin的荧光强度变化不大,但对apo-malanin荧光强度却有明显的静态猝灭现象,其离解常数K_d为2.37×10-4 mol·L-1;而Ca2+对malanin和apo-malanin荧光强度均无明显变化,说明Ca2+对维持malanin分子天然构象具有重要作用。     

Wind tunnel measurements of the preferential concentration of inertial droplets in homogeneous isotropic turbulence

We describe an experimental setup aimed at studying turbulent-induced droplet collisions in a laboratory setting. Our goal is to reproduce conditions relevant to warm-rain formation in clouds. In these conditions, the trajectories of small inertial droplets are strongly influenced by the background air turbulence, and collisions can potentially explain the droplet growth rates and spectrum broadening observed in this type of clouds. Warm-rain formation is currently under strong scrutiny because it is an important source of uncertainty in atmospheric models. A grid at the entrance of a horizontal wind tunnel produces homogeneous isotropic turbulence at a Re _λ in the range of 400–500. Water droplets are injected from the nodes of the turbulence-inducing grid at a volume fraction (?) of 2.7?×?10^?5 and with sizes of 10–200?μm. A complex manifold-injection system was developed to obtain uniform water droplet seeding, in terms of both water content and size distribution. We characterize the resulting droplet-laden turbulent flow, and the statistics of droplet pairs are measured and analyzed. We found that the radial distribution function (RDF), a measure of preferential concentration of droplets that plays a key role in collision kernel models, has a large peak at distances below the Kolmogorov microscale of the turbulence. At very long separations, comparable with the integral length scale of the turbulence, these RDFs show a slow decay to the average probability given by the mean droplet number density. Consistent with this result, conditional analysis shows an increased local concentration of droplets within the inertial length scale (≈ 10–100 Kolmogorov lengths). These results are in good agreement with previous experiments that found clustering of inertial droplets with St?≈ 1 at scales on the order of 10η. Ultimately, our results support the hypothesis that turbulence-induced preferential concentration and enhanced settling can lead to significant increases in the collision probability for inertial droplets in the range 10–50?μm.     

High-performance liquid chromatography assays for desmethoxyyangonin, methysticin, kavain and their microsomal metabolites

Three novel, simple and reproducible high-performance liquid chromatography quantitative assays with UV detection were developed and validated for three major kavalactones--desmethoxyyangonin, methysticin and kavain--in rat liver microsomes using diazepam as an internal standard; liquid-liquid extraction was used for sample preparation and analysis was performed on a Shimadzu 10A high-performance liquid chromatography system. The analysis was carried out in reversed-phase mode with a Luna C(18) column (150 x 2.00 mm, 3 microm) at 40 degrees C. The limit of quantitation was 0.1 microg/mL using 0.25 mL of microsomal solution. The assays were linear over the range 0.1-10 microg/mL for desmethoxyyangonin, methysticin and kavain. Quality control samples exhibited good accuracy and precision with relative standard deviations lower than 15% and recoveries between 85 and 105%. The assays exhibited satisfactory performance with high sensitivity for quantifying desmethoxyyangonin, methysticin and kavain in rat liver microsomes and were successfully used to determine the three kavalactones and their microsomal metabolites.     

Gold Manno‐Glyconanoparticles: Multivalent Systems to Block HIV‐1 gp120 Binding to the Lectin DC‐SIGN

The HIV envelope glycoprotein gp120 takes advantage of the high‐mannose clusters on its surface to target the C‐type lectin dendritic cell‐specific intracellular adhesion molecule‐3‐grabbing non‐integrin (DC‐SIGN) on dendritic cells. Mimicking the cluster presentation of oligomannosides on the virus surface is a strategy for designing carbohydrate‐based antiviral agents. Bio‐inspired by the cluster presentation of gp120, we have designed and prepared a small library of multivalent water‐soluble gold glyconanoparticles (manno‐GNPs) presenting truncated (oligo)mannosides of the high‐mannose undecasaccharide Man₉GlcNAc₂ and have tested them as inhibitors of DC‐SIGN binding to gp120. These glyconanoparticles are ligands for DC‐SIGN, which also interacts in the early steps of infection with a large number of pathogens through specific recognition of associated glycans. (Oligo)mannosides endowed with different spacers ending in thiol groups, which enable attachment of the glycoconjugates to the gold surface, have been prepared. manno‐GNPs with different spacers and variable density of mannose (oligo)saccharides have been obtained and characterized. Surface plasmon resonance (SPR) experiments with selected manno‐GNPs have been performed to study their inhibition potency towards DC‐SIGN binding to gp120. The tested manno‐GNPs completely inhibit the binding from the micro‐ to the nanomolar range, while the corresponding monovalent mannosides require millimolar concentrations. manno‐GNPs containing the disaccharide Manα1‐2Manα are the best inhibitors, showing more than 20 000‐fold increased activity (100 % inhibition at 115 nM ) compared to the corresponding monomeric disaccharide (100 % inhibition at 2.2 mM ). Furthermore, increasing the density of dimannoside on the gold platform from 50 to 100 % does not improve the level of inhibition.     

A Cobalt Metallacrown Anion Host with Guest‐Dependent Redox Activity

Two bowl‐shaped cavities , each having three OH^? hydrogen‐bond donors at its base, are present in double‐cone‐shaped metallacrown anion host [Co₆(μ‐OH)₆(μ‐L)₆]^m+ ( 1 ^{m +} ; HL=3{5}‐(pyrid‐2‐yl)‐5{3}‐(tert‐butyl)pyrazole). Depending on its affinity for the anions present, it can be isolated in its Co^III₃Co^II₃ (m=3; e.g., 1 (ClO₄)₃) and Co^III₂Co^II₄ (m=2; e.g., 1 (BF₄)₂ ? n H₂O) oxidation states. See picture for photographs of isolated salts.

     

Hypothermic renal preservation with a sucrose/ polyethylene glycol solution in a rabbit renal transplant model

Renal preservation at for 24 hours at hypothermia was studied in a rabbit model after flush cooling with sucrose-based solution (SBS), compared with a standard preservation solution (in this case, Marshall's Hypertonic Citrate solution - HCA). Polyethylene glycol supplementation to SBS (SBS-PEG) was also investigated. Renal function was measured by plasma creatinine assays during 1 months post transplantation, and pathology of the explanted kidneys was undertaken. Results showed that survival at 28 days was similar in all groups, (HCA - 3 out of 6; SBS - 2 out of 5; SBS-PEG - 3 out of 5), and there were no differences in recovery of plasma creatinine values. Histopathological evaluation of the grafts indicated that SBS preservation resulted in more severe damage after transplantation (P less than 0.05 in both corticomedullary region and medulla compared to HCA), whilst addition of PEG reduced the damage score to that seen with HCA. SBS can be used as a simple, inexpensive preservation solution for kidney cold storage provided that PEG is used as an additional colloid.     

Yielding and flow in adhesive and nonadhesive concentrated emulsions

The nonlinear rheological response of soft glassy materials is addressed experimentally by focusing on concentrated emulsions where interdroplet attraction is tuned through varying the surfactant content. Velocity profiles are recorded using ultrasonic velocimetry simultaneously to global rheological data in the Couette geometry. Our data show that nonadhesive and adhesive emulsions have radically different flow behaviors in the vicinity of yielding: while the flow remains homogeneous in the nonadhesive emulsion and the Herschel-Bulkley model for a yield stress fluid describes the data very accurately, the adhesive system displays shear localization and does not follow a simple constitutive equation, suggesting that the mechanisms involved in yielding transitions are not universal.     

Electrophotocatalysis with a Trisaminocyclopropenium Radical Dication

Visible‐light photocatalysis and electrocatalysis are two powerful strategies for the promotion of chemical reactions. Here, these two modalities are combined in an electrophotocatalytic oxidation platform. This chemistry employs a trisaminocyclopropenium (TAC) ion catalyst, which is electrochemically oxidized to form a cyclopropenium radical dication intermediate. The radical dication undergoes photoexcitation with visible light to produce an excited‐state species with oxidizing power (3.33 V vs. SCE) sufficient to oxidize benzene and halogenated benzenes via single‐electron transfer (SET), resulting in C?H/N?H coupling with azoles. A rationale for the strongly oxidizing behavior of the photoexcited species is provided, while the stability of the catalyst is rationalized by a particular conformation of the cis‐2,6‐dimethylpiperidine moieties.     

Hemilabile Ligands as Mechanosensitive Electrode Contacts for Molecular Electronics

Single‐molecule junctions that are sensitive to compression or elongation are an emerging class of nanoelectromechanical systems (NEMS). Although the molecule–electrode interface can be engineered to impart such functionality, most studies to date rely on poorly defined interactions. We focused on this issue by synthesizing molecular wires designed to have chemically defined hemilabile contacts based on (methylthio)thiophene moieties. We measured their conductance as a function of junction size and observed conductance changes of up to two orders of magnitude as junctions were compressed and stretched. Localised interactions between weakly coordinating thienyl sulfurs and the electrodes are responsible for the observed effect and allow reversible monodentate?bidentate contact transitions as the junction is modulated in size. We observed an up to ≈100‐fold sensitivity boost of the (methylthio)thiophene‐terminated molecular wire compared with its non‐hemilabile (methylthio)benzene counterpart and demonstrate a previously unexplored application of hemilabile ligands to molecular electronics.