racemic propargylic halides: Topics by WorldWideScience.org

Fluoride ion catalyzed alkylation of purines, pyrimidines, nucleosides and nucleotides using alky halides.

Data on the reactions of thiocyanogen and thiocyanogen halides with unsaturated compounds are systematised. The kinetic and stereo- and regiochemical regularities of these reactions are analysed. The bibliography includes 81 references.

1998-05-31

UK PubMed Central (United Kingdom)

Alkyl halides react rapidly with purines and pyrimidines in the presence of fluoride ion. Alkylation of thymidine leads to novel dimeric nucleoside derivatives bridged through N3. Alkylation of thymidine...Full Text Available

1979-04-01

Electrolysis of halide-containing solutions with platinum based amorphous metal alloy anodes

Terrestrial and Meteorite Carbon Appear to Have the Same Isotopic Composition

A process for the generation of halogens from halide-containing solutions includes the step of conducting electrolysis of the solutions in an electrolytic cell having a platinum based amorphous metal alloy anode.

1985-12-24

UK PubMed Central (United Kingdom)

The carbon-isotope ratio recently obtained for the carbon found in the Murchison meteorite, which has been shown (by the racemic nature of twelve component amino acids) to be free of terrestrial contamination,...Full Text Available

1971-02-01

Endocrine and Neurochemical Effects of 3,4-Methylenedioxymethamphetamine and Its Stereoisomers in Rhesus Monkeys

UK PubMed Central (United Kingdom)

3,4-Methylenedioxymethamphetamine (MDMA) is an amphetamine derivative that elicits complex biological effects in humans. One plausible mechanism for this phenomenon is that racemic MDMA is composed...Full Text Available

2010-08-01

Some observations on amino acid racemization under pyrolytic temperatures and inorganic oxide-catalyzed intermolecular condensation.

Preparation of radioactive lead complexes utilizing Chelex methodology

The problem of homochirality is of crucial importance for the origins of Life. While most laboratory studies are focused on the search of physical and chemical sources of handedness in the Universe, they reflect only one aspect of the problem: the origin of homochiral biomolecules. At the same time, any space environments where biomolecules are expected to form and where they have to pass through before the first primitive forms of Life emerge, include strong irradiation or/and high temperatures. This automatically implies the possibility of losing the optical activity, i.e. racemization. The simulation experiments performed by our group deal with the following two aspects of amino acid abiotic chemistry: (1) amino acid pyrolysis associated with their extraterrestrial delivery; and (2) peptide formation from amino acids catalyzed by inorganic oxides. According to our observations, the racemization phenomena are very common in the systems ...

2001-01-01

Preparation of radioactive lead complexes utilizing Chelex methodology

The use of Chelex resin for the synthesis of radioactive lead complexes has been explored. The process involved immobilization of {sup 203}Pb on the resin and subsequent elution of complexed lead by chelating agents. {sup 203}Pb complexes derived from meso- and racemic dimercaptosuccinic acid (meso-DMSA, rac-DMSA) were prepared and assessed for stability in vitro.

1996-11-01

Esterification of chiral secondary alcohols with fatty acid in organic solvents by polyethylene glycol-modified lipase.

The use of Chelex resin for the synthesis of radioactive lead complexes has been explored. The process involved immobilization of "2"0"3Pb on the resin and subsequent elution of complexed lead by chelating agents. "2"0"3Pb complexes derived from meso- and racemic dimercaptosuccinic acid (meso-DMSA, rac-DMSA) were prepared and assessed for stability in vitro.

1996-11-01

Structure of molten alkali halides

Lipase from Pseudomonas fragi 22.39B was modified with polyethylene glycol. The modified lipase (PEG-lipase) was soluble and active in organic solvents such as benzene and 1,1,1-trichloroethane. PEG-lipase catalyzed esterification of chiral secondary alcohols with fatty acids in benzene and exhibited preference for R isomers over S isomers. Km and Vmax values for each isomer of various alcohols were obtained by kinetic study of the esterification in benzene. PEG-lipase-catalyzed esterification leads to optical resolution of a racemic alcohol. PMID:2635854

1989-11-01

Structure of molten alkali halides

The results of X-ray and neutron diffraction experiments on molten alkali halides in which some data of our experiments by X-ray diffraction such as those of molten LiCl, NaCl, KCl, LiBr and KBr are included were summarized. The first peak positions in the radial distribution function in molten alkali halides by X-ray or neutron diffraction experiments are always longer than those by computer simulations and the differences of 0.1 -- 0.3 A exceed the experimental error. It seems to be due to the deformation of the electron shell. In the computer simulation, the shell model which has the spherical deformation was expected to have a closer value of the first peak position to the experimental one than the rigid ion model by taking the polarization of ions. However, no change in the first peak position was found. Therefore, the non-spherical deformation of electron shell at the point where ions are in contact with each other has to be taken into ...

1982-06-01

Role of the triple bond in acid corrosion inhibition

The results of X-ray and neutron diffraction experiments on molten alkali halides in which some data of our experiments by X-ray diffraction such as those of molten LiCl, NaCl, KCl, LiBr and KBr are included were summarized. The first peak positions in the radial distribution function in molten alkali halides by X-ray or neutron diffraction experiments are always longer than those by computer simulations and the differences of 0.1 -- 0.3 A exceed the experimental error. It seems to be due to the deformation of the electron shell. In the computer simulation, the shell model which has the spherical deformation was expected to have more closer value of the first peak position to the experimental one than the rigid ion model by taking the polarization of ions. However, no change in the first peak position was found. Therefore, the non-spherical deformation of electron shell at the point where ions are in contact with each other has to be taken into ...

1982-01-01

Inhibition of corrosion resistant alloys in hot hydrochloric acid solutions

It is now over 30 yr since the original discovery was made that acetylenic compounds are effective in inhibiting the corrosion of iron in acid media. Since then, the industrial practice of oil-well acidizing has become well-established, with key acetylenic compounds such as propargyl alcohol, hexynol, and ethyl octynol assuming increasingly important roles. New and more stable triple-bonded compounds properly formulated and synergized with nitrogen compounds are expected to be used more extensively as temperature, stability, and performance requirements increase. An evaluation is made of the structural features which enhance or limit the corrosion performance of a given acetylenic. New data involving mixtures of acetylenics, hydrogen-bonded complexes, and the use of new nitrogen synergists are covered also. Tabular data at 200/sup 0/F approximate the more strenuous conditions of an oil-well acidizing job using N-80 tubing. The performance of such inhibitors as ...

1970-01-01

Preparation of AgX (X = Cl, I) nanoparticles using ionic liquids

Weight loss measurements were performed in 20% and 28% hydrochloric acid at 90/sup 0/C on carbon steel, 22Cr5Ni duplex stainless steel, and two superaustenitic steels - 27Cr31Ni3Mo and 19Cr25Ni4Mo -, in presence of organic substances used singly or mixed. The organic substances examined were quaternary ammonium salts (1-4-pyridyl)-pyridinium chloride hydrochloride, dodecylpyridiniumchloride, benzyldimethylstearylammonium chloride, and dodecyltrimethylammonium bromide), alkynols (1-octyn-3-ol, propargyl alcohol) and trans-cinnamaldehyde. The synergistic effect of potassium iodide on the inhibitive efficiency of the organic substances was studied. The variations of corrosion rate during the test time (normally six hours) were recorded by means of polarization resistance measurements. Polarization curves were also recorded. The results showed that the corrosion rates of the four steels examined can be reduced to less than 1 mg/cm/sup -2/ . h/sup -1/ using ternary ...

1988-12-01

Laboratory studies of the sensitivity of tropospheric ozone to the chemistry of sea salt aerosol. Final report, September 15, 1993--September 14, 1994

Nanoparticles of silver halides have been prepared by mixing silver halide powder with a single liquid phase consisting of an ionic liquid, isooctane, n-decanol and water. Much higher nanoparticle concentrations may be formed with ionic liquids using this new simple method than are found with conventionally applied surfactants. This method also emphasizes the applicability of ionic liquids as versatile components in microemulsions and as solvents for the synthesis of nanomaterials. The effect on the nanoparticles of changing the composition of the liquid mixtures and the nature of the ionic liquid is analysed. High nanoparticle concentrations were only found with chloride based ionic liquids, indicating the importance of the ionic liquid anion in the mechanism of the reaction.

2008-03-12

New b-amino-a-trifluoromethyl alcohols and their exploration in the synthesis of trifluoromethylated imidazole derivatives

Ozone plays a critical role in both the chemistry and radiation balance of the troposphere. Understanding the factors controlling tropospheric ozone levels is critical to our understanding of a variety of issues in global chemistry and climate change. Chlorine atoms have the potential to contribute significantly to the ozone balance in the free troposphere. They can react directly with ozone or alternately, with organics and may actually lead to the formation of ozone in the presence of sufficient NO. Reactions of alkali halides in sea salt particles are a potential source of atomic chlorine, hence reactions of these alkali halides, especially those producing precursors to atomic chlorine, are of great interest. Finally, the mechanisms, intermediates and products of the Cl-biogenic reactions are unknown; these could serve as unique markers of chlorine atom chemistry in the troposphere, and hence are important to define.

1994-11-15

British Library Electronic Table of Contents (United Kingdom)

Racemic and enantiomerically pure b-amino-a-trifluoromethyl alcohols were obtained via sequential nucleophilic trifluoromethylation of selected a-imino ketones, derived from arylglyoxals, and subsequent removal of the MeO or Ph(Me)CH substituent, respectively, located at the N-atom. The obtained products, containing a primary amino group, were used for the synthesis of imidazole N-oxides bearing a trifluoromethyl group as a part of the N(1)-alkyl chain. Imidazole N-oxides with an electron-withdrawing ester group at C(4) underwent spontaneous isomerization under the reaction conditions, and the corresponding imidazol-2-ones derivatives were isolated as final products.

2011-01-01

Stable halogen complexes of astatine cations in aqueous solutions

Efficient synthesis of unsymmetric diarylalkynes from decarboxylative coupling in a continuous flow reaction system

Halide complexes of astatine cations At"+ and AtO"+ were prepared and their rate of migration was measured. The complexes are of the type AtX_2"- and AtOX_2"- (X = Cl"-, Br"-, I"-). The bromo complexes, AtBr_2"- and AtOBr_2"-, have a higher stability than the chloro complexes. The hydrolysis in weakly alkaline solution of AtX_2"- resulted At"-, and that of AtOX_2"- AtO_2"-. (author).

British Library Electronic Table of Contents (United Kingdom)

Unsymmetric diaryl alkynes were synthesized from the palladium-catalyzed decarboxylative coupling of aryl halides and propiolic acid using a continuous flow reaction system. This flow chemistry system continuously gave the desired products in moderate to good yields, and produced less byproduct than was formed in the batch reaction.

2011-01-01

Experimental determination of the thermal diffusivity of molten alkali halides by the forced Rayleigh scattering method. I. Molten LiCl, NaCl, KCl, RbCl, and CsCl

Electron spin resonance study of the equilibrium between tetrahalogeno- and pentahalogeno-nitridotechnetate (VI) ions in solution

As a series of experimental determinations of the thermal diffusivity of molten alkali halides, this paper describes measurements on five molten alkali metal chlorides (LiCl, NaCl, KCl, RbCl, and CsCl) in the temperature range up to 1440 K by the forced Rayleigh scattering method. K[sub 2]Cr[sub 2]O[sub 7] is employed as a dye substance to color the transparent molten salts. In comparison with the present results converted into thermal conductivity, most of the previous experimental data obtained by steady-state methods show larger values, up to about five times, which may be due to the systematic error caused by the presence of convection and radiation. It is found that the thermal conductivity of these series of molten alkali metal chlorides decreases with increasing molecular weight, and their temperature coefficients are weakly negative. 24 refs., 9 figs., 6 tabs.

1992-07-01

1 2 3

Comparison of LaBr_3:Ce and NaI(Tl) Scintillators for Radio-Isotope Identification Devices

The e.s.r. spectra of (AsPh/sub 4/)(TcNCl/sub 4/), Cs/sub 2/(TcNCl/sub 5/), (AsPh/sub 4/)(TcNBr/sub 4/), and Cs/sub 2/(TcNBr/sub 5/) have been studied in non-aqueous and concentrated aqueous acid solutions. None of the spectra shows evidence for the co-ordination of a fifth halide ligand in the trans position, even under circumstances such as a 2 000-fold excess of halide ion, which would be expected to favour the formation of the pentahalogenonitridotechnetate ion. The predominant species in solution is the tetrahalogenonitridotechnetate ion, where the trans position may be vacant or occupied by a solvent molecule in the case of the non-aqeuous solvents and by a water molecule in the case of HCl and HBr solutions. This conclusion may be contrasted with the behaviour of a number of tetra- and penta-halogeno-oxometal complexes, where the equilibrium (MOX/sub 4/)sup(n-) + X/sup -/< - - > (MOX/sub 5/)sup(n + 1)/sup -/ is clearly established.

1987-07-01

An electron spin resonance study of the equilibrium between tetrahalogeno- and pentahalogeno-nitridotechnetate (VI) ions in solution

Lanthanum halide (LaBr_3:Ce) scintillators offer significantly better resolution (< 3% at 662 keV) relative to NaI(Tl) and have recently become commercially available in sizes large enough for the handheld, Radio-Isotope Identification Device (RIID) market. Drawbacks to lanthanum halide detectors, however, include internal radioactivity contributing to spectral counts, and a low-energy response which can cause detector resolution to be worse than that of NaI(Tl) below 100 keV. To study the potential of this new material for RIIDs we performed a series of measurements comparing a 1.5 x 1.5-inch LaBr_3:Ce detector with an Exploranium GR-135 RIID, which contains a 1.5 x 2.2-inch NaI(Tl) detector. Measurements were taken for short timeframes, as typifies RIID usage. Measurements included examples of naturally occurring radioactive material (NORM), typically found in cargo, and special nuclear materials. Some measurements were non-contact, ...

2005-10-23

Pitting corrosion of zirconium and hafnium

The e.s.r. spectra of [AsPh_4][TcNCl_4], Cs_2[TcNCl_5], [AsPh_4][TcNBr_4], and Cs_2[TcNBr_5] have been studied in non-aqueous and concentrated aqueous acid solutions. None of the spectra shows evidence for the co-ordination of a fifth halide ligand in the trans position, even under circumstances such as a 2 000-fold excess of halide ion, which would be expected to favour the formation of the pentahalogenonitridotechnetate ion. The predominant species in solution is the tetrahalogenonitridotechnetate ion, where the trans position may be vacant or occupied by a solvent molecule in the case of the non-aqeuous solvents and by a water molecule in the case of HCl and HBr solutions. This conclusion may be contrasted with the behaviour of a number of tetra- and penta-halogeno-oxometal complexes, where the equilibrium [MOX_4]sup(n-) + X"-< - - > [MOX_5]sup(n + 1)"- is clearly established. (author).

Pitting corrosion of nickel base alloys in halide media

The initiation and inhibition of pitting corrosion on zirconium and hafnium in aqueous solutions have been investigated by potentiodynamic, potentiostatic and galvanostatic measurements at 25/sup 0/C. Effects of Cl/sup -/, Br/sup -/and I/sup -/ have been examined over a range of salt concentrations and pH. All three halide ions cause pitting attack on the two metals, but this may be inhibited by other anions. The results show that hafnium is more easily protected against pitting than is zirconium. The data are treated by the Butler-Volmer equation to yield more information about the mechanisms of the pitting corrosion.

1988-02-01

Mechanism of the metal-mediated carbalkoxylation of vinyl electrophiles. 1. Preparation, molecular structure, and alcoholysis of vinylic acyl platinum(II) complexes

A computerized corrosion measuring system (EG and G model 350 A) was used to study the influence of Cr, Mo, Ti, Nb and W on the pitting corrosion of nickel base alloys in 3% NaCl at 90"0C. The electrochemical parameters under investigation are the corrosion potential E_c_o_r_r, pitting potential E_p and protection potential E_p_p. The corrosion behaviour of nickel base alloys were studied by using pitting scan and potentiostatic techniques. Values of corrosion potential, pitting potential and protection potential were used for a ranking of alloys for corrosion resistance.

1988-03-06

Inorganic chemistry of univalent astatine

Carbalkoxylation of vinyl electrophiles was investigated using platinum complexes. This reaction occurs in two steps: (a) carbonyl insertion of {sigma}-vinyl Pt(II) halides and (b) alcoholysis of vinylic acyl Pt(II) complexes. Alcoholysis of vinylic acyl Pt(II) triflate complexes is investigated kinetically. Vinylic acyl Pt(II) complexes were isolated and characterized. 51 refs., 5 figs., 6 tabs.

1992-03-01

Development of a chemically assisted micro-beam etching system for three-dimensional microanalysis

A review is given of the state of knowledge of the chemistry of astatine with the oxidation number +1. According to the position in the periodic system, astatine has metalloidal properties. The existence of a singly-charged cation in acid solution and the complex formation reactions with halide ions (Cl"-, Br"-, and I"-), with pseudohalide ions (SCN"-, CN"-, C(CN)_3"-, and N_3"-), and with thioureas and their derivatives underline the metalloidal character of At(I). Optimal preparation conditions, chemical composition of astatine compounds, existence and stability regions of At(I) complexes, and stability constants have been investigated by means of electromigration in free electrolyte solutions.

Incompatibility of metam sodium with halogenated fumigants.

A chemically assisted micro-beam etching system for 3D microanalysis was designed. Using chemically assisted ion beam etching (CAIBE) method with FIB shave-off scanning, about several hundred micrometers clean cross-section will be acquired in a few hours. We use focused ion beam (FIB) and electron beam (EB) as micro-beams, halogen or halide mainly as reactive gases. The apparatus was manufactured based on this concept. We found that the FIB, Q-MS and SED worked as expected. The instrumentation has been completed.

2003-01-15

Lipase catalyzed esterification of glycidol in organic solvents

Metam sodium (metam) is a widely used soil fumigant. Combined application of metam and other available fumigants is intended to produce synergic pesticidal effects for a broad spectrum of pest control in soil fumigation. This study aimed to test the compatibility of metam with the halogenated fumigants 1,3-dichloropropene (1,3-D), chloropicrin, methyl bromide, methyl iodide and propargyl bromide. Halogenated fumigants and metam were spiked simultaneously into organic solvents, water and moist soils, and metam-induced degradation of these halogenated chemicals was evaluated. In all three media, the halogenated fumigants were incompatible with metam and degraded via rapid chemical reactions. The degradation rate varied with halogenated fumigant species and increased as the amount of metam present was increased. In moist soil, 15-95% of the halogenated fumigants were decomposed within 72 h by metam at a 1:1 molar ratio. Combined application of Telone C-35 (62.5% 1,3-D ...

2005-05-01

Histamine Molecule and Dianion Oxalate are Efficient Blocks for Building 2D Supramolecular Networks

The authors studied the resolution of racemic glycidol through esterification with butyric acid catalyzed by porcine pancreatic lipase in organic media. A screening of seven solvents (log P values between 0.49 and 3.0, P being the n-octanol-water partition coefficient of the solvent) showed that neither log P nor the logarithm of the molar solubility of water in the solvent provides good correlations between enantioselectivity and the properties of the organic media. Chloroform was one of the best solvents as regards the enantiometic purity (e.p.) of the ester produced. In this solvent, the optimum temperature for the reaction was determined to be 35C. The enzyme exhibited maximum activity at a water content of 13 [plus minus] 2% (w/w). The enantiomeric purity obtained was 83 [plus minus] 2% of (S)-glycidol butyrate and did not depend on the alcohol concentration or the enzyme water content for values of these parameters up to 200 mM and 25% (w/w), respectively. ...

1993-08-05

British Library Electronic Table of Contents (United Kingdom)

One salt and two Cu(II) complexes (H2hsm)(ox), 1, [Cu(hsm)(ox)], 2, and [Cu(hsm)(ox)H2O], 3, have been synthesized and X-ray characterized (hsm is histamine and ox2? is the oxalate dianion). Starting from the prochiral tetracoordinated complex 2, pentacoordinated complex 3 crystallizes as a racemic mixture of the enantiomeric ? and ? isomers, in space group P21/c. In all cases, the side chain of the hsm group is gauche, allowing the formation of strong hydrogen bonds in the salt 1, and to chelate the metal center in complexes 2 and 3. The combination hsm/ox seems to favor the formation of 2D supramolecular structures (planes or wavy planes), through efficient networks of N?H???O hydrogen bonds. Cell parameters: 1, P21/c, a?=?6.260 (2) ?, b?=?11.500 (4) ?, c?=?12.525 (4) ?, ??=?104.047 (17)...

2011-01-01

Dating techniques in fault investigations

Chiral salicyloxazolines as auxiliaries for the asymmetric synthesis of ruthenium polypyridyl complexes.

Determining the time of most recent fault movement is an important part of assessing a possible site for a nuclear power plant. The purpose of this paper is not to present research information but to provide a practical guide to some of the dating techniques available to the engineering geologist working on nuclear power plant siting. Emphasis is placed on the practical aspects, such as usable minerals, conditions necessary for them to yield correct dates, degree of accuracy, sample collection, sample size, and sample packaging. In this paper, the usual geologic field techniques are taken for granted (such as those used in stratigraphy, paleontology, and structural analysis) for assessing fault history. Laboratory techniques used in conjunction with or supplemental to field methods are discussed. The specific radiometric methods discussed are "1"4C(carbon-14), fission track, K-Ar (potassium-argon), thermoluminescense, Rb-Sr (rubidium-strontium), and U-Th (uranium-thorium). ...

Luminescent unit computerization to research spectral characteristics of fine film alkali halide crystal

Chiral auxiliaries are promising emerging tools for the asymmetric synthesis of octahedral metal complexes. We recently introduced chiral salicyloxazolines as coordinating bidentate chiral ligands which provide excellent control over the metal-centered configuration in the course of ligand substitution reactions and can be removed afterward in an acid-induced fashion under complete retention of configuration (J. Am. Chem. Soc. 2009, 131, 9602-9603). Here reported is our detailed investigation of this sequence of reactions, affording virtually enantiopure ruthenium polypyridyl complexes. The control of the metal-centered chirality by the coordinated chiral salicyloxazolinate ligand was evaluated as a function of reaction conditions, the employed bidentate 2,2'-bipyridine and 1,10-phenanthroline ligands, and the substituent at the asymmetric 5-position of the oxazoline heterocycle. Most striking was the strong influence of the reaction solvent, with aprotic solvents of lower polarity ...

2010-09-01

Thermoluminescence studies in lead doped KCl and KBr crystals

The fundamental optical absorption of ion crystals characterizes the creation of different free low energetic electronic excitation (the excitons and electron-hole pairs), but their straight registration is not possible because of incommensurable big absorption factor of alkali halide monocrystals. So to registration the spectrums of alkali halide monocrystal very fine layers are necessary. We have received fine films of Nal and KCl in system of KCl-Nal-KCl, KCl-KI-KCl on the base of universal vacuum post VUP-4, VUP-5 by thermal evaporation. A unique spectral unit has been created For this on the basic the SDL-2 complex. Complex consists of radiator, systems of condensers, monochromators MDR-12 and MDR-23, receivers of radiation, controller by unit. Connect and control of monochromators by means of IBM-compatible computer has been created. Kinematics schemes of monochromators provide consequent removing on output slot of monochromatic radiation ...

Reaction of the derivatives of trivalent phosphorus acids with 3-azido-. beta. -lactams and the properties of the obtained phosphine imide derivatives

Lead is known to enter substitutionally in divalent state when doped in alkali halides. When irradiated at room temperature these lead centers (Pb"+"+) act as traps for electrons knocked off from the halogen ions and become Pb"+ and Pb"0 (for large doses of irradiation). These changes could be followed in the optical absorption studies. These lead-doped crystals after X-ray irradiation yield a thermoluminescence output smaller than that observed in 'pure' crystals. However, two new glow peaks are observed in additions to those due to F-centers. In KCl : Pb and Kbr : Pb crystals part of the F-center glow preceds the new glow peaks. The new peaks are attributed to the Pb"+ and Pb"0 centers. The glow peak temperatures and trap depths for these peaks an obtained by total-curve fitting method are reported. (author).

1975-02-12

Reaction of the derivatives of trivalent phosphorus acids with 3-azido-#beta#-lactams and the properties of the obtained phosphine imide derivatives

3-Azido-..beta..-lactams react with the derivatives of trivalent phosphorus acids under mild conditions with the formation of 3-phosphoranediylamino-1,4-diaryl-2-azetidinones, which are readily hydrolyzed with the elimination of alcohol (thiol) to 3-phosphoranylamino-1,4-diaryl-2-azetidinones. The phosphine imide compounds obtained from the aryl alkyl phosphites are hydrolyzed with the elimination of phenols. 3-Phosphoranediylamino-1,4-diaryl-2-azetidinones react readily with alkyl and acyl halides with the formation of 3-(N-alkylphosphoryl-amino)- and 3-(N-acylphosphorylamino)-1,4-diaryl-2-azetidinones, respectively.

1986-04-20

RF conditioned dc discharges for excitation of rare gas halide lasers. Final report

3-Azido-#beta#-lactams react with the derivatives of trivalent phosphorus acids under mild conditions with the formation of 3-phosphoranediylamino-1,4-diaryl-2-azetidinones, which are readily hydrolyzed with the elimination of alcohol (thiol) to 3-phosphoranylamino-1,4-diaryl-2-azetidinones. The phosphine imide compounds obtained from the aryl alkyl phosphites are hydrolyzed with the elimination of phenols. 3-Phosphoranediylamino-1,4-diaryl-2-azetidinones react readily with alkyl and acyl halides with the formation of 3-(N-alkylphosphoryl-amino)- and 3-(N-acylphosphorylamino)-1,4-diaryl-2-azetidinones, respectively.

Properties of the passive films formed on ferritic stainless steels in Cl/sup -/ Solutions

Results of experiments performed utilizing high-power microwave sources for laser-discharge switching and preionization are reported. These results are not definitive, but are promising. Significant preionization using microwaves is possible. Some ability to switch the discharge and operate a laser have been demonstrated. More work needs to be performed to perfect the microwave coupling to the laser mixture. In particular, experiments with the microwaves better concentrated between the electrodes should be performed. The best way to accomplish this appears to be using the side-feed geometry; however, a large expansion of the microwaves should occur (to well below the power able to break down the window), and then a cylindrical lens should be used to focus the microwaves between the electrodes. 2 references.

1983-01-01

Pitting corrosion of stainless steels; Lochkorrosion an nichtrostenden Staehlen

The pitting resistance of Fe-Cr and Fe-Cr-Mo alloys has been correlated with characteristics of the passive films analyzed by Auger electron spectroscopy (AES). Increased film protectiveness as a result of increased Cr in the alloy can be directly attributed to Cr enrichment of the film and decreased film thickness. Increased Mo in the alloy or passivation at noble potentials promotes passive film resistance to breakdown, but neither does much to change the macrocharacteristics of the film. Rather, it is suggested that the roles of alloying and/or passivation conditions are related to the susceptibility and distribution of weak points of the film. In solutions in which pitting occurs, chloride is generally not incorporated into the film, suggesting that the role of halides is to interact with weak points of the film at the solution/film interface. At 260/sup 0/C, the films are much thicker and likely to be much more defective in structure than those formed at ...

1986-10-01

Mechanism of conjugated oxidation with hydrogen peroxide in presence of halide ions

Stainless steels can get pitting corrosion in halide containing solution, which make them a big risk in industrial production. Many investigations were made in the past in order to understand processes involved in pitting corrosion, pit initiation and pit growth. Results about the influence of alloying elements, their contents, the state of the structure, the condition of the surface, the content of chloride, the temperature, the pH-value, the velocity of flow and of the oxidizer on the chloride induced pitting corrosion of passive stainless steels are presented. Electrochemical measurements and the application of surface analytical methods (SEM, SAM, XPS) with high lateral resolution are carried out. A part of the samples received a diffusion annealing in order to obtain reproducible results. Pitting Resistance Equivalents (PRE) - Pitting Index - with different multipliers are given and discussed critical. An electrochemical method for selecting materials without ...

1996-01-01

1 2 3

Cost effectiveness analysis of proposed effluent limitations guidelines for the pulp, paper, and paperboard industry

The change in the concentration of hydrogen peroxide in the course of its decomposition was shown, catalyzed by 0.02 M PbI/sub 2/, 0.03 M CuI, 0.02 M KI, 0.02 M FeSo/sub 4/, 6 M HCl, and 1 M HCL + 2 M H/sub 2/SO/sub 4/ at 25 C. It was suggested that in the process of the catalytic decomposition at the initial stage of the reaction, the formation of an intermediate active species containing positively charged halogen occurs; depending on the oxidative power of the counterion, the relative proportions of the hydrogen peroxide decomposing under the action of either the cation or the anion varied.

1988-01-10

The cost-effectiveness (CE) analysis presents an evaluation of the technical efficiency of pollutant control options for the proposed effluent limitations guidelines. The proposed BAT and PSES apply to six subcategories: Dissolving Kraft; Dissolving Sulfite; Bleached Papergrade Kraft; Papergrade Sulfite; Unbleached Kraft; and Semichemical. The document compares the total annualized cost incurred for each of the regulatory options within each subcategory to the corresponding effectiveness of that option in reducing the discharge of pollutants. Section Two discusses the cost-effectiveness methodology and identifies the pollutants included in the analysis and their toxic weighting factors. Section Three describes the options evaluated for each subcategory. Section Four presents the results of the CE analysis. Section Five presents a separate analysis of AOX (adsorbable organic halides).

1993-11-01

Chemistry of strontium

Solid-state precursor routes to III-V type electronic (13-15) and magnetic (3-15) materials

This paper describes stable strontium as composed of four stable isotopes ( Sr 88, Sr 87, Sr 86, and Sr 84), of which Sr 88 contributes more than 82% to its composition. Strontium exists in three crystalline, plymorphic forms; face-centered cubic alpha form, hexagonal beta form and body-centered cubic gamma form. Strontium occupies in many physicochemical aspects an intermediate position between calcium and barium, as does the solubility of strontium salts. As a result of its oxidation potential, strontium readily forms oxides, halides, and sulfide. The author proposes that the slight discrimination against strontium incorporation into bony tissues may be due to the difference in ionic potential (14%) between strontium and calcium. Ionic potential is an indicator of the strength of ionic bonds: strontium has a smaller ratio of ionic charge to ionic radius when compared with calcium.

Thermoluminescence studies in cerium doped NaCl crystals

An interest in electronic materials has led me to investigate new synthetic approaches to III-V' type semiconducting (13-15, current IUPAC designation for B and N groups in the Periodic Table) and magnetic (3-15) compounds. It is now possible to prepare binary (GaAs and GdP) and ternary mixed-metal (Al[sub x]Ga[sub 1-x]As) and mixed-pnictide (GaP[sub x]As[sub 1-x]) compounds in seconds from rapid, low-temperature-initiated metathesis reactions between a metal (III) trihalide and a trisodium pnictide, exemplified by MX[sub 3] + Na[sub 3]Pn [yields] MPn + 3 NaX, where M is Al, Ga, In, (Al,Ga), or a lanthanide; X is F, Cl, or I; and Pn is P, As, Sb, or (P,As). The precursors are mixed together in a dry box and ignited by light grinding with a mortar and pestle, or by brief, local heating from a hot filament. These reactions are very exothermic (calculated [Delta]H[sub rxn] (GaAs) = 138 kcal/mol) and typically reach temperatures in excess of 700[degrees]C within seconds of ...

1992-01-01

Synthesis, luminescence quantum yields, and lifetimes of trischelated ruthenium(II) mixed-ligand complexes including 3,3'-dimethy1-2,2'-bipyridyl

Cerium is known to enter substitutionally in trivalent state when doped in alkali halides. Cerium doped NaCl crystals exhibit greatly enhanced thermoluminescence output upon X-irradiation at RT, the intensity of emission being about 10 times that in undoped crystals for similar dosage of irradiation. The cerium doped crystals give upon X-irradiation a very intense glow peak at 145degC with shoulders at 120degC and 210degC. Upon partially bleaching the crystal with F-light, the peak at 120degC becomes prominent probably due to faster bleaching of the glow at 145degC. From further optical bleaching studies, it is concluded that the glow peak at around 120degC is due to cerium centres in the irradiated crystal and the 145degC peak due to F centres. This F centre emission occurs at lower temperature, compared to that in the undoped crystals where it occurs at around 180degC. The spectral emission in the Ce doped crystals is in the blue-green region as compared to the ...

Methyl bromide and methyl chloride fluxes from temperate forest litter

New five complexes of the type of [RuL sub(3-x)(dmby) sub(x)]X sub(2)(x = 1,2,3, L = 2,2'-bipyridyl or 1,10-phenanthroline, dmby = 3,3'-dimethy1-2,2'-bipyridyl, X = halide ion) have been synthesized in order to investigate the effects of two methyl groups of dmby on the absorption and emission spectra, luminescence quantum yields, and lifetimes. Values of the radiative and nonradiative rate constants have been calculated from these data at 77K. Although the absorption and emission maxima and the lifetimes are not much affected by the dmby ligand substitution, the molar extinction coefficients and emission quantum yields are decreased compared with trischelated complexes of the parent bipyridyl or phenanthroline ligands. At 25"0C the emission yields of the complexes containing dmby decrease by 3 - 4 orders of magnitude than at 77K. Possible causes of the decrease in the quantum yields are discussed. (author).

1982-01-01

British Library Electronic Table of Contents (United Kingdom)

Methyl halide fluxes were measured from fine (nonwoody) litter samples at a temperate deciduous forest site in Scotland on 16 occasions over more than a year and at a coniferous forest site. The resulting mean (+-1 sd) CH3Br and CH3Cl fluxes were 4.1 +- 3.7 ng kg-1 h-1 and 0.98 +- 0.62 mg kg-1 h-1, respectively, for dry mass leaf litter and 5.7 +- 6.3 ng kg-1 h-1 and 0.47 +- 0.14 mg kg-1 h-1 for dry mass needle litter. Temporal variations of net fluxes from leaf litter were significantly greater than spatial variations suggesting seasonality in the fluxes. The mean CH3Cl/CH3Br mass ratio of fluxes was 200 (to 1 sig. fig.), an order of magnitude larger than the ratio of their estimated global turnovers. Temperate forest litter may be a moderate net source of CH3Cl globally but a negligible ...

2011-01-01

Determination of the minor disinfection by-products formed in the water plant of Sant Joan Despi (Barcelona, Spain); Determinacion de los subproductos de desinfeccion minoritarios formados en la planta de Sant Joan Despi (Barcelona)

Comparative crystal field study of Ni{sup 2+} energy levels in NiCl{sub 2}, NiBr{sub 2}, and NiI{sub 2} crystals

Chlorine is widely used in drinking water disinfection due to be a powerful and not expense disinfection. Although the benefits of disinfection, the formation of stable disinfection by-products of the health concern, is the result of the interaction of aqueous chlorine with natural organic matter presents in water. Disinfection by-products generated in major concentration are trihalomethane and haloacetic acids. Disinfection by-products generated in minor concentration are haloacetonitriles, haloketones,chloral hydrate and chloropicrin and some new groups such as cyanogen halides and trihaloacetaldydes. In this work two analytical methods.: headspace/gas chromatography/electron capture detector and liquid-liquid microextraction/gas chromatography/electron capture detector are studied and compared to determine the minor by-products and to establish finally, a systematic control of them in the different stages of the Water Treatment Plant of San Joan Despi ...

1997-09-01

Comparative crystal field study of Ni"2"+ energy levels in NiCl_2, NiBr_2, and NiI_2 crystals

The exchange charge model of crystal field theory has been used to analyze systematically the ground state absorption spectra of octahedrally coordinated Ni{sup 2+} ion in isostructural nickel halide crystals NiCl{sub 2}, NiBr{sub 2}, and NiI{sub 2}. The parameters of the crystal field acting on the Ni{sup 2+} ion are calculated from the available crystal structure data. The obtained energy level schemes are compared with experimental absorption spectra; a good agreement with experimental data is demonstrated. Dependencies of the crystal field invariants and covalence effects on the type of ligands are considered. It is shown numerically that the overlap effects between Ni{sup 2+} ion and ligands increase with an increase of the ligands' atomic number resulting in the following order of the degree of covalence: NiI{sub 2}>NiBr{sub 2}>NiCl{sub 2}.

2006-01-15

BIMETALLIC LITHIUM BOROHYDRIDES TOWARD REVERSIBLE HYDROGEN STORAGE

The exchange charge model of crystal field theory has been used to analyze systematically the ground state absorption spectra of octahedrally coordinated Ni"2"+ ion in isostructural nickel halide crystals NiCl_2, NiBr_2, and NiI_2. The parameters of the crystal field acting on the Ni"2"+ ion are calculated from the available crystal structure data. The obtained energy level schemes are compared with experimental absorption spectra; a good agreement with experimental data is demonstrated. Dependencies of the crystal field invariants and covalence effects on the type of ligands are considered. It is shown numerically that the overlap effects between Ni"2"+ ion and ligands increase with an increase of the ligands' atomic number resulting in the following order of the degree of covalence: NiI_2>NiBr_2>NiCl_2.

2006-01-15

2008 Data Report: Groundwater Monitoring Program Area 5 Radioactive Waste Management Site

Borohydrides such as LiBH{sub 4} have been studied as candidates for hydrogen storage because of their high hydrogen contents (18.4 wt% for LiBH{sub 4}). Limited success has been made in reducing the dehydrogenation temperature by adding reactants such as metals, metal oxides and metal halides. However, full rehydrogenation has not been realized because of multi-step decomposition processes and the stable intermediate species produced. It is suggested that adding second cation in LiBH{sub 4} may reduce the binding energy of B-H. The second cation may also provide the pathway for full rehydrogenation. In this work, several bimetallic borohydrides were synthesized using wet chemistry, high pressure reactive ball milling and sintering processes. The investigation found that the thermodynamic stability was reduced, but the full rehydrogenation is still a challenge. Although our experiments show the partial reversibility of the bimetallic borohydrides, it was not ...

2010-10-21

2006 Data Report: Groundwater Monitoring Program Area 5 Radioactive Waste Management Site

This report is a compilation of the groundwater sampling results from the Area 5 Radioactive Waste Management Site (RWMS) including calendar year 2008 results. Each of the three Pilot Wells was sampled on March 11, 2008, and September 10, 2008. These wells were sampled for the following indicators of contamination: pH, specific conductance, total organic carbon, total organic halides, and tritium. Indicators of general water chemistry (cations and anions) were also monitored. Results from all samples collected in 2008 were within the limits established by agreement with the Nevada Division of Environmental Protection for each analyte. These data indicate that there has been no measurable impact to the uppermost aquifer from the Area 5 RWMS. There were no significant changes in measured groundwater parameters compared to previous years. Other information in the report includes an updated Cumulative Chronology for the Area 5 RWMS Groundwater Monitoring Program and ...

2009-01-13

(Phospinoalkyl)silyl complexes. 10. Formation of chelated bis[(diphenylphosphinoethyl)diorganosilyl]platinum(II) complexes. Precoordination through phosphorus, intermediacy of a platinum(IV) disilyl, and diastereoisomerism at planar platinum(II) in 'chelate-assisted' hydrosilylation

This report is a compilation of the groundwater sampling results from the Area 5 Radioactive Waste Management Site (RWMS) for calendar year 2006. Pilot wells UE5PW-1, UE5PW-2, and UE5PW-3 were sampled in April and October 2006 for the following indicators of contamination: pH, specific conductance, total organic carbon, total organic halides, and tritium. Indicators of general water chemistry (cations and anions) were also monitored. Results from all samples collected in 2006 were within the limits established by agreement with the Nevada Division of Environmental Protection for each analyte. These data indicate that there has been no measurable impact to the uppermost aquifer from the Area 5 RWMS. There were no significant changes in measured groundwater parameters compared to previous years. Other information in the report includes an updated Cumulative Chronology for the Area 5 RWMS Groundwater Monitoring Program and a brief description of the site hydrogeology.

2007-02-01

Small-molecule screen identifies inhibitors of a human intestinal calcium-activated chloride channel.

Addition of the silane PPh[sub 2]CH[sub 2]CH[sub 2]SiMe[sub 2]H (chelH, 1a) to Pt(COD)[sub 2] (COD = cycloocta-1,5-diene) affords in high yield the cis-bis chelate Pt(chel)[sub 2] (2); formation of the same product from Pt(COD)(X)Y (X = Y = Me; X = Me, Y = Cl) has been shown by NMR spectroscopy ([sup 1]H, [sup 31]P, [sup 195]Pt) to proceed via prior coordination of chelH through P to afford Pt(chelH)[sub 2](X)(Y) (cis and trans isomers) and through intermediacy of PtH(chel)[sub 2]Cl (22) in which P trans to Si at Pt(IV) leads to an exceptionally low [sup 2]J(Pt-P) = 1084 Hz. Cleavage of Pt-Si bonds in 2 by HCl can be controlled to give the monochelate species Pt(chel)(chelH)Cl (7), from which chelH is displaced by PMe[sub 2]Ph, or trans-PtH(PPh[sub 2]CH[sub 2]SiMe[sub 2]Cl)[sub 2]Cl (9). Products related to 9 result from Pt-Si bond cleavage by I[sub 2] or MeI. Using the analogue PPh[sub 2]CH[sub 2]CH[sub 2]SiMe(Ph)H (1c) of 1a, the analogue Pt-[PPh[sub 2]CH[sub 2]CH[sub 2]SiMe(Ph)][sub ...

1991-08-21

Formation and stabilization of anionic metal complexes in concentrated aqueous quaternary ammonium salt solutions

Calcium-activated chloride channels (CaCCs) are widely expressed in mammalian tissues, including intestinal epithelia, where they facilitate fluid secretion. Potent, selective CaCC inhibitors have not been available. We established a high-throughput screen for identification of inhibitors of a human intestinal CaCC based on inhibition of ATP/carbachol-stimulated iodide influx in HT-29 cells after lentiviral infection with the yellow fluorescent halide-sensing protein YFP-H148Q/I152L. Screening of 50,000 diverse, drug-like compounds yielded six classes of putative CaCC inhibitors, two of which, 3-acyl-2-aminothiophenes and 5-aryl-2-aminothiazoles, inhibited by >95% iodide influx in HT-29 cells in response to multiple calcium-elevating agonists, including thapsigargin, without inhibition of calcium elevation, calcium-calmodulin kinase II activation, or cystic fibrosis transmembrane conductance regulator chloride channels. These compounds also inhibited ...

2007-12-14

Development of Novel Polycrystalline Ceramic Scintillators

Anionic complexes of transition metals were stabilized in aqueous solutions containing high concentrations of various short-chain quaternary ammonium salts. Compounds with longer paraffin chains were effective in much less concentrated solution. Complex ions were detected spectrophotometrically. FeCl/sub 4//sup -/, which is usually formed in concentrated HCl, was the predominant Fe(III) complex in 30 m choline chloride containing only 0.12 M HCl. A yellow transitory Tc(VII) chloro-addition intermediate, formed in the reduction of TcO/sub 4//sup -/ by concentrated HCl, was stabilized when the solution also contained 25 m choline chloride. Its spectrum, as well as the isolation of an already known Tc(VII) bipyridyl complex, is reported. Concentrated organic electrolytes also stabilized Tc(V) oxide halides against disproportionation and Tc(IV) hexahalides against hydrolysis. Halochromates of Cr(VI) were formed and stabilized in dilute acid containing quaternary ...

1985-02-04

2003 Data Report: Groundwater Monitoring Program, Area 5 Radioactive Waste Management Site, Nevada Test Site

For several decades most of the efforts to develop new scintillator materials have concentrated on high-light-yield inorganic single-crystals while polycrystalline ceramic scintillators, since their inception in the early 1980 s, have received relatively little attention. Nevertheless, transparent ceramics offer a promising approach to the fabrication of relatively inexpensive scintillators via a simple mechanical compaction and annealing process that eliminates single-crystal growth. Until recently, commonly accepted concepts restricted the polycrystalline ceramic approach to materials exhibiting a cubic crystal structure. Here, we report our results on the development of two novel ceramic scintillators based on the non-cubic crystalline materials: Lu SiO:Ce (LSO:Ce) and LaBr:Ce. While no evidence for texturing has been found in their ceramic microstructures, our LSO:Ce ceramics exhibit a surprisingly high level of transparency/ translucency and very good scintillation ...

2008-06-01

Buried Paleo-Phreatic Playa is the Primary Source of Salinity in the Rio Grande and Rio Grande Aquifer, El Paso-Juarez Valley

This report is a compilation of the calendar year 2003 groundwater sampling results from the Area 5 Radioactive Waste Management Site, Nevada Test Site. Wells Ue5PW-1, Ue5PW-2, and Ue5PW-3 were sampled semi-annually for the required analytes: pH, specific conductance, total organic carbon (TOC), total organic halides (TOX), tritium, and major cations/anions. Results from all samples collected in 2003 were within established criteria. These data indicate that there has been no measurable impact to the uppermost aquifer from the Resource Conservation and Recovery Act (RCRA) regulated unit within the Area 5 Radioactive Waste Management Site and confirm that any previous detections of TOC and TOX were false positives. Contamination indicator data are presented in control chart and tabular form with investigation levels indicated. Gross water chemistry data are presented in graphical and tabular form. There were no major changes noted in the monitored groundwater ...

2004-02-01

Fundamental Chemistry And Thermodynamics Of Hydrothermal Oxidation Processes

The Rio Grande alluvial floodplain aquifer between El Paso/Juarez and Fort Quitman, Texas has been intensively tilled and irrigated since 1910. Almost since that time, the Rio Grande and its interconnected alluvial aquifer in this stream reach have been affected by excessive salinity problems. Presently, salinity of surface water and groundwater increases from 800 to 2000 mg/L total dissolved solids (TDS) near El Paso, Texas to 2500 to 5500 mg/L TDS near Fort Quitman, Texas, approximately 115 km downstream. Chloride (Cl) and Chloride/Bromide (Cl/Br) ratios increase downstream, with a marked increase in salinity beginning about 45 km below El Paso. Groundwater sampling in an intensively investigated reach of the floodplain aquifer, extending from 35 to 60 km below El Paso identified two distinct water types. The first water type (17 samples) is a relatively dilute groundwater containing 1000 to 2000 mg/L TDS, 250 to 600 mg/L Cl, and Cl/Br weight ratios of 550 to 900. The second ...

2005-12-01