Sulfur Nitrogen Compounds Research Articles

Heterogeneous Nucleation of Trichloroethylene Ozonation Products in the Formation of New Fine Particles

Free radicals in atmosphere have played an important role in the atmospheric chemistry. The chloro-Criegee free radicals are produced easily in the decomposition of primary ozonide (POZ) of the trichloroethylene, and can react with O2, NO, NO2, SO2 and H2O subsequently. Then the inorganic salts, polar organic nitrogen and organic sulfur compounds, oxygen-containing heterocyclic intermediates and polyhydroxy compounds can be obtained. The heterogeneous nucleation of oxidation intermediates in the formation of fine particles is investigated using molecular dynamics simulation. The detailed nucleation processes are reported. According to molecular dynamics simulation, the nucleation with a diameter of 2 nm is formed in the Organic Compounds-(NH4)2SO4-H2O system. The spontaneous nucleation is an important process in the formation of fine particles in atmosphere. The model study gives a good example from volatile organic compounds to new fine particles.

Inorganic sulfur-nitrogen compounds: from gunpowder chemistry to the forefront of biological signaling.

The reactions between inorganic sulfur and nitrogen-bearing compounds to form S-N containing species have a long history and, besides assuming importance in industrial synthetic processes, are of relevance to microbial metabolism; waste water treatment; aquatic, soil and atmospheric chemistry; and combustion processes. The recent discovery that hydrogen sulfide and nitric oxide exert often similar, sometimes mutually dependent effects in a variety of biological systems, and that the chemical interaction of these two species leads to formation of S-N compounds brought this chemistry to the attention of physiologists, biochemists and physicians. We here provide a perspective about the potential role of S-N compounds in biological signaling and briefly review their chemical properties and bioactivities in the context of the chronology of their discovery. Studies of the biological role of NO revealed why its chemistry is ideally suited for the tasks Nature has chosen for it; realising how the distinctive properties of sulfur can enrich this bioactivity does much to revive 'die Freude am experimentellen Spiel' of the pioneers in this field.

Biological activity of various radish species

The radish (Raphanus sativus L.; Cruciferae) is cultivated and used as a food worldwide, and has many useful biological properties. Increasingly, it is apparent that the radish may potentially be used to treat various diseases. The radish contains alkaloids and nitrogen compounds, coumarins, enzymes, gibberellins, glucosinolates, organic acids, phenolic compounds, pigments, polysaccharides, proteoglycans, and sulfur compounds; these exhibit antimicrobial, antioxidative, antitumor, and antiviral activities, and act as calmodulin antagonists, growth inhibitors, anti-hypotensive agents, and inhibitors of platelet aggregation. Some components have immunological properties. The radish contains phytoalexins and a “pungent principle”. Certain components exhibit serological activity, stimulate intestinal motility, and prevent cardiovascular disease. The biological effects of the radish are inexorably linked to materials therein that exert antioxidant and anti-inflammatory effects. This review summarizes the biological effects of radish components.

The Effect of Iron-Containing Powders on Chemical Compositions of Oils

The effect of a composite material based on micron iron powder, modified with cobalt and nickel ions on the composition of oils with different contents of heteroatoms and resin-asphaltene components (a mixture of West Siberian light oils and Usinskaya heavy oil) is studied. It is shown using analytical methods, including elemental and structural group analysis, GC-MS, IR and 1H-NMR - spectroscopy that a composite based on micron sized iron powder modified with cobalt and nickel ions could be used for pretreatment of hydrocarbon feedstock with high content of heteroatom components. It is found out during treatment of the mixture of light West Siberian oil that its qualitative composition remains virtually invariable. Heavy oil treatment from the Usinskoye oil field using composite results in a decreased concentration of nitrogen and organic sulfur compounds.

Vibrational spectrum and gas-phase structure of disulfur dinitride (S2N2).

Gas-phase FTIR spectra of the ν6 (B-type) and the ν4 (C-type) fundamental bands of S2 N2 (D2h ) were recorded with a resolution of ≤0.004 cm(-1) and the vibrational spectrum of S2 N2 (D2h ) in solid Ar has been revisited. All IR-active fundamentals and four combination bands were assigned in excellent agreement with calculated values from anharmonic VPT2 and VCI theory based on (explicitly correlated) coupled-cluster surfaces. Accurate experimental vibrational ground- and excited-state rotational constants of (32) S2 (14) N2 are obtained from a rovibrational analysis of the ν6 and ν4 fundamental bands, and precise zero-point average rz (Rz (SN)=1.647694(95) Å, αz (NSN)=91.1125(33)°) and semi-experimental equilibrium structures (Re (SN)=1.64182(33) Å, αe (NSN)=91.0716(93)°) of S2 N2 have been established. These are compared to the solid-state structure of S2 N2 and structural properties of related sulfur nitrogen compounds and to results of ab initio structure calculations.

Gaseous pollutants emitted from a mechanical biological treatment plant for municipal solid waste: Odor assessment and photochemical reactivity

The concentrations and chromatographic profiles of gaseous pollutants emitted from a municipal solid waste (MSW) biological treatment plant were investigated to identify the major odor substances and atmospheric photochemical reactive species (PRS). Four methods were used to measure different gaseous pollutants in this study, including colorimetric tubes, gas chromatography with mass spectrometry/flame ionization detection/pulsed flame photometric detection (GC-MS/FID/PFPD) preceded by cold trap concentration, GC-FID preceded by solid-phase microextraction (SPME), and high-performance liquid chromatography (HPLC) after derivation by 2,4-dinitrophenylhydrazine (DNPH). Seventy-five gaseous compounds belonging to nine groups (nitrogen compounds, sulfur compounds, alkanes, alkenes, aromatics, terpenes, alcohols, carbonyls, and volatile fatty acids [VFAs]) were identified. In the pre-biotreatment facility, the total concentration of the gaseous pollutants reached the maximum value on day 7 (317 ppm). During the post-biotreatment process, the total concentration of gaseous pollutants decreased from 331 ppm at the beginning to 162 ppm in the end. The group with the greatest decrease was carbonyls, from 64 to 7.4 ppm, followed by alcohols, from 40 to 4.5 ppm, which were both oxygenated compounds. The proportion of aromatics was notably high in the pre-mechanical treatment facility, accounting for 50.6% of the total, revealing the xenobiotic compounds disseminated by stirring and agitating the waste in the initial stage. The proportions of nitrogen compounds were lower in the pre- and post-mechanical treatment facilities (1.5% and 6.9%) than in the pre- and post-biotreatment facilities (11.9% and 13.8%), suggesting that their generation was closely associated with waste degradation. The major odor compounds in the facilities were acetic acid, butyric acid, valeric acid, isovaleric acid, and dimethyl sulfide. The major PRS in the facilities were aromatics, acetaldehyde, butyraldehyde, hexanal, isopentyl aldehyde, alcohol, α-pinene, limonene, and terpinene. Outside the facilities, VFAs and aromatics were the most important compounds causing an environmental impact. Implications: The aim of this work is to assess the gaseous environmental impacts of mechanical biological treatment technology. The emission of gaseous pollutants greatly affects the living quality of nearby residents and odor complaints are becoming a major problem now. In this study, the authors utilized various pretreatment and analytical methods to obtain integrated emission information of gaseous pollutants. The results showed the transformation and fate of the gas pollutants during the treatment processes, which would help to improve the processes and to mitigate gaseous pollution. Supplemental Materials: Supplemental materials are available for this paper. Go to the publisher's online edition of the Journal of the Air & Waste Management Association for information on the concentrations of the nine compound families at different sampling locations in the plant.

The grand challenges to air pollution

The grand challenges to air pollution

Impacts of Exogenously Derived Nitrogen Oxide and Sulfur Compounds on the Structure and Function of the Vascular Endothelium Link Pregnancy Hypertension with Later Life Hypertension

The relationship between pregnancy hypertension and later life hypertension is explained by long-term impacts of environmental oxidants on the vascular endothelium. These impacts may precede the onset of the disease as a primary defect and may participate in the pathogenesis of hypertension itself. Continuous exposure to strong exogenous oxidants such as NOx (NO and NO 2 ) reversibly oxidizes oxyhemoglobin (Fe 2+ ) to methemoglobin (Fe 3+ ), and irreversible methemoglobinemia can arise because of disruption of the oxidant/antioxidant balance supported by SO 2 metabolites, as inhibitors of antioxidants, and by synergistic degradation of antioxidant thiols . Methemoglobin by itself and from heme, redox-active ferric iron as product of methemoglobin catabolism, have prooxidant properties and cause important structural and functional changes in the vascular endothelium such as growth arrest, senescence, morphological alterations and cell apoptosis. In 1975, an epidemiological study among 204 pregnant women in Labin (Croatia) identified 30 (14.7%) cases of preeclampsia and 25 (12.3%) cases of hypertension in pregnancy. Ten years later, we found a significant number of hypertension cases (N=5; P=0.0027), and among them, we found a significant number of pregnancy-induced hypertension cases (N=3; P=0.0003) and a significant number of psychoneurotic disturbances (P=0.0190), but these conditions were not found in the normotensive women ten years after giving birth (P = 0.1161). Our original findings confirm that hypertension in pregnancy is not a transient impairment but instead is an extension of the effects of exogenously induced oxidative stress on the structure and function of the vascular endothelial, and indicate delayed effects plausibly manifesting as hypertension in later life.

Composition and antioxidant capacity of a novel beverage produced with green tea and minimally-processed byproducts of broccoli

Abstract Organic green tea, one of the most-consumed beverages worldwide, is rich in bioactive compounds (flavonols and flavanols) with healthy properties. Broccoli byproducts, consisting of leaves and stalks, are rich in bioactive compounds, including nitrogen–sulphur compounds (glucosinolates and isothiocyanates) and phenolics (chlorogenic and sinapic acid derivatives, and flavonoids), as well as essential nutrients (minerals and vitamins). They are of high interest as a source of health-promoting compounds, useful as ingredients for the development of functional foods. This work analyses minimally-processed broccoli byproducts as a source of bioactive ingredients to design novel beverages, using organic green tea as a food matrix. Green tea enriched with broccoli concentrates showed improved physical quality, phytochemical composition and antioxidant capacity. The functional quality of these novel beverages depends on the proportion of broccoli extracts added to the green tea. The results obtained in the present work should encourage the use of broccoli byproducts as ingredients in novel functional foods. Industrial relevance The industrial use of broccoli byproducts as an ingredient in the development of novel, functional foods may help to add value to the large amount of plant wastes generated in every cropping season, thus reducing their environmental impact. The objectives and aims of the EU producers, industry and stakeholders on the relationships between foods, nutrition and health, and therefore, the use of suitable ingredients from the agriculture to have impact on human health and the environment, with a sustainable use of natural resources are in agreement with this work, adding value to broccoli byproducts and encouraging the production of novel products and applications for nutritional and/or health claims under the EU Regulations (EC) No. 1924/2006 and 834/2007.

Interaction of 1,3,2,4-Benzodithiadiazines and Their 1-Se Congeners with Ph3P and Some Properties of the Iminophosphorane Products

Interaction between Ph(3)P and 1,3,2,4-benzodithiadiazine (1); its 6,7-difluoro (2), 5,6,8-trifluoro (3) and 5,6,7,8-tetrafluoro (4) derivatives; and 5,6,8-trifluoro-3,1,2,4-benzothiaselenadiazine (5) proceeded via a 1:1 condensation to give Ph(3)P═N-R iminophosphoranes (1a-5a, R = corresponding 1,2,3-benzodichalcogenazol-2-yls), which are inaccessible by general approaches based on the Staudinger and Kirsanov reactions. In contrast, neither Ph(3)As nor Ph(3)Sb reacted with 1 and 4. Molecular structures of 1a-5a and 5 were confirmed by X-ray diffraction (XRD). The crystals formed by chiral molecules of 2a-5a were racemic, whereas the crystal of 1a was formed by a single enantiomer. In all of the Ph(3)P═N-R derivatives, one of the Ph rings is oriented face-to-face to the hetero ring, R. Upon heating to ∼120 °C in squalane (1a, 3a, 4a) or dissolving in chloroform at ambient temperatures (1a, 2a, 4a), the Ph(3)P═N-R derivatives generated the 1,2,3-benzodithiazolyls (1b-4b, respectively) whose identity was confirmed by electron paramagnetic resonance (EPR). 2,1,3-Benzothiaselenazolyls 5b and 6b were detected by EPR as the main paramagnetic products of solution thermolysis of 5 and its 5,6,7,8-tetrafluoro congener (6), respectively. Passing a chloroform solution of 4a through silica column unexpectedly gave 5-6-6-6 tetracyclic (9) and 6-10-6 tricyclic (10) sulfur-nitrogen compounds, which were characterized by XRD.

ChemInform Abstract: Naturally Occurring Nitrogen—Sulfur Compounds. Part 2. 1,4‐Thiazine and Benzo‐1,4‐thiazine Alkaloids.

AbstractReview: ca. 80 refs.

Water-Soluble Atmospheric Organic Matter in Fog: Exact Masses and Chemical Formula Identification by Ultrahigh-Resolution Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

The detailed molecular composition of water-soluble atmospheric organic matter (AOM) contained in fog water was studied by use of electrospray ionization ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry. We identified 1368 individual molecular masses in the range of 100-400 Da from negative-ion spectra obtained after reversed-phase extraction with a hydrophilic solid phase sorbent. The detected organic anions are multifunctional with a variety of oxygenated functional groups. We observe organic nitrogen, organic sulfur, and organic nitrogen-sulfur compounds as well as many species with only C, H, and O elemental composition. Analysis of the double bond equivalents (DBE = the number of rings plus the number of double bonds to carbon) suggests that these compound structures range from highly aliphatic to aromatic with DBE values of 1-11. The compounds range in their extent of oxidation with oxygen to carbon ratios from 0.2 to 2 with an average value of 0.43. Several homologous series of compounds and multifunctional oligomers were identified in this AOM. The high extent of homologous series of compounds likely originates from primary components that have become oxidized. The multifunctional oligomers appear to represent atmospheric processing of primary and secondary compounds. The isolated water-soluble components identified here are amphiphilic, meaning that they contain both hydrophilic oxygenated functional groups and hydrophobic aliphatic and aromatic structural moieties. Despite the high number of compounds with very high oxygen content, 60% of assigned chemical formulas have measured organic mass-to-organic carbon ratios <or=2.25 (ranging from 1.25 to 3.5). Because the results reported here are not quantitative, an average ratio cannot be determined.

Combining the chemistries of silylene and sulfur-nitrogen compounds—SiS2N2 and related systems

A new class of inorganic systems is introduced in which a silylene fragment is combined with a sulfur-nitrogen fragment. The properties of the resulting "sulfur-nitrogen silylenes" have been studied using quantum chemical calculations, focussing on isodesmic reaction energies, dimerization, electro- and nucleophilicity, and the singlet-triplet energy gap-a number of as yet unsuccessful attempts to prepare the compounds is also reported. These new systems are found to be stable silylenes in which the sulfur-nitrogen fragment stabilizes both the singlet and the triplet states through extensive electron delocalization.

ChemInform Abstract: Naturally Occurring Nitrogen—Sulfur Compounds. The Benzothiazole Alkaloids.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a “Full Text” option. The original article is trackable via the “References” option.

Correlation of Electronic Structure of Some Nitrogen Sulfur Derivatives with Corrosion Inhibition Performance

In this paper a correlation between performance of corrosion inhibitors and quantum chemical, thermodynamic parameters has been made. The Quantum chemical calculations were done using semi-empirical method (PM3). The Inhibition efficiency (IE) is predicted for some Nitrogen Sulfur compounds. The electronic parameters entering our model are the energy of the highest occupied molecular orbital E HOM O, the lowest unoccupied molecular orbital ELUM O and the dipole moment. All of these parameters relate to IE, so their cumulative index is correlated with IE obtained from experiments. Our method predicts IE of selected compounds with good accuracy. This approach can be useful in design and analysis of high performance inhibitors.

Naturally Occurring Nitrogen–Sulfur Compounds. The Benzothiazole Alkaloids

Several alkaloids contain both nitrogen and sulfur, and a subset of these interesting terrestrial and marine natural products – the benzothiazoles – forms the subject of the present short review. Benzothiazole alkaloids are relatively rare in Nature, but they range in structural complexity from benzothiazole itself and simple derivatives thereof, through the well-known firefly luciferin, to more complex molecules such as the thiazo-rifamycins and the dercitin-kuanoniamine family. Although the biosynthesis of benzothiazoles has not been studied in many cases, the evidence suggests that they are derived from cysteine addition to benzoquinone derivatives followed by ring contraction of the resulting benzothiazine adducts. The review also highlights the fact that little synthetic work has been done on benzothiazole-containing natural products.

ORGANIC-08 Research Highlights

The 23rd RACI Organic Division Conference, ORGANIC-08, was held at Wrest Point, Hobart, Tasmania, from 7 to 12 December 2008. More than 270 delegates attended to celebrate the breadth and share the excitement of organic chemistry. The conference program included eight plenary lectures, the Birch Medal lecture by Associate Professor Michael Sherburn (ANU), and invited and other oral presentations by researchers and postgraduate students. Topics covered exemplified the diversity of our discipline, and included natural products chemistry and synthesis, new synthetic methods and catalysis, bioorganic and medicinal chemistry, physical and mechanistic chemistry, and supramolecular chemistry and nanotechnology. The papers published in this special issue of Aust. J. Chem. include review articles from three of the plenary lectures at ORGANIC-08. Professor Ian Paterson (Cambridge, UK) reports on ‘Recent Advances in the Total Synthesis of Polyketide Natural Products as PromisingAnticancerAgents’,[1] while Professor Chris Moody (Nottingham, UK) describes a unique class of natural products, the benzothiazole alkaloids, in his review entitled, ‘Naturally Occurring Nitrogen–Sulfur Compounds. The Benzothiazole Alkaloids’.[2] A review in the supramolecular chemistry–nanotechnology area is provided by Professor Jean-Francois Nierengarten (Strasbourg, France) on ‘Synthesis and Properties of Fullerene-Rich Dendrimers’.[3] Professor Yasuyuki Kita, Ritsumeikan University, Japan, also a plenary speaker, reports on the unique chemistry of hypervalent iodine compounds in a Rapid Communication entitled ‘Organoiodine-Catalyzed Oxidative Spirocyclization of Phenols using Peracetic Acid as Green and Economic Terminal Oxidant’.[4] Plenary lecturer, Professor Stephen Hashmi (Heidelberg, Germany) communicates more of his fascinating gold catalyzed chemistry in a full paper entitled ‘Gold Catalysis: Chemoselective Indolin Synthesis in the Presence of Acrylate Units’.[5] Articles by some of the invited speakers highlight the different themes of the conference and include the synthesis of bioactive

Selective Adsorption for Removal of Nitrogen Compounds from Liquid Hydrocarbon Streams over Carbon- and Alumina-Based Adsorbents

In order to explore the adsorptive denitrogenation of liquid hydrocarbon streams for producing ultraclean fuels, the adsorption performance of seven representative activated carbon samples and three activated alumina samples was evaluated in a batch adsorption system and a fixed-bed flow adsorption system for removing quinoline and indole from a model diesel fuel in the coexistence of sulfur compounds and aromatics. Different adsorbents show quite different selectivity toward basic and nonbasic nitrogen compounds (quinoline and indole) and sulfur compounds (dibenzothiophene and 4,6-dimethyldibenzothiophene). The activated carbons generally show higher capacity than activated alumina samples for removing the nitrogen compounds. The adsorption capacity and selectivity of the activated carbons for nitrogen compounds were further correlated with their textural properties and oxygen content. It was found that (1) the microporous surface area and micropore volume are not a key factor for removal of the nitrogen compounds in the tested activated carbons; (2) the oxygen functionality of the activated carbons may play a more important role in determining the adsorption capacity for the nitrogen compounds since the adsorption capacity for nitrogen compounds increases with increase in the oxygen concentration of the activated carbons; and (3) the type of the oxygen-functional groups may be crucial in determining their selectivity for various nitrogen or sulfur compounds. In addition, regeneration of the saturated adsorbents was conducted by the toluene washing followed by the heating to remove the remained toluene. The results show that the spent activated carbons can be regenerated to completely recover the adsorption capacity. The high capacity and selectivity of carbon-based adsorbents for the nitrogen compounds, along with their good regenerability, indicate that the activated carbons may be promising adsorbents for deep denitrogenation of liquid hydrocarbon streams.

Effects of Chemical Components on Stability of FCC Gasoline

The effects of the mercaptan sulfur, nitrogen compounds, phenolic compounds, and conjugated dienes on the stability of FCC naphtha were investigated by means of chemical treatment and addition of model compounds. Experimental results indicated that conjugated dienes in spite of its very small content in naphtha played the most important effect on the stability of naphtha. After the conjugated dienes have been removed, the stability would increase significantly. A high amount of mono-olefins is another important reason for naphtha oxidation although its effect is less than that of dienes. A certain amount of phenolic compounds should be retained during the naphtha refining. Nitrogen compounds and sulfur compounds cause poor effects on the stability of naphtha, but their effects are minimal because of the small quantity in the naphtha.

Adventures in Sulfur−Nitrogen Chemistry

This account reviews our efforts over the past 37 years to understand the chemistry of a select group of sulfur-nitrogen compounds including sulfinimines (N-sulfinyl imines) and N-sulfonyloxaziridines. Our early exploration of the thermal properties of sulfenamides, a class of sulfur-nitrogen compounds about which little was known, resulted in a new procedure, the silver-assisted method, for the construction of sulfenimines (N-sulfenyl imines). Selective oxidations of these compounds resulted in the production of N-sulfinyl imines (sulfinimines) and N-sulfonyloxaziridines. N-Sulfonyloxaziridines turned out to be a new class of aprotic neutral oxidizing reagents. Enantiomerically pure examples afford high ee values in the oxidation of enolates to alpha-hydroxy carbonyl compounds and in the oxidation of sulfides and selenides to sulfoxides and selenoxides. Additions of organometallic reagents to enantiomerically pure sulfinimines provide the best and most versatile method for the asymmetric construction of the carbon-nitrogen stereocenters found in many biologically active compounds. Sulfinimine-derived chiral building blocks provide efficient access to many classes of nitrogen heterocycles including aziridines, 2H-azirines, pyrrolidines, and piperidines.