The chemical shift tensor for the hydroxyl proton: Ca(OH)2

The proton chemical shift tensor of the hydroxyl proton in calcium hydroxide has been measured using multiple pulse NMR techniques. The tensor is axially symmetric with susceptibility corrected components σ_tT = ?9.3 ± 1 ppm and

ppm relative to TMS. 792 79     

N,N-difluorotris(tert-butyl)silylamine-the first organosilyl difluoroamine. Synthesis and computational studies

The synthesis and characterization of the first stable trialkyl(difluoroamino)silane, R3SiNF2, as well as of R3SiNHF and R3SiN(CH3)F in moderate yields are reported. The (difluoroamino)silane has promise as a new synthon for the introduction of the -NF2 group into a variety of electrophilic inorganic and organic substrates. Activation barriers and relative energies were calculated for the unimolecular decompositions of Me3SiCF3 and t-Bu3SiNF2 using density functional theory (B3LYP/6-31G). The calculated activation energies confirm the long-assumed kinetic stability of Me3SiCF3.     

The theory and practice of liquid-liquid partition chromatography of phenols

An equation is given for the design of liquid-liquid partition Chromatographie columns which relates the separation factors and column, characteristics with the number of theoretical plates required for a desired separation. This equation should be applicable to the separation of acids or bases when a buffered stationary phase is used, thus permitting a more rational approach to this technique.Using this approach a complete separation of the three isomeric cresols has been achieved. Methods are given for this determination and also for the determination of phenol in tar acid mixtures.     

PHOTOSENSITIZATION OF MURINE TUMOR, VASCULATURE and SKIN BY 5-AMINOLEVULINIC ACID-INDUCED PORPHYRIN

Abstract— The effects of topical and systemic administration of 5-aminolevulinic acid (ALA) were examined in several murine tumor systems with regard to porphyrin accumulation kinetics in tumor, skin and blood, vascular and tumor cell photosensitization and tumor response after light exposure. Marked, transient increases in porphyrin levels were observed in tumor and skin after systemic and topical ALA. Rapid, transient, dose-dependent porphyrin increases were also observed in blood; these were pronounced after systemic ALA injection and mild after topical application. They were highest within 1 h after ALA injection, thereafter declining rapidly. This matched the clearing kinetics of injected exogenous protoporphyrin IX (PpIX). Initially, vascular photosensitivity changed inversely to blood porphyrin levels, increasing gradually up to 5 h post-ALA, as porphyrin was clearing from the bloodstream. This pattern was again matched by injected, exogenous PpIX. After therapeutic tumor treatment vascular disruption of the tumor bed, while observed, was incomplete, especially at the tumor base. Minimal direct tumor cell kill was found at low photodynamic therapy (PDT) doses (250 mg/kg ALA, 135 J/cm² light). Significant, but limited (<1 log) direct photodynamic tumor cell kill was obtained when the PDT dose was raised to 500 mg/kg systemic ALA, followed 3 h later by 270 J/cm², a dose that was however toxic to the animals. The further reduction of clonogenic tumor cells over 24 h following treatment was moderate and probably limited by the incomplete disruption of the vasculature. Tumor responses were highest when light treatment was carried out at the time of highest tumor porphyrin content rather than at the time of highest vascular photosensitivity. Tumor destruction did not reach the tumor base, regardless of treatment conditions.     

Diatropicity of 3,4,7,8,9,10,13,14-octadehydro[14]annulenes: a combined experimental and theoretical investigation

The synthesis and study of a series of octadehydro[14]annulenes is described. The aromaticity of these annulenes was investigated through examination of experimental data from arene-fused systems as well as calculated nucleus-independent chemical shifts (NICS) and bond lengths. Benzene ring fusion to the parent system results in a stepwise loss in aromaticity as the number of fused rings is increased from one to two to three. This decrease in annulenic ring current is manifested in the alkene proton chemical shifts (0-2 benzenes) as well as the NICS (0-3 benzenes). Comparison of isomeric thiophene-fused annulenes shows further evidence of ring current competition as these allow for observation of intermittent degrees of delocalization throughout the annulenic core. A consistent relationship between the magnitude of the NICS values and the degree of benzannelation is also observed.     

Influence of vanadium doping on the behavior of YBa_2Cu_3O_7-y

YBa2Cu3-xVxO7-y(x=0, 0.1, 0.2, 0.3, 0.4, 0.5 and 0.6) superconductors have been prepared. X-ray diffraction shows that the system remains orthorhombic for all compositions studied, but for x > 0.4 V2O5 was detected as an impurity phase. Substitution of V5+ for Cu2+ occurs in the Cu(2) sites on the Cu(2)-O planes. The introduction of the high valence element, vanadium, produces the extra free-electrons. These electrons recombine with the positive carrier of the system. It makes depression of the mobility and the Hall number of YBa2Cu3-xVxO7-v and also results in a depression of TC.     

Syntheses of perfluorinated epoxides,diepoxides, and a novel rearrangement

t-Butylhydroperoxide/butyl-lithium is a good reagent for synthesis of epoxides and diepoxides from polyfluorinated-alkenes and-polyenes. This reagent and calcium hypochlorite both give a novel diepoxide 5 from perfluoro-3,4-dimethyl-2,4-diene 1; diepoxide 5 undergoes a novel rearrangement, at 200°C, to the corresponding 1,4-dioxine derivative 18. Possible mechanisms are discussed.     

CHEMILUMINESCENCE AND FLUORESCENCE OF THE EUROPIUM IONS-ADENINE NUCLEOTIDES SYSTEM AND ITS POSSIBLE BIOLOGICAL SIGNIFICANCE

Abstract— Chemiluminescence of the Eu(II)/Eu(III)-adenine nucleotide-H₂O₂ system and fluorescence of the Eu(III)-adenosine triphosphate system have been investigated. The spectral distribution of the chemiluminescence emission has shown an occurrence of three main bands (Λ=470–480,590–620 and ca. 700 nm). The energy transfer process from the adenosine triphosphate molecules to the Eu(III) ions has been observed in the fluorescence spectrum. The examined chemiluminescence and fluorescence spectra show that these both kinds of emission originate from the ⁵ D _***τ⁷F_*** ( n =1–4) transitions in the Eu(III) ions.     

Self-assembly of tetrahedral and trigonal antiprismatic clusters [Fe4(L4)4] and [Fe6(L5)6] on the basis of trigonal tris-bidentate chelators

In a one-pot reaction, the tetranuclear iron chelate complex [Fe4(L4)4] 6 was generated from benzene-1,3,5-tricarboxylic acid trichloride (4), bis-tert-butyl malonate (5a), methyllithium, and iron(II) dichloride under aerobic conditions. Alternatively, hexanuclear iron chelate complex [Fe(L5)6] 7 was formed starting from bis-para-tolyl malonate (5b) by employing identical reaction conditions to those applied for the synthesis of 6. The clusters 6 and 7 are present as racemic mixtures of homoconfigurational (delta,delta,delta,delta)/(lambda,lambda,lambda,lambda)-fac or (delta,delta,delta,delta,delta,delta)/(lambda,lambda,lambda,lambda,lambda,lambda)-fac stereoisomers. The structures of 6 and 7 were unequivocally resolved by single-crystal X-ray analyses. The all-iron(III) character of 6 and 7 was determined by M?ssbauer spectroscopy.