NH SO Research Articles

Tolerance of cattle to increased dietary sulfur and effect of dietary cation-anion balance

The objective of this study was to determine if dietary cation-anion balance (DCAB) affects the concentration of S that can be tolerated by growing and finishing cattle without adversely affecting performance. Angus cross and Bradford steers (n=114; average initial BW=252.8 kg) were blocked by BW and breed, and randomly assigned within a block to treatment. The design was a 3 × 2 factorial arrangement of treatments with S (from NH(4)SO(4)) supplemented at 0, 0.15, or 0.30% of DM, and NaHCO(3) added at 0 or 1.0% of DM. Each treatment consisted of 3 pens containing 5 steers and 1 pen containing 4 steers. Steers were used in an 84-d growing study followed by a finishing study. A corn silage-based diet was fed during the growing study and a corn-based diet was fed during the finishing study. Steers were not randomized between experiments. The analyzed concentrations of S in the growing diets were 0.12, 0.30, and 0.46%, whereas the analyzed concentrations of S in the finishing diets were 0.13, 0.31, and 0.46% for treatments supplemented with 0, 0.15, and 0.30% S, respectively. Increasing DCAB by approximately 15 mEq/100 g of DM, by the addition of NaHCO(3,) did not affect (P > 0.36) performance during the growing or finishing studies. During the growing study DMI was not affected (P=0.29) by dietary S. Steers fed diets containing 0.30% S had greater ADG (P=0.02) and G:F (P=0.01) than those receiving 0.46% S, but similar (P > 0.36) performance to steers fed 0.12% S. During the finishing study, steers fed diets containing 0.46% S had less ADG than steers fed 0.13 (P=0.004) or 0.31% S (P=0.07), whereas ADG did not differ (P=0.18) among steers fed 0.13 and 0.31% S. Steers fed diets containing 0.31 (P=0.01) or 0.46% S (P=0.001) had less DMI than controls, but G:F was not affected (P=0.52) by S during the finishing study. Carcass characteristics did not differ (P > 0.18) among steers fed diets containing 0.13 and 0.31% S. Steers receiving diets containing 0.46% S had decreased HCW (P=0.001), quality (P=0.02), and yield grades (P=0.04) than steers receiving 0.13% S. Plasma Cu concentrations on d 101 of the finishing phase and liver Cu concentrations at slaughter were greater (P ≤ 0.05) in control steers compared with those fed diets containing 0.31 or 0.46% S. This study indicates that steers fed growing diets can tolerate up to 0.46% S with minimum effects on performance. Finishing steers tolerated diets containing 0.31% S without adverse affects on ADG or G:F. However, 0.46% S greatly decreased ADG and DMI, and increasing DCAB did not prevent these depressions.

A new route to the syntheses of N-(fluorosulfuryl)sulfonamide salts: Crystal structure of Ph 4P + [CF 3SO 2NSO 2F] −

A new route for the preparation of potassium and tetraphenylphosphonium salts of N-(fluorosulfuryl)trifluoromethane sulfonamide is described. N-(chlorosulfuryl)-trifluoromethane sulfonamide CF 3SO 2–NH–SO 2Cl, that was used for preparations of both salts, was prepared by the reaction of trifluoromethane sulfonamide CF 3SO 2NH 2 and chlorosulfonic acid in the presence of SOCl 2. The obtained N-(chlorosulfuryl)trifluoromethane sulfonamide was converted to potassium N-(fluorosulfuryl)trifluoromethane sulfonamide by using anhydrous KF. Potassium N-(fluorosulfuryl)trifluoromethane sulfonamide served as a starting material for the preparation of the corresponding tetraphenylphosphonium N-(fluorosulfuryl)trifluoromethane sulfonamide that crystallizes from the aqueous solution of potassium N-(fluorosulfuryl)trifluoromethane sulfonamide and tetraphenylphosphonium chloride. N-(fluorosulfuryl)trifluoromethane sulfonamide tetraphenylphosphonium salt is tetragonal, space group P 4 ¯ .

Micro-patterns of Au@SiO 2 core-shell nanoparticles formed by electrostatic interactions

In this paper, silica-coated Au nanoparticles (Au@SiO 2) were prepared by the technique of vortex mixing. Subsequently, these monodisperse Au@SiO 2 nanoparticles were functionalized by the silane reagents 3-aminopropyltriethoxysilane (APS) and 3-mercaptopropyltriethoxysilane (MPTS) respectively. Then, these NH 2-terminated and SO 3 2−-terminated Au@SiO 2 nanoparticles were respectively assembled onto the substrates, which have been patterned with different self-assembly monolayers (SAMs), to form close-packed two-dimensional Au@SiO 2 nanoparticle arrays by electrostatic interactions. The morphologies and the optical properties of Au@SiO 2 nanoparticles with different silica-shell thicknesses were characterized by TEM and UV–vis. The compositions and zeta potentials of the functionalized Au@SiO 2 nanoparticles were examined by X-ray photoelectron spectroscopy (XPS) and dynamic light scattering (DLS). The morphologies of the patterns formed on different templates were characterized by atomic force microscopy (AFM).

Structure and stability of Li(I) and Na(I) – Carboxylate, sulfate and phosphate complexes

DFT was used to investigate molecular structure and metal affinity of the systems CH 3CO 2M ( 1), CH 3–O–SO 3M ( 2), CH 3–NH–SO 3M ( 3), (CH 3–O–PO 3M) − ( 4), CH 3–O–PO 3M 2 ( 5), CH 3–O–(CH 3)PO 2M ( 6), and 1,4-DiOMe IdoA-2SM 2 ( 7; 2S o conformation) (M = Li + and Na +), respectively. Interaction enthalpies, entropies and Gibbs energies of the metal-coordinated systems were determined on the B3LYP/6-311+G(d,p) level. The computed Gibbs energies, Δ G o , of the isolated systems 1– 7 are negative and span a rather broad energy interval (from −500 to −1500 kJ mol −1). The lithium and sodium binding enthalpies and Gibbs energies of a series of phosphate, carboxylate, N-, and O-sulfate anions indicate that multidentate chelation plays an important role in the binding. In particular, the glycosaminoglycan structural unit of heparin 1,4-DiOMe IdoA-2SM 2 (M = Li + and Na +) with coordinating groups in the hexopyranose ring exhibits enhanced metal ion binding energies. Computations that include the effect of solvation showed that in water the relative stability of Li +⋯Ligand and Na +⋯Ligand ionic bonds is rapidly diminished. The computed interaction Gibbs energy in water is small, slightly negative and/or positive, i.e. destabilizing. Thus in water, both contact ion pairs and solvent-separated ion pairs may coexist.

Cellulose based macromolecular chelator having pyrocatechol as an anchored ligand: synthesis and applications as metal extractant prior to their determination by flame atomic absorption spectrometry

Pyrocatechol is immobilized on cellulose via NHCH 2CH 2NHSO 2C 6H 4NN linker and the resulting macromolecular chelator characterized by IR, TGA, CPMAS 13C NMR and elemental analyses. It has been used for enrichment of Cu(II), Zn(II), Fe(III), Ni(II), Co(II), Cd(II) and Pb(II) prior to their determination by flame atomic absorption spectrometry (FAAS). The pH ranges for quantitative sorption (98.0–99.4%) are 4.0–7.0, 5.0–6.0, 3.0–4.0, 5.0–7.0, 5.0–8.0, 7.0–8.0 and 4.0–5.0, respectively. The desorption was found quantitative with 0.5 mol dm −3 HCl/HNO 3 (for Pb). The sorption capacity of the matrix for the seven metal ions has been found in the range 85.3–186.2 μmol g −1. The optimum flow rate of metal ion solution for quantitative sorption of metal onto pyrocatechol functionalized cellulose as determined by column method, is 2–6 cm 3 min −1, whereas for desorption it is 2–4 cm 3 min −1. The tolerance limits for NaCl, NaBr, NaI, NaNO 3, Na 2SO 4, Na 3PO 4, humic acid, EDTA, ascorbic acid, citric acid, sodium tartrate, Ca(II) and Mg(II) in the sorption of all the seven metal ions are reported. Ascorbic acid is tolerable up to 0.8 mmol dm −3 with Cu and Pb where as sodium tartrate does not interfere up to 0.6 mmol dm −3 with Pb. There is no interference of NaBr, NaCl and NaNO 3 up to a concentration of 0.5 mol dm −3, in the sorption of Cu(II), Cd(II) and Fe(III) on to the chelating cellulose matrix The preconcentration factors are between 75 and 300 and t 1/2 values ≤5 min for all the metal ions. Simultaneous sorption of Cu, Zn, Ni and Co is possible at pH 5.0 if their total concentration does not exceed lowest sorption capacity. The present matrix coupled with FAAS has been used to enrich and determine the seven metal ions in river and tap water samples (relative standard deviation (R.S.D.) 1.05–7.20%) and synthetic certified water sample SLRS-4 (NRC, Canada) with R.S.D. ∼2.03%. The cobalt present in pharmaceutical vitamin tablets was also preconcentrated on the modified cellulose and determined by FAAS (R.S.D. ∼1.87%).

Cellulose functionalized with 8-hydroxyquinoline: new method of synthesis and applications as a solid phase extractant in the determination of metal ions by flame atomic absorption spectrometry

8-Hydroxyquinoline has been immobilized on cellulose via a moderate size NHCH 2CH 2NHSO 2C 6H 4NN linker and the resulting macromolecular chelator (and intermediates) characterized by infrared spectrometry, cross-polarization magic angle spinning (CPMAS) 13 C NMR spectrometry and thermogravimetric analysis (TGA). It has been used for enrichment of Cu(II), Zn(II), Fe(III), Ni(II), Co(II), Cd(II) and Pb(II) prior to their determination by flame atomic absorption spectrometry (FAAS), which are quantitatively sorbed (recoveries>97%) at pH 4.2–6.7, 4.2–7.5, 2.0–3.0, 5.3–6.7, 5.3–6.2, 6.2–9.0 and 4.2–5.3, respectively. The sorption capacity for the seven cations varies from 93.8 to 629.9 μmol g −1. HCl or HNO 3 (1 mol dm −3) may be used to desorb all the cations. The optimum flow rate for sorption and desorption has been found to be 2–4 cm 3 min −1. The tolerance limits of electrolytes NaCl, NaBr, NaNO 3, Na 2SO 4, Na 3PO 4 and cations Ca 2+ and Mg 2+ (added as chloride and sulphate, respectively) in the sorption of all these metal ions are reported. The preconcentration factor is between 90 and 300. Simultaneous sorption of the cations other than iron(III) is possible if their total concentration does not exceed sorption capacity. The present matrix coupled with FAAS has been used to enrich and determine the seven metal ions in river water samples (R.S.D.<7.4%) and water samples having a composition similar to certified water sample SLRS-4 (NRC, Canada) with R.S.D. ∼2.3%.

Metalloporphyrin-mediated asymmetric nitrogen-atom transfer to hydrocarbons: aziridination of alkenes and amidation of saturated C-H bonds catalyzed by chiral ruthenium and manganese porphyrins.

Chiral metalloporphyrins [Mn(Por*)(OH)(MeOH)] (1) and [Ru(Por*)(CO)(EtOH)] (2) catalyze asymmetric aziridination of aromatic alkenes and asymmetric amidation of benzylic hydrocarbons to give moderate enantiomeric excesses. The mass balance in these nitrogen-atom-transfer processes has been examined. With PhI=NTs as the nitrogen source, the aziridination of styrenes, trans-stilbene, 2-vinylnaphthalene, indene, and 2,2-dimethylchromene catalyzed by complex 1 or 2 resulted in up to 99 % substrate conversions and up to 94 % aziridine selectivities, whereas the amidation of ethylbenzenes, indan, tetralin, 1-, and 2-ethylnaphthalene catalyzed by complex 2 led to substrate conversions of up to 32 % and amide selectivities of up to 91 %. Complex 1 or 2 can also catalyze the asymmetric amidation of 4-methoxyethylbenzene, tetralin, and 2-ethylnaphthalene with "PhI(OAc)(2) + NH(2)SO(2)Me", affording the N-substituted methanesulfonamides in up to 56 % ee with substrate conversions of up to 34 % and amide selectivities of up to 92 %. Extension of the "complex 1 + PhI=NTs" or "complex 1 + PhI(OAc)(2) + NH(2)R (R=Ts, Ns)" amidation protocol to a steroid resulted in diastereoselective amidation of cholesteryl acetate at the allylic C-H bonds at C-7 with substrate conversions of up to 49 % and amide selectivities of up to 90 % (alpha:beta ratio: up to 4.2:1). An aziridination- and amidation-active chiral bis(tosylimido)ruthenium(VI) porphyrin, [Ru(Por*)(NTs)(2)] (3), and a ruthenium porphyrin aziridine adduct, [Ru(Por*)(CO)(TsAz)] (4, TsAz=N-tosyl-2- (4-chlorophenyl)aziridine), have been isolated from the reaction of 2 with PhI=NTs and N-tosyl-2-(4-chlorophenyl)aziridine, respectively. The imidoruthenium porphyrin 3 could be an active species in the aziridination or amidation catalyzed by complex 2 described above. The second-order rate constants for the reactions of 3 with styrenes, 2-vinylnaphthalene, indene, ethylbenzenes, and 2-ethylnaphthalene range from 3.7-42.5x10(-3) dm(3) mol(-1) s(-1). An X-ray structure determination of complex 4 reveals an O- rather than N-coordination of the aziridine axial ligand. The fact that the N-tosylaziridine in 4 does not adopt an N-coordination mode disfavors a concerted pathway in the aziridination by a tosylimido ruthenium porphyrin active species.

An efficient synthesis of N,N′-linked oligoureas

This paper reports an efficient synthesis of N-alkyl- N,N′-linked oligoureas [NRCONHCH 2CH 2] n, which involves the repetition of three steps: (1) main-chain extension by ring-opening of N-(2-nitrobenzenesulfonyl)-2-imidazolidone ( 1) by a secondary amine RR′NH to afford sulfonamide RR′NCONHCH 2CH 2NHSO 2Ar (2) side-chain attachment by N-alkylation of the sulfonamide with alkyl halide R″X, and (3) removal of the sulfonyl group to give a new secondary amine RR′NCONHCH 2CH 2NHR″). A tetraurea was prepared in 10 steps and 58% overall yield by this method.

New Polymer Synthesis: Polymers Possessing Diiminosulfoxide Functionality in the Backbone

Abstract Three new monomers with sulfinylimine functionality have been prepared. They react with appropriate aromatic diamines to give a new class of polymers having the diiminosulfoxide (—NH—SO—NH—) functional group in their backbone. the monomers as well as polymers are characterized by spectral data and elemental analysis. Experiments were carried out to find the effect of reaction time and solvent on the polymerization reaction. the polymers are soluble in electron-donating organic solvents, such as DMF, NMP, and DMAC, and insouble in most nonpolar solvents. They are thermostable up to 200°C, but their stability in the presence of sulfuric acid and aqueous sodium hydroxide is low.

Mutagenic and inactivating effects of methyl alkylaminosulfonates on Escherichia coli

Methyl alkylamino methanesulfonates are mutagenic agents as shown by treating several strains of E. coli at pH 7. Methyl methylaminosulfonate (CH 3NH-SO 3CH 3) was more efficient than methyl ethylaminosulfonate (C 2H 5NHSO 3CH 3) which itself was more efficient than methyl isopropylaminosulfonate (C 3H 7NHSO 3CH 3). Methyl methylaminosulfonate seemed to be at least as effective as methyl methanesulfonate (CH 3SO 3CH 3). Methyl methylaminosulfonate produced a yield of up to 1% of auxotrophic mutants. All three new mutagens appeared to react according to the same mechanism by ester fission and methylation of nucleophilic groups as is known for methyl methanesulfonate. The reaction mechanism seems to be of the S N2 type.

Photolytic cleavage of sulfonamide bonds.

It has been found that the sulfonamide bond is relatively susceptible to photolytic cleavage. The breakdown was effected either by irradiation with a source having a continuous emission above the wavelengths of 1800 angstroms or by another source emitting principally at 2537 angstroms. Less destruction of the amino acids was seen with the latter relative to the sulfonamide bond cleavage. The cleavage was not effected by irradiation at wavelengths greater than about 3000 angstroms. Side reactions were noted involving decarboxylation, demination, and destruction of certain susceptible amino acids such as tryptophan. In only one case was a product found that arose from cleavage of a carboxamide bond; glycyltyrosine gave glycine and tyrosine upon irradiation. A yield of 75 percent of the corresponding amino acid has been obtained by irradiation of tosylhistidine; yields of 75 to 100 percent have been obtained from sulfamic acid (NH(2)SO(3)H). A qualitative method for identifying sulfonylated amino acids is described.

The effect of ionizing radiation on phagocytosis and the bactericidal power of the blood. II. The effect of radiation on ingestion and digestion of bacteria.

Rats irradiated with 600 r (total body) showed increased indices of both opsonophagic and surface phagocytosis 2, 12, and 24 hours after irradiation. The indices decreased 72 hours after exposure and returned to normal by the 4th to 5th postirradiation day. Bactericidal power of the blood of irradiated animals was depressed when measured 3 and 6 days after exposure to x-rays. Decomplemented serum from irradiated animals was more bactericidal against M. aureus than decomplemented serum from the control rats. This bactericidal substance was destroyed at 78 degrees C. and was found not to require any complement or specific antibodies for action. Extracts of leucocytes from animals 3 days after irradiation demonstrated no bactericidal activity against M. aureus, while extracts from the control animals or rats 1 day after irradiation were actively bactericidal. The extracts from leucocytes of non-irradiated animals were thermolabile, non-dialyzable, had a pH optimum of 7.5, and were capable of being precipitated by NH(4)SO(4) and of calcium phosphate fractionation. The observed increase in susceptibility of irradiated rats to infection with M. aureus was correlated not only with granulopenia but also with the alteration of the above indicated functions of the granulocytes of the irradiated animals.