Ammonium eneselenolates: stereochemistry and electronic properties.

Ammonium eneselenolates were generated with high efficiency by reacting selenothioic acid S-esters with a THF solution of TBAF. The methylation of ammonium eneselenolates gave ketene selenothioacetals as stereoisomeric mixtures. The ratio of the two stereoisomers depended on the duration of the reaction before the addition of MeI. Ammonium eneselenolates were characterized by examining their (1)H, (13)C, and (77)Se NMR spectra, which indicated that ammonium eneselenolates were present almost exclusively as Z-isomers. These results suggested that ammonium eneselenolates are kinetically generated as stereoisomeric mixtures, and isomerization of E-isomers to Z-isomers then takes place to result in the exclusive formation of Z-isomers. During the methylation of Z-isomers of ammonium eneselenolates, the isomerization of Z-isomers to E-isomers occurs to give stereoisomeric mixtures of ketene selenothioacetals. NMR spectra of ammonium eneselenolates implied that the electrons at the selenium atom are somewhat delocalized to the carbon-carbon double bond and the carbon-selenium bond shows partial double-bond character.     

Kinetics and mechanism of thermal decomposition of ammonium nitrate and sulfate mixtures

Fundamental kinetic aspects of the decomposition of mixtures and double salts of ammonium nitrate and ammonium sulfate were studied. The effect of water and sulfuric acid additives on the thermal decomposition rate of ammonium nitrate and sulfate mixtures was examined. The constant of proton exchange between nitric acid and the sulfate anion in molten ammonium nitrate was estimated.     

Solid-liquid phase equilibria of binary salt hydrate mixtures involving ammonium alum

Summary The solid-liquid phase diagrams of binary mixtures of ammonium alum with ammonium iron(III) alum, with aluminum nitrate nonahydrate and with ammonium nitrate and of aluminum sulfate hexadecahydrate with aluminum nitrate nonahydrate are presented. The alum rich branches of the former three-phase diagrams were fitted by the Ott equation. The specific enthalpy of fusion/freezing of some compositions of the former three mixtures was determined by differential drop calorimetry.     

On the synthesis of sulphides in combustion regime

The present investigation deals with combustion (in inert atmosphere) of mixtures based on metal nitrates and sulphur-containing compounds possessing reductive properties, such as ammonium thiocyanate, thiosemicarbazide, thiocarbamide. It is demonstrated that at definite component ratios these mixtures burn forming sulphides of the corresponding metals. Morphology and disperse state of the resulting sulphides can be controlled by changing combustion conditions and ratios between components. This revised version was published online in July 2006 with corrections to the Cover Date.     

Thermal behavior of ammonium dinitramide and amine nitrate mixtures

Journal of Thermal Analysis and Calorimetry - This paper focuses on the thermal behavior of mixtures of ammonium dinitramide (ADN) and amine nitrates. Because some mixtures of ADN and amine nitrate...     

Enhanced detection of phosphopeptides in matrix-assisted laser desorption/ionization mass spectrometry using ammonium salts

Matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS) has been used successfully to detect phosphorylation sites in proteins. Applications may be limited by the low response of phosphopeptides compared to nonphosphorylated peptides in MALDI MS. The addition of ammonium salts to the matrix/analyte solution substantially enhances the signal for phosphopeptides. In examples shown for equimolar mixtures, the phosphorylated peptide peaks become the largest peaks in the spectrum upon ammonium ion addition. This can allow for the identification of phosphopeptides in an unfractionated proteolytic digestion mixture. Sufficient numbers of protonated phosphopeptides can be generated such that they can be subjected to postsource decay analysis, in order to confirm the number of phosphate groups present. The approach works well with the common MALDI matrices such as α-cyano-4-hydroxycinnamic acid and 2,5-dihydroxybenzoic acid, and with ammonium salts such as diammonium citrate and ammonium acetate.     

全氟辛酸铵与全氟壬酸铵混合物的表面活性

测定了全氟辛酸铵和全氟壬酸铵及其不同比例混合物的0.1mol/L氯化铵水溶液表面张力曲线。讨论了它们的胶团化作用、吸附作用和降低水表面张力的能力。改进了Ingram-Luckhurst自单一表面活性剂活性张力曲线得到混合溶液表面张力曲线的方法。     

Study of the reactivity of ammonium carboxylates in the synthesis of amides under high-pressure deformation conditions

On deformation under pressures up to 10 GPa the ammonium salts of aliphatic and aromatic acids, as well as mixtures of a free carboxylic acid with the ammonium salts of strong mineral acids, are converted into the corresponding amides. The amide yields increase with pressure, the magnitude of shearing deformation, and temperature. The temperature and pressure coefficients for amide formation are low and have values of 2.5–4 kJ/mole and –1 to –2 cm³/mole, respectively. The reactivity of ammonium salts in the synthesis of amides alternates in the homologous series of aliphatic acids in a similar way to the shear stress of these salts. The reactivity of the ammonium salts of aliphatic acids increases when the reaction is conducted in a matrix of an ammonium salt which possesses plasticity and a high shear stress.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2289–2292, October, 1989.     

Non-modified stationary phases for the analysis of basic compounds

The analysis of some basic solutes, particularly quaternary ammonium compounds, utilizing reversed-phase liquid chromatography on chemically modified silica, is still difficult. One alternative is the application of unmodified stationary phases, such as alumina and silica, in combination with aqueous solvent mixtures for the separation of these analytes.     

Equilibrium phase diagrams of aqueous mixtures of malonic acid and sulfate/ammonium salts

Tropospheric aerosols are usually complex mixtures of inorganic and organic components. Although the thermodynamic properties of inorganic aerosols have been widely studied, the effect of organics on such properties is still under discussion. In this study, solubility in water, water activity (a(w)) of aqueous solutions, deliquescence relative humidity (DRH), eutonic composition, and eutonic DRH were determined for bulk mixtures of malonic acid (MA) with ammonium sulfate (AS) and ammonium bisulfate (ABS) at 25 degrees C over the full range of composition (from 0 wt % to the solubility limit of the mixture components). The data were used to construct equilibrium phase diagrams, which show the phase of the mixtures as a function of total composition, dry mixture composition, water content, and ambient relative humidity (RH). This work complements previous reports on the thermodynamic properties of AS/MA mixtures because the range of concentrations investigated is larger than in any other published single study. On the other hand, this is the first report on the a(w), deliquescence, and water absorption of ABS/MA mixtures. The eutonic composition for AS/MA mixtures was found to be 66.8 MA dry wt % (MA dry wt % = MA mass x 100/(AS mass + MA mass) with a DRH of 0.437. The eutonic composition for the ABS/MA mixtures was lower than for the AS/MA mixtures: 20.9 MA dry wt % with a DRH of 0.327. Measured a(w) of liquid AS/MA and ABS/MA solutions is compared with an extended Zdanovskii-Stokes-Robinson expression, obtaining a good agreement (error < 5-6%). The expression was used to predict water uptake of mixtures and might be useful to interpret particle hygroscopic growth experiments. Comparison of the AS/MA and ABS/MA systems indicates that ABS reduces the DRH and enhances water uptake, relative to mixtures with AS. The results confirm that ambient particles containing sulfate and water-soluble organic compounds can remain liquid or partially liquid at very low ambient RH conditions, especially if the sulfate is not completely neutralized.     

A first principles molecular dynamics study of the solvation structure and migration kinetics of an excess proton and a hydroxide ion in binary water-ammonia mixtures

We have investigated the solvation structure and migration kinetics of an excess proton and a hydroxide ion in water-ammonia mixed liquids of varying composition by means of ab initio molecular dynamics simulations. The excess proton is always found to be attached to an ammonia molecule to form the ammonium ion. Migration of the excess proton is found to occur very occasionally from one ammonia to the other but no proton transfer to a water molecule is observed during the entire simulations. Also, when the ammonium ion is solvated in water only, its hydrogen bond dynamics and rotation are found to occur at a faster rate than those in water-ammonia mixtures. For water-ammonia mixtures containing a proton less, the defect is found to stay like the hydroxide ion. For these systems, occasional proton transfer is found to occur only through the hydrogen bonded chains of water molecules in these water-ammonia mixtures. No proton transfer is found to take place from an ammonia molecule. The presence of ammonia molecules makes the realization of proper presolvated state of the hydroxide ion to accept a proton a more difficult process and, as a result, the rate of proton transfer and migration kinetics of the hydroxide ion in water-ammonia mixtures are found to be slower than that in liquid water and these rates are found to slow down further with increase of ammonia concentration.     

Analysis of oligodeoxynucleotides by negative-ion matrix-assisted laser desorption mass spectrometry

Thirty compounds were tested in combination with ammonium acetate for the ability to desorb and ionize oligodeoxynucleotides by ultraviolet matrix-assisted laser desorption mass spectrometry. Negative ion yields using matrices such as 2,5-dihydroxybenzoic acid and 3-hydroxy-4-methoxybenzaldehyde are enhanced by the addition of ammonium salts at a molar ratio of 1:1, pH 7. 3-Hydroxy-4-methoxybenzaldehyde was tested with 12 different ammonium, alkylammonium, and pyridinium salts for the ability to cocrystallize with oligodeoxynucleotides and to improve desorption and ionization. Ions of oligodeoxynucleotides 9, 10, and 11 nucleotides in length were observed with a matrix of 3-hydroxy-4-methoxybenzaldehyde and ammonium acetate, pH 7, at a mass resolution of 100–150 (fwhm). A small oligodeoxynucleotide (11-mer) was observed at the femtomole level with a combination of 2,5-dihydroxybenzoic acid and ammonium acetate as the matrix. Ions from single stranded DNA (60 nucleotides in length) were also observed using this same matrix combination. The results of these studies have shown that both sensitivity and desorption conditions need to be further improved before complex mixtures of large pieces of DNA can be effectively analyzed.     

Study of the mechanism of intumescence in fire retardant polymers: Part VI—Mechanism of ester formation in ammonium polyphosphate-pentaerythritol mixtures

It is shown that, on heating ammonium polyphosphate-pentaerythritol mixtures, phosphoric ester bonds are formed first by alcoholysis of the polyphosphate chain. Further intramolecular alcoholysis and/or esterification leads to cyclic pentaerythritol phosphate structures inserted in the polyphosphate chains. Evidence is also given of intermolecular dehydration of pentaerythritol in mixtures with a large excess of alcoholic hydroxy groups over phosphorus atoms. The intumescent behaviour of the mixtures is discussed in relation to the final structure of the product of reaction which depends on the composition of the original mixture.     

Mixed Micellization Behavior of 12-2-12 Gemini Surfactant with Some Alkyltrimetyl Ammonium Bromide Surfactants

Mixed micellization behavior of dimeric cationic surfactant ethanediyl-1,2-bis (dimethyldodecylammonium bromide) (12-2-12) with a series of monomeric cationic surfactants dodecyltrimethyl ammonium bromide (DTAB), tetradecyltrimethyl ammonium bromide (TTAB), and cetyltrimethyl ammonium bromide (CTAB) has been studied in aqueous and aqueous polyvinylpyrrolidone (PVP) solutions at 298.15, 308.15, and 318.15 K, respectively, using conductometric method. Various thermodynamic parameters like mixed micelle concentration (C_m), micelle mole fraction (X₁), interaction parameter (β), and free energy of mixing (ΔG_ex) of the mixed systems have been determined and analyzed using Rubingh's regular solution theory. The results indicate that in aqueous solutions the binary mixtures of 12-2-12 with DTAB/TTAB behave nonideally with mutual synergism whereas that with CTAB shows almost ideal behavior at 298.15 K. At 318.15 K, all these binary mixtures exhibit antagonistic behavior. The effect of variation in chain length of alkyltrimethyl ammonium bromide surfactants on the interactions with 12-2-12 have also been evaluated and discussed.     

Thermal-spectroscopic characterization of acetone peroxide and acetone peroxide mixtures with nitrocompounds

Triacetone triperoxide (TATP), also known as acetone peroxide, is a powerful homemade energetic compound, highly unstable and not detectable by traditional detection technologies. The calorimetric profiles of TATP mixtures with TNT, ammonium nitrate, and nitroguanidine were evaluated and compared to pure materials. Raman spectroscopy was used to identify possible interactions between mixture components that may arise on contact. Typical results show a shift of the TATP decomposition temperature to higher temperatures, as well as decomposition of the nitrocompound initiated by TATP decomposition. The vibrational spectra were used as spectroscopic signatures for these mixtures, which can be used to understand detection challenges and for the development of desensitization approaches.     

Analysis of Quaternary Ammonium Compounds by Ion-Pair Thin Layer Chromatography on Silica Gel

Abstract

A general approach to the chromatographic analysis of quaternary ammonium compounds on silica gel thin layers is described. The quaternary cations migrate as ion pairs with bromide or iodide as counter ions. Methanol or chloroform-methanol mixtures serve as developing solvents, in which excess amounts of NaBr or NaI are dissolved. If the solvent cannot dissolve sufficient quantities of halide salts, the latter can be sprayed onto the plate as a methanol solution prior to development. The separation patterns of the quaternary ammonium compounds can be influenced by the choice of counter ion and by the choice of the organic solvent components.     

High Performance Liquid Chromatography of Enkephalin and Endorphin Peptide Analogs

Abstract

Reverse phase systems are presented which utilize a μ alkylphenyl column and ammonium acetate buffered aqueous acetonitrile mobile phases to separate mixtures of enkephalin and endorphin peptide analogs. High pressure liquid chromatographic separations of mixtures of enkephalin diastereomers as well as mixtures of other closely similar analogs have been developed.

Endorphin analogs were observed to be quite hydrophobic and required mobile phases containing 40% or more acetonitrile for reasonable elution times. The enkephalin analogs by comparison required 20% or more acetonitrile. Detection at both 254 and 280 nm was useful in recognizing the important peaks in the elution profile.     

Organocatalytic synthesis of amides from nitriles via the Ritter reaction

A simple, inexpensive, environmentally friendly, and efficient route for the synthesis of a wide variety of amides in high yields via the Ritter reaction of alcohols with nitriles has been demonstrated. Pentafluorophenyl ammonium triflate (PFPAT) is used as an organocatalyst and is air-stable, cost-effective, easy to handle, and easily removed from the reaction mixtures.     

Extraction of oxalic acid from solutions of electrolyte mixture

Extraction of oxalic acid with tributyl phosphate and triisoamyl phosphate from solutions of its mixtures with nitric, phosphoric, sulfuric, and hydrochloric acid and with ammonium nitrate and chloride was studied. In the extractability series, oxalic acid occupies the position between nitric and phosphoric acids, with sulfuric and hydrochloric acids acting as strong salting-out agents. Nitric acid salts drastically decrease the distribution ratios of oxalic acid.