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Alpha-chloro alkanoyl valine methyl esters analyzed, finding that diastereoisomeric pairs separation by gas-liquid chromatography can assess steric conditions around amide bond
Aliphatic amines react with phosphoimidazolide-activated derivatives of guanosine and cytidine (ImpN) by replacing the imidazole group. The kinetics of reaction of guanosine 5'-phospho-2-methylimidazolide (2-MeImpG) with glycine ethyl ester, glycinamide, 2-methoxyethylamine, n-butylamine, morpholine, dimethylamine (Me2NH), ethylmethylamine (EtNHMe), diethylamine (Et2NH), pyrrolidine, and piperidine were determined in water at 37 degrees C. With primary amines, a plot of the logarithm of the rate constant for attack by the amine on the protonated substrate, log kSH(A), versus the pKa of the amine exhibits a good linear correlation with a Bronsted slope, beta nuc = 0.48. Most of the secondary amines tested react with slightly higher reactivity than primary amines of similar pKa. Interestingly, some secondary amines show substantially lower reactivity than might be expected: EtNHMe reacts about eight times, and Et2NH at least 100 times, more slowly than Me2NH although all three amines are of similar basicity. For comparison, the kinetics of reaction of guanosine 5'-phosphoimidazolide (ImpG) and cytidine 5'-phosphoimidazolide (ImpC) were determined with Me2NH, EtNHMe, and Et2NH, and similar results were obtained. These results establish that the increased steric hindrance observed with the successive addition of ethyl groups are not due to any special steric requirements imposed by the guanosine or the methyl on the 2-methylimidazole leaving group of 2-MeImpG. It is concluded that addition of ethyl and, perhaps, groups larger than ethyl dramatically increases the kinetic barrier for addition of aliphatic secondary amines to the P-N bond of ImpN. This study supports the observation that the primary amino groups on the natural polyamines are at least 2 orders of magnitude more reactive than the secondary amino groups in the reaction with ImpN.
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Today more than 100 million people worldwide live on coastlines within one meter of mean sea level; any short-term or long-term sea level change relative to vertical ground motion is of great societal and economic concern. As palm-environment and historical data have clearly indicated the existence and prevalence of such changes in the past, new scientific information regarding to the nature and causes and a prediction capability are of utmost importance for the future. The 10-20 cm global sea-level rise recorded over the last century has been broadly attributed to two effects: (1) the steric effect (thermal expansion and salinity-density compensation of sea water) following global climate; (2) mass-budget changes due to a number of competing geophysical and hydrological processes in the Earth-atmosphere-hydrosphere-cryosphere system, including water exchange from polar ice sheets and mountain glaciers to the ocean, atmospheric water vapor and land hydrological variations, and anthropogenic effects such as water impoundment in artificial reservoirs and extraction of groundwater, all superimposed on the vertical motions of solid Earth due to tectonics, rebound of the mantle from past and present deglaciation, and other local ground motions. As remote-sensing tools, a number of space geodetic measurements of sea surface topography (e.g., TOPEX/Poseidon, Jason), ice mass (e.g., ICESat), time-variable gravity (e.g. GRACE), and ground motions (SLR, VLBI, GPS, InSAR, Laser altimetry, etc.) become directly relevant. Understanding sea level changes "anywhere, anytime" in a well-defined terrestrial reference frame in terms of climate change and interactions among ice masses, oceans, and the solid Earth, and being able to predict them, emerge as one of the scientific challenges in the Solid Earth Science Working Group (SESWG, 2003) conclusions.
Single-crystal X-ray structures of four nickel dithiocarbamate complexes, the homoleptic mixed-organic bis-dithiocarbamates Ni[S2CN(isopropyl)(benzyl)]2, Ni[S2CN(ethyl)(n-butyl)]2, and Ni[S2CN(phenyl)(benzyl)]2, as well as the heteroleptic mixed-ligand complex NiCl[P(phenyl)3][(S2CN(phenyl)(benzyl)], were determined. Synthetic, spectroscopic, structural, thermal, and sulfide materials studies are discussed in light of prior literature. The spectroscopic results are routine. A slightly distorted square-planar nickel coordination environment was observed for all four complexes. The organic residues adopt conformations to minimize steric interactions. Steric effects also may determine puckering, if any, about the nickel and nitrogen atoms, both of which are planar or nearly so. A trans-influence affects the Ni-S bond distances. Nitrogen atoms interact with the CS2 carbons with a bond order of about 1.5, and the other substituents on nitrogen display transoid conformations. There are no strong intermolecular interactions, consistent with prior observations of the volatility of nickel dithiocarbamate complexes. Thermogravimetric analysis of the homoleptic species under inert atmosphere is consistent with production of 1:1 nickel sulfide phases. Thermolysis of nickel dithiocarbamates under flowing nitrogen produced hexagonal or -NiS as the major phase; thermolysis under flowing forming gas produced millerite (-NiS) at 300 C, godlevskite (Ni9S8) at 325 and 350 C, and heazlewoodite (Ni3S2) at 400 and 450 C. Failure to exclude oxygen results in production of nickel oxide. Nickel sulfide phases produced seem to be primarily influenced by processing conditions, in agreement with prior literature. Nickel dithiocarbamate complexes demonstrate significant promise to serve as single-source precursors to nickel sulfides, a quite interesting family of materials with numerous potential applications.
Via mass transport, the interannual meteorological oscillations (ENSO, NAO, etc.) produce slight variations in the global gravitational field, which can be observed by satellite laser ranging (SLR) and anticipated space missions such as GRACE. The meteorological oscillation modes are identified using empirical orthogonal function and principal component decomposition using de-seasoned surface fields produced from the 40-years of NCEP reanalysis. This decompositional analysis requires an accounting for issues associated with area-weighting and non-zero mean. The atmospheric contributions to gravitational variation, mode by mode and in combinations, are then computed via regional integration. To address the corresponding oceanic contributions, we examine the output of the numerical POCM ocean circulation model (1992-1998) in two ways: ocean bottom pressure field and ocean surface topography minus steric effect. The resulting lowest-degree Stokes coefficients for both NCEP reanalysis and POCM are then compared with space geodetic SLR observations, to identify the importance of each meteorological oscillations in gravitational variation signals.
Inverted barometer effects and steric changes effects on hydrostatic response of ocean
Thermal copolymers of amino acids have been examined as a novel material for photovoltaic devices. Due to the steric effects of amino acids during polymerization, these polymers are highly ordered, and pigments such as flavins and pterins are formed as part of the polymer. The controllably varied composition of the amino acids in the polymer makes it possible to get either electron-donor or electron-acceptor, or both kinds of groups in varying degrees. The constituent photosensitive element has been made either of photosensitive polymer film or spherule.
Cox and Chao [2002] reported the detection of a large anomaly in the form of a positive "jump" in the time series of Earth's lowest-degree gravity harmonic J2, or the dynamic oblateness, during 1998. This prompted us to examine the mass redistribution in the global oceans. We report here a seesaw of the sea-surface height (SSH) in the extratropic north + south Pacific basins -- the leading (nonseasonal) EOF/PC mode in SSH derived from the 10-year TOPEX/Poseidon altimetry data in the extratropic Pacific region. The mode underwent a step-like jump with time evolution that match remarkably well with the observed J2 anomaly. However, the magnitude is several times too small to explain the observed J2, even if assuming the SSH jump was all mass-induced (as opposed to any steric effect which causes no time-variable gravity signal). If one accepts the notion that this extratropic Pacific seesaw is part of the geophysical process that produced the observed 1998 J2 anomaly, then this finding suggests strong geophysical connection of the interannual-to-decadal variation of J2 with the Pacific Decadal Oscillation (PDO), as the time series of the above EOF/PC mode is actually a formally defined PDO Index series.
Any large mass transport in the Earth system produces changes in the gravity field. Low harmonic degree components of such gravity variations have been observed by the satellite-laser-ranging (SLR) technique for the past quarter century, particularly in 52, the Earth's dynamic oblateness. 52 undergoes a slight decrease due primarily to the post-glacial rebound of the mantle, but large interannual anomalies have been observed, notably during 1998-2002. Intriguing evidences for the cause of the latter have been found in the extratropical Pacific basins, especially related to the Pacific Decadal Oscillation, and perhaps in related land hydrology. We will examine the latest results based on ocean altimetry, sea-surface temperature, and ocean and hydrology model outputs. Without firm estimates for the steric effects (which have no gravity signal), we will point out possible underestimation of OGCMs with respect to temporal variabilities. Besides J2, SLR also derived time series for other low-degree gravity components. While the formal uncertainty of these terms is significantly higher, some of these series have significant signal that show correlation to various climatic signals. For example, there is a significant correlation of the sectoral S2,2 with the Southern Oscillation Index signifying the influence of El Nino/La Nina. Cases such as these demonstrate the utility of assessing the mass component of climate variations, and anticipate the utility of GRACE-type space gravity observations with much higher spatial resolution.
Guanosine 5'-phosphate 2-methylimidazolide (2-MeImpG), a labile phosphoimidazolide analog of guanosine triphosphate, was used to test the reactivity of the natural polyamines (PAs), spermine (spm) and spermidine (spd). The products are the guanosine 5'-phosphate-polyamine derivatives (PA-pG: spd-pG and spm-pG) which are quite stable in the range 4 < pH < 11. Our study is the first of which we are aware that reports on the nucleophilicity of these amines. The main findings are as follows. (i) HPLC analysis of the products indicates the formation of only two of the three possible spd products and only one of the two possible spm products. These results can be explained if only the primary amino groups of the two polyamines are reactive, while the secondary amino groups are rendered unreactive by a steric effect. The reactions of 2-MeImpG and other phosphoimidazolide derivatives of nucleosides (ImpNs) with primary and secondary monoamines support this interpretation (Kanavarioti et al. J. Org. Chem. 1995, 60, 632). (ii) The product ratio of the two spd-pG adducts derived from the primary amino groups varies between 2.40 and 0.71 in the range 6.1 < or equal to pH < or equal to 11.9. Such small variation in the product ratio can only be rationalized by the similar, but not identical, basicity of the two primary amino groups and provides strong support for a previously reported model for polyamine ionization (Onasch et. al. Biophys. Chem. 1984, 19, 245). (iii) On the basis of our kinetic determinations conditions at which the nucleophilicity of these amines is at a minimum and at which other interactions with ImpNs could be tested can be chosen.
We estimate the total land water storage (LWS) change between 2003 and 2013 using a global water mass budget approach. Hereby we compare the ocean mass change (estimated from GRACE space gravimetry on the one hand, and from the satellite altimetry-based global mean sea level corrected for steric effects on the other hand) to the sum of the main water mass components of the climate system: glaciers, Greenland and Antarctica ice sheets, atmospheric water and LWS (the latter being the unknown quantity to be estimated). For glaciers and ice sheets, we use published estimates of ice mass trends based on various types of observations covering different time spans between 2003 and 2013. From the mass budget equation, we derive a net LWS trend over the study period. The mean trend amounts to +0.30 +/- 0.18 mm/yr in sea level equivalent. This corresponds to a net decrease of −108 +/- 64 cu km/yr in LWS over the 2003-2013 decade. We also estimate the rate of change in LWS and find no significant acceleration over the study period. The computed mean global LWS trend over the study period is shown to be explained mainly by direct anthropogenic effects on land hydrology, i.e. the net effect of groundwater depletion and impoundment of water in man-made reservoirs, and to a lesser extent the effect of naturally-forced land hydrology variability. Our results compare well with independent estimates of human-induced changes in global land hydrology.
Solvent effect in catalytic hydrogenation reaction of Schiff bases of alpha-keto acids with optically active alpha-alkylbenzylamine
Topex/Poseidon altimetry data are used to estimate the non-tidal mass redistribution as a function of space-time. The goal is to study the contribution of ocean circulations in the geodynamic effects including Earth's rotational and gravitational variations. We examine the non-seasonal anomalies at monthly sampling rate over the T/P span of eight years, concentrating especially on interannual variabilities. Since the sea-surface height data obtained from altimetry is the combined effect of steric change (primarily thermal effect) and the mass flux, and because the former has zero contribution to the geodynamic effects, one needs to do a so-called steric correction by removing from the altimetry data the steric contributions. We achieve it using multiyear monthly sea-surface temperature maps, together with monthly "climatology" for mixed-layer depth maps for mean-months of the year. We analyze both sets of the altimetry data and the steric correction data using the empirical orthogonal function/principal component analysis (in which we take care of issues associated with the area-weighting and non-zero mean), and examine the most important modes, either globally or regionally. In particular, the ENSO in the tropical Pacific/Indian Oceans exhibits the most prominent pattern. The net mass transport after the steric correction can then be compared with: (1) ocean general circulation model outputs for the same period of time (such as from POCM-4B); (2) non-atmospheric Earth rotation variations obtained from space geodesy data and atmospheric angular momentum data; (3) non-atmospheric low-degree gravitational variations from satellite-laser-ranging observations and global atmospheric data.
The polymerization of amino acids into peptides and ultimately proteins is critical to evolution of life. Ribosomally-synthesized proteins are homochiral, composed entirely of L-amino acids. Abiotic syntheses of amino acids, however, produce racemic mixtures(equal amounts of L and D enantiomers), meaning that the pool of monomers available for abiotic protein synthesis would be racemic or nearly so. There are no prebiotically plausible mechanisms known to yield homochiral peptides from racemic pools of amino acids. While some mechanisms capable of producing or amplifying enantiomeric excesses have been observed, these excesses are small or not applicable to all biologically relevant amino acids. As a result, a prebiotically-feasible mechanism to create enantiopure pools of amino acids has not been identified. However, it is not clear that these enantio-enriched or enantiopure pools are necessary to produce homochiral peptides. Steric and electronic effects, or a combination of both, may influence how different enantiomers interact with each other, potentially leading to homochiral peptides from racemic mixtures. Here, we use density functional theory (DFT) calculations to assess the stability of homochiral and heterochiral reactive complexes produced during polymerization via the salt-induced peptide formation (SIPF) reaction. Experimental studies of the SIPF reaction have shown that it enables the formation of peptides under diverse environmental conditions, making it a plausible pathway to peptide formation on early Earth. In the SIPF reaction, NaCl acts as a condensation reagent while a divalent metal cation, primarily Cu2+, facilitates polymerization by complexing and activating amino acids forming a monochlorocuprate complex. To assess if hetero-or homochiral monochlorocuprate complexes were energetically favored, we compared the stability of LL, DD, and LD enantiomers of Cu2+–(alanine)2and Cu2+–(valine) 2 complexes. Gaussian 09 density DFT energy-minimization calculations were made for each Cu –amino acid complex in the cis and trans configuration. Models were energy minimized using the BH and HLYP/6-31++G(d,p) level of theory and free energies were compared to determine the most stable configuration.
Co gamma irradiation of 2-hydroxyethyl methacrylate in the presence or in the absence of other acrylic monomers was found to constitute an effective technique for the synthesis of hydrophilic functional microspheres in the size range of approximately 0.3 to 3 microns in diameter. The effect of monomer concentration, steric stabilization, and electrostatic interaction on the particle size was investigated. Experimental conditions were determined to obtain desired particle sizes of relatively narrow distribution. It was shown that particles may be formed without intermediate micelles, i.e., by homogeneous nucleation, and the rate of particle formation is affected primarily by the rate of particle coalescence in the initial stages of the reaction. When covalently bound to antibodies these microspheres were successfully used to label murine and human lymphocytes.
A series of surface-modified clays containing nanophase (np) iron oxide/oxyhydroxides of extremely small particle sizes, with total iron contents as high as found in Mars soil, were prepared by iron deposition on the clay surface from ferrous chloride solution. Comprehensive studies of the iron mineralogy in these "Mars-soil analogs" were conducted using chemical extractions, solubility analyses, pH and redox, x ray and electron diffractometry, electron microscopic imaging, specific surface area and particle size determinations, differential thermal analyses, magnetic properties characterization, spectral reflectance, and Viking biology simulation experiments. The clay matrix and the procedure used for synthesis produced nanophase iron oxides containing a certain proportion of divalent iron, which slowly converts to more stable, fully oxidized iron minerals. The clay acted as an effective matrix, both chemically and sterically, preventing the major part of the synthesized iron oxides from ripening, i.e., growing and developing larger crystals. The precipitated iron oxides appear as isodiametric or slightly elongated particles in the size range 1-10 nm, having large specific surface area. The noncrystalline nature of the iron compounds precipitated on the surface of the clay was verified by their complete extractability in oxalate. Lepidocrocite (gamma-FeOOH) was detected by selected area electron diffraction. It is formed from a double iron Fe(II)/Fe(III) hydroxy mineral such as "green rust," or ferrosic hydroxide. Magnetic measurements suggested that lepidocrocite converted to the more stable maghemite (gamma-Fe2O3) by mild heat treatment and then to nanophase hematite (alpha-Fe2O3) by extensive heat treatment. After mild heating, the iron-enriched clay became slightly magnetic, to the extent that it adheres to a hand-held magnet, as was observed with Mars soil. The chemical reactivity of the iron-enriched clays strongly resembles, and offers a plausible mechanism for, the somewhat puzzling observations of the Viking biology experiments. Their unique chemical reactivities are attributed to the combined catalytic effects of the iron oxide/oxyhydroxides and silicate phase surfaces. The reflectance spectrum of the clay-iron preparations in the visible range is generally similar to the reflectance curves of bright regions on Mars. This strengthens the evidence for the predominance of nanophase iron oxides/oxyhydroxides in Mars soil. The mode of formation of these nanophase iron oxides on Mars is still unknown. It is puzzling that despite the long period of time since aqueous weathering took place on Mars, they have not developed from their transitory stage to well-crystallized end-members. The possibility is suggested that these phases represent a continuously on-going, extremely slow weathering process.
Ovostatin is a 780,000 MW protein, originally isolated from chicken egg white, which is active as a protease inhibitor. Structural studies indicate that the protein is a tetramer of identical subunits of 165,000 MW which can be separated upon reduction with beta- mercaptoethanol. Chicken ovostatin is an inhibitor of metalloproteases such as collagenase and thermolysin, and of acid proteases such as pepsin and rennin. Ovostatin isolated from duck eggs and from crocodile eggs appears to be similar to chicken egg ovostatin, but with significant differences in structure and function. Duck ovostatin contains a reactive thiol ester which is not found in the chicken protein, and duck and crocodile ovostatin inhibit serine protease such as trypsin and chymotrypsin, while chicken ovostatin does not. Electron microscopy of ovostatin indicates that two subunits associated near the middle of each polypeptide to form a dimer with four arms. Two of these dimers then associate to produce a tetramer with eight arms, with the protease binding site near the center of the molecule. Upon binding of the protease, a conformational change causes all eight arms to curl toward the center of the molecule, effectively trapping the protease and sterically hindering access of the substrates to its active site. The structural organization and mechanism of action proposed for ovostatin are nearly identical to that proposed for alpha(sub 2)- macroglobulin, a serum protease inhibitor which may play an important role in regulation of proteases in animal tissues. Although the general arrangement of subunits appears to be the same for all ovostatins studied, some differences have been observed, with chicken ovostatin more closely resembling reptilian ovostatin than the duck protein. This is a surprising result, given the evolutionary relatedness of chickens and ducks. It is possible that the differences in structures may be due to deformed subunit arrangements which occur during the processing and fixing necessary for electron microscopy. Examination of the native structure of these proteins using X-ray crystallography would help clarify these discrepancies.