Reinforcement of Natural Rubber from Hydroxyl-Terminated Liquid Natural Rubber Grafted Carbon Black. I. Grafting of Acyl Chloride Capped Liquid Natural Rubber onto Carbon Black

Abstract

This paper deals with the grafting of acyl chloride capped liquid natural rubber (LNR–COCl) onto carbon black by the reaction of the acyl chloride group with the phenolic hydroxyl group on the surface. LNR–COCl was prepared by the reaction of hydroxyl-terminated liquid natural rubber (HTNR) with adipoyl dichloride. The percentage of grafting was estimated to be 18–21% depending on the grafting temperature and the molecular weight of HTNR used. It increased with an increase in the molecular weight of LNR–COCl. The LNR grafted onto carbon black was investigated by IR spectroscopy and by hydrolysis with a dilute THF solution of KOH. It was shown that LNR grafted onto the carbon black surface with ester bonds.     

Purified oxygen- and nitrogen-modified multi-walled carbon nanotubes as metal-free catalysts for selective olefin hydrogenation

Oxygen- and nitrogen-functionalized carbon nanotubes (OCNTs and NCNTs) were applied as metal-free catalysts in selective olefin hydrogenation. A series of NCNTs was synthesized by NH₃ post-treatment of OCNTs. Temperature-programmed desorption, N₂ physisorption, Raman spectroscopy, high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy were employed to characterize the surface properties of OCNTs and NCNTs, aiming at a detailed analysis of the type and amount of oxygen- and nitrogen-containing groups as well as surface defects. The gas-phase treatments applied for oxygen and nitrogen functionalization at elevated temperatures up to 600 °C led to the increase of surface defects, but did not cause structural damages in the bulk. NCNTs showed a clearly higher activity than the pristine CNTs and OCNTs in the hydrogenation of 1,5-cyclooctadiene, and also the selectivity to cyclooctene was higher. The favorable catalytic properties are ascribed to the nitrogen-containing surface functional groups as well as surface defects related to nitrogen species. In contrast, oxygen-containing surface groups and the surface defects caused by oxygen species did not show clear contribution to the hydrogenation catalysis.     

Direct Visualization of Atomic Structure in Multivariate Metal-Organic Frameworks (MOFs) for Guiding Electrocatalysts Design

The direct utilization of metal–organic frameworks (MOFs) for electrocatalytic oxygen evolution reaction (OER) has attracted increasing interests. Herein, we employ the low-dose integrated differential phase contrast-scanning transmission electron microscopy (iDPC-STEM) technique to visualize the atomic structure of multivariate MOFs (MTV-MOFs) for guiding the structural design of bulk MOFs for efficient OER. The iDPC-STEM images revealed that incorporating Fe³⁺ or 2-aminoterephthalate (ATA) into Ni-BDC (BDC: benzenedicarboxylate) can introduce inhomogeneous lattice strain that weaken the coordination bonds, which can be selectively cleaved via a mild heat treatment to simultaneously generate coordinatively unsaturated metal sites, conductive Ni@C and hierarchical porous structure. Thus, excellent OER activity with current densities of 10 and 100 mA cm⁻² are achieved over the defective MOFs at small overpotentials of 286 mV and 365 mV, respectively, which is superior to the commercial RuO₂ catalyst and most of the bulk MOFs.     

An inhibitor of sequence-specific proteolysis that targets the substrate rather than the enzyme

BACKGROUND: Traditional protease inhibitors target the active site of the enzyme. However, since most proteases act on multiple substrates, even the most specific protease inhibitors will affect the levels of a number of different proteins. However, if substrate-targeted inhibitors could be developed, much higher levels of specificity could be achieved. In theory, compounds that bind the cleavage site of a particular substrate could block its interaction with a protease without having any effect on the processing of other substrates of that protease. RESULTS: A model system is presented that demonstrates the feasibility of substrate-targeted inhibition of proteolysis. A peptide selected genetically to bind a 14-residue epitope that encompasses the cleavage site of human pro-IL-1beta was shown to inhibit interleukin-converting enzyme (ICE)-mediated proteolysis of model substrates containing the 14-mer target sequence. However, the peptide had no effect on the cleavage of other ICE substrates with different amino acids flanking the minimal cleavage site. CONCLUSIONS: This study demonstrates the feasibility of substrate-targeted inhibition of proteolysis. More potent compounds must be developed before substrate-targeted inhibitors can be used routinely. Nonetheless, this novel strategy for protease inhibition seems promising for the development of extremely selective molecules with which to manipulate the maturation of many important pro-hormones, -cytokines and -proteins.     

Reaction of 3-chloroquinoline-2,4-diones with ethanolamine and rearrangement of the reaction products

The reaction of tertiary α-chloroketones with ethanolamine has not been hitherto described in the literature. Herein, we describe the reaction of tertiary 3-chloroquinoline-2,4-diones with ethanolamine to give novel 3-(2-hydroxyethylamino)quinoline-2,4-diones. These compounds provide 3-(2-oxooxazolidin-3-yl)quinoline-2,4(1H,3H)-diones and new compounds with dimeric character after reaction with triphosgene. Molecular rearrangement proceeds during the reaction of 3-(2-hydroxyethylamino)quinoline-2,4-diones with isocyanic acid. Three types of reaction products arise: 2-(2-hydroxyethyl)imidazo[1,5-c]quinazoline-3,5-diones, 3-(2-hydroxyethyl)-3,3a-dihydro-2H-imidazo[4,5-]quinoline-4(5H)diones and primarily 5-hydroxy-1-(hydroxyethyl)-1′H-spiro[imidazolidine-5,3′-indole]-2,2′-diones. The reaction mechanism and product stereochemistry are discussed. The ¹H, ¹³C and ¹⁵N NMR spectra of the prepared compounds were measured, and all resonances were assigned from appropriate two-dimensional experiments.     

An existence result for a quadrature surface free boundary problem

The aim of this paper is to present two different approachs in order to obtain an existence result to the so-called quadrature surface free boundary problem. The first one requires the shape derivative calculus while the second one depends strongly on the compatibility condition of the Neumann problem. A necessary and sufficient condition of existences is given in the radial case.     

Square-wave cathodic stripping voltammetric analysis of RDX using mercury-film plated glassy carbon electrode

A mercury film (MF) is prepared by an electrochemical deposition on a glassy carbon electrode (GCE), and employed for an analysis of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) using square-wave stripping voltammetry (SWSV). RDX was deposited at -0.15 V (vs. Ag/AgCl) for 120 s, then reduced at -0.7 V on the MF coated GCE(MFGCE). Optimal experimental conditions were searched and reported for the analysis. Two linear concentration ranges were observed: one in a lower RDX concentration range of 0.2-10 mg l(-1) and the other in a higher RDX concentration range of 10.0-100.0 mg l(-1) with a 120 s of pre-concentration time. At RDX concentrations of 2 and 8 mg l(-1), the relative standard deviations in measured concentrations (n=16) were 9.79 and 0.49%, respectively. The detection limit found to be 0.12 mg l(-1) with the 120 s accumulation time. The method was applied to determine RDX in several soil samples that yielded a relative error of 1% in the concentrations.     

Using ESI-MS to probe protein structure by site-specific noncovalent attachment of 18-crown-6

A new method for probing the equilibrium structures and folding states of proteins utilizing electrospray ionization mass spectrometry is described. Protein structure is explored as a function of side-chain availability as determined by a specific interaction between lysine and 18-crown-6 ether (18C6). Various intramolecular interactions are competitive with the lysine/18C6 interaction and can prevent noncovalent attachment of 18C6. Changes to protein structure modify these inhibiting intramolecular interactions, which leads to a change in the number of 18C6s that attach to the protein. Experiments conducted with cytochrome c, ubiquitin, and melittin reveal that the method is sensitive to changes in both tertiary and secondary structure. In addition, the structure of each charge state can be examined independently. Experiments can be performed under conditions where the pH and amount of organic cosolvent are varied. Control experiments conducted with pentalysine, which lacks structural organization, are also presented.     

Pinacol Rearrangement of 3,4‐Dihydro‐3,4‐dihydroxyquinolin‐2(1H)‐ones: An Alternative Pathway to Viridicatin Alkaloids and Their Analogs

3‐Alkyl/aryl‐3‐hydroxyquinoline‐2,4‐diones were reduced with NaBH₄ to give cis‐3‐alkyl/aryl‐3,4‐dihydro‐3,4‐dihydroxyquinolin‐2(1H)‐ones. These compounds were subjected to pinacol rearrangement by treatment with concentrated H₂SO₄, resulting in 4‐alkyl/aryl‐3‐hydroxyquinolin‐2(1H)‐ones. When a benzyl (Bn) group was present in position 3 of the starting compound, its elimination occurred during the rearrangement, and the corresponding 3‐hydroxyquinolin‐2(1H)‐one was formed. The reaction mechanisms are discussed for all transformations. All compounds were characterized by IR, ¹H‐ and ¹³C‐NMR spectroscopy, as well as mass spectrometry.