Aryl fluorosulfate analogues as potent antimicrobial agents: SAR, cytotoxicity and docking studies.

A series of aryl fluorosulfate analogues (1-37) were synthesized and tested for in vitro antibacterial and antifungal studies, and validated by docking studies. The compounds 9, 12, 14, 19, 25, 26, 35, 36 and 37 exhibited superior antibacterial potency against tested bacterial strains, while compounds 2, 4, 5, 15, 35, 36 and 37 were found to have better antifungal activity against tested fungal strains, compared to standard antibiotic gentamicin and ketoconazole respectively. Among all the synthesized 37 analogs, compounds 25, 26, 35, 36 and 37 displayed excellent anti-biofilm property against Staphylococcus aureus. The structure-activity relationship (SAR) revealed that the antimicrobial activity depends upon the presence of -OSO2F group and slender effect of different substituent's on the phenyl rings. The electron donating (OCH3) groups in analogs increase the antibacterial activity, and interestingly the electron withdrawing (Cl, NO2, F and Br) groups increase the antifungal activity (except compound 35, 36 and 37). The mechanism of potent compounds showed membrane damage on bacteria confirmed by SEM. Compounds 35, 36 and 37 exhibited highest glide g-scores in molecular docking studies and validated the biocidal property.

Copper and cobalt recovery from pyrite ashes of a sulphuric acid plant.

The pyrite ashes formed as waste material during the calcination of concentrated pyrite ore used for producing sulphuric acid not only has a high iron content but also contains economically valuable metals. These wastes, which are currently landfilled or dumped into the sea, cause serious land and environmental pollution problems owing to the release of acids and toxic substances. In this study, physical (sulphation roasting) and hydrometallurgical methods were evaluated for their efficacy to recover non-iron metals with a high content in the pyrite ashes and to prevent pollution thereby. The preliminary enrichment tests performed via sulphation roasting were conducted at different roasting temperatures and with different acid amounts. The leaching tests investigated the impact of the variables, including different solvents, acid concentrations and leach temperatures on the copper and cobalt leaching efficiency. The experimental studies indicated that the pre-enrichment via sulphation roasting method has an effect on the leaching efficiencies of copper and cobalt, and that approximate recoveries of 80% copper and 70% cobalt were achieved in the H2O2-added H2SO4 leaching tests.

Search for new catalysts for the oxidation of SO2.

The focus of this paper is the search and characterization of novel catalysts for the gas phase oxidation of concentrated SO2 for the production of sulfuric acid. Modern high-throughout (HT) methods such as emissivity corrected Infrared Thermography (ecIRT) and automated synthesis techniques were used for the synthesis and activity measurements of the samples. In addition a plug flow reactor that uses UV-vis online analytics for the quantification of the SO2 conversion was designed, built and used for validation of the HT results. The study started with a highly diverse search space of elemental compositions designed for potential discovery. About a thousand samples were synthesized using sol-gel recipes and screened for catalytic SO2 oxidation activity over a temperature range of 330-450 °C. Several novel catalyst systems were discovered during the screening process and the most interesting systems were further characterized. The most important doping effects on activity found were the influence of bismuth and selenium doping on standard sulfuric acid catalysts, the activity gain of chromium based catalysts caused by the doping with antimony and the activity gain of chromium as well as iron and vanadium based catalysts caused by the doping with tin.

Sonochemical synthesis of silica and silica sulfuric acid nanoparticles from rice husk ash: a new and recyclable catalyst for the acetylation of alcohols and phenols under heterogeneous conditions.

Silica nanoparticles were synthesized from rice husk ash at room temperature by sonochemical method. The feeding rate of percipiteting agent and time of sonication were investigated. The nanostructure of the synthesized powder was realized by the FE-SEM photomicrograph, FT-IR spectroscopy, XRD and XRF analyses. These analytical observations have revealed that the nano-sized amorphous silica particles are formed and they are spheroidal in shape. The average particle size of the silica powders is found to be around 50 nm. The as-synthesized silica nanoparticles were subsequently modified with chlorosulfonic acid and prepared silica sulfuric acid nanoparticles, which were employed as an efficient catalyst for the acylation of alcohols and phenols with acetic anhydride in excellent yields under solvent-free conditions at room temperature. This reported method is simple, mild, and environmentally viable and catalyst can be simply recovered and reused over 9 times without any significant loss of its catalytic activity.

Formic acid catalyzed hydrolysis of SO3 in the gas phase: a barrierless mechanism for sulfuric acid production of potential atmospheric importance.

Computational studies at the B3LYP/6-311++G(3df,3pd) and MP2/6-311++G(3df,3pd) levels are performed to explore the changes in reaction barrier height for the gas phase hydrolysis of SO(3) to form H(2)SO(4) in the presence of a single formic acid (FA) molecule. For comparison, we have also performed calculations for the reference reaction involving water assisted hydrolysis of SO(3) at the same level. Our results show that the FA assisted hydrolysis of SO(3) to form H(2)SO(4) is effectively a barrierless process. The barrier heights for the isomerization of the SO(3)···H(2)O···FA prereactive collision complex, which is the rate limiting step in the FA assisted hydrolysis, are found to be respectively 0.59 and 0.08 kcal/mol at the B3LYP/6-311++G(3df,3pd) and MP2/6-311++G(3df,3pd) levels. This is substantially lower than the ~7 kcal/mol barrier for the corresponding step in the hydrolysis of SO(3) by two water molecules--which is currently the accepted mechanism for atmospheric sulfuric acid production. Simple kinetic analysis of the relative rates suggests that the reduction in barrier height facilitated by FA, combined with the greater stability of the prereactive SO(3)···H(2)O···FA collision complex compared to SO(3)···H(2)O···H(2)O and the rather plentiful atmospheric abundance of FA, makes the formic acid mediated hydrolysis reaction a potentially important pathway for atmospheric sulfuric acid production.

Growth, spectral studies, thermal and dielectric aspects of L-lysine doped triglycine sulpho phosphate (TGSP) crystals.

Single crystals of ferroelectric material triglycine sulpho phosphate (TGSP) have been grown by slow evaporation method. The effect of L-lysine addition on the growth of TGSP crystal has been studied for various concentrations (5, 10 and 20 mol%). Unit cell parameters were determined from powder XRD analysis. Functional groups present in the grown crystal were confirmed from the vibrational frequencies of recorded FTIR and FT-Raman spectrum. The L-lysine doping into the crystal lattice has been qualitatively confirmed by spectral analysis. Thermogravimetric studies confirm that the lysine is incorporated into TGSP crystals. Dielectric studies reveal that the incorporation of lysine into TGSP enhances its dielectric strength.

Trace element transformations and partitioning during the roasting of pyrite ores in the sulfuric acid industry.

Total concentrations combined with chemical partitioning of trace elements (Cd, Co, Cr, Mn, Ni, Pb, Tl, and Zn) in raw pyrite ore and solid roasting wastes were investigated in order to elucidate their transformations and partitioning during the roasting of raw pyrite ores in sulfuric acid production. In order to better understand the behavior of these elements during roasting, mineral transformations accompanying roasting were also investigated by using microscopy. Results indicated that the mode of occurrence of trace elements in raw pyrite ore and the thermostability of trace element-bearing species formed during roasting played major roles in the transformations of the selected trace elements. Silicate- and amorphous iron (hydr)oxide-bound elements (Cr and Pb) were stable and mainly retained in their original phases. However, acid-exchangeable and sulfide-bound elements tended to transform into other forms via different pathways: elements that tend to form low thermostable species (Cd, Pb and Tl) were significantly vaporized, whereas elements that tend to form high thermostable species (Co, Mn and Ni) mainly reacted with iron oxides or silicates, which then remained in the solid residues. The volatility of trace elements during the roasting has a significant effect on their subsequent partitioning in roasting wastes. Nonvolatile element (Co, Cr, Mn, and Ni) partitioning was determined by settling of the particulate in which they are bound, whereas the partitioning of (semi)volatile elements (Cd, Pb, Tl, and Zn) was controlled by the adsorption of their gaseous species on the particulate.

The effect of silica fume on biodegradation of cement paste and its capacity to immobilize strontium during exposure to microbial sulfur oxidation.

The disposal of low-level radioactive waste containing isotopes such as strontium by immobilization in cement paste has become common practice. However, the stability of cement paste in the environment may be impaired by sulfuric acid produced by sulfur-oxidizing bacteria. Since biodegradation rates in the environment of most radioactive waste burial sites are too low to be measured, determination of the degradation kinetics of cement paste is a difficult task. This study reports on the development of an accelerated biodegradation system for cement pastes in which the cement paste is exposed to a continuous culture of the sulfur-oxidizing bacterium Halothiobacillus neapolitanus. This system facilitated detection of the biodegradation processes in cement paste after as short a time as 15 days. A comparison of the durability of a cement paste blended with silica fume with that of unblended cement paste showed that the silica fume induced an increase in the leaching of Ca(+2) and Si and enhanced weight loss, indicating rapid deterioration in the structural integrity of the cement paste. The leaching of Sr(+2) from the silica fume amended cement paste was slightly reduced as compared with the non amended cement paste, indicating an increase in immobilization of strontium. Nevertheless, our findings do not support the use of silica fume as a suitable additive for immobilization of low-level radioactive waste.

CF3 oxonium salts, O-(trifluoromethyl)dibenzofuranium salts: in situ synthesis, properties, and application as a real CF3+ species reagent.

We report in situ synthesis of the first CF(3) oxonium salts, thermally unstable O-(trifluoromethyl)dibenzofuranium salts, which furthermore have different counteranions (BF(4)-, PF(6)-, SbF(6)-, and Sb(2)F(11)-) and ring substituents (tert-butyl, F, and OCH(3)), by photochemical decomposition of the corresponding 2-(trifluoromethoxy)biphenylyl-2'-diazonium salts at -90 to -100 degrees C. The yields markedly increased in the order of BF(4)- < PF(6)- < SbF(6)- < Sb(2)F(11)-. The CF(3) oxonium salts were fully assigned by means of (1)H and (19)F NMR spectroscopy at low temperature. The CF(3) salts decomposed to form CF(4) and dibenzofurans. The half-life times at -60 degrees C of the 2-tert-butyl salts having different counteranions were 29 min for BF(4)- salt 2d, 36 min for PF(6)- salt 2c, 270 min for SbF(6)- salt 2a, and 415 min for Sb(2)F(11)- salt 2b. Those at -60 degrees C of the Sb(2)F(11)- salts having different 2-substituents were 13 min for F salt 3b, 63 min for H (unsubstituted) salt 1b, and 415 min for tert-butyl salt 2b. Thus, the stability of the CF(3) oxonium salts increased in the order of BF(4)- < PF(6)- < SbF(6)- < Sb(2)F(11)- and F < H < tert-butyl, which is in accord with the increasing orders of the non-nucleophilicity of counteranions and the electron-donating effect of ring substituents. 2-tert-Butyl-O-(trifluoromethyl)dibenzofuranium hexafluoroantimonate (2a) was thus chosen and successfully applied as a real CF(3)+ species source to the direct O- and N-trifluoromethylations of alcohols, phenols, amines, anilines, and pyridines under very mild conditions. The thermal decomposition method with a mixture of diazonium salt 17a and aryl- or alkylsulfonic acids, pyridine, or pyridines having an electron-withdrawing group also afforded CF(3)O or CF(3)N products. The trifluoromethylation mechanism is discussed and an S(N)2 mechanism containing the transient formation of free CF(3)+ is proposed. Thus, the present study has demonstrated that the exceedingly reactive CF(3)+ species can be generated much easier than the CH(3)+ species, contrary to the common sense that CF(3)+ is extremely difficult to generate in solution.

Synthesis of alpha-fluorosulfonate and alpha-fluorosulfonamide analogues of a sulfated carbohydrate.

The first synthesis of sulfonamide and sulfonate analogues of a sulfated carbohydrate in which the ester oxygen of the sulfate is replaced with a CHF or CF2 group is reported. This was accomplished by electrophilic fluorination of the protected sulfonate and sulfonamide precursors. [reaction: see text].

Investigations on the semi-batch precipitation of silica.

The semi-batch precipitation process of silica from sodium silicate and sulphuric acid has been structured into a primary particle production stage, an aggregation process until the gel point is reached and finally a gel fragmentation and compaction process. The progress of aggregation was analyzed by photon correlation spectroscopy. The reaction limited aggregation kernel was found to be proportional to B'(t)(q(p - q))A/2, where A assumes the value of one. The quantity B'(t) varies between 3.4 x 10(-20) and 2.6 x 10(-20) 1/min and is only a weak function of time. The stability ratio W for the aggregation process decreases with increasing aggregate size. During the period after the gel point the gel fragmentates. The gel clusters have an initial fractal dimension of approximately 1.8 which rapidly increases to 2.4 and stays roughly constant until the end of the process. The specific surface area decreases from 480 to 300 m2/g. The primary particles have a uniform size of 22.7 nm.

Transformations of hydroxy cyclic sulfates: stereospecific conversion into 2,3,5-trisubstituted tetrahydrofurans.

1,2-Cyclic sulfates have been prepared from O-protected ricinoleate and ricinelaidate esters. Upon deprotection of the 12-hydroxy moiety, the resulting 12-hydroxy-9,10-cyclic sulfates underwent stereospecific cyclization to the corresponding 2,3,5-trisubstituted tetrahydrofurans. The cyclization occurs by backside attack of the hydroxy oxygen on the distal carbon of the 1,2-cyclic sulfate, with inversion at that center.

Synthesis of analogues of myo-inositol 1,4,5-trisphosphate that contain sulfonamide, sulfate, methylphosphonate, and carboxymethyl groups.

The syntheses are described of four isosteric racemic myo-inositol 1,4,5-trisphosphate (1) analogues with the phosphate groups replaced by sulfonamide (2), sulfate (3), methylphosphonate (4), and carboxymethyl (5). None of these compounds had any affinity for the IP3 receptor or induced platelet aggregation.

Synthesis and properties of sulfated alkyl glycosides.

Alkyl glycosides were sulfated with sulfur trioxide-pyridine. Dodecyl alpha- and beta-D-glucopyranoside gave the corresponding 6-sulfates in 75 and 51% yields, respectively. Separation from polysulfated compounds was carried out by reversed-phase HPLC. Tetradecyl beta-maltopyranoside (16) gave a 88: 12 mixture of 6'- and 6-sulfates. The sulfated compounds were characterized by 1H-, 13C-, and 2-dimensional NMR spectroscopy. Surfactant and thermotropic liquid-crystalline properties of the sugar derivatives were examined. All of the glycosides show smectic phases (SA), and the clearing points rise by introduction of sulfate groups. Even glycosides having no unprotected hydroxy groups may show SA-phases when bearing sulfate groups. The mesomorphic properties cannot be explained by formation of distinct aggregates, but rather must be interpreted by an effective intramolecular contrast.

Synthesis of the sulfates derived from 5 alpha-cholestane-3 beta,6 alpha-diol.

Three new steroid sulfates--3 beta-hydroxy-5 alpha-cholestan-6 alpha-yl sulfate, 6 alpha-hydroxy-5 alpha-cholestan-3 beta-yl sulfate, and 5 alpha-cholestan-3 beta,6 alpha-diyl disulfate--were synthesized. For the syntheses of the key intermediates, 3 beta-hydroxy-5 alpha-cholestan-6 alpha-yl acetate and 6 alpha-hydroxy-5 alpha-cholestan-3 beta-yl acetate, selective protection of hydroxy groups in 5 alpha-cholestane-3 beta,6 alpha-diol was necessary. This problem was solved by using a combination of acetyl, tetrahydropyranyl, and methoxymethyl protective groups, which represents a new approach leading to these hydroxy acetates. Sulfated derivatives of 5 alpha-cholestane-3 beta,6 alpha-diol are present in marine invertebrates and were synthesized for the purposes of biologic testing.

Syntheses of disaccharides with (1----4)-beta glycosidic linkages related to the 4- and 6-sulfates and the 4,6-disulfates of chondroitin.

The solution salts of the 6'-sulfate 12, the 4'-sulfate 15 and the 4',6'-disulfate 17 of benzyl 4-O-(beta-D-galactopyranosyl)-beta-D-glucopyranosiduronate 10 have been synthesized. Methyl [benzyl 2,3-di-O-benzoyl-4-O-(2,3-di-O-benzoyl-beta-D-galactopyranosyl)-beta-D-+ ++glucopyranosid]uronate (9) has been prepared as a key intermediate from benzyl 4',6'-O-benzylidene-beta-D-lactopyranoside (2). Protection of 2 at C-6 with the tert-butyldimethylsilyl group, followed by O-perbenzoylation and disilylation, gave benzyl 2,3-di-O-benzoyl-4-O-(2,3-di-O-benzoyl-4,6-O-benzylidene-beta-D-galac top yranosyl)-beta-D-glucopyranoside (7). Oxidation of the 6-position of 7 proved to be difficult. However, 7 could be converted into the tert-butyl glucuronate 8 using chromium trioxide-pyridine and tert-butanol. Simultaneous hydrolysis of the benzylidene acetal and the tert-butyl ester groups, followed by esterification of the resulting free acid with diazomethane, yielded 9. Compound was directly sulfated with sulfur trioxide-trimethylamine within 12 h to give the 6'-sulfate 11. The 4',6-disulfate 16 was accessible by running the reaction under the same conditions for 14 days. The 4'-sulfate 14 was obtained after protecting the 6'-OH group of 9 with benzoyl cyanide to give the 6'-benzoate 13 followed by sulfation under more vigorous reaction conditions. Deesterification of 9, 11, 14, and 16 was achieved by treatment with aqueous sodium hydroxide in tetrahydrofuran to give 10, 12, 15, and 17, respectively.

Sulfation of some chemically-modified heparins. Formation of a 3-sulfate analog of heparin.

A modified form of heparin containing residues of nonsulfated alpha-L-idopyranosyluronic acid (7) in place of the normal 2-sulfate (1) was sulfated with sulfur trioxide-trimethylamine in dimethylformamide at 0 and 25 degrees. Examination of the reaction products by n.m.r. spectroscopy showed that sulfation occurred selectively at C-3 of residue 7, to give a new polymer that may be described as a 3-sulfate analog of heparin. A slower substitution reaction led subsequently to sulfation at C-3 of 2-deoxy-2-sulfamino-alpha-D-glucopyranosyl 6-sulfate residues (2), although this was accompanied by partial N-desulfation of 2. An analogous pattern of O-sulfation-N-desulfation was observed for the residues of 2 in two other modified heparins, one containing residues of 2,3-anhydro-alpha-L-gulopyranosyluronic acid and the other residues of alpha-L-galactopyranosyluronic acid, in place of residues of 1. The galacto diastereomer exhibited relatively low regioselectivity, as it was found to be sulfated at C-2 or C-2.3, or both. Selective resulfation of free amino groups gave the products that were examined for anticoagulant activity and susceptibility to enzymolysis by heparinase. Antithrombin-binding affinity measurements were also carried out. Although none of the materials had significant anti-Xa activity, nor were they affected by heparinase, their patterns of binding to antithrombinagarose were not dissimilar to that of heparin.

Tumor inhibiting [1,2-bis(fluorophenyl)ethylenediamine]platinum(II) complexes, III: Evaluation of the mammary tumor inhibiting properties.

Diastereomeric diaqua[1,2-bis(4-fluorophenyl)ethylenediamine]platinum(II) sulfates and nitrates produce a strong inhibition of the hormone-dependent MXT-M 3.2 mammary carcinoma of the B6D2F1 mouse. Besides an interference in the DNA synthesis in analogy to cisplatin a lowering of the estrogen level due to an interference in steroid biosynthesis is suggested as the mode of action. In contrast to the R,R/S,S configurated diaqua[1,2-bis(4-fluorophenyl)ethylenediamine]platinum(II) salts the corresponding R,S configurated compounds are also markedly active on the hormone-independent MXT-Ovex mammary carcinoma of the B6D2F1 mouse.