GFP-related chromophores: photoisomerization, thermal reversion, and DNA labelling.

Due to the pronounced effect of the confined environment on the photochemical properties of 4-hydroxybenzylidene imidazolinone (HBI), a GFP-related chromophore, imidazolidinone and imidazothiazolone analogues have been studied as fluorescent probes. Their photoisomerization and their thermal reversion were studied under 365-nm-irradiation, resulting in observation of an enthalpy-entropy compensation effect. Theoretical studies were carried out to shed light on the thermal reversion mechanism.

Products of the quenching of NO A 2Σ+ (v = 0) by N2O and CO2.

Collisional quenching of NO A (2)Σ(+) (v = 0) by N(2)O and CO(2) has been studied through measurements of vibrationally excited products by time resolved Fourier transform infrared emission. In both cases vibrationally excited NO X (2)Π (v) is seen and quantified in levels v≥ 2 with distributions which are close to statistical. However the quantum yields to produce these levels are markedly different for the two quenchers.

Infrared study of trifluoroacetic acid unpurified synthetic peptides in aqueous solution: trifluoroacetic acid removal and band assignment.

Synthetic peptide or protein samples are mostly unpurified with trifluoroacetic acid (TFA) used during the synthesis procedure, which strongly interferes with structure determination by infrared (IR) spectroscopy. The aim of this work was to propose a simple strategy to remove TFA contribution from attenuated total reflection (ATR)-IR spectra of the hexahistidine peptide (His6) in aqueous solution to study the conformation of this synthetic peptide without previous purification. Such a strategy is based on the subtraction mode widely employed to remove water contribution, and it is tested with TFA unpurified histidine as a model system.

Trifluoromethyl fluoroformyl trioxicarbonate, CF3OC(O)OOOC(O)F: the first nonsymmetric acyl trioxide.

This paper reports for the first time the synthesis and characterization of trifluoromethyl fluoroformyl trioxicarbonate, CF(3)OC(O)OOOC(O)F. The new trioxide is obtained from the gas-phase photolytic reaction of CF(3)C(O)OC(O)CF(3) and FC(O)C(O)F at 223-228 K. It is a very thermally labile molecule that decomposes at room temperature by rupture of either of the CF(3)OC(O)O-O-OC(O)F bonds.

Thermal decomposition of the perfluorinated peroxides CF3OC(O)OOC(O)F and CF3OC(O)OOCF3.

Gas phase thermal decomposition of CF(3)OC(O)OOC(O)F and CF(3)OC(O)OOCF(3) was studied at temperatures between 64 and 98 degrees C (CF(3)OC(O)OOC(O)F) and 130-165 degrees C (CF(3)OC(O)OOCF(3)) using FTIR spectroscopy to follow the course of the reaction. For both substances, the decompositions were studied with N(2) and CO as bath gases. The rate constants for the decomposition of CF(3)OC(O)OOC(O)F in nitrogen and carbon monoxide fit the Arrhenius equations k(N)2 = (3.

Structural and conformational properties of fluoroformic acid anhydride, FC(O)OC(O)F.

The conformational properties and geometric structures of fluoroformic acid anhydride, FC(O)OC(O)F, have been studied by vibrational spectroscopy, gas electron diffraction (GED), single-crystal X-ray diffraction, and quantum chemical calculations (HF, MP2, and B3LYP methods with 6-31G* and B3LYP/6-311+G* basis sets). Satellite bands in the IR matrix spectra, which increase in intensity when the matrix gas mixture is heated prior to deposition as a matrix, indicate the presence of two conformers at room temperature. According to the electron diffraction analysis, the prevailing conformer is of C(2) symmetry with both C=O bonds synperiplanar with respect to the opposite C-O bond ([sp, sp] conformer).

Novel synthesis of trifluoromethylnitrate, CF3ONO2.

Irradiation of the equilibrated gas mixture CF(3)O(2)NO(2)<==>CF(3)O(2) + NO(2) at room temperature using the output from UV fluorescent "blacklamps" provides a rapid and simple method for the production of pure samples of CF(3)ONO(2) in high yield (ca. 80%). This synthetic procedure is superior to that described in the literature in two aspects: (i) the yield of CF(3)ONO(2) is approximately a factor of 5 greater, and (ii) the present method avoids the need for a high pressure (70 bar) reactor.

A systematic investigation into the mechanism of the reaction between CF3 radicals and CO/O2.

A complete study of the reaction of CF(3) radicals in the presence of CO and O(2) was carried out by using isotopically labeled reagents to form, selectively, all the possible isotopomers of the intermediate trioxide, CF(3)OC(O)OOOC(O)OCF(3), and of the stable peroxide, CF(3)OC(O)OOC(O)OCF(3). Analyses were carried out by means of FTIR spectroscopy in combination with ab initio calculations. At temperatures close to 0 degrees C, the acyloxy radicals formed were shown to exist long enough to yield a statistical mixture of isotopomers.

The open-chain trioxide CF3OC(O)OOOC(O)OCF3.

The open-chain trioxide CF(3)OC(O)OOOC(O)OCF(3) is synthesised by a photochemical reaction of CF(3)C(O)OC(O)CF(3), CO and O(2) under a low-pressure mercury lamp at -40 degrees C. The isolated trioxide is a colourless solid at -40 degrees C and is characterised by IR, Raman, UV and NMR spectroscopy. The compound is thermally stable up to -30 degrees C and decomposes with a half-life of 1 min at room temperature.

Synthesis and characterization of trifluoromethyl fluoroformyl peroxycarbonate, CF3OC(O)OOC(O)F.

The synthesis of CF(3)OC(O)OOC(O)F is accomplished by the photolysis of a mixture of (CF(3)CO)(2)O, FC(O)C(O)F, CO, and O(2) at -15 degrees C using a low-pressure mercury lamp. The new peroxide is obtained in pure form in low yield after repeated trap-to-trap condensation and is characterized by NMR, IR, Raman, and UV spectroscopy. Geometrical parameters were studied by ab initio methods [B3LYP/6-311+G(d)].