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At least 19 records

Demand and supply of hydrogen as chemical feedstock in USA

Projections are made for the demand and supply of hydrogen as chemical feedstock in USA. Industrial sectors considered are petroleum refining, ammonia synthesis, methanol production, isocyanate manufacture, edible oil processing, coal liquefaction, fuel cell electricity generation, and direct iron reduction. Presently, almost all the hydrogen required is produced by reforming of natural gas or petroleum fractions. Specific needs and emphases are recommended for future research and development to produce hydrogen from other sources to meet the requirements of these industrial sectors. The data and the recommendations summarized in this paper are based on the Workshop 'Supply and Demand of Hydrogen as Chemical Feedstock' held at the University of Houston on December 12-14, 1977.

Huang, C. J.↗

Studies on the use of supercritical ammonia for ceramic nitride synthesis and fabrication

The extractability of ammonia halides (including ammonium thiocyanate) formed as byproducts from the synthesis of Si(NH)2 via ammonolysis of the corresponding silicon tetrahalides using supercritical NH3 as the extraction medium was investigated. It was found that the NH4SCN byproduct of ammonolysis of Si(SCN)4 can be almost completely extracted from the insoluble Si(NH)2 forming a promising system for the synthesis of pure Si(NH)2, one of the best precursors for Si3N4. In addition it was found that Si3N4, AlN, BN, and Si(NH)2 are insoluble in SC ammonia. Also discussed are design considerations for a supercritical ammonia extraction unit.

Cornell, Linda↗

A detailed investigation of proposed gas-phase syntheses of ammonia in dense interstellar clouds

The initial reactions of the Herbst and Klemperer (1973) and the Dalgarno (1974) schemes (I and II, respectively) for the gas-phase synthesis of ammonia in dense interstellar clouds were investigated. The rate of the slightly endothermic reaction between N(+) and H2 to yield NH(+) and H (scheme I) under interstellar conditions was reinvestigated under thermal and nonthermal conditions based on laboratory data. It was found that the relative importance of this reaction in synthesizing ammonia is determined by how the laboratory data at low temperature are interpreted. On the other hand, the exothermic reaction between N and H3(+) to form NH2(+) + H (scheme II) was calculated to possess significant activation energy and, therefore, to have a negligible rate coefficient under interstellar conditions. Consequently, this reaction cannot take place appreciably in interstellar clouds.

Herbst, Eric↗

Lignification in young plant seedlings grown on earth and aboard the Space Shuttle

The Space Shuttle era has provided an opportunity for investigators to conduct experiments in a microgravity environment. Two Shuttle flights, STS-3 and STS-51F, each contained an experiment designed principally to determine whether young plant seedlings exposed to microgravity had reduced lignin content in comparison to seedlings grown at one gravity. Three different plant species, pine, oats, and mung beans, were exposed for eight days to the microgravity environment of the Shuttle. The lignin content of in-flight seedlings was less than the control seedlings in all seven sets of seedlings included in these two experiments. In five sets of seedlings, the reduction in lignin content in flight seedlings ranged from 6 to 24 percent and was statistically significant. In addition, the activity of two enzymes involved in lignin synthesis, phenylalanine ammonia lyase and peroxidase, were significantly reduced in pine seedlings. It was therefore concluded that microgravity, as perceived by young plant seedlings, results in reduced lignin synthesis.

Cowles, Joe R.↗

Reduced phenylalanine ammonia-lyase and tyrosine ammonia-lyase activities and lignin synthesis in wheat grown under low pressure sodium lamps

Wheat (Triticum aestivum L. cv Fremont) grown in hydroponic culture under 24-hour continuous irradiation at 560 to 580 micromoles per square meter per second from either metalhalide (MH), high pressure sodium (HPS), or low pressure sodium (LPS) lamps reached maturity in 70 days. Grain yields were similar under all three lamps, although LPS-grown plants lodged at maturity. Phenylalanine ammonia-lyase (PAL) and a tyrosine ammonia lyase (TAL) with lesser activity were detected in all extracts of leaf, inflorescence, and stem. Ammonia-lyase activities increased with age of the plant, and plants grown under the LPS lamp displayed PAL and TAL activities lower than wheat cultured under MH and HPS radiation. Greenhouse solar-grown wheat had the highest PAL and TAL activities. Lignin content of LPS-grown wheat was also significantly reduced from that of plants grown under MH or HPS lamps or in the greenhouse, showing a correlation with the reduced PAL and TAL activities. Ratios of far red-absorbing phytochrome to total phytochrome were similar for all three lamps, but the data do not yet warrant a conclusion about specific wavelengths missing from the LPS lamps that might have induced PAL and TAL activities in plants under the other lamps.

Triticum/enzymology/growth & development/metabolis↗

Prebiotic Amino Acid Thioester Synthesis: Thiol-Dependent Amino Acid Synthesis from Formose substrates (Formaldehyde and Glycolaldehyde) and Ammonia

Formaldehyde and glycolaldehyde (substrates of the formose autocatalytic cycle) were shown to react with ammonia yielding alanine and homoserine under mild aqueous conditions in the presence of thiol catalysts. Since similar reactions carried out without ammonia yielded alpha-hydroxy acid thioesters, the thiol-dependent synthesis of alanine and homoserine is presumed to occur via amino acid thioesters-intermediates capable of forming peptides. A pH 5.2 solution of 20 mM formaldehyde, 20 mM glycolaldehyde, 20 mM ammonium chloride, 23 mM 3-mercaptopropionic acid, and 23 mM acetic acid that reacted for 35 days at 40 C yielded (based on initial formaldehyde) 1.8% alanine and 0.08% homoserine. In the absence of thiol catalyst, the synthesis of alanine and homoserine was negligible. Alanine synthesis required both formaldehyde and glycolaldehyde, but homoserine synthesis required only glycolaldehyde. At 25 days the efficiency of alanine synthesis calculated from the ratio of alanine synthesized to formaldehyde reacted was 2.1%, and the yield (based on initial formaldehyde) of triose and tetrose intermediates involved in alanine and homoserine synthesis was 0.3 and 2.1%, respectively. Alanine synthesis was also seen in similar reactions containing only 10 mM each of aldehyde substrates, ammonia, and thiol. The prebiotic significance of these reactions that use the formose reaction to generate sugar intermediates that are converted to reactive amino acid thioesters is discussed.

Weber, Arthur L.↗

Ammonia from Iron(II) Reduction of Nitrite and the Strecker Synthesis: Do Iron(II) and Cyanide Interfere with Each Other?

The question of whether the production of ammonia, from the reduction of nitrite by iron(II), is compatible with its use in the Strecker synthesis of amino acids, or whether the iron and the cyanide needed for the Strecker synthesis interfere with each other, is addressed. Results show that the presence of iron(II) appears to have little, or no, affect on the Strecker synthesis. The presence of cyanide does interfere with reduction of nitrite, but the reduction proceeds at cyanide/iron ratios of less than 4:1. At ratios of about 2:1 and less there is only a small effect. The two reactions can be combined to proceed in each other's presence, forming glycine from nitrite, Fe(+2), formaldehyde, and cyanide.

Summers, David P.↗

Ammonia from iron(II) reduction of nitrite and the Strecker synthesis: do iron(II) and cyanide interfere with each other?

The question of whether the production of ammonia, from the reduction of nitrite by iron(II), is compatible with its use in the Strecker synthesis of amino acids, or whether the iron and the cyanide needed for the Strecker synthesis interfere with each other, is addressed. Results show that the presence of iron(II) appears to have little, or no, effect on the Strecker synthesis. The presence of cyanide does interfere with reduction of nitrite, but the reduction proceeds at cyanide/iron ratios of less than 4:1. At ratios of about 2:1 and less there is only a small effect. The reduction of nitrite and the Strecker can be combined to proceed in each other's presence, to yield glycine from a mixture of nitrite, Fe+2, formaldehyde, and cyanide.

NASA Discipline Exobiology↗

Aqueous Phase Non Enzymatic Chemistry of Cyanide, Formaldehyde and RNH2

It is postulated that amino acids were produced on the early earth from dilute aqueous solution of cyanide, carbonyls and ammonia (the Strecker synthesis RNH2 + R"R""C=O + KCN yields H-N(R)-C(R")(R"")-CO2H. We have studied the products obtained from dilute aqueous solutions of cyanide, formaldehyde (R"=R""=H), ammonia (R=H) and amino acids. Solutions in the pH range from 8 to 10. at room temperature and at reactant concentrations from 0.001 M to 0.3 M have been studied. With R= H product yields were low (less than 3%). Only with R"=R""=H and R represented by the following: CH2CO2H (glycine); CH(CH3)CO2H (alanine); CH(CH2CH3)CO2H (a-amino n=butyric acids); C(CH3)2(CO2H) (a-aminoisobutyric acid); CH(CH(CH3)2)CO2H (valine); and CH(CH2CO2H)CO2H (aspartic acid), were product yields high (greater than 10%). The yields of glycine were larger with R not equal to H. The prebiotic implications of these findings will be discussed.

Lerner, Narcinda R.↗

Distribution of Extraterrestrial Nucleobases, Other N-Heterocycles, and Their Precursors in A Sample From Asteroid Bennu

The recent discovery of all five canonical nucleobases in samples from Bennu provides compelling evidence that some of life’s ingredients were synthesized abiotically in the parent body of this asteroid and/or its precedent components. However, due to the sample availability and the limited method for the analysis, the detailed distribution of nucleobases in the samples remains elusive. Here we report the concentrations of a diverse suite of nitrogen (N)-heterocycles including nucleobases extracted by 2% and 20% hydrochloric acid from a homogenized Bennu sample. The detection of both canonical and non-canonical nucleobase pairs confirms that these biologically important compounds are extraterrestrial. Pyrimidines are more abundant than purines—like the Orgueil meteorite, but unlike the Murchison meteorite and asteroid Ryugu samples—suggesting preferential synthesis in ammonia-rich ices from the outer Solar System. The distribution of other N-heterocycles is consistent with extensive aqueous alteration on the parent body. High concentrations of urea underscore its role in N-heterocycle synthesis. Our findings offer important information on the prebiotic inventory of N-heterocycles in the Solar System.

Yasuhiro Oba↗

The synthesis of glutamic acid in the absence of enzymes: Implications for biogenesis

This paper reports on the non-enzymatic aqueous phase synthesis of amino acids from keto acids, ammonia and reducing agents. The facile synthesis of key metabolic intermediates, particularly in the glycolytic pathway, the citric acid cycle, and the first step of amino acid synthesis, lead to new ways of looking at the problem of biogenesis.

Morowitz, Harold↗

Prevention of metabolic alterations caused by suspension hypokinesia in leg muscles of rats

Rats were subjected to tail-cast suspension hypokinesia for 6 days with one leg immobilized in dorsal flexion by casting. Control animals were also tail-casted. The soleus, gastrocnemius and plantaris muscles of uncasted hypokinetic legs were smaller than control muscles. Dorsal flexion prevented atrophy of these muscles and caused the soleus to hypertrophy. The anterior muscles were unaffected by hypokinesia. The smaller size of the soleus of the uncasted leg relative to the dorsal flexed and weight bearing limbs correlated with slower protein synthesis and faster proteolysis. The capacity of this muscle to synthesize glutamine (gln), which carries nitrogenous waste from muscle was also measured. Although tissue homogenates showed higher activities of gln synthetase, the rate of de novo synthesis was not altered in intact muscle but the tissue ratio of gln/glutamate was decreased. Glutamate and ATP were not limiting for gln synthesis, but availability of ammonia may be a limiting factor for this process in hypokinesia.

Tischler, M. E.↗

Impact of Phyllosilicates on Amino Acid Formation under Asteroidal Conditions

The emergence of life on Earth could have benefitted from an extraterrestrial source of amino acids. Yet, the origin of these amino acids is still debated because they may have formed prior to the solar nebula or inside the parent body of meteorites. Here, we experimentally produced amino acids by exposing an interstellar model molecule (hexamethylenetetramine) to asteroid-like hydrothermal conditions (150 °C; pH 10). We conducted additional experiments in the presence of carboxylic acids and phyllosilicates to simulate asteroidal environments. Analyses via liquid chromatography–mass spectrometry show that glycine is the most abundant amino acid formed, but non-proteinogenic α-, β-, and γ-amino acids are also produced. This production of amino acids seems to be hampered by the presence of Fe-rich smectites, while the presence of Al-rich smectites largely stimulates it. Our findings evidence (1) the production of amino acids during hydrothermal alteration of a putative interstellar precursor, (2) the importance of the formose reaction from formaldehyde and ammonia, for amino acid synthesis in meteorites, and (3) the impact of organic–mineral interactions on the nature/distribution of the amino acids produced. Altogether, the fact that the production of amino acids, which are so central to living structures, can be achieved via organo–mineral interactions under hydrothermal conditions should put these processes at a focal point for research on the origin of extraterrestrial organic compounds and into the origin of life.

Jason Peter Dworkin↗