Formaldoxime hydrogen bonded complexes with ammonia and hydrogen chloride.

An infrared spectroscopic and MP2/6-311++G(2d,2p) study of hydrogen bonded complexes of formaldoxime with ammonia and hydrogen chloride trapped in solid argon matrices is reported. Both 1:1 and 1:2 complexes between formaldoxime and ammonia, hydrogen chloride have been identified in the CH2NOH/NH3/Ar, CH2NOH/HCl/Ar matrices, respectively, their structures were determined by comparison of the spectra with the results of calculations. In the 1:1 complexes present in the argon matrices the OH group of formaldoxime acts as a proton donor for ammonia and the nitrogen atom acts as a proton acceptor for hydrogen chloride. In the 1:2 complexes ammonia or hydrogen chloride dimers interact both with the OH group and the nitrogen atom of CH2NOH to form seven membered cyclic structures stabilized by three hydrogen bonds. The theoretical spectra generally agree well with the experimental ones, but they seriously underestimate the shift of the OH stretch for the 1:1 CH2NOH⋯NH3 complex.

Alkylation of gold surface by treatment with C18H37HgOTs and anodic Hg stripping.

Treatment of a gold surface with a solution of C18H37HgOTs under ambient conditions results in the formation of a covalently adsorbed monolayer containing alkyl chains attached directly to gold, Hg(0) atoms, and no tosyl groups. It is stable against a variety of chemical agents. When the initial deposition is performed at a positive applied potential and is followed by oxidative electrochemical stripping, the mercury can be completely removed, leaving a gold surface covered only with alkyl chains. The details of the attachment structure are not known. The conclusions are based on infrared spectroscopy, X-ray and UV photoelectron spectroscopy, ellipsometry, contact angle goniometry, differential pulse polarography, and measurements of electrode blocking and electrochemical admittance.

Postoperative pain combating and evaluation of patient's satisfaction from analgesic treatment.

UNLABELLED: Pain is an inherent element of human life and one of the most unpleasant and unwanted experiences, causing fear, anxiety, or even anger. Pain is one of the strongest and most annoying experiences with a clear subjective character indicating risk to an organism or personality, or expressing its damage. Despite the intense development of medicine and modern surgical methods, surgery is still dealing with the huge problem of pain and its proper control. Effective combating of postoperative pain is currently a priority of modern surgical treatment, since it not only minimizes the patient's suffering, but also improves the quality of his/her life, decreases the number of complications, shortens the hospital stay, and at the same time decreases the costs of treatment. OBJECTIVE: The purpose of the presented study is analysis of the frequency of occurrence, intensity of postoperative pain and evaluation of patients' satisfaction with analgesic treatment. MATERIAL AND METHODS: The research included 100 patients from the Department of Trauma and Orthopaedic Surgery, 54% of women and 46% of men, 38% of whom were urban inhabitants and 62% rural inhabitants of the Podkarpackie voivodeship in south-east Poland. The research method used in was a diagnostic survey, analysis of documentation and pain measurement with numerical and visual analogue scales. RESULTS: Pain occurred from 12 - 24 hours before the procedure in the case of 20% of the patients, whereas 48% of the respondents complained about pain more than 1 day before the procedure. Pain before the procedure was a partial difficulty in self-care and physical activity for 26% of the subjects. The biggest amount of patients (30%) were afraid of postoperative complications. In the first day after the procedure, as much as 84% of the respondents complained about pain, on the second day the pain was felt by 74% of the patients, and on the third day by 57% of the respondents. Pain intensity, which was moderate in accordance with the VAS scale, was signalized by 35% of patients, strong pain was reported by 60% of the patients, and 5% of men evaluated the pain as very strong. CONCLUSIONS: Postoperative pain was only a partial difficulty for the majority of patients, administration of a painkiller brought relief to the majority of patients, who had been afraid of the surgical procedure because of postoperative complications, not postoperative pain.

Complexation of formaldoxime with water. Infrared matrix isolation and theoretical studies.

The 1:1, 1:2 and 2:1 formaldoxime-water complexes isolated in the argon matrices have been studied by help of FTIR spectroscopy and MP2/6-311++G(2d,2p) method. The calculations predicted the stability of the three CH(2)NOH···H(2)O isomeric complexes, three CH(2)NOH···(H(2)O)(2) ones and one (CH(2)NOH)(2)···H(2)O complex. The analysis of the experimental spectra and their comparison with theoretical ones indicated that both the 1:1 and 1:2 complexes trapped in solid argon have the most stable cyclic structures stabilized by the O-H···O and O-H···N bonds between the formaldoxime and water molecules. In the 1:2 complex formaldoxime interacts with the water dimer, one H(2)O molecule acts as a proton acceptor for the OH group of formaldoxime whereas the second H(2)O molecule acts as a proton donor toward the nitrogen atom of the formaldoxime molecule. In the (CH(2)NOH)(2)···H(2)O complex the OH group of the water molecule acts as a proton donor toward one of the oxygen atoms of the formaldoxime cyclic dimer.

Preparation of covalent long-chain trialkylstannyl and trialkylsilyl salts and an examination of their adsorption on gold.

We report the attachment of alkyl residues to a gold surface through a tin atom. Covalent trialkylstannyl and trialkylsilyl salts of trifluoromethanesulfonic, trifluoroacetic, and p-toluenesulfonic acids containing one to three C(18)H(37) chains and two to no CH(3) groups in the molecule have been synthesized. They were tested for adsorption on gold from solution under ambient conditions using ellipsometry, FTIR spectroscopy, contact angle, and electrode-blocking measurements. All nine trialkylstannyl salts form similar stable monolayers with the loss of the acid residue and form no multilayers. The monolayers differ from those formed from alkanethiols. They are much thinner, less ordered, less hydrophobic, and only slightly electrode-blocking. Their stability to solvents, bases, acids, and reductants is somewhat lower than that of a 1-octadecanethiol monolayer, but their resistance to heat and oxidants, including air, is slightly better. The distinctive properties of these monolayers may be of interest in certain circumstances, but we expect the attachment of molecules to gold through a tin atom to be of the most value in work with single-molecule structures. The trialkylsilyl salts showed no tendency to adsorb onto gold under these conditions.

Photo-induced hydrogen exchange reaction between methanol and glyoxal: formation of hydroxyketene.

We study the structure and photochemistry of the glyoxal-methanol system (G-MeOH) by means of FTIR matrix isolation spectroscopy and ab initio calculations. The FTIR spectra show that the non-hydrogen-bonded complex, G-MeOH-1, is present in an inert environment of solid argon. MP2/aug-cc-pVDZ calculations indicate that G-MeOH-1 is the most stable complex among the five optimized structures. The interaction energy partitioned according to the symmetry-adapted perturbation theory (SAPT) scheme demonstrates that the dispersion energy gives a larger contribution to the stabilization of a non-hydrogen-bonded G-MeOH-1 complex than compared to the hydrogen-bonded ones. The irradiation of G-MeOH-1 with the filtered output of a mercury lamp (lambda>370 nm) leads to its photo-conversion into the hydroxyketene-methanol complex HK-MeOH-1. The identity of HK-MeOH-1 is confirmed by both FTIR spectroscopy and MP2/aug-cc-pVDZ calculations. An experiment with deuterated methanol (CH(3)OD) evidences that hydroxyketene is formed in a photo-induced hydrogen exchange reaction between glyoxal and methanol. The pathway for the photo-conversion of G-MeOH-1 to HK-MeOH-1 is studied by a coupled-cluster method [CR-CC(2,3)]. The calculations confirm our experimental findings that the reaction proceeds via hydrogen atom exchange between the OH group of methanol and CH group of glyoxal.

Complexes of atmospheric alpha-dicarbonyls with water: FTIR matrix isolation and theoretical study.

The complexes of glyoxal (Gly), methylglyoxal (MGly), and diacetyl (DAc) with water have been studied using Fourier transform infrared (FTIR) matrix isolation spectroscopy and MP2 calculations with 6-311++G(2d,2p) basis set. The analysis of the experimental spectra of the Gly(MGly,DAc)/H2O/Ar matrixes indicates formation of one Gly...H2O complex, three MGly...H2O complexes, and two DAc...H2O ones. All the complexes are stabilized by the O-H...O(C) hydrogen bond between the water molecule and carbonyl oxygen as evidenced by the strong perturbation of the O-H, C=O stretching vibrations. The blue shift of the CH stretching vibration in the Gly...H2O complex and in two MGly...H2O ones suggests that these complexes are additionally stabilized by the improper C-H...O(H2) hydrogen bonding. The theoretical calculations confirm the experimental findings. They evidence the stability of three hydrogen-bonded Gly...H2O and DAc...H2O complexes and six MGly...H2O ones stabilized by the O-H...O(C) hydrogen bond. The calculated vibrational frequencies and geometrical parameters indicate that one DAc..H2O complexes, two Gly...H2O, and three MGly...H2O ones are additionally stabilized by the improper hydrogen bonding between the C-H group and water oxygen. The comparison of the theoretical frequencies with the experimental ones allowed us to attribute the calculated structures to the complexes present in the matrixes.