Ring‐Opening of Benzocyclobutenol with Mild Bases and Trapping with Dieneophiles

The treatment of benzocyclobutenol with a mild base has been investigated. This reaction results in an electrocyclic opening of the cyclobutene to the corresponding o‐quinodimethane, which has been successfully treated with aldehydes and electron‐deficient alkenes to form benzolactols and benzocyclohexenes respectively.     

O-phosphorylation of Oligopeptides with Phosphoramidite

Phosphoproteinsplayimportantrolesinbiologicalsignallingcascades,bywhichchemicalsignalsarepassedacrossthecellmembraneandfurthertothecellnucleusl.Forthestudythisprocess,structurallywell-definedpeptidescontainingthecharacteristiclinkageregionofthepeptidebackbonewiththephosphoricacidestercanusedwithmanyadvantages.Ingeneral,estersofoligopeptideswerephosphorylatedwithphosphorylchlorideorwithdialkylordiarylphosphorochloridates'.Butaminogroupsinoligopeptidesshouldbeprotectedwhenhydroxylgroupswerephosp…     

Triclosan-loaded with high encapsulation efficiency into PLA nanoparticles coated with β-cyclodextrin polymer

The purpose was to prepare triclosan-loaded polylactic acid nanoparticles containing β-cyclodextrin polymer shell, evaluate triclosan release from the particles using Franz diffusion cells and to study the stability of the particles in presence of a model protein, bovine serum albumin. The nanoparticles were prepared by a solvent displacement process. The nanoparticles were characterized by their size, encapsulation efficiency and morphology. They were of spherical shape with hydrodynamic diameter of about 100 or 200 nm depending on the polylactic acid used. Their high encapsulation efficiency (~90%) indicated that triclosan is easily incorporated into the nanoparticles. The nanoparticles displayed slow and sustained triclosan release patterns (diffusion coefficient about 10^?22 m²/s) and the β-cyclodextrin polymer coating was stable under simulated physiological conditions. All these data indicated that these novel core–shell nanoparticles might provide a promising carrier system for controlled release of triclosan and other hydrophobic drugs after systemic administration.     

Copolymerization of N-Phenylmaleimide with Cyclohexene

MalebodeanditSderivatvesarewell-bowntopolyInrizetogivethermallystablepolyTnersandthecopolymeriZationwithvariousvinylmonomershasbeenexaminedtohaProvethethermalpropeniesofthepolymers[';-'].HoweverlessworkhasbeendoneonthecopolyInerizationofN-phenylmaletride(PHMI)withcyclohexene(CH).Inthisletter,wesynthesizedanewcopolymerfromthepolymerizahonofPHMIwithCH.ThemonomerPHMIwaspreparedfrommaleicanhydrideandedlineaccordingtoT.OkadaI41.2,2'-Azobisisobutyronitrile(AIBN)wasrecrystallizedtWicefro…     

Cyclopropanation of Diazoacetate with Olefins

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Hybrid supramolecular hydrogels induced by Au nanoparticles protected with MPEG-b-PCL copolymers with α-cyclodextrin

To fabricate supramolecular hydrogel hybridised with well-dispersed gold nanoparticles (AuNPs), water-soluble AuNPs protected with methoxy poly(ethylene glycol)-b-poly(?-caprolactone) (MPEG-b-PCL) self-assembled monolayers (MPEG-b-PCL/AuNPs) were synthesised and used as guest molecules to interact with α-cyclodextrin (α-CD) in aqueous solutions. Transmission electron microscopy measurement results showed that the diameter of the AuNPs produced was about 6–10 nm with a narrow particle size distribution, and stained MPEG-b-PCL/AuNPs micelles made in water clearly displayed the formation of a core-shell structure with a single gold core per micelle. X-ray diffraction measurement results confirmed that there existed the characteristic peaks of both AuNPs and polypseudorotaxanes formed via the inclusion complexation of MPEG-b-PCL moieties with α-CD in as-obtained hydrogels. UV–visible spectra displayed that the same surface plasma resonance absorption peaks appeared at 526 nm for both aqueous dispersion of MPEG-b-PCL/AuNPs and resultant hybrid hydrogel with α-CD. Rheological measurements showed that the hybrid hydrogel has a lower mechanical strength and viscosity, and a relatively prolonged gelation time in comparison with the corresponding native hydrogel. The mechanical strength of the hydrogel nanocomposites could be tailored by modulating the concentration of MPEG-b-PCL/AuNPs and α-CD as well as the composition of MPEG-b-PCL/AuNPs.     

Morphological characterization of metal porphyrin tailed with aspirin interacting with bovine serum albumin congeries

The porphyrins tailed with acetylsalicylic acid (ASA) and Zn (or Cu) complexes were prepared.Meanwhile,morphological images,such as shape and size of porphyrins-BSA congeries were observed by using atomic force microscopy (AFM).The result showed the interaction of BSA and prepared porphyrins led to obvious change of shape and size of BSA congeries.     

A biocatalytic cascade with several output signals—towards biosensors with different levels of confidence

The biocatalytic cascade based on enzyme-catalyzed reactions activated by several biomolecular input signals and producing output signal after each reaction step was developed as an example of a logically reversible information processing system. The model system was designed to mimic the operation of concatenated AND logic gates with optically readable output signals generated at each step of the logic operation. Implications include concurrent bioanalyses and data interpretation for medical diagnostics.

β-Aminovinyl ketonates with heterocyclic fragments

-Aminovinyl ketones containing heterocyclic fragments (tetrahydro-1-6,2-benzothiazine 1,1-dioxide and 2,3-dimethyl-1-phenyl-2,5-dihydro-1H-pyrazole-5-one) (LH) and their complexes with 3d-metals (Co^II, Ni^II, Cu^II, and Zn^II) were synthesized. The obtained ligands give rise to two types of ML₂ chelates with coordinated (coordination number 6; Co, Ni, Zn) and uncoordinated carbonyl group in the pyrazole fragment (coordination number 5; Cu).Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 10, 2004, pp. 1709–1713.Original Russian Text Copyright © 2004 by Anpilova, Korshunov, Bicherov, Burlov, Borodkin, Zaletov, Uflyand, Garnovskii.This revised version was published online in April 2005 with a corrected cover date.     

DNA Modification with Photochromic Spiro Compounds

The photochromic spiropyrans and spirooxazine having a succinimidyl ester or isothiocyanate pendant group can form covalent products with transaminated DNA.The absorption spectra and solid reflection spectra of modified DNA with these photochromic spiro compounds were investigated.     

Reactions of α-nitroacrylates with thiophenols

Reactions of α-nitroacrylates with aromatic thiols like 4-methyl- and 4-chlorothiophenols afford a series of new 3-arylsulfanyl-2-nitropropanoates. The latter were isolated as diastereomerically pure substances or mixtures of two diastereomers. Structures of the obtained S-adducts were confirmed by IR, ¹H and ¹³C-{¹H} NMR spectroscopy using HMQC and HMBC experiments.     

Complexes of β-cyclodextrin with chloronitrobenzenes and with solvents in water + organic solvent mixtures

Inclusion complexes of chloronitrobenzenes with -cyclodextrin in aqueous 0.1 M phosphate buffer solutions containing various concentrations of ethanol, dimethylsulfoxide, dimethylformamide, acetone and acetonitrile have been studied by a polarographic method. The diffusion coefficients and the stability constants of the corresponding complexes have been determined. Using an equation derived by us which takes account of the change in the cyclodextrin concentration due to the simultaneous complexation of the solvent, both stability constants have been calculated. The influence of solvent on the stability constant of chloronitrobenzenes is discussed     

Transparent conductors from carbon nanotubes LBL-assembled with polymer dopant with π-π electron transfer

Single-walled carbon nanotube (SWNT) and other carbon-based coatings are being considered as replacements for indium tin oxide (ITO). The problems of transparent conductors (TCs) coatings from SWNT and similar materials include poor mechanical properties, high roughness, low temperature resilience, and fast loss of conductivity. The simultaneous realization of these desirable characteristics can be achieved using high structural control of layer-by-layer (LBL) deposition, which is demonstrated by the assembly of hydroethyl cellulose (HOCS) and sulfonated polyetheretherketone (SPEEK)-SWNTs. A new type of SWNT doping based on electron transfer from valence bands of nanotubes to unoccupied levels of SPEEK through π-π interactions was identified for this system. It leads to a conductivity of 1.1 × 10(5) S/m at 66 wt % loadings of SWNT. This is better than other polymer/SWNT composites and translates into surface conductivity of 920 Ω/? and transmittance of 86.7% at 550 nm. The prepared LBL films also revealed unusually high temperature resilience up to 500 °C, and low roughness of 3.5 nm (ITO glass -2.4 nm). Tensile modulus, ultimate strength, and toughness of such coatings are 13 ± 2 GPa, 366 ± 35 MPa, and 8 ± 3 kJ/m(3), respectively, and exceed corresponding parameters of all similar TCs. The cumulative figure of merit, ∏(TC), which included the critical failure strain relevant for flexible electronics, was ∏(TC) = 0.022 and should be compared to ∏(TC) = 0.006 for commercial ITO. Further optimization is possible using stratified nanoscale coatings and improved doping from the macromolecular LBL components.     

Heterocycles with a β-nitroenamine fragment

Reactions of dimedone and dihydroesorcinol with arylidenenitroacetonitriles yield fused 2-amino-3-nitropyrans. The crystal and molecular structure of one of the reaction products was determined by X-ray diffraction analysis. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1142–1145, June, 1999.     

Tracking lithiation with transmission electron microscopy

Li-ion batteries(LIBs) have dominated energy-storage techniques for portable electronic devices and electric cars, and are expanding their territory into the large-scale energy storage. The energy storage of LIBs is realized by the reversible shuttle of lithium ions between electrodes. It is essential to track the lithium diffusion and obtain a profound insight into the lithiation mechanism during the work cycle of LIBs. Transmission electron microscopy(TEM) is a powerful tool for the structural...     

Synthesis of Indomethacin Conjugates with D-Glucosamine

Two series of indomethacin conjugates with D-glucosamine were prepared with the objectives of reducing ulcerogenic potency, increasing the bioavailability of indomethacin and exerting the coordinative effects on osteoarthritis. The structures of the conjugates were identified by ^1H NMR and ^13C NMR. The ester conjugates inhibited edema as potent as indomethacin.     

Electrochemical CO2 reduction with power generation in SOFCs with Cu-added LSCF–GDC cathode

Solid oxide fuel cell (SOFC) unit was constructed with Ni–GDC (gadolinia-doped ceria) as the anode, YSZ as the electrolyte, and Cu-added La_0.58Sr_0.4Co_0.2Fe_0.8O_3–δ–GDC as the cathode. Electrochemical CO₂ reduction occurs. The CO formation rate, the CO₂ conversion and the generated current density increase with increasing CO₂ concentration and temperature. The CO₂ conversion rate equals exactly the CO formation rate. No carbon deposition occurs. The activation energy is 2.72 kcal mol^?1. The electrochemical CO₂ reduction (dissociation) can have much lower activation barrier than the catalytic one. Simultaneous CO₂ reduction with power generation in SOFCs can be feasible.     

Enantioselective water-soluble iron–porphyrin-catalyzed epoxidation with aqueous hydrogen peroxide and hydroxylation with iodobenzene diacetate

The asymmetric epoxidation of styrene derivatives by H₂O₂ (or UHP) to give optically active epoxides (ee up to 81%) and hydroxylation of alkanes to give optically active secondary alcohols (ee up to 78%) were carried out in methanol and water using chiral water-soluble iron porphyrins as catalysts.