Formation of sulfur and nitrogen cross-linked macromolecules under aqueous conditions

被引:37
作者
Amrani, Alon [1 ]
Turner, Jeffrey W.
Ma, Qisheng
Tang, Yongchun
Hatcher, Patrick G.
机构
[1] Ohio State Univ, Dept Chem, Columbus, OH 43210 USA
[2] CALTECH, Power Environm & Energy Res Ctr, Div Chem & Chem Engn, Pasadena, CA 91125 USA
基金
美国国家科学基金会;
关键词
D O I
10.1016/j.gca.2007.06.051
中图分类号
P3 [地球物理学]; P59 [地球化学];
学科分类号
0708 ; 070902 ;
摘要
Polysulfides and ammonia are abundant in young depositional environments and play an important role in the formation of macromolecular structures such as protokerogen and humics. In this work, we study the co-incorporation of polysulfides and ammonia into simple carbonyl model compounds, octanal and trans 2-octenal, in order to study their effect on the formation of a cross-linked macromolecule and suggest a feasible mechanism. The reactions, performed in aqueous solutions at ambient temperature and pH similar to 6 to 9, simulate formation of S and N cross-linked polymers in the natural environment. The complex S and N containing polymer was studied by N-15 enrichment coupled to 2D NMR (H-1, C-13, N-15) techniques and chemical degradation of S-S bonds followed by deuterium labeling and GC-MS analyses. In addition, molecular modeling techniques were used to provide theoretical interpretations and important insights at the molecular level. The results indicate that polysulfide out competes ammonia in the formation of Michael adducts while ammonia is equally competitive with polysulfides when the reaction is addition to the carbonyl position. The co-incorporation of ammonia and polysulfides into carbonyls rapidly forms N and S cross-linked polymers. The effects of ammonia and amines on the polymerization processes are by two means: (i) reaction with carbonyls through an imine functionality to form oligomers and polymers and (ii) catalysis of sulfur nucleophiles onto carbonyls by transfer of a proton which enhances the rate of polymerization. A similar catalytic effect is observed when glycine is used instead of ammonia. This mechanism is especially important under basic to neutral conditions like those that prevail in marine environments. The results show that ammonia and glycine or possibly other amino acids and/or peptides are intimately involved with sulfur nucleophiles throughout the polymerization processes that occur at low temperatures and thus are suggested as key reactants in diagenetic formation of protokerogen and humics. (C) 2007 Elsevier Ltd. All rights reserved.
引用
收藏
页码:4141 / 4160
页数:20
相关论文
共 59 条
[1]   Clues to early diagenetic sulfurization processes from mild chemical cleavage of labile sulfur-rich geomacromolecules [J].
Adam, P ;
Schneckenburger, P ;
Schaeffer, P ;
Albrecht, P .
GEOCHIMICA ET COSMOCHIMICA ACTA, 2000, 64 (20) :3485-3503
[2]  
Aizenshtat Z, 1998, MICR EXTREM UNUSUAL, P89
[3]  
AIZENSHTAT Z, 1983, ADV ORG GEOCHEM, V1981, P279
[4]   Sulfur stable isotope distribution of polysulfide anions in an (NH4)2Sn aqueous solution [J].
Amrani, A ;
Kamyshny, A ;
Lev, O ;
Aizenshtat, Z .
INORGANIC CHEMISTRY, 2006, 45 (04) :1427-1429
[5]   Mechanisms of sulfur introduction chemically controlled:: δ34S imprint [J].
Amrani, A ;
Aizenshtat, Z .
ORGANIC GEOCHEMISTRY, 2004, 35 (11-12) :1319-1336
[6]   Photosensitized oxidation of naturally occurring isoprenoid allyl alcohols as a possible pathway for their transformation to thiophenes in sulfur rich depositional environments [J].
Amrani, A ;
Aizenshtat, Z .
ORGANIC GEOCHEMISTRY, 2004, 35 (06) :693-712
[7]   Reaction of polysulfide anions with α, β, unsaturated isoprenoid aldehydes in aquatic media:: simulation of oceanic conditions [J].
Amrani, A ;
Aizenshtat, Z .
ORGANIC GEOCHEMISTRY, 2004, 35 (08) :909-921
[8]  
ASINGER F, 1959, LIEBIGS ANN CHEM, V627, P195
[9]   SOME CHEMICAL CHARACTERISTICS OF THE BRINES IN BANNOCK AND TYRO BASINS - SALINITY, SULFUR-COMPOUNDS, CA-2+, F-, PH, AT, PO43-, SIO2, NH3 [J].
BREGANT, D ;
CATALANO, G ;
CIVITARESE, G ;
LUCHETTA, A .
MARINE CHEMISTRY, 1990, 31 (1-3) :35-62
[10]   SULFATE REDUCTION AND OXIC RESPIRATION IN MARINE-SEDIMENTS - IMPLICATIONS FOR ORGANIC-CARBON PRESERVATION IN EUXINIC ENVIRONMENTS [J].
CANFIELD, DE .
DEEP-SEA RESEARCH PART A-OCEANOGRAPHIC RESEARCH PAPERS, 1989, 36 (01) :121-138