Immobilization of a primary amine-containing drug,adriamycin

Literature reports have described the covalent coupling of the primary amine-containing anticancer drug, adriamycin, to polymeric supports through the amine group on the drug. These reports also have described drug mechanism studies with the immobilized adriamycin, where the release of the drug would undermine the validity of the conclusions. In the present paper, detailed experimental conditions are given for preparation of nonwater-soluble particles of polyvinyl alcohol by crosslinking water-soluble polyvinyl alcohol with 1,4-benzenedicarboxaldehyde, and for activation with cyanuric chloride and covalent attachment of adriamycin. The expected stability of this drug-support linkage against hydrolytic cleavage is compared mechanistically to that expected for less stable coupling through a carbamate linkage or for less stable coupling via an azomethine link.     

Polarographic study of the acid hydrolysis of ketoximes

Kinetics of the acid hydrolysis of acetophenone exime and its substituted compounds have been investigated polarographically. A detailed study of the hydrolysis of acetophenone oxime in 0·05–1·0 M HCl indicated that the rate determining step varied with acid concentration. The reaction in acid concentrations below 0·3M is catalysed by hydrogen ions while general base catalysis by water is predominant in high acid concentrations. Addition of methanol is found to decrease the rate of hydrolysis predominantly.     

Zur Reaktionsweise von Diphenylcyclopropenon mit β-Carbonyl-enolaten. I. Einsatz von Acetylaceton,Acetessigsäure-methylester, 2-Äthoxycarbonyl-cyclododecanon und Malonsäure-dimethylester

Reaction of Diphenylcyclopropenone with β-Carbonyl-enolates. I. Use of Acetylacetone, Methyl Acetoacetate, 2-Ethoxycarbonyl-cyclododecanone and Dimethyl Malonate The reaction of the sodium salts of acetylacetone ( 6 ), methyl acetoacetate (7) , 2-ethoxycarbonyl-cyclododecanone (8) , dimethyl malonate (19) and its methyl derivative 20 with diphenylcyclopropenone ( 5 ) in dimethylformamide at room temperature led to the unsaturated γ-lactones 14, 15, 17, 22 and 36 . In the case of dimethyl malonate ( 19 ), the halfester 21 , the acyl-malonic ester 24 and the indenone-malonic ester 23 were also isolated. Several intermediates and the final products were characterised by reactions and spectroscopically. A general mechanism is discussed for the addition of cyclo-propenones ( 1 ) to the enolate salts of β-dicarbonyl compounds 4 involving the bicyclic lactone-enolates 18 and 32 as intermediates. The products formed via 18 and 32 are considered to be the result of an attack of one of the oxygen atoms of the β-carbonyl-enolate anion ( 4 ), the product 24 , on the other hand, of the attack of the α-carbon atom of 4 ; in both cases the attack is on the carbonyl C-atom of 5 .     

1,4-cycloaddition of nitrosobenzene to N-ethoxycarbonylazepine

A new stable product from the reaction of nitrosobenzene and N-ethoxycarbonylazepine is shown to be a 1,4-cycloadduct.     

Crystal and molecular structure of 1-methyl-2,3,5,6-tetraphenylpiperidin-4-ol,C30H29NO

The structure of the the title compound, C₃₀H₂₉NO, was determined by X-rays.M _r =419.57, triclinic, space groupP1,a=5.8922(12),b=8.5855(11),c=12.2216(20) Å,=78.145(12)°,=79.181(15)°, =76.108(14)°,V _c =581.1(1) ų,Z=1,D _x =1.199 Mg m^–3. CuK radiation (graphite crystal monochromator, =1.54184 Å),(CuK)=5.17 cm^–1,T=290K. Final conventionalR-factor=0.039,R _w =0.042 for 2795 observed reflections and 377 variables. The structure was solved usingMultan andDirdif. With a view to determining the conformational preference of the piperidine ring when it is highly sustituted with a bulky group like the phenyl group, the present X-ray investigation was undertaken.     

A facile domino metathetic route to a thapsigargin skeleton

A facile synthesis of a 5,7,5-fused ring system that is present in thapsigargins belonging to a novel family of sesquiterpene lactones, guainanolides, using domino enyne-RCM is reported here.     

Recovery of spectral features readout with frequency-chirped laser fields

A data-processing technique is proposed for use with conventional frequency-chirped absorption spectroscopy to ensure accurate mapping of spectral features into time-domain signatures with arbitrarily fast readout chirp rates. This technique recovers the spectrum from a signal that is distorted owing to the fast chirp rate and therefore facilitates fast measurement of the spectral features over a broad spectral range with high resolution. Both numerical simulations and experimental results are presented.     

Two-point time-series measurements of minor-species concentrations in a turbulent nonpremixed flame

We report a technique that is capable of making simultaneous two-point time-series measurements of minor-species concentrations in turbulent flames. The experimental setup, which incorporates picosecond time-resolved laser-induced fluorescence, has a spatial resolution of less than 250 microm and a temporal resolution of less than 100 micros, which spatially and temporally resolve microscales in many turbulent flows. Two-point time-series data are given for a standard turbulent nonpremixed flame at Re= 10,000, including a discussion of potential implications.     

Force field parametrization through fitting on inflection points in isotherms

We present a method to determine potential parameters in molecular simulations of confined systems through fitting on experimental isotherms with inflection points. The procedure uniquely determines the adsorbent-adsorbate interaction parameters and is very sensitive to the size parameter. The inflection points in the isotherms are often related to a subtle interplay between different adsorption sites. If a force field can predict this interplay, it also reproduces the remaining part of the isotherm correctly, i.e., the Henry coefficients and saturation loadings.     

Detection of hypophosphite, phosphite, and orthophosphate in natural geothermal water by ion chromatography

Current doctrine states that phosphorus is incorporated into cells in the pentavalent(V) oxidation state as orthophosphate. However, recent studies show that microorganisms contain enzymes used to metabolize reduced forms of phosphorous, including phosphite(III) and hypophosphite(I), which suggests that there is a natural source for these chemical species. This paper will discuss suppressed conductivity ion chromatography methods developed to detect hypophosphite, phosphite, and orthophosphate in a geothermal water matrix containing fluoride, chloride, bromide, nitrate, hydrogen carbonate and sulfate. All peaks were clearly resolved, and calibrations were linear with estimated 3sigma detection limits of 0.83, 0.39, and 0.35 microM for hypophosphite, phosphite, and orthophosphate, respectively.