The synthesis of some benzo[4,5]cyclohept[1,2,3-ij]isoquinolines

A facile synthesis and spectroscopic properties of various oxidation states of the novel benzo[4,5]cyclohept[1,2,3-ij]isoquinoline system are described. The synthesis involves the condensation of 5H-dibenzo[a,d]cyclohepten-5-one, or of its 10,11-dihydro derivative, with amino-acetaldehyde diethylacetal, followed by treatment of the resultant imines with polyphosphoric acid to afford the novel tetracyclic system in high yields.     

Spectrophotometric determination of bismuth in copper and cartridge brass by the iodide method

An improved spectrophotometric method is proposed for the determination with iodide of trace amounts of bismuth in copper and cartridge brass. The sample is dissolved in nitric acid and the bismuth is separated from the copper by an ammoniacal precipitation in the presence of iron(III) hydroxide as a gathering agent. The hydroxide precipitate is dissolved in hydrochloric acid, sulfuric acid is added, the solution is evaporated to a few ml, hydrobromic acid is added to volatilize the antimony and tin, and the solution is evaporated to fumes of sulfuric acid. The bismuth iodide color is then developed with a composite potassium iodide—sodium hypophosphite reagent. Factors affecting the bismuth iodide color are investigated.     

Immobilized enzyme electrode for the determination of salicylate in blood serum

This determination of salicylate in blood serum is based on application of an immobilized enzyme electrode. Salicylate hydroxylase (E.C.1.14.13.1) is chemically immobilized onto a pig intestine mounted on an oxygen electrode. The signals are monitored amperometrically and the resulting output voltage is read using a simple adapter. The experimental parameters and possible interferences are discussed. Samples containing 1.0 × 10^?5?1.87 × 10^?3 M (1.6–300 μg ml^?1) salicylate were assayed with relative standard deviations between 1.3% and 6% and recoveries between 98.7 and 103%. Results obtained by the proposed method and by the established clinical method for randomly spiked pooled serum samples correlated well (r = 0.99).     

A systematic nomenclature for cascade polymers

Cascade (dendritic) polymers are discrete, highly branched, monodisperse polymers that possess branching patterns described by a mathematical progression. A systematic nomenclature that accurately represents these molecules is described. © 1993 John Wiley & Sons, Inc.     

Eliminating positively charged lysine epsilon-NH3+ groups on the surface of carbonic anhydrase has no significant influence on its folding from sodium dodecyl sulfate

This study compares the folding of two polypeptides--bovine carbonic anhydrase (BCA) and peracetylated BCA (BCA-Ac(18))--having the same sequence of amino acids but differing by 18 formal units of charge, from a solution containing denaturing concentrations of sodium dodecyl sulfate (SDS). Acetylation of BCA with acetic anhydride converts all 18 lysine-epsilon-NH(3)(+) groups to lysine-epsilon-NHCOCH(3) groups and generates BCA-Ac(18). Both BCA and BCA-Ac(18) are catalytically active, and circular dichroism spectroscopy (CD) suggests that they have similar secondary and tertiary structures. SDS at concentrations above approximately 10 mM denatured both proteins. When the SDS was removed by dialysis, both proteins were regenerated in native form. This study suggests that large differences in the net charge of the polypeptide have no significant influence on the structure, the ability to refold, or the rate of refolding of this protein from solutions containing SDS. This study reinforces the idea that charged residues on the surface of BCA do not guide protein folding and raises the broader question of why proteins have charged residues on their surface, outside of the region of the active site.     

Polystyrene resins with immobilized polyamines: Preparation,characterization, and ability to bind Cu(II) ions

Three polyamine ligands, ethylenediamine (EDA), diethylenetriamine (DTA), and triethylenetetramine (TETA), were bound to three chloromethylated “popcorn” polystyrene resins (16, 50, and 100% phenyl ring substitution) with the use of pyridine as the reaction medium. The rate of chloride displacement decreased with increasing molecular weight of the amine and higher degree of resin chloromethylation, while the extent of multiple attachments to the polymer matrix increased. The additional crosslinking, a result of multiple attachments, caused the polyamine resins to swell to a lesser extent in pyridine and water. The ability of the insoluble polyamine–polystyrene resins to chelate Cu²⁺ ions from dilute solutions (200 ppm) was determined at pH 5. With EDA resins the capacity for Cu²⁺ increased with increasing amount of the bound polyamine, with DTA it remained unchanged, while with TETA it was found to decrease.     

Understanding the factors controlling the photo-oxidation of natural DNA by enantiomerically pure intercalating ruthenium polypyridyl complexes through TA/TRIR studies with polydeoxynucleotides and mixed sequence oligodeoxynucleotides

Ruthenium polypyridyl complexes which can sensitise the photo-oxidation of nucleic acids and other biological molecules show potential for photo-therapeutic applications. In this article a combination of transient visible absorption (TrA) and time-resolved infra-red (TRIR) spectroscopy are used to compare the photo-oxidation of guanine by the enantiomers of [Ru(TAP)₂(dppz)]²⁺ in both polymeric {poly(dG-dC), poly(dA-dT) and natural DNA} and small mixed-sequence duplex-forming oligodeoxynucleotides. The products of electron transfer are readily monitored by the appearance of a characteristic TRIR band centred at ca. 1700 cm⁻¹ for the guanine radical cation and a band centered at ca. 515 nm in the TrA for the reduced ruthenium complex. It is found that efficient electron transfer requires that the complex be intercalated at a G-C base-pair containing site. Significantly, changes in the nucleobase vibrations of the TRIR spectra induced by the bound excited state before electron transfer takes place are used to identify preferred intercalation sites in mixed-sequence oligodeoxynucleotides and natural DNA. Interestingly, with natural DNA, while it is found that quenching is inefficient in the picosecond range, a slower electron transfer process occurs, which is not found with the mixed-sequence duplex-forming oligodeoxynucleotides studied.

Efficient electron transfer requires the complex to be intercalated at a G-C base-pair. Identification of preferred intercalation sites is achieved by TRIR monitoring of the nucleobase vibrations before electron transfer.     

Investigation of the behavior of arenediazonium salts with olefins in BmimPF6

The palladium-catalyzed reactions of olefins with arenediazonium salts in ionic liquids were investigated. For methyl acrylate and methyl acrylonitrile, normal Heck cross-coupling products are obtained in good yields. However, highly selective dimerization products are formed in excellent yields for styrenes. The catalyst system can be recycled.     

A convenient synthesis of cis and trans 4-tert-butoxycarbonyl-substituted cyclohexylglycine

A novel synthesis of cis and trans substituted 4-tert-butoxycarbonyl cyclohexylglycines via asymmetric aminohydroxylation of vinyl styrene followed by reduction of the aromatic ring and subsequent oxidation is reported.     

13C-NMR relaxation studies of alkali metal cryptate complexes

The ¹³C spin-lattice relaxation times (T₁'s) of cryptands [2.1.1], [2.2.1] and [2.2.2] as well as those of the corresponding cryptate complexes with Li⁺, Na⁺, and K⁺ in CDCl₃ and CH₃OH:D₂O (90:10) were measured and the results are interpreted in terms of molecular compression and desolvation effects.