Temperature-sensitive polypeptide brushes-coated mesoporous silica nanoparticles for dual-responsive drug release

A multifunctional nanohybrid based on mesoporous silica nanoparticle and biocompatible polypeptide was fabricated for targeted and dual-responsive therapy of tumor cells.     

MCSCF reaction-path energetics and thermal rate-constants for the reaction of3NH with H2

Summary The intrinsic reaction-path, reactants, transition state and products for the reaction of NH (^3–)+H₂ (¹ _g ⁺ ) NH₂ (²B₁)+H (²S) involving the lowest triplet electronic state of NH₃ were calculated using multi-configuration (MC) SCF methods. The calculated change of internal energy for the reaction of 11.0 kcal mol^–1 agrees with the experimental value within 2 kcal mol^–1. The barrier to reaction is 23.4 kcal mol^–1 high. The harmonic MCSCF reaction-path potential was calculated and canonical variational transition state theory calculations of the rate constants performed over a temperature range from 400 to 2500 K. The computed rate constants are generally two orders of magnitude smaller than those of the comparable reaction of OH with H₂, whereas those of the reverse reaction are by a factor of 20 larger than those of OH₂ with H.     

Covalent attachment of trypsin on plasma polymerized allylamine

This paper focuses on the immobilization of a proteolytic enzyme, trypsin, on plasma polymerized allylamine (ppAA) films. The later have been deposited onto silicon substrate by means of radiofrequency glow discharge. The covalent attachment of the enzyme was achieved in three steps: (i) activation of the polymer surface with glutaraldehyde (GA) as a linker, (ii) immobilization of trypsin and (iii) imino groups reduction treatment. The effects and efficiency of each step were investigated by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Fluorescent spectroscopy was used to evaluate the change of the biological activity following the immobilization steps. The results showed that enzyme immobilization on GA-modified substrate increases the enzyme activity by 50% comparing to adsorbed enzymes, while the imino reduction treatment improves the enzyme retention by about 30% comparing to untreated samples. In agreement with XPS and AFM data, UV–vis absorption spectroscopy, used to quantify the amount of immobilized enzyme, showed that allylamine plasma polymer presents a high adsorption yield of trypsin. Although the adsorbed enzymes exhibit a lower activity than that measured for enzymes grafted through GA linkers, the highest catalytic activity obtained was for the enzymes that underwent the three steps of the immobilization process.     

Trinuclear Gold Clusters Supported by Cyclic (alkyl)(amino)carbene Ligands: Mimics for Gold Heterogeneous Catalysts

The synthesis of air‐ and moisture‐stable trinuclear mixed‐valence gold(I)/gold(0) clusters is described. They promote the catalytic carbonylation of amines under relatively mild conditions. The synthetic route leading to the trinuclear clusters involves a simple ligand exchange from the readily available μ³‐oxo‐[(Ph₃PAu)₃O]⁺ complex. This synthetic method paves the way for the preparation of a variety of mixed‐valence gold(I)/gold(0) polynuclear clusters. Moreover, the well‐defined nature of the complexes demonstrates that the catalytic process involves a rare example of a definite change of oxidation state of gold from Au⁰₂Au^I to Au^I₃.     

Ring current and anisotropy effects on OH chemical shifts in resonance-assisted intramolecular H-bonds

Ring current effects on resonance-assisted and intramolecularly bridged hydrogen bond protons for 10-hydroxybenzo[h]quinoline 1 and a number of related compounds were calculated and the through-space NMR shieldings (TSNMRS) obtained hereby visualized as iso-chemical-shielding surfaces (ICSS) of various size and direction. These calculations revealed that this through-space effect is comparably large (up to 2?ppm) dependent on the position of the intramolecularly bridged OH proton, and therefore, contribute considerably to the chemical shift of the latter making it questionable to use δ(OH)/ppm in the estimation of intramolecular hydrogen bond strength without taking this into account. Furthermore, the anisotropy effects of additional groups on the aromatic moiety (e.g. the carbonyl group in salicylaldehyde or in o-hydroxyacetophenone of ca. 0.6?ppm deshielding) should also be considered. These through-space effects need to be taken into account when using OH chemical shifts to estimate hydrogen bond strength.     

Rheological properties of fresh and cryopreserved human arteries tested in vitro

Cryopreservation is widely used to preserve blood vessels for a while but is controversially suspected to affect the mechanical behavior of these allografts. The aim of this study was to determine whether differences in the three-dimensional mechanical behavior exist or not between fresh and cryopreserved arteries. Using a previously developed experimental system, in vitro inflation tests were performed on twenty segments of human fresh and cryopreserved arteries, in static conditions. Opening angles were also measured from images of rings in zero-stress state. The initial reference state was chosen as the unloaded state and tests were performed on specimens stretched at natural “in vivo” length. Mechanical measures calculated are “natural” (Hencky) strains (finite deformations), “true” (Cauchy) stresses in radial, circumferential, and longitudinal directions as well as strain energy per unit volume. Tangent moduli are derived from radial and circumferential stress-strain characteristics using non-linear curve fitting. Values of incremental and pressure-strain elastic parameters, wall stiffness, and compliance per unit length are also calculated. Results are presented in terms of characteristics of stresses and strains in the three directions, axial force, tangent moduli vs strains or stresses, and energy per unit volume, for both types of artery, with reference to transmural pressure. Detailed numerical results are given at mean transmural pressure or in the physiological range. Significant differences are indicated by statistic Student T-tests. Results obtained show that significant differences exist between rheological properties of fresh and cryopreserved segments of human artery. Strains, stresses, axial force, strain energy, and wall stiffness values highlight those differences whereas elastic parameters, compliance, and opening angle do not. The usefulness of some parameters to compare the mechanical behavior existing between fresh and cryopreserved arteries is therefore underlined. Received: 3 January 2000 Revision received: 12 April 2000 Accepted: 8 May 2000     

State of the art of the sphere method, a unique characterization technique for non-linear crystals

We report the sphere method as a unique characterization technique for the complete study of non-linear optical properties for frequency conversion in new materials belonging to the uniaxial or biaxial optical class. It relies on the use of a single crystal with millimetre dimensions cut as a sphere, combined with a tuneable laser source. With the sphere method we perform direct measurements of phase-matching angles and associated conversion efficiencies for second harmonic, sum- and difference-frequency generation. Furthermore, we follow the orientation of the dielectric frame as a function of the wavelength for monoclinic and triclinic crystals. It also allows the determination of the magnitude of the principal refractive indices in biaxial crystals based on the study of the double refraction affect at the exit of a sphere. By combining the analysis of all these data simultaneously, we determine Sellmeier equations reliable over the whole transparency domain and we are able to get the non-zero elements of the second-order susceptibility tensor of uniaxial or biaxial crystals. Finally, the sphere method is completely self-sufficient for the study of biaxial crystals.