These are representative sample records from related to your search topic.
For comprehensive and current results, perform a real-time search at

Complex formation and decay in ion-molecule reactions  

NASA Astrophysics Data System (ADS)

The potential energy surfaces for ion-molecule reactions typically have several minima that lie lower in energy than the asymptotes for the reactant and product channels. Such complexes can be covalently bound, hydrogen bonded or electrostatically bound. The nature of these complexes can have dramatic effects on the outcome of the reaction. We review three experimental studies that show three different cases of such influence. The reaction of acetylene cation with methane shows channels that proceed via a long-lived, covalently bound complex, and one channel that proceeds by a short-lived, weakly bound encounter complex. Specific reactant vibrations strongly influence both total reactivity and branching between the product channels, and the effect is related to the mode-specific coupling of vibration to the reaction coordinate. The reaction of phenol cation with ammonia is a case involving both electrostatically bound and hydrogen-bonded complexes, with ring-coordination complexes acting as precursors to the formation of the hydrogen-bonded complexes where reaction can occur. Again, vibration has a significant effect, related to the isomerization between coordination and hydrogen-bonded geometries. Finally, the reaction of ammonia cation with methanol involves competition between formation of different hydrogen-bonded intermediates, and the complex that forms largely determines the outcome of the reaction.

Green, Richard J.; Anderson, Scott L.


Formation of stable sessile interstitial complexes in reactions between glissile dislocation loops in bcc Fe  

NASA Astrophysics Data System (ADS)

Clusters of self-interstitial atoms (loops) are commonly observed in the microstructure of irradiated metals. These clusters can be formed directly in high-energy displacement cascades or by growth as a result of interaction between individual self interstitials. The majority of these clusters have features of glissile dislocation loops and migrate by fast one-dimensional glide. In this paper, we present results of a systematic molecular dynamics (MD) study of reactions involving glissile interstitial loops. By the example of bcc iron we demonstrate that the reactions can produce a number of specific, stable microstructural features, with different properties compared to the reactants. Namely, the reactions between the most common glissile clusters of <1 1 1> crowdions can result in coarsening or formation of immobile self interstitial complexes. The coarsening leads to a decrease of the total dislocation line length and therefore is favourable. The structure and stability of the junction formed in the reactions has been studied using many-body potentials and density functional theory (DFT) techniques. No evidence of the formation of a <1 0 0> loop from two glissile <1 1 1> clusters was found among the studied reactions. The immobile self interstitial complexes that form as a result of these reaction have, however, high binding energies, of the order of tens of eV, implying that a relatively long life time should be assigned to the resulting configurations and therefore that such objects are expected to contribute to the evolution of the microstructure under irradiation.

Terentyev, Dmitry; Malerba, Lorenzo; Klaver, Peter; Olsson, Par



Reactions of a Dinitrogen Complex of Molybdenum: Formation of a Carbon-Nitrogen Bond.  

ERIC Educational Resources Information Center

Reports a procedure for the formation of alkyldiazenido complexes of molybdenum in the absence of dioxygen, suitable for inclusion in an advanced inorganic chemistry laboratory. Includes background information and experimental procedures for two complexes. (SK)

Busby, David C.; And Others



Intermediates in Reactions of Copper(I) Complexes with N-Oxides: From Formation of Stable Adducts to Oxo Transfer  

PubMed Central

Reactions of Cu(I) complexes of bidentate N-donor supporting ligands with pyridine- and trimethylamine-N-oxides or PhIO were explored. Key results include the identification of novel Cu(I)-N-oxide adducts, aryl substituent hydroxylation, and bis(?-oxo)dicopper complex formation via a route involving oxo transfer. PMID:19425587

Hong, Sungjun; Gupta, Aalo K.; Tolman, William B.



Reactions of dioxygen complexes. Oxidative dehydrogenation of 1,6-bis(2-pyridyl)-2,5-diazahexane through cobalt dioxygen complex formation  

Microsoft Academic Search

The formation constants and oxygenation constants of the cobalt(II) complexes of 1,6-bis(2-pyridyl)-2,5-diazahexane (PYEN) have been determined by potentiometric equilibrium measurements under nitrogen and oxygen. The kinetics of the oxidative degradation of the coordinated ligand in the cobalt dioxygen complex have been measured spectrophotometrically, and the rate constants of two parallel degradation reactions have been determined. Both reactions were found to

Arup K. Basak; Arthur E. Martell



Complexation versus thiadiazole formation for reactions of thiosemicarbazides with copper(II).  


The reactions of N,N-substituted thiosemicarbazides with copper salts have been investigated and either copper(II) thiosemicarbazide complexes, 1,3,4-thiadiazolium salts or 1,3,5-thiadiazoles are obtained depending on the Cu(II) salt and solvent used. PMID:17353950

López-Torres, Elena; Cowley, Andrew R; Dilworth, Jonathan R



Neutral metal cluster formation and oxidation reactions in the photolysis of iron carbonyl van der Waals complexes  

SciTech Connect

Iron pentacarbonyl van der Waals complexes and mixed complexes containing iron pentacarbonyl and oxygen, carbon dioxide, or water are produced in pulsed supersonic expansions and probed with ultraviolet multiphoton ionization time-of-flight mass spectroscopy. Photochemical rearrangement and oxidation reactions occur within these complexes prior to photoionization, resulting in the formation of neutral iron clusters, iron cluster carbonyls, and iron cluster monoxides. Two laser time-delayed experiments, as well as excimer laser wavelength and power dependences, are used to probe the mechanism of this fascinating photoinduced chemistry, which occurs in cluster species containing 1-25 iron atoms.

Wheeler, R.G.; Duncan, M.A.



Reactions of guanine with methyl chloride and methyl bromide: O6-methylation versus charge transfer complex formation  

NASA Astrophysics Data System (ADS)

Density functional theory (DFT) at the B3LYP/6-31+G* and B3LYP/AUG-cc-pVDZ levels was employed to study O6-methylation of guanine due to its reactions with methyl chloride and methyl bromide and to obtain explanation as to why the methyl halides cause genotoxicity and possess mutagenic and carcinogenic properties. Geometries of the various isolated species involved in the reactions, reactant complexes (RCs), and product complexes (PCs) were optimized in gas phase. Transition states connecting the reactant complexes with the product complexes were also optimized in gas phase at the same levels of theory. The reactant complexes, product complexes, and transition states were solvated in aqueous media using the polarizable continuum model (PCM) of the self-consistent reaction field theory. Zero-point energy (ZPE) correction to total energy and the corresponding thermal energy correction to enthalpy were made in each case. The reactant complexes of the keto form of guanine with methyl chloride and methyl bromide in water are appreciably more stable than the corresponding complexes involving the enol form of guanine. The nature of binding in the product complexes was found to be of the charge transfer type (O6mG+ · X-, X dbond Cl, Br). Binding of HCl, HBr, and H2O molecules to the PCs obtained with the keto form of guanine did not alter the positions of the halide anions in the PCs, and the charge transfer character of the PCs was also not modified due to this binding. Further, the complexes obtained due to the binding of HCl, HBr, and H2O molecules to the PCs had greater stability than the isolated PCs. The reaction barriers involved in the formation of PCs were found to be quite high (?50 kcal/mol). Mechanisms of genotoxicity, mutagenesis and carcinogenesis caused by the methyl halides appear to involve charge transfer-type complex formation. Thus the mechanisms of these processes involving the methyl halides appear to be quite different from those that involve the other strongly carcinogenic methylating agents.

Shukla, P. K.; Mishra, P. C.; Suhai, S.


Kinetics of actinide complexation reactions  

SciTech Connect

Though the literature records extensive compilations of the thermodynamics of actinide complexation reactions, the kinetics of complex formation and dissociation reactions of actinide ions in aqueous solutions have not been extensively investigated. In light of the central role played by such reactions in actinide process and environmental chemistry, this situation is somewhat surprising. The authors report herein a summary of what is known about actinide complexation kinetics. The systems include actinide ions in the four principal oxidation states (III, IV, V, and VI) and complex formation and dissociation rates with both simple and complex ligands. Most of the work reported was conducted in acidic media, but a few address reactions in neutral and alkaline solutions. Complex formation reactions tend in general to be rapid, accessible only to rapid-scan and equilibrium perturbation techniques. Complex dissociation reactions exhibit a wider range of rates and are generally more accessible using standard analytical methods. Literature results are described and correlated with the known properties of the individual ions.

Nash, K.L.; Sullivan, J.C.



Reactions of dioxygen complexes. Oxidative dehydrogenation of 1,6-bis(2-pyridyl)-2,5-diazahexane through cobalt dioxygen complex formation  

SciTech Connect

The formation constants and oxygenation constants of the cobalt(II) complexes of 1,6-bis(2-pyridyl)-2,5-diazahexane (PYEN) have been determined by potentiometric equilibrium measurements under nitrogen and oxygen. The kinetics of the oxidative degradation of the coordinated ligand in the cobalt dioxygen complex have been measured spectrophotometrically, and the rate constants of two parallel degradation reactions have been determined. Both reactions were found to be second order, first order with respect to the concentration of the dioxygen complex and first order with respect to the hydroxide ion concentration. Kinetics and product analysis reveal that one of the terminal aminomethyl residues of the ligand PYEN undergoes two-electron oxidation to form the corresponding imine, which under the reaction conditions employed is converted to pyridine-2-carboxyaldehyde, identified semiquantitatively as the (2,6-dinitrophenyl)hydrazone. Comparisons of these results with those of systems investigated previously, and the large kinetic deuterium isotope effect for the dehydrogenation reaction, are employed as the basis of a proposed reaction mechanism, which involves deprotonation of an aliphatic amino group in a preequilibrium step. Reaction mechanisms are suggested. 30 references, 10 figures, 3 tables.

Basak, A.K.; Martell, A.E.



Electronic structure and formation of simple ferryloxo complexes: mechanism of the Fenton reaction.  


The Fenton reaction is a famous reaction in inorganic chemistry, with relevance to topics such as bioinorganic oxidation and fundamental redox chemistry of water and oxygen. It is also a reaction concerning which there has been very extensive mechanistic debate, with experimental and computational work leading to extensive evidence concerning its mechanism-not all of which is consistent. Here, we use this reaction as a challenge to modern electronic structure theory methods and show that density functional theory, when validated by accurate ab initio methods, can yield a picture of this reaction that is consistent with experiment. The article also highlights some of the challenges in accurate studies of reaction mechanisms of ionic species in water solution. PMID:24785907

Petit, Alban S; Pennifold, Robert C R; Harvey, Jeremy N



Complex Pattern Formation in the Polyacrylamide-Methylene Blue-Oxygen Reaction Oliver Steinbock,*, Eric Kasper, and Stefan C. Mu1ller  

E-print Network

Complex Pattern Formation in the Polyacrylamide-Methylene Blue-Oxygen Reaction Oliver SteinbockVersita¨tsplatz 2, D-39106 Magdeburg, Germany ReceiVed: February 23, 1999 The polyacrylamide-methylene blue of reaction time and initial sulfide concentration. Introduction The polyacrylamide-methylene blue-oxygen (PA

Steinbock, Oliver


Intermediates in reactions of copper(I) complexes with N-oxides: from the formation of stable adducts to oxo transfer.  


Reactions of copper(I) complexes of bidentate N-donor supporting ligands with pyridine- and trimethylamine-N-oxides or PhIO were explored. Key results include the identification of novel copper(I) N-oxide adducts, aryl substituent hydroxylation, and bis(mu-oxo)dicopper complex formation via a route involving oxo transfer. PMID:19425587

Hong, Sungjun; Gupta, Aalo K; Tolman, William B



Bacterial formate hydrogenlyase complex  

PubMed Central

Under anaerobic conditions, Escherichia coli can carry out a mixed-acid fermentation that ultimately produces molecular hydrogen. The enzyme directly responsible for hydrogen production is the membrane-bound formate hydrogenlyase (FHL) complex, which links formate oxidation to proton reduction and has evolutionary links to Complex I, the NADH:quinone oxidoreductase. Although the genetics, maturation, and some biochemistry of FHL are understood, the protein complex has never been isolated in an intact form to allow biochemical analysis. In this work, genetic tools are reported that allow the facile isolation of FHL in a single chromatographic step. The core complex is shown to comprise HycE (a [NiFe] hydrogenase component termed Hyd-3), FdhF (the molybdenum-dependent formate dehydrogenase-H), and three iron-sulfur proteins: HycB, HycF, and HycG. A proportion of this core complex remains associated with HycC and HycD, which are polytopic integral membrane proteins believed to anchor the core complex to the cytoplasmic side of the membrane. As isolated, the FHL complex retains formate hydrogenlyase activity in vitro. Protein film electrochemistry experiments on Hyd-3 demonstrate that it has a unique ability among [NiFe] hydrogenases to catalyze production of H2 even at high partial pressures of H2. Understanding and harnessing the activity of the FHL complex is critical to advancing future biohydrogen research efforts. PMID:25157147

McDowall, Jennifer S.; Murphy, Bonnie J.; Haumann, Michael; Palmer, Tracy; Armstrong, Fraser A.; Sargent, Frank




SciTech Connect

I. This study reports the rapid reaction under mild conditions of internal or terminal alkynes with methyl (acetyl~ acetonato) (triphenylphosphine) nickel (1) in either aromatic or ether solvents. In all cases vinylnickel products 2 are formed by insertion of the alkyne into the nickel=methyl bond. These complexes may be converted into a variety of organic products (e.g. alkenes, esters, vinyl halides) by treatment with appropriate reagents. Unsymmetrical alkynes give selectively the one regioisomer with the sterically largest substituent next to the nickel atom. In order to investigate the stereochemistry of the initial insertion, a x-ray diffraction study of the reaction of 1 with diphenylacetylene was carried out. This showed that the vinylnickel complex formed by overall trans insertion was the product of the reaction. Furthermore, subsequent slow isomerization of this complex, to a mixture of it and the corresponding cis isomer, demonstrated that this trans addition product is the kinetic product of the reaction. In studies with other alkynes, the product of trans addition was not always exclusively (or even predominantly) formed, but the ratio of the stereoisomers formed kinetically was substantially different from the thermodynamic ratio. Isotope labeling, added phosphine, and other experiments have allowed us to conclude that the mechanism of this reaction does involve initial cis addition. However, a coordinatively unsaturated vinylnickel complex is initially formed which can undergo rapid, phosphine-catalyzed cis-trans isomerization in competition with its conversion to the isolable phosphine-substituted kinetic reaction products. II. The reaction of CpMo(CO){sub 3}H (1a) with CpMo(CO){sub 3}R (2, R= CH{sub 3}, C{sub 2}H{sub 5}) at 50{degrees} C in THF gives the aldehyde RCHO and the dimers [CpMo(CO){sub 3}]{sub 2} (3a) and [CpMo(CO){sub 2}]{sub 2} (4a). Labeling one of the reactants with a methylcyclopentadienyl ligand it was possible to show that the mixed dimers MeCpMo(CO){sub 3}-(CO){sub 3}MoCp (3b) and MeCpMo(CO){sub 2}{triple_bond}(CO){sub 2}MoCp (4b) are the predominant kinetic products of the reaction. Additionally labeling the carbonyl ligands of 1a with {sup 13}CO led to the conclusion that all three of the carbonyl ligands in 1a end up in the tetracarbonyl dimers 4a if the reaction is carried out under a continuous purge of argon Trapping studies failed to find any evidence for the intermediacy of either [CpMo(CO){sub 3}]{sup -} or [CpMo(CO){sub 3}]{sup +} in this reaction. A mechanism is proposed that involves the initial migration of the alkyl ligand in 2 to CO forming an unsaturated acyl complex which reacts with 1a to give a binuclear complex containing a three center-two electron Mo-H-Mo bond. This complex then selectively looses a carbonyl from the acyl molybdenum, migrates the hydride to that same metal, and forms a metal-metal bond. This binuclear complex with the hydride and acyl ligands on one metal reductively eliminates aldehyde, and migrates a carbonyl ligand, to give 4a directly. The other product 3a is formed by addition of two molecules of free CO to 4a.

Huggins, John Mitchell



Diverse reactions of PhI(OTf)2 with common 2-electron ligands: complex formation, oxidation, and oxidative coupling.  


The crystal structures of bis-pyridine stabilized iodine dications [PhI(pyr)(2)](2+) are reported as triflate salts, representing the first ligand supported iodine dications to be structurally characterized. The pyridine complexes are susceptible to ligand exchange in reaction with stronger N-based donors such as 4-dimethylaminopyridine. Attempts to extend this reactivity to N-heterocyclic carbene and phosphine ligands, as has been accomplished in the earlier p-block groups, resulted in redox chemistry, with oxidation of the ligands rather than coordination. PMID:23148595

Pell, Thomas P; Couchman, Shannon A; Ibrahim, Sara; Wilson, David J D; Smith, Brian J; Barnard, Peter J; Dutton, Jason L



Determination of boron at sub-ppm levels in uranium oxide and aluminum by hyphenated system of complex formation reaction and high-performance liquid chromatography (HPLC).  


Boron, at sub-ppm levels, in U3O8 powder and aluminum metal, was determined using complex formation and dynamically modified reversed-phase high-performance liquid chromatography (RP-HPLC). Curcumin was used for complexing boron extracted with 2-ethyl-1,3-hexane diol (EHD). Separation of complex from excess reagent and thereafter its determination using the online diode array detector (DAD) was carried out by HPLC. Calibration curve was found to be linear for boron amounts in the sample ranging from 0.02 microg to 0.5 microg. Precision of about 10% was achieved for B determination in samples containing less than 1 ppmw of boron. The values obtained by HPLC were in good agreement with the data available from other analytical techniques. The precision in the data obtained by HPLC was much better compared to that reported by other techniques. The present hyphenated methodology of HPLC and complex formation reaction is interesting because of cost performance, simplicity, versatility and availability when compared to other spectroscopic techniques like ICP-MS and ICP-AES. PMID:18371924

Rao, Radhika M; Aggarwal, Suresh K



Measurements of Enthalpy Change of Reaction of Formation, Molar Heat Capacity and Constant-Volume Combustion Energy of Solid Complex Yb(Et 2dtc) 3 (phen)  

Microsoft Academic Search

A ternary solid complex Yb(Et2dtc)3(phen) was obtained from the reaction of hydrous ytterbium chloride with sodium diethyldithiocarbamate (NaEt2dtc), and 1, 10-phenanthroline (o-phen·H2O) in absolute ethanol. The bonding characteristics of the complex were characterized by IR. The result shows Yb3+ bands with two sulfur atoms in the Na(Et2dtc)3 and two nitrogen atoms in the o-phen. The enthalpy change of liquid-phase reaction

Weiming Song; Qilin Hu; Xuan Chang; Sanping Chen; Gang Xie; Shengli Gao



Unusual Complex Formation and Chemical Reaction of Haloacetate Anion on the Exterior Surface of Cucurbit[6]uril in the Gas Phase  

NASA Astrophysics Data System (ADS)

Noncovalent interactions of cucurbit[6]uril (CB[6]) with haloacetate and halide anions are investigated in the gas phase using electrospray ionization ion mobility mass spectrometry. Strong noncovalent interactions of monoiodoacetate, monobromoacetate, monochloroacetate, dichloroacetate, and trichloroacetate on the exterior surface of CB[6] are observed in the negative mode electrospray ionization mass spectra. The strong binding energy of the complex allows intramolecular SN2 reaction of haloacetate, which yields externally bound CB[6]-halide complex, by collisional activation. Utilizing ion mobility technique, structures of exteriorly bound CB[6] complexes of haloacetate and halide anions are confirmed. Theoretically determined low energy structures using density functional theory (DFT) further support results from ion mobility studies. The DFT calculation reveals that the binding energy and conformation of haloacetate on the CB[6] surface affect the efficiency of the intramolecular SN2 reaction of haloacetate, which correlate well with the experimental observation.

Choi, Tae Su; Ko, Jae Yoon; Heo, Sung Woo; Ko, Young Ho; Kim, Kimoon; Kim, Hugh I.



Reactions of coordinated dinitrogen. 8. Formation of ammonia by protonation of a molybdenum-dinitrogen complex and isolation and characterization of the molybdenum-containing product  

SciTech Connect

This is the first reported conversion of metal-coordinated dinitrogen into ammonia in which the fate of the metal has been determined. This reaction is shown in the following equation, where triphos = PhP(CH/sub 2/CH/sub 2/PPh/sub 2/)/sub 2/ and L = PPh/sub 3/:2Mo(N/sub 2/)/sub 2/(triphos)(L) + 8HBr ..-->.. 2NH/sub 4/Br + 2MoBr/sub 3/(triphos) + 3N/sub 2/ + 2L. The metal complex which is a new subclass of bis(dinitrogen) complexes of molybdenum, reacted in tetrahydrofuran (THF) solution with anhydrous hydrogen bromide to produce ammonium bromide. No hydrazine or hydrazinium bromide was detected among the reaction products. Ammonium bromide was detected by infrared spectroscopy among the reaction products after solvent and excess HBr had been removed in vacuo. The yield of ammonia was determined quantitatively by the indophenol method after either aqueous, nonaqueous (ethanol), or two-phase (dichloromethane-water) extraction of ammonium bromide from the residue. The molybdenum-containing product slowly decomposed during the dichloromethane-water extraction step. Isolation of pure MoBr/sub 3/(triphos) was carried out in a separate experiment in which only N/sub 2/ evolution was measured. All volatiles were removed from the reaction vessel and the resulting yellow solid was washed with ethanol and dried. Its identity was confirmed by elemental analysis.

Baumann, J.A.; George, T.A.




Microsoft Academic Search

Complex trauma occurs repeatedly and escalates over its duration. In families, it is exemplified by domestic violence and child abuse and in other situations by war, prisoner of war or refugee status, and human trafficking. Complex trauma also refers to situations such as acute\\/chronic illness that requires intensive medical intervention or a single traumatic event that is calamitous. Complex trauma

Christine A. Courtois



Complex Trauma, Complex Reactions: Assessment and Treatment  

Microsoft Academic Search

Complex trauma occurs repeatedly and escalates over its duration. In families, it is exemplified by domestic violence and child abuse and in other situations by war, prisoner of war or refugee status, and human trafficking. Complex trauma also refers to situations such as acute\\/chronic illness that requires intensive medical intervention or a single traumatic event that is calamitous. Complex trauma

Christine A. Courtois



Markovian Dynamics on Complex Reaction Networks  

E-print Network

Complex networks, comprised of individual elements that interact with each other through reaction channels, are ubiquitous across many scientific and engineering disciplines. Examples include biochemical, pharmacokinetic, epidemiological, ecological, social, neural, and multi-agent networks. A common approach to modeling such networks is by a master equation that governs the dynamic evolution of the joint probability mass function of the underling population process and naturally leads to Markovian dynamics for such process. Due however to the nonlinear nature of most reactions, the computation and analysis of the resulting stochastic population dynamics is a difficult task. This review article provides a coherent and comprehensive coverage of recently developed approaches and methods to tackle this problem. After reviewing a general framework for modeling Markovian reaction networks and giving specific examples, the authors present numerical and computational techniques capable of evaluating or approximating the solution of the master equation, discuss a recently developed approach for studying the stationary behavior of Markovian reaction networks using a potential energy landscape perspective, and provide an introduction to the emerging theory of thermodynamic analysis of such networks. Three representative problems of opinion formation, transcription regulation, and neural network dynamics are used as illustrative examples.

John Goutsias; Garrett Jenkinson



Markovian dynamics on complex reaction networks  

NASA Astrophysics Data System (ADS)

Complex networks, comprised of individual elements that interact with each other through reaction channels, are ubiquitous across many scientific and engineering disciplines. Examples include biochemical, pharmacokinetic, epidemiological, ecological, social, neural, and multi-agent networks. A common approach to modeling such networks is by a master equation that governs the dynamic evolution of the joint probability mass function of the underlying population process and naturally leads to Markovian dynamics for such process. Due however to the nonlinear nature of most reactions and the large size of the underlying state-spaces, computation and analysis of the resulting stochastic population dynamics is a difficult task. This review article provides a coherent and comprehensive coverage of recently developed approaches and methods to tackle this problem. After reviewing a general framework for modeling Markovian reaction networks and giving specific examples, the authors present numerical and computational techniques capable of evaluating or approximating the solution of the master equation, discuss a recently developed approach for studying the stationary behavior of Markovian reaction networks using a potential energy landscape perspective, and provide an introduction to the emerging theory of thermodynamic analysis of such networks. Three representative problems of opinion formation, transcription regulation, and neural network dynamics are used as illustrative examples.

Goutsias, J.; Jenkinson, G.



Analysis of chemical reactions of ?-radiolysis, hydrolysis and complex formation in alkali solutions of the object ``Shelter". Investigations of transfer coefficients of UO22+, PuO22+ ions in aqueous solutions (in Ukrainian)  

NASA Astrophysics Data System (ADS)

Chemical reactions of ?-radiolysis, hydrolysis and complex formation as well as oxidizing-reducing processes in alkali solutions of ions UO^{2+}_2, PuO^{2+}_2, AmO^{2+}_2 have been analyzed. It has been established that polyuranites and superuranites, phosphate, carbonate and nitrate precipitates of uraninite and plutoninite may arise in aqueous solutions, which are characteristic of the object ``Shelter". Hydrodynamic-fluctuation theory for calculation of bimolecular reactions is presented. Calculation of mutual diffusion and viscosity transfer coefficients for ions UO^{2+}_2, PuO^{2+}_2 and atomic hydrohen in aqueous solutions is carried out.

Yukhnovskii, I. R.; Tokarchuk, M. V.; Kobryn, O. E.; Dmytriv, G. S.; Humenyuk, Y. A.


Reaction Dynamics on the Formation of Styrene: A Crossed Molecular Beam Study of the Reaction of Phenyl Radicals with  

E-print Network

Reaction Dynamics on the Formation of Styrene: A Crossed Molecular Beam Study of the Reaction that the reaction followed indirect scattering dynamics via complex formation and was initiated by an addition nebulae, they on Earth are considered as toxic byproducts in combustion processes of fossil fuel. Here

Kaiser, Ralf I.


Equilibrium investigation of complex formation reactions involving copper(II), nitrilo-tris(methyl phosphonic acid) and amino acids, peptides or DNA constitutents. The kinetics, mechanism and correlation of rates with complex stability for metal ion promoted hydrolysis of glycine methyl ester  

Microsoft Academic Search

The complex formation reactions of [Cu(NTP)(OH2)] (NTP?=?nitrilo-tris(methyl phosphonic acid)) with some selected bio-relevant ligands containing different functional groups, are investigated. Stoichiometry and stability constants for the complexes formed are reported. The results show that the ternary complexes are formed in a stepwise mechanism whereby NTP binds to copper(II), followed by coordination of amino acid, peptide or DNA. Copper(II) is found

Ahmed A. El-Sherif; Mohamed M. Shoukry



Photoinduced reaction of methylpolyynes H(C?C)nCH3 (n = 5-7) and polyyne H(C?C)5H with I2 molecules. Formation of molecular complex vs. degradation  

NASA Astrophysics Data System (ADS)

Methylpolyynes, H(C?C) n CH3 ( n = 5-7), were photo-irradiated under the presence of iodine molecules in hexane to confirm the formation of a series of molecular complexes, H(C?C) n CH3(I6) ( n = 5-7), by systematic changes in their UV absorption spectra. In order to investigate the reaction mechanism, solutions of hydrogen-capped polyyne, H(C?C)5H, and I2 molecules in hexane were irradiated with a cw-laser beam at 532 nm, then their UV absorption spectra were recorded to obtain temporal decay profiles for the polyyne C10H2. At C10H2 concentrations of about 7 ?mol L-1, the rate of reaction in the decay profile for C10H2 increased with increasing I2 concentration (8.2-126 ?mol L-1) as well as with increasing laser power (0.34-6.2 mW). Based on a kinetic model, the degradation of C10H2 was shown to compete with the formation of the polyyne-iodine molecular complex, H(C?C)5H(I6). The formation of the complex was found to be efficient under the condition that the I2 concentration is orders of magnitude higher than the C10H2 concentration as this suppresses the degradation process.

Wada, Y.; Koma, K.; Ohnishi, Y.; Sasaki, Y.; Wakabayashi, T.



In-Situ Formation of Cobalt-Phosphate Oxygen-Evolving Complex-Anchored Reduced Graphene Oxide Nanosheets for Oxygen Reduction Reaction  

NASA Astrophysics Data System (ADS)

Oxygen conversion process between O2 and H2O by means of electrochemistry or photochemistry has lately received a great deal of attention. Cobalt-phosphate (Co-Pi) catalyst is a new type of cost-effective artificial oxygen-evolving complex (OEC) with amorphous features during photosynthesis. However, can such Co-Pi OEC also act as oxygen reduction reaction (ORR) catalyst in electrochemical processes? The question remains unanswered. Here for the first time we demonstrate that Co-Pi OEC does be rather active for the ORR. Particularly, Co-Pi OEC anchoring on reduced graphite oxide (rGO) nanosheet is shown to possess dramatically improved electrocatalytic activities. Differing from the generally accepted role of rGO as an ``electron reservoir'', we suggest that rGO serves as ``peroxide cleaner'' in enhancing the electrocatalytic behaviors. The present study may bridge the gap between photochemistry and electrochemistry towards oxygen conversion.

Zhao, Zhi-Gang; Zhang, Jing; Yuan, Yinyin; Lv, Hong; Tian, Yuyu; Wu, Dan; Li, Qing-Wen



In-Situ Formation of Cobalt-Phosphate Oxygen-Evolving Complex-Anchored Reduced Graphene Oxide Nanosheets for Oxygen Reduction Reaction  

PubMed Central

Oxygen conversion process between O2 and H2O by means of electrochemistry or photochemistry has lately received a great deal of attention. Cobalt-phosphate (Co-Pi) catalyst is a new type of cost-effective artificial oxygen-evolving complex (OEC) with amorphous features during photosynthesis. However, can such Co-Pi OEC also act as oxygen reduction reaction (ORR) catalyst in electrochemical processes? The question remains unanswered. Here for the first time we demonstrate that Co-Pi OEC does be rather active for the ORR. Particularly, Co-Pi OEC anchoring on reduced graphite oxide (rGO) nanosheet is shown to possess dramatically improved electrocatalytic activities. Differing from the generally accepted role of rGO as an “electron reservoir”, we suggest that rGO serves as “peroxide cleaner” in enhancing the electrocatalytic behaviors. The present study may bridge the gap between photochemistry and electrochemistry towards oxygen conversion. PMID:23877331

Zhao, Zhi-Gang; Zhang, Jing; Yuan, Yinyin; Lv, Hong; Tian, Yuyu; Wu, Dan; Li, Qing-Wen



Three-component reaction of tautomeric amidines with 3-ferrocenylmethylidene-2,4-pentanedione. Formation of polymeric coordination complexes of potassium ferrocenyl-(hexahydro)pyrimidoxides.  


Acetamidine hydrochloride and p-aminobenzamidine dihydrochloride interact with 3-ferrocenylmethylidene-2,4-pentanedione at 80-82 °C in the presence of K2CO3 in the water-alcohol medium in two tautomeric forms (the amidoimine and enediamine ones) with formation of mixtures of pyrimidine and piperidone derivatives and polymeric coordination complexes of potassium ferrocenyl(hexahydro)pyrimidoxides. The structure of the resultant compounds is elucidated on the basis of IR, 1H- and 13C-NMR spectroscopy, mass spectrometry and elemental analysis data. The crystal structures of 6-ferrocenyl-4-hydroxy-4-methyl-2-piperidone, potassium 6-ferrocenyl-4-methyl-2-methylidene(hexahydro)pyrimidin-4-oxide and 2-(4-aminophenyl)-4-ferrocenyl-6-methyl-pyrimidine were determined by X-ray analysis of suitable single crystals. PMID:24362624

Klimova, Elena I; Flores-Alamo, Marcos; Klimova, Tatiana; Maya, Sandra Cortez; Beletskaya, Irina P



Preequilibrium reactions with complex particle channels  

SciTech Connect

Investigations of nucleon induced reactions at incident energies of 14-90 MeV resulting in the emission of complex particles (A=2-4) have provided insights which complement those previously obtained from (N,xN) reactions. The description of the preequilibrium energy spectra required modifications to an earlier phenomenological model for direct pickup reactions. This model supplements the usual exciton preequilibrium model. Work on complex particle induced reactions confirms some of these results, extends them to include stripping and exchange reactions, and provides evidence for a projectile dependence of the average effective matrix elements for the residual interactions in the exciton model. A full description of reactions with complex projectiles will require the inclusion of a realistic breakup component and the resulting reduction of the cross section available for the exciton model calculations. Reactions with complex particles in the entrance and/or exit channels have provided indirect evidence for the amount of surface peaking of the initial target-projectile interaction. A summary of additional data needed to help resolve remaining questions is presented.

Kalbach, C. [Physics Department, Duke University, Durham, North Carolina 27708-0305 (United States)



The reactions of SO3 with HO2 radical and H2O...HO2 radical complex. Theoretical study on the atmospheric formation of HSO5 and H2SO4.  


The influence of a single water molecule on the gas-phase reactivity of the HO(2) radical has been investigated by studying the reactions of SO(3) with the HO(2) radical and with the H(2)O...HO(2) radical complex. The naked reaction leads to the formation of the HSO(5) radical, with a computed binding energy of 13.81 kcal mol(-1). The reaction with the H(2)O...HO(2) radical complex can give two different products, namely (a) HSO(5) + H(2)O, which has a binding energy that is computed to be 4.76 kcal mol(-1) more stable than the SO(3) + H(2)O...HO(2) reactants (Delta(E + ZPE) at 0K) and an estimated branching ratio of about 34% at 298K and (b) sulfuric acid and the hydroperoxyl radical, which is computed to be 10.51 kcal mol(-1) below the energy of the reactants (Delta(E + ZPE) at 0K), with an estimated branching ratio of about 66% at 298K. The fact that one of the products is H(2)SO(4) may have relevance in the chemistry of the atmosphere. Interestingly, the water molecule acts as a catalyst, [as it occurs in (a)] or as a reactant [as it occurs in (b)]. For a sake of completeness we have also calculated the anharmonic vibrational frequencies for HO(2), HSO(5), the HSO(5)...H(2)O hydrogen bonded complex, H(2)SO(4), and two H(2)SO(4)...H(2)O complexes, in order to help with the possible experimental identification of some of these species. PMID:20165760

Gonzalez, Javier; Torrent-Sucarrat, Miquel; Anglada, Josep M



Photosynthetic reaction center complexes from heliobacteria  

NASA Technical Reports Server (NTRS)

The goal of this project is to understand the early evolutionary development of photosynthesis by examining the properties of reaction centers isolated from certain contemporary organisms that appear to contain the simplest photosynthetic reaction centers. The major focus of this project is the family of newly discovered strictly anaerobic photosynthetic organisms known as Heliobacteria. These organisms are the only known photosynthetic organisms that are grouped with the gram-positive phylum of bacteria. The properties of these reaction centers suggest that they might be the decendants of an ancestor that also gave rise to Photosystem 1 found in oxygen-evolving photosynthetic organisms. Photoactive reaction center-core antenna complexes have been isolated from the photosynthetic bacteria Heliobacillus mobilis and Heliobacterium gestii. The absorption and fluorescence properties of membranes and reaction centers are almost identical, suggesting that a single pigment-protein complex serves as both antenna and reaction center. Experiments in progress include sequence determination of the 48,000 Mr reaction center protein, and evolutionary comparisons with other reaction center proteins.

Trost, J. T.; Vermaas, W. F. J.; Blankenship, R. E.



Reactions of Ph3Sb?S with copper(I) complexes supported by N-donor ligands: formation of stable adducts and S-transfer reactivity.  


In the exploration of sulfur-delivery reagents useful for synthesizing models of the tetracopper-sulfide cluster of nitrous oxide reductase, reactions of Ph(3)Sb?S with Cu(I) complexes of N,N,N',N'-tetramethyl-2R,3R-cyclohexanediamine (TMCHD) and 1,4,7-trialkyltriazacyclononanes (R(3)tacn; R = Me, Et, iPr) were studied. Treatment of [(R(3)tacn)Cu(NCCH(3))]SbF(6) (R = Me, Et, or iPr) with 1 equiv of S?SbPh(3) in CH(2)Cl(2) yielded adducts [(R(3)tacn)Cu(S?SbPh(3))]SbF(6) (1-3), which were fully characterized, including by X-ray crystallography. The adducts slowly decayed to [(R(3)tacn)(2)Cu(2)(?-?(2):?(2)-S(2))](2+) species (4-6) and SbPh(3), or more quickly in the presence of additional [(R(3)tacn)Cu(NCCH(3))]SbF(6) to 4-6 and [(R(3)tacn)Cu(SbPh(3))]SbF(6) (7-9). The results of mechanistic studies of the latter process were consistent with rapid intermolecular exchange of S?SbPh(3) between 1-3 and added [(R(3)tacn)Cu(NCCH(3))]SbF(6), followed by conversion to product via a dicopper intermediate formed in a rapid pre-equilibrium step. Key evidence supporting this step came from the observation of saturation behavior in a plot of the initial rate of loss of 1 versus the initial concentration of [(Me(3)tacn)Cu(NCCH(3))]SbF(6). Also, treatment of [(TMCHD)Cu(CH(3)CN)]PF(6) with S?SbPh(3) led to the known tricopper cluster [(TMCHD)(3)Cu(3)(?(3)-S)(2)](PF(6))(3) in good yield (79%), a synthetic procedure superior to that previously reported (Brown, E. C.; York, J. T.; Antholine, W. E.; Ruiz, E.; Alvarez, S.; Tolman, W. B. J. Am. Chem. Soc. 2005, 127, 13752-13753). PMID:21338053

Yang, Lei; Tehranchi, Jacqui; Tolman, William B



Reactions of Ph3Sb=S with Copper(I) Complexes Supported by N-Donor Ligands: Formation of Stable Adducts and S-Transfer Reactivity  

PubMed Central

In the exploration of sulfur-delivery reagents useful for synthesizing models of the tetracopper-sulfide cluster of nitrous oxide reductase, reactions of Ph3Sb=S with Cu(I) complexes of N,N,N’,N’-tetramethyl-2R,3R-cyclohexanediamine (TMCHD) and 1,4,7-trialkyltriazacyclononanes (R3tacn; R = Me, Et, iPr) were studied. Treatment of [(R3tacn)Cu(NCCH3)]SbF6 (R = Me, Et, or iPr) with one equivalent of S=SbPh3 in CH2Cl2 yielded adducts [(R3tacn)Cu(S=SbPh3)]SbF6 (1–3), which were fully characterized, including by X-ray crystallography. The adducts slowly decayed to [(R3tacn)2Cu2(µ-?2: ?2-S2)]2+ species (4–6) and SbPh3, or more quickly in the presence of additional [(R3tacn)Cu(NCCH3)]SbF6 to 4–6 and [(R3tacn)Cu(SbPh3)]SbF6 (7–9). The results of mechanistic studies of the latter process were consistent with rapid intermolecular exchange of S=SbPh3 between 1–3 and added [(R3tacn)Cu(NCCH3)]SbF6, followed by conversion to product via a dicopper intermediate formed in a rapid pre-equilibrium step. Key evidence supporting this step came from the observation of saturation behavior in a plot of the initial rate of loss of 1 versus the initial concentration of [(Me3tacn)Cu(NCCH3)]SbF6. Also, treatment of [(TMCHD)Cu(CH3CN)]PF6 with S=SbPh3 led to the known tricopper cluster [(TMCHD)3Cu3(µ3-S)2](PF6)3 in good yield (79%), a synthetic procedure superior to that previously reported (Brown, E. C.; York, J. T.; Antholine, W. E.; Ruiz, E.; Alvarez, S.; Tolman, W. B. J. Am. Chem. Soc. 2005, 127, 13752–13753). PMID:21338053

Yang, Lei; Tehranchi, Jacqui; Tolman, William B.



Reaction front formation in contaminant plumes  

NASA Astrophysics Data System (ADS)

The formation of successive fronts in contaminated groundwater plumes by subsoil bacterial action is a commonly accepted feature of their propagation, but it is not obviously clear from a mathematical standpoint quite how such fronts are formed or propagate. In this paper we show that these can be explained by combining classical reaction-diffusion theory involving just two reactants (oxidant and reductant), and a secondary reaction in which a reactant on one side of such a front is (re-)formed on the other side of the front via diffusion of its product across the front. We give approximate asymptotic solutions for the reactant profiles, and the propagation rate of the front.

Cribbin, Laura B.; Winstanley, Henry F.; Mitchell, Sarah L.; Fowler, Andrew C.; Sander, Graham C.



New Pathways for the Formation of Complex Organics and Prebiotic Synthesis in the Gas Phase  

NASA Astrophysics Data System (ADS)

We study the formation mechanisms of complex organics that are present in interstellar clouds. The reaction of acetylene ion with water produces vinyl alcohol while the reaction of benzene ion with acetylene produces naphthalene-type ion.

El-Shall, M. S.



Photosynthetic reaction center complexes from heliobacteria  

NASA Technical Reports Server (NTRS)

Photosynthetic reaction centers are pigment-protein complexes that are responsible for the transduction of light energy into chemical energy. Considerable evidence indicates that photosynthetic organisms were present very early in the evolution of life on Earth. The goal of this project is to understand the early evolutionary development of photosynthesis by examining the properties of reaction centers isolated from certain contemporary organisms that appear to contain the simplest photosynthetic reaction centers. The major focus is on the family of newly discovered strictly anaerobic photosynthetic organisms that are grouped with the gram-positive phylum of bacteria. The properties of these reactions centers suggest that they may be the descendants of an ancestor that also gave rise to Photosystem 1 found in oxygen-evolving photosynthetic organisms. Photoactive reaction center-core antenna complexes were isolated from the photosynthetic bacteria, Heliobacillus mobilis and Heliobacterium gestii, by extraction of membranes with Deriphat 160C followed by differential centrifugation and sucrose density gradient centrifugation. Other aspects of this investigation are briefly discussed.

Trost, J. T.; Vermaas, W. F. J.; Blankenship, R. E.



Formation of ammonia and hydrazine from the reactions of acids with bis(dinitrogen) complexes of molybdenum. Identification and isolation of intermediates. Possible analogy with the hydrazine-forming property of nitrogenase  

SciTech Connect

The reactions of anhydrous HBr and HCl with trans-(Mo(N/sub 2/)/sub 2/(triphos)(PR/sub 3/)), where triphos = PhP(CH/sub 2/CH/sub 2/PPh/sub 2/)/sub 2/(PR/sub 3/ = PPh/sub 3/(1), PMePh/sub 2/ (2)), in tetrahydrofuran (THF) solution to produce ammonia and in benzene solution to produce hydrazine and ammonia have been examined. Complex 1 reacted with HBr in THF to produce 1.5 mol of N/sub 2//mol of 1 and routinely ca. 0.72 mol of NH/sub 3//mol of 1, respectively, and MoBr/sub 3/(triphos) (greater than or equal to94% yield). No more than a trace of hydrazine was detected. Total nitrogen balance was increased to 100% when amounts of HBr were added periodically during the reaction. The reaction of 1 or 2 with HBr or HCl led to the rapid loss of 1 mol of N/sub 2/ and the formation of a pair of isomeric hydrazido(2-) complexes, (MoX(NNH/sub 2/)(triphos)(PR/sub 3/))X (PR/sub 3/ = PPh/sub 3/ for 1 A(X) and 1 B(X), PPh/sub 2/Me for 2A(X) and 2B(X); X = Br, Cl). The same mixtures were formed in the absence of solvent. The presence of two isomers was the result of the position of the phenyl group on the central phosphorus atom of the triphos ligand relative to the hydrazido(2-) ligand. 48 references, 3 figures, 3 tables.

Baumann, J.A.; Bossard, G.E.; George, T.A.; Howell, D.B.; Koczon, L.M.; Lester, R.K.; Noddings, C.M.



Unraveling reaction pathways and specifying reaction kinetics for complex systems.  


Many natural and industrial processes involve a complex set of competing reactions that include several different species. Detailed kinetic modeling of such systems can shed light on the important pathways involved in various transformations and therefore can be used to optimize the process conditions for the desired product composition and properties. This review focuses on elucidating the various components involved in modeling the kinetics of pyrolysis and oxidation of polymers. The elementary free radical steps that constitute the chain reaction mechanism of gas-phase/nonpolar liquid-phase processes are outlined. Specification of the rate coefficients of the various reaction families, which is central to the theme of kinetics, is described. Construction of the reaction network on the basis of the types of end groups and reactive moieties in a polymer chain is discussed. Modeling frameworks based on the method of moments and kinetic Monte Carlo are evaluated using illustrations. Finally, the prospects and challenges in modeling biomass conversion are addressed. PMID:22468596

Vinu, R; Broadbelt, Linda J



Kinetic analysis of complex reactions using FEMLAB  

SciTech Connect

A finite element method software FEMALB has been implemented to the kinetic analysis of complex reaction systems. The established protocol provides fast solutions to the coupled differential-algebraic equations. It shows significant advantages over the conventional coding process with the standard implicit Runge-Kutta (IRK) method. The accuracy and high efficiency have been demonstrated in the simulation of the reaction processes such as glucose/fructose hydrogenation and catalytic cracking of gasoil. As model validation, the numerical results showed satisfactory agreement with the exact solutions. With the powerful capability of solving large matrixes of differential equations (both ODE and PDE) with nonlinear algebraic constrains, such an algorithm has greatly reduced the coding labor in reaction mechanistic studies and provided a unique tool in reactor design and optimization.

Cao, Chunshe; Wang, Yong



Reaction-diffusion controlled growth of complex structures  

NASA Astrophysics Data System (ADS)

Understanding how the emergence of complex forms and shapes in biominerals came about is both of fundamental and practical interest. Although biomineralization processes and organization strategies to give higher order architectures have been studied extensively, synthetic approaches to mimic these self-assembled structures are highly complex and have been difficult to emulate, let alone replicate. The emergence of solution patterns has been found in reaction-diffusion systems such as Turing patterns and the BZ reaction. Intrigued by this spontaneous formation of complexity we explored if similar processes can lead to patterns in the solid state. We here identify a reaction-diffusion system in which the shape of the solidified products is a direct readout of the environmental conditions. Based on insights in the underlying mechanism, we developed a toolbox of engineering strategies to deterministically sculpt patterns and shapes, and combine different morphologies to create a landscape of hierarchical multi scale-complex tectonic architectures with unprecedented levels of complexity. These findings may hold profound implications for understanding, mimicking and ultimately expanding upon nature's morphogenesis strategies, allowing the synthesis of advanced highly complex microscale materials and devices.

Noorduin, Willem; Mahadevan, L.; Aizenberg, Joanna



Modelling the formation of maillard reaction intermediates for the generation of flavour  

Microsoft Academic Search

The Maillard reaction comprises a very complex, thermally-driven, set of reactions that leads to the formation of colour and flavour. In producing flavours, it is important to be able to quantitatively follow the course of this reaction system and thence control it by manipulating key input parameters, such as temperature, pH, type and concentration of the sugar and amino acid.

Guillaume Desclaux; Tahir I. Malik; Chris Winkel; D. Leo Pyle; Donald S. Mottram



Alternative reaction pathways in domino reactions of hydrazinediidozirconium complexes with alkynes.  


Reaction of [Zr{(NAr)(2)N(py)}(NMe(2))(2)] (Ar=3,5-xylyl: 2?a, mesityl: 2?b) with one or two molar equivalents of 1,1-diphenylhydrazine gave the mixed amido/hydrazido(1-) complex [Zr{(NMes)(2)N(py)}(HNNPh(2))(NMe(2))] (3), the bis-hydrazido complex [Zr{(NMes)(2)N(py)}(HNNPh(2))(2)] (4), and, in the presence of excess 4-dimethylaminopyridine (DMAP), hexacoordinate hydrazinediidozirconium complexes [Zr{(NXyl)(2)N(py)}(=NN(Me)Ph)(dmap)(2)] (5) and [Zr{(NXyl)(2)N(py)}(=NNPh(2))(dmap)(2)] (6). The reaction of one equivalent of the zirconium-hydrazinediide [Zr{(NTBS)(2)N(py)}(NNPh(2))(py)] (1) with disubstituted alkynes at RT for 16?h led to the formation of seven-membered diazazirconacycles 7?a-7?e in high yields. Similar reactivity was observed by reacting bis-amido complex 2?b with one molar equivalent of the corresponding alkyne and diphenylhydrazine. The formation of the seven-membered zirconacycles implied a key coupling step that involved the alkyne and one of the aryl rings of the diphenylhydrazinediido ligand. In some cases, such as the reaction with 2-butyne, the corresponding metallacycle was only obtained in modest yields (45?% for the reaction with 2-butyne) and a second major product, vinylimido complex 9, was formed in almost equal amounts (42?%) by 1,2-amination (formal insertion of the alkyne). The formation of compounds 7?a and 9 followed in part the same sequence of reaction steps and a key intermediate, an azirinido complex, represented a "bifurcation point" in the reaction network. Reaction of 1.2?equivalents of several diarylhydrazines and various substituted alkynes (1?equiv) at ambient temperature (or at 80?°C) in the presence of 10?mol?% [Zr{(NXyl)(2)N(py)}(NMe(2))(2)] (2?a) gave the corresponding indole derivatives. On the other hand, the replacement of 1,1-diarylhydrazines by 1-methyl-1-phenyl hydrazine led to head-to-head cis-1,3-enynes in good yields. PMID:22345083

Gehrmann, Thorsten; Scholl, Solveig A; Fillol, Julio Lloret; Wadepohl, Hubert; Gade, Lutz H



Complex-anisotropy-induced pattern formation in bistable media.  


A construct of anisotropy in bistable media is adopted to characterize the effects of anisotropy on pattern formation by means of anisotropic line tension. A velocity curvature relation is further derived to account for the anisotropic wave propagations. Stability analysis of transverse perturbations indicates that a sufficiently strong complex anisotropy can induce dynamical instabilities and even lead to a breakup of the wave patterns. Numerical simulations show that complex anisotropy can induce rich spatiotemporal behaviors in bistable media. The results of analysis and simulations demonstrate that this method successfully incorporates complex anisotropy into the reaction diffusion model and has general significance. PMID:19391804

He, Zhi Zhu; Liu, Jing



Quantum-chemical approach to serine formation in the interstellar medium: A possible reaction pathway  

NASA Astrophysics Data System (ADS)

Radical-radical and radical-neutral interaction schemes are very important for the formation of comparatively complex molecules in low-temperature chemistry. The formation of amino acids, such as serine, in the interstellar medium is quite difficult. We explored the possibility of serine formation in the interstellar medium through detected interstellar molecules such as CH, CO, and OH by radical-radical and radical-neutral interactions in the gaseous phase using rigorous quantum-chemical calculations. The reaction energies, the low potential barrier and the structures of all the geometries involved in the reaction path show that serine formation is possible in interstellar space via the reaction paths.

Shivani; Singh, Amresh; Gupta, Vineet; Misra, Alka; Tandon, Poonam



Formate ester synthesis via reaction of 2-bromoethylamines with dimethylformamide  

Microsoft Academic Search

2-Bromoethylamines are converted to the corresponding formate esters in the presence of DMF. Both primary and secondary bromides are smoothly transformed to the esters in satisfactory yields. The reaction mechanism involves the formation of an aziridinium ion, which upon reaction with DMF forms a Vilsmeier-type intermediate that is further hydrolyzed to the corresponding formates. Participation of the ?-amino group appears

Marianna Dakanali; George K. Tsikalas; Harald Krautscheid; Haralambos E. Katerinopoulos



Reaction Dynamics of the Bromine-Bromoform Complex in Solution  

NASA Astrophysics Data System (ADS)

We have followed the evolution of the bromine species that arise from the photolysis of bromoform in the condensed phase. Solvent caging promotes the formation of iso-bromoform (CHBr_2-Br), which can then release a Br atom by breaking the newly formed Br-Br bond. This ejected Br can form a van der Waals complex (Br-CHBr_3) with a nearby un-photolyzed bromoform molecule, which is stable during our 1 ns time-window. Using the van der Waals complex as a reservoir for Br atoms, we now proceed to drive hydrogen abstraction from CHBr_3 by Br. Estimates indicate that the barrier to this reaction is a few thousand wavenumbers. Our goal is to introduce excitation into the C-H stretching motion of a nearby solvent CHBr_3 to access the activated complex region of the bimolecular potential energy surface.

Preston, Thomas J.; Dutta, Maitreya; Crim, F. Fleming



Turbulent edge structure formation in complex configurations  

Microsoft Academic Search

Formation of nonlinear structures in drift-Alfvén turbulence is investigated in the often complex edge geometries of stellarator and tokamak configurations, by analysis of drift wave turbulence simulations using a model in which three-dimensional magnetic geometries are approximated. The structures of parallel mode extension, radially sheared zonal flows and perpendicular mode spectra are highlighted in particular for three-dimensional stellarator magnetic fields

A. Kendl; B. D. Scott; R. Ball; R. L. Dewar



Nitrene transfer reactions by late transition metal complexes  

E-print Network

This thesis presents nitrene transfer reactions that are catalyzed or mediated by late transition metal complexes. Sterically large, fluorinated supporting ligands are used to minimize potential side reactions. A new ...

Hamilton, Charles W., Ph. D. Massachusetts Institute of Technology



Reactions of pd and pt complexes with molecular oxygen.  


Knowledge of exactly how metal complexes react with molecular oxygen is still limited and this has hampered efforts to develop catalysts for oxidation reactions using O2 as the oxidant and/or oxygen-atom source. A better understanding of the reactions of different types of metal complexes with O2 will be of great utility in rational catalyst development. Reactions between molecular oxygen and Pd(0-II) and Pt(0-IV) complexes are reviewed here. PMID:25303084

Scheuermann, Margaret L; Goldberg, Karen I



Formation of ultracold molecules in chemical reactions  

Microsoft Academic Search

We demonstrate that chemical reactions in collisions of high-energy molecular beams can generally produce molecules with zero velocity in the laboratory-fixed frame. Our analysis shows that collisions of beams may simultaneously yield slow reactant molecules and slow products. The reaction products are formed in selected ro-vibrational states and scattered in a specific direction, which can be controlled by tuning the

Timur Tscherbul; Girts Barinovs; Jacek Klos; Roman Krems



Photochemical reaction dynamics in SO2-acetylene complexes  

NASA Astrophysics Data System (ADS)

The dynamics of photoinduced reactions between electronically excited SO2 molecule (A~ 1A2<--X~ 1A1) and acetylene molecule (X~ 1?g+) in the SO2-acetylene van der Waals (vdW) complexes (clusters) was studied. The SO2 molecule was excited by frequency-doubled radiation of a tunable dye laser, and resonance enhancement multiphoton photoionization of the produced photofragments was induced by ArF (193 nm) laser radiation or by frequency-doubled radiation of a second tunable dye laser to observe the C2H radical. The HOSO radical was detected by its IR emission. We found that the main photodecomposition channel of the vdW complexes (clusters) involves the SO2*+C2H2-->HOSO+C2H reaction. Indeed, the analysis of the action spectra of the excitation laser radiation showed that the photofragments emerging in our experimental conditions (SO2, 5% C2H2, 5% and Xe; P0=2 atm) originate from the SO2...C2H2 vdW complex (cluster). We analyzed the structure of this vdW complex theoretically, obtaining Cs symmetry, with the acetylene molecule located above the OSO plane. The resonance-enhanced multiphoton photoionization action spectra of the C2H (A~<--X~) photofragmentation and the IR emission spectra of the HOSO radical allowed the authors to probe the energy distribution between the photofragments formed. The reaction that involves transition of the acetylene H atom to the SO2 oxygen should be the primary step of the process considered, followed by nonstatistic dissociation of the vdW complex (cluster), with the C2H radical formed in its vibrationless state and excited both rotationally and translationally, and the HOSO radical excited vibrationally, rotationally and translationally. The proposed reaction mechanism was discussed, employing transition-state and Rice-Ramsperger-Kassel-Marcus (RRKM) approaches. The kinetics of photofragment formation was investigated, yielding characteristic radical build-up time of 0.64 ?s.

Makarov, Vladimir I.; Kochubei, Sergei A.; Khmelinskii, Igor



Linear metal-metal-bonded tetranuclear M-Mo-Mo-M complexes (M = Ir and Rh): oxidative metal-metal bond formation in a tetrametallic system and 1,4-addition reaction of alkyl halides.  


Reaction of Mo2(pyphos)4 (1) with [MCl(CO)2]2 (M = Ir and Rh) afforded linear tetranuclear complexes of a formula Mo2M2(CO)2(Cl)2(pyphos)4 (2, M = Ir; 3, M = Rh). X-ray diffraction studies confirmed that two "MCl(CO)" fragments are introduced into both axial sites of the Mo2 core in 1 and coordinated by two PPh2 groups in a trans fashion, thereby forming a square-planar geometry around each M(I) metal. Treatment of 2 and 3 with an excess amount of tBuNC and XylNC induced dissociation of the carbonyl and chloride ligands to yield the corresponding dicationic complexes [Mo2M2(pyphos)4(tBuNC)4](Cl)2 (5a, M = Ir; 6a, M = Rh) and [Mo2M2(pyphos)4(XylNC)4](Cl)2 (7, M = Ir; 8, M = Rh). Their molecular structures were characterized by spectroscopic data as well as X-ray diffraction studies of BPh4 derivatives [Mo2M2(pyphos)4(tBuNC)4](BPh4)2 (5b, M = Ir; 6c, M = Rh), which confirmed that there is no direct sigma-bonding interaction between the M(I) atom and the Mo2 core. The M(I) atom in 5 and 6 can be oxidized by either 2 equiv of [Cp2Fe][PF6] or an equimolar amount of I2 to afford Mo(II)2M(II)2 complexes, [Mo2M2(X)2(tBuNC)4(pyphos)4]2+ in which two Mo-M(II) single bonds are formed and the bond order of the Mo-Mo moiety has been decreased to three. The Ir(I) complex 5a reacted not only with methyl iodide but also with dichloromethane to afford the 1,4-oxidative addition products [Mo2Ir2(CH3)(I)(tBuNC)4(pyphos)4](Cl)2 (13) and [Mo2Ir2(CH2Cl)(Cl)(tBuNC)4(pyphos)4](Cl)2 (15), respectively, although the corresponding reactions using the Rh(I) analogue 6 did not proceed. Kinetic analysis of the reaction with CH3I suggested that the 1,4-oxidative addition to the Ir(I) complex occurs in an SN2 reaction mechanism. PMID:17608413

Ohashi, Masato; Shima, Asuka; Rüffer, Tobias; Mizomoto, Hitoshi; Kaneda, Yutaka; Mashima, Kazushi



Steric Aspects of the Formation of Metal Chelate Complexes  

Microsoft Academic Search

The geometrical and thermodynamic aspects of the formation of complexes between metal cations and organic ligands are examined theoretically from the standpoint of conformational analysis. Particular attention has been devoted to the problem of the selectivity of the complex formation, which is of practical importance. It is shown that the selectivity of complex formation is largely determined by the steric

V G Dashevskii; A P Baranov; Martin I Kabachnik



Polychronous formation of mantle complexes in ophiolites  

NASA Astrophysics Data System (ADS)

The paper presents new determinations of the U-Pb zircon age of high-Al chromitite from dunite of the mantle section of the Voikar-Synya massif at the Kershor site in the boundary zone with rocks of the dunite-wehrlite-clinopyroxenite complex. The high-Cr chromitite from dunite in the central part of the same massif contains zircon dated at ca. 0.6 Ga [10]. It is suggested that Paleoproterozoic (2.0-1.9 Ga) zircons from chromitites of the mantle section near the petrological Moho boundary were formed in the course of partial melting of peridotites and/or their interaction with migrating MORB-type melts. The occurrence of Vendian and Paleoproterozoic zircons in chromitites from different parts of the mantle section, as well as previously published petrological, geochemical, and geological data [2, 11, 22] allow us to suggest a complex multistage evolution of the mantle section in ophiolites. The arguments stated below show that chromitites and host dunites could have been formed at different times and were probably related to different processes. Thus, not only various complexes of the pre-Paleozoic oceanic crust reworked in the suprasubduction setting differ in age, but also the mantle rock of similar petrography, vary in the time of their formation.

Savelieva, G. N.; Batanova, V. G.; Berezhnaya, N. A.; Presnyakov, S. L.; Sobolev, A. V.; Skublov, S. G.; Belousov, I. A.



Vortex formation in a complex plasma  

NASA Astrophysics Data System (ADS)

Complex plasma experiments in ground-based laboratories as well as in microgravity conditions have shown the formation of vortex structures in various conditions (e.g., 1,2,3,4). The vortex structures formed in a complex plasma are visible by naked eyes with the help of irradiating laser and the individual dust particles in the structure give us the opportunity to study detailed physics of the commonly observed natural phenomena known such as tornadoes, typhoons, hurricanes and dust devils. Based on the Navier-Stokes equation with proper complex plasma conditions we analyze as much as possible in a universal way the vortex structure and clarifies the role of the controlling parameters like flow velocity and external magnetic field. 1. G. E. Morfill,H. M. Thomas, U. Konopka,H. Rothermel, M. Zuzic, A. Ivlev, and J. Goree, Phys,. Rev. Lett. 83, 1598 (1999). 2. E. Nebbat and R. Annou, Phys. Plasmas 17, 093702 (2010). 3. Y. Saitou and O. Ishihara, Phys. Rev. Lett. 111, 185003 (2013). 4. V. N. Tsytovich and N. G. Gusein-zade, Plasma Phys. Rep. 39, 515 (2013).

Ishihara, Osamu


Holographic Grating Formation in Cationic Photopolymers with Dark Reaction  

Microsoft Academic Search

We propose a new formula to describe the dynamics of holographic grating formation under low intensity pulse exposures in cationic photopolymers, in which the dark reaction contributes dominantly to the grating strength. The formula is based on the living polymerization mechanism and the diffusion-free approximation. The analytical solution indicates that the grating formation time depends on the termination rate constant,

Hao-Yun Wei; Liang-Cai Cao; Claire Gu; Zhen-Feng Xu; Ming-Zhao He; Qing-Sheng He; Shu-Rong He; Guo-Fan Jin



Formation of superheavy nuclei in cold fusion reactions  

Microsoft Academic Search

Within the concept of the dinuclear system (DNS), a dynamical model is proposed for describing the formation of superheavy nuclei in complete fusion reactions by incorporating the coupling of the relative motion to the nucleon transfer process. The capture of two heavy colliding nuclei, the formation of the compound nucleus, and the de-excitation process are calculated by using an empirical

Zhao-Qing Feng; Gen-Ming Jin; Jun-Qing Li; Werner Scheid



Complex formation processes in 3d metal hexacyanoferrate(II) gelatin-immobilised matrices  

NASA Astrophysics Data System (ADS)

Data on nontraditional complex formation reactions in iron(II, III), cobalt(II), cobalt(III), nickel(II), and copper(II) hexacyanoferrate(II) gelatin-immobilised matrixes with fixation of the immobilised substances by intermolecular forces are surveyed and described systematically. Such reactions proceed when the matrices come into contact with aqueous solutions of nitrogen-, oxygen-, and sulfur-containing polydentate ligands. The practical possibilities for complex formation reactions in metal hexacyanoferrate(II) gelatin-immobilised matrixes are demonstrated. The bibliography includes 147 references.

Mikhailov, Oleg V.



A simplified reaction mechanism for soot formation in nonpremixed flames  

SciTech Connect

The present article outlines a simplified reaction mechanism for the formation, growth, and combustion of soot particles in laminar nonpremixed flames. The model can be combined with detailed chemistry descriptions for the gas phase, as in the present case, or with reduced chemical reaction mechanisms. The reaction mechanism involves nucleation, surface growth, particle coagulation, and combustion steps. The model outlined has been created with the intention of being applicable to the prediction of turbulent flames via different approaches. The soot nucleation and surface growth reactions are linked to the gas phase by presuming that pyrolysis products, in the present case acetylene, and not the fuel itself, are of primary importance in the soot formation process. The deduced reaction mechanism is applied to counterflow ethylene and propane flames burning with a range of oxygen-enriched and depleted air streams. The results obtained show excellent qualitative and quantitative agreement with measured data for soot volume fraction, particle growth, and number density.

Leung, K.M.; Lindstedt, R.P. (Fluids Section, Dept. of Mechanical Engineering, Imperial College, London SW7 2BX (GB)); Jones, W.P. (Dept. of Chemical Engineering and Chemical Technology, Imperial College, London SW7 2BY (GB))



Complex formation between benzene carboxylic acids and ?-cyclodextrin  

NASA Astrophysics Data System (ADS)

Complex formation between benzene carboxylic acids and ?-cyclodextrin in aqueous solutions at 290 300 K was studied using UV spectroscopy. The formation of 1:1 supramolecular inclusion compounds ?-cyclodextrin-benzene and ?-cyclodextrin-salicylic acid was found. Stability constants (Ks) of the complexes and thermodynamic parameters for formation of the inclusion compounds (?G, ?H, and ?S) were calculated.

Belyakova, L. A.; Lyashenko, D. Yu.



Understanding bistability in complex enzyme-driven reaction networks  

E-print Network

to variations in enzyme transcription activity (or even to enzyme malformation) when, in fact, those changesUnderstanding bistability in complex enzyme-driven reaction networks Gheorghe Craciun* , Yangzhong for enzyme catalysis of a single overall reaction. We present a theorem that distinguishes between those mass

Craciun, Gheorghe


f 1 (1285) formation in photon-photon fusion reactions  

NASA Astrophysics Data System (ADS)

We have observed formation of the f 1 (1285) in the reaction e +e -?e +e -?+?-?( ?? ??). Its ?? ? width is determined in several Q2 bins. The ?? coupling parameter for the f 1 (1285) is found to be 2.4±0.5±0.5 keV. This value is compared to that for the X (1420), another J=1 state formed in ?? fusion reactions, which may belong to the same meson nonet.

Aihara, H.; Alston-Garnjost, M.; Avery, R. E.; Barbaro-Galtieri, A.; Barker, A. R.; Barnett, B. A.; Bauer, D. A.; Bay, A.; Bengtsson, H.-U.; Bobbink, G. J.; Buchanan, C. D.; Buijs, A.; Caldwell, D. O.; Chao, H.-Y.; Chun, S.-B.; Clark, A. R.; Cowan, G. D.; Crane, D. A.; Dahl, O. I.; Daoudi, M.; Derby, K. A.; Eastman, J. J.; Eberhard, P. H.; Edberg, T. K.; Eisner, A. M.; Enomoto, R.; Erné, F. C.; Fairfield, K. H.; Hauptman, J. M.; Hofmann, W.; Hylen, J.; Kamae, T.; Kaye, H. S.; Kenney, R. W.; Khacheryan, S.; Kofler, R. R.; Langeveld, W. G. J.; Layter, J. G.; Lin, W. T.; Linde, F. L.; Loken, S. C.; Lu, A.; Lynch, G. R.; Madaras, R. J.; Magnuson, B. D.; Masek, G. E.; Mathis, L. G.; Matthews, J. A. J.; Maxfield, S. J.; Miller, E. S.; Moses, W.; Nygren, D. R.; Oddone, P. J.; Paar, H. P.; Park, S. K.; Pellett, D. E.; Pripstein, M.; Ronan, M. T.; Ross, R. R.; Rouse, F. R.; Schwitkis, K. A.; Sens, J. C.; Shapiro, G.; Shen, B. C.; Slater, W. E.; Smith, J. R.; Steinman, J. S.; Stephens, R. W.; Stevenson, M. L.; Stork, D. H.; Strauss, M. G.; Sullivan, M. K.; Takahashi, T.; Toutounchi, S.; Van Tyen, R.; Van Dalen, G. J.; Vernon, W.; Wagner, W.; Wang, E. M.; Wang, Y.-X.; Wenzel, W. A.; Wolf, Z. R.; Yamamoto, H.; Yellin, S. J.; Zeitlin, C.; TPC/Two-Gamma Collaboration



Formation of superheavy elements in cold fusion reactions  

Microsoft Academic Search

The process of the synthesis of superheavy elements (SHEs) is not yet understood completely. In the presented work we make an attempt to describe the cold fusion reactions of the type X+(Pb,Bi)-->SHE+1n at subbarrier energies. The process of the formation of SHEs is subdivided into three steps. (1) The capture of two spherical nuclei and the formation of a common

V. Yu. Denisov; S. Hofmann



A complex reaction time study (Sternberg) in space flight  

NASA Technical Reports Server (NTRS)

Simple and complex (Sternberg) reaction time studies were flown on three and seven day Shuttle flights in 1985. Three subjects did selftesting with an onboard handheld calculator without difficulty. There was little change in simple reaction time. One subject demonstrated a decrease in the processing rate during space motion sickness while a second exhibited an increase in complex reaction time without a change in processing rate during a period of high work load. The population was too small to demonstrate significant changes. This study demonstrates the ease and practicality of such measurements and indicates the potential value of such studies in space.

Thornton, W.; Uri, John; Moore, Tom



A physical organic mechanistic approach to understanding the complex reaction  

E-print Network

Review A physical organic mechanistic approach to understanding the complex reaction network the mechanistic approach of physical organic chemistry can be used to elucidate the mechanisms behind complex individual electrons and atomic nuclei. Physical organic chemists have developed a useful set of tools

Ismagilov, Rustem F.


Formation of superheavy nuclei in cold fusion reactions  

E-print Network

Within the concept of the dinuclear system (DNS), a dynamical model is proposed for describing the formation of superheavy nuclei in complete fusion reactions by incorporating the coupling of the relative motion to the nucleon transfer process. The capture of two heavy colliding nuclei, the formation of the compound nucleus and the de-excitation process are calculated by using an empirical coupled channel model, solving a master equation numerically and applying statistical theory, respectively. Evaporation residue excitation functions in cold fusion reactions are investigated systematically and compared with available experimental data. Maximal production cross sections of superheavy nuclei in cold fusion reactions with stable neutron-rich projectiles are obtained. Isotopic trends in the production of the superheavy elements Z=110, 112, 114, 116, 118 and 120 are analyzed systematically. Optimal combinations and the corresponding excitation energies are proposed.

Feng, Zhao-Qing; Li, Jun-Qing; Scheid, Werner



Reaction of an iron(IV) nitrido complex with cyclohexadienes: cycloaddition and hydrogen-atom abstraction.  


The iron(IV) nitrido complex PhB(MesIm)3Fe?N reacts with 1,3-cyclohexadiene to yield the iron(II) pyrrolide complex PhB(MesIm)3Fe(?(5)-C4H4N) in high yield. The mechanism of product formation is proposed to involve sequential [4 + 1] cycloaddition and retro Diels-Alder reactions. Surprisingly, reaction with 1,4-cyclohexadiene yields the same iron-containing product, albeit in substantially lower yield. The proposed reaction mechanism, supported by electronic structure calculations, involves hydrogen-atom abstraction from 1,4-cyclohexadiene to provide the cyclohexadienyl radical. This radical is an intermediate in substrate isomerization to 1,3-cyclohexadiene, leading to formation of the pyrrolide product. PMID:25068927

Lee, Wei-Tsung; Juarez, Ruth A; Scepaniak, Jeremiah J; Muñoz, Salvador B; Dickie, Diane A; Wang, Haobin; Smith, Jeremy M



Thermodynamics for complex formation between palladium(ii) and oxalate.  


Complex formation between [Pd(H2O)4](2+) and oxalate (ox = C2O4(2-)) has been studied spectrophoto-metrically in aqueous solution at variable temperature, ionic strength and pH. Thermodynamic parameters at 298.2 K and 1.00 mol dm(-3) HClO4 ionic medium for the complex formation [Pd(H2O)4](2+) + H2ox ? [Pd(H2O)2(ox)] + 2H3O(+) with equilibrium constant K1,H (in mol dm(-3)) are log10K1,H = 3.38 ± 0.08, ?H = -33 ± 3 kJ mol(-1), and ?S = -48 ± 11 J K(-1) mol(-1), as determined from spectrophotometric equilibrium titrations at 15.0, 20.0, 25.0 and 31.0 °C. Thermodynamic overall stability constants ? (in (mol dm(-3))(-n), n = 1,2) for [Pd(H2O)2(ox)] and [Pd(ox)2](2-) at zero ionic strength and 298.2 K, defined as the equilibrium constants for the reaction Pd(2+) + nox(2-) ? [Pd(ox)n](2-2n) (water molecules omitted) are log10? = 9.04 ± 0.06 and log10? = 13.1 ± 0.3, respectively, calculated by use of Specific Ion Interaction Theory from spectrophotometric titrations with initial hydrogen ion concentrations of 1.00, 0.100 and 0.0100 mol dm(-3) and ionic strengths of 1.00, 2.00 or 3.00 mol dm(-3). The values derived together with literature data give estimated overall stability constants for Pd(ii) compounds such as [Pd(en)(ox)] and cis-[Pd(NH3)2Cl2], some of them analogs to Pt(ii) complexes used in cancer treatment. The palladium oxalato complexes are significantly more stable than palladium(ii) complexes with monodentate O-bonding ligands. A comparison between several different palladium complexes shows that different parameters contribute to the stability variations observed. These are discussed together with the so-called chelate effect. PMID:24912768

Pilný, Radomír; Lubal, P?emysl; Elding, Lars I



Light induced electron transfer reactions of metal complexes  

SciTech Connect

Properties of the excited states of tris(2,2'-bipyridine) and tris(1,10-phenanthroline) complexes of chromium(III), iron(II), ruthenium(II), osmium(II), rhodium(III), and iridium(III) are described. The electron transfer reactions of the ground and excited states are discussed and interpreted in terms of the driving force for the reaction and the distortions of the excited states relative to the corresponding ground states. General considerations relevant to the conversion of light into chemical energy are presented and progress in the use of polypyridine complexes to effect the light decomposition of water into hydrogen and oxygen is reviewed.

Sutin, N.; Creutz, C.



Enumeration of flux routes through complex biochemical reactions  

SciTech Connect

In the present work, a general algorithm for enumeration of the flux routes via which a chemical species {open_quotes}flows{close_quotes} through a complex biochemical reaction is outlined and presented by way of a biological example, a kinetic model for potassium ion permeation through a voltage-gated ion channel. The algorithm is readily amenable to computer based implementation and when used in conjunction with an existing algorithm provides a convenient means for simulation of the equilibrium and steady-state isotope exchange kinetics of complex biochemical reactions. 9 refs., 3 figs.

Wagg, J.; Sellers, P. [Rockefeller Univ., NY (United States)



Microkinetics of oxygenate formation in the Fischer-Tropsch reaction.  


Microkinetics simulations are presented on the intrinsic activity and selectivity of the Fischer-Tropsch reaction with respect to the formation of long chain oxygenated hydrocarbons. Two different chain growth mechanisms are compared: the carbide chain growth mechanism and the CO insertion chain growth mechanism. The microkinetics simulations are based on quantum-chemical data on reaction rate parameters of the elementary reaction steps of the Fischer-Tropsch reaction available in the literature. Because the overall rate constant of chain growth remains too low the CO insertion chain growth mechanism is not found to produce higher hydrocarbons, except for ethylene and acetaldehyde or the corresponding hydrogenated products. According to the carbide mechanism available quantum-chemical data are consistent with high selectivity to long chain oxygenated hydrocarbon production at low temperature. The anomalous initial increase with temperature of the chain growth parameter observed under such conditions is reproduced. It arises from the competition between the apparent rate of C-O bond activation to produce "CHx" monomers to be inserted into the growing hydrocarbon chain and the rate of chain growth termination. The microkinetics simulations data enable analysis of selectivity changes as a function of critical elementary reaction rates such as the rate of activation of the C-O bond of CO, the insertion rate of CO into the growing hydrocarbon chain or the rate constant of methane formation. Simulations show that changes in catalyst site reactivity affect elementary reaction steps differently. This has opposing consequences for oxygenate production selectivity, so an optimizing compromise has to be found. The simulation results are found to be consistent with most experimental data available today. It is concluded that Fischer-Tropsch type catalysis has limited scope to produce long chain oxygenates with high yield, but there is an opportunity to improve the yield of C2 oxygenates. PMID:24509610

van Santen, Rutger A; Ghouri, Minhaj; Hensen, Emiel M J



Pathway of Actin Filament Branch Formation by Arp2/3 Complex*S  

E-print Network

Pathway of Actin Filament Branch Formation by Arp2/3 Complex*S Received for publication,July 18/3 complex revealed that the complex binds to and disso- ciates from actin filaments extremely slowly and actin monomers with high affinity. These two ligands have only modest impacts on the interaction


Solvent influence in the formation of normal and abnormal carbene complexes in reactions of imidazolium salts with [Ir(H)2(PPh3)2(OCMe2)2]BF4  

E-print Network

: Abnormal Normal Carbene Iridium compounds Tetrahydrofuran Dichloromethane a b s t r a c t Abnormal)2(OCMe2)2]BF4 at room temperature in tetrahydrofuran (THF) or dichloromethane (CH2Cl2). Reactions in THF

Baltisberger, Jay H.


DNA Branch Migration Reactions Through Photocontrollable Toehold Formation  

PubMed Central

Strand displacement cascades are commonly used to make dynamically assembled structures. Particularly, the concept of “toehold-mediated DNA branch migration reactions” has attracted considerable attention in relation to dynamic DNA nanostructures. However, it is a challenge to obtain and control the formation of pure 1:1 ratio DNA duplexes with toehold structures. Here, for the first time, we report a photocontrolled toehold formation method, which is based on the photocleavage of 2-nitrobenzyl linker-embedded DNA hairpin precursor structures. UV light irradiation (??365 nm) of solutions containing these DNA hairpin structures causes the complete cleavage of the nitrobenzyl linker, and pure 1:1 DNA duplexes with toehold structures are easily formed. Our experimental results indicate that the amount of toehold can be controlled by simply changing the dose of UV irradiation and that the resulting toehold structures can be used for subsequent toehold-mediated DNA branch migration reactions, e.g., DNA hybridization chain reactions. This newly established method will find broad application in the construction of light-powered, controllable and dynamic DNA nanostructures or large-scale DNA circuits. PMID:23642046

Huang, Fujian; You, Mingxu; Han, Da; Xiong, Xiangling



Kinetics of enol formation from reaction of OH with propene.  


Kinetics of enol generation from propene has been predicted in an effort to understand the presence of enols in flames. A potential energy surface for reaction of OH with propene was computed by CCSD(T)/cc-pVDZ//B3LYP/cc-pVTZ calculations. Rate constants of different product channels and branching ratios were then calculated using the Master Equation formulation (J. Phys. Chem. A 2006, 110, 10528). Of the two enol products, ethenol is dominant over propenol, and its pathway is also the dominant pathway for the OH + propene addition reactions to form bimolecular products. In the temperature range considered, hydrogen abstraction dominated propene + OH consumption by a branching ratio of more than 90%. Calculated rate constants of enol formation were included in the Utah Surrogate Mechanism to model the enol profile in a cyclohexane premixed flame. The extended model shows consistency with experimental data and gives 5% contribution of ethenol formation from OH + propene reaction, the rest coming from ethene + OH. PMID:19271758

Huynh, Lam K; Zhang, Hongzhi R; Zhang, Shaowen; Eddings, Eric; Sarofim, Adel; Law, Matthew E; Westmoreland, Phillip R; Truong, Thanh N



Information-Theoretical Complexity Analysis of Selected Elementary Chemical Reactions  

NASA Astrophysics Data System (ADS)

We investigate the complexity of selected elementary chemical reactions (namely, the hydrogenic-abstraction reaction and the identity SN2 exchange reaction) by means of the following single and composite information-theoretic measures: disequilibrium (D), exponential entropy(L), Fisher information (I), power entropy (J), I-D, D-L and I-J planes and Fisher-Shannon (FS) and Lopez-Mancini-Calbet (LMC) shape complexities. These quantities, which are functionals of the one-particle density, are computed in both position (r) and momentum (p) spaces. The analysis revealed that the chemically significant regions of these reactions can be identified through most of the single information-theoretic measures and the two-component planes, not only the ones which are commonly revealed by the energy, such as the reactant/product (R/P) and the transition state (TS), but also those that are not present in the energy profile such as the bond cleavage energy region (BCER), the bond breaking/forming regions (B-B/F) and the charge transfer process (CT). The analysis of the complexities shows that the energy profile of the abstraction reaction bears the same information-theoretical features of the LMC and FS measures, however for the identity SN2 exchange reaction does not hold a simple behavior with respect to the LMC and FS measures. Most of the chemical features of interest (BCER, B-B/F and CT) are only revealed when particular information-theoretic aspects of localizability (L or J), uniformity (D) and disorder (I) are considered.

Molina-Espíritu, M.; Esquivel, R. O.; Dehesa, J. S.


Lead(II) Complex Formation with Glutathione  

PubMed Central

A structural investigation of complexes formed between the Pb2+ ion and glutathione (GSH, denoted AH3 in its triprotonated form) the most abundant non2protein thiol in biological systems, was carried out for a series of aqueous solutions at pH 8.5 and CPb2+ = 10 mM, and in the solid state. The Pb LIII-edge EXAFS oscillation for a solid compound with the empirical formula [Pb(AH2)]ClO4 was modeled with one Pb-S and two short Pb-O bond distances at 2.64 ± 0.04 Å and 2.28 ± 0.04 Å, respectively. In addition Pb···Pb interactions at 4.15 ± 0.05 Å indicate dimeric species in a network where the thiolate group forms an asymmetrical bridge between two Pb2+ ions. In aqueous solution at the mole ratio GSH / Pb(II) = 2.0 (CPb2+ = 10 mM, pH 8.5), lead(II) complexes with two thiolate ligands form, characterized by a ligand-to-metal charge transfer band (LMCT) S- ? Pb2+ at 317 nm in the UV-vis spectrum and mean Pb-S and Pb-(N/O) bond distances of 2.65 ± 0.04 Å and 2.51 ± 0.04 Å, respectively, from a Pb LIII-edge EXAFS spectrum. For solutions with higher mole ratios, GSH / Pb(II) ? 3.0, ESI-MS spectra identified a trisglutathionyl lead(II) complex, for which Pb LIII-edge EXAFS spectroscopy shows a mean Pb-S distance of 2.65 ± 0.04 Å in PbS3 coordination, 207Pb NMR spectroscopy displays a chemical shift of 2793 ppm, and in the UV-vis spectrum an S- ? Pb2+ LMCT band appears at 335 nm. The complex persists at high excess of glutathione, and also at ~25 K in frozen glycerol (33%) / water glasses for GSH / Pb(II) mole ratios from 4.0 to 10 (CPb2+ = 10 mM) measured by Pb LIII-edge EXAFS spectroscopy. PMID:22594853

Mah, Vicky



Photochemistry of group 6 Fischer carbene complexes: beyond the photocarbonylation reaction.  


The seminal report by Hegedus in 1982, showing that alkoxychromium(0) carbenes reacted with imines under bright Colorado sunlight to yield ?-lactams, marked the beginning of a key reaction in organometallic chemistry. Very little was known about the mechanism of this reaction. In fact, Hegedus proposed the reversible generation of a chromium-coordinated ketene, which would react with nucleophiles. This coordinated species would show all the advantages of ketenes without their shortcomings, namely, dimerization, formation of undesired adducts, and so forth. The quest for the detection of these species and the pursuit of the mechanism of the photocarbonylation (a reaction exclusive to Cr(0) and Mo(0) carbene complexes, not W(0) carbene complexes) remained unabated over the next 15 years. In fact, all attempts to experimentally determine the mechanism of this useful reaction have been fruitless. At the same time, the photocarbonylation of Cr(0) carbenes matured into a valuable synthetic reaction, allowing access to several families of organic compounds. Unfortunately, reactions other than photocarbonylation remained elusive. We used a combination of experimental and computational methodologies to study the photocarbonylation of Cr(0) carbene complexes and the subsequent reaction of the photogenerated ketenes with nucleophiles. In parallel, we discovered new photochemical processes and succeeded in making photoreactive the so-called "unreactive" W(0) carbene complexes. In this Account, we discuss the disentangling of the mechanisms of these transformations, thereby shedding some light onto the photochemistry of group 6 metal (Fischer) carbene complexes. The original designation of the electronic transitions of group 6 carbene complexes was reassigned, and the photocarbonylation step was analyzed again, resulting in the sequence S(0)-T(1)-S(0), which is far removed from conventional organic photochemistry. The T(1) species is a chromacyclopropanone; its unpaired electrons are primarily localized in the metal fragment and in the former carbene carbon atom. The T(1)-S(0) intersystem crossing occurs with the participation of the solvent through an unusual loose-bolt radiationless mechanism. The photogenerated S(0) species reacts with imines to form the final ?-lactams in a mechanism that resembles the organic Staudinger reaction, but here the metal is present during the entire reaction coordinate. The selectivity of these reactions is defined by the nucleophilic attack on the O-bonded metallaketene instead of the subsequent conrotatory ring closure, a distinct departure from the organic reaction. Appropriate modification of the substituents of the carbene ligand or in the coordination sphere of the complex results in new photoprocesses; these include 1,2-metalladyotropic rearrangements as well as ?-fragmentations in which W(0) carbene complexes become photoreactive. Moreover, the inclusion of additional metal centers usually results in new reactions, such as the formation of fulvenes by ?(5)? ?(3) photoslippage, or in the complete inhibition of the photoreactivity. The photochemistry of group 6 metal-carbene complexes thus offers unexplored territory for pursuing new reactions and reaction mechanisms. PMID:21517052

Fernández, Israel; Cossío, Fernando P; Sierra, Miguel A



Enantioselective Henry reaction catalyzed by "ship in a bottle" complexes.  


Two chiral Schiff-base complexes of copper(II) have been successfully encapsulated inside the cavity of zeolite-NaY via a "ship in a bottle" synthesis method. The presence of the two complexes inside the cages of zeolite-Y has been confirmed based on various spectrochemical and physicochemical techniques, viz. FTIR, UV-vis/DRS, ESR, XPS, CV, EDX, SEM, and TGA. Zeolite-encapsulated chiral copper(II) Schiff-base complexes are found to give a high-enantioselective (84% ee, R conformation) nitro-aldol product at -20 °C. The encapsulated copper complexes are found to show higher catalytic efficiency than their homogeneous counterparts under identical conditions. Density functional theory (DFT) calculation has been implemented to understand the effect of the zeolite matrix on structural, electronic, and reactivity properties of the synthesized complexes. Theoretical calculation predicts that upon encapsulation into the zeolite matrix the Cu center becomes more susceptible to nucleophilic attack, favoring a nitro-aldol reaction. A plausible mechanism is suggested based on the experimental and theoretical results. The structures of reaction intermediates and transition state(s) involved in the catalytic cycle are derived using DFT. PMID:23848182

Bania, Kusum K; Karunakar, Galla V; Goutham, Kommuru; Deka, Ramesh C



Polyaniline–transition metal salt complexes: insight into formation mechanisms  

Microsoft Academic Search

Two basic morphologies of emeraldine base of polyaniline–transition metal salt complex films cast from N-methylpyrrolidinone solutions are described. The first morphology consists of grains and the other consists of loose aggregates, respectively. The correlation of the film morphology with formation of precipitate in the complex solution, kinetics of solvent evaporation from the cast film, amount of solvent entrapped in the

O. P. Dimitriev; P. S. Smertenko; B. Stiller; L. Brehmer



Spectrofluorometric determination of certain quinolone through charge transfer complex formation  

Microsoft Academic Search

A spectrofluorimetric method was developed for the determination of three fluoroquinolones antibacterials, namely, ofloxacin (OFL), levofloxacin (LEV), lomefloxacin (LOM), and pipemidic acid (PIP) through charge transfer (CT) complex formation with 7,7,8,8-tetracyanoquinodimethane (TCNQ). TCNQ was found to react with these drugs to produce stable complexes and the fluorescence intensity of the complexes was enhanced in 15–90 times higher than that of

Li Ming Du; Ya Qin Yang; Qing Mei Wang



Formation of molecular oxygen in ultracold O + OH reaction  

SciTech Connect

We discuss the formation of molecular oxygen in ultracold collisions between hydroxyl radicals and atomic oxygen. A time-independent quantum formalism based on hyperspherical coordinates is employed for the calculations. Elastic, inelastic and reactive cross sections as well as the vibrational and rotational populations of the product O{sub 2} molecules are reported. A J-shifting approximation is used to compute the rate coefficients. At temperatures T = 10--100 mK for which the OH molecules have been cooled and trapped experimentally, the elastic and reactive rate coefficients are of comparable magnitude, while at colder temperatures, T < 1 mK, the formation of molecular oxygen becomes the dominant pathway. The validity of a classical capture model to describe cold collisions of OH and O is also discussed. While very good agreement is found between classical and quantum results at T = 0.3 K, at higher temperatures, the quantum calculations predict a higher rate coefficient than the classical model, in agreement with experimental data for the O + OH reaction. The zero-temperature limiting value of the rate coefficient is predicted to be about 6 x 10{sup -12} cm{sup 3} s{sup 01}, a value comparable to that of barrierless alkali metal atom-dimer systems and about a factor of five larger than that of the tunneling dominated F + H{sub 2} reaction.

Kendrick, Brian Kent [Los Alamos National Laboratory; Quemener, Goulven [UNLV; Balakrishman, Naduvalath [UNLV



Evolution of heliobacteria: implications for photosynthetic reaction center complexes  

NASA Technical Reports Server (NTRS)

The evolutionary position of the heliobacteria, a group of green photosynthetic bacteria with a photosynthetic apparatus functionally resembling Photosystem I of plants and cyanobacteria, has been investigated with respect to the evolutionary relationship to Gram-positive bacteria and cyanobacteria. On the basis of 16S rRNA sequence analysis, the heliobacteria appear to be most closely related to Gram-positive bacteria, but also an evolutionary link to cyanobacteria is evident. Interestingly, a 46-residue domain including the putative sixth membrane-spanning region of the heliobacterial reaction center protein show rather strong similarity (33% identity and 72% similarity) to a region including the sixth membrane-spanning region of the CP47 protein, a chlorophyll-binding core antenna polypeptide of Photosystem II. The N-terminal half of the heliobacterial reaction center polypeptide shows a moderate sequence similarity (22% identity over 232 residues) with the CP47 protein, which is significantly more than the similarity with the Photosystem I core polypeptides in this region. An evolutionary model for photosynthetic reaction center complexes is discussed, in which an ancestral homodimeric reaction center protein (possibly resembling the heliobacterial reaction center protein) with 11 membrane-spanning regions per polypeptide has diverged to give rise to the core of Photosystem I, Photosystem II, and of the photosynthetic apparatus in green, purple, and heliobacteria.

Vermaas, W. F.; Blankenship, R. E. (Principal Investigator)



Characterization of reversible reactions of isocyanides with molybdenum dithiolate complexes  

SciTech Connect

Dimeric molybdenum complexes with bridging dithiocarbonimidate ligands of the formula (C/sub 5/H/sub 5/MoS/sub 2/CNR)/sub 2/ (where R = CH/sub 3/, CH/sub 2/C/sub 6/H/sub 5/, C/sub 6/H/sub 11/, and n-C/sub 4/H/sub 9/) have been synthesized and characterized. The syntheses involve the room-temperature reactions of excess isocyanides with solutions of the dimeric complex (C/sub 5/H/sub 5/MoSC/sub 3/H/sub 6/S)/sub 2/. During the course of these reactions, propene is displaced from the sulfur atoms of the bridging dithiolate ligands. Addition of excess alkene reverses the above reactions. Equilibrium constants have been calculated for the following reactions by integration of NMR resonances: (CH/sub 3/C/sub 5/H/sub 4/MoSC/sub 2/H/sub 4/S)/sub 2/ + RNC reversible (CH/sub 3/C/sub 5/H/sub 4/Mo)/sub 2/(SC/sub 2/H/sub 4/S)(S/sub 2/CNR) + C == C, K/sub 1/ = 2.9 +- 0.2; (CH/sub 3/C/sub 5/H/sub 4/Mo)/sub 2/(SC/sub 2/H/sub 4/S)(S/sub 2/CNR) + RNC reversible (CH/sub 3/C/sub 5/H/sub 4/MoS/sub 2/CNR)/sub 2/ + C == C, K/sub 2/ = 0.7 +- 0.1 (R = CH/sub 2/C/sub 6/H/sub 5/). The dithiocarbonimidate complexes react cleanly with the electrophiles CH/sub 3/OSO/sub 2/F and HOSO/sub 2/CF/sub 3/ to form (C/sub 5/H/sub 5/MoS/sub 2/CNRR')/sub 2//sup 2 +/ where R' = H or CH/sub 3/. These products have been characterized by spectral and conductivity methods. The reactions of the dithiocarbonimidate complexes with reducing agents and with carbon monoxide are discussed. 1 figure, 2 tables.

Miller, D.J.; DuBois, M.R.



Roles of acetone and diacetone alcohol in coordination and dissociation reactions of uranyl complexes.  


Combined collision-induced dissociation mass spectrometry experiments with DFT and MP2 calculations were employed to elucidate the molecular structures and energetics of dissociation reactions of uranyl species containing acetone and diacetone alcohol ligands. It is shown that solutions containing diacetone alcohol ligands can produce species with more than five oxygen atoms available for coordination. Calculations confirm that complexes with up to four diacetone alcohol ligands can be energetically stable but that the effective number of atoms coordinating with uranium in the equatorial plane does not exceed five. Water elimination reactions of diacetone alcohol ligands are shown to have two coordination-dependent reaction channels, through formation of mesityl oxide ligands or formation of alkoxide and protonated mesityl oxide species. The present results provide an explanation for the implausible observation of "[UO(2)(ACO)(6,7,8)](2+)" in and observed water-elimination reactions from purportedly uranyl-acetone complexes (Rios, D.; Rutkowski, P. X.; Van Stipdonk, M. J.; Gibson, J. K. Inorg. Chem. 2011, 50, 4781). PMID:23146003

Rios, Daniel; Schoendorff, George; Van Stipdonk, Michael J; Gordon, Mark S; Windus, Theresa L; Gibson, John K; de Jong, Wibe A



Generating functional analysis of complex formation and dissociation in large protein interaction networks  

NASA Astrophysics Data System (ADS)

We analyze large systems of interacting proteins, using techniques from the non-equilibrium statistical mechanics of disordered many-particle systems. Apart from protein production and removal, the most relevant microscopic processes in the proteome are complex formation and dissociation, and the microscopic degrees of freedom are the evolving concentrations of unbound proteins (in multiple post-translational states) and of protein complexes. Here we only include dimer-complexes, for mathematical simplicity, and we draw the network that describes which proteins are reaction partners from an ensemble of random graphs with an arbitrary degree distribution. We show how generating functional analysis methods can be used successfully to derive closed equations for dynamical order parameters, representing an exact macroscopic description of the complex formation and dissociation dynamics in the infinite system limit. We end this paper with a discussion of the possible routes towards solving the nontrivial order parameter equations, either exactly (in specific limits) or approximately.

Coolen, A. C. C.; Rabello, S.



Electrochemistry and metal complex formation of organic diselenides  

Microsoft Academic Search

This review article is devoted to electrochemical investigations of symmetric organic diselenides and to their specific interactions with metals. Diselenides, as well as their metal complexes, are interesting from the biological, pharmacological and synthetic points of view. Special attention has been paid to their electroreduction on mercury electrodes in protic and aprotic solutions where mercury-assisted reactions proceed. Recent investigations of

Ji?í Ludvík; Bengt Nygård



Complex formation of p-boronophenylalanine with some monosaccharides.  


To increase the solubility of p-boronophenylalanine (p-bpa) in neutral pH solution, the complex formation of p-bpa with some monosaccharides has been studied by 11B-NMR and UV spectroscopy. The complex formation constants (log K) obtained by the UV method in pH 7.4 solution are 2.43 (fructose), 2.19 (mannitol), 1.28 (galactose), 1.10 (mannose), and 0.85 (glucose), respectively. One hundred milligrams of p-bpa is able to dissolve in 3 ml of 0.3 M fructose solution at pH 7.98. Based on the results obtained, the behavior of p-bpa-monosaccharide complexes in vivo after injection of the complex solution is described. PMID:2508079

Mori, Y; Suzuki, A; Yoshino, K; Kakihana, H



Isospin Properties of ($K^-$, $N$) Reactions for the Formation of Deeply-bound Antikaonic Nuclei  

E-print Network

The formation of deeply-bound antikaonic $K^-/\\bar{K}^0$ nuclear states by nuclear ($K^-$, $N$) reactions is investigated theoretically within a distorted-wave impulse approximation (DWIA), considering the isospin properties of the Fermi-averaged $K^-+ N \\to N + \\bar{K}$ elementary amplitudes. We calculate the formation cross sections of the deeply-bound $\\bar{K}$ states by the ($K^-$, $N$) reactions on the nuclear targets, $^{12}$C and $^{28}$Si, at incident $K^-$ lab momentum $p_{K^-}$ = 1.0 GeV/c and $\\theta_{\\rm lab} = 0^{\\circ}$, introducing a complex effective nucleon number $N_{\\rm eff}$ for unstable bound states in the DWIA. The results show that the deeply-bound $\\bar{K}$ states can be populated dominantly by the ($K^-$, $n$) reaction via the total isoscalar $\\Delta T=0$ transition owing to the isospin nature of the $K^-+ N \\to N + \\bar{K}$ amplitudes, and that the cross sections described by ${\\rm Re}N_{\\rm eff}$ and ${\\rm Arg}N_{\\rm eff}$ enable to deduce the structure of the $\\bar{K}$ nuclear states; the calculated inclusive nucleon spectra for a deep $\\bar{K}$-nucleus potential do not show distinct peak structure in the bound region. The few-body $\\bar{K}\\otimes [NN]$ and $\\bar{K}\\otimes [NNN]$ states formed in ($K^-$, $N$) reactions on $s$-shell nuclear targets, $^3$He, $^3$H and $^4$He, are also discussed.

T. Koike; T. Harada



A tethering complex dimer catalyzes trans-SNARE complex formation in intracellular membrane fusion  

PubMed Central

SNARE complexes mediate membrane fusion in the endomembrane system. They consist of coiled-coil bundles of four helices designated as Qa, Qb, Qc and R. A critical intermediate in the fusion pathway is the trans-SNARE complex generated by the assembly of SNAREs residing in opposing membranes. Mechanistic details of trans-SNARE complex formation and topology in a physiological system remain largely unresolved. Our studies on native yeast vacuoles revealed that SNAREs alone are insufficient to form trans-SNARE complexes and that additional factors, potentially tethering complexes and Rab GTPases, are required for the process. Here we report a novel finding that a HOPS tethering complex dimer catalyzes Rab GTPase-dependent formation of a topologically preferred QbQcR-Qa trans-SNARE complex. PMID:22754631

Kulkarni, Aditya; Alpadi, Kannan; Namjoshi, Sarita; Peters, Christopher



Formation and characterization of OH–Al–humate–montmorillonite complexes  

Microsoft Academic Search

We studied the formation of OH–Al–humate–montmorillonite complexes as affected by the nature of the humic acid and the sequence of addition of montmorillonite, humic acid and hydrolytic species of Al. Complexes were prepared at pH 7.0 by different addition sequences of montmorillonite, 3 or 6 mmol Al and 5, 10 or 20 mg of humic acid per g of clay.

A Violante; M Arienzo; F Sannino; C Colombo; A Piccolo; L Gianfreda



Reaction of Li/Cl phosphinidenoid complexes with a phosphite substituted ketone: access to complexes with a novel mixed-valence polycyclic P,C-ligand system.  


Reaction of Li/Cl phosphinidenoid pentacarbonyltungsten(0) complexes 2a,b (R = CH(SiMe3)2, Cp*) with bifunctional phosphite-substituted ketone 3 yielded tungsten complexes 4a,b having a novel mixed-valence polycyclic P,C-cage ligand with a P–P bond. DFT calculations provide insight into an unusual product formation pathway. PMID:23760069

Abdrakhmanova, Liliya; Espinosa, Arturo; Streubel, Rainer



The formation of Kuiper-belt binaries through exchange reactions.  


Recent observations have revealed that an unexpectedly high fraction--a few per cent--of the trans-Neptunian objects (TNOs) that inhabit the Kuiper belt are binaries. The components have roughly equal masses, with very eccentric orbits that are wider than a hundred times the radius of the primary. Standard theories of binary asteroid formation tend to produce close binaries with circular orbits, so two models have been proposed to explain the unique characteristics of the TNOs. Both models, however, require extreme assumptions regarding the size distribution of the TNOs. Here we report a mechanism that is capable of producing binary TNOs with the observed properties during the early stages of their formation and growth. The only required assumption is that the TNOs were initially formed through gravitational instabilities in the protoplanetary dust disk. The basis of the mechanism is an exchange reaction in which a binary whose primary component is much more massive than the secondary interacts with a third body, whose mass is comparable to that of the primary. The low-mass secondary component is ejected and replaced by the third body in a wide but eccentric orbit. PMID:14765188

Funato, Yoko; Makino, Junichiro; Hut, Piet; Kokubo, Eiichiro; Kinoshita, Daisuke



The formation of bifurcated charge transfer complexes with molecular iodine  

NASA Astrophysics Data System (ADS)

I 2 complexes with triptycene and several di- and triaryl derivatives of methane and ethane were studied. For these complexes the values of ? CT are virtually identical to those reported for the complexes with the analogous monoaryl donors, while the values of ? for their blue shifted I 2 peaks are significantly lower than those for the monoaryl complexes. Both the equilibrium constants and - ?H 0 values for the formation of complexes from the components lead to the conclusion that the complexes with the di- and triaryl compounds are more stable than those with the monoaryl donors. For the diaryl donors, the ? S0298 values for complex formation are less favorable than those of the monoaryl donors. The dipole moment for I 2 in diphenylmethane is larger than the moment of I 2 in toluene. All of these observations can be explained by taking into account the transannular effect of one aromatic ring on another and viewing the complexes as bifurcated ones in which the I atom at one end of an I 2 molecule simultaneously interacts with two rings in the donor molecules.

Kulevsky, Norman; Pierce, Ken



Study of complex formation between aluminum bromide and benzene by 27Al NMR spectroscopy  

Microsoft Academic Search

The reaction of aluminum bromide with benzene in n-hexane was studied by 27Al NMR spectroscopy in the temperature range from –80 to +20 °C. The formation of C6H6·Al2Br6 (1 : 2) complexes is accompanied by broadening of the resonance line with d 178. No peak splitting following a decrease in the temperature was observed but the temperature dependence of the

V. B. Murachev; A. I. Nesmelov



New insights into formation of trivalent actinides complexes with DTPA.  


Complexation of trivalent actinides with DTPA (diethylenetriamine pentaacetic acid) was studied as a function of pcH and temperature in (Na,H)Cl medium of 0.1 M ionic strength. Formation constants of both complexes AnHDTPA(-) and AnDTPA(2-) (where An stands for Am, Cm, and Cf) were determined by TRLFS, CE-ICP-MS, spectrophotometry, and solvent extraction. The values of formation constants obtained from the different techniques are coherent and consistent with reinterpreted literature data, showing a higher stability of Cf complexes than Am and Cm complexes. The effect of temperature indicates that formation constants of protonated and nonprotonated complexes are exothermic with a high positive entropic contribution. DFT calculations were also performed on the An/DTPA system. Geometry optimizations were conducted on AnDTPA(2-) and AnHDTPA(-) considering all possible protonation sites. For both complexes, one and two water molecules in the first coordination sphere of curium were also considered. DFT calculations indicate that the lowest energy structures correspond to protonation on oxygen that is not involved in An-DTPA bonds and that the structures with two water molecules are not stable. PMID:23152978

Leguay, Sébastien; Vercouter, Thomas; Topin, Sylvain; Aupiais, Jean; Guillaumont, Dominique; Miguirditchian, Manuel; Moisy, Philippe; Le Naour, Claire



Carbon-heteroatom bond formation catalysed by organometallic complexes  

PubMed Central

At one time the synthetic chemist’s last resort, reactions catalysed by transition metals are now the preferred method for synthesizing many types of organic molecule. A recent success in this type of catalysis is the discovery of reactions that form bonds between carbon and heteroatoms (such as nitrogen, oxygen, sulphur, silicon and boron) via complexes of transition metals with amides, alkoxides, thiolates, silyl groups or boryl groups. The development of these catalytic processes has been supported by the discovery of new elementary reactions that occur at metal–heteroatom bonds and by the identification of factors that control these reactions. Together, these findings have led to new synthetic processes that are in daily use and have formed a foundation for the development of processes that are likely to be central to synthetic chemistry in the future. PMID:18800130

Hartwig, John F.



Snapshot of a Reaction Intermediate: Analysis of Benzoylformate Decarboxylase in Complex with a Benzoylphosphonate Inhibitor  

SciTech Connect

Benzoylformate decarboxylase (BFDC) is a thiamin diphosphate- (ThDP-) dependent enzyme acting on aromatic substrates. In addition to its metabolic role in the mandelate pathway, BFDC shows broad substrate specificity coupled with tight stereo control in the carbon-carbon bond-forming reverse reaction, making it a useful biocatalyst for the production of chiral-hydroxy ketones. The reaction of methyl benzoylphosphonate (MBP), an analogue of the natural substrate benzoylformate, with BFDC results in the formation of a stable analogue (C2{alpha}-phosphonomandelyl-ThDP) of the covalent ThDP-substrate adduct C2{alpha}-mandelyl-ThDP. Formation of the stable adduct is confirmed both by formation of a circular dichroism band characteristic of the 1',4'-iminopyrimidine tautomeric form of ThDP (commonly observed when ThDP forms tetrahedral complexes with its substrates) and by high-resolution mass spectrometry of the reaction mixture. In addition, the structure of BFDC with the MBP inhibitor was solved by X-ray crystallography to a spatial resolution of 1.37 {angstrom} (PDB ID 3FSJ). The electron density clearly shows formation of a tetrahedral adduct between the C2 atom of ThDP and the carbonyl carbon atom of the MBP. This adduct resembles the intermediate from the penultimate step of the carboligation reaction between benzaldehyde and acetaldehyde. The combination of real-time kinetic information via stopped-flow circular dichroism with steady-state data from equilibrium circular dichroism measurements and X-ray crystallography reveals details of the first step of the reaction catalyzed by BFDC. The MBP-ThDP adduct on BFDC is compared to the recently solved structure of the same adduct on benzaldehyde lyase, another ThDP-dependent enzyme capable of catalyzing aldehyde condensation with high stereospecificity.

Brandt, Gabriel S.; Kneen, Malea M.; Chakraborty, Sumit; Baykal, Ahmet T.; Nemeria, Natalia; Yep, Alejandra; Ruby, David I.; Petsko, Gregory A.; Kenyon, George L.; McLeish, Michael J.; Jordan, Frank; Ringe, Dagmar; (Michigan); (Rutgers); (Brandeis)



Structure of solvated Fe(CO)5: complex formation during solvation in alcohols.  


The equilibrium structure of iron pentacarbonyl, Fe(CO)5, solvated in various alcohols has been investigated by Fourier transform infrared (FTIR) measurements and density functional theory calculations. This system was studied because it is prototypical of a larger class of monometallic systems, which are electronically saturated but not sterically crowded. Upon solvation, the Fe(CO)5 is not just surrounded by a solvation shell. Instead, solute-solvent complexes are formed with the oxygen of the alcohol oriented toward an axial ligand of the Fe(CO)5 giving a formation energy on the order of -5 kJ/mol. This complexation is not a chemical reaction but rather a "preassembly" of the solute molecules with a single solvent molecule. For instance, at room temperature the interaction between Fe(CO)5 and ethanol results in 87% of all Fe(CO)5 molecules being complexated with a single ethanol molecule. This complexation was found in all the alcohol systems studied in this paper. The stability of these complexes was found to depend on the alcohol chain length and branching. The observed complexation mechanism is accompanied by an electron density shift from the complexed alcohol molecule toward Fe(CO)5 where it induces a dipole moment. The finding that Fe(CO)5 forms a complex with the hydroxyl group of a single solvent molecule might have significant implications for ligand substitution reactions. This implies that ligand substitution reactions do not have to proceed via a dissociative mechanism. Instead, the reaction might proceed through a concerted mechanism with the leaving CO simultaneously being replaced by the incoming alcohol that was complexed to Fe(CO)5 prior to the photoexcitation. PMID:18284220

Lessing, Joshua; Li, Xiaodi; Lee, Taewoo; Rose-Petruck, Christoph G



Palladium- and copper-mediated N-aryl bond formation reactions for the synthesis of biological active compounds.  


N-Arylated aliphatic and aromatic amines are important substituents in many biologically active compounds. In the last few years, transition-metal-mediated N-aryl bond formation has become a standard procedure for the introduction of amines into aromatic systems. While N-arylation of simple aromatic halides by simple amines works with many of the described methods in high yield, the reactions may require detailed optimization if applied to the synthesis of complex molecules with additional functional groups, such as natural products or drugs. We discuss and compare in this review the three main N-arylation methods in their application to the synthesis of biologically active compounds: Palladium-catalysed Buchwald-Hartwig-type reactions, copper-mediated Ullmann-type and Chan-Lam-type N-arylation reactions. The discussed examples show that palladium-catalysed reactions are favoured for large-scale applications and tolerate sterically demanding substituents on the coupling partners better than Chan-Lam reactions. Chan-Lam N-arylations are particularly mild and do not require additional ligands, which facilitates the work-up. However, reaction times can be very long. Ullmann- and Buchwald-Hartwig-type methods have been used in intramolecular reactions, giving access to complex ring structures. All three N-arylation methods have specific advantages and disadvantages that should be considered when selecting the reaction conditions for a desired C-N bond formation in the course of a total synthesis or drug synthesis. PMID:21286396

Fischer, Carolin; Koenig, Burkhard



Complexation of Al(III) with gluconate in alkaline to hyperalkaline solutions: formation, stability and structure.  


Contrary to suggestions in the literature, it has been proven that Al(III) forms a 1?:?1 complex with gluconate (hereafter Gluc(-)) in strongly alkaline (pH > 12) aqueous solutions. The complex formation was proven via(27)Al and (1)H NMR, freezing-point depression, polarimetric measurements as well as potentiometric and conductometric titrations. This complexation is a pH independent process, i.e., a condensation reaction takes place. The stability constant of the complex formed was derived from (1)H NMR and polarimetric measurements, and was found to be log K = 2.4 ± 0.4. In the complex formed, Al(III) has a tetrahedral geometry, and the Al(OH)4(-) is most probably statistically distributed between the alcoholate groups of the Gluc(-). PMID:23897548

Pallagi, Attila; Tasi, Ágost Gyula; Peintler, Gábor; Forgo, Péter; Pálinkó, István; Sipos, Pál



Pattern formation in oscillatory complex networks consisting of excitable nodes  

E-print Network

Oscillatory dynamics of complex networks has recently attracted great attention. In this paper we study pattern formation in oscillatory complex networks consisting of excitable nodes. We find that there exist a few center nodes and small skeletons for most oscillations. Complicated and seemingly random oscillatory patterns can be viewed as well-organized target waves propagating from center nodes along the shortest paths, and the shortest loops passing through both the center nodes and their driver nodes play the role of oscillation sources. Analyzing simple skeletons we are able to understand and predict various essential properties of the oscillations and effectively modulate the oscillations. These methods and results will give insights into pattern formation in complex networks, and provide suggestive ideas for studying and controlling oscillations in neural networks.

Liao Xuhong; Xia Qinzhi; Qian Yu; Zhang Lisheng; Hu Gang; Mi Yuanyuan



Potentiometric studies of complex formation between methylmercury(II) and EDTA.  


The protonation of EDTA (ethylenediaminetetra-acetic acid) and its complex formation with methylmercury(II) ions was studied by a potentiometric method at 25 degrees in 1.0M NaNO(3). The protonation constants of EDTA and the equilibrium constants for the complexation reactions between methylmercuric ions and EDTA were evaluated by analysing the experimental data with the ETITR version of the general error-minimizing program LETAGROP. The results were used to develop an analytical method, based on complexometric titration and ion-exchange separation, for the determination of inorganic and organic mercury in the presence of one another. PMID:18962242

Jawaid, M



Oxygen atom transfer reactions from Mimoun complexes to sulfides and sulfoxides. A bonding evolution theory analysis.  


In this research, a comprehensive theoretical investigation has been conducted on oxygen atom transfer (OAT) reactions from Mimoun complexes to sulfides and sulfoxides. The joint use of the electron localization function (ELF) and Thom's catastrophe theory (CT) provides a powerful tool to analyze the evolution of chemical events along a reaction pathway. The progress of the reaction has been monitored by structural stability domains from ELF topology while the changes between them are controlled by turning points derived from CT which reveal that the reaction mechanism can be separated in several steps: first, a rupture of the peroxo O1-O2 bond, then a rearrangement of lone pairs of the sulfur atom occurs and subsequently the formation of S-O1 bond. The OAT process involving the oxidation of sulfides and sulfoxides is found to be an asynchronous process where O1-O2 bond breaking and S-O1 bond formation processes do not occur simultaneously. Nucleophilic/electrophilic characters of both dimethyl sulfide and dimethyl sulfoxide, respectively, are sufficiently described by our results, which hold the key to unprecedented insight into the mapping of electrons that compose the bonds while the bonds change. PMID:25010751

González-Navarrete, Patricio; Sensato, Fabricio R; Andrés, Juan; Longo, Elson



Formation of cation-anion complexes in the photochemical reaction of molybdenocene dihydrode with iron pentacarbonyl. Crystal structures of (Cp/sub 2/Mo(CO)H)/sup +/(Fe/sub 3/(CO)/sub 11/H)/sup -/ and (Cp/sub 2/Mo(CO)H)/sup +/(CoMo(CO)/sub 3/)/sup -/ (triclinic modification)  

SciTech Connect

The reaction of Cp/sub 2/MoH/sub 2/ with Fe(CO)/sub 5/ in boiling benzene under UV irradiation gives the ionic complexes (Cp/sub 2/Mo(CO)H)/sup +/(Fe/sub 3/(CO)/sub 11/H)/sup -/ (I) and (Cp/sub 2/Mo(CO)H)/sup +/(CpMo(CO)/sub 3/)/sup -/ (II), whose structures were established by x-ray diffraction analysis (Syntex P2/sub 1/ automatic diffractometer, lambda Mo K/sub ..cap alpha../, graphite monochromator, theta/2theta scan technique, full-matrix least-squares method, isotropic variant for I on the basis of 2112 reflections to % = 0.11 and anisotropic variant for II on the basis of 3770 values of hkl to R = 0.052). In complexes I and II the (CpMo(CO)H)/sup +/ fragment is a tapered sandwich with an eclipsed conformation of the rings. In complex I the angle between the rings is 33.9/sup 0/, the mean Mo-C(C/sub 5/H/sub 5/) distance is 2.28(3) A, the mean Mo-C(CO) distance is 2.03(3) A, and the mean Mo-H distance is 1.78(10) A. The corresponding parameters in complex II are: 32.4/sup 0/, 2.296(7), 2.020(6), and 1.87(7) A. The anion in complex I is based on a triangular cluster of Fe atoms, in which one Fe-Fe distance is significantly shorter (2.488(5) A) than the other two (2.702(5) and 2.697(5) A). The Fe atoms forming the short bond are joined additionally by hydride (Fe-H = 2.14 A) and carbonyl (Fe-C = 1.90(3) and 1.93(3) A) Bridges. The remaining groups are terminal. A probable scheme for the process of the formation of complexes I and II has been discussed.

Antsyshkina, A.S.; Dikareva, L.M.; Porai-Koshits, M.A.; Ostrikova, V.N.; Skripkin, Yu.V.; Volkov, O.G.; Pasynskii, A.A.; Kalinnikov, V.T.



Cu(I) Amido Complexes in the Ullmann Reaction. Reactions of Cu(I)-Amido Complexes with Iodoarenes with and without Autocatalysis by CuI  

PubMed Central

A series of Cu(I)-amido complexes both lacking ancillary ligands and containing 1,10-phenanthroline (phen) as ligand have been prepared. These complexes react with iodoarenes to form arylamine products, and these data are consistent with the intermediacy of such complexes in catalytic Ullmann amination reactions. The stoichiometric reactions of the Cu(I)-amido complexes with iodoarenes are autocatalytic, with the free CuI generated during the reaction serving as the catalyst. Such autocatalytic behavior was not observed for reactions of iodoarenes with Cu(I)-amidates, -imidates and -phenoxides. The selectivity of these complexes for two sterically distinct aryl halides under various conditions imply that the autocatalytic reaction proceeds by forming highly-reactive [CuNPh2]n lacking phen. Reactions with radical probes imply that the reactions of phen-ligated Cu(I)-amido complexes with iodoarenes occur without the intermediacy of aryl radicals. DFT calculations of the oxidative addition of iodoarenes to Cu(I) species are consistent with faster reactions of iodoarenes with CuNPh2 species lacking phen in DMSO than with phen-ligated LCuNPh2. The free energy barrier computed for reaction of PhI with (DMSO)CuNPh2 was 21.8 kcal/mol, while the free energy barrier computed for reaction of PhI with (phen)CuNPh2 was 33.4 kcal/mol. PMID:20977264

Giri, Ramesh; Hartwig, John F.



Reactivity of thiosemicarbazides with redox active metal ions: controlled formation of coordination complexes versus heterocyclic compounds.  


The reactions of 1,1-dimethyl-4-phenylthiosemicarbazide (LH) with Cu(II) and Sn(IV) have been investigated. If THF or methanol is used as solvent with Cu(II), oxidative cyclisation and coupling are observed, yielding a 1,2,4-thiadiazole or a 1,3,4-thiadiazolium salt. SnI(4) is also able to induce oxidative coupling of two thiosemicarbazide ligands, yielding 1,2,4-thiadiazolium or 1,2,4-triazolium salts, with I(3)(-) as the counterion, depending on the reaction conditions. By contrast, reaction of LH with SnI(4) in acetone yields a 1,3-thiazolium salt, with I(-) as counterion. Reaction with Cu(II) salts or SnI(4) in basic media leads to the formation of metal complexes containing two deprotonated thiosemicarbazide ligands. In the reaction of CuCl(2) in water in the presence of acid a complex containing two neutral ligands is obtained. Reactions with SnCl(4) are not able to induce ligand cyclisation, although a coordination compound with two neutral ligands was isolated from methanol. PMID:19180593

López-Torres, Elena; Dilworth, Jonathan R



Substitution reactions involving cyclometalated platinum(II) complexes: Kinetic investigations  

Microsoft Academic Search

Substitution reaction of the labile SMe2 ligand in the cyclometalated platinum(II) complexes of general formula [PtAr(ppy)(SMe2)], 1, in which ppy = deprotonated 2-phenylpyridyl and Ar = p-MeC6H4 or p-MeOC6H4, by several N or P donor reagents were studied; the N-donors, N, are pyridine (Py) and substituted pyridines, N = 4-MePy, Py, Py-d5, 2-MePy, 3-PhPy, 3,4-Me2Py, 4-tBuPy or 3-C(O)OMePy, and the P-donors, L, are phosphines or phosphites,

S. Masoud Nabavizadeh; Hamid R. Shahsavari; Masoud Namdar; Mehdi Rashidi



Complex fragment emission in low energy light-ion reactions  

E-print Network

Inclusive energy spectra of the complex fragments (3 $\\leq$ Z $\\leq$ 5) emitted in the reactions $^{12}$C (77 MeV)+ $^{28}$Si, $^{11}$B (64 MeV)+ $^{28}$Si and $^{12}$C (73 MeV)+ $^{27}$Al (all having the same excitation energy of $ \\sim$ 67 MeV), have been measured in the angular range of 10$^\\circ$ $\\lesssim \\theta_{lab} \\lesssim$ 60$^\\circ$. The fully energy damped (fusion-fission) and the partially energy damped (deep inelastic) components of the fragment energy spectra have been extracted. It has been found that the yields of the fully energy damped fragments for all the above reactions are in conformity with the respective statistical model predictions. The time scales of various deep inelastic fragment emissions have been extracted from the angular distribution data. The angular momentum dissipation in deep inelastic collisions has been estimated from the data and it has been found to be close to the corresponding sticking limit value.

S. Kundu; C. Bhattacharya; K. Banerjee; T. K. Rana; S. Bhattacharya; A. Dey; T. K. Ghosh; G. Mukherjee; J. K. Meena; P. Mali; S. Mukhopadhyay; D. Pandit; H. Pai; S. R. Banerjee; D. Gupta; P. Banerjee; Suresh Kumar; A. Shrivastava; A. Chatterjee; K. Ramachandran; K. Mahata; S. K. Pandit; S. Santra



Three-Coordinate Terminal Imidoiron(III) Complexes: Structure, Spectroscopy, and Mechanism of Formation  

PubMed Central

Reaction of 1-adamantyl azide with iron(I) diketiminate precursors gives metastable but isolable imidoiron(III) complexes LFe=NAd (L = bulky ?-diketiminate ligand; Ad = 1-adamantyl). This paper addresses: (1) the spectroscopic and structural characterization of the Fe=N multiple bond in these interesting three-coordinate iron imido complexes, and (2) the mechanism through which the imido complexes form. The iron(III) imido complexes have been examined by 1H NMR and EPR spectroscopies and temperature-dependent magnetic susceptibility (SQUID), and structurally characterized by crystallography and/or X-ray absorption (EXAFS) measurements. These data show that the imido complexes have quartet ground states and short (1.68 ± 0.01 Å) iron-nitrogen bonds. The formation of the imido complexes proceeds through unobserved iron–RN3 intermediates, which are indicated by QM/MM computations to be best described as iron(II) with an RN3 radical anion. The radical character on the organoazide bends its NNN linkage to enable easy N2 loss and imido complex formation. The product distribution between imidoiron(III) products and hexazene-bridged diiron(II) products is solvent-dependent, and the solvent dependence can be explained by coordination of certain solvents to the iron(I) precursor prior to interaction with the organoazide. PMID:20524625

Cowley, Ryan E.; DeYonker, Nathan J.; Eckert, Nathan A.; Cundari, Thomas R.; DeBeer, Serena; Bill, Eckhard; Ottenwaelder, Xavier; Flaschenriem, Christine; Holland, Patrick L.



Iridium complex catalyzed germylative coupling reaction between alkynes and iodogermanes - a new route to alkynylgermanium and alkynylgermasilicon compounds.  


The new reaction of terminal alkynes with iodogermanes proceeding in the presence of an Ir(I)-complex [{Ir(?-Cl)(CO)2}2] () and NEt((i)Pr)2, as a hydrogen iodide acceptor, leads to the formation of functionalized alkynylgermanes. This reaction occurs via direct activation of the Csp-H bond in the starting alkyne. Detailed stoichiometric experiments using [Ir(cod)(CCPh)(PCy3)] () and iodogermane were performed and resulted in a proposal of a reasonable mechanism for the germylative coupling reaction between alkynes and iodogermanes. PMID:25286331

Rzonsowska, Monika; Kownacki, Ireneusz; Dudziec, Beata; Marciniec, Bogdan



Time-dependent kinetic complexities in cholinesterase-catalyzed reactions.  


Cholinesterases (ChEs) display a hysteretic behavior with certain substrates and inhibitors. Kinetic cooperativity in hysteresis of ChE-catalyzed reactions is characterized by a lag or burst phase in the approach to steady state. With some substrates damped oscillations are shown to superimpose on hysteretic lags. These time dependent peculiarities are observed for both butyrylcholinesterase and acetylcholinesterase from different sources. Hysteresis in ChE-catalyzed reactions can be interpreted in terms of slow transitions between two enzyme conformers E and E'. Substrate can bind to E and/or E', both Michaelian complexes ES and ?'S can be catalytically competent, or only one of them can make products. The formal reaction pathway depends on both the chemical structure of the substrate and the type of enzyme. In particular, damped oscillations develop when substrate exists in different, slowly interconvertible, conformational, and/or micellar forms, of which only the minor form is capable of binding and reacting with the enzyme. Biphasic pseudo-first-order progressive inhibition of ChEs by certain carbamates and organophosphates also fits with a slow equilibrium between two reactive enzyme forms. Hysteresis can be modulated by medium parameters (pH, chaotropic and kosmotropic salts, organic solvents, temperature, osmotic pressure, and hydrostatic pressure). These studies showed that water structure plays a role in hysteretic behavior of ChEs. Attempts to provide a molecular mechanism for ChE hysteresis from mutagenesis studies or crystallographic studies failed so far. In fact, several lines of evidence suggest that hysteresis is controlled by the conformation of His438, a key residue in the catalytic triad of cholinesterases. Induction time may depend on the probability of His438 to adopt the operative conformation in the catalytic triad. The functional significance of ChE hysteresis is puzzling. However, the accepted view that proteins are in equilibrium between preexisting functional and non-functional conformers, and that binding of a ligand to the functional form shifts equilibrium towards the functional conformation, suggests that slow equilibrium between two conformational states of these enzymes may have a regulatory function in damping out the response to certain ligands and irreversible inhibitors. This is particularly true for immobilized (membrane bound) enzymes where the local substrate and/or inhibitor concentrations depend on influx in crowded organellar systems, e.g. cholinergic synaptic clefts. Therefore, physiological or toxicological relevance of the hysteretic behavior and damped oscillations in ChE-catalyzed reactions and inhibition cannot be ruled out. PMID:23157295

Masson, P



Direct detection of pyridine formation by the reaction of CH (CD) with pyrrole: a ring expansion reaction  

SciTech Connect

The reaction of the ground state methylidyne radical CH (X2Pi) with pyrrole (C4H5N) has been studied in a slow flow tube reactor using Multiplexed Photoionization Mass Spectrometry coupled to quasi-continuous tunable VUV synchrotron radiation at room temperature (295 K) and 90 oC (363 K), at 4 Torr (533 Pa). Laser photolysis of bromoform (CHBr3) at 248 nm (KrF excimer laser) is used to produce CH radicals that are free to react with pyrrole molecules in the gaseous mixture. A signal at m/z = 79 (C5H5N) is identified as the product of the reaction and resolved from 79Br atoms, and the result is consistent with CH addition to pyrrole followed by Helimination. The Photoionization Efficiency curve unambiguously identifies m/z = 79 as pyridine. With deuterated methylidyne radicals (CD), the product mass peak is shifted by +1 mass unit, consistent with the formation of C5H4DN and identified as deuterated pyridine (dpyridine). Within detection limits, there is no evidence that the addition intermediate complex undergoes hydrogen scrambling. The results are consistent with a reaction mechanism that proceeds via the direct CH (CD) cycloaddition or insertion into the five-member pyrrole ring, giving rise to ring expansion, followed by H atom elimination from the nitrogen atom in the intermediate to form the resonance stabilized pyridine (d-pyridine) molecule. Implications to interstellar chemistry and planetary atmospheres, in particular Titan, as well as in gas-phase combustion processes, are discussed.

Soorkia, Satchin; Taatjes, Craig A.; Osborn, David L.; Selby, Talitha M.; Trevitt, Adam J.; Wilson, Kevin R.; Leone, Stephen R.



Direct detection of pyridine formation by the reaction of CH (CD) with pyrrole: a ring expansion reaction.  


The reaction of the ground state methylidyne radical CH (X(2)Pi) with pyrrole (C(4)H(5)N) has been studied in a slow flow tube reactor using Multiplexed Photoionization Mass Spectrometry coupled to quasi-continuous tunable VUV synchrotron radiation at room temperature (295 K) and 363 K, at 4 Torr (533 Pa). Laser photolysis of bromoform (CHBr(3)) at 248 nm (KrF excimer laser) is used to produce CH radicals that are free to react with pyrrole molecules in the gaseous mixture. A signal at m/z = 79 (C(5)H(5)N) is identified as the product of the reaction and resolved from (79)Br atoms, and the result is consistent with CH addition to pyrrole followed by H-elimination. The photoionization efficiency curve unambiguously identifies m/z = 79 as pyridine. With deuterated methylidyne radicals (CD), the product mass peak is shifted by +1 mass unit, consistent with the formation of C(5)H(4)DN and identified as deuterated pyridine (d-pyridine). Within detection limits, there is no evidence that the addition intermediate complex undergoes hydrogen scrambling. The results are consistent with a reaction mechanism that proceeds via the direct CH (CD) cycloaddition or insertion into the five-member pyrrole ring, giving rise to ring expansion, followed by H atom elimination from the nitrogen atom in the intermediate to form the resonance stabilized pyridine (d-pyridine) molecule. Implications to interstellar chemistry and planetary atmospheres, in particular Titan, as well as gas-phase combustion processes, are discussed. PMID:20463997

Soorkia, Satchin; Taatjes, Craig A; Osborn, David L; Selby, Talitha M; Trevitt, Adam J; Wilson, Kevin R; Leone, Stephen R



Single-stranded nucleic acids promote SAMHD1 complex formation.  


SAM domain and HD domain-containing protein 1 (SAMHD1) is a dGTP-dependent triphosphohydrolase that degrades deoxyribonucleoside triphosphates (dNTPs) thereby limiting the intracellular dNTP pool. Mutations in SAMHD1 cause Aicardi-Goutières syndrome (AGS), an inflammatory encephalopathy that mimics congenital viral infection and that phenotypically overlaps with the autoimmune disease systemic lupus erythematosus. Both disorders are characterized by activation of the antiviral cytokine interferon-? initiated by immune recognition of self nucleic acids. Here we provide first direct evidence that SAMHD1 associates with endogenous nucleic acids in situ. Using fluorescence cross-correlation spectroscopy, we demonstrate that SAMHD1 specifically interacts with ssRNA and ssDNA and establish that nucleic acid-binding and formation of SAMHD1 complexes are mutually dependent. Interaction with nucleic acids and complex formation do not require the SAM domain, but are dependent on the HD domain and the C-terminal region of SAMHD1. We finally demonstrate that mutations associated with AGS exhibit both impaired nucleic acid-binding and complex formation implicating that interaction with nucleic acids is an integral aspect of SAMHD1 function. PMID:23371319

Tüngler, Victoria; Staroske, Wolfgang; Kind, Barbara; Dobrick, Manuela; Kretschmer, Stefanie; Schmidt, Franziska; Krug, Claudia; Lorenz, Mike; Chara, Osvaldo; Schwille, Petra; Lee-Kirsch, Min Ae



Demixing-stimulated lane formation in binary complex plasma  

SciTech Connect

Recently lane formation and phase separation have been reported for experiments with binary complex plasmas in the PK3-Plus laboratory onboard the International Space Station (ISS). Positive non-additivity of particle interactions is known to stimulate phase separation (demixing), but its effect on lane formation is unknown. In this work, we used Langevin dynamics (LD) simulation to probe the role of non-additivity interactions on lane formation. The competition between laning and demixing leads to thicker lanes. Analysis based on anisotropic scaling indices reveals a crossover from normal laning mode to a demixing-stimulated laning mode. Extensive numerical simulations enabled us to identify a critical value of the non-additivity parameter {Delta} for the crossover.

Du, C.-R.; Jiang, K.; Suetterlin, K. R.; Ivlev, A. V.; Morfill, G. E. [Max Planck Institute for Extraterrestrial Physics, 85748, Garching (Germany)



Oxidation Reactions of Dithiocarbamate Complexes of Ruthenium(II).  


The reaction of Ru(Et(2)dtc)(2)(DMSO)(2) (Et(2)dtc = N,N-diethyldithiocarbamate; DMSO = dimethyl sulfoxide) with t-BuNC gave trans-Ru(Et(2)dtc)(2)(CN-t-Bu)(2), 1. Complex 1 crystallizes in the monoclinic space group P2(1)/n with a = 9.753(2) Å, b = 11.583(2) Å, c = 12.974(2) Å, and beta = 91.8(2) degrees for Z = 2. The crystal structure of 1 shows the trans disposition of the two isocyanides; the mean Ru-S and Ru-C distances are 2.409 and 1.977(2) Å, respectively. Treatment of [Ru(diene)Cl(2)](n)() with Na(Et(2)dtc) afforded Ru(Et(2)dtc)(2)(diene) (diene = bicyclo[2.2.1]hepta-2,5-diene (NBD), 2, 1,5-cyclooctadiene (COD), 3). Complex 2 crystallizes in the triclinic space group P&onemacr; with a = 7.316(1) Å, b = 10.346(1) Å, c = 15.123(2) Å, alpha = 103.69(2) degrees, beta = 93.54(2) degrees, and gamma = 100.61(2) degrees for Z = 2. The mean Ru-S and Ru-C distances in 2 are 2.416 and 2.137 Å, respectively. The reaction of cis-Ru(Et(2)dtc)(2)(CO)(2) with iodine gave the 2:1 molecular iodine complex cis-Ru(Et(2)dtc)(2)(CO)(2).(1)/(2)I(2) 4, which crystallizes in the monoclinic space group P2(1)/c with a = 7.347(2), b = 22.227(2) Å, c = 12.891(2) Å, and beta =95.98 (2) degrees for Z = 4. The mean Ru-S and Ru-C and the I-I distances in complex 4 are 2.427, 1.903, and 2.745(1) Å, respectively. Treatment of Ru(Et(2)dtc)(2)(DMSO)(2) with I(2) gave the linear Ru(II)-Ru(III)-Ru(III) trimer [Ru(3)(Et(2)dtc)(6)(DMSO)(2)](I(3))(2), 5, which crystallizes in the triclinic space group P&onemacr; with a = 14.125(3) Å, b = 20.829(6) Å, c = 13.658(3) Å, alpha = 97.57(2) degrees, beta = 110.01(2) degrees, and gamma = 71.25(2) degrees for Z = 2. The structure of complex 6 can be viewed as consisting of a {Ru(2)(III)(Et(2)dtc)(4)}(2+) core and a {Ru(II)(Et(2)dtc)(2)(DMSO)(2)} moiety, which are linked together via the two dithiocarbamate sulfurs of the latter. While the two Ru(III) centers are connected by a Ru-Ru single bond (Ru-Ru = 2.826(2) Å), there is no direct interaction between the Ru(III) and Ru(II) centers. Oxidation of Ru(Et(2)dtc)(2)L(2) (L = PPh(3), t-BuNC) by I(2) gave the respective [Ru(Et(2)dtc)(2)L(2)](+) cations. The reaction of cis-Ru(Et(2)dtc)(2)(PPh(3))(2) with excess tosyl azide gave the diamagnetic Ru(IV) tetrazene complex Ru(Et(2)dtc)(2)(Ts(2)N(4)), 7. Complex 7 crystallizes in the triclinic space group P&onemacr; with a = 10.380(1) Å, b = 11.322(1) Å, c = 15.310(1) Å, alpha = 106.84(2) degrees, beta = 106.87(2) degrees, and gamma = 92.63(2) degrees for Z = 2. The Ru-S and Ru-N(alpha) distances in 7 are 2.385 and 1.98 Å, respectively. The formal potentials of the Ru dithiocarbamate complexes were determined by cyclic voltammetry. PMID:11670104

Leung, Wa-Hung; Chim, Joyce L. C.; Hou, Hongwei; Hun, Tom S. M.; Williams, Ian D.; Wong, Wing-Tak



a Model Study of Complex Behavior in the Belousov - Reaction.  

NASA Astrophysics Data System (ADS)

We have studied the complex oscillatory behavior in a model of the Belousov-Zhabotinskii (BZ) reaction in a continuously-fed stirred tank reactor (CSTR). The model consisted of a set of nonlinear ordinary differential equations derived from a reduced mechanism of the chemical system. These equations were integrated numerically on a computer, which yielded the concentrations of the constituent chemicals as functions of time. In addition, solutions were tracked as functions of a single parameter, the stability of the solutions was determined, and bifurcations of the solutions were located and studied. The intent of this study was to use this BZ model to explore further a region of complex oscillatory behavior found in experimental investigations, the most thorough of which revealed an alternating periodic-chaotic (P-C) sequence of states. A P-C sequence was discovered in the model which showed the same qualitative features as the experimental sequence. In order to better understand the P-C sequence, a detailed study was conducted in the vicinity of the P-C sequence, with two experimentally accessible parameters as control variables. This study mapped out the bifurcation sets, and included examination of the dynamics of the stable periodic, unstable periodic, and chaotic oscillatory motion. Observations made from the model results revealed a rough symmetry which suggests a new way of looking at the P-C sequence. Other nonlinear phenomena uncovered in the model were boundary and interior crises, several codimension-two bifurcations, and similarities in the shapes of areas of stability for periodic orbits in two-parameter space. Each earlier model study of this complex region involved only a limited one-parameter scan and had limited success in producing agreement with experiments. In contrast, for those regions of complex behavior that have been studied experimentally, the observations agree qualitatively with our model results. Several new predictions of the model should be easily verifiable experimentally. The wealth of behavior this detailed exploration revealed invites further experimental studies and suggests that additional refinement of the model itself is in order.

Lindberg, David Mark



Redox interaction of Mn-bicarbonate complexes with reaction centres of purple bacteria  

PubMed Central

It is found that dark reduction of photooxidized primary electron donor P870+ in reaction centres from purple anoxygenic bacteria (two non-sulphur Fe-oxidizing Rhodovulum iodosum and Rhodovulum robiginosum, Rhodobacter sphaeroides R-26 and sulphur alkaliphilic Thiorhodospira sibirica) is accelerated upon the addition of Mn2+ jointly with bicarbonate (30–75?mM). The effect is not observed if Mn2+ and HCO3? have been replaced by Mg2+ and HCO2?, respectively. The dependence of the effect on bicarbonate concentration suggests that formation of Mn2+–bicarbonate complexes, Mn(HCO3)+ and/or Mn(HCO3)2, is required for re-reduction of P870+ with Mn2+. The results are considered as experimental evidence for a hypothesis on possible participation of Mn–bicarbonate complexes in the evolutionary origin of oxygenic photosynthesis in the Archean era. PMID:17971330

Khorobrykh, A.A; Terentyev, V.V; Zharmukhamedov, S.K; Klimov, V.V



Redox interaction of Mn-bicarbonate complexes with reaction centres of purple bacteria.  


It is found that dark reduction of photooxidized primary electron donor P870+ in reaction centres from purple anoxygenic bacteria (two non-sulphur Fe-oxidizing Rhodovulum iodosum and Rhodovulum robiginosum, Rhodobacter sphaeroides R-26 and sulphur alkaliphilic Thiorhodospira sibirica) is accelerated upon the addition of Mn2+ jointly with bicarbonate (30-75 mM). The effect is not observed if Mn2+ and HCO3(-) have been replaced by Mg2+ and HCO2(-), respectively. The dependence of the effect on bicarbonate concentration suggests that formation of Mn2+-bicarbonate complexes, Mn(HCO3)+ and/or Mn(HCO3)2, is required for re-reduction of P870+ with Mn2+. The results are considered as experimental evidence for a hypothesis on possible participation of Mn-bicarbonate complexes in the evolutionary origin of oxygenic photosynthesis in the Archean era. PMID:17971330

Khorobrykh, A A; Terentyev, V V; Zharmukhamedov, S K; Klimov, V V



New fluorescence reactions in DNA cytochemistry. 2. Microscopic and spectroscopic studies on fluorescent aluminum complexes  

SciTech Connect

Metal-dye complexes are widely applied in light microscopic techniques for chromatin staining (e.g., hematoxylin and carmine), but fluorescent complexes between phosphate-binding cations and suitable ligands have been little used. Preformed and postformed Al complexes with different anionic dyes induced strong and selective fluorescence reactions in nuclei from chicken blood smears, frozen sections, paraffin-embedded sections and Epon-embedded sections of mouse and rat tissues, mitotic chromosomes, meiotic chromosomes and kinetoplasts of Trypanosoma cruzi epimastigotes. The DNA-dependent fluorescence of these structures showed a very low fading rate. The emission colors were related to the ligand. The most suitable compounds for forming fluorescent Al chelates were 8-hydroxyquinoline, morin, nuclear fast red and purpurin. Staining with diluted carmine solutions and InCl3 mordanting, followed by 8-hydroxyquinoline, also induced chromatin fluorescence. After treating isolated mouse chromosomes with the preformed complex Al-nuclear fast red, x-ray microanalysis indicated a P:Al:dye binding ratio of about 40:15:1. The selectivity, stability and easy formation of these fluorescent Al complexes are obvious advantages for their use as new cytochemical probes in cytologic studies.

Del Castillo, P.; Llorente, A.R.; Gomez, A.; Gosalvez, J.; Goyanes, V.J.; Stockert, J.C. (Autonomous Univ., Madrid (Spain))



C-NH2 bond formation mediated by iridium complexes.  


In the presence of phosphanes (PR3 ), the amido-bridged trinuclear complex [{Ir(?-NH2 )(tfbb)}3 ] (tfbb=tetrafluorobenzobarrelene) transforms into mononuclear discrete compounds [Ir(1,2-?(2) -4-?-C12 H8 F4 N)(PR3 )3 ], which are the products of the C?N coupling between the amido moiety and a vinylic carbon of the diolefin. An alternative synthetic approach to these species involves the reaction of the 18?e(-) complex [Ir(Cl)(tfbb)(PMePh2 )2 ] with gaseous ammonia and additional phosphane. DFT studies show that both transformations occur through nucleophilic attack. In the first case the amido moiety attacks a diolefin coordinated to a neighboring molecule following a bimolecular mechanism induced by the highly basic NH2 moiety; the second pathway involves a direct nucleophilic attack of ammonia to a coordinated tfbb molecule. PMID:25044533

Mena, Inmaculada; Casado, Miguel A; Polo, Víctor; García-Orduña, Pilar; Lahoz, Fernando J; Oro, Luis A



Synthesis and Hydride Transfer Reactions of Cobalt and Nickel Hydride Complexes to BX3 Compounds  

SciTech Connect

Hydrides of numerous transition metal complexes can be generated by the heterolytic cleavage of H{sub 2} gas such that they offer alternatives to using main group hydrides in the regeneration of ammonia borane, a compound that has been intensely studied for hydrogen storage applications. Previously, we reported that HRh(dmpe){sub 2}, dmpe = 1,2-bis(dimethylphosphinoethane) was capable of reducing a variety of BX{sub 3} compounds having hydride affinity (HA) greater than or equal to HA of BEt{sub 3}. This study examines the reactivity of less expensive cobalt and nickel hydride complexes, (HCo(dmpe){sub 2} and [HNi(dmpe){sub 2}]{sup +}), to form B-H bonds. The hydride donor abilities ({Delta}G{sub H{sup -}}{sup o}) of HCo(dmpe){sub 2} and [HNi(dmpe){sub 2}]{sup +} were positioned on a previously established scale in acetonitrile that is cross-referenced with calculated HAs of BX{sub 3} compounds. The collective data guided our selection of BX{sub 3} compounds to investigate and aided our analysis of factors that determine favorability of hydride transfer. HCo(dmpe){sub 2} was observed to transfer H{sup -} to BX{sub 3} compounds with X = H, OC{sub 6}F{sub 5} and SPh. The reaction with B(SPh){sub 3} is accompanied by formation of (BH{sub 3}){sub 2}-dmpe and (BH{sub 2}SPh){sub 2}-dmpe products that follow from reduction of multiple BSPh bonds and loss of a dmpe ligand from Co. Reactions between HCo(dmpe){sub 2} and B(SPh){sub 3} in the presence of triethylamine result in formation of Et{sub 3}N-BH{sub 2}SPh and Et{sub 3}N-BH{sub 3} with no loss of dmpe ligand. Reactions of the cationic complex [HNi(dmpe){sub 2}]{sup +} with B(SPh){sub 3} under analogous conditions give Et{sub 3}N-BH{sub 2}SPh as the final product along with the nickel-thiolate complex [Ni(dmpe){sub 2}(SPh)]{sup +}. The synthesis and characterization of HCo(dedpe){sub 2} (dedpe = diethyldiphenyl(phosphino)ethane) from H{sub 2} and a base is also discussed; including the formation of an uncommon trans dihydride species, trans-[(H{sub 2})Co(dedpe){sub 2}][BF{sub 4}].

Mock, Michael T.; Potter, Robert G.; O'Hagan, Molly J.; Camaioni, Donald M.; Dougherty, William G.; Kassel, W. S.; DuBois, Daniel L.



Magnetic resonance for downhole complex-lithology earth formation evaluation  

NASA Astrophysics Data System (ADS)

Many petroleum-bearing reservoirs are known as complex-lithology, complex-mineralogy earth formations where the existing nuclear magnetic resonance (NMR) analysis models require modification and extension to work properly. This paper discusses the effects of mineralogy variation in complex-lithology formation rocks that will cause NMR response variations. In particular, the existence of iron-rich authigenic clays and the nonquartz grains in siliciclastics affect the surface relaxivity and the internal field inhomogeneity. Using a simplified pore-lining clay model, we estimated that the magnitude of the internal gradient in siliciclastics is comparable with or greater than that of the instrument-generated field gradient common to the currently used NMR logging tools. To account for these effects for reservoir fluid identification and quantification from NMR data, an inversion model is created, which includes the mean susceptibility of the grain minerals, the correlation between pore size and the relaxation time of the wetting-phase fluid in the pores and the geometric restriction to the fluid molecular diffusion.

Chen, Songhua; Li, Lilong; Zhang, Gigi; Chen, Jason



Syntheses and Structures of Dinuclear Gold(I) Dithiophosphonate Complexes and the Reaction of the Dithiophosphonate Complexes with  

E-print Network

Syntheses and Structures of Dinuclear Gold(I) Dithiophosphonate Complexes and the Reaction, Cambridge, Massachusetts 02138 Received January 31, 2003 The dinuclear gold(I) dithiophosphonate complex. Introduction Gold(I) thiolate complexes have been used in a variety of applications in modern technology1

Abdou, Hanan E.


Complex Interactions between Formative Assessment, Technology, and Classroom Practices  

NSDL National Science Digital Library

Interactive engagement (IE) methods provide instructors with evidence of student thinking that can guide instructional decisions across a range of timescales: facilitating an activity, determining the flow of activities, or modifying the curriculum. Thus, from the instructor's perspective, IE activities can function as formative assessments. As a practical matter, the ability to utilize this potential depends on how the activities are implemented. This paper describes different tools for small group problem solving, including whiteboards, Tablet PCs, digital cameras, and photo-sharing websites. These tools provide the instructor with varying levels of access to student work during and after class, and therefore provide a range of support for formative assessment. Furthermore, the tools differ in physical size, ease of use, and the roles for students and instructor. These differences lead to complex, often surprising interactions with classroom practices.

Price, Edward



Complex formation between uranyl and various thiosemicarbazide derivatives  

SciTech Connect

Complex formation between hexavalent uranium and salicylaldehyde thiosemicarbazone (H/sub 2/L), salicylaldehyde S-methyl-isothiosemicarbazone (H/sub 2/Q), S-methyl-N/sub 1/,N/sub 4/-bis(salicylidene)isothiosemicarbazide(H/sub 2/Z), and thiosemicarbazidodiacetic acid (H/sub 2/R) has been studied spectrophotometrically in solution. Stability constants for complexes having the composition UO/sub 2/A have been calculated. Solid uranyl derivatives having the composition UO/sub 2/L x 2H/sub 2/O, UO/sub 2/Q x 2H/sub 2/O, UO/sub 2/Z x 2H/sub 2/O, and UO/sub 2/R x 2H/sub 2/O have been obtained. These derivatives were isolated and their IR spectroscopic behavior and thermal properties were investigated.

Chuguryan, D.G.; Dzyubenko, V.I.



Intrinsic Barriers for Electron and Hydrogen Atom Transfer Reactions of Biomimetic Iron Complexes  

E-print Network

Intrinsic Barriers for Electron and Hydrogen Atom Transfer Reactions of Biomimetic Iron Complexes. Kinetic and thermodynamic results preclude stepwise mechanisms of sequential proton and then electron) Meunier, B., Ed. Biomimetic Oxidations Catalyzed by Transition Metal Complexes; Imperial College Press

Roth, Justine P.


Noble reactions for the actinides: safe gold-based access to organouranium and azide complexes  

SciTech Connect

Gold has had a profound impact on organic chemistry; its compounds are spectacular catalysts for many organic transformations involving the formation of C-C, C-O, C-N and CoS bonds, and have enabled unprecedented pathways for the functionalization of C-H and C-C bonds. In general, gold complexes have not been exploited as reagents in organometallic or inorganic chemistry, although a few gold(l) aryl and alkynyl compounds have been reported to undergo transmetalation with transition metal complexes. We have been developing methods for functionalizing uranium complexes and have shown that Cu(l)-X reagents effect the oxidation of uranium with formation of U-X bonds, providing easy chemical control over uranium in oxidation states ranging from U{sup III}{yields}U{sup VI}. Although a logical approach for the direct generation of U-carbon and U-azide bonds, this Cu-based platform is limited in scope as it only works for pure and isolable copper compounds. This is problematic given the instability of organocuprates and copper azides, which can detonate violently as isolated solids. As such, this route has been confined to the synthesis of select uranium phenylacetylide complexes. Over the past few years, a variety of stable gold(l) alkyl, alkenyl, aryl, alkynyl, and azide complexes have been reported, propelling us to investigate their potential as reagents within the oxidative functionalization platform. Unlike the related CU{sup I} systems, Au{sup I} reagents are easily derivatized, and are safe to handle and isolate. Herein, we report that gold(l)-phosphine compounds can undergo a new class of reaction, and are excellent reagents for the oxidative functionalization of uranium with azide and carbon anions.

Thomson, Robert K [Los Alamos National Laboratory; Graves, Christopher R [Los Alamos National Laboratory; Scott, Brian L [Los Alamos National Laboratory; Kiplinger, Jaqueline L [Los Alamos National Laboratory



Multiphasic Kinetics of Myoglobin/Sodium Dodecyl Sulfate Complex Formation  

PubMed Central

We have carried out a kinetic analysis of the conformational changes that myoglobin (Mb) undergoes in the presence of the anionic surfactant sodium dodecyl sulfate (SDS). The time-resolved results have been combined with steady-state circular dichroism (CD) and resonance Raman (RR) spectroscopy. Time-resolved absorption spectra indicate that SDS induces changes in the heme coordination with the formation of three different Mb species, depending on SDS concentration. The formation of the Mb/SDS complex involves three or four phases, depending on surfactant concentration. The kinetic data are analyzed assuming two modes of interaction according to whether SDS is monomeric or micellar. The two pathways are separated but interconnected through free Mb. At the lowest concentrations a six-coordinated, low-spin form dominates. Two distinct five-coordinated species are formed at higher SDS concentrations: one is a protein-free heme and the other reequilibrates slowly with the six-coordinated, low-spin form. The resulting complexes have been characterized by CD and RR. In addition, CD spectra show that the local changes in the heme environment are coupled to changes in the protein structure. PMID:17369406

Feis, Alessandro; Tofani, Luca; De Sanctis, Giampiero; Coletta, Massimo; Smulevich, Giulietta



Reaction path and crystallograpy of cobalt silicide formation on silicon(001) by reaction deposition epitaxy  

NASA Astrophysics Data System (ADS)

CaF2-structure CoSi2 layers were formed on Si(001) by reactive deposition epitaxy (RDE) and compared with CoSi2 layers obtained by conventional solid phase growth (SPG). In the case of RDE, CoSi 2 formation occurred during Co deposition at elevated temperature while for SPG, Co was deposited at 25°C and silicidation took place during subsequent annealing. My results demonstrate that RDE CoSi2 layers are epitaxial with a cube-on-cube relationship, 001CoSi2 ?001Si and 100CoSi2 ?100 Si . In contrast, SPG films are polycrystalline with a mixed 111/002/022/112 orientation. I attribute the striking difference to rapid Co diffusion during RDE for which the high Co/Si reactivity gives rise to a flux-limited reaction resulting in the direct formation of the disilicide phase. Initial formation of CoSi2(001) follows the Volmer-Weber mode with two families of island shapes: inverse pyramids and platelets. The rectangular-based pyramidal islands extend along orthogonal <110> directions, bounded by four {111} CoSi2/Si interfaces, and grow with a cube-on-cube orientation with respect to Si(001). Platelet-shaped islands are bounded across their long <110> directions by {111} twin planes and their narrow <110> directions by 511CoSi2 ?111Si interfaces. The top and bottom surfaces are {22¯1}, with 22¯1 CoSi2?001 Si , and {1¯1¯1}, with 1¯1¯ 1CoSi2? 11¯1Si , respectively. The early stages of film growth (tCo ? 13 A) are dominated by the twinned platelets due to a combination of higher nucleation rates and rapid elongation along preferred <110> directions. However, at tCo ? 13 A, island coalescence becomes significant as orthogonal platelets intersect and block elongation along fast growth directions. Further island growth becomes dominated by the untwinned islands. I show that high-flux low-energy Ar+ ion irradiation during RDE growth dramatically increases the area fraction of untwinned regions from 0.17 in films grown under standard magnetically balanced conditions in which the ratio JAr+/JCo of the incident Ar> to Co fluxes is 1.4 to 0.72 with JAr+/JCo= 13.3. TEM analyses reveal that increasing JAr+/J Co results in larger values of both the number density and area of untwinned islands. The intense Ar+ ion bombardment under high-ion-flux conditions creates additional low-energy adsorption sites that favor the nucleation of untwinned islands and collisionally enhances the Co adatom surface mobility which, in turn, increases the probability of itinerant Co adatoms reaching these sites.

Lim, Chong Wee


Incipient species formation in salamanders of the Ensatina complex  

PubMed Central

The Ensatina eschscholtzii complex of plethodontid salamanders, a well-known “ring species,” is thought to illustrate stages in the speciation process. Early research, based on morphology and coloration, has been extended by the incorporation of studies of protein variation and mitochondrial DNA sequences. The new data show that the complex includes a number of geographically and genetically distinct components that are at or near the species level. The complex is old and apparently has undergone instances of range contraction, isolation, differentiation, and then expansion and secondary contact. While the hypothesis that speciation is retarded by gene flow around the ring is not supported by molecular data, the general biogeographical hypothesis is supported. There is evidence of a north to south range expansion along two axes, with secondary contact and completion of the ring in southern California. Current research targets regions once thought to show primary intergradation, but which molecular markers reveal to be zones of secondary contact. Here emphasis is on the subspecies E. e. xanthoptica, which is involved in four distinct secondary contacts in central California. There is evidence of renewed genetic interactions upon recontact, with greater genetic differentiation within xanthoptica than between it and some of the interacting populations. The complex presents a full array of intermediate conditions between well-marked species and geographically variable populations. Geographically differentiated segments represent a diversity of depths of time of isolation and admixture, reflecting the complicated geomorphological history of California. Ensatina illustrates the continuing difficulty in making taxonomic assignments in complexes studied during species formation. PMID:9223261

Wake, David B.



Viewer Reactions to Content and Presentational Format of Television News  

Microsoft Academic Search

From the theoretical perspective of activation theory and using an on-line, real-time, computerized response system, the purpose of the present study was to investigate the pattern of viewer reactions to local television newscasts. Of specific concern was the overall interest pattern for the entire newscast, as well as comparative interest levels for the various component segments and the characteristics of

Ralph R. Behnke; Phyllis Miller



Catalytic asymmetric carbon-carbon bond-forming reaction utilizing rare earth metal complexes  

Microsoft Academic Search

Novel optically active rare earth complexes have made possible a catalytic asymmetric nitroaldol reaction for the first time. Structural elucidation reveals that the complexes consist of one rare earth metal, three lithium atoms, and three BINOL units. Applications of the catalytic asymmetric nitroaldol reaction to syntheses of several p-blockers and erythro-AYA have been also achieved. Although the lithium containing rare

Masakatsu Shibasaki; Hiroaki Sasai



Sodium ferric gluconate complex in hemodialysis patients: Adverse reactions compared to placebo and iron dextran  

Microsoft Academic Search

Sodium ferric gluconate complex in hemodialysis patients: Adverse reactions compared to placebo and iron dextran.BackgroundParenteral iron is often required by hemodialysis patients to maintain adequate iron stores. Until recently, the only available form of intravenous iron was iron dextran, which is associated with significant adverse reactions, including anaphylaxis and death. Sodium ferric gluconate complex (SFGC) was recently approved for use

Beckie Michael; Daniel W. Coyne; Steven Fishbane; Vaughn Folkert; Robert Lynn; Allen R. Nissenson; Rajiv Agarwal; Joseph W. Eschbach; Stephen Z. Fadem; J. Richard Trout; Jur Strobos; David G. Warnock



Catalytic Reactions of DNT and TNT Molecules on Porphyrin Complexes  

NASA Astrophysics Data System (ADS)

Reactions of molecules with substrates can be used to identify them, as in sensor applications. Here we examine reactions of DNT and TNT molecules on porphyrin and metal-porphyrin via first-principles DFT calculations. We find that the oxidation of DNT by O2 using Fe-porphyrin as a catalyst is exothermic. The affinity of O2 to Fe-porphyrin weakens the O2 intramolecular bond, which lowers the oxidation reaction barrier is lowered by ˜1 eV. Substrate effects on this process are accounted for. One way to use this selective oxidation reaction for DNT/TNT sensor applications is to exploit the metal-semiconductor transition in thin-film VO2 to detect the energy deposited by the exothermic reaction between the adsorbed molecules. This work was supported in part by DTRA grant HDTRA1-10-0047.

Warnick, Keith; Wang, Bin; Pantelides, Sokrates



Complex Reaction Dynamics in the Cerium-Bromate-2-Methyl-1,4-hydroquinone Photoreaction.  


Spontaneous oscillations with a long induction time were observed in the bromate-2-methyl-1,4-hydroquinone photoreaction in a batch reactor, where removal of illumination effectively quenched any reactivity. A substantial lengthening of the oscillatory window and a dramatic increase in the complexity of the reaction behavior arose upon the addition of cerium ions, in which separate bifurcation regions and mixed mode oscillations were present. The complexity has a strong dependence on the intensity of illumination supplied to the system and on the initial concentrations of the reactants. (1)H NMR spectroscopy measurements show that the photoreduction of 2-methyl-1,4-benzoquinone leads to the formation of 2-methyl-1,4-hydroquinone and the compound 2-hydroxy-3-methyl-1,4-benzoquinone. Spectroscopic investigation also indicates that the presence of methyl group hinders the bromination of the studied organic substrate 2-methyl-1,4-hydroquinone, resulting in the formation of 2-methyl-1,4-benzoquinone. PMID:25279948

Bell, Jeffrey G; Green, James R; Wang, Jichang



Formation of methyl nitrite in the surface reaction of nitrogen dioxide and methanol. 1. Dark reaction  

Microsoft Academic Search

The reaction of nitrogen dioxide and methanol which has been known in the gas phase to proceed thermally as CHâOH + 2NOâ ..-->.. CHâONO + HNOâ, was found to proceed heterogeneously on various surfaces as well, in an 11-L Pyrex cell and a 6065-L evacuable smog chamber. An FTIR study has revealed that the reaction products are the same as

Hiroo Takagi; Shiro Hatakeyama; Hajime Akimoto; Seiichiro Koda



Structural Assessment of D-Regions Affected by Alkali-Silica Reaction/Delayed Ettringite Formation  

E-print Network

A combined experimental and analytical program was conducted to investigate the effects of Alkali-Silica Reaction (ASR) and Delayed Ettringite Formation (DEF) on D-regions in reinforced concrete (RC) bridge bents. Four large-scale RC specimens...

Liu, Shih-Hsiang 1979-



Kinetics of Enol Formation from Reaction of OH with Propene  

Microsoft Academic Search

Kinetics of enol generation from propene has been predicted in an effort to understand the presence of enols in flames. A potential energy surface for reaction of OH with propene was computed by CCSD(T)\\/cc-pVDZ\\/\\/ B3LYP\\/cc-pVTZ calculations. Rate constants of different product channels and branching ratios were then calculated using the Master Equation formulation ( J. Phys. Chem. A 2006 ,

Lam K. Huynh; Hongzhi R. Zhang; Shaowen Zhang; Eric Eddings; Adel Sarofim; Matthew E. Law; Phillip R. Westmoreland; Thanh N. Truong



Physical volcanology of the Gubisa Formation, Kone Volcanic Complex, Ethiopia  

NASA Astrophysics Data System (ADS)

Despite their significance for understanding the potential environmental factors involved in hominin evolution in Ethiopia, very few modern volcanologic studies have been carried out on the Quaternary calderas and associated silicic tephra deposits of the Ethiopian Rift. We present here the second of a set of papers reporting the findings of fieldwork and laboratory analyses of one of the largest of these structures, Kone Caldera, located within the Kone Volcanic Complex in the northern Main Ethiopian Rift. The most recent major episode of explosive eruptive activity at Kone Caldera was apparently associated with formation of part of the overall 8-km-diameter collapse area, and deposited a widely-dispersed alkali rhyolite tephra that reaches a thickness of up to 60 m in vent-proximal deposits. We report here the physical characteristics of this unit in order to constrain eruptive conditions. The pumice fall deposit suggests that an abrupt decrease in magma discharge rate occurred part way through the eruption.

Rampey, Michael L.; Oppenheimer, Clive; Pyle, David M.; Yirgu, Gezahegn



Molybdenum alkylidene complexes : syntheses and applications to olefin metathesis reactions  

E-print Network

Chapter 1. Alkylimido Molybdenum Complexes: Synthesis, Characterization and Activity as Chiral Olefin Metathesis Catalysts. Molybdenum olefin metathesis catalysts that contain previously unexplored aliphatic 1- ...

Pilyugina, Tatiana



Fluoridonitrosyl complexes of technetium(I) and technetium(II). Synthesis, characterization, reactions, and DFT calculations.  


A mixture of [Tc(NO)F5](2-) and [Tc(NO)(NH3)4F](+) is formed during the reaction of pertechnetate with acetohydroxamic acid (Haha) in aqueous HF. The blue pentafluoridonitrosyltechnetate(II) has been isolated in crystalline form as potassium and rubidium salts, while the orange-red ammine complex crystallizes as bifluoride or PF6(-) salts. Reactions of [Tc(NO)F5](2-) salts with HCl give the corresponding [Tc(NO)Cl4/5](-/2-) complexes, while reflux in neat pyridine (py) results in the formation of the technetium(I) cation [Tc(NO)(py)4F](+), which can be crystallized as hexafluoridophosphate. The same compound can be synthesized directly from pertechnetate, Haha, HF, and py or by a ligand-exchange procedure starting from [Tc(NO)(NH3)4F](HF2). The technetium(I) cation [Tc(NO)(NH3)4F](+) can be oxidized electrochemically or by the reaction with Ce(SO4)2 to give the corresponding Tc(II) compound [Tc(NO)(NH3)4F](2+). The fluorido ligand in [Tc(NO)(NH3)4F](+) can be replaced by CF3COO(-), leaving the "[Tc(NO)(NH3)4](2+) core" untouched. The experimental results are confirmed by density functional theory calculations on [Tc(NO)F5](2-), [Tc(NO)(py)4F](+), [Tc(NO)(NH3)4F](+), and [Tc(NO)(NH3)4F](2+). PMID:24797021

Balasekaran, Samundeeswari Mariappan; Spandl, Johann; Hagenbach, Adelheid; Köhler, Klaus; Drees, Markus; Abram, Ulrich



Module Based Complexity Formation: Periodic Patterning in Feathers and Hairs  

PubMed Central

Patterns describe order which emerges from homogeneity. Complex patterns on the integument are striking because of their visibility throughout an organism's lifespan. Periodic patterning is an effective design because the ensemble of hair or feather follicles (modules) allows the generation of complexity, including regional variations and cyclic regeneration, giving the skin appendages a new lease on life. Spatial patterns include the arrangements of feathers and hairs in specified number, size, and spacing. We explore how a field of equivalent progenitor cells can generate periodically arranged modules based on genetic information, physical-chemical rules and developmental timing. Reconstitution experiments suggest a competitive equilibrium regulated by activators / inhibitors involving Turing reaction-diffusion. Temporal patterns result from oscillating stem cell activities within each module (micro-environment regulation), reflected as growth (anagen) and resting (telogen) phases during the cycling of feather and hair follicles. Stimulating modules with activators initiates the spread of regenerative hair waves, while global inhibitors outside each module (macro-environment) prevent this. Different wave patterns can be simulated by Cellular Automata principles. Hormonal status and seasonal changes can modulate appendage phenotypes, leading to “organ metamorphosis”, with multiple ectodermal organ phenotypes generated from the same precursors. We discuss potential evolutionary novel steps using this module based complexity in several amniote integument organs, exemplified by the spectacular peacock feather pattern. We thus explore the application of the acquired knowledge of patterning in tissue engineering. New hair follicles can be generated after wounding. Hairs and feathers can be reconstituted through self-organization of dissociated progenitor cells. PMID:23539312

Chuong, Cheng-Ming; Yeh, Chao-Yuan; Jiang, Ting-Xin; Widelitz, Randall



Direct detection of key reaction intermediates in photochemical CO2 reduction sensitized by a rhenium bipyridine complex.  


Photochemical CO2 reduction sensitized by rhenium-bipyridyl complexes has been studied through multiple approaches during the past several decades. However, a key reaction intermediate, the CO2-coordinated Re-bipyridyl complex, which should govern the activity of CO2 reduction in the photocatalytic cycle, has never been detected in a direct way. In this study on photoreduction of CO2 catalyzed by the 4,4'-dimethyl-2,2'-bipyridine (dmbpy) complex, [Re(dmbpy)(CO)3Cl] (1), we successfully detect the solvent-coordinated Re complex [Re(dmbpy)(CO)3DMF] (2) as the light-absorbing species to drive photoreduction of CO2. The key intermediate, the CO2-coordinated Re-bipyridyl complex, [Re(dmbpy)(CO)3(COOH)], is also successfully detected for the first time by means of cold-spray ionization spectrometry (CSI-MS). Mass spectra for a reaction mixture with isotopically labeled (13)CO2 provide clear evidence for the incorporation of CO2 into the Re-bipyridyl complex. It is revealed that the starting chloride complex 1 was rapidly transformed into the DMF-coordinated Re complex 2 through the initial cycle of photoreduction of CO2. The observed induction period in the time profile of the CSI-MS signals can well explain the subsequent formation of the CO2-coordinated intermediate from the solvent-coordinated Re-bipyridyl complex. An FTIR study of the reaction mixture in dimethyl sulfoxide clearly shows the appearance of a signal at 1682 cm(-1), which shifts to 1647 cm(-1) for the (13)CO2-labeled counterpart; this is assigned as the CO2-coordinated intermediate, Re(II)-COOH. Thus, a detailed understanding has now been obtained for the mechanism of the archetypical photochemical CO2 reduction sensitized by a Re-bipyridyl complex. PMID:24689747

Kou, Youki; Nabetani, Yu; Masui, Dai; Shimada, Tetsuya; Takagi, Shinsuke; Tachibana, Hiroshi; Inoue, Haruo



Scope and mechanism of formal S(N)2' substitution reactions of a monomeric imidozirconium complex with allylic electrophiles.  


The zirconium imido complex Cp2(THF)Zr=NSi(t-Bu)Me2 (1) reacts with allylic ethers, chlorides, and bromides to give exclusively the products of the SN2' reaction; i.e., attack at the allylic position remote from the leaving group with migration of the double bond. The primary amine products can be isolated in excellent yields, after in situ Cbz protection, in the presence of variety of functional groups. Good diastereoselectivity and complete stereoselectivity allowed the formation of enantioenriched allylic amines from enantioenriched allylic ethers. Regiospecific substitution with 1 has also been achieved with allylic fluorides, which are notoriously poor substrates in other substitution reactions. On the basis of rate and kinetic isotope effect studies, we propose a general mechanism for the allylic substitution reactions with 1 which involves dissociation of THF and binding of the substrate, followed by the substitution step. In a DFT study of the substitution reaction, we identified a six-membered closed transition state for the substitution step and other relevant stationary points along the reaction coordinate. This study shows that the substitution reaction can be described as a concerted asynchronous [3,3]-sigmatropic rearrangement. This detailed knowledge of the reaction mechanism provides a rationale for the origins of the observed regio-, diastereo-, and stereoselectivity and of the unusual reactivity profile observed in the reaction. PMID:18327942

Lalic, Gojko; Krinsky, Jamin L; Bergman, Robert G



Complex behavior of self-propagating reaction waves in heterogeneous media  

PubMed Central

Self-propagating high temperature reaction waves, leading to the synthesis of advanced materials, are investigated in a variety of heterogeneous reaction systems by using a digital high-speed microscopic video recording technique. It is shown that, although on the macroscopic length and time scales, the reaction appears to move in a steady mode, on the microscopic level it has a complex character that is related to the reaction mechanism. PMID:9736688

Varma, Arvind; Rogachev, Alexander S.; Mukasyan, Alexander S.; Hwang, Stephen



Study of the Ternary Complex Formation Between Vanadium(III), Dipicolinic Acid and Small Blood Serum Bioligands  

Microsoft Academic Search

Ternary complex formation reactions were studied between vanadium(III), dipicolinic acid and small molecular weight blood\\u000a serum components: lactic, oxalic, citric and ortophosphoric acids. The electromotive force measurement permitted us to determine\\u000a the chemical speciation of the complexes formed. In the vanadium(III)–dipicolinic acid–lactic acid system the complexes detected\\u000a were: V(dipic)(lac), V(dipic)(lac)(OH)? and V(dipic)(lac). In the vanadium(III)–dipicolinic acid–oxalic acid system the observed

Freya Da Costa; Giuseppe Lubes; Mildred Rodríguez; Vito Lubes



Kinetics and mechanism of reactions of the drug tiopronin with platinum(IV) complexes.  


Tiopronin, a synthetic thiol-containing drug being used in treatments of cystinuria and certain types of rare arthritis, is also a hepatoprotective and a detoxifying agent. Many analytical methods have been developed based on its redox chemistry with metal ions/complexes, but the kinetic and mechanistic aspects are poorly understood. In this work, the oxidation of tiopronin by cisplatin prodrug and a model compound, cis-[Pt(NH3)2Cl4] and trans-[PtCl2(CN)4](2-), was investigated. The oxidation kinetics was followed by a stopped-flow spectrophotometer over a wide pH range under the pseudo first-order conditions of [Tiopronin]?[Pt(IV)]. Time-resolved spectra were also recorded for both Pt(IV) complexes, enabling to establish an overall second-order rate law: -d[Pt(IV)]/dt=k'[Tiopronin][Pt(IV)], where k' pertains to observed second-order rate constants. Under the kinetic conditions, tiopronin was oxidized to form the tiopronin-disulfide exclusively as identified by mass spectrometry. A reaction mechanism was proposed, involving parallel reductions of the Pt(IV) complexes by the three protolytic tiopronin species as rate-determining steps. The rate constants for the rate-determining steps were derived. The fully deprotonated tiopronin is about 4×10(4) more reactive than its corresponding thiol form for both Pt(IV) complexes; the huge reactivity difference orchestrates closely with the fact that the nucleophilicity of thiolate is much higher than the corresponding thiol. Hence, the attack of the sulfur atom in thiol/thiolate of tiopronin on the axially-coordinated chloride in the Pt(IV) complexes is nucleophilic in nature in the rate-determining steps, resulting in a bridge formation and a subsequent bridged electron-transfer. PMID:23665090

Huo, Shuying; Shi, Hongmei; Liu, Dongzhi; Shen, Shigang; Zhang, Jiong; Song, Changying; Shi, Tiesheng



Incorporation of polyoxotungstate complexes in silica spheres and in situ formation of tungsten trioxide nanoparticles.  


In this paper, we demonstrated a new convenient route for in situ fabrication of well separated small sized WO(3) nanoparticles in silica spheres, through a predeposition of surfactant encapsulated polyoxotungates as tungsten source, and followed by a calcination process. In a typical procedure, selected polyoxotungates with different charges were enwrapped with dioctadecyldimethylammonium cations through electrostatic interaction. Elemental analysis, thermogravimetric analysis, and spectral characterization confirmed the formation of prepared complexes with the anticipated chemical structure. The complexes were then phase-transferred into aqueous solution that predissolved surfactant cetyltrimethylammonium bromide, and finally incorporated into silica spheres through a joint sol-gel reaction with tetraethyl orthosilicate in a well dispersed state under the protection of organic layer for polyoxotungates from the alkaline reaction condition. Transmission electron microscopic images illustrated the well dispersed WO(3) nanoparticles in the size range of ca. 2.2 nm in the silica spheres after the calcination at 465 °C. The sizes of both the silica spheres and WO(3) nanoparticles could be adjusted independently through changing the doping content to a large extent. Meanwhile, the doped polyoxotungate complexes acted as the template for the mesoporous structure in silica spheres after the calcination. Along with the increase of doping content and surfactant, the mesopore size changed little (2.0-2.9 nm), but the specific surface areas increased quite a lot. Importantly, the WO(3)-nanoparticle-doped silica spheres displayed an interesting photovoltaic property, which is favorable for the funtionalization of these nanomaterials. PMID:20715875

Zhao, Yuanyuan; Fan, Haimei; Li, Wen; Bi, Lihua; Wang, Dejun; Wu, Lixin



A Macroscopic Reaction: Direct Covalent Bond Formation between Materials Using a Suzuki-Miyaura Cross-Coupling Reaction  

NASA Astrophysics Data System (ADS)

Cross-coupling reactions are important to form C-C covalent bonds using metal catalysts. Although many different cross-coupling reactions have been developed and applied to synthesize complex molecules or polymers (macromolecules), if cross-coupling reactions are realized in the macroscopic real world, the scope of materials should be dramatically broadened. Here, Suzuki-Miyaura coupling reactions are realized between macroscopic objects. When acrylamide gel modified with an iodophenyl group (I-gel) reacts with a gel possessing a phenylboronic group (PB-gel) using a palladium catalyst, the gels bond to form a single object. This concept can also be adapted for bonding between soft and hard materials. I-gel or PB-gel selectively bonds to the glass substrates whose surfaces are modified with an electrophile or nucleophile, respectively.

Sekine, Tomoko; Kakuta, Takahiro; Nakamura, Takashi; Kobayashi, Yuichiro; Takashima, Yoshinori; Harada, Akira



Kinetic modeling of polychlorinated dibenzo-p-dioxin and dibenzofuran formation based on carbon degradation reactions.  


Combustion experiments in a laboratory-scale fixed bed reactor were performed to determine the role of temperature and time in polychlorinated dibenzo-p-dioxin (PCDD) and polychlorinated dibenzofuran (PCDF) formation, allowing a global kinetic expression to be written for PCDD/F formation due to soot oxidation in fly ash deposits. Rate constants were calculated for the reactions of carbon degradation, PCDD/F formation, desorption, and degradation. For the first time, values for activation and thermodynamic parameters for the overall reactions have been calculated for PCDD/F formation, desorption, and destruction reactions. Good agreement was found between the calculated rate constants for carbon degradation and for PCDD/F formation, indicating that the two processes have a common rate-determining step. Moreover, PCDD/F formation was found to be still active after long reaction times (24 h). These results points out the importance of carbon deposits in the postcombustion stages that can account for emissions long after their formation (memory effects). The calculated formation rates were 7-15 times higher than those reported in the literature from fly ash-only experiments, indicating the importance of both soot and a continuous source of chlorine. A comparison between full-scale incinerator rates and model calculated rates indicates that our model based on carbon degradation kinetic can be a tool to estimate emissions. PMID:18939549

Grandesso, Emanuela; Ryan, Shawn; Gullett, Brian; Touati, Abderrahmane; Collina, Elena; Lasagni, Marina; Pitea, Demetrio



Paper Number 15736-PA Title Reaction Kinetics of Fuel Formation for In-Situ Combustion  

E-print Network

believed to cause fuel formation for in-situ combustion have been studied and modeled. A thin, packed bedPaper Number 15736-PA Title Reaction Kinetics of Fuel Formation for In-Situ Combustion Authors Abu-Khamsin, Sidqi A., Stanford U.; Brigham, William E., Stanford U.; Ramey Jr., Henry J., Stanford U. Journal SPE

Abu-Khamsin, Sidqi


Reaction mechanism of Ru(II) piano-stool complexes: umbrella sampling QM/MM MD study.  


Biologically relevant interactions of piano-stool ruthenium(II) complexes with ds-DNA are studied in this article by hybrid quantum mechanics-molecular mechanics (QM/MM) computational technique. The whole reaction mechanism is divided into three phases: (i) hydration of the [Ru(II) (?(6) -benzene)(en)Cl](+) complex, (ii) monoadduct formation between the resulting aqua-Ru(II) complex and N7 position of one of the guanines in the ds-DNA oligomer, and (iii) formation of the intrastrand Ru(II) bridge (cross-link) between two adjacent guanines. Free energy profiles of all the reactions are explored by QM/MM MD umbrella sampling approach where the Ru(II) complex and two guanines represent a quantum core, which is described by density functional theory methods. The combined QM/MM scheme is realized by our own software, which was developed to couple several quantum chemical programs (in this study Gaussian 09) and Amber 11 package. Calculated free energy barriers of the both ruthenium hydration and Ru(II)-N7(G) DNA binding process are in good agreement with experimentally measured rate constants. Then, this method was used to study the possibility of cross-link formation. One feasible pathway leading to Ru(II) guanine-guanine cross-link with synchronous releasing of the benzene ligand is predicted. The cross-linking is an exergonic process with the energy barrier lower than for the monoadduct reaction of Ru(II) complex with ds-DNA. PMID:24865949

Futera, Zden?k; Burda, Jaroslav V



The formate-pyruvate exchange reaction by Streptococcus faecalis  

E-print Network

of these inter. . onversions kn . '. ; metabokksm are kinked ivkth derivatives of tetrehydrofolic acid. '}uennekens et al. (1958), emphasi'. ed the role of reduced folic acid as the co?nzyme or carrier of Ci groups. t, " right et al. (1958) showed, in a... bacterial system. that folic acid may be reduced to dihydrofolic acid by pyruvic ox}des?. Pine and Guthrie (1959) studied the influence of folic acid in the lncorporatlon of formats-C14 into the pyrimidine ring of thiagdne. ", 'hiteley et al. (1959) have...

Yeager, Robert Lee



The formation of illite from nontronite by mesophilic and thermophilic bacterial reaction  

USGS Publications Warehouse

The formation of illite through the smectite-to-illite (S-I) reaction is considered to be one of the most important mineral reactions occurring during diagenesis. In biologically catalyzed systems, however, this transformation has been suggested to be rapid and to bypass the high temperature and long time requirements. To understand the factors that promote the S-I reaction, the present study focused on the effects of pH, temperature, solution chemistry, and aging on the S-I reaction in microbially mediated systems. Fe(III)-reduction experiments were performed in both growth and non-growth media with two types of bacteria: mesophilic (Shewanella putrefaciens CN32) and thermophilic (Thermus scotoductus SA-01). Reductive dissolution of NAu-2 was observed and the formation of illite in treatment with thermophilic SA-01 was indicated by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). A basic pH (8.4) and high temperature (65??C) were the most favorable conditions forthe formation of illite. A long incubation time was also found to enhance the formation of illite. K-nontronite (non-permanent fixation of K) was also detected and differentiated from the discrete illite in the XRD profiles. These results collectively suggested that the formation of illite associated with the biologically catalyzed smectite-to-illite reaction pathway may bypass the prolonged time and high temperature required for the S-I reaction in the absence of microbial activity.

Jaisi, D.P.; Eberl, D.D.; Dong, H.; Kim, J.



Kinetic study of model reactions in the gas phase at the early stage of coke formation  

SciTech Connect

This paper reports that the most probable gas-phase reactions at the early stage of coke formation were elucidated by kinetic study on the model reactions adopted for formation of cyclic compounds and growth of ring. It was revealed that the formation and growth of ring proceeded mainly through cycloaddition of butadiene or allyl radicals to unsaturated hydrocarbons at relatively low temperatures ({approximately}600{degrees}C), i.e., through a Diels-Alder type reaction. On the other hand, such growth of ring as formation of biphenyl accompanying dehydrogenation from benzene can proceed only at the higher temperatures. It was also revealed that in the growth of the ring, cycloaddition of butadiene favors a cyclic olefin molecule that possesses a nonconjugated double bond and a nearly planar structure.

Nohara, D.; Sakai, T. (Dept. of Chemical Reaction Engineering, Faculty of Pharmaceutical Sciences, Nagoya City Univ., Mizuho-ku, Nagoya 467 (JP))



The ?-Effect and Competing Mechanisms: The Gas-Phase Reactions of Microsolvated Anions with Methyl Formate  

NASA Astrophysics Data System (ADS)

The enhanced reactivity of ?-nucleophiles, which contain an electron lone pair adjacent to the reactive site, has been demonstrated in solution and in the gas phase and, recently, for the gas-phase SN2 reactions of the microsolvated HOO-(H2O) ion with methyl chloride. In the present work, we continue to explore the significance of microsolvation on the ?-effect as we compare the gas-phase reactivity of the microsolvated ?-nucleophile HOO-(H2O) with that of microsolvated normal alkoxy nucleophiles, RO-(H2O), in reactions with methyl formate, where three competing reactions are possible. The results reveal enhanced reactivity of HOO-(H2O) towards methyl formate, and clearly demonstrate the presence of an overall ?-effect for the reactions of the microsolvated ?-nucleophile. The association of the nucleophiles with a single water molecule significantly lowers the degree of proton abstraction and increases the SN2 and BAC2 reactivity compared with the unsolvated analogs. HOO-(H2O) reacts with methyl formate exclusively via the BAC2 channel. While microsolvation lowers the overall reaction efficiency, it enhances the BAC2 reaction efficiency for all anions compared with the unsolvated analogs. This may be explained by participation of the solvent water molecule in the BAC2 reaction in a way that continuously stabilizes the negative charge throughout the reaction.

Thomsen, Ditte L.; Nichols, Charles M.; Reece, Jennifer N.; Hammerum, Steen; Bierbaum, Veronica M.



Reactions of nitric oxide with mitochondrial cytochrome c: a novel mechanism for the formation of nitroxyl anion and peroxynitrite.  

PubMed Central

The aerobic reactions of nitric oxide with cytochrome c were analysed. Nitric oxide (NO) reacts with ferrocytochrome c at a rate of 200 M-1 s-1 to form ferricytochrome c and nitroxyl anion (NO-). Ferricytochrome c was detected by optical spectroscopy; NO- was detected by trapping with metmyoglobin (Mb3+) to form the EPR-detectable Mb-nitrosyl complex, and by the formation of dimers in yeast ferrocytochrome c via cross-linking of the free cysteine residue. The NO- formed subsequently reacted with oxygen to form peroxynitrite, as measured by the oxidation of dihydrorhodamine 123. NO binds to ferricytochrome c to form the ferricytochrome c-NO complex. The on-rate for this reaction is 1.3+/-0.4x10(3) M-1.s-1, and the off-rate is 0.087+/-0.054 s-1. The dissociation constant (Kd) of the complex is 22+/-7 microM. These reactions of NO with cytochrome c are likely to be relevant to mitochondrial metabolism of NO. Ferricytochrome c can act as a reversible sink for excess NO in the mitochondria. The reduction of NO to NO- by ferrocytochrome c may play a role in the irreversible inhibition of mitochondrial oxygen consumption by peroxynitrite. It is generally assumed that peroxynitrite would be formed in mitochondria via the reaction of NO with superoxide. The finding that NO- is formed from the reaction of NO and ferrocytochrome c provides a means of producing peroxynitrite in the absence of superoxide, via the reaction of NO- with oxygen. PMID:9576846

Sharpe, M A; Cooper, C E




Microsoft Academic Search

Summary. The Shroud of Turin is a large piece of linen that shows the faint image of a man on its surface: it has been claimed to be the shroud of Jesus. Here we report evidences that colour can be produced by reactions between reducing sugars, left on the cloth by the manufacturing procedure, and amines deriving from the decomposition

Raymond N. Rogers; Anna Arnoldi


Deciphering complex soil/site formation in sands  

NASA Astrophysics Data System (ADS)

This paper summarizes aspects of the geoarchaeological research at two adjacent multi-component archaeological sites, 13JP86 and 13JP87, along Indian Creek in central Iowa, USA. The sites, both recently salvaged but now destroyed, formed in late Pleistocene sands reworked from glacial sediments that emanated from the wasting Des Moines Lobe glacier some 13,000-14,000 years ago. The soils contained shallowly dispersed and mixed artifacts that span the Paleoindian-to-historic cultural spectrum. In open areas, as at Indian Creek, site formation processes equate to natural soil genetic processes, plus human imprints. Cultural materials, once deposited, become part of the soil and subject to dynamic soil processes. These soils had reasonably well expressed Ap, A, and E horizons that collectively formed thick one-layered biomantles, underlain by well expressed argillic Bt horizons. The biomantles had been well bioturbated, deeply in some pedons, but still exhibited organized A and E horizons. The Bt horizons were also bioturbated, though less so, and consisted of multiple thin to thick sandy clay bands, termed illuvial clay lamellae (icl's). The icl's contained modest to appreciable amounts of illuvial clay as bridges between grains, and as diffuse splotches and blebs separated by less clayey, E horizon-like interlamellar sandy zones. Deeper and less bioturbated E-like sandy zones had accumulated so much clay that they had coalesced with icl's into thick, complexly banded argillic Bt horizons. The process histories of the sandy pedons were obviously extremely complex. The geoarchaeological aspects of the project, which were mainly complex pedologic ones, were largely interpreted by drawing on the genetic principles of dynamic denudation to explain soil/site evolution. Many questions were raised, and most were answered under these principles. New concepts and perspectives were gained in this study, and the resulting interpretive scenarios carry explanatory implications for sandy soils everywhere, whether charged with cultural materials or not.

Johnson, D. L.; Johnson, D. N.; Benn, D. W.; Bettis, E. A., III



Flow partitioning in the lithosphere during core complex formation: An interactive evolutionary computation  

E-print Network

Flow partitioning in the lithosphere during core complex formation: An interactive evolutionary the dynamics of core complex formation in a three-layer model of the lithosphere. In this method a mathematical largely by lower crustal flow. Introduction Metamorphic core complexes form when continental lithosphere

Boschetti, Fabio


Complementarity of reaction force and electron localization function analyses of asynchronicity in bond formation in Diels-Alder reactions.  


We have computationally compared three Diels-Alder cycloadditions involving cyclopentadiene and substituted ethylenes; one of the reactions is synchronous, while the others are slightly or highly asynchronous. Synchronicity and weak asynchronicity are characterized by the reaction force constant ?(?) having just a single minimum in the transition region along the intrinsic reaction coordinate ?, while for high asynchronicity ?(?) has a negative maximum with minima on both sides. The electron localization function (ELF) shows that the features of ?(?) can be directly related to the formation of the new C-C bonds between the diene and the dienophile. There is thus a striking complementarity between ?(?) and ELF; ?(?) identifies the key points along ? and ELF describes what is happening at those points. PMID:24589878

Yepes, Diana; Murray, Jane S; Pérez, Patricia; Domingo, Luis R; Politzer, Peter; Jaque, Pablo



Reactions of Group III Biheterocyclic Complexes Colin T. Carver,  

E-print Network

oil supplies dictate a shift toward hydrocarbon sources containing larger amounts of N-heterocy- cles external bases and electrophilic reagents. The strong thorium-oxygen bond can drive the ring-opening of pyridine- N-oxides by thorium bis-cyclopentadienyl complexes.24 In a previous communication, the ring

Goddard III, William A.


Star Formation in the Northern Cloud Complex of NGC 2264  

NASA Astrophysics Data System (ADS)

We have made continuum and spectral line observations of several outflow sources in the Mon OB1 dark cloud (NGC 2264) using the Heinrich Hertz Telescope (HHT) and ARO 12 m millimeter-wave telescope. This study explores the kinematics and outflow energetics of the young stellar systems observed and assesses the impact star formation is having on the surrounding cloud environment. Our data set incorporates 12CO (3-2),13CO (3-2), and 12CO (1-0) observations of outflows associated with the sources IRAS 06382+1017 and IRAS 06381+1039, known as IRAS 25 and 27, respectively, in the northern cloud complex. Complementary 870 ?m continuum maps were made with the HHT 19 channel bolometer array. Our results indicate there is a weak <=0.5% coupling between outflow kinetic energy and turbulent energy of the cloud. An analysis of the energy balance in the IRAS 25 and 27 cores suggests they are maintaining their dynamical integrity except where outflowing material directly interacts with the core, such as along the outflow axes.

Hedden, Abigail S.; Walker, Christopher K.; Groppi, Christopher E.; Butner, Harold M.



Adhesion and formation of microbial biofilms in complex microfluidic devices  

SciTech Connect

Shewanella oneidensis is a metal reducing bacterium, which is of interest for bioremediation and clean energy applications. S. oneidensis biofilms play a critical role in several situations such as in microbial energy harvesting devices. Here, we use a microfluidic device to quantify the effects of hydrodynamics on the biofilm morphology of S. oneidensis. For different rates of fluid flow through a complex microfluidic device, we studied the spatiotemporal dynamics of biofilms, and we quantified several morphological features such as spatial distribution, cluster formation and surface coverage. We found that hydrodynamics resulted in significant differences in biofilm dynamics. The baffles in the device created regions of low and high flow in the same device. At higher flow rates, a nonuniform biofilm develops, due to unequal advection in different regions of the microchannel. However, at lower flow rates, a more uniform biofilm evolved. This depicts competition between adhesion events, growth and fluid advection. Atomic force microscopy (AFM) revealed that higher production of extra-cellular polymeric substances (EPS) occurred at higher flow velocities.

Kumar, Aloke [ORNL; Karig, David K [ORNL; Neethirajan, Suresh [University of Guelph; Suresh, Anil K [ORNL; Srijanto, Bernadeta R [ORNL; Mukherjee, Partha P [ORNL; Retterer, Scott T [ORNL; Doktycz, Mitchel John [ORNL



Integrin activation and focal complex formation in cardiac hypertrophy  

NASA Technical Reports Server (NTRS)

Cardiac hypertrophy is characterized by both remodeling of the extracellular matrix (ECM) and hypertrophic growth of the cardiocytes. Here we show increased expression and cytoskeletal association of the ECM proteins fibronectin and vitronectin in pressure-overloaded feline myocardium. These changes are accompanied by cytoskeletal binding and phosphorylation of focal adhesion kinase (FAK) at Tyr-397 and Tyr-925, c-Src at Tyr-416, recruitment of the adapter proteins p130(Cas), Shc, and Nck, and activation of the extracellular-regulated kinases ERK1/2. A synthetic peptide containing the Arg-Gly-Asp (RGD) motif of fibronectin and vitronectin was used to stimulate adult feline cardiomyocytes cultured on laminin or within a type-I collagen matrix. Whereas cardiocytes under both conditions showed RGD-stimulated ERK1/2 activation, only collagen-embedded cells exhibited cytoskeletal assembly of FAK, c-Src, Nck, and Shc. In RGD-stimulated collagen-embedded cells, FAK was phosphorylated only at Tyr-397 and c-Src association occurred without Tyr-416 phosphorylation and p130(Cas) association. Therefore, c-Src activation is not required for its cytoskeletal binding but may be important for additional phosphorylation of FAK. Overall, our study suggests that multiple signaling pathways originate in pressure-overloaded heart following integrin engagement with ECM proteins, including focal complex formation and ERK1/2 activation, and many of these pathways can be activated in cardiomyocytes via RGD-stimulated integrin activation.

Laser, M.; Willey, C. D.; Jiang, W.; Cooper, G. 4th; Menick, D. R.; Zile, M. R.; Kuppuswamy, D.



Reaction layer formation at the graphite/copper-chromium alloy interface  

NASA Technical Reports Server (NTRS)

Sessile drop tests were used to obtain information about copper chromium alloys that suitably wet graphite. Characterization of graphite/copper-chromium alloy interfaces subjected to elevated temperatures were conducted using scanning electron micrography, energy dispersive spectroscopy, Auger electron spectroscopy, and X-ray diffraction analyses. These analyses indicate that during sessile drop tests conducted at 1130 C for one hour, copper alloys containing greater than 0.98 percent chromium form continuous reaction layers of approximately 10 micron thickness. The reaction layers adhere to the graphite surface. The copper wets the reaction layer to form a contact angle of 60 degrees or less. X-ray diffraction results indicate that the reaction layer is chromium carbide. The kinetics of reaction layer formation were modelled in terms of bulk diffusion mechanisms. Reaction layer thickness is controlled initially by the diffusion of Cr out of Cu alloy and later by the diffusion of C through chromium carbide.

Devincent, Sandra M.; Michal, Gary M.



Reaction layer formation at the graphite/copper-chromium alloy interface  

NASA Technical Reports Server (NTRS)

Sessile drop tests were used to obtain information about copper chromium alloys that suitably wet graphite. Characterization of graphite/copper-chromium alloy interfaces subjected to elevated temperatures were conducted using scanning electron micrography, energy dispersive spectroscopy, auger electron spectroscopy, and x ray diffraction analyses. These analyses indicate that during sessile drop tests conducted at 1130 C for one hour, copper alloys containing greater than 0.98 percent chromium form continuous reaction layers of approximately 10 micron thickness. The reaction layers adhere to the graphite surface. The copper wets the reaction layer to form a contact angle of 60 degrees or less. X ray diffraction results indicate that the reaction layer is chromium carbide. The kinetics of reaction layer formation were modelled in terms of bulk diffusion mechanisms. Reaction layer thickness is controlled initially by the diffusion of Cr out of Cu alloy and later by the diffusion of C through chromium carbide.

Devincent, Sandra M.; Michal, Gary M.



A peroxynitrite complex of copper: formation from a copper-nitrosyl complex, transformation to nitrite and exogenous phenol oxidative coupling or nitration  

PubMed Central

Reaction of nitrogen monoxide with a copper(I) complex possessing a tridentate alkylamine ligand gives a Cu(I)–(·NO) adduct, which when exposed to dioxygen generates a peroxynitrite (O=NOO?)–Cu(II) species. This undergoes thermal transformation to produce a copper(II) nitrito (NO2?) complex and 0.5 mol equiv O2. In the presence of a substituted phenol, the peroxynitrite complex effects oxidative coupling, whereas addition of chloride ion to dissociate the peroxynitrite moiety instead leads to phenol ortho nitration. Discussions include the structures (including electronic description) of the copper–nitrosyl and copper–peroxynitrite complexes and the formation of the latter, based on density functional theory calculations and accompanying spectroscopic data. PMID:19662443

Park, Ga Young; Deepalatha, Subramanian; Puiu, Simona C.; Lee, Dong-Heon; Mondal, Biplab; Sarjeant, Amy A. Narducci; del Rio, Diego; Pau, Monita Y. M.; Solomon, Edward I.; Karlin, Kenneth D.



Complex Structure Formation in a Ternary Mixture Driven Through the Patterned Microchannel  

NASA Astrophysics Data System (ADS)

Through the computer simulations, we probe the behavior of a A/B/C ternary mixture in which two immiscible components, A and B, undergo the interfacial chemical reaction and produce third component, C. The reverse chemical reaction, namely consumption of the A and B species from the C components, is also possible. This mixture is driven by the imposed pressure gradient (Poiseuille flow) through the three dimensional microchannel. The microchannel is decorated with chemically distinct patches that display preferential wetting interactions for the A or B components. Namely, A(B)-like patches are placed in the way of B(A)-rich fluid stream. At the beginning of the simulation two streams of fluid, A and B, are flowing parallel each other. As system evolves to it's steady state, the C component is formed in the A/B interfacial area. Simultaneously, A(B) reach fluid diffuses to A(B) -like patches, so that two stream flow distorts and additional interfacial regions, where chemical reaction may occur, are created. Interplay between the advection of all three components by imposed flow and all the diffusion processes in the presence of spatially non-uniform interactions with the substrate, lead to the formation of complex structures, periodic in space and time.

Kuksenok, Olga; Balazs, Anna



Mechanism for the uncatalyzed cyclic acetone-peroxide formation reaction: an experimental and computational study.  


In this study, a mechanism for the uncatalyzed reaction between acetone and hydrogen peroxide is postulated. The reaction leads to the formation of the important homemade explosives collectively known as cyclic acetone peroxides (CAP). The proposed mechanistic scheme is based on Raman, GC-MS, and nuclear magnetic resonance measurements, and it is supported by ab initio density functional theory (DFT) calculations. The results demonstrate that the proposed mechanism for the uncatalyzed formation reaction of CAP occurs in three steps: monomer formation, polymerization of the 2-hydroperoxipropan-2-ol monomer, and cyclization. The temporal decay of the intensities of important assigned-bands is in excellent agreement with the proposed mechanism. Previous reports also confirm that the polymerization step is favored in comparison to other possible pathways. PMID:24050655

Espinosa-Fuentes, Eduardo A; Pacheco-Londoño, Leonardo C; Hidalgo-Santiago, Migdalia; Moreno, Martha; Vivas-Reyes, Ricardo; Hernández-Rivera, Samuel P



Formation of degradation compounds from lignocellulosic biomass in the biorefinery: sugar reaction mechanisms.  


The degradation compounds formed during pretreatment when lignocellulosic biomass is processed to ethanol or other biorefinery products include furans, phenolics, organic acids, as well as mono- and oligomeric pentoses and hexoses. Depending on the reaction conditions glucose can be converted to 5-(hydroxymethyl)-2-furaldehyde (HMF) and/or levulinic acid, formic acid and different phenolics at elevated temperatures. Correspondingly, xylose can follow different reaction mechanisms resulting in the formation of furan-2-carbaldehyde (furfural) and/or various C-1 and C-4 compounds. At least four routes for the formation of HMF from glucose and three routes for furfural formation from xylose are possible. In addition, new findings show that biomass monosaccharides themselves can react further to form pseudo-lignin and humins as well as a wide array of other compounds when exposed to high temperatures. Hence, several aldehydes and ketones and many different organic acids and aromatic compounds may be generated during hydrothermal treatment of lignocellulosic biomass. The reaction mechanisms are of interest because the very same compounds that are possible inhibitors for biomass processing enzymes and microorganisms may be valuable biobased chemicals. Hence a new potential for industrial scale synthesis of chemicals has emerged. A better understanding of the reaction mechanisms and the impact of the reaction conditions on the product formation is thus a prerequisite for designing better biomass processing strategies and forms an important basis for the development of new biorefinery products from lignocellulosic biomass as well. PMID:24412507

Rasmussen, Helena; Sørensen, Hanne R; Meyer, Anne S



Atomistic theory of mesoscopic pattern formation induced by bimolecular surface reactions between oppositely charged molecules  

NASA Astrophysics Data System (ADS)

The kinetics of mesoscopic pattern formation is studied for a reversible A+B?0 reaction between mobile oppositely charged molecules at the interface. Using formalism of the joint correlation functions, non-equilibrium charge screening and reverse Monte Carlo methods, it is shown that labyrinth-like percolation structure induced by (even moderate-rate) reaction is principally non-steady-state one and is associated with permanently growing segregation of dissimilar reactants and aggregation of similar reactants into mesoscopic size domains. A role of short-range and long-range reactant interactions in pattern formation is discussed.

Kuzovkov, V. N.; Kotomin, E. A.; Zvejnieks, G.



EUV resist simulation based on process parameters of pattern formation reaction  

NASA Astrophysics Data System (ADS)

We simulated the process parameters of a pattern formation reaction that included during-the-exposure and post exposure bake (PEB) processes using an originally developed simulator. From the simulation results, the relationship between process parameters of pattern formation reaction and quencher concentration has been clarified. Moreover, we simulated the present target process parameters of extreme ultraviolet (EUV) resist for breaking the RLS trade-off. In this simulation, the process parameters were calculated from lithographic results (sensitivity, LWR, and CD) using real SEM images. This methodology was used to determine the process parameters required to break the RLS trade-off to obtain the required lithographic target of the EUV resist. We simulated the present lithography performance target using the process parameters of pattern formation reactions. These simulation results showed that a large reaction radius is necessary to break the RLS trade-off. Furthermore, we confirmed that increasing the PEB temperature leads to an improvement in the reaction radius. However, there is a discrepancy between the target radius and the controllable range of reaction radius that can be obtained by varying the PEB temperature.

Sugie, Norihiko; Itani, Toshiro; Kozawa, Takahiro



H2O3 as a reactive oxygen species: formation of 8-oxoguanine from its reaction with guanine.  


Reaction of guanine with H2O3 in the absence and presence of a water molecule leading to the formation of 8-oxoguanine (8-oxoG) was investigated. Initial calculations were performed using imidazole (Im) as a model for the five-membered ring of guanine. The reactant, intermediate, and product complexes as well as transition states were obtained in gas phase at the B3LYP/6-31+G* and B3LYP/AUG-cc-pVDZ levels of theory. In all the cases, except for the reactions involving imidazole, single-point energy calculations were performed in gas phase at the MP2/AUG-cc-pVDZ level of theory. Solvation calculations in aqueous media were carried out using the polarizable continuum model (PCM) of the self-consistent reaction field (SCRF) theory. Vibrational frequency analysis and intrinsic reaction coordinate (IRC) calculations were performed to ensure that the transition states connected the reactant and product complexes properly. Zero-point energy (ZPE)-corrected total energies and Gibbs free energies at 298.15 K in gas phase and aqueous media were obtained. When a reaction of H2O3 in place of H2O2 with guanine is considered, the major barrier energy which is encountered at the first step is almost halved showing that H2O3 would be much more reactive than H2O2. Considering the reaction schemes investigated here and the observed fact that H2O3 is dissociated easily under ambient conditions, it appears that H2O3 would serve as an effective reactive oxygen species. PMID:17417902

Shukla, P K; Mishra, P C



Statistical considerations on the formation of circular photosynthetic light-harvesting complexes from Rhodopseudomonas palustris.  


Depending on growth conditions, some species of purple photosynthetic bacteria contain peripheral light-harvesting (LH2) complexes that are heterogeneous owing to the presence of different protomers (containing different ??-apoproteins). Recent spectroscopic studies of Rhodopseudomonas palustris grown under low-light conditions suggest the presence of a C 3-symmetric LH2 nonamer comprised of two distinct protomers. The software program Cyclaplex, which enables generation and data-mining of virtual libraries of molecular rings formed upon combinatorial reactions, has been used to delineate the possible number and type of distinct nonamers as a function of numbers of distinct protomers. The yield of the C 3-symmetric nonamer from two protomers (A and B in varying ratios) has been studied under the following conditions: (1) statistical, (2) enriched (preclusion of the B-B sequence), and (3) seeded (pre-formation of an A-B-A block). The yield of C 3-symmetric nonamer is at most 0.98 % under statistical conditions versus 5.6 % under enriched conditions, and can be dominant under conditions of pre-seeding with an A-B-A block. In summary, the formation of any one specific nonamer even from only two protomers is unlikely on statistical grounds but must stem from enhanced free energy of formation or a directed assembly process by as-yet unknown factors. PMID:24510549

Taniguchi, Masahiko; Henry, Sarah; Cogdell, Richard J; Lindsey, Jonathan S



Ubiquinol oxidation in the cytochrome bc1 complex: Reaction mechanism and prevention of short-circuiting  

E-print Network

Review Ubiquinol oxidation in the cytochrome bc1 complex: Reaction mechanism and prevention This review is focused on the mechanism of ubiquinol oxidation by the cytochrome bc1 complex (bc1 oxidized, the reduced FeS domain remains docked to cytochrome b until electron(s) pass through cytochrome b

Steinhoff, Heinz-Jürgen


Reactions in HostGuest Complexes Molecular Mousetraps: Gas-Phase Studies of the  

E-print Network

Reactions in Host­Guest Complexes Molecular Mousetraps: Gas-Phase Studies of the Covalent Coupling of purposes.[1,2] These noncovalent complexes are easily transferred to the gas phase by electrospray. May The Arnold and Mabel Beckman Laboratories of Chemical Syn- thesis, Division of Chemistry

Stoltz, Brian M.


Stark effect spectroscopy of carotenoids in photosynthetic antenna and reaction center complexes  

Microsoft Academic Search

The effects of electric fields on the absorption spectra of the carotenoids spheroidene and spheroidenone in photosynthetic antenna and reaction center complexes (wild-type and several mutants) from purple non-sulfur bacteria are compared with those for the isolated pigments in organic glasses. In general, the field effects are substantially larger for the carotenoid in the protein complexes than for the extracted

David S. Gottfried; Martin A. Steffen; Steven G. Boxer



Selenium-ligated palladium(II) complexes as highly active catalysts for carbon-carbon coupling reactions: the Heck reaction.  


Three selenium-ligated Pd(II) complexes were readily synthesized and shown to be extremely active catalysts for the Heck reaction of various aryl bromides, including deactivated and heterocyclic ones. The catalytic activity of the selenide-based Pd(II) complexes not only rivals but vastly outperforms that of the corresponding phosphorus and sulfur analogues. Practical advantages of the selenium-based catalysts include their straightforward synthesis and high activity in the absence of any additives as well as the enhanced stability of the selenide ligands toward air oxidation. PMID:15330667

Yao, Qingwei; Kinney, Elizabeth P; Zheng, Chong



Reaction Rates for the Formation of Deuterium Tritide from Deuterium and Tritium  

SciTech Connect

The rates of formation of DT in a mixture of D2 and T2 have been measured as a function of initial T2 concentration, pressure, temperature,and methane concentration in a stainless steel reaction container which had been treated to inhibit protium ingrowth. An attempt has been made to explain the experimental resuts on the basis of ion-molecule chain reactions. Some of the observations are consistent with a gas-phase ion, ground-state molecule reaction, but some of the more interesting observations require more complicated models. The addition of excited state molecules or heterogeneous catalytic effects are possibilities that will need further experiments for confirmation.

McConville, G. T.; Menke, D. A.; Ellefson, R. E.



Reactions of Complex Phenols on Aerosols with Gaseous Ozone  

NASA Astrophysics Data System (ADS)

We report that ?-tocopherol (?-TOH/?-TO-), as a model of substituted phenols in atmosphere, reacts with closed shell O3(g) on the surface of inert solvent microdroplets within 1 ms to produce persistent (n = 1 - 4) adducts detectable by online electrospray ionization mass spectrometry. The prototype phenolate PhO- undergoes electron transfer under identical conditions. These reactions occur at the gas/liquid interface since their rates: (1) depend on pH, (2) are several orders of magnitude faster than those in the bulk of O33-saturated microdroplets, and (3) approach O3(g) mass accommodation rates. Furthermore, they fail to incorporate solvent into the products: the same species are formed on acetonitrile or nucleophilic methanol microdroplets. Signals initially evolve with the concentration of ozone as expected from first-generation species. However, ?-TO- reacts further with ozone via a collision-induced dissociation into a C19H40 fragment (vs. C19H38 from ?-TO-, carrying the phytyl side-chain, whereas the higher homologues (?-TO-On ? 2-) are not reactive with O3(g). On this basis, ?-TO- is assigned to a chroman-6-ol (4a, 8a)-ene oxide (an epoxide), ?-TO-O2- to an endoperoxide, and ?-TO-O3- to a secondary ozonide. These products are previous unreported. The atmospheric degradation of the substituted phenols detected in forest fires and combustion emissions is therefore expected to produce related oxidants on aerosol particles.

Hoffmann, M. R.; Enami, S.; Colussi, A. J.



Synthesis, mechanism of formation, and catalytic activity of Xantphos nickel ?-complexes.  


A general synthetic route to the first Xantphos nickel alkyne and alkene complexes has been discovered. Various Ni ?-complexes were prepared and characterized. NMR experiments indicate benzonitrile undergoes ligand exchange with a Xantphos ligand of (Xant)2Ni, a compound that was previously believed to be unreactive. The Ni ?-complexes were also shown to be catalytically competent in cross coupling and cycloaddition reactions. (Xant)2Ni is also catalytically active for these reactions when activated by a nitrile or coordinating solvent. PMID:25356514

Staudaher, Nicholas D; Stolley, Ryan M; Louie, Janis



An isoelectronic NO dioxygenase reaction using a nonheme iron(III)-peroxo complex and nitrosonium ion.  


Reaction of a nonheme iron(III)-peroxo complex, [Fe(III)(14-TMC)(O2)](+), with NO(+), a transformation which is essentially isoelectronic with that for nitric oxide dioxygenases [Fe(III)(O2?(-)) + NO], affords an iron(IV)-oxo complex, [Fe(IV)(14-TMC)(O)](2+), and nitrogen dioxide (NO2), followed by conversion to an iron(III)-nitrato complex, [Fe(III)(14-TMC)(NO3)(F)](+). PMID:24394960

Yokoyama, Atsutoshi; Han, Jung Eun; Karlin, Kenneth D; Nam, Wonwoo



Formation of core-shell structured composite microparticles via cyclic gas-solid reactions.  


This work reports a novel low-cost and environmental-friendly preparation strategy for core-shell structured composite microparticles and discusses its formation mechanism. Different from most conventional strategies, which involve coating or coating-like processes, this reported strategy uses irreversible solid-phase ionic diffusion in a gas-solid reaction cycle (e.g., reduction and oxidation of Fe) to gradually move the shell material from a core-and-shell material mixture microparticle to the surface. Without the need for solvent as do many conventional processes, this novel process only involves gas-solid reactions, which reduces environmental impact. To substantiate this conceived strategy, a micrometer-sized microparticle made up of a mixture of Fe2O3 and Al2O3 powders is first reduced by H2 and then oxidized by O2 over 50 cycles at 900 °C. These reactions are known to proceed mainly through the diffusion of solid-phase Fe cations. SEM and EDX analyses verify the formation of an Al2O3 core-Fe2O3 shell structure at the end of the 50 reaction cycles. If the cyclic reactions of a microparticle proceed mainly through the diffusion of gaseous-reactant-derived O anions such as the mixture of Fe2O3 and TiO2 instead of solid-phase Fe cation diffusion, no formation of the core-shell structure is observed in the resulting microparticle. These two opposing results underscore the dominating role of solid-phase ionic diffusion in the formation of the core-shell structure. A 2-D continuum diffusion model is applied to account for the inter-Fe-particle bridging and directional product layer growth phenomena during an oxidation reaction. The simulation further verifies the conceived core-shell formation strategy. PMID:24044419

Sun, Zhenchao; Zhou, Qiang; Fan, Liang-Shih



Redox reactions of Cu(II)-amine complexes in aqueous solutions  

NASA Astrophysics Data System (ADS)

A number of amines can be employed for all volatile treatment (AVT) of steam generator (SG) systems of nuclear power reactors. These amines form complexes with Cu 2+ and Ni 2+ ions which come into water due to corrosion. The redox reactions of a number of Cu(II)-AVT amine complexes and the stability of the transient species formed have been studied by pulse radiolysis technique. Rate constants for the reaction of e aq- with a number of Cu(II)-amine complexes have been determined by following the decay of e aq- absorption. Stability of Cu(I)-amine complexes was studied by following the kinetics of the bleaching signal formed at the ?max of the Cu(II) amine complex. Except for Cu(I)-triethanolamine complex all other Cu(I)-amine complexes were found to be stable. One-electron oxidation of Cu(II) amine complexes was studied using azidyl radicals for the oxidation reaction as OH radicals react with the alcohol groups present in the amines used in this study. Cu(III)-amine complexes were found to be unstable and decayed by second-order kinetics.

Kumbhar, A. G.; Kishore, Kamal



Oligomerization reactions of deoxyribonucleotides on montmorillonite clay - The effect of mononucleotide structure on phosphodiester bond formation  

NASA Technical Reports Server (NTRS)

The formation of oligomers from deoxynucleotides, catalyzed by Na(+)-montmorillonite, was investigated with special attention given to the effect of the monomer structure on the phosphodiester bond formation. It was found that adenine deoxynucleotides bind more strongly to montmorillonite than do the corresponding ribonucleotides and thymidine nucleotides. Tetramers of 2-prime-dpA were detected in the reaction of 2-prime-d-5-prime-AMP with a water-soluble carbodiimide EDAC in the presence of Na(+)-montmorillonite, illustrating the possible role of minerals in the formation of biopolymers on the primitive earth.

Ferris, James P.; KAMALUDDIN



Theoretical investigation of the thermodynamic structures and kinetic water-exchange reactions of aqueous Al(III)-salicylate complexes  

NASA Astrophysics Data System (ADS)

Density functional theory (DFT) calculations were performed on the structures and water-exchange reactions of aqueous Al(III)-salicylate complexes. Based on the four models (gas phase (GP); polarizable continuum model (PCM), which estimates the bulk solvent effect; supermolecule model (SM), which considers the explicit solvent effect, and supermolecule-polarizable continuum model (SM-PCM), which accounts for both types of solvent effects), we systematically conducted this study by examining three different properties of the complexes. (1) The microscopic properties of the aqueous Al(III)-salicylate complexes were studied by optimizing their various structures (including the possible 1:1 mono- and bidentate complexes, cis and trans isomers of the 1:2 bidentate complexes and 1:3 bidentate complexes) at the B3LYP/6-311+G(d, p) level. (2) The 27Al and 13C NMR chemical shifts were calculated using the GIAO method at the HF/6-311+G(d, p) level. The calculation results show that the values obtained with the SM-PCM models are in good agreement with the experimental data available in the literature, indicating that the models we employed are appropriate for Al(III)-salicylate complexes. (3) The water-exchange reactions of 1:1 mono- and bidentate Al(III)-salicylate complexes were simulated using supermolecule models at the B3LYP/6-311+G(d, p) level. The logarithm of the water-exchange rate constant (log kex) of the 1:1 bidentate complex predicted using the “log kex-dAl-OH2” correlation is 4.0, which is in good agreement with the experimental value of 3.7, whereas the calculated range of log kex of the 1:1 monodentate complexes is 1.3-1.9. By effectively combining the results for the thermodynamic static structures with the simulations of the kinetic water-exchange reactions, this work promotes further understanding of the configurations and formation mechanism of Al(III)-salicylate complexes.

Shi, Wenjing; Jin, Xiaoyan; Dong, Shaonan; Bi, Shuping



Interfacial reactions in the formation of ohmic contacts to wide bandgap semiconductors  

NASA Astrophysics Data System (ADS)

The influence of interfacial reactions on the formation of ohmic contacts to GaAs, ZnSe and GaN based semiconductor layers is reviewed. In the case of semiconductors whose Fermi levels are not pinned (ZnSe and GaN), disruption of interfacial contamination layers is critical during the interfacial reaction step. In these cases, interfacial phase formation appears to be detrimental to the contact properties. In GaAs where the Fermi level is pinned near midgap, interfacial reactions which consist of dissociation of the GaAs lattice and regrowth of this lattice in the presence of a dopant, are critical to successful formation of the ohmic contact. Dopant incorporation during GaAs regrowth leads to a heavily doped surface layer, charge transport across the interface by thermionic field emission, and ohmic behavior with a low specific contact resistance. The most difficult contacts to form are those to p-type ZnSe and GaN since the top of the valence band is at too low an energy to match with the work function of any known metal or compound. To date no metallization scheme has been identified which will lead to lattice reactions with ZnSe or GaN and yield a p ++ surface layer and subsequent ohmic contact formation.

Holloway, P. H.; Kim, T.-J.; Trexler, J. T.; Miller, S.; Fijol, J. J.; Lampert, W. V.; Haas, T. W.



Optical and Modeling Studies of Sodium/Halide Reactions for the Formation of Titanium and Boron  

E-print Network

for reaction were found to dramatically influence the reactive flow. Simulations using a counterflow diffusion also be used to form a variety of metals as well as ceramic powders such as TiB2. The gas the influence of concentration and transport on particle formation. Reactant concentration and time available

Zachariah, Michael R.



E-print Network


Granada, Universidad de


Formation of Secondary Particulate Matter by Reactions of Gas Phase Hexanal with Sulfate Aerosol Particles  

NASA Astrophysics Data System (ADS)

The formation of secondary particulate matter from the atmospheric oxidation of organic compounds can significantly contribute to the particulate burden, but the formation of organic secondary particulate matter is poorly understood. One way of producing organic secondary particulate matter is the oxidation of hydrocarbons with seven or more carbon atoms to get products with low vapor pressure. However, several recent reports suggest that relatively low molecular weight carbonyls can enter the particle phase by undergoing heterogeneous reactions. This may be a very important mechanism for the formation of organic secondary particulate matter. Atmospheric aldehydes are important carbonyls in the gas phase, which form via the oxidation of hydrocarbons emitted from anthropogenic and biogenic sources. In this poster, we report the results on particle growth by the heterogeneous reactions of hexanal. A 5 L Continuous Stirred Tank Reactor (CSTR) is set up to conduct the reactions in the presence of seed aerosol particles of deliquesced ammonia bisulfate. Hexanal is added into CSTR by syringe pump, meanwhile the concentrations of hexanal are monitored with High Pressure Liquid Chromatograph (HPLC 1050). A differential Mobility Analyzer (TSI 3071) set to an appropriate voltage is employed to obtain monodisperse aerosols, and another DMA associated with a Condensation Nuclear Counter (TSI 7610) is used to measure the secondary particle size distribution by the reaction in CSTR. This permits the sensitive determination of particle growth due to the heterogeneous reaction, very little growth occurs when hexanal added alone. Results for the simultaneous addition of hexanal and alcohols will also be presented.

Zhang, J.



Calculated formation and reaction energies of 3d transition metal oxides using a hierachy of exchange-correlation functionals  

NASA Astrophysics Data System (ADS)

The formation and oxidation reaction energies of 16 transition metal oxides (TMOs) are benchmarked against experiments with an increasing complexity of the exchange-correlation (xc) functionals: PBE, PBE + U with a single U for each transition metal element, PBE0 (25% exact exchange included), EXX (100% exact exchange), and EXX + RPA (random phase approximation for the correlation energy). Although rather challenging on standard CPU computing facilities, the RPA calculations were performed efficiently on graphic processing units (GPUs). For the formation energies, the PBE + U, PBE0, EXX + RPA improves significantly over PBE with mean absolute errors (MAE) of 0.83 (PBE), 0.39 (PBE + U), 0.34 (PBE0), and 0.39 (EXX + RPA) eV per oxygen. In addition, EXX + RPA improves over the other xc functionals on the oxidation reaction energies, with MAE of 0.27 (PBE), 0.28 (PBE + U), 0.30 (PBE0), to 0.13 (EXX + RPA) eV per oxygen. The distinct trend observed for the calculated oxidation reaction energies compared to the formation energies is due to that the errors in formation energies for PBE and EXX + RPA are systematic; while for PBE + U and PBE0 the deviations have both signs, so that the error cancellations between different valence states work better for PBE and EXX + RPA. Finally, we compared the performance of the EXX + RPA for total energies and G0W0, which uses the random phase approximation in constructing the W kernel, for band gaps, and discuss a few challenges for the EXX + RPA method on TMOs.

Yan, Jun; Nørskov, Jens K.



Formation and use of poly-L-histidine-catalase complexes  

Microsoft Academic Search

Insoluble complexes of poly-L-histidine (polyhistidine) and catalase were prepared by mixing the two reactants together in solution at pH 5.5 and subsequently elevating the pH to approximately 7.0, at which point they precipitated. Complexes formed at optimal ratios of polyhistidine to catalase contained essentially all of the catalase present in the original solution. The catalase present in such complexes contained

Douglas Gibbs; James Varani; Isaac Ginsburg



Hair dye-incorporated poly-?-glutamic acid/glycol chitosan nanoparticles based on ion-complex formation  

PubMed Central

Background p-Phenylenediamine (PDA) or its related chemicals are used more extensively than oxidative hair dyes. However, permanent hair dyes such as PDA are known to have potent contact allergy reactions in humans, and severe allergic reactions are problematic. Methods PDA-incorporated nanoparticles were prepared based on ion-complex formation between the cationic groups of PDA and the anionic groups of poly(?-glutamic acid) (PGA). To reinforce PDA/PGA ion complexes, glycol chitosan (GC) was added. PDA-incorporated nanoparticles were characterized using field-emission scanning electron microscopy, Fourier- transform infrared (FT-IR) spectroscopy, dynamic light scattering, and powder X-ray diffractometry (XRD). Results Nanoparticles were formed by ion-complex formation between the amine groups of PDA and the carboxyl groups of PGA. PDA-incorporated nanoparticles are small in size (<100 nm), and morphological observations showed spherical shapes. FT-IR spectra results showed that the carboxylic acid peak of PGA decreased with increasing PDA content, indicating that the ion complexes were formed between the carboxyl groups of PGA and the amine groups of PDA. Furthermore, the intrinsic peak of the carboxyl groups of PGA was also decreased by the addition of GC. Intrinsic crystalline peaks of PDA were observed by XRD. This crystalline peak of PDA was completely nonexistent when nanoparticles were formed by ion complex between PDA, PGA, and GC, indicating that PDA was complexed with PGA and no free drug existed in the formulation. During the drug-release experiment, an initial burst release of PDA was observed, and then PDA was continuously released over 1 week. Cytotoxicity testing against HaCaT human skin keratinocyte cells showed PDA-incorporated nanoparticles had lower toxicity than PDA itself. Furthermore, PDA-incorporated nanoparticles showed reduced apoptosis and necrosis reaction at HaCaT cells. Conclusion The authors suggest that these microparticles are ideal candidates for a vehicle for decreasing side effects of hair dye. PMID:22131834

Lee, Hye-Young; Jeong, Young-IL; Choi, Ki-Choon



Secondary organic aerosol formation initiated from reactions between ozone and surface-sorbed squalene  

NASA Astrophysics Data System (ADS)

Previous research has shown that ozone reactions on surface-sorbed D-limonene can promote gas phase secondary organic aerosol (SOA) formation indoors. In this work, we conducted 13 steady state chamber experiments to measure the SOA formation entirely initiated by ozone reactions with squalene sorbed to glass, at chamber ozone of 57-500 ppb for two relative humidity (RH) conditions of 21% and 51%, in the absence of seed particles. Squalene is a nonvolatile compound that is a component of human skin oil and prevalent on indoor surfaces and in settled dust due to desquamation. The size distributions, mass and number secondary emission rates (SER), aerosol mass fractions (AMF), and aerosol number fractions (ANF) of formed SOA were quantified. The surface AMF and ANF are defined as the change in SOA mass or number formed, respectively, per ozone mass consumed by ozone-squalene reactions. All experiments but one exhibited nucleation and mass formation. Mass formation was relatively small in magnitude and increased with ozone, most notably for the RH = 51% experiments. The surface AMF was a function of the chamber aerosol concentration, and a multi-product model was fit using the 'volatility basis set' framework. Number formation was relatively strong at low ozone and low RH conditions. Though we cannot extrapolate our results because experiments were conducted at high air exchange rates, we speculate that this process may enhance particle number more than mass concentrations indoors.

Wang, Chunyi; Waring, Michael S.



Implementation of the NCN pathway of prompt-NO formation in the detailed reaction mechanism  

SciTech Connect

This work presents revised detailed reaction mechanism for small hydrocarbons combustion with possibly full implementation of available kinetic data related to the prompt NO route via NCN. It was demonstrated that model predictions with the rate constant of reaction CH + N{sub 2} = NCN + H measured by Vasudevan and co-workers are much higher than experimental concentrations of NO in rich premixed flames at atmospheric pressure. Analysis of the correlations of NO formation with calculated concentrations of C{sub 2}O radicals strongly supports the inclusion of reaction between C{sub 2}O and N{sub 2} and reduction of the rate constant of reaction between CH and N{sub 2}. Rate constants of the reactions of NCN consumption were mostly taken from the works of Lin and co-workers. Some of these reactions affect calculated profiles of NCN in flames. Proposed modifications allow accurate prediction of NO formation in lean and rich flames of methane, ethylene, ethane and propane. Agreement of the experiments and the modeling was much improved as compared to the previous Release 0.5 of the Konnov mechanism. Satisfactory agreement with available measurements of NCN radicals in low pressure flames was also demonstrated. (author)

Konnov, A.A. [Department of Mechanical Engineering, Technische Universiteit Eindhoven, P.O. Box 513, 5600 MB Eindhoven (Netherlands)



Lattice Boltzmann study of pattern formation in reaction-diffusion systems  

NASA Astrophysics Data System (ADS)

Pattern formation in reaction-diffusion systems is of great importance in surface micropatterning [Grzybowski , Soft Matter1744-683X10.1039/B501769F 1, 114 (2005)], self-organization of cellular micro-organisms [Schulz , Annu. Rev. Microbiol.ARMIAZ0066-422710.1146/annurev.micro.55.1.105 55, 105 (2001)], and in developmental biology [Barkai , FEBS Journal1742-464X10.1111/j.1742-4658.2008.06854.x 276, 1196 (2009)]. In this work, we apply the lattice Boltzmann method to study pattern formation in reaction-diffusion systems. As a first methodological step, we consider the case of a single species undergoing transformation reaction and diffusion. In this case, we perform a third-order Chapman-Enskog multiscale expansion and study the dependence of the lattice Boltzmann truncation error on the diffusion coefficient and the reaction rate. These findings are in good agreement with numerical simulations. Furthermore, taking the Gray-Scott model as a prominent example, we provide evidence for the maturity of the lattice Boltzmann method in studying pattern formation in nonlinear reaction-diffusion systems. For this purpose, we perform linear stability analysis of the Gray-Scott model and determine the relevant parameter range for pattern formation. Lattice Boltzmann simulations allow us not only to test the validity of the linear stability phase diagram including Turing and Hopf instabilities, but also permit going beyond the linear stability regime, where large perturbations give rise to interesting dynamical behavior such as the so-called self-replicating spots. We also show that the length scale of the patterns may be tuned by rescaling all relevant diffusion coefficients in the system with the same factor while leaving all the reaction constants unchanged.

Ayodele, S. G.; Varnik, F.; Raabe, D.



The competition for graphene formation on Re(0001): A complex interplay between carbon  

E-print Network

) structure. In the range 500­700 K, the formation of a high-quality single-layer of graphene is strongly conditions, the formation of a long-range ordered graphene layer on Re(0001) without carbon bulk saturationThe competition for graphene formation on Re(0001): A complex interplay between carbon segregation

Alfè, Dario


Cycloaddition reactivity studies of first-row transition metal-azide complexes and alkynes: an inorganic click reaction for metalloenzyme inhibitor synthesis.  


The studies described herein focus on the 1,3-dipolar cycloaddition reaction between first-row transition metal-azide complexes and alkyne reagents, i.e. an inorganic variant of the extensively used "click reaction". The reaction between the azide complexes of biologically-relevant metals (e.g., Fe, Co and Ni) found in metalloenzyme active sites and alkyne reagents has been investigated as a proof-of-principle for a novel method of developing metalloenzyme triazole-based inhibitors. Six Fe, Co and Ni mono-azide complexes employing salen- and cyclam-type ligands have been synthesized and characterized. The scope of the targeted inorganic azide-alkyne click reaction was investigated using the electron-deficient alkyne dimethyl acetylenedicarboxylate. Of the six metal-azide complexes tested, the Co and Ni complexes of the 1,4,8,11-tetrametyl-1,4,8,11-tetraazacyclotetradecane (Me(4)cyclam) ligand showed a successful cycloaddition reaction and formation of the corresponding metal-triazolate products, which were crystallographically characterized. Moreover, use of less electron deficient alkynes resulted in a loss of cycloaddition reactivity. Analysis of the structural parameters of the investigated metal-azide complexes suggests that a more symmetric structure and charge distribution within the azide moiety is needed for the formation of a metal-triazolate product. Overall, these results suggest that a successful cycloaddition reaction between a metal-azide complex and an alkyne substrate is dependent both on the ligand and metal oxidation state, that determine the electronic properties of the bound azide, as well as the electron deficient nature of the alkyne employed. PMID:22517535

Evangelio, Emi; Rath, Nigam P; Mirica, Liviu M



Topology and Complexity of Formations Abubakr Muhammad1  

E-print Network

, animal herds, bacterial colonies, schools of fish, formations of flying birds, and so on. These group colonies and fish schools provide a lot of insight into the study and design of artificial multi

Egerstedt, Magnus


Kinetics of exciplex formation/dissipation in reaction following Weller Scheme II  

NASA Astrophysics Data System (ADS)

Creation of exciplexes from the charged products of photoionization is considered by means of Integral Encounter Theory. The general kinetic equations of such a reaction following the Weller scheme II are developed. The special attention is given to the particular case of irreversible remote ionization of primary excited electron donor. Kinetics of exciplex formation is considered at fast biexponential geminate transformation of exciplexes in cage that gives way to subsequent bulk reaction of equilibrated reaction products controlled by power law recombination of ions. It is shown that the initial geminate stage of exciplex kinetics is observed only in diffusion controlled regime of the reaction and disappears with increasing mobility of ions in passing to kinetic regime. The quantum yield of exciplexes is studied along with their kinetics.

Fedorenko, S. G.; Burshtein, A. I.



Carbon-bridged biphenolate lanthanide complexes: synthesis and their catalytic activity for the Diels Alder reaction  

NASA Astrophysics Data System (ADS)

Reaction of anhydrous ErCl 3 with sodium salt of carbon-bridged biphenolate, MBMPNa 2 (MBMP 2-=2,2'-methylene-bis (6- tert-butyl-4-methyl-phenoxo)), in 1:2 molar ratio in THF at room temperature gave the lanthanide 'ate' complexes (THF)Er(MBMP) 2Na(THF) 2 ( 1) in high isolated yield. Similarly reaction of anhydrous SmCl 3 with 2 equiv. of MBMPNa 2 in THF, then crystallization from toluene in the presence of TMEDA, afforded the final product (THF)Sm(MBMP) 2Na(TMEDA) ( 2). Both complexes 1 and 2 were well characterized by elemental analysis, IR spectra, and X-ray diffraction analysis. Preliminary results revealed that these complexes are able to act as Lewis acid to catalyze the Diels-Alder reaction of cyclopentadiene with methyl acrylate in good activity and stereoselectivity.

Xu, Xiaoping; Ma, Mengtao; Yao, Yingming; Zhang, Yong; Shen, Qi



A short note on the Lyapunov function for complex-balanced chemical reaction networks  

E-print Network

, by the monotonicity of log function, can only happen if xi = ci for all i. References [1] M. Feinberg, Lectures the span of the reaction vectors by S = span{yk - yk}. The ODE governing the dynamics of the system is x reactions for which is the product complex. Now define the function V by V (x) = N i=1 xi(ln(xi) - ln ci

Anderson, David F.


Quantum chemical study on influence of substituents and solvents in reaction complexing ethylene with nickel dithiolene  

Microsoft Academic Search

The influences induced by various terminal substituents and solvents on the reaction mechanism and chemical dynamics of complexing ethylene with Ni dithiolene are theoretically studied by using B3LYP method and Onsager model. It is shown that the reaction should be a two-step process, and the first step is the rate-determining step. We find that the rate constant of the rate-determining

Qing-Zhen Han; Yue-Hong Zhao; Hao Wen



Formation of hydroxyl radicals from the reaction of water and oxygen over basic metal oxides  

SciTech Connect

The reaction of water and oxygen to form hydroxyl radicals over the metal oxide catalysts La{sub 2}O{sub 3}, Nd{sub 2}O{sub 3}, Sm{sub 2}O{sub 3}, Yb{sub 2}O{sub 3}, CeO{sub 2}, and MgO was studied at pressures up to several Torr. After reaction over 27 mg of La{sub 2}O{sub 3} at 900{degree}C, the measured concentration of hydroxyl radicals in the gas phase, detected by laser induced fluorescence spectroscopy, was equivalent to the expected equilibrium concentration. The reaction becomes kinetically controlled at catalyst loadings below 5 mg. Oxygen incorporation at the surface sites may be the rate limiting step in the catalytic cycle. The activities of the catalysts decrease from La{sub 2}O{sub 3}, the most active, to CeO{sub 2}, which is inactive under these reaction conditions. This order is the same as that found for methyl radical formation over these oxides, suggesting that the active site on the catalyst surface is the same for both hydroxyl radical formation and methyl radical formation. 40 refs., 7 figs., 2 tabs.

Hewett, K.B.; Anderson, L.C.; Rosynek, M.P.; Lunsford, J.H. [Texas A& M Univ., College Station, TX (United States)] [Texas A& M Univ., College Station, TX (United States)



Towards a density functional treatment of chemical reactions in complex media  

SciTech Connect

We discuss two techniques involving density functional theory (i.e., ab initio molecular dynamics simulations and frozen density functional theory) which show promise for applications directed towards understanding reactions in complex media. Preliminary results for the simulation of the conformational dynamics of an isolated analogue of alanine dipeptide and for the interaction between F{sup -} and H{sub 2}O are included. These results represent the first steps towards a combined theoretical approach of reactions in complex media. 23 refs., 4 figs.

Berard, D.R.; Wei, D. [Centre de Recherche en Calcul Applique, Montreal, Quebec (Canada); Salahub, D.R. [Universite de Montreal, Quebec (Canada); [Centre de Recherche en Calcul Applique, Montreal, Quebec (Canada)



Relation between State-Selected or State-Averaged Cross Sections of Endothermic Reactions and Rate Constants of Exothermic Reactions. Application of Bimolecular Microcanonical Activated Complex Theory  

Microsoft Academic Search

An expression is derived relating state-selected or state-averaged molecular beam reaction cross sections of endothermic reactions to observed rate constants for the inverse (exothermic) reactions. An approximation of Anlauf, Maylotte, Polanyi, and Bernstein is used, together with bimolecular microcanonical activated complex theory [R. A. Marcus, J. Chem. Phys. 45, 2138 (1966)].

R. A. Marcus



Pattern formation on networks with reactions: A continuous-time random-walk approach  

NASA Astrophysics Data System (ADS)

We derive the generalized master equation for reaction-diffusion on networks from an underlying stochastic process, the continuous time random walk (CTRW). The nontrivial incorporation of the reaction process into the CTRW is achieved by splitting the derivation into two stages. The reactions are treated as birth-death processes and the first stage of the derivation is at the single particle level, taking into account the death process, while the second stage considers an ensemble of these particles including the birth process. Using this model we have investigated different types of pattern formation across the vertices on a range of networks. Importantly, the CTRW defines the Laplacian operator on the network in a non-ad hoc manner and the pattern formation depends on the structure of this Laplacian. Here we focus attention on CTRWs with exponential waiting times for two cases: one in which the rate parameter is constant for all vertices and the other where the rate parameter is proportional to the vertex degree. This results in nonsymmetric and symmetric CTRW Laplacians, respectively. In the case of symmetric Laplacians, pattern formation follows from the Turing instability. However in nonsymmetric Laplacians, pattern formation may be possible with or without a Turing instability.

Angstmann, C. N.; Donnelly, I. C.; Henry, B. I.



Catalytic C-N and C-F bond formation by organometallic group 11 complexes  

E-print Network

This thesis presents a study of the reaction between an (NHC)gold(I) fluoride complex (NHC = N-heterocyclic carbene) and alkynes (Chapter 1). Gold(I) and fluoride add trans across the triple bond of 3-hexyne and ...

Akana, Jennifer Anne



Theoretical study on reaction mechanism of ground-state cyano radical with 1,3-butadiene: prospect of pyridine formation.  


The reaction of ground-state cyano radicals, CN(X(2)?(+)), with the simplest polyene, 1,3-butadiene (C4H6(X(1)Ag)), is investigated to explore probable routes and feasibility to form pyridine at ultralow temperatures. The isomerization and dissociation channels for each of the seven initial collision complexes are characterized by utilizing the unrestricted B3LYP/cc-pVTZ and the CCSD(T)/cc-pVTZ calculations. With facilitation of RRKM rate constants, through ab initio paths composed of 7 collision complexes, 331 intermediates, 62 hydrogen atom, 71 hydrogen molecule, and 3 hydrogen cyanide dissociated products, the most probable paths at collision energies up to 10 kcal/mol, and thus the reaction mechanism, are determined. Subsequently, the corresponding rate equations are solved that the concentration evolutions of collision complexes, intermediates, and products versus time are obtained. As a result, the final products and yields are determined. The low-energy routes for the formation of most thermodynamically stable product, pyridine, are identified. This study, however, predicts that seven collision complexes would produce predominately 1-cyano-1,3-butadiene, CH2CHCHCHCN (p2) plus atomic hydrogen via the collision complex c1(CH2CHCHCH2CN) and intermediate i2(CH2CHCH2CHCN), with a very minor amount of pyridine. Our scheme also effectively excludes the presence of 2-cyano-1,3-butadiene, which has energy near-degenerate to 1-cyano-1,3-butadiene, as supported by experimental findings. PMID:25116460

Sun, B J; Huang, C H; Chen, S Y; Chen, S H; Kaiser, R I; Chang, A H H



Quantifying the ionic reaction channels in the Secondary Organic Aerosol formation from glyoxal  

NASA Astrophysics Data System (ADS)

Glyoxal, a common organic gas in the atmosphere, has been identified in recent years as an important Secondary Organic Aerosol (SOA) precursor (Volkamer et al., 2007). But, unlike with other precursors, the SOA is largely produced by particle-phase reactions (Volkamer et al., 2009) and equilibria (Kampf et al. 2013) that are still not entirely characterized. Since 2009 series of smog chamber experiments have been performed within the Eurochamp program at the Paul Scherrer Institute, Switzerland, to investigate SOA formation from glyoxal. In these experiments, glyoxal was produced by the gas-phase oxidation of acetylene in the presence of seeds, the seed composition and other conditions being varied. The 2011 campaign resulted in the identification of salting processes controlling the glyoxal partitioning in the seeds (Kampf et al. 2013). This presentation will report results of the 2013 campaign focusing on the identification of the various reactions (ionic or photo-induced) contributing to the SOA mass. In particular, the contribution of the ionic reactions, i.e. mediated by NH4+, were investigated by quantifying the formation of imidazoles (imidazole, imidazole-2-carboxaldehyde, 2,2'-biimidazole) from the small condensation channel of glyoxal with ammonia. For this, the SOA produced were collected on quartz filters and analyzed by Orbitrap LC/MS (Q-Exactive Thermo Fisher). The formation of other products such as organic acids was also investigated to determine potential competing reactions. Time-resolved MOUDI sampling coupled with nano-DESY/ESI-MS/MS analysis was also used to identify nitrogen- and sulphur-containing products from all the reactions. The results obtained for a range of conditions will be presented and compared with recent mechanistic information on the ionic reaction channels (Nozière et al., in preparation, 2013). The implementation of all this new information into a glyoxal-SOA model will be discussed.

Maxut, Aurelia; Nozière, Barbara; Rossignol, Stéphanie; George, Christian; Waxman, Eleanor Marie; Laskin, Alexander; Slowik, Jay; Dommen, Josef; Prévôt, André; Baltensperger, Urs; Volkamer, Rainer



The formation of the dolomite-analogue norsethite: Reaction pathway and cation ordering  

NASA Astrophysics Data System (ADS)

Reaction pathways and cation ordering mechanisms involved in the formation of the mineral dolomite in nature still remain poorly understood. This is mainly due to the experimental problems posed by the synthesis of dolomite at ambient conditions, which preclude monitoring its formation in reasonable time scales. However, processes leading to the crystallization of fully-ordered dolomite-like structures can be studied by conducting experiments with mineral analogues, which are more readily precipitated. In this paper we present a study of the formation of the dolomite-analogue norsethite [BaMg(CO3)2] from a slurry which was aged at room temperature during 14 days. We found that norsethite forms by two dissolution-crystallization reactions from an initial amorphous nano-sized precipitate. The first reaction produces a mineral assemblage composed by witherite [BaCO3], northupite [Na3Mg(CO3)2Cl] and norsethite. The second dissolution-crystallization process leads to the almost complete depletion of witherite and northupite in favor of norsethite. While the composition of norsethite crystals rapidly reaches a Ba/Mg = 1 ratio, X-ray diffraction peaks indicate an increase in the crystallinity of those crystals during the first 48 h of reaction. Simultaneously, Ba-Mg cation ordering increases, as shown by the evolution of intensity ratios of certain superstructure and structure reflections. Altogether, these results demonstrate that the formation of fully-ordered norsethite occurs by a sequence of solvent-mediated processes which involve a number of precursors. Our study also suggests that similar processes might lead to the formation of dolomite in natural environments.

Pimentel, Carlos; Pina, Carlos M.



Mechanism of production of light complex particles in nucleon-induced reactions  

E-print Network

The Improved Quantum Molecular Dynamics (ImQMD) model incorporated with the statistical decay model is successful in describing emission of nucleons in the intermediate energy spallation reactions, but not good enough in describing productions of light complex particles, i.e. $d$, $t$, $^3$He and $^4$He. To improve the description on emission of light complex particles, a phenomenological mechanism called surface coalescence and emission is introduced into ImQMD model: nucleon ready to escape from the compound nuclei can coalesce with the other nucleon(s) to form light complex particle and be emitted. With updated ImQMD model, the description on the experimental data of light complex particles produced in nucleon-induced reactions are great improved.

Dexian Wei; Ning Wang; Li Ou



A highly efficient and selective aerobic cross-dehydrogenative-coupling reaction photocatalyzed by a platinum(II) terpyridyl complex.  


Thanks to the superior redox potential of platinum(II) complex compared with that of Ru(bpy)3(2+) in the excited state, an efficient and selective visible-light-induced CDC reaction has been developed by using a catalytic amount (0.25?%) of 1. With the aid of FeSO4 (2?equiv), the corresponding amide could not be detected under visible-light irradiation (?=450?nm), but the desired cross-coupling product was exclusively obtained under ambient air conditions. A spectroscopic study and product analysis revealed that the CDC reaction is initiated by photoinduced electron-transfer from N-phenyltetrahydroisoquinoline to the complex. An EPR (electron paramagnetic resonance) experiment provides direct evidence on the generation of superoxide radical anion (O2(-·)) rather than singlet oxygen ((1)O2) under irradiation of the reaction system, in contrast to that reported in the literature. Combined, the photoinduced electron-transfer and subsequent formation of superoxide radical anion (O2(-·)) results in a clean and facile transformation. PMID:23504986

Zhong, Jian-Ji; Meng, Qing-Yuan; Wang, Ge-Xia; Liu, Qiang; Chen, Bin; Feng, Ke; Tung, Chen-Ho; Wu, Li-Zhu



Shock-induced hotspot formation and chemical reaction initiation in PETN containing a spherical void  

NASA Astrophysics Data System (ADS)

We present results of reactive molecular dynamics simulations of hotspot formation and chemical reaction initiation in shock-induced compression of pentaerythritol tetranitrate (PETN) with the ReaxFF reactive force field. A supported shockwave is driven through a PETN crystal containing a 20 nm spherical void at a sub-threshold impact velocity of 2 km/s. Formation of a hotspot due to shock-induced void collapse is observed. During void collapse, NO2 is the dominant species ejected from the upstream void surface. Once the ejecta collide with the downstream void surface and the hotspot develops, formation of final products such as N2 and H2O is observed. The simulation provides a detailed picture of how void collapse and hotspot formation leads to initiation at sub-threshold impact velocities.

Shan, Tzu-Ray; Thompson, Aidan P.



Dependence of the enthalpies of formation of glycylglycinate complexes of nickel(II) on the composition of a mixed water-dimethylsulfoxide solvent  

NASA Astrophysics Data System (ADS)

The heat effects of the complexation reactions of nickel(II) with a glycylglycinate ion in a water-dimethylsulfoxide solvent in a range of compositions of 0.00-0.60 molar parts of dimethylsulfoxide (DMSO) (an ionic strength of 0.1 was maintained using sodium perchlorate) were determined by means of calorimetry at 298.15 K. It is established that the exothermicity of complexation reactions rises by the first two steps and falls upon the addition of a third glycylglycinate anion with an increase in the concentration of DMSO. It is shown that the formation of mono- and bis-glycylglycinate complexes of nickel(II) in a water-DMSO solvent is determined mostly by the enthalpic contribution. It is concluded that the formation of tris-ligand complexes is more associated with the entropic contribution.

Naumov, V. V.; Kovaleva, Yu. A.; Isaeva, V. A.; Usacheva, T. R.; Sharnin, V. A.



Synthesis, Characterization, and Reactions of Isolable (?-Diketiminato)Nb(III) Imido Complexes*  

PubMed Central

We have investigated both the chemical reduction of (BDI)Nb(V) imido complexes (BDI = HC[C(Me)NAr]2; Ar = 2,6-iPr2-C6H3) to the formal Nb(III) oxidation state and the ability of these Nb(III) complexes to behave as two-electron reductants. The reduction of the Nb(V) species was found to depend heavily on the nature of available supporting ligands, but the chemistry of the reduced compounds proceeded cleanly with a number of unsaturated organic reagents. Accordingly, the novel Nb(V) bis(imido) complexes supported by the monoazabutadiene (mad) ligand (mad)Nb(NtBu)(NAr)(L?) (L? = py, thf) were formed by either KC8 reduction of (BDI)Nb(NtBu)Cl2(py) in the absence of strong ?-acids or by H2 reduction of the Nb(V) dimethyl complex (BDI)Nb(NtBu)Me2 in THF. These products are likely formed though an intramolecular, 2 e? reductive C–N bond cleavage, as has been observed previously for related Group 4 systems, suggesting that transient Nb(III) intermediates were present in both cases. In the presence of 1,2-bis(dimethylphosphino)ethane (dmpe), KC8 reduction of (BDI)Nb(NtBu)Cl2(py) was arrested at the Nb(IV) oxidation state to give (BDI)Nb(NtBu)Cl(dmpe), which was characterized by solution-state EPR spectroscopy as a Nb-centered paramagnet with strong coupling to the two equivalent phosphorus nuclei (Aiso{93Nb} = 120.5×10?4 cm?1, Aiso{31P} = 31.0×10?4 cm?1, giso = 1.9815). When strong ?-acids were used to intercept the thermally unstable Nb(III) complex (BDI)Nb(NtBu)(py) prior to reductive cleavage of the ligand C–N bond, the thermally stable Nb(III) species (BDI)Nb(NtBu)(CX)2(L?) (X = O, L? = py; X = NXyl, L? = CNXyl; Xyl = 2,6-Me2-C6H3) were obtained in good yields. The Nb(III) complexes (BDI)Nb(NtBu)py, (BDI)Nb(NtBu)(CO)2(py) and (BDI)Nb(NtBu)(CO)2 were subsequently investigated for their ability to serve as two-electron reducing reagents for both metal-ligand multiple bond formation and for the reduction of organic ?-systems. The reduction of mesityl azide by (BDI)Nb(NtBu)(py) and diphenylsulfoxide by (BDI)Nb(NtBu)(CO)2 led to the monomeric bis(imido) and dimeric oxo complexes (BDI)Nb(NtBu)(NMes)(py) and [(BDI)Nb(NtBu)]2(?2-O)2, respectively. MeLi addition to (BDI)Nb(NtBu)(CO)2(py) resulted in the formation of a Nb-acylate via methide addition to one of the carbonyl carbons. The acylate product was revealed to have a short Nb–Cacylate bond distance (2.059(4) Å), consistent with multiple Nb–C bond character resulting from Nb(III) back-bonding into the acylate carbon. The interaction of (BDI)Nb(NtBu)(CO)2 with two equivalents of 4,4?-dichlorobenzophenone resulted in the clean, quantitative formation of the corresponding pinacol coupling product, but introduction of the ketone in 1: 1 molar ratios resulted in mixtures of the pinacol product and the starting material, suggesting that ketone coordination to the Nb(III) complex may be reversible. Relatedly, addition of 1-phenyl-1-propyne to (BDI)Nb(NtBu)(CO)2 formed a thermally unstable 1: 1 Nb/alkyne complex, as characterized by NMR and IR spectroscopies; reaction of this species with HCl/MeOH yielded a 2: 1 mixture of 1-phenyl-1-propene and the free alkyne, suggesting a high degree of covalency in the Nb–C bonds. PMID:21116450

Tomson, Neil C.; Arnold, John; Bergman, Robert G.



Scale-dependent rates of uranyl surface complexation reaction in sediments  

NASA Astrophysics Data System (ADS)

Scale-dependency of uranyl[U(VI)] surface complexation rates was investigated in stirred flow-cell and column systems using a U(VI)-contaminated sediment from the US Department of Energy, Hanford site, WA. The experimental results were used to estimate the apparent rate of U(VI) surface complexation at the grain-scale and in porous media. Numerical simulations using molecular, pore-scale, and continuum models were performed to provide insights into and to estimate the rate constants of U(VI) surface complexation at the different scales. The results show that the grain-scale rate constant of U(VI) surface complexation was over 3-10 orders of magnitude smaller than the rate constant calculated using the molecular simulations. The largest rate constant at the grain-scale decreased additional 2 orders of magnitude when the rate was scaled to the porous media in the column. The scaling effect from the grain-scale to the porous media became less important for the slower sorption sites. Pore-scale simulations revealed the importance of coupled mass transport and reactions in both intragranular and inter-granular domains, which caused both spatial and temporal dependence of U(VI) surface complexation rates in the sediment. Pore-scale simulations also revealed that the rate of coupled diffusion and molecular surface complexation reaction in the intragranular porous domains was slower than either individual process alone. The results provide important implications for developing models to scale geochemical/biogeochemical reactions.

Liu, Chongxuan; Shang, Jianying; Kerisit, Sebastien; Zachara, John M.; Zhu, Weihuang



Particle-chain formation in a dc dielectrophoretic trap; a reaction-diffusion approach  

NASA Astrophysics Data System (ADS)

Dielectrophoresis has proven to be an effective method for the separation of bioparticles such as cells. Nevertheless, the electric polarization induced by nonuniform electric fields leads to a dipole-dipole interaction between particles and therefore the formation of chains is likely to occur. In this paper, we will present an approach based on a drift-diffusion dynamics to quantitatively study formation and kinetics of particle-chains via the introduction of the particle stitching as chemical-like reactions. This approach will allow us to dynamically describe, in the framework of a numerical simulation, particle clustering, thus providing a suitable tool for reproducing data from dielectrophoretic experimental setup.

Nicotra, O. E.; La Magna, A.; Coffa, S.



Formation and Nonvolatile Memory Application of Ge Nanocrystals by Using Internal Competition Reaction of and Layers  

Microsoft Academic Search

In this study, the authors proposed a formation mechanism of Ge nanocrystals (NCs) embedded in the dielectric by using Si1.33Ge0.67O2 and Si2.67Ge1.33N2 films for nonvolatile memory (NVM) application. Because of internal competition reaction, this formation process reduced the thermal budget and eliminated the use of high-pressure H2 treatment or steam process. The metal\\/oxide\\/insulator\\/oxide\\/silicon capacitor structure with NCs was also studied,

Wei-Ren Chen; Ting-Chang Chang; Yen-Ting Hsieh; Chun-Yen Chang



Formation of Kaonic Atoms and Kaonic Nuclei by In-flight ($K^-,p$) reactions  

E-print Network

We study the kaonic atom and kaonic nucleus formation by the in-flight ($K^-, p$) reactions for C, O, Si and Ca target cases theoretically. Deeply bound kaonic atoms were predicted to exist as quasi-stable states and were expected to be observed in some proper experimental methods. Kaonic nuclear states are also expected to exist with large decay widths. We evaluate the formation cross sections of the kaonic atoms and kaonic nuclei using an effective number approach. We show that the indications of the kaonic bound states can be observed in the outgoing proton energy spectra.

Junko Yamagata; Hideko Nagahiro; Yuko Okumura; Satoru Hirenzaki



The formation of glycine and other complex organic molecules in exploding ice mantles.  


Complex Organic Molecules (COMs), such as propylene (CH3CHCH2) and the isomers of C2H4O2 are detected in cold molecular clouds (such as TMC-1) with high fractional abundances (Marcelino et al., Astrophys. J., 2007, 665, L127). The formation mechanism for these species is the subject of intense speculation, as is the possibility of the formation of simple amino acids such as glycine (NH2CH2COOH). At typical dark cloud densities, normal interstellar gas-phase chemistries are inefficient, whilst surface chemistry is at best ill defined and does not easily reproduce the abundance ratios observed in the gas phase. Whatever mechanism(s) is/are operating, it/they must be both efficient at converting a significant fraction of the available carbon budget into COMs, and capable of efficiently returning the COMs to the gas phase. In our previous studies we proposed a complementary, alternative mechanism, in which medium- and large-sized molecules are formed by three-body gas kinetic reactions in the warm high density gas phase. This environment exists, for a very short period of time, after the total sublimation of grain ice mantles in transient co-desorption events. In order to drive the process, rapid and efficient mantle sublimation is required and we have proposed that ice mantle 'explosions' can be driven by the catastrophic recombination of trapped hydrogen atoms, and other radicals, in the ice. Repeated cycles of freeze-out and explosion can thus lead to a cumulative molecular enrichment of the interstellar medium. Using existing studies we based our chemical network on simple radical addition, subject to enthalpy and valency restrictions. In this work we have extended the chemistry to include the formation pathways of glycine and other large molecular species that are detected in molecular clouds. We find that the mechanism is capable of explaining the observed molecular abundances and complexity in these sources. We find that the proposed mechanism is easily capable of explaining the large abundances of all three isomers of C2H4O2 that are observationally inferred for star-forming regions. However, the model currently does not provide an obvious explanation for the predominance of methyl formate, suggesting that some refinement to our (very simplistic) chemistry is necessary. The model also predicts the production of glycine at a (lower) abundance level, that is consistent with its marginal detection in astrophysical sources. PMID:25302390

Rawlings, J M C; Williams, D A; Viti, S; Cecchi-Pestellini, C; Duley, W W



Photocatalytic CO2 reduction with high turnover frequency and selectivity of formic acid formation using Ru(II) multinuclear complexes  

PubMed Central

Previously undescribed supramolecules constructed with various ratios of two kinds of Ru(II) complexes—a photosensitizer and a catalyst—were synthesized. These complexes can photocatalyze the reduction of CO2 to formic acid with high selectivity and durability using a wide range of wavelengths of visible light and NADH model compounds as electron donors in a mixed solution of dimethylformamide–triethanolamine. Using a higher ratio of the photosensitizer unit to the catalyst unit led to a higher yield of formic acid. In particular, of the reported photocatalysts, a trinuclear complex with two photosensitizer units and one catalyst unit photocatalyzed CO2 reduction (?HCOOH = 0.061, TONHCOOH = 671) with the fastest reaction rate (TOFHCOOH = 11.6 min-1). On the other hand, photocatalyses of a mixed system containing two kinds of model mononuclear Ru(II) complexes, and supramolecules with a higher ratio of the catalyst unit were much less efficient, and black oligomers and polymers were produced from the Ru complexes during photocatalytic reactions, which reduced the yield of formic acid. The photocatalytic formation of formic acid using the supramolecules described herein proceeds via two sequential processes: the photochemical reduction of the photosensitizer unit by NADH model compounds and intramolecular electron transfer to the catalyst unit. PMID:22908243

Tamaki, Yusuke; Morimoto, Tatsuki; Koike, Kazuhide; Ishitani, Osamu



Equilibrium and 1 H NMR Kinetic Study of the Reactions of Dichlorido [S-Methyl-L-Cysteine(N,S)]Platinum(II) Complex with Some Relevant Biomolecules  

Microsoft Academic Search

The formation equilibria of the [Pt(SMC)(H2O)2]+ complex with some biologically relevant ligands such as L-methionine (L-met) and glutathione (GSH) were studied. The stoichiometry\\u000a and stability constants of the formed complexes are reported, and the concentration distribution of the various complex species\\u000a has been evaluated as a function of pH. The reaction between [PtCl2(SMC)] and guanosine-5?-monophosphate (5?-GMP) was studied by 1H

Tanja Soldatovi?; Predrag ?anovi?; Radivoje Nikoli?; Ratomir Jeli?; Živadin D. Bugar?i?



Formaldehyde Reactions with Amines and Ammonia: Particle Formation and Product Identification  

NASA Astrophysics Data System (ADS)

Aqueous phase reactions between carbonyls and amines or ammonium salts have recently been implicated in secondary organic aerosol and brown carbon formation processes. Formaldehyde is ubiquitous in the atmosphere, and is present in both the gas and aqueous phases. However, the reactions of formaldehyde in the aqueous phase have not been completely characterized. This study aims to determine the interactions between formaldehyde and amines or ammonium salts present in atmospheric droplets. Bulk phase reactions of formaldehyde with these reactive nitrogen-containing compounds were monitored with ESI-MS and NMR to determine reaction kinetics and for product characterization, while UV-Vis spectroscopy was used to monitor changes in light absorption over time. Hexamethylenetetramine was found to be a major product of the formaldehyde/ammonium sulfate reaction, appearing within minutes of mixing. No products were formed that absorbed light beyond 225 nm. Mono-disperse particles containing mixtures of formaldehyde and ammonium sulfate or an amine were dried and analyzed via SMPS to determine the non-volatile fraction of the reaction products. Similarly, aqueous droplets were dried in a humid atmosphere to determine residual aerosol sizes over time as a function of formaldehyde concentration. This work indicates that formaldehyde plays a key role in aqueous-phase organic processing, as it has been observed to contribute to both an increase and reduction in the diameter and volume of residual aerosol particles.

Galloway, M. M.; Millage, K. D.; Rodriguez, A.; Sedehi, N.; Powelson, M. H.; De Haan, D. O.



The formation and decay of superheavy nuclei produced in $^{48}Ca$-induced reactions  

E-print Network

The formation of superheavy nuclei in $^{48}Ca+^{232}Th$, $^{238}U$, $^{242,244}Pu$ and $^{248}Cm$ reactions and their subsequent decay are studied within the quantum mechanical fragmentation theory (QMFT) and the QMFT based preformed cluster-decay model (PCM) of Gupta and collaborators. According to QMFT, all these $^{48}Ca$-induced reactions are cold fusion reactions with relative excitation energies larger than for the $Pb$-induced cold fusion reactions and smaller than for the lighter beam i.e. $Mg$, $Si$ or $S$-induced hot fusion reactions. The same reactions were first suggested by Gupta et al. in 1977 on the basis of QMFT, and this study re-establishes the same result. In fact, for such heavy isotopes of Z=110 to 116, $^{50}Ca$ is shown to be a better beam for cold fusion, but $^{50}Ca$ is a radioactive nucleus. The $\\alpha$-decay half-lives of these nuclei after 3n and/ or 4n evaporations, i.e. of the evaporation residues of these compound systems, calculated on PCM compare reasonably well with experi...

Kumar, Sushil; Gupta, Raj K; Munzenberg, G; Scheid, W; 10.1088/0954-3899/29/4/303



Analysis of diatomic bond dissociation and formation in terms of the reaction force and the position-dependent reaction force constant  

Microsoft Academic Search

Bond dissociation and formation in diatomic molecules are analyzed in terms of the reaction force F(R) and the reaction force constant ?(R). These were determined for a group of 13 molecules from their extended-Rydberg potential energy functions V(R), which are of near-experimental quality. From F(R) and ?(R) comes a two-stage description of dissociation\\/formation. In dissociation, the first stage involves stretching

Jane S. Murray; Alejandro Toro-Labbé; Tim Clark; Peter Politzer



Ruthenium Derivatives of NiS2N2 Complexes as Analogues of Bioorganometallic Reaction Centers  

E-print Network

, respectively, to give [Cp*Ru(NiS2N2)(2- E2)]+ (E ) O, S), which were characterized spectroscopicallyRuthenium Derivatives of NiS2N2 Complexes as Analogues of Bioorganometallic Reaction Centers Recent results from structural biology demonstrate the catalytic significance of Ni(SR)2L2 centers

Rauchfuss, Thomas B.


Placebo Effect upon Complex Reaction Time When Hypnotic Suggestibility is Controlled.  

ERIC Educational Resources Information Center

This study was designed to investigate the effect of a placebo (sugar pill) accompanied by suggestions that the pill would either (1) improve performance as a stimulant or (2) cause a deterioration in performance as a depressant when the performance in question was the subjects' complex reaction time to a light stimulus. The Harvard Group Scale of…

Eskridge, Veronica L.


Reliable Protein Folding on Complex Energy Landscapes: The Free Energy Reaction Path  

E-print Network

Reliable Protein Folding on Complex Energy Landscapes: The Free Energy Reaction Path Gregg Lois be calculated from measurements of the free energy. We test these predictions against numerical simulations folding problem (2­4). Each protein conformation has a free energy that determines its probability

Gelfond, Michael


Thermochemistry and reaction barriers for the formation of levoglucosenone from cellobiose.  

SciTech Connect

Cellobiose jumps the barrier: High-level quantum mechanical studies show that the ether bond cleavage in cellobiose occurs through internal hydrogen transfer in the gas phase and that the activation energy required is similar to that required for activating cellulose. The reaction barriers are computed for various pathways for the formation of levoglucosenone from levoglucosan, and the most likely pathway requires a relatively low activation barrier compared to that for the activation of cellobiose.

Assary, R. S.; Curtiss, L. A. (Center for Nanoscale Materials); ( MSD); (Northwestern Univ.)



Thermochemistry and Reaction Barriers for the Formation of Levoglucosenone from Cellobiose  

SciTech Connect

Cellobiose jumps the barrier: High-level quantum mechanical studies show that the ether bond cleavage in cellobiose occurs through internal hydrogen transfer in the gas phase and that the activation energy required is similar to that required for activating cellulose. The reaction barriers are computed for various pathways for the formation of levoglucosenone from levoglucosan, and the most likely pathway requires a relatively low activation barrier compared to that for the activation of cellobiose.

Assary, Rajeev S.; Curtiss, Larry A.



On the influence of the char gasification reactions on NO formation in flameless coal combustion  

SciTech Connect

Flameless combustion is a well known measure to reduce NO{sub x} emissions in gas combustion but has not yet been fully adapted to pulverised coal combustion. Numerical predictions can provide detailed information on the combustion process thus playing a significant role in understanding the basic mechanisms for pollutant formation. In simulations of conventional pulverised coal combustion the gasification by CO{sub 2} or H{sub 2} O is usually omitted since its overall contribution to char oxidation is negligible compared to the oxidation with O{sub 2}. In flameless combustion, however, due to the strong recirculation of hot combustion products, primarily CO{sub 2} and H{sub 2} O, and the thereby reduced concentration of O{sub 2} in the reaction zone the local partial pressures of CO{sub 2} and H{sub 2} O become significantly higher than that for O{sub 2}. Therefore, the char reaction with CO{sub 2} and H{sub 2} O is being reconsidered. This paper presents a numerical study on the importance of these reactions on pollutant formation in flameless combustion. The numerical models used have been validated against experimental data. By varying the wall temperature and the burner excess air ratio, different cases have been investigated and the impact of considering gasification on the prediction of NO formation has been assessed. It was found that within the investigated ranges of these parameters the fraction of char being gasified increases up to 35%. This leads to changes in the local gas composition, primarily CO distribution, which in turn influences NO formation predictions. Considering gasification the prediction of NO emission is up to 40% lower than the predicted emissions without gasification reactions being taken into account. (author)

Stadler, Hannes; Toporov, Dobrin; Foerster, Malte; Kneer, Reinhold [Institute of Heat and Mass Transfer, RWTH Aachen University, Eilfschornsteinstrasse 18, 52056 Aachen (Germany)



Formation of methyl glyoxal in dihydroxyacetone and glycine Maillard reaction: A computational study  

Microsoft Academic Search

By considering the formation of methyl glyoxal as one of the possible intermediates, mechanisms for the intermediate stage of the Maillard reaction of dihydroxyacetone and glycine under different pH conditions have been proposed, following the Hodge-scheme. Density functional theory calculations have been performed at the standard state on the proposed mechanisms to calculated the Gibb’s free energy changes for the



Reaction of furan-based o-quinodimethanes with triplet oxygen. Formation of cyclic peroxides  

SciTech Connect

Formation of cyclic peroxides 2a,2b, and 2c from the reactions of 2,3-dimethylene-2,3-dihydrofuran (1a) and the 5-methyl (1b) and 5-tert-butyl (1c) derivatives with triplet oxygen is reported. Thermolysis of cyclic peroxide 2c gives dialdehyde 5, hydroxy aldehydes 6 and 7, and diol 8 as products. 1 fig.

Chou, Chin-Hsing; Trahanovsky, W.S. [Iowa State Univ., Ames, IA (United States)



Some new reaction pathways for the formation of cytosine in interstellar space - A quantum chemical study  

NASA Astrophysics Data System (ADS)

The detection of nucleic acid bases in carbonaceous meteorites suggests that their formation and survival is possible outside of the Earth. Small N-heterocycles, including pyrimidine, purines and nucleobases, have been extensively sought in the interstellar medium. It has been suggested theoretically that reactions between some interstellar molecules may lead to the formation of cytosine, uracil and thymine though these processes involve significantly high potential barriers. We attempted therefore to use quantum chemical techniques to explore if cytosine can possibly form in the interstellar space by radical-radical and radical-molecule interaction schemes, both in the gas phase and in the grains, through barrier-less or low barrier pathways. Results of DFT calculations for the formation of cytosine starting from some of the simple molecules and radicals detected in the interstellar space are being reported. Global and local descriptors such as molecular hardness, softness and electrophilicity, and condensed Fukui functions and local philicity indices were used to understand the mechanistic aspects of chemical reaction. The presence and nature of weak bonds in the molecules and transition states formed during the reaction process have been ascertained using Bader's quantum theory of atoms in molecules (QTAIMs). Two exothermic reaction pathways starting from propynylidyne (CCCH) and cyanoacetylene (HCCCN), respectively, have been identified. While the first reaction path is found to be totally exothermic, it involves a barrier of 12.5 kcal/mol in the gas phase against the lowest value of about 32 kcal/mol reported in the literature. The second path is both exothermic and barrier-less. The later has, therefore, a greater probability of occurrence in the cold interstellar clouds (10-50 K).

Gupta, V. P.; Tandon, Poonam; Mishra, Priti



Formation of complex structures in dusty plasmas under temperature gradients  

Microsoft Academic Search

Thermophoretic effects on dust structures under temperature gradients in glow and radio-frequency discharge plasmas are studied\\u000a experimentally. The geometry of dust structures consisting of micrometer-sized polydisperse grains depends on heat release\\u000a in the plasma. Thermophoretic forces associated with heat release can control the formation of dust structures of different\\u000a geometries. A theoretical model is proposed to describe dust separation with

L. M. Vasilyak; S. P. Vetchinin; D. N. Polyakov; V. E. Fortov



Enolization and racemization reactions of glucose and fructose on heating with amino-acid enantiomers and the formation of melanoidins as a result of the Maillard reaction  

Microsoft Academic Search

This study investigated the enolization and racemization reactions of glucose and fructose on heating with amino acid enantiomers\\u000a and the formation of melanoidins as a result of the Maillard reaction. The study measured reducing sugars and L- and D- amino acids using HPLC as an index for the amount of enolization of the sugars and isomerization of the amino acids.

Ji-Sang Kim; Young-Soon Lee



Dynamics, transition states, and timing of bond formation in Diels-Alder reactions.  


The time-resolved mechanisms for eight Diels-Alder reactions have been studied by quasiclassical trajectories at 298 K, with energies and derivatives computed by UB3LYP/6-31G(d). Three of these reactions were also simulated at high temperature to compare with experimental results. The reaction trajectories require 50-150 fs on average to transverse the region near the saddle point where bonding changes occur. Even with symmetrical reactants, the trajectories invariably involve unequal bond formation in the transition state. Nevertheless, the time gap between formation of the two new bonds is shorter than a C ? C vibrational period. At 298 K, most Diels-Alder reactions are concerted and stereospecific, but at high temperatures (approximately 1,000 K) a small fraction of trajectories lead to diradicals. The simulations illustrate and affirm the bottleneck property of the transition state and the close connection between dynamics and the conventional analysis based on saddle point structure. PMID:22753502

Black, Kersey; Liu, Peng; Xu, Lai; Doubleday, Charles; Houk, Kendall N



Mono(pentamethylcyclopentadienyl)thorium chemistry. Formation and structural characterization of a novel triflate-bridged dimeric thorium complex  

SciTech Connect

We have shown that the reaction of an actinide amide complex, such as Th[N(SiMe{sub 3}){sub 2}]{sub 3}(OTf) (2), with Cp{sup *}H can provide an alternative to the traditional halide metathesis routes to mono(pentamethylcyclopentadienyl)actinide species. As reported recently for the Group IV metals, this synthetic method can offer distinct advantages over halide metathesis procedures, most notably by eliminating the problem of salt retention by the actinide product. The X-ray crystal structure of the dinuclear actinide complex Cp{sup *}[(Me{sub 3}Si){sub 2}N]Th({mu}{sub 2}-OSO{sub 2}CF{sub 3}) [N(SiMe{sub 3})(SiMe{sub 2}CH{sub 2})]Cp{sup *} (4), formed from reaction of 2 with Cp{sup *}H, has been determined and reveals an unusual molecular geometry in which three {eta}{sup 2}-triflate ligands bridge the two thorium metal centers. We have proposed a mechanism to explain the formation of 4 and have shown that several of the proposed mechanistic steps may be verified in independent reactions. Further studies of the reactivity and catalytic properties of mono-Cp{sup *} thorium complexes with alkoxide and alkyl supporting ligands are currently underway. 17 refs., 1 fig., 3 tabs.

Butcher, R.J.; Clark, D.L.; Grumbine, S.K.; Watkin, J.G. [Los Alamos National Lab., NM (United States)



Structural basis for cooperativity of CRM1 export complex formation  

PubMed Central

In eukaryotes, the nucleocytoplasmic transport of macromolecules is mainly mediated by soluble nuclear transport receptors of the karyopherin-? superfamily termed importins and exportins. The highly versatile exportin chromosome region maintenance 1 (CRM1) is essential for nuclear depletion of numerous structurally and functionally unrelated protein and ribonucleoprotein cargoes. CRM1 has been shown to adopt a toroidal structure in several functional transport complexes and was thought to maintain this conformation throughout the entire nucleocytoplasmic transport cycle. We solved crystal structures of free CRM1 from the thermophilic eukaryote Chaetomium thermophilum. Surprisingly, unbound CRM1 exhibits an overall extended and pitched superhelical conformation. The two regulatory regions, namely the acidic loop and the C-terminal ?-helix, are dramatically repositioned in free CRM1 in comparison with the ternary CRM1–Ran–Snurportin1 export complex. Single-particle EM analysis demonstrates that, in a noncrystalline environment, free CRM1 exists in equilibrium between extended, superhelical and compact, ring-like conformations. Molecular dynamics simulations show that the C-terminal helix plays an important role in regulating the transition from an extended to a compact conformation and reveal how the binding site for nuclear export signals of cargoes is modulated by different CRM1 conformations. Combining these results, we propose a model for the cooperativity of CRM1 export complex assembly involving the long-range allosteric communication between the distant binding sites of GTP-bound Ran and cargo. PMID:23277578

Monecke, Thomas; Haselbach, David; Voß, Béla; Russek, Andreas; Neumann, Piotr; Thomson, Emma; Hurt, Ed; Zachariae, Ulrich; Stark, Holger; Grubmüller, Helmut; Dickmanns, Achim; Ficner, Ralf



Decay of activity complexes and the formation of coronal holes  

NASA Astrophysics Data System (ADS)

Analysis of long-term measurements of solar magnetic fields and the flux of UV radiation from the Sun indicates a cause-effect relationship between activity complexs, their residual magnetic fields, and coronal holes. A comparison of the background magnetic fields of the Sun and the evolution of former activity complexes reveals unipolar magnetic regions that form after the decay of these complexes. The latitude and time evolution of unipolar magnetic regions in solar cycles 21-24 is studied. A North-South asymmetry in solar activity is manifest in the distribution of unipolar regions migrating toward higher latitudes. It is shown that, when residual magnetic fields of the opposite polarity reach the polar regions, this leads to a sign change of the polar magnetic field and a decrease in the area of polar coronal holes, or even their complete disappearance. These interactions can explain the triple sign change of the polar magnetic field of the Sun in cycle 21 and the short-term polarity reversals observed in 2010 and 2011.

Mordvinov, A. V.; Yazev, S. A.



Contributions to the Sudbury Igneous Complex and the Depth of Excavation: Evidence from Onaping Formation Zircon  

NASA Astrophysics Data System (ADS)

U-Pb data for zircon preserved in the crater-fill sequence (Onaping Formation) of the Sudbury impact structure reveal a previously unrecognized but significant contributor to the Sudbury Igneous Complex.

Petrus, J. A.; Ayer, J. A.; Long, D. G. F.; Lightfoot, P. C.; Kamber, B. S.



Complex Formation between Bovine Serum Albumin and Strong Polyelectrolytes: Effect of Polymer Charge Density  

E-print Network

Complex Formation between Bovine Serum Albumin and Strong Polyelectrolytes: Effect of Polymer serum albumin (BSA) to poly- (diallyldimethylammonium chloride) (PDADMAC), poly Form: February 25, 1998 Light scattering and pH titration were used to examine the binding of bovine

Dubin, Paul D.


Ab initio study of hydride abstraction reaction in the Mg +-NH 2CH 3 complex  

NASA Astrophysics Data System (ADS)

The hydride abstraction reaction in the Mg +-NH 2CH 3 complex has been investigated by using the DFT and MP2 methods. Two local minima and two transition states have been found along the reaction pathway. Accompanied with IRC calculations, the reaction is revealed to be a three-step process, i.e., a hydrogen-migration process followed by a charge-transfer process and a nonreactive-dissociation process. On the basis of single-point calculations using CCSD(T) in conjunction with 6-311++G(d, pd) basis set with the geometries optimized at B3LYP/6-311++G** with zero point energy (ZPE) corrections, the reaction energies for all the steps are predicted.

Guo, Wenyue; Lu, Xiaoqing; Hu, Songqing; Yang, Shihe



Universal reaction mechanism of boronic acids with diols in aqueous solution: kinetics and the basic concept of a conditional formation constant.  


To establish a detailed reaction mechanism for the condensation between a boronic acid, RB(OH)2, and a diol, H2L, in aqueous solution, the acid dissociation constants (Ka(BL)) of boronic acid diol esters (HBLs) were determined based on the well-established concept of conditional formation constants of metal complexes. The pKa values of HBLs were 2.30, 2.77, and 2.00 for the reaction systems, 2,4-difluorophenylboronic acid and chromotropic acid, 3-nitrophenylboronic acid and alizarin red?S, and phenylboronic acid and alizarin red?S, respectively. A general and precise reaction mechanism of RB(OH)2 with H2L in aqueous solution, which can serve as a universal reaction mechanism for RB(OH)2 and H2L, was proposed on the basis of (a)?the relative kinetic reactivities of the RB(OH)2 and its conjugate base, that is, the boronate ion, toward H2L, and (b)?the determined pKa values of HBLs. The use of the conditional formation constant, K', based on the main reaction: RB(OH)2 + H2L (K1)? RB(L)(OH)(-) + H3O(+) instead of the binding constant has been proposed for the general reaction of uncomplexed boronic acid species (B') with uncomplexed diol species (L') to form boronic acid diol complex species (esters, BL') in aqueous solution at pH?5-11: B' + L' (K')? BL'. The proposed reaction mechanism explains perfectly the formation of boronic acid diol ester in aqueous solution. PMID:25169423

Furikado, Yuki; Nagahata, Tomomi; Okamoto, Takuya; Sugaya, Tomoaki; Iwatsuki, Satoshi; Inamo, Masahiko; Takagi, Hideo D; Odani, Akira; Ishihara, Koji



Aqueous-Phase Reactions of Isoprene with Sulfoxy Radical Anions as a way of Wet Aerosol Formation in the Atmosphere  

NASA Astrophysics Data System (ADS)

Atmospheric aerosols exhibit an important role in the environment. They have implications on human health and life, and - in the larger scale - on climate, the Earth's radiative balance and the cloud's formation. Organic matter makes up a significant fraction of atmospheric aerosols (~35% to ~90%) and may originate from direct emissions (primary organic aerosol, POA) or result from complex physico-chemical processes of volatile organic compounds (secondary organic aerosol, SOA). Isoprene (2-methyl-buta-1,3-diene) is one of the relevant volatile precursor of ambient SOA in the atmosphere. It is the most abundant non-methane hydrocarbon emitted to the atmosphere as a result of living vegetation. According to the recent data, the isoprene emission rate is estimated to be at the level of 500 TgC per year. While heterogeneous transformations of isoprene have been well documented, aqueous-phase reactions of this hydrocarbon with radical species that lead to the production of new class of wet SOA components such as polyols and their sulfate esters (organosulfates), are still poorly recognized. The chain reactions of isoprene with sulfoxy radical-anions (SRA) are one of the recently researched route leading to the formation of organosulfates in the aqueous phase. The letter radical species originate from the auto-oxidation of sulfur dioxide in the aqueous phase and are behind the phenomenon of atmospheric acid rain formation. This is a complicated chain reaction that is catalyzed by transition metal ions, such as manganese(II), iron(III) and propagated by sulfoxy radical anions . The presented work addresses the chemical interaction of isoprene with sulfoxy radical-anions in the water solution in the presence of nitrite ions and nitrous acid, which are important trace components of the atmosphere. We showed that nitrite ions and nitrous acid significantly altered the kinetics of the auto-oxidation of SO2 in the presence of isoprene at different solution acidity from 2 to 8.7. The presence of nitrogen-containing inorganic salts strongly impact the formation of novel organosulfur products, whereas no organonitrates were observed. A detailed characterization of these products with the triple-quadruple negative electrospray mass spectrometry (-)ESI-MS/MS revealed oxygenated polar species with C-5 skeleton bearing SO3H (MW 182, 180) and SO2H (MW 166, 164) moieties on the hydroxyl group. The structures of these products were firmly confirmed by comparison of their liquid chromatography and mass spectrometry behaviors with that corresponding to the synthesized model compounds. It is believed that newly discovered highly polar low molecular weight compounds may contribute to the growth of wet aerosol particles by the formation of higher molecular weight species.

Kuznietsova, I.; Rudzinski, K. J.; Szmigielski, R.; Laboratory of the Environmental Chemistry



Complex mineral zoning patterns caused by ultra-local equilibrium at reaction interfaces  

NASA Astrophysics Data System (ADS)

Chemical compositions of zoned minerals record a time-series of conditions experienced by the rock. They are a function of the prevailing pressure, temperature and effective bulk chemical composition as well as any post-growth modification processes e.g. volume diffusion and deformation. In fluid-buffered systems, zoned mineral compositions should be expected to reflect directly the evolution of fluid composition. Here we show that during rapid fluid-rock reactions, ultra-local equilibrium can form complex mineral zoning patterns, even when the overall system is highly fluid buffered. We reacted calcite single crystals with arsenate-phosphate solutions with molar ratios of As/(As+P) between 0.011 - 0.145 at 250°C and water-saturated pressure with fluid-rock mass ratios in excess of 2500%. Porous, fine-grained apatite polycrystals with varying arsenic contents replaced the calcite by an interface-coupled dissolution reprecipitation mechanism. During the first few hours of the reaction, complex zoning patterns of arsenic content within the apatite formed. The scale of the arsenic variations corresponds with the scale of corrugations of the reaction interface. The variations in arsenic content of the apatite result from spatially and temporally varying increases in the arsenic content of the reaction interface fluid. Since phosphate diffusion cannot keep pace with the reaction rate arsenic becomes enriched in the reaction interface fluid as phosphate is preferentially used in the reaction. The most arsenic rich parts of the apatite crystal show an 8-fold enrichment in arsenic with respect to the bulk fluid composition but only at an ultra-local scale. Once the calcite is completely consumed, the porous crystal equilibrates with the bulk fluid over a few days because the grain size is much finer and diffusion can keep pace with the equilibration reaction. This study highlights the complexity that can arise from ultra-local fluid composition variations due to rapid fluid-rock interaction in a short-lived fluid flow event, such as that can occur during a seismic cycle. Subsequent interpretation of the complex zoning patterns to reflect the evolution of bulk fluid would not only be extremely complex but also erroneous.

Pearce, Mark; Liu, Weihua; Borg, Stacey; Cleverley, James



Ultrasonic absorption associated with tertiary butanol complex formation in normal-hexane solutions  

E-print Network

ULTRASONIC ABSORPTION ASSOCIATED WITH TERTIARY BUTANOL COMPLEX FORMATION IN NORMAL-HEXANE SOLUTIONS A Thesis by SALIM MICHEL BUCARAM Submitted to the Graduate School of the Agricultural and Mechanical College of Texas in partial fulfillment... of the requirements for the degree of MASTER OF SCIENCE May 196l Major Subject; Physics ULTRASONIC ABSORPTION ASSOCIATED WITH TERTIARY BUTANOL COMPLEX FORMATION IN NORMAL-HEXANE SOLUTIONS A Thesis by SALIM MICHEL BUCARAM Approved as to style and content by...

Bucaram, Salim Michel



OH formation from the C 2H 5CO + O 2 reaction: An experimental marker for the propionyl radical  

Microsoft Academic Search

The reaction between C2H5CO and O2(R1) is observed to directly form OH. This reaction proceeds via the formation of energised C2H5CO(O2), which can either dissociate to OH or be collisionally thermalized. This reaction mechanism is analogous to CH3CO+O2(R4), which we have previously studied and extended in this study. The kinetics and OH yield of reactions R1 and R4 are reported

M. Teresa Baeza Romero; Mark A. Blitz; Dwayne E. Heard; Michael J. Pilling; Ben Price; Paul W. Seakins



Protein-free parallel triple-stranded DNA complex formation  

PubMed Central

A 14 nt DNA sequence 5?-AGAATGTGGCAAAG-3? from the zinc finger repeat of the human KRAB zinc finger protein gene ZNF91 bearing the intercalator 2-methoxy,6-chloro,9-amino acridine (Acr) attached to the sugar–phosphate backbone in various positions has been shown to form a specific triple helix (triplex) with a 16 bp hairpin (intramolecular) or a two-stranded (intermolecular) duplex having the identical sequence in the same (parallel) orientation. Intramolecular targets with the identical sequence in the antiparallel orientation and a non-specific target sequence were tested as controls. Apparent binding constants for formation of the triplex were determined by quantitating electrophoretic band shifts. Binding of the single-stranded oligonucleotide probe sequence to the target led to an increase in the fluorescence anisotropy of acridine. The parallel orientation of the two identical sequence segments was confirmed by measurement of fluorescence resonance energy transfer between the acridine on the 5?-end of the probe strand as donor and BODIPY-Texas Red on the 3?-amino group of either strand of the target duplex as acceptor. There was full protection from OsO4-bipyridine modification of thymines in the probe strand of the triplex, in accordance with the presumed triplex formation, which excluded displacement of the homologous duplex strand by the probe–intercalator conjugate. The implications of these results for the existence of protein-independent parallel triplexes are discussed. PMID:11160932

Shchyolkina, A. K.; Timofeev, E. N.; Lysov, Yu. P.; Florentiev, V. L.; Jovin, T. M.; Arndt-Jovin, D. J.



Reaction of benzophenone UV filters in the presence of aqueous chlorine: kinetics and chloroform formation.  


The transformation of two benzophenone UV filters (Oxybenzone and Dioxybenzone) was examined over the pH range 6-11 in the presence of excess aqueous chlorine. Under these conditions, both UV filters were rapidly transformed by aqueous chlorine just above circumneutral pH while transformation rates were significantly lower near the extremes of the pH range investigated. Observed first-order rate coefficients (k(obs)) were obtained at each pH for aqueous chlorine concentrations ranging from 10 to 75 ?M. The k(obs) were used to determine the apparent second-order rate coefficient (k(app)) at each pH investigated as well as determine the reaction order of aqueous chlorine with each UV filter. The reaction of aqueous chlorine with either UV filter was found to be an overall second-order reaction, first-order with respect to each reactant. Assuming elemental stoichiometry described the reaction between aqueous chlorine and each UV filter, models were developed to determine intrinsic rate coefficients (k(int)) from the k(app) as a function of pH for both UV filters. The rate coefficients for the reaction of HOCl with 3-methoxyphenol moieties of oxybenzone (OXY) and dioxybenzone (DiOXY) were k(1,OxY) = 306 ± 81 M?¹s?¹ and k(1,DiOxY) = 154 ± 76 M?¹s?¹, respectively. The k(int) for the reaction of aqueous chlorine with the 3-methoxyphenolate forms were orders of magnitude greater than the un-ionized species, k(2,OxY) = 1.03(±0.52) × 10? M?¹s?¹ and k(2_1,DiOxY) = 4.14(±0.68) × 10? M?¹s?¹. Also, k(int) for the reaction of aqueous chlorine with the DiOXY ortho-substituted phenolate moiety was k(2_2,DiOxY) = 2.17(±0.30) × 10³ M?¹s?¹. Finally, chloroform formation potential for OXY and DiOXY was assessed over the pH range 6-10. While chloroform formation decreased as pH increased for OXY, chloroform formation increased as pH increased from 6 to 10 for DiOXY. Ultimate molar yields of chloroform per mole of UV filter were pH dependent; however, chloroform to UV filter molar yields at pH 8 were 0.221 CHCl?/OXY and 0.212 CHCl?/DiOXY. PMID:23168312

Duirk, Stephen E; Bridenstine, David R; Leslie, Daniel C



Synthesis of mono(dinitrogen) complexes of molybdenum. Formation of ammonia and hydrazine  

SciTech Connect

The synthesis and reactivity of a series of mono-N/sub 2/ complexes of molybdenum are reported. Reduction of MoCl/sub 3/(triphos), where triphos = PhP(CH/sub 2/CH/sub 2/PPh/sub 2/)/sub 2/, with sodium amalgam in the presence of 2L or L/sub 2/ and with a regulated amount of N/sub 2/ led to the formation of Mo(N/sub 2/)(triphos)(L/sub 2/) (1-5): 1, L = PMe/sub 2/Ph; 2, L/sub 2/ = Me/sub 2/PCH/sub 2/PMe/sub 2/, dmpm; 3, L/sub 2/ = 1,2-(Me/sub 2/As)/sub 2/C/sub 6/H/sub 4/, diars; 4, L/sub 2/ = Ph/sub 2/PCH/sub 2/PPh/sub 2/, dppm; 5, L/sub 2/ = Ph/sub 2/PCH/sub 2/CH/sub 2/PPh/sub 2/, dppe. Complexes 3 and 5 were each a mixture of two isomeric mono-N/sub 2/ complexes. Complexes 1-5 reacted with excess HX (X = Br, Cl) to afford varying yields of ammonia, hydrazine, and N/sub 2/ (and some H/sub 2/). Loss of N/sub 2/ occurred readily from 1 when it was evacuate in the solid state to give 7. Five-coordinate 7 reacted with H/sub 2/, CO, and C/sub 2/H/sub 4/ in the solid state to form MoH/sub 2/(triphos)(PMe/sub 2/Ph)/sub 2/ (8), Mo(CO)(triphos)(PMe/sub 2/Ph)/sub 2/ (9), and Mo(C/sub 2/H/sub 4/)(triphos)(PMe/sub 2/Ph)/sub 2/ (10), respectively. Reaction of solids 7, 8, and 10 with N/sub 2/ regenerated 1. Structural assignments of the new complexes are based upon /sup 31/P and /sup 1/H NMR spectral data. Triphos is shown to adopt both fac and mer configurations. 33 references, 1 table.

George, T.A.; Tisdale, R.C.



Characterizing Pyroxene Reaction Space in Calcium-Aluminum Rich Inclusions: Oxidation During CAI Rim Formation  

NASA Astrophysics Data System (ADS)

We define the reaction space that controls changes in pyroxene composition in CAIs and Wark-Lovering (WL) rims in an oxidizing solar nebula. Ti-rich pyroxenes in CAIs record a sub-solar oxygen fugacity (Ti3+/Ti4+~1.5). WL rim pyroxenes in the CAI Leoville 144A have a distinctly lower oxidation state.This difference supports WL rim condensation in an environment of increasing O2(g) and Mg(g) (Simon et al. 2005). We used the following phase components to identify four linearly independent reactions (Thompson 1982): diopside, CaTs (Al2Mg-1Si-1), T3 (Ti3+AlMg-1Si-1), T4 (Ti4+Al2Mg-1Si-2), En (MgCa-1), perovskite, O(g), Mg(g), SiO(g), and Ca(g). Compositional variation in this system is dominated by two reactions. The first is oxidation of Ti3+ via reaction with O and Mg in the gas phase: 1.5 O(g) + Mg(g) ? ¼ Di + [Ti4+Mg3/4Ti3+-1Ca-1/4Si-1/2] (1). Pyroxene is produced and En is introduced. The second reaction (2) is perovskite formation. It is observed in the WL rim of Leoville 144A, and experiments confirm that an elevated Ti component converts pyroxene to perovskite(Gupta et al. 1973). MgCa-1 is the third linearly independent reaction (3). They combine to give: ½ Di + x Ca(g)? x Mg(g)+ Pv + [Mg1/2-xSiTi4+-1Ca-1/2+x](2,3). Unlike (1), pyroxene is consumed in this reaction. The parameter x defines the extent of Mg-Ca exchange. When x > 0.5, WL rim formation occurs in an environment where Mg is volatile and Ca condenses. The reaction space defined by reactions (1) and (2,3) describes the transition from CAI interior to WL rims. WL rim pyroxene Ti contents, [CaTs], and Ca < 1 pfu are all explained in this space. The fourth linearly independent reaction is SiO(g):1/8 Di + ¼ Mg(g)? ¾ SiO(g) + [Mg3/8Ca1/8Ti4+Ti3+-1Si-1/2](4). Silica reduction forms Ti4+, releasing SiO(g). (4) does not describe the oxidation of Ti3+ in WL rim pyroxene, but (1) - (4) results in En formation directly from the gas phase. This may explain WL rim analyses that have Si contents in excess of those predicted from reactions (1) and (2,3). Simon et al. (2005) EPSL 41, 272-283; Thompson (1982)Rev. Min. 10, 33-52; Gupta et al. (1973) Contr. Mineral. Petrol. 41, 333-344 Reaction space for CAI pyroxene. Pyroxenes plotted using titanium contents.

Dyl, K. A.; Young, E. D.



Asymmetric 1,3-Dipolar Cycloaddition Reactions Catalyzed by Heterocycle-Based Metal Complexes  

NASA Astrophysics Data System (ADS)

Highly enantioselective 1,3-dipolar cycloaddition reactions of several 1,3-dipoles, such as nitrones, nitrile oxides, nitrile imines, diazoalkanes, azomethine imines and carbonyl ylides, catalyzed by heterocyclic supramolecular type of metal complexes consisting of chiral heterocyclic compounds and metal salts were described in terms of their ability of asymmetric induction and enantioface differentiation. The scope and limitations of each cycloaddition reactions were also briefly described. Of the chiral hererocycle-based ligands, chiral bisoxazoline, 2,6-bis(oxazolinyl)pyridine, and related oxazoline ligands are shown to be quite effective in obtaining high levels of asymmtric induction. The combination of the bisoxazoline ligand derived from (1S,2R)-cis-1-amino-2-indanol and metal salts was especially efficient for asymmetric cycloaddition reactions of a number of 1,3-dipoles, such as nitrones, nitrile oxide, nitrile imines, diazoacetates and azomethine imines. The metals utilized for the heterocycle-based complexes show a crucial role for degree of asymmetric induction depending upon the 1,3-dipole used. High levels of enantioselectivity were achieved in 1,3-dipolar cycloaddition reactions of unstable carbonyl ylides with benzyloxyacetaldehyde derivatives, ?-keto esters, 3-(2-alkenoyl)-2-oxazolidinones, and even vinyl ethers, which were catalyzed by Pybox-lanthanoid metal complexes.

Suga, Hiroyuki


EXAFS studies on the reaction of gold (III) chloride complex ions with sodium hydroxide and glucose.  


EXAFS and QEXAFS experiments were carried out at Hasylab laboratory in DESY center (X1 beamline, Hamburg, Germany) to monitor the course of the hydrolysis reactions of [AuCl(4)](-) complex ions as well as their reduction using glucose. As a result, changes in the spectra of [AuCl(4)](-) ions and disappearance of absorption Au-L(3) edge were registered. From the results of the experiments we have carried out, the changes in bond lengths between Au(3+) central ion and Cl(-) ligands as well as the reduction of Au(3+) to metallic form (colloidal gold was formed in the system) are evident. Good quality spectra obtained before and after the reactions gave a chance to determine the bond length characteristic of Au-Cl, Au-OH and Au-Au pairs. Additionally, the obtained results were compared with the simulated spectra of different gold (III) complex ions, possibly present in the solution. Finally, the mechanism of these reactions was suggested. Unfortunately, it was not possible to detect the changes in the structure of gold (III) complex ions within the time of reaction, because of too high rates of both processes (hydrolysis and reduction) as compared with the detection time. PMID:20958005

Pac?awski, K; Zajac, D A; Borowiec, M; Kapusta, Cz; Fitzner, K



Orientation of the Central Pair Complex During Flagellar Bend Formation in  

E-print Network

Orientation of the Central Pair Complex During Flagellar Bend Formation in Chlamydomonas David R Thin section electron micrographs of rapidly fixed Chlamydomonas cells were used to establish a relationship between flagellar bends and orientation of the central pair microtubule complex. Using conditions

Mitchell, David


Formation of an Intrapolymer Complex from Human Serum Albumin and Poly(ethylene glycol)  

E-print Network

Formation of an Intrapolymer Complex from Human Serum Albumin and Poly(ethylene glycol) Shinji Form: October 13, 1998 Complexation between human serum albumin (HSA) and poly(ethylene glycol) (PEG, it has been demonstrated that poly(dial- lyldimethylammonium chloride) and bovine serum albu- min give

Dubin, Paul D.


Complexation facilitated reduction of aromatic N-oxides by aqueous Fe(II)-tiron complex: reaction kinetics and mechanisms.  


Rapid reduction of carbadox (CDX), olaquindox and several other aromatic N-oxides were investigated in aqueous solution containing Fe(II) and tiron. Consistent with previous work, the 1:2 Fe(II)-tiron complex, FeL2(6-), is the dominant reactive species as its concentration linearly correlates with the observed rate constant kobs under various conditions. The N-oxides without any side chains were much less reactive, suggesting direct reduction of the N-oxides is slow. UV-vis spectra suggest FeL2(6-) likely forms 5- or 7-membered rings with CDX and olaquindox through the N and O atoms on the side chain. The formed inner-sphere complexes significantly facilitated electron transfer from FeL2(6-) to the N-oxides. Reduction products of the N-oxides were identified by HPLC/QToF-MS to be the deoxygenated analogs. QSAR analysis indicated neither the first electron transfer nor N-O bond cleavage is the rate-limiting step. Calculations of the atomic spin densities of the anionic N-oxides confirmed the extensive delocalization between the aromatic ring and the side chain, suggesting complex formation can significantly affect the reduction kinetics. Our results suggest the complexation facilitated N-oxide reduction by Fe(II)-tiron involves a free radical mechanism, and the subsequent deoxygenation might also benefit from the weak complexation of Fe(II) with the N-oxide O atom. PMID:23957215

Chen, Yiling; Zhang, Huichun



Ion wake formation with dust charge fluctuation in complex plasma  

SciTech Connect

In complex plasma, the interaction mechanism among dust grains near the plasma sheath is significantly influenced by the downward ion flow towards the sheath and dust charge fluctuation over grain surface. Asymmetric ion flow towards the sheath gives rise to well known attractive wake potential in addition to repulsive Yukawa type of potential. The present work shows that the charging dynamics play a significant role in modification of plasma dielectric response function and hence the interaction mechanism among test dust particulates. The effective Debye length is found to be a characteristic of dust size and background plasma response towards the grain along with ion flow speed. The potentials thus obtained show a damping in strength of interaction in the presence of dynamical charging of dust as compared to that of constant charge dust grains. The result also shows decrease in focal length of ion lensing with increase in grain size.

Bhattacharjee, Saurav; Das, Nilakshi [Department of Physics, Tezpur University, Tezpur, Assam, 784 028 (India)] [Department of Physics, Tezpur University, Tezpur, Assam, 784 028 (India)



Monitoring benzene formation from benzoate in model systems by proton transfer reaction-mass spectrometry  

NASA Astrophysics Data System (ADS)

The presence of benzene in food and in particular in soft drinks has been reported in several studies and should be considered in fundamental investigations about formation of this carcinogen compound as well as in quality control. Proton transfer reaction-mass spectrometry (PTR-MS) has been used here for rapid, direct quantification of benzene and to monitor its formation in model systems related to the use of benzoate, a common preservative, in presence of ascorbic acid: a widespread situation that yields benzene in, e.g., soft drinks and fruit juices. Firstly, we demonstrate here that PTR-MS allows a rapid determination of benzene that is in quantitative agreement with independent solid phase micro-extraction/gas chromatography (SPME/GC) analysis. Secondly, as a case study, the effect of different sugars (sucrose, fructose and glucose) on benzene formation is investigated indicating that they inhibit its formation and that this effect is enhanced for reducing sugars. The sugar-induced inhibition of benzene formation depends on several parameters (type and concentration of sugar, temperature, time) but can be more than 80% in situations that can be expected in the storage of commercial soft drinks. This is consistent with the reported observations of higher benzene concentrations in sugar-free soft drinks.

Aprea, Eugenio; Biasioli, Franco; Carlin, Silvia; Märk, Tilmann D.; Gasperi, Flavia




SciTech Connect

In the interstellar medium (ISM), an important channel of water formation is the reaction of atoms on the surface of dust grains. Here, we report on a laboratory study of the formation of water via the O+D reaction network. While prior studies were done on ices, as appropriate to the formation of water in dense clouds, we explored how water formation occurs on bare surfaces, i.e., in conditions mimicking the transition from diffuse to dense clouds (Av {approx} 1-5). Reaction products were detected during deposition and afterward when the sample is brought to a high temperature. We quantified the formation of water and intermediary products, such as D{sub 2}O{sub 2}, over a range of surface temperatures (15-25 K). The detection of OD on the surface signals the importance of this reactant in the overall scheme of water formation in the ISM.

Jing Dapeng; He Jiao; Vidali, Gianfranco [Physics Department, Syracuse University, Syracuse, NY 13244 (United States); Brucato, John; Tozzetti, Lorenzo [INAF, Astrophysical Observatory of Arcetri, Florence (Italy); De Sio, Antonio [Department of Astronomy and Space Science, University of Florence, Florence (Italy)



Complex Formation History of Highly Evolved Basaltic Shergottite, Zagami  

NASA Technical Reports Server (NTRS)

Zagami, a basaltic shergottite, contains several kinds of lithologies such as Normal Zagami consisting of Fine-grained (FG) and Coarse-grained (CG), Dark Mottled lithology (DML), and Olivine-rich late-stage melt pocket (DN). Treiman and Sutton concluded that Zagami (Normal Zagami) is a fractional crystallization product from a single magma. It has been suggested that there were two igneous stages (deep magma chamber and shallow magma chamber or surface lava flow) on the basis of chemical zoning features of pyroxenes which have homogeneous Mg-rich cores and FeO, CaO zoning at the rims. Nyquist et al. reported that FG has a different initial Sr isotopic ratio than CG and DML, and suggested the possibility of magma mixing on Mars. Here we report new results of petrology and mineralogy for DML and the Olivine-rich lithology (we do not use DN here), the most evolved lithology in this rock, to understand the relationship among lithologies and reveal Zagami s formation history

Niihara, T.; Misawa, K.; Mikouchi, T.; Nyquist, L. E.; Park, J.; Hirata, D.



Scale-Dependent Rates of Uranyl Surface Complexation Reaction in Sediments  

SciTech Connect

Scale-dependency of uranyl[U(VI)] surface complexation rates was investigated in stirred flow-cell and column systems using a U(VI)-contaminated sediment from the US Department of Energy, Hanford site, WA. The experimental results were used to estimate the apparent rate of U(VI) surface complexation at the grain-scale and in porous media. Numerical simulations using molecular, pore-scale, and continuum models were performed to provide insights into and to estimate the rate constants of U(VI) surface complexation at the different scales. The results showed that the grain-scale rate constant of U(VI) surface complexation was over 3 to 10 orders of magnitude smaller, dependent on the temporal scale, than the rate constant calculated using the molecular simulations. The grain-scale rate was faster initially and slower with time, showing the temporal scale-dependency. The largest rate constant at the grain-scale decreased additional 2 orders of magnitude when the rate was scaled to the porous media in the column. The scaling effect from the grain-scale to the porous media became less important for the slower sorption sites. Pore-scale simulations revealed the importance of coupled mass transport and reactions in both intragranular and inter-granular domains, which caused both spatial and temporal dependence of U(VI) surface complexation rates in the sediment. Pore-scale simulations also revealed a new rate-limiting mechanism in the intragranular porous domains that the rate of coupled diffusion and surface complexation reaction was slower than either process alone. The results provided important implications for developing models to scale geochemical/biogeochemical reactions.

Liu, Chongxuan; Shang, Jianying; Kerisit, Sebastien N.; Zachara, John M.; Zhu, Weihuang



The ORC/Cdc6/MCM2-7 complex facilitates MCM2-7 dimerization during prereplicative complex formation.  


The replicative mini-chromosome-maintenance 2-7 (MCM2-7) helicase is loaded in Saccharomyces cerevisiae and other eukaryotes as a head-to-head double-hexamer around origin DNA. At first, ORC/Cdc6 recruits with the help of Cdt1 a single MCM2-7 hexamer to form an 'initial' ORC/Cdc6/Cdt1/MCM2-7 complex. Then, on ATP hydrolysis and Cdt1 release, the 'initial' complex is transformed into an ORC/Cdc6/MCM2-7 (OCM) complex. However, it remains unclear how the OCM is subsequently converted into a MCM2-7 double-hexamer. Through analysis of MCM2-7 hexamer-interface mutants we discovered a complex competent for MCM2-7 dimerization. We demonstrate that these MCM2-7 mutants arrest during prereplicative complex (pre-RC) assembly after OCM formation, but before MCM2-7 double-hexamer assembly. Remarkably, only the OCM complex, but not the 'initial' ORC/Cdc6/Cdt1/MCM2-7 complex, is competent for MCM2-7 dimerization. The MCM2-7 dimer, in contrast to the MCM2-7 double-hexamer, interacts with ORC/Cdc6 and is salt-sensitive, classifying the arrested complex as a helicase-loading intermediate. Accordingly, we found that overexpression of the mutants cause cell-cycle arrest and dominant lethality. Our work identifies the OCM complex as competent for MCM2-7 dimerization, reveals MCM2-7 dimerization as a limiting step during pre-RC formation and defines critical mechanisms that explain how origins are licensed. PMID:24234446

Evrin, Cecile; Fernández-Cid, Alejandra; Riera, Alberto; Zech, Juergen; Clarke, Pippa; Herrera, M Carmen; Tognetti, Silvia; Lurz, Rudi; Speck, Christian



Reaction path in the formation of titanium diboride by a magnesium thermite process  

SciTech Connect

TiB{sub 2} was formed by a thermite reaction amongst Mg, amorphous B{sub 2}O{sub 3} and TiO{sub 2} powders. Mixtures consisting of 2Mg-TiO{sub 2}, 3Mg-B{sub 2}O{sub 3} and 5Mg-TiO{sub 2}-B{sub 2}O{sub 3} were heat treated using DTA and separately via ignition with a nichrome wire; product phases were identified using XRD. MgO and Ti were products from the first mixture reacted in argon, whereas an incomplete transformation forming Mg{sub 3}TiO{sub 4} occurred in air. For the second mixture, a reaction forming Mg{sub 3}B{sub 2}O{sup 6} occurred in air, but no reaction occurred in argon due to deficiency of oxygen. Minor amounts Of Mg{sub 3}B{sub 2}O{sub 6} and Mg{sub 2}TiO{sub 4} were detected in addition to the predicted product phases of MgO and TiB{sub 2} for the third mixture ignited both in air and argon. Based on available evidence, a path for this reaction was deduced; Mg particles in contact with TiO{sub 2} reacted to form Ti, which in turn reacted with B{sub 2}O{sub 3} to form TiB{sub 2}. TiB{sub 2} product particles from the reaction in argon had a more faceted appearance than those formed during the reaction in air. This was interpreted to be the result of glassy B{sub 2}O{sub 3} surface layer formation on TiB{sub 2} particles in air.

Sundaram, V.; Logan, K.V.; Speyer, R.F. [Georgia Inst. of Technology, Atlanta, GA (United States)



Factors leading to the formation of arc cloud complexes  

NASA Technical Reports Server (NTRS)

A total of 12 mesoscale convective systems (MCSs) were investigated. The duration of the gust front, produced by each MCS, was used to classify the MCSs. Category 1 MCSs were defined as ones that produced a gust front and the gust front lasted for more than 6 h. There were 7 category 1 MCSs in the sample. Category 2 MCSs were defined as ones that produced a gust front and the gust front lasted for 6 h or less. There were 4 category 2 MCSs. The MCS of Case 12 was not categorized because the precipitation characteristics were similar to a squall line, rather than an MCS. All of the category 1 MCSs produced arc cloud complexes (ACCs), while only one of the category 2 MCSs produced an ACC. To determine if there were any differences in the characteristics between the MCSs of the two categories, composite analyses were accomplished. The analyses showed that there were significant differences in the characteristics of category 1 and 2 MCSs. Category 1 MCSs, on average, had higher thunderstorm heights, greater precipitation intensities, colder cloud top temperatures and produced larger magnitudes of surface divergence than category 2 MCSs.

Welshinger, Mark John; Brundidge, Kenneth C.



Interferogram formation in the presence of complex and large deformation  

USGS Publications Warehouse

Sierra Negra volcano in Isabela island, Gala??pagos, erupted from October 22 to October 30 in 2005. During the 8 days of eruption, the center of Sierra Negra's caldera subsided about 5.4 meters. Three hours prior to the onset of the eruption, an earthquake (Mw 5.4) occurred, near the caldera. Because of the large and complex phase gradient due to the huge subsidence and the earthquake, it is difficult to form an interferogram inside the caldera that spans the eruption. The deformation is so large and spatially variable that the approximations used in existing InSAR software (ROI, ROI_PAC, DORIS, GAMMA) cannot properly coregister SAR image pairs spanning the eruption. We have developed here a two-step algorithm that can form intra-caldera interferograms from these data. The first step involves a "rubber-sheeting" SAR image coregistration. In the second step we use range offset estimates to mitigate the steep phase gradient. Using this new algorithm, we retrieve an interferogram with the best coverage to date inside the caldera of Sierra Negra. Copyright 2007 by the American Geophysical Union.

Yun, S.-H.; Zebker, H.; Segall, P.; Hooper, A.; Poland, M.



ADMR of carotenoid triplet states in bacterial photosynthetic antenna and reaction center complexes  

NASA Astrophysics Data System (ADS)

Using absorption detected magnetic resonance (ADMR) the triplet states of carotenoids have been detected in B880—RC complexes of the purple photosynthetic bacteria Rhodocyclus gelatinosus 149, Rhodopseudomonas acidophila 7050, Rhodopseudomonas palustris 8252, and Rhodospirillum rubrum S1, and in reaction center (RC) complexes of Rhodospirillum rubrum S1. The triplet states were identified as belonging to antenna carotenois in the all-trans conformation with conjugated chain lengths ranging from 10 to 13 double bonds, and to the RC carotenoid 15,15'-cis spirilloxanthin. Carotenoids with different numbers of conjugated double bonds have similar ability to quench the triplet states of the bacteriochlorophylls.

Aust, V.; Angerhofer, A.; Ullrich, J.; von Schütz, J. U.; Wolf, H. C.; Cogdell, R. J.



Pressure dependent product formation in the photochemically initiated allyl + allyl reaction.  


Photochemically driven reactions involving unsaturated radicals produce a thick global layer of organic haze on Titan, Saturn's largest moon. The allyl radical self-reaction is an example for this type of chemistry and was examined at room temperature from an experimental and kinetic modelling perspective. The experiments were performed in a static reactor with a volume of 5 L under wall free conditions. The allyl radicals were produced from laser flash photolysis of three different precursors allyl bromide (C3H5Br), allyl chloride (C3H5Cl), and 1,5-hexadiene (CH2CH(CH2)2CHCH2) at 193 nm. Stable products were identified by their characteristic vibrational modes and quantified using FTIR spectroscopy. In addition to the (re-) combination pathway C3H5+C3H5 ? C6H10 we found at low pressures around 1 mbar the highest final product yields for allene and propene for the precursor C3H5Br. A kinetic analysis indicates that the end product formation is influenced by specific reaction kinetics of photochemically activated allyl radicals. Above 10 mbar the (re-) combination pathway becomes dominant. These findings exemplify the specificities of reaction kinetics involving chemically activated species, which for certain conditions cannot be simply deduced from combustion kinetics or atmospheric chemistry on Earth. PMID:24192913

Seidel, Lars; Hoyermann, Karlheinz; Mauß, Fabian; Nothdurft, Jörg; Zeuch, Thomas



Roles of Acetone and Diacetone Alcohol in Coordination and Dissociation Reactions of Uranyl Complexes  

SciTech Connect

Combined collision-induced dissociation mass-spectrometry experiments and DFT calculations were employed to elucidate the molecular structure of "hypercoordinated" species and the energetics of water-elimination reactions of uranyl acetone complexes observed in earlier work (Rios, D.; Rutkowski, P. X.; Van Stipdonk, M. J.; Gibson, J. K. Inorg. Chem. 2011, 50, 4781). It is shown that the "hypercoordinated" species contain diacetone alcohol ligands bonded in either bidentate or monodentate fashion, which are indistinguishable from (acetone)2 in mass spectrometry. Calculations confirm that four diacetone ligands can form stable complexes, but that the effective number of atoms coordinating with uranium in the equatorial plane does not exceed five. Diacetone alcohol ligands are shown to form mesityl oxide ligands and alkoxide species through the elimination of water, providing an explanation for the observed water-elimination reactions.

Rios, Daniel; Schoendorff, George E.; Van Stipdonk, Michael J.; Gordon, Mark S.; Windus, Theresa L.; Gibson, John K.; De Jong, Wibe A.



Urea-acetylene dicarboxylic acid reaction: A likely pathway for prebiotic uracil formation  

NASA Astrophysics Data System (ADS)

A number of routes have been suggested for the prebiotic synthesis of uracil involving the reaction of urea with malic acid, propiolic acid, cyanoacetylene and others. Cyanoacetylene has been detected in the interstellar medium as well as simulated prebiotic experiments. It is therefore plausible that dicyanoacetylene and its hydrolytic product acetylene dicarboxylic acid, (ADCA) may have played a role in chemical evolution. This aspect has been examined in the present work for the synthesis of uracil from ADCA and urea reaction. It was found that when ADCA reacted with urea, uracil was formed only in the presence of phosphoric acid and phosphates. Ammonium phosphates gave higher yields of uracil than other phosphates. In the absence of phosphoric acid or phosphates no uracil formation took place. This type of synthesis could have taken place in prebiotic oceans which contained ammonium phosphates and other salts.

Subbaraman, A. S.; Kazi, Z. A.; Choughuley, A. S. U.; Chadha, M. S.



Dichotomous-noise-induced pattern formation in a reaction-diffusion system  

NASA Astrophysics Data System (ADS)

We consider a generic reaction-diffusion system in which one of the parameters is subjected to dichotomous noise by controlling the flow of one of the reacting species in a continuous-flow-stirred-tank reactor (CSTR) -membrane reactor. The linear stability analysis in an extended phase space is carried out by invoking Furutzu-Novikov procedure for exponentially correlated multiplicative noise to derive the instability condition in the plane of the noise parameters (correlation time and strength of the noise). We demonstrate that depending on the correlation time an optimal strength of noise governs the self-organization. Our theoretical analysis is corroborated by numerical simulations on pattern formation in a chlorine-dioxide-iodine-malonic acid reaction-diffusion system.

Das, Debojyoti; Ray, Deb Shankar



Dichotomous-noise-induced pattern formation in a reaction-diffusion system.  


We consider a generic reaction-diffusion system in which one of the parameters is subjected to dichotomous noise by controlling the flow of one of the reacting species in a continuous-flow-stirred-tank reactor (CSTR) -membrane reactor. The linear stability analysis in an extended phase space is carried out by invoking Furutzu-Novikov procedure for exponentially correlated multiplicative noise to derive the instability condition in the plane of the noise parameters (correlation time and strength of the noise). We demonstrate that depending on the correlation time an optimal strength of noise governs the self-organization. Our theoretical analysis is corroborated by numerical simulations on pattern formation in a chlorine-dioxide-iodine-malonic acid reaction-diffusion system. PMID:23848765

Das, Debojyoti; Ray, Deb Shankar



Effect of Physical Factors on Reactions of Horse-Radish Peroxidase Complexes with Reduced Cytochrome c  

PubMed Central

This investigation concerns the effect of certain physical factors—viscosity, dielectric constant, ionic strength, and temperature of the medium—on the reaction of hydrogen peroxide and ferrocytochrome c in the presence of the enzyme horse-radish peroxidase. From study of the effects of viscosity and dielectric constant, it was concluded that the reaction between the secondary complex of hydrogen peroxide and enzyme on the one hand and ferrocytochrome c on the other is controlled by diffusion in media of high viscosity and by electrostatic effects at low viscosities. With respect to ionic strength, the data at pH 4.7 indicated a dipole-dipole interreaction. The temperature dependence of the over-all reaction had a Q10 of 1.25. PMID:14070362

Farwell, Robert W.; Ackerman, Eugene



Multinuclear Pd/Zn complex-catalyzed asymmetric alkylative ring-opening reaction of oxabicyclic alkenes.  


A multinuclear palladium catalyst can be used to realize the efficient catalytic asymmetric alkylative ring-opening reaction of oxabicyclic alkenes using dimethylzinc. The use of (R)-BINOL-PHOS bearing bisphosphine and diol moieties is essential for achieving excellent catalytic performance; the corresponding monophosphine and hydroxy-protected derivatives showed lower catalytic activities and/or enantioselectivities. The generation of Pd/Zn-multinuclear complexes is a key feature of the present catalysis. PMID:21261272

Endo, Kohei; Tanaka, Keisuke; Ogawa, Mika; Shibata, Takanori



Characterization of self-propagating formation reactions in Ni/Zr multilayered foils using reaction heats, velocities, and temperature-time profiles  

We report on intermetallic formation reactions in vapor-deposited multilayered foils of Ni/Zr with 70 nm bilayers and overall atomic ratios of Ni:Zr, 2 Ni:Zr, and 7 Ni:2 Zr. The sequence of alloy phase formation and the stored energy is evaluated at slow heating rates (~1 K/s) using differential scanning calorimetry (DSC) traces to 725ºC. All three chemistries initially form a Ni-Zr amorphous phase which crystallizes first to the intermetallic NiZr. The heat of reaction to the final phase is 34-36 kJ/mol atom for all chemistries. Intermetallic formation reactions are also studied at rapid heating rates (greater than 105 K/s) in high temperature, self-propagating reactions which can be ignited in these foils by an electric spark. We find that reaction velocities and maximum reaction temperatures (Tmax) are largely independent of foil chemistry at 0.6 ± 0.1 m/s and 1220 ± 50 K, respectively, and that the measured Tmax is more than 200 K lower than predicted adiabatic temperatures (Tad). The difference between Tmax and Tad is explained by the prediction that transformation to the final intermetallic phases occurs after Tmax and results in the release of 20-30 % of the total heat of reaction and a delay in rapid cooling.

Barron, S. C.; Knepper, R.; Walker, N.; Weihs, T. P.



Formation of phenol and carbonyls from the atmospheric reaction of OH radicals with benzene.  


The gas-phase reaction of OH radicals with benzene has been studied in a flow tube operated at 295 +/- 2 K and 950 mbar of synthetic air or O2. Ozonolysis of tetramethylethylene (dark reaction) with a measured OH radical yield of 0.92 +/- 0.08 or photolysis of methyl nitrite in the presence of NO served as the OH sources. For investigations in the presence of NOx, the conditions were chosen so that more than 95% of the OH/benzene adduct reacted with O2 even for the highest NO2 concentration occurring in the experiment. In the absence of NOx, a phenol yield from the reaction of OH radicals with benzene of 0.61 +/- 0.07 was measured by means of long-path FT-IR and UV spectroscopy over a wide range of experimental conditions. This yield was confirmed by measurements performed in the presence of NOx. Detected carbonyls were glyoxal, cis-butenedial and trans-butenedial with formation yields of 0.29 +/- 0.10, 0.08 +/- 0.03 and 0.023 +/- 0.007, respectively, measured in synthetic air and in the presence of NOx. There was no significant difference in the product yields applying both experimental approaches for OH generation (dark reaction or photolysis). Nitrobenzene and o-nitrophenol were detected in traces. The yield of nitrobenzene increased with increasing NOx resulting in a maximum formation yield of 0.007. The detected products in the presence of NOx account for approximately 78% of the reacted carbon. Butenedial yields from benzene degradation are reported for the first time. In the absence of NOx, glyoxal, cis-butenedial and trans-butenedial were also detected, but with distinctly lower yields compared to the experiments with NOx. PMID:16633601

Berndt, Torsten; Böge, Olaf




EPA Science Inventory

The generation by combustion processes of airborne species of current health concern such as polycyclic aromatic hydrocarbons (PAH) and soot particles necessitates a detailed understanding of chemical reaction pathways responsible for their formation. The present review discus...


Stark effect spectroscopy of carotenoids in photosynthetic antenna and reaction center complexes.  


The effects of electric fields on the absorption spectra of the carotenoids spheroidene and spheroidenone in photosynthetic antenna and reaction center complexes (wild-type and several mutants) from purple non-sulfur bacteria are compared with those for the isolated pigments in organic glasses. In general, the field effects are substantially larger for the carotenoid in the protein complexes than for the extracted pigments and larger for spheroidenone than spheroidene. Furthermore, the electrochromic effects for carotenoids in all complexes are much larger than those for the Qx transitions of the bacteriochlorophyll and bacteriopheophytin pigments which absorb in the 450-700 nm spectral region. The underlying mechanism responsible for the Stark effect spectra in the complexes is found to be dominated by a change in permanent dipole moment of the carotenoid upon excitation. The magnitude of this dipole moment change is found to be considerably larger in the B800-850 complex compared to the reaction center for spheroidene; it is approximately equivalent in the two complexes for spheroidenone. These results are discussed in terms of the effects of differences in the carotenoid functional groups, isomers and perturbations on the electronic structure from interactions with the organized environment in the proteins. these data provide a quantitative basis for the analysis of carotenoid bandshifts which are used to measure transmembrane potential, and they highlight some of the pitfalls in making such measurements on complex membranes containing multiple populations of carotenoids. The results for spheroidenone should be useful for studies of mutant proteins, since mutant strains are often grown semi-aerobically to minimize reversion. PMID:1873299

Gottfried, D S; Steffen, M A; Boxer, S G



Quasifission and difference in formation of evaporation residues in the $^{16}$O+$^{184}$W and $^{19}$F+$^{181}$Ta reactions  

E-print Network

The excitation functions of capture, complete fusion, and evaporation residue formation in the $^{16}$O+$^{184}$W and $^{19}$F+$^{181}$Ta reactions leading to the same $^{200}$Pb compound nucleus has been studied theoretically to explain the experimental data showing more intense yield of evaporation residue in the former reaction in comparison with that in the latter reaction. The observed difference is explained by large capture cross section in the former and by increase of the quasifission contribution to the yield of fission-like fragments in the $^{19}$F+$^{181}$Ta reaction at large excitation energies. The probability of compound nucleus formation in the $^{16}$O+$^{184}$W reaction is larger but compound nuclei formed in both reactions have similar angular momentum ranges at the same excitation energy. The observed decrease of evaporation residue cross section normalized to the fusion cross section in the $^{19}$F+$^{181}$Ta reaction in comparison with the one in the $^{16}$O+$^{184}$W reaction at high excitation energies is explained by the increase of hindrance in the formation of compound nucleus connected with more quick increase of the quasifission contribution in the $^{19}$F induced reaction. The spin distributions of the evaporation residue cross sections for the two reactions are also presented.

A. K. Nasirov; G. Mandaglio; M. Manganaro; A. I. Muminov; G. Fazio; G. Giardina



Laboratory investigation on the formation of unsaturated nitriles in Titan's atmosphere via reactions of CN radicals with unsaturated hydrocarbons as studied in crossed molecular beams experiments  

NASA Astrophysics Data System (ADS)

Reactions of CN radicals with unsaturated hydrocarbons are thought to be of fundamental relevance to form unsaturated nitriles in Titan's atmosphere. Because of that, numerous studies of CN reactions with unsaturated molecules have been performed by exploiting the most modern kinetic techniques. Nevertheless, only the CN decay rates were recorded and the reaction mechanisms speculated. A deeper understanding of CN reaction mechanisms requires investigation at the microscopic level. The reaction mechanism has been elucidated, so far, only for the simplest CN radical reaction, that with molecular hydrogen. Even if this system may be regarded as a prototype for CN reactions because of its simplicity, the reaction mechanism with unsaturated hydrocarbons is expected to be different with the addition of CN to the pi bond being dominant. In this contribution we report on the first systematic investigation of reactions of CN radicals with unsaturated hydrocarbons by using the crossed molecular beam technique with mass spectrometric detection. The first reactions we have looked at are those involving simple unsaturated hydrocarbons with respect to the CN/H exchange channels: (1) CN + C_2H_2 -> HCCCN + H (2) CN + C_2H_4 -> C_2H_3CN + H (3) CN + CH_3CCH -> CH_3CCCN + H \\ H_2CCCH(CN) + H (4) CN + CH_3CCCH_3 -> CH_2CC(CN)CH_3 + H (5) CN + H_2CCCH_2 -> H_2CCCH(CN) + H Our results show that reactions (1) - (5) proceed without entrance barrier through the formation of a complex following the addition of the CN radical to the pi system of the unsaturated hydrocarbon. Each complex decomposes to form the nitrile and a H atom. The explicit identification of this CN - H exchange channel opens a versatile route to form unsaturated nitriles and predict their formation in Titan's atmosphere. Further, our studies provide a solid data base on reaction products and shall guide chemical investigation of the NASA-ESA Cassini-Huygens mission to identify these nitriles in Titan.

Kaiser, R. I.; Balucani, N.; Asvany, O.; Lee, Y. T.



Search for reaction conditions and catalyst for selective prebiotic formation of Aldopentoses from Glycolaldehyde and Formaldehyde  

NASA Astrophysics Data System (ADS)

Formation of organic compounds from simple precursors appears to have been one of the first steps from geochemistry towards modern biochemistry. The Earth lagoons, hydrothermal springs, cosmic dust, meteorites, protoplanetary disk, etc. has been considered as the possible ``reactors'' in which the prebiotic synthesis could have taken place. The finding of reactions and reaction conditions which allow to produce the high yields of the biologically relevant substances from simple compounds could help us to verify different hypothesis of plausible prebotic conditions. In this work we have studied the formation of vitally important sugars, namely aldopentoses (ribose, xylose, lyxose and arabinose), from glycolaldehyde and formaldehyde over catalysts. Aldopentoses nowadays play the important roles as the components of polysaccharides, glycosides, nucleic acids and ATP. Glycolaldehyde is the simplest monosaccharide, which was found in the interstellar space [1], where it could be generated as a result of several processes, for instance, condensation of formaldehyde under UV-radiation [2]. In this work the peculiarities of interaction between glycolaldehyde and formaldehyde in the presence of soluble (phosphate and borate buffers) and solid (minerals apatite and montmorillonites) catalysts were studied. The dependences of composition of the reaction products on the catalyst nature, molar ratio of substrates, pH value of reaction mixture were revealed. The yields of aldopentoses amount to ca. 60-65% in the presence of borate catalyst under optimized reaction conditions. Borate acts not only as a catalyst, but also as the stabilizer of active intermediates and aldopentoses from side reactions [3]. Borates are present in some mineral and clays (serpentine, montmorillonite etc.) and in water of Cityhot springs (Geyser valley, placeKamchatka) in rather high concentrations. Therefore catalysis by borates could be considered as plausible prebotic condition. Acknowledgements. We thank Dr. S. Yashnik for providing the montmorillonite clays. The financial support of Program RAS (program ``Origin of biosphere and evolution biogeology systems'') is gratefully acknowledged. Hollis, J., Jewell, P., Lovas, F., et al., The Astrophysical Journal. 613, L45--L48, 2004 Pestunova, O., Simonov, A., Snytnikov, V., et al., Adv. Space Res. 36/2, 214-219, 2005. Ricardo, A., Carrigan, M.A., Olcott, A.N., Benner, S.A. Science. 303, 5655, 196, 2004.

Delidovich, Irina; Taran, Oxana; Parmon, Valentin; Gromov, Nikolay



Complex dynamic behavior in the bromate-oxalic acid-acetone-Mn(II) oscillating reaction in a continuous stirred tank reactor (CSTR)  

NASA Astrophysics Data System (ADS)

The oscillating reaction bromate-oxalic acid-acetone-Mn(II)-sulfuric acid was observed for the first time in a CSTR at 20 °C. Depending on the bromate concentrations and flow rate, the system showed large amplitude oscillations, two kinds of mixed mode oscillations, quasiperiodicity and bursts of large amplitude oscillations, all mapped in a phase diagram. More complex behavior was favored at low bromate concentrations. The system without acetone was discovered to oscillate too, but the more complex patterns were not seen, indicating that acetone is implied in their formation.

Silva, Lucyane C.; Faria, Roberto B.



Asymmetric aldol reactions between acetone and benzaldehydes catalyzed by chiral Zn2+ complexes of aminoacyl 1,4,7,10-tetraazacyclododecane: fine-tuning of the amino-acid side chains and a revised reaction mechanism.  


We previously reported that chiral Zn(2+) complexes that were designed to mimic the actions of class-I and class-II aldolases catalyzed the enantioselective aldol reactions of acetone and its analogues thereof with benzaldehyde derivatives. Herein, we report the synthesis of new chiral Zn(2+) complexes that contain Zn(2+)-tetraazacyclododecane (Zn(2+)-[12]aneN4) moieties and amino acids that contain aliphatic, aromatic, anionic, cationic, and dipeptide side chains. The chemical and optical yields of the aldol reaction were improved (up to 96?% ee) by using ZnL complexes of L-decanylglycyl-pendant [12]aneN4 (L-ZnL(7)), L-naphthylalanyl-pendant [12]aneN4 (L-ZnL(10)), L-biphenylalanyl-pendant [12]aneN4 (L-ZnL(11)), and L-phenylethylglycyl-pendant [12]aneN4 ligands (L-ZnL(12)). UV/Vis and circular dichroism (CD) titrations of acetylacetone (acac) with ZnL complexes confirmed that a ZnL-(acac)(-) complex was exclusively formed and not the enaminone of ZnL and acac, as we had previously proposed. Moreover, the results of stopped-flow experiments indicated that the complexation of (acac)(-) with ZnL was complete within milliseconds, whereas the formation of an enaminone required several hours. X-ray crystal-structure analysis of L-ZnL(10) and the ZnL complex of L-diphenylalanyl-pendant [12]aneN4 (L-ZnL(13)) shows that the NH2 groups of the amino-acid side chains of these ligands are coordinated to the Zn(2+) center as the fourth coordination site, in addition to three nitrogen atoms of the [12]aneN4 rings. The reaction mechanism of these aldol reactions is discussed and some corrections are made to our previous mechanistic hypothesis. PMID:23780779

Itoh, Susumu; Tokunaga, Takuya; Sonoike, Shotaro; Kitamura, Masanori; Yamano, Akihito; Aoki, Shin



Cleavage and formation of molecular dinitrogen in a single system assisted by molybdenum complexes bearing ferrocenyldiphosphine.  


The N?N bond of molecular dinitrogen bridging two molybdenum atoms in the pentamethylcyclopentadienyl molybdenum complexes that bear ferrocenyldiphosphine as an auxiliary ligand is homolytically cleaved under visible light irradiation at room temperature to afford two molar molybdenum nitride complexes. Conversely, the bridging molecular dinitrogen is reformed by the oxidation of the molybdenum nitride complex at room temperature. This result provides a successful example of the cleavage and formation of molecular dinitrogen induced by a pair of two different external stimuli using a single system assisted by molybdenum complexes bearing ferrocenyldiphosphine under ambient conditions. PMID:25214300

Miyazaki, Takamasa; Tanaka, Hiromasa; Tanabe, Yoshiaki; Yuki, Masahiro; Nakajima, Kazunari; Yoshizawa, Kazunari; Nishibayashi, Yoshiaki



Studies on the Reactive Species in Fluoride-Mediated Carbon-Carbon Bond-Forming Reactions: Carbanion Formation  

E-print Network

Studies on the Reactive Species in Fluoride-Mediated Carbon-Carbon Bond-Forming Reactions: Carbanion Formation by Desilylation with Fluoride and Enolates Margaret M. Biddle and Hans J. ReichVed October 27, 2005 The reactive species in fluoride-mediated carbon-carbon bond-forming reactions

Reich, Hans J.


Pathways to inflammation induced by immune complexes: development of the Arthus reaction.  


The changes associated with inflammation induced by immune complexes (reversed passive Arthus reaction induced with egg albumin-anti-egg albumin) were quantitated and the kinetics of the various vascular phenomena were ascertained. Hyperemia, increase in vascular permeability, platelet accumulation, and polymorphonuclear (PMN) leukocyte accumulation occurred relatively early after induction of the inflammatory lesions, and peaked in 2-4 h. Hemorrhage peaked in 6-h-old lesions. Morphological studies confirmed that almost all infiltrating cells were PMN leukocytes and immunofluorescent tracer studies showed immune complexes in vessel walls as early as 15 min after i.v. injection of the fluoresceinated antigen and the intradermal injection of antibody. By 8 h the progression of the lesions had subsided and by 24 h there were signs of resolution. A pathway for the development of the inflammatory lesions induced with immune complexes is proposed. PMID:6211371

Crawford, J P; Movat, H Z; Ranadive, N S; Hay, J B



Sn(iv) Schiff base complexes: triplet photosensitizers for photoredox reactions.  


We present the synthesis and characterization of a series of four fluorescent Sn(iv) Schiff base complexes, which also possess long-lived triplet excited states. The complexes absorb visible light (?max = 420 to 462 nm) and the optical properties are easily tunable without laborious synthetic elaboration. The triplet excited states are not luminescent, but can be observed and followed using nanosecond transient absorption spectroscopy. The lifetimes of the triplet excited states are on the order of 500 ?s-10 ms in PMMA matrices. The triplet state energies were estimated via energy transfer reactions with a series of organic triplet acceptors. In addition, the photoexcited complexes react with electron donors and acceptors in solution. These results demonstrate the potential for the development of photosensitizers based on main group elements with high spin orbit coupling constants. PMID:25043697

Grusenmeyer, Tod A; King, Albert W; Mague, Joel T; Rack, Jeffrey J; Schmehl, Russell H



OH formation from the C2H5CO + O2 reaction: An experimental marker for the propionyl radical  

Microsoft Academic Search

The reaction between C2H5CO and O2 Figs. and is observed to directly form OH. This reaction proceeds via the formation of energised C2H5CO(O2), which can either dissociate to OH or be collisionally thermalized. This reaction mechanism is analogous to CH3CO + O2 Figs. and , which we have previously studied and extended in this study. The kinetics and OH yield

M. Teresa Baeza Romero; Mark A. Blitz; Dwayne E. Heard; Michael J. Pilling; Ben Price; Paul W. Seakins



Phosphonato complexes of platinum(II): kinetics of formation and phosphorus-31 NMR characterization studies  

SciTech Connect

Reactions of cis-diamminedichloroplatinum(II) with phosphonoformic acid (PFA), phosphonoacetic acid (PAA), and methylenediphosphonic acid (MDP) yield various phosphonatoplatinum(II) chelates which were characterized by phosphorus-31 NMR spectroscopy. The P-31 resonances for the chelates appear at 6-12 ppm downfield as compared to the uncomplexed ligands. All complexes exhibit monoprotic acidic behavior in the pH range 2-10. The chemical shift-pH profiles yielded acidity constants, 1.0 x 10(-4), 1.5 x 10(-4), and 1.3 x 10(-6) M-1, for the PFA, PAA, and MDP chelates. In addition to the monomeric chelate, MDP formed a bridged diplatinum(II,II) complex when it reacted with cis-Pt (NH3)2(H2O)2(2)+. The P-31 resonance for this binuclear complex appears at 22 ppm downfield from the unreacted ligand. Rate data for the complexation reactions of the phosphonate ligands with the dichloroplatinum complex are consistent with a mechanism in which a monodentate complex is formed initially through rate-limiting aquation process of the platinum complex, followed by a rapid chelation. For the PFA and PAA complexes, initial binding sites are the carboxylato oxygens. Implications of the various binding modes of the phosphonates in relationship to their antiviral activities are discussed.

Slavin, L.L.; Bose, R.N. (Chemistry Department, Kent State University, OH (USA))



Phosphonato complexes of platinum(II): kinetics of formation and phosphorus-31 NMR characterization studies.  


Reactions of cis-diamminedichloroplatinum(II) with phosphonoformic acid (PFA), phosphonoacetic acid (PAA), and methylenediphosphonic acid (MDP) yield various phosphonatoplatinum(II) chelates which were characterized by phosphorus-31 NMR spectroscopy. The P-31 resonances for the chelates appear at 6-12 ppm downfield as compared to the uncomplexed ligands. All complexes exhibit monoprotic acidic behavior in the pH range 2-10. The chemical shift-pH profiles yielded acidity constants, 1.0 x 10(-4), 1.5 x 10(-4), and 1.3 x 10(-6) M-1, for the PFA, PAA, and MDP chelates. In addition to the monomeric chelate, MDP formed a bridged diplatinum(II,II) complex when it reacted with cis-Pt (NH3)2(H2O)2(2)+. The P-31 resonance for this binuclear complex appears at 22 ppm downfield from the unreacted ligand. Rate data for the complexation reactions of the phosphonate ligands with the dichloroplatinum complex are consistent with a mechanism in which a monodentate complex is formed initially through rate-limiting aquation process of the platinum complex, followed by a rapid chelation. For the PFA and PAA complexes, initial binding sites are the carboxylato oxygens. Implications of the various binding modes of the phosphonates in relationship to their antiviral activities are discussed. PMID:2150856

Slavin, L L; Bose, R N



Ambient measurement of nitrotriphenylenes and possibility of nitrotriphenylene formation by atmospheric reaction  

SciTech Connect

Environmental nitration of PAHs by nitrogen oxides on airborne particulates and identification and quantification of nitro-PAHs in them have been studied on fluoranthene and pyrene because of their large abundance. However, the direct mutagenic activity of these nitro-PAHs can account for only up to about 20% of the total direct mutagenic activity of airborne particulate samples, and the presence of unknown mutagenic nitro-PAHs was suggested. 1-and 2-Nitrotriphenylenes were first identified and quantified in ambient particulate samples collected in Tokyo. Their mutagenicity and formation by laboratory reactions of triphenylene deposited on a filter with NO{sub 2}/NO{sub 3}/N{sub 2}O{sub 5} were also investigated. The concentrations of 1- and 2-nitrotriphenylenes were much higher than that of 1-nitropyrene in the same samples. 2-Nitrotriphenylene showed over 2 orders of magnitude greater mutagenic activity than 1-nitrotriphenylene in both strains TA98 and YG1024. The mutagenic 2-nitrotriphenylene was expected to contribute largely to the total mutagenic activity of the extracts from airborne particles. In addition, more effective formation of nitrotriphenylenes by the nighttime reaction of triphenylene in the presence of O{sub 3} in the dark can explain the observation of high nitrotriphenylene concentration in the nighttime samples.

Ishii, Satoko; Hisamatsu, Yoshiharu; Inazu, Koji; Kadoi, Morio; Aika, Kenichi



Probing 'Spin-Forbidden' Oxygen Atom Transfer: Gas-Phase Reactions of Chromium-Porphyrin Complexes  

PubMed Central

Oxygen-atom transfer reactions of metalloporphyrin species play an important role in biochemical and synthetic oxidation reactions. An emerging theme in this chemistry is that spin-state changes can play important roles, and a ‘two-state’ reactivity model has been extensively applied especially in iron-porphyrin systems. Herein we explore the gas phase oxygen-atom transfer chemistry of meso-tetrakis(pentafluorophenyl)porphyrin (TPFPP) chromium complexes, as well as some other tetradentate macrocyclic ligands. Electrospray ionization in concert with Fourier transform ion cyclotron resonance (FT-ICR) spectrometry has been used to characterize and observe reactivity of the ionic species [(TPFPP)CrIII]+ (1) and [(TPFPP)CrVO]+ (2). These are an attractive system to examine the effects of spin state change on oxygen atom transfer because the d1 CrV species are doublets while the CrIII complexes have quartet ground states with high-lying doublet excited states. In the gas phase, [(TPFPP)CrIII]+ forms adducts with a variety of neutral donors but O-atom transfer is only observed for NO2. Pyridine N-oxide adducts of 1 do yield 2 upon collision induced dissociation (CID), but the ethylene oxide, DMSO, and TEMPO analogs do not. [(TPFPP)CrVO]+ is shown by its reactivity and by CID experiments to be a terminal metal-oxo with a single vacant coordination site. It also displays limited reaction chemistry, being deoxygenated only by the very potent reductant P(OMe)3. In general, [(TPFPP)CrVO]+ species are much less reactive than the Fe and Mn analogs. Thermochemical analysis of the reactions points towards the involvement of spin issues in the lower observed reactivity of the chromium complexes. PMID:20218631

Fornarini, Simonetta; Lanucara, Francesco; Warren, Jeffrey J.



Noble reactions for the actinides: safe gold-based access to organouranium and azide complexes  

Microsoft Academic Search

Gold has had a profound impact on organic chemistry; its compounds are spectacular catalysts for many organic transformations involving the formation of C-C, C-O, C-N and CoS bonds, and have enabled unprecedented pathways for the functionalization of C-H and C-C bonds. In general, gold complexes have not been exploited as reagents in organometallic or inorganic chemistry, although a few gold(l)

Robert K Thomson; Christopher R Graves; Brian L Scott; Jaqueline L Kiplinger



A common intermediate for N2 formation in enzymes and zeolites: side-on Cu-nitrosyl complexes  

SciTech Connect

Understanding the mechanisms of catalytic processes requires the identification of reaction centers and key intermediates, both of which are often achieved by the use of spectroscopic characterization tools. Due to the heterogeneity of active centers in heterogeneous catalysts, it is frequently difficult to identify the specific sites that are responsible for the overall activity. Furthermore, the simultaneous presence of a large number of surface species on the catalyst surface often poses a great challenge for the unambiguous determination of the relevant species in the reaction mechanism. In contrast, enzymes possess catalytically active centers with precisely defined coordination environments that are only able to accommodate intermediates relevant to the specific catalytic process. Here we show that side-on Cu+-NO+ complexes characterized by high magnetic field solid state magic angle spinning nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectroscopies are the key intermediates in the selective catalytic reduction of NO over Cu-SSZ-13 zeolite catalysts. Analogous intermediates have been observed and characterized in nitrite reductase enzymes, and shown to be the critical intermediates in the formation of N2 for anaerobic ammonium oxidation reactions.[1] The identification of this key reaction intermediate, combined with the results of our prior kinetic studies, allows us to propose a new reaction mechanism for the selective catalytic reduction of NO with NH3 under oxygen-rich environments over Cu-SSZ-13 zeolites, a key reaction in automotive emission control. The authors acknowledge the US Department of Energy (DOE), Office of Energy Efficiency and Renewable Energy/Vehicle Technologies Program for the support of this work. The research described in this paper was performed at the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility sponsored by the DOE’s Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is operated for the US DOE by Battelle Memorial Institute.

Kwak, Ja Hun; Lee, Jong H.; Burton, Sarah D.; Lipton, Andrew S.; Peden, Charles HF; Szanyi, Janos



Chemically Activated Formation of Organic Acids in Reactions of the Criegee Intermediate with Aldehydes and Ketones  

SciTech Connect

Reactions of the Criegee intermediate (CI, .CH2OO.) are important in atmospheric ozonolysis models. In this work, we compute the rates for reactions between .CH2OO. and HCHO, CH3CHO and CH3COCH3 leading to the formation of secondary ozonides (SOZ) and organic acids. Relative to infinitely separated reactants, the SOZ in all three cases is found to be 48–51 kcal mol-1 lower in energy, formed via 1,3- cycloaddition of .CH2OO. across the CQO bond. The lowest energy pathway found for SOZ decomposition is intramolecular disproportionation of the singlet biradical intermediate formed from cleavage of the O–O bond to form hydroxyalkyl esters. These hydroxyalkyl esters undergo concerted decomposition providing a low energy pathway from SOZ to acids. Geometries and frequencies of all stationary points were obtained using the B3LYP/MG3S DFT model chemistry, and energies were refined using RCCSD(T)-F12a/cc-pVTZ-F12 single-point calculations. RRKM calculations were used to obtain microcanonical rate coefficients (k(E)) and the reservoir state method was used to obtain temperature and pressure dependent rate coefficients (k(T, P)) and product branching ratios. At atmospheric pressure, the yield of collisionally stabilized SOZ was found to increase in the order HCHO o CH3CHO o CH3COCH3 (the highest yield being 10-4 times lower than the initial .CH2OO. concentration). At low pressures, chemically activated formation of organic acids (formic acid in the case of HCHO and CH3COCH3, formic and acetic acid in the case of CH3CHO) was found to be the major product channel in agreement with recent direct measurements. Collisional energy transfer parameters and the barrier heights for SOZ reactions were found to be the most sensitive parameters determining SOZ and organic acid yield.

Jalan, Amrit; Allen, Joshua W.; Green, William H.



DOI: 10.1002/asia.201100535 Indene Formation under Single-Collision Conditions from the Reaction of  

E-print Network

DOI: 10.1002/asia.201100535 Indene Formation under Single-Collision Conditions from the Reaction. Mebel*[b] Introduction Soot from fossil fuel combustion is widely accepted as caus- ing detrimental),[5] to aromatic mol- ecules, such as benzene (C6H6) and the phenyl radical (C6H5), followed by the formation

Kaiser, Ralf I.


Formation of Molecular Bromine from the Reaction of Ozone with Deliquesced NaBr Aerosol: Evidence for Interface Chemistry  

E-print Network

Formation of Molecular Bromine from the Reaction of Ozone with Deliquesced NaBr Aerosol: Evidence modeling, and molecular dynamics simulations. The molecular bromine production in the chamber experiments on bromine formation in the marine boundary layer shows that several ppt of bromine could potentially

Dabdub, Donald


Polynucleotides. XXVI1) Complex formation of polynucleotides derived from formycin and laurusin with cyclonucleoside oligonucleotides  

PubMed Central

Poly(formycin phosphate) and poly(laurusin phosphate) were synthesized by polymerizing formycin and laurusin 5?-diphosphate by means of E. coli polynucleotide phosphorylase. The complex formation of these polynucleotides with cyclonucleoside polynucleotides were investigated. While poly(formycin phosphate) did not form the complex with an octanucleotide of 6,2?-anhydro-6-oxy-1-?-D-arabinofuranosyluracil, poly(laurusin phosphate) did form a 1: 1 complex with octanucleotide of 8,2?-anhydro-8-mercapto-9-?-D-arabinofuranosyladenine in the presence of 0.15M Na ion at neutrality and 3o. CD spectrum of this complex showed a couple of a trough at 286 nm and a peak at 262 nm. This fact suggests that the complex has a left-handed helical conformation, which is opposite to the natural double helical polynucleotides. The cause of this phenomenon was discussed in connection with the complex of cyclonucleoside oligonucleotides. PMID:10793723

Ikehara, Morio; Tezuka, Toru



Formation of the diphenyl molecule in the crossed beam reaction of phenyl radicals with benzene  

SciTech Connect

The chemical dynamics to form the D5-diphenyl molecule, C{sub 6}H{sub 5}C{sub 6}D{sub 5}, via the neutral-neutral reaction of phenyl radicals (C{sub 6}H{sub 5}) with D6-benzene (C{sub 6}D{sub 6}), was investigated in a crossed molecular beams experiment at a collision energy of 185 kJ mol{sup -1}. The laboratory angular distribution and time-of-flight spectra of the C{sub 6}H{sub 5}C{sub 6}D{sub 5} product were recorded at mass to charge m/z of 159. Forward-convolution fitting of our data reveals that the reaction dynamics are governed by an initial addition of the phenyl radical to the {pi} electron density of the D6-benzene molecule yielding a short-lived C{sub 6}H{sub 5}C{sub 6}D{sub 6} collision complex. The latter undergoes atomic deuterium elimination via a tight exit transition state located about 30 kJ mol{sup -1} above the separated reactants; the overall reaction to form D5-diphenyl from phenyl and D6-benzene was found to be weakly exoergic. The explicit identification of the D5-biphenyl molecules suggests that in high temperature combustion flames, a diphenyl molecule can be formed via a single collision event between a phenyl radical and a benzene molecule.

Zhang Fangtong; Gu Xibin; Kaiser, Ralf I. [Department of Chemistry, University of Hawai'i at Manoa, Honolulu, Hawaii 96822 (United States)



Effects of amylose chain length and heat treatment on amylose-glycerol monocaprate complex formation.  


Aqueous mixtures of amylose with different chain lengths (DP 23-849), which had been enzymatically synthesized or isolated from potato and maize starches, and glycerol monocaprate (GMC, 5:1 weight ratio) were analyzed by using a differential scanning calorimeter (DSC). The mixtures were thermally treated (first DSC scan: 20-140 °C, 5 °C/min and prolonged heat treatment: 100 °C for 24 h) and its effect on the amylose-GMC complex formation was analyzed by DSC and X-ray diffractometer. The amylose, especially short ones, readily associated in the dispersion forming the amylose-amylose crystals but the presence of GMC inhibited the crystal formation. The longer amylose had the greater possibility for the complex formation with GMC, and the prolonged heat treatment facilitated the amylose-GMC complex formation. Both type I and type II complexes were formed during quenching after the initial DSC heating. However, only the type II complexes were formed after the prolonged heat treatment with improved crystallinity and thermostability. PMID:23618264

Zhou, Xing; Wang, Ren; Zhang, Yuxian; Yoo, Sang-Ho; Lim, Seung-Taik



Thermodynamics of cationic lipid-DNA complex formation as studied by isothermal titration calorimetry.  

PubMed Central

The detailed analysis of the cationic lipid-DNA complex formation by means of isothermal titration calorimetry is presented. Most experiments were done using 1,2-dioleyl-sn-glycero-3-ethylphosphocholine (EDOPC), but basic titrations were also done using DOTAP, DOTAP:DOPC, and DOTAP:DOPE mixtures. Complex formation was endothermic with less than 1 kcal absorbed per mole of lipid or DNA charge. This enthalpy change was attributed to DNA-DNA mutual repulsion within the lamellar complex. The exception was DOTAP:DOPE-containing lipoplex for which the enthalpy of formation was exothermic, presumably because of DOPE amine group protonation. Experimental conditions, namely, direction and titration increment as well as concentration of titrant, which dictate the structure of resulting lipoplex (whether lamellar complex or DNA-coated vesicle), were found to affect the apparent thermodynamics of complex formation. The structure, in turn, influences the biological properties of the lipoplex. If the titration of lipid into DNA was carried out in large increments, the DeltaH was larger than when the injection increments were smaller, a finding that is consistent with increased vesicle disruption under large increments and which is expected theoretically. Cationic lipid-DNA binding was weak in high ionic strength solutions, however, the effective binding constant is within micromolar range because of macromolecular nature of the interaction. PMID:12080142

Pozharski, Edwin; MacDonald, Robert C



Formation of P450oP450 Complexes and Their Effect on P450 Function  

PubMed Central

Cytochromes P450 (P450) are membrane-bound enzymes that catalyze the monooxygenation of a diverse array of xenobiotic and endogenous compounds. The P450s responsible for foreign compound metabolism generally are localized in the endoplasmic reticulum of the liver, lung and small intestine. P450 enzymes do not act alone but require an interaction with other electron transfer proteins such as NADPH-cytochrome P450 reductase (CPR) and cytochrome b5. Because P450s are localized in the endoplasmic reticulum with these and other ER-resident proteins, there is a potential for protein-protein interactions to influence P450 function. There has been increasing evidence that P450 enzymes form complexes in the ER, with compelling support that formation of P450•P450 complexes can significantly influence their function. Our goal is to review the research supporting the formation of P450•P450 complexes, their specificity, and how drug metabolism may be affected. This review describes the potential mechanisms by which P450s may interact, and provides evidence to support each of the possible mechanisms. Additionally, evidence for the formation of both heteromeric and homomeric P450 complexes are reviewed. Finally, direct physical evidence for P450 complex formation in solution and in membranes is summarized, and questions directing the future research of functional P450 interactions are discussed with respect to their potential impact on drug metabolism. PMID:22155419

Reed, James R.; Backes, Wayne L.



Rotational effects in complex-forming bimolecular substitution reactions: A quantum-mechanical approach  

NASA Astrophysics Data System (ADS)

The quantum dynamics of the complex-forming SN2 reaction Cl-+CH3Br?ClCH3+Br- is studied with emphasis on rotational effects. The pseudotriatomic system Cl-Me-Br is treated with a corresponding three-dimensional (3D) potential energy surface as a function of the two scattering coordinates and the enclosed angle where the geometry of the methyl group Me is optimized at each point. The 3D space is divided into three different parts, the interaction region, an intermediate region, and the asymptotic region. In line with simple classical-mechanical arguments and previous classical trajectory calculations, initial rotational motion of CH3Br seemingly decreases the reaction probability. However, the dynamical inclusion of the rotational degree of freedom and the presence of the many rovibrational product states overall lead to a large increase in reactivity compared to our previous collinear study on this reaction. If the reactant is rotationally excited, the higher vibrational product states are depleted in favor of lower-lying levels. Starting the reaction with rotationless reactants may end up in significant rotational excitation in the product molecules (translation-to-rotation energy transfer). On the other hand, initial rotational energy in rotationally highly excited reactants is to a large amount converted into translational and vibrational energy. The average amount of rotational energy in the products shows a twofold vibrational excitation-independent saturation (i.e., memorylessness), with respect to both initial rotational excitation and translational energy. Since only about one-half of all reactant states end in rotationless products, the reaction probability should be increased by a factor of 2; the actually larger reactivity points to other dynamical effects that play an important role in the reaction.

Hennig, Carsten; Schmatz, Stefan



Formation of porous surface layers in reaction bonded silicon nitride during processing  

NASA Technical Reports Server (NTRS)

An effort was undertaken to determine if the formation of the generally observed layer of large porosity adjacent to the as-nitride surfaces of reaction bonded silicon nitrides could be prevented during processing. Isostatically pressed test bars were prepared from wet vibratory milled Si powder. Sintering and nitriding were each done under three different conditions:(1) bars directly exposed to the furnance atmosphere; (2) bars packed in Si powder; (3) bars packed in Si3N4 powder. Packing the bars in either Si of Si3N4 powder during sintering retarded formation of the layer of large porosity. Only packing the bars in Si prevented formation of the layer during nitridation. The strongest bars (316 MPa) were those sintered in Si and nitrided in Si3N4 despite their having a layer of large surface porosity; failure initiated at very large pores and inclusions. The alpha/beta ratio was found to be directly proportional to the oxygen content; a possible explanation for this relationship is discussed.

Shaw, N. J.; Glasgow, T. K.



Formation of bromophenoxy radicals from complete series reactions of bromophenols with H and OH radicals.  


The bromophenoxy radicals (BPRs) are key intermediate species involved in the formation of polybrominated dibenzo-p-dioxin/dibenzofurans (PBDD/Fs). In this work, the formation of BPRs from the complete series reactions of 19 bromophenol (BP) congeners with H and OH radicals were investigated theoretically by using the density functional theory (DFT) method and the direct dynamics method. The geometries and frequencies of the reactants, transition states, and products were calculated at the MPWB1K/6-31+G(d,p) level, and the energetic parameters were further refined by the MPWB1K/6-311+G(3df,2p) method. The rate constants were evaluated by the canonical variational transition-state (CVT) theory with the small curvature tunneling (SCT) contribution over a wide temperature range of 600-1200K. The present study indicates that the reactivity of the O-H bonds in BPs as well as the formation potential of BPRs from BPs is strongly related to the bromine substitution pattern. The obtained results can be used for future estimates of PBDD/F emissions quantity based on the well estimated PCDD/F inventory. PMID:23402922

Gao, Rui; Xu, Fei; Li, Shanqing; Hu, Jingtian; Zhang, Qingzhu; Wang, Wenxing



Kinetics and Thermochemistry of ClCO Formation from the Cl + CO Association Reaction  

NASA Technical Reports Server (NTRS)

Laser flash photolysis of Cl2/CO/M mixtures (M = N2, CO, Ar, CO2) has been employed in conjunction with Cl((sup 2)P(sub J)) detection by time-resolved resonance fluorescence spectroscopy to investigate equilibration kinetics in the reactions Cl((sup 2)P(sub J)) + CO ClCO as a function of temperature (185-260 K) and pressure (14-200 Torr). The association and dissociation reactions are found to be in the low-pressure limit over the range of experimental conditions investigated. In N2 and/or CO buffer gases, the temperature dependences of the ClCO formation and dissociation reaction rate constants are described by the Arrhenius expressions k(sub 1) = (1.05 +/- 0.36) x 10(exp -34) exp[(810 +/- 70)/T] cm(exp 6)/molecules(exp 2).s and k(sub -1) = (4.1 +/- 3.1) x 10(exp -10) exp[(-2960 +/- 60)/T]cu cm/(molecule.s) (errors are 2 sigma). Second- and third-law analyses of the temperature dependence of the equilbrium constant (k/k-1) lead to the following thermodynamic parameters for the association reaction: Delta-H(sub 298) = -7.7 +/- 0.6 kcal/mol, Delta-H(sub 0) = -6.9 +/- 0.7 kcal/mol, Delta-S(sub 298) = -23.8 +/- 2.0 cal/mole.K, Delta-H(sub f,298)(ClCO) = 5.2 +/- 0.6 kcal/mol (errors are 2 sigma). The results repported in this study significantly reduce the uncertainties in all reported kinetic and thermodynamic parameters.

Nicovich, J. M.; Kreutter, K. D.; Wine, P. H.



Complex formation between alkylpyridines and Na 3 PO 4 under gas chromatography conditions  

Microsoft Academic Search

1.The specific retention volumes, the differential molar free energies, enthalpies, and entropies of sorption for twelve pyridine bases have been determined by gas chromatography on columns containing equimolar amounts of the salts sodium orthophosphate and potassium fluoride, with hydrogenated Apiezon L as the stationary phase.2.Alkylpyridines form donor-acceptor complexes with sodium orthophosphate and the thermodynamic characteristics of complex formation have been

R. V. Golovnya; I. L. Zhuravleva; B. M. Polanuer



Radical coupling for directed C-C/C-S bond formation in the reaction of Cp*IrS2C2B10H10 with 1-azido-3-nitrobenzene.  


Reactions of half-sandwich complex Cp*IrS2C2B10H10 (1) with 1-azido-3-nitrobenzene (3-NO2C6H4N3, L) upon heating or under light led to new complexes 2-6. Complexes 2 and 3 contain a five-membered cyclometalated ligand arising from C(sp(2))-H activation of the azide ligand L. Complex 4 is a 16 electron species containing a new-generated C-C bond between the azide ligand L and the Cp* unit where C(sp(3))-H activation of the methyl unit occurred. Complexes 5 and 6 contain two types of the ligand which appear in complexes 2, 3 and 4. Further reactions of complexes 5 and 6 with L under more harsh conditions gave rise to the nucleophilic addition products 7 and 8, where ring expansion of the azide ligand at the imido site of complexes 5 and 6 happened. Complexes 2-8 were characterized by NMR, MS, IR, and elemental analysis, and X-ray structural analyses were performed for complexes 2-4 and 6-8. The radical mechanisms for the formation of complexes 2-6 were proposed on the basis of capture experiments by EPR and ESI-MS. And the formation mechanism of complexes 7 and 8 was also suggested. PMID:24108087

Zhong, Wei; Jiang, Qibai; Zhang, Qian; Shang, Yi; Yan, Hong; Bregadze, Vladimir



Accelerating the Computation of Detailed Chemical Reaction Kinetics for Simulating Combustion of Complex Fuels  

SciTech Connect

Combustion of hydrocarbon fuels has been a very challenging scientific and engineering problem due to the complexity of turbulent flows and hydrocarbon reaction kinetics. There is an urgent need to develop an efficient modeling capability to accurately predict the combustion of complex fuels. Detailed chemical kinetic models for the surrogates of fuels such as gasoline, diesel and JP-8 consist of thousands of chemical species and Arrhenius reaction steps. Oxygenated fuels such as bio-fuels and heavier hydrocarbons, such as from newer fossil fuel sources, are expected to have a much more complex chemistry requiring increasingly larger chemical kinetic models. Such models are beyond current computational capability, except for homogeneous or partially stirred reactor type calculations. The advent of highly parallel multi-core processors and graphical processing units (GPUs) promises a steep increase in computational performance in the coming years. This paper will present a software framework that translates the detailed chemical kinetic models to high- performance code targeted for GPU accelerators.

Grout, Ray W [ORNL



Accelerating the Computation of Detailed Chemical Reaction Kinetics for Simulating Combustion of Complex Fuels  

SciTech Connect

Combustion of hydrocarbon fuels has been a very challenging scientific and engineering problem due to the complexity of turbulent flows and hydrocarbon reaction kinetics. There is an urgent need to develop an efficient modeling capability to accurately predict the combustion of complex fuels. Detailed chemical kinetic models for the surrogates of fuels such as gasoline, diesel and JP-8 consist of thousands of chemical species and Arrhenius reaction steps. Oxygenated fuels such as bio-fuels and heavier hydrocarbons, such as from newer fossil fuel sources, are expected to have a much more complex chemistry requiring increasingly larger chemical kinetic models. Such models are beyond current computational capability, except for homogeneous or partially stirred reactor type calculations. The advent of highly parallel multi-core processors and graphical processing units (GPUs) promises a steep increase in computational performance in the coming years. This paper will present a software framework that translates the detailed chemical kinetic models to high-performance code targeted for GPU accelerators.

Sankaran, R.; Grout, R.



Efficient and Selective Formation of Macrocyclic Disubstituted Z Alkenes by Ring-Closing Metathesis (RCM) Reactions Catalyzed by Mo- or W-Based Monoaryloxide Pyrrolide (MAP) Complexes: Applications to Total Syntheses of Epilachnene, Yuzu Lactone, Ambrettolide, Epothilone C, and Nakadomarin A  

E-print Network

The first broadly applicable set of protocols for efficient Z-selective formation of macrocyclic disubstituted alkenes through catalytic ring-closing metathesis (RCM) is described. Cyclizations are performed with 1.2–7.5?mol?% ...

Wang, Chenbo


Multiple proton-transfer reactions in DNA base pairs by coordination of pt complex.  


The possibility of multiple proton-transfer reactions in DNA base pairs because of coordination of cisplatin is theoretically elucidated by density functional theory (DFT) and by quantum mechanics/molecular mechanics (QM/MM) methods with an ONIOM method. From the energetics of two base pairs with the cisplatin, it is theoretically confirmed that the Pt complex is likely to bind in the order cis-(CG)-Pt-(GC), cis-(CG)-Pt-(AT), cis-(TA)-Pt-(AT), where G, C, A, and T are guanine, cytosine, adenine, and thymine, respectively, and the Pt atom bonds to the N7 site of G and A. This result supports the experimental evidence, where the structure cis-A-Pt-A is seldom observed at room temperature. The single proton-transfer reaction occurs in one of the two GC pairs. No simultaneous single proton-transfer reaction can occur in both base pairs. Two different single proton-transferred structures (cis-(CG*)(d)-Pt-(GC)(p) and cis-(CG)(d)-Pt-(G*C)(p), where the asterisk means a proton donor of G) are as stable as the original structures (CG)(d)-Pt-(GC)(p). The same tendency was observed with cis-(CG*)-Pt-(AT). In contrast to cisplatin, multiple single proton-transfer reactions occur in the system consisting of two base pairs with transplatin. The optimized structure agrees with the experimental data for Pt-G coordination except for the hydrogen-bonding length. PMID:17266272

Matsui, Toru; Shigeta, Yasuteru; Hirao, Kimihiko



In situ investigations of bromine-storing complex formation in a zinc-flow battery at gold electrodes  

SciTech Connect

One of the most promising candidates for affordable energy storage systems for electric vehicles is the zinc/bromine battery. The reversible cell voltage of 1.82 V, a theoretical specific energy of 430 Wh kg{sup {minus}1}, robustness, high cycle life, unlimited standby periods in the charged or discharged state, low self-discharge rates, and operation at ambient temperature explain the scientific and industrial interest in this system. The storage reactions of the zinc/bromine battery are the cathodic deposition of zinc and the anodic formation of a nonaqueous polybromide phase. Quaternary ammonium cations, N-methylethylpyrrolidinium (MEP{sup +}) and N-methylethylmorpholinium (MEM{sup +}), store the bromine as polybromide complexes. The mechanism of this complicated reaction determines the polarization and self-discharge rate of the bromine electrode. Electrochemical in situ techniques, phase-stabilized electrochemical quartz microbalance, and in situ reflection-absorption Fourier transform infrared spectroscopy were employed for the first time to investigate these electrode processes. It was shown that specifically adsorbed polybromide anions (Br{sub n}{minus}) formed MEM-Br{sub n}. Therefore, a homogeneous chemical reaction of the dissolved MEP{sup +} cation with electrochemically generated bromine leads to the storage complex MEP-Br{sub n} much more rapidly than the heterogeneous electrochemical reaction of the strongly adsorbed MEM{sup +} to MEM-Br{sub n}. These results demonstrate that in situ techniques not only support the evaluation of the mechanism but also provide key information for battery development.

Kautek, W.; Conradi, A.; Sahre, M.; Fabjan, C.; Drobits, J.; Bauer, G.; Schuster, P.



Analysis of the association constants for charge-transfer complex formation  

NASA Astrophysics Data System (ADS)

The phenomenon of charge transfer (CT) complex formation has been of interest for more than 50 years and has led to the development of numerous applications. Even with the prolonged interest in these complexes the interactions responsible for complex formation have yet to be fully characterized and remain an area of sustained relevance. This report outlines the measurement of the association constants for CT complex formation of a series of methylated benzene donors with tetracyanoethylene, pyromellitic dianhydride, 2,3-dichloro-5,6-dicyano-p-benzoquinone, and 1,2,4,5-tetracyanobenzene acceptors in 1,2-dichloroethane solvent. The evaluation of the position of the CT absorption maximum and the magnitudes of the association constants within a theoretical model is described. The influence of solvent polarity on the magnitudes of the association constants was also discussed. These studies show that non-bonding interactions are important in most complexes while ion-pair interactions play a significant role in a select few of the complexes studied.

McKim, William D.; Ray, Jayanta; Arnold, Bradley R.



Conformational heterogeneity in antibody-protein antigen recognition: implications for high affinity protein complex formation.  


Specific, high affinity protein-protein interactions lie at the heart of many essential biological processes, including the recognition of an apparently limitless range of foreign proteins by natural antibodies, which has been exploited to develop therapeutic antibodies. To mediate biological processes, high affinity protein complexes need to form on appropriate, relatively rapid timescales, which presents a challenge for the productive engagement of complexes with large and complex contact surfaces (?600-1800 ?(2)). We have obtained comprehensive backbone NMR assignments for two distinct, high affinity antibody fragments (single chain variable and antigen-binding (Fab) fragments), which recognize the structurally diverse cytokines interleukin-1? (IL-1?, ?-sheet) and interleukin-6 (IL-6, ?-helical). NMR studies have revealed that the hearts of the antigen binding sites in both free anti-IL-1? Fab and anti-IL-6 single chain variable exist in multiple conformations, which interconvert on a timescale comparable with the rates of antibody-antigen complex formation. In addition, we have identified a conserved antigen binding-induced change in the orientation of the two variable domains. The observed conformational heterogeneity and slow dynamics at protein antigen binding sites appears to be a conserved feature of many high affinity protein-protein interfaces structurally characterized by NMR, suggesting an essential role in protein complex formation. We propose that this behavior may reflect a soft capture, protein-protein docking mechanism, facilitating formation of high affinity protein complexes on a timescale consistent with biological processes. PMID:24436329

Addis, Philip W; Hall, Catherine J; Bruton, Shaun; Veverka, Vaclav; Wilkinson, Ian C; Muskett, Frederick W; Renshaw, Philip S; Prosser, Christine E; Carrington, Bruce; Lawson, Alastair D G; Griffin, Robert; Taylor, Richard J; Waters, Lorna C; Henry, Alistair J; Carr, Mark D



Capture and dissociation in the complex-forming CH + H2 ? CH2 + H, CH + H2 reactions.  


The rate coefficients for the capture process CH + H(2)? CH(3) and the reactions CH + H(2)? CH(2) + H (abstraction), CH + H(2) (exchange) have been calculated in the 200-800 K temperature range, using the quasiclassical trajectory (QCT) method and the most recent global potential energy surface. The reactions, which are of interest in combustion and in astrochemistry, proceed via the formation of long-lived CH(3) collision complexes, and the three H atoms become equivalent. QCT rate coefficients for capture are in quite good agreement with experiments. However, an important zero point energy (ZPE) leakage problem occurs in the QCT calculations for the abstraction, exchange and inelastic exit channels. To account for this issue, a pragmatic but accurate approach has been applied, leading to a good agreement with experimental abstraction rate coefficients. Exchange rate coefficients have also been calculated using this approach. Finally, calculations employing QCT capture/phase space theory (PST) models have been carried out, leading to similar values for the abstraction rate coefficients as the QCT and previous quantum mechanical capture/PST methods. This suggests that QCT capture/PST models are a good alternative to the QCT method for this and similar systems. PMID:21212873

González, Miguel; Saracibar, Amaia; Garcia, Ernesto



Probing Complex Free-Radical Reaction Pathways of Fuel Model Compounds  

SciTech Connect

Fossil (e.g. coal) and renewable (e.g. woody biomass) organic energy resources have received considerable attention as possible sources of liquid transportation fuels and commodity chemicals. Knowledge of the reactivity of these complex materials has been advanced through fundamental studies of organic compounds that model constituent substructures. In particular, an improved understanding of thermochemical reaction pathways involving free-radical intermediates has arisen from detailed experimental kinetic studies and, more recently, advanced computational investigations. In this presentation, we will discuss our recent investigations of the fundamental pyrolysis pathways of model compounds that represent key substructures in the lignin component of woody biomass with a focus on molecules representative of the dominant beta-O-4 aryl ether linkages. Additional mechanistic insights gleaned from DFT calculations on the kinetics of key elementary reaction steps will also be presented, as well as a few thoughts on the significant contributions of Jim Franz to this area of free radical chemistry.

Buchanan III, A C [ORNL; Kidder, Michelle [ORNL; Beste, Ariana [ORNL; Britt, Phillip F [ORNL



Reactions of heteroatom and carbon nucleophiles with the cationic bridging methylidyne complex  

SciTech Connect

The reaction of the complex /((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/( +/PF/sub 6//sup -/ (1) with NMe/sub 3/ and (C/sub 6/H/sub 5/)/sub 2/C=NH gave the cationic 1:1 adducts /((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/( 3/)//sup +/PF/sub 6//sup -/ (3) and /((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/( 6/H/sub 5/)/sub 2/)//sup +/PF/sub 6//sup -/ (9), respectively, arising from attack of nitrogen on the methylidyne carbon. The reaction of 1 with KOC(CH/sub 3/)/sub 3/ gave the neutral complex ((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/( 3/)P/sub 3/) (4). Reaction of 1 with water afforded a 1:1 mixture of complex ((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/( 2/) (2) and ((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/( 2/; these products are proposed to arise from disproportionation of an initially formed hydroxy carbene species. Reaction of 1 with Et/sub 4/N/sup +/Br/sup -/ gave the unstable /sup +/-carbene complex ((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/( (6). Reaction of 1 with the carbon nucleophiles CH/sub 3/Li and Li(C/sub 6/H/sub 5/CuCN) gave the complexes ((C/sub 5/H/sub 5/)(CO)Fe/sub 2/( 3/) (11) and ((C/sub 5/H/sub 5/)(CO)Fe)/sub 2/( 6/H/sub 5/ (12), while reaction of 1 with HFe(CO)/sub 4//sup -/ afforded 2. 1 reacted with acetone via nucleophilic addition of the enol affording the neutral complex (C/sub 5/H/sub 5/)-(CO)Fe)/sub 2/( 2/COCH/sub 3/)) (13). 1 also reacted with cyclohexanone, 2-butanone, 4-methyl-2-pentanone, 2,4-pentanedione, 5,5-dimethyl-1,3-cyclohexanedione, ethyl acetoacetate, and the sodium salt of diethyl malonate to give similar products.

Casey, C.P.; Crocker, M.; Vosejpka, P.C.; Fagan, P.J.; Marder, S.R.; Gohdes, M.A.



Hydrogen-atom abstraction reactions by manganese(V)- and manganese(IV)-oxo porphyrin complexes in aqueous solution.  


High-valent manganese(IV or V)-oxo porphyrins are considered as reactive intermediates in the oxidation of organic substrates by manganese porphyrin catalysts. We have generated Mn(V)- and Mn(IV)-oxo porphyrins in basic aqueous solution and investigated their reactivities in C-H bond activation of hydrocarbons. We now report that Mn(V)- and Mn(IV)-oxo porphyrins are capable of activating C-H bonds of alkylaromatics, with the reactivity order of Mn(V)-oxo>Mn(IV)-oxo; the reactivity of a Mn(V)-oxo complex is 150 times greater than that of a Mn(IV)-oxo complex in the oxidation of xanthene. The C-H bond activation of alkylaromatics by the Mn(V)- and Mn(IV)-oxo porphyrins is proposed to occur through a hydrogen-atom abstraction, based on the observations of a good linear correlation between the reaction rates and the C-H bond dissociation energy (BDE) of substrates and high kinetic isotope effect (KIE) values in the oxidation of xanthene and dihydroanthracene (DHA). We have demonstrated that the disproportionation of Mn(IV)-oxo porphyrins to Mn(V)-oxo and Mn(III) porphyrins is not a feasible pathway in basic aqueous solution and that Mn(IV)-oxo porphyrins are able to abstract hydrogen atoms from alkylaromatics. The C-H bond activation of alkylaromatics by Mn(V)- and Mn(IV)-oxo species proceeds through a one-electron process, in which a Mn(IV)-oxo porphyrin is formed as a product in the C-H bond activation by a Mn(V)-oxo porphyrin, followed by a further reaction of the Mn(IV)-oxo porphyrin with substrates that results in the formation of a Mn(III) porphyrin complex. This result is in contrast to the oxidation of sulfides by the Mn(V)-oxo porphyrin, in which the oxidation of thioanisole by the Mn(V)-oxo complex produces the starting Mn(III) porphyrin and thioanisole oxide. This result indicates that the oxidation of sulfides by the Mn(V)-oxo species occurs by means of a two-electron oxidation process. In contrast, a Mn(IV)-oxo porphyrin complex is not capable of oxidizing sulfides due to a low oxidizing power in basic aqueous solution. PMID:19810056

Arunkumar, Chellaiah; Lee, Yong-Min; Lee, Jung Yoon; Fukuzumi, Shunichi; Nam, Wonwoo



A photoionization study of the formation of NO2/+/ by reaction of excited O2/+/ ions with NO  

NASA Technical Reports Server (NTRS)

Photoionization mass spectrometer results are presented for the first observation of the ion-molecule reaction in which O2(+) + NO yields NO2(+) + O. The reaction is energetically possible for ground state O2(+) ions in the lowest vibrational level. Photoionization efficiency curves for NO(+), O2(+), and NO2(+) are presented and compared, with special emphasis on autoionization features. In addition to the production of NO2(+) by the cited reaction, there is also a possibility for NO2(+) formation by the process O2 + NO(+) yielding NO2(+) + O. This reaction is calculated to be exothermic for incident photon energies of 11.73 eV.

Ajello, J. M.; Rayermann, P.



Reaction of Elemental Sulfur with a Copper(I) Complex Forming a trans--1,2 End-On Disulfide Complex: New Directions in Copper-Sulfur Chemistry  

E-print Network

Reaction of Elemental Sulfur with a Copper(I) Complex Forming a trans-µ-1,2 End-On Disulfide Complex: New Directions in Copper-Sulfur Chemistry Matthew E. Helton, Peng Chen, Partha P. Paul, Zolta, investigations into copper-sulfur interactions have been of marked interest in the research fields of copper

Chen, Peng


Autocatalytic formation of an iron(IV)-oxo complex via scandium ion-promoted radical chain autoxidation of an iron(II) complex with dioxygen and tetraphenylborate.  


A non-heme iron(IV)-oxo complex, [(TMC)Fe(IV)(O)](2+) (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), was formed by oxidation of an iron(II) complex ([(TMC)Fe(II)](2+)) with dioxygen (O2) and tetraphenylborate (BPh4(-)) in the presence of scandium triflate (Sc(OTf)3) in acetonitrile at 298 K via autocatalytic radical chain reactions rather than by a direct O2 activation pathway. The autocatalytic radical chain reaction is initiated by scandium ion-promoted electron transfer from BPh4(-) to [(TMC)Fe(IV)(O)](2+) to produce phenyl radical (Ph(•)). The chain propagation step is composed of the addition of O2 to Ph(•) and the reduction of the resulting phenylperoxyl radical (PhOO(•)) by scandium ion-promoted electron transfer from BPh4(-) to PhOO(•) to produce phenyl hydroperoxide (PhOOH), accompanied by regeneration of phenyl radical. PhOOH reacts with [(TMC)Fe(II)](2+) to yield phenol (PhOH) and [(TMC)Fe(IV)(O)](2+). Biphenyl (Ph-Ph) was formed via the radical chain autoxidation of BPh3 by O2. The induction period of the autocatalytic radical chain reactions was shortened by addition of a catalytic amount of [(TMC)Fe(IV)(O)](2+), whereas addition of a catalytic amount of ferrocene that can reduce [(TMC)Fe(IV)(O)](2+) resulted in elongation of the induction period. Radical chain autoxidation of BPh4(-) by O2 also occurred in the presence of Sc(OTf)3 without [(TMC)Fe(IV)(O)](2+), initiating the autocatalytic oxidation of [(TMC)Fe(II)](2+) with O2 and BPh4(-) to yield [(TMC)Fe(IV)(O)](2+). Thus, the general view for formation of non-heme iron(IV)-oxo complexes via O2-binding iron species (e.g., Fe(III)(O2(•-))) without contribution of autocatalytic radical chain reactions should be viewed with caution. PMID:24809677

Nishida, Yusuke; Lee, Yong-Min; Nam, Wonwoo; Fukuzumi, Shunichi



Recent advances in catalytic C-N bond formation: a comparison of cascade hydroaminomethylation and reductive amination reactions with the corresponding hydroamidomethylation and reductive amidation reactions.  


The design and catalytic implementation of tandem reactions to selectively create nitrogen-containing products under mild conditions has encountered numerous challenges in synthetic chemistry. Several known classes of homogeneously catalyzed carbon-nitrogen bond formation including hydroamination, hydroamidation, hydroaminoalkylation, hydroaminomethylation and reductive amination were reported in the literature. More recently, a new class of C-N bond formation consisting of hydroamidomethylation and reductive amidation extended the applicability of these synthetic methodologies. The tandem reactions do considerably impact on the selectivity and efficiency of synthetic strategies. This review highlights and compares selected examples of the hydroaminomethylation, reductive amination, hydroamidomethylation and reductive amidation reactions, and thus consequently reveals their potential applications in synthetic chemistry as well as chemical industries. PMID:25098332

Raoufmoghaddam, Saeed



Communication: Structure, formation, and equilibration of ensembles of Ag-S complexes on an Ag surface  

SciTech Connect

We have utilized conditions of very low temperature (4.7 K) and very low sulfur coverage to isolate and identify Ag-S complexes that exist on the Ag(111) surface. The experimental conditions are such that the complexes form at temperatures above the temperature of observation. These complexes can be regarded as polymeric chains of varying length, with an Ag4S pyramid at the core of each monomeric unit. Steps may catalyze the formation of the chains and this mechanism may be reflected in the chain length distribution.

Russell, Selena M. [Ames Laboratory; Kim, Yousoo [RIKEN Advanced Science Institute; Liu, Da-Jiang [Ames Laboratory; Evans, J. W. [Ames Laboratory; Thiel, P. A. [Ames Laboratory



URDME: a modular framework for stochastic simulation of reaction-transport processes in complex geometries  

PubMed Central

Background Experiments in silico using stochastic reaction-diffusion models have emerged as an important tool in molecular systems biology. Designing computational software for such applications poses several challenges. Firstly, realistic lattice-based modeling for biological applications requires a consistent way of handling complex geometries, including curved inner- and outer boundaries. Secondly, spatiotemporal stochastic simulations are computationally expensive due to the fast time scales of individual reaction- and diffusion events when compared to the biological phenomena of actual interest. We therefore argue that simulation software needs to be both computationally efficient, employing sophisticated algorithms, yet in the same time flexible in order to meet present and future needs of increasingly complex biological modeling. Results We have developed URDME, a flexible software framework for general stochastic reaction-transport modeling and simulation. URDME uses Unstructured triangular and tetrahedral meshes to resolve general geometries, and relies on the Reaction-Diffusion Master Equation formalism to model the processes under study. An interface to a mature geometry and mesh handling external software (Comsol Multiphysics) provides for a stable and interactive environment for model construction. The core simulation routines are logically separated from the model building interface and written in a low-level language for computational efficiency. The connection to the geometry handling software is realized via a Matlab interface which facilitates script computing, data management, and post-processing. For practitioners, the software therefore behaves much as an interactive Matlab toolbox. At the same time, it is possible to modify and extend URDME with newly developed simulation routines. Since the overall design effectively hides the complexity of managing the geometry and meshes, this means that newly developed methods may be tested in a realistic setting already at an early stage of development. Conclusions In this paper we demonstrate, in a series of examples with high relevance to the molecular systems biology community, that the proposed software framework is a useful tool for both practitioners and developers of spatial stochastic simulation algorithms. Through the combined efforts of algorithm development and improved modeling accuracy, increasingly complex biological models become feasible to study through computational methods. URDME is freely available at PMID:22727185



Kinetic studies of dicopper complexes in catechol oxidase model reaction by using an approximationless evaluating method  

Microsoft Academic Search

The oxidation of 3,5-di-tert-butylcatechol to 3,5-di-tert-butyl-o-benzoquinone catalyzed by dinuclear copper(II) complexes {[Cu2(L1)(CF3SO3)2(H2O)4]-(CF3SO3)2 (1) and [Cu2(L2O)](CF3SO3)2 (2)| has been investigated in methanol saturated with O2 at ambient temperature. Detailed kinetic studies were carried out and for the treatment the fitting software ZiTa was applied. On the basis of the results in the kinetic studies a possible mechanism of the catalytic reaction

Katalin Selmeczi; Marius Réglier; Gábor Speier; Gábor Peintler



Theoretical study of structural, spectroscopic and reaction properties of trans-bis(imido) uranium(VI) complexes.  


To advance the understanding of the chemical behavior of actinides, a series of trans-bis(imido) uranium(VI) complexes, U(NR)2(THF)2(cis-I2) (2R; R = H, Me, (t)Bu, Cy, and Ph), U(NR)2(THF)3(trans-I2) (3R; R = H, Me, (t)Bu, Cy, and Ph) and U(N(t)Bu)2(THF)3(cis-I2) (3(t)Bu'), were investigated using relativistic density functional theory. The axial U?N bonds in these complexes have partial triple bonding character. The calculated bond lengths, bond orders, and stretching vibrational frequencies reveal that the U?N bonds of the bis-imido complexes can be tuned by the variation of their axial substituents. This has been evidenced by the analysis of electronic structures. 2H, for instance, was calculated to show iodine-based high-lying occupied orbitals and U(f)-type low-lying unoccupied orbitals. Its U?N bonding orbitals, formed by U(f) and N(p), occur in a region of the relatively low energy. Upon varying the axial substituent from H to (t)Bu and Ph, the U?N bonding orbitals of 2(t)Bu and 2Ph are greatly destabilized. We further compared the U?E (E = N and O) bonds of 2H with 3H and their uranyl analogues, to address effects of the equatorial tetrahydrofuran (THF) ligand and the E group. It is found that the U?N bonds are slightly weaker than the U?O bonds of their uranyl analogues. This is in line with the finding that cis-UNR2 isomers, although energetically unfavorable, are more accessible than cis-UO2 would be. It is also evident that 2H and 3H display lower U?(NH) stretching vibrations at 740 cm(-1) than the U?O at 820 cm(-1) of uranyl complexes. With the inclusion of both solvation and spin-orbit coupling, the free energies of the formation reactions of the bis-imido uranium complexes were calculated. The formation of the experimentally synthesized 3Me, 3Ph, and 2(t)Bu are found to be thermodynamically favorable. Finally, the absorption bands previously obtained from experimental studies were well reproduced by time-dependent density functional theory calculations. PMID:23834342

Guo, Yuan-Ru; Wu, Qian; Odoh, Samuel O; Schreckenbach, Georg; Pan, Qing-Jiang



Alumina plate containing photosystem I reaction center complex oriented inside plate-penetrating silica nanopores.  


The photosynthetic photosystem I reaction center complex (PSI-RC), which has a molecular diameter of 21 nm with 100 pigments, was incorporated into silica nanopores with a 100-nm diameter that penetrates an alumina plate of 60-?m thickness to make up an inorganic-biological hybrid photocell. PSI-RCs, purified from a thermophilic cyanobacterium, were stable inside the nanopores and rapidly photoreduced a mediator dye methyl viologen. The reduced dye was more stable inside nanopores suggesting the decrease of dissolved oxygen. The analysis by a cryogenic electron spin paramagnetic resonance indicated the oriented arrangement of RCs inside the 100-nm nanopores, with their surface parallel to the silica wall and perpendicular to the plane of the alumina plate. PSI RC complex in the semicrystalline orientation inside silica nanopores can be a new type of light energy conversion unit to supply strong reducing power selectively to other molecules inside or outside nanopores. PMID:23888886

Kamidaki, Chihiro; Kondo, Toru; Noji, Tomoyasu; Itoh, Tetsuji; Yamaguchi, Akira; Itoh, Shigeru



Insights into the binding specificity and catalytic mechanism of N-acetylhexosamine 1-phosphate kinases through multiple reaction complexes.  


Utilization of N-acetylhexosamine in bifidobacteria requires the specific lacto-N-biose/galacto-N-biose pathway, a pathway differing from the Leloir pathway while establishing symbiosis between humans and bifidobacteria. The gene lnpB in the pathway encodes a novel hexosamine kinase NahK, which catalyzes the formation of N-acetylhexosamine 1-phosphate (GlcNAc-1P/GalNAc-1P). In this report, seven three-dimensional structures of NahK in complex with GlcNAc, GalNAc, GlcNAc-1P, GlcNAc/AMPPNP and GlcNAc-1P/ADP from both Bifidobacterium longum (JCM1217) and B. infantis (ATCC15697) were solved at resolutions of 1.5-2.2 Å. NahK is a monomer in solution, and its polypeptide folds in a crescent-like architecture subdivided into two domains by a deep cleft. The NahK structures presented here represent the first multiple reaction complexes of the enzyme. This structural information reveals the molecular basis for the recognition of the given substrates and products, GlcNAc/GalNAc, GlcNAc-1P/GalNAc-1P, ATP/ADP and Mg(2+), and provides insights into the catalytic mechanism, enabling NahK and mutants thereof to form a choice of biocatalysts for enzymatic and chemoenzymatic synthesis of carbohydrates. PMID:24816108

Wang, Kuei-Chen; Lyu, Syue-Yi; Liu, Yu-Chen; Chang, Chin-Yuan; Wu, Chang-Jer; Li, Tsung-Lin



Reaction-diffusion model as a framework for understanding biological pattern formation.  


The Turing, or reaction-diffusion (RD), model is one of the best-known theoretical models used to explain self-regulated pattern formation in the developing animal embryo. Although its real-world relevance was long debated, a number of compelling examples have gradually alleviated much of the skepticism surrounding the model. The RD model can generate a wide variety of spatial patterns, and mathematical studies have revealed the kinds of interactions required for each, giving this model the potential for application as an experimental working hypothesis in a wide variety of morphological phenomena. In this review, we describe the essence of this theory for experimental biologists unfamiliar with the model, using examples from experimental studies in which the RD model is effectively incorporated. PMID:20929839

Kondo, Shigeru; Miura, Takashi



Formation of porous surface layers in reaction bonded silicon nitride during processing  

NASA Technical Reports Server (NTRS)

Microstructural examination of reaction bonded silicon nitride (RBSN) has shown that there is often a region adjacent to the as-nitrided surfaces that is even more porous than the interior of this already quite porous material. Because this layer of large porosity is considered detrimental to both the strength and oxidation resistance of RBSN, a study was undertaken to determine if its formation could be prevented during processing. All test bars studied were made from a single batch of Si powder which was milled for 4 hours in heptane in a vibratory mill using high density alumina cylinders as the grinding media. After air drying the powder, bars were compacted in a single acting die and hydropressed.

Shaw, N. J.; Glasgow, T. K.



Geranic Acid Formation, an Initial Reaction of Anaerobic Monoterpene Metabolism in Denitrifying Alcaligenes defragrans  

PubMed Central

Monoterpenes with an unsaturated hydrocarbon structure are mineralized anaerobically by the denitrifying ?-proteobacterium Alcaligenes defragrans. Organic acids occurring in cells of A. defragrans and culture medium were characterized to identify potential products of the monoterpene activation reaction. Geranic acid (E,E-3,7-dimethyl-2,6-octadienoic acid) accumulated to 0.5 mM in cells grown on ?-phellandrene under nitrate limitation. Cell suspensions of A. defragrans 65Phen synthesized geranic acid in the presence of ?-myrcene, ?-phellandrene, limonene, or ?-pinene. Myrcene yielded the highest transformation rates. The alicyclic acid was consumed by cell suspensions during carbon limitation. Heat-labile substances present in cytosolic extracts catalyzed the formation of geranic acid from myrcene. These results indicated that a novel monoterpene degradation pathway must be present in A. defragrans. PMID:10877798

Heyen, Udo; Harder, Jens



Uranyl triazolate formation via an in situ Huisgen 1,3-dipolar cycloaddition reaction  

SciTech Connect

A two dimensional UO{sub 2}{sup 2+} coordination polymer, (UO{sub 2}){sub 3}(C{sub 10}H{sub 5}N{sub 3}O{sub 4}){sub 2}(OH){sub 2}(H{sub 2}O){sub 2}, has been synthesized under solvothermal conditions. The triazolate ligand, 1-(4-carboxyphenyl)-1H-1,2,3-triazole-4-carboxylic acid (CPTAZ) has been generated via a 1,3-dipolar cycloaddition of 4-azidobenzoic acid and propiolic acid. Reactions of the UO{sub 2}{sup 2+} cation with both the in situ generated triazolate ligand and the presynthesized ligand have been explored. The structure, fluorescent and thermal behaviour of this material are presented, as is a discussion of the utility of in situ ligand formation versus direct assembly.

Knope, Karah E.; Cahill, Christopher L.



Diastereoselection in the Formation of Contiguous Quaternary Carbon Stereocenters by the Intramolecular Heck Reaction  

PubMed Central

The second in a series of two papers, this study examines the origins of diastereoselection in the second ring closure of the highly diastereoselective double Heck cyclization of cyclohexenes 1 and 3 that form contiguous quaternary stereocenters. Seven model substrates were synthesized and cyclized to examine the structural features responsible for imparting diastereoselection in the second intramolecular Heck reaction. These studies demonstrate that stereoselection in the formation of the second spirooxindole ring results from the avoidance of steric interactions in the insertion step with the spirooxindole formed in the first Heck cyclization. An axial substituent (carbonyl or arene) is required at the allylic position for high levels of diastereoselection to be realized. PMID:16555810

Overman, Larry E.; Watson, Donald A.



Medium corrections in the formation of light charged particles in heavy ion reactions  

E-print Network

Within a microscopic statistical description of heavy ion collisions, we investigate the effect of the medium on the formation of light clusters. The dominant medium effects are self-energy corrections and Pauli blocking that produce the Mott effect for composite particles and enhanced reaction rates in the collision integrals. Microscopic description of composites in the medium follows the Dyson equation approach combined with the cluster mean-field expansion. The resulting effective few-body problem is solved within a properly modified Alt-Grassberger-Sandhas formalism. The results are incorporated in a Boltzmann-Uehling-Uhlenbeck simulation for heavy ion collisions. The number and spectra of light charged particles emerging from a heavy ion collision changes in a significant manner in effect of the medium modification of production and absorption processes.

C. Kuhrts; M. Beyer; P. Danielewicz; G. Roepke



Complex Formation by Electrostatic Interaction between Carboxyl-Terminated Dendrimers and Oppositely Charged  

E-print Network

- enon in biological systems1 as well as in a number of technological processes;2 however, in the case because of the technological relevance of colloid-polymer interactions, we focus on complex formation charged particles depends predominantly on three variables: the ionic strength (I), the polymer linear

Dubin, Paul D.


The standard enthalpies of combustion and formation of crystalline cobalt tetrakis(4-metoxyphenyl)porphin complex  

NASA Astrophysics Data System (ADS)

The energy of combustion of cobalt tetrakis(4-metoxyphenyl)porphin was determined in an isothermic-shell liquid calorimeter with a stationary calorimetric bomb. The standard enthalpies of combustion and formation of the complex were calculated, -? c H o = 27334.06 ± 50.98 kJ/mol and ?f H o = 3062.90 ± 50.97 kJ/mol.

Tarasov, R. P.; Volkov, A. V.; Bazanov, M. I.; Semeikin, A. S.



Transcription by RNA polymerase II: initiator-directed formation of transcription-competent complexes  

Microsoft Academic Search

Studies of transcription by RNA polymer- ase II have revealed two promoter elements, the TATA motif and the initiator (Inr), capable of directing specific transcription initiation. Although binding to the TATA motif by one of the components of the transcription machinery has been shown to be the initial recognition step in transcription complex formation, many promoters that lack a traditional




Facile tandem Suzuki coupling/transfer hydrogenation reaction with a bis-heteroscorpionate Pd-Ru complex.  


Design and synthesis of the bis(pyrazol-1-yl)methane based bis-heteroscorpionate Pd-Ru complex results in efficient tandem Suzuki coupling/transfer hydrogenation reaction with a broad range of substrate reactivity. PMID:25297718

Dehury, Niranjan; Tripathy, Suman Kumar; Sahoo, Anupam; Maity, Niladri; Patra, Srikanta



Atmospheric Secondary Aerosol Formation by Heterogeneous Reactions of Aldehydes in the Presence of a Sulfuric Acid Aerosol Catalyst  

NASA Astrophysics Data System (ADS)

Particle growth by the heterogeneous reaction of aldehydes was observed in 0.5 m3 indoor Teflon bags in the presence of background seed aerosols. The aldehydes used were: glyoxal, butanal, hexanal, octanal, and decanal. To study acid catalyst effects on aldehyde heterogeneous reactions, one of the Teflon bags was initially filled with seed aerosols composed of ammonium sulfate-aerosol acidified with sulfuric acid. This result was compared to particle growth reactions that contained only ammonium sulfate as a background seed aerosol. The gas phase aldehydes were then added to the Teflon bags. In selected experiments, 1-decanol was also added to the Teflon bags with aldehydes to clarify particle growth via a heterogeneous hemiacetal/acetal formation in the presence/absence of an acid catalyst. The particle size distribution and growth were measured using a differential mobility analyzer (DMA), and the results were applied to predicting aerosol growth and size distribution changes by condensation and heterogeneous reactions. Aerosols created from the heterogeneous reactions of aldehydes were collected directly on an ungreased zinc selenide (ZnSe) FTIR disk (25 mm in diameter) by impaction. The ZnSe disks were directly analyzed for product functional groups in the aerosol phase using a Fourier transform infrared (FTIR) spectrometer with a deuterated triglycine sulfate (DTGS) detector. Aerosol growth by heterogeneous aldehyde reactions proceeds via a hydration, polymerization process, hemiacetal/acetal formation from the reaction of aldehydes with alcohols. These aldehyde heterogeneous reactions were accelerated in the presence of an acid catalyst, H2SO4, and led to higher aerosol yields than when H2SO4 was not present in the seed aerosol. The FTIR spectra obtained from the growing aerosol, also illustrated aldehyde group transformation in the particle phase as a function of the heterogeneous reaction. It was concluded that aldehydes, which can be produced by atmospheric photochemical reactions, can significantly contribute on secondary aerosol formation through heterogeneous reactions in the presence of an acid catalyst.

Jang, M.; Kamens, R. M.



(Phenoxyimidazolyl-salicylaldimine)iron complexes: synthesis, properties and iron catalysed ethylene reactions.  


The reaction of 2-{[2-(1H-imidazol-4-yl)-ethylimino]-methyl}-phenol (L1), 2,4-di-tert-butyl-6-{[2-(1H-imidazol-4-yl)-ethylimino]-methyl}-phenol (L2) or 4-tert-butyl-2-{[2-(1H-imidazol-4-yl)-ethylimino]-methyl}-phenol (L3) with iron(ii) precursors produced either iron(ii) or iron(iii) complexes, depending on the nature of the anions in the iron(ii) precursor and the ligand. When the anion is chloride and the ligand L1, the product is [(L1)2Fe][FeCl4] (1), but when the anion is triflate (OTf(-)) and the ligand is L2, the product is [(L2)2Fe][OTf]2 (2). With iron(ii) halides and tert-butyl groups on the phenoxy ligands L2 and L3, the iron(iii) complexes [(L2)FeX2] {where X = Cl (3), Br (4) and I = (5)} and [(L3)FeCl2] (6) were formed. Complexes 1-6 were characterised by a combination of elemental analyses, IR spectroscopy and mass spectrometry; and in selected cases (3 and 4) by single crystal X-ray crystallography. The crystal structures of 3 and 4 indicated that the iron(ii) precursors oxidised to iron(iii) in forming complexes 3-6; an observation that was corroborated by the magnetic properties and the (57)Fe Mössbauer spectra of 3 and 4. The iron(iii) complexes 3-6 were used as pre-catalysts for the oligomerisation and polymerisation of ethylene. Products of these ethylene reactions depended on the solvent used. In toluene ethylene oligomerised mainly to 1-butene and was followed by the 1-butene alkylating the solvent to form butyl-toluenes via a Friedel-Crafts alkylation reaction. In chlorobenzene, ethylene oligomerised mainly to a mixture of C4-C12 alkenes. Interestingly small amounts of butyl-chlorobenzenes and hexyl-chlorobenzenes were also formed via a Friedel-Crafts alkylation with butenes and hexenes from the oligomerisation of ethylene. PMID:25111396

Yankey, Margaret; Obuah, Collins; Guzei, Ilia A; Osei-Twum, Emmanuel; Hearne, Giovanni; Darkwa, James



Formation and alteration of complex amino acid precursors in cosmic dusts and their relevance to origins of life  

NASA Astrophysics Data System (ADS)

A wide variety of organic compounds including many kinds of amino acids have been detected in carbonaceous chondrites. It has been known that comets also bring complex organic compounds. The relevance of extraterrestrial organics to the origin of life is extensively discussed. There have been many scenarios of the origin of amino acids found in meteorites or comets, including the Strecker synthesis in the parent bodies of meteorites, the Fischer-Tropsch type reaction in the solar nebula and reactions in cosmic dusts. We examined possible formation of amino acids or their precursors in interstellar dust environments. When possible interstellar media (a mixture of carbon monoxide, ammonia and water) was irradiated with high energy protons, complex organic compounds whose molecular weights are thousands were formed [1], which gave amino acids after acid hydrolysis: Hereafter we will refer them simulated interstellar organics. It was suggested that complex amino acid precursors could be formed in ice mantles of interstellar dust particles in prior to the formation of the solar system. We are planning to irradiate simulated interstellar ices with high-energy heavy ions from the Digital Accelerator (KEK) to confirm the scenario. The simulated interstellar oraganics were so hydrophilic that they were easy to dissolve in water. Complex organics found in meteorites are generally so hydrophobic and are insoluble to water. Organics found in cometary dusts sampled by the Stardust Mission contains organics with various hydrophobicity. We irradiated the simulated interstellar organics with UV and/or soft X-rays. Soft X-rays irradiation of the simulated interstellar organics resulted in the formation of more hydrophobic compounds as seen in some of cometary dusts. It was suggested that organics of interstellar origin on dusts were altered when the solar system was being formed with soft X-rays from the young Sun in prior to the incorporation to planetesimals or comets. Dusts have another important role: Delivery of extraterrestrial organics to the primitive Earth. We are planning a novel astrobiology mission named Tanpopo by utilizing the Exposed Facility of Japan Experimental Module (JEM/EF) of the International Space Station (ISS). We will collect cosmic dusts by using ultra-low density silica gel (aerogel), and will analyze them after returning them to the Earth. Details will be presented in the other session of COSPAR 2014 [2]. [1] Y. Takano et al., Appl. Phys. Lett., 84 (2004) 1410-1412. [2] K. Kobayashi et al., COSPAR 2014, Session F31, #14256, Moscow, Russia.

Kobayashi, Kensei; Kaneko, Takeo; Mita, Hajime; Obayashi, Yumiko; Kawamoto, Yukinori; Kanda, Kazuhiro; Takayama, Ken; Shibata, Hiromi


The significance of ACTH for the process of formation of complex heparin compounds in the blood during immobilization stress  

NASA Technical Reports Server (NTRS)

Adrenocorticotropin (ACTH) was administered to rats at different times following adrenalectomy. Adrenocorticotropin caused a significant increase in the formation of heparin complexes even in the absence of stress factor. When ACTH secretion is blocked, immobilization stress is not accompanied by an increase in the process of complex formation. The effect of ACTH on the formation of heparin complexes was mediated through its stimulation of the adrenal cortex.

Kudryashov, B. A.; Shapiro, F. B.; Lomovskaya, F. B.; Lyapina, L. A.



Characterization of self-propagating formation reactions in Ni/Zr multilayered foils using reaction heats, velocities, and temperature-time profiles  

SciTech Connect

We report on intermetallic formation reactions in vapor-deposited multilayered foils of Ni/Zr with 70 nm bilayers and overall atomic ratios of Ni:Zr, 2 Ni:Zr, and 7 Ni:2 Zr. The sequence of alloy phase formation and the stored energy is evaluated at slow heating rates (~1 K/s) using differential scanning calorimetry (DSC) traces to 725ºC. All three chemistries initially form a Ni-Zr amorphous phase which crystallizes first to the intermetallic NiZr. The heat of reaction to the final phase is 34-36 kJ/mol atom for all chemistries. Intermetallic formation reactions are also studied at rapid heating rates (greater than 105 K/s) in high temperature, self-propagating reactions which can be ignited in these foils by an electric spark. We find that reaction velocities and maximum reaction temperatures (Tmax) are largely independent of foil chemistry at 0.6 ± 0.1 m/s and 1220 ± 50 K, respectively, and that the measured Tmax is more than 200 K lower than predicted adiabatic temperatures (Tad). The difference between Tmax and Tad is explained by the prediction that transformation to the final intermetallic phases occurs after Tmax and results in the release of 20-30 % of the total heat of reaction and a delay in rapid cooling.

Barron, S. C.; Knepper, R.; Walker, N.; Weihs, T. P.



Furfural-cysteine model reaction in food grade nonionic oil/water microemulsions for selective flavor formation.  


The thermal reaction between cysteine and furfural was investigated at 65 degrees C in five-component food grade oil/water (O/W) microemulsions of R-(+)-limonene/ethanol, EtOH/water/propylene glycol, PG/Tween 60 as apart of a systematic study on the generation of aroma compounds by utilizing structured W/O and O/W fluids. The furfural-cysteine reaction led to the formation of unique aroma compounds such as 2-furfurylthiol (FFT), 2-(2-furanyl)thiazolidine (main reaction product), 2-(2-furanyl)thiazoline, and N-(2-mercaptovinyl)-2-(2-furanyl)thiazolidine. These products were determined and characterized by GC-MS. Enhancement in flavor formation is termed "microemulsion catalysis". The chemical reaction occurs preferably at the interfacial film, and therefore a pseudophase model was assumed to explain the enhanced flavor formation. The product internal composition is dictated by process conditions such as temperature, time, pH, and mainly the nature of the interface. Increasing water/PG ratio leads to a dramatic increase in the initial reaction rate (V(0)). V(0) increased linearly as a function of the aqueous phase content, which could be due to the increase in the interfacial concentration of furfural. Microemulsions offer a new reaction medium to produce selective aroma compounds and to optimize their formation. PMID:11982414

Yaghmur, Anan; Aserin, Abraham; Garti, Nissim



X-ray diffraction study of the complex of the enzyme SAICAR synthase with the reaction product  

NASA Astrophysics Data System (ADS)

The three-dimensional structure of the complex of the enzyme SAICAR synthase with the product of the enzymatic reaction, SAICAR, was solved and refined by methods of protein crystallography. The SAICAR-binding site in the active site of the enzyme was found. The amino-acid residues providing the binding of the reaction product with the protein were revealed. These residues were compared with those involved in the substrate binding in the complex with AICAR and succinic acid studied earlier.

Urusova, D. V.; Levdikov, V. M.; Antonyuk, S. V.; Grebenko, A. I.; Lamzin, V. S.; Melik-Adamyan, V. R.



X-ray diffraction study of the complex of the enzyme SAICAR synthase with the reaction product  

SciTech Connect

The three-dimensional structure of the complex of the enzyme SAICAR synthase with the product of the enzymatic reaction, SAICAR, was solved and refined by methods of protein crystallography. The SAICAR-binding site in the active site of the enzyme was found. The amino-acid residues providing the binding of the reaction product with the protein were revealed. These residues were compared with those involved in the substrate binding in the complex with AICAR and succinic acid studied earlier.

Urusova, D. V., E-mail:; Levdikov, V. M. [Russian Academy of Sciences, Shubnikov Institute of Crystallography (Russian Federation); Antonyuk, S. V. [CCLRC Daresbury Laboratory (United Kingdom)], E-mail:; Grebenko, A. I. [Russian Academy of Sciences, Shubnikov Institute of Crystallography (Russian Federation); Lamzin, V. S. [European Molecular Biology Laboratory, EMBL Hamburg Outstation (Germany)], E-mail:; Melik-Adamyan, V. R. [Russian Academy of Sciences, Shubnikov Institute of Crystallography (Russian Federation)



Reaction of neptunium with molecular and atomic oxygen: Formation and stability of surface oxides  

NASA Astrophysics Data System (ADS)

The surface reactions of thin films of Np metal with molecular and atomic oxygen were investigated by X-ray and Ultra-Violet Photoelectron Spectroscopy (XPS and UPS, respectively). Goal of this work was to study the entire range of oxides, starting with the very early reaction stages, in presence of metal, up to the highest possible oxides, reached at saturation under highly reactive, oxidative conditions. Emphasis was given to the surface layers, whose properties often differ from the bulk, and which are directly involved in corrosion processes of solids. Molecular O 2 reacts readily with the metallic neptunium surface to form the sesquioxide and dioxide. The sesquioxide is observed as thin 'bulk' species of up to nine monolayers thickness. A higher oxide, identified as Np 2O 5, is formed when the NpO 2 surface is exposed to atomic oxygen. It is stable under UHV conditions up to a temperature of about 200 °C. The high oxide, Np 2O 5, is still capable of chemisorbing further oxygen. This is shown in UPS spectra by the additional O-2p line at 5-6 eV BE, superimposing onto the valence band (VB). The formation of both a lower (Np 2O 3) and higher oxide (Np 2O 5) besides the dioxide is discussed in the framework of ongoing 5f localization throughout the actinide series.

Seibert, A.; Gouder, T.; Huber, F.



Formation of cysteine-S-conjugates in the Maillard reaction of cysteine and xylose.  


Cysteine-S-conjugates (CS-conjugates) occur in foods derived from plant sources like grape, passion fruit, onion, garlic, bell pepper and hops. During eating CS-conjugates are degraded into aroma-active thiols by ?-lyases that originate from oral microflora. The present study provides evidence for the formation of the CS-conjugates S-furfuryl-l-cysteine (FFT-S-Cys) and S-(2-methyl-3-furyl)-l-cysteine (MFT-S-Cys) in the Maillard reaction of xylose with cysteine at 100°C for 2h. The CS-conjugates were isolated using cationic exchange and reversed-phase chromatography and identified by (1)H NMR, (13)C NMR and LC-MS(2). Spectra and LC retention times matched those of authentic standards. To the best of our knowledge, this is the first time that CS-conjugates are described as Maillard reaction products. Furfuryl alcohol (FFA) is proposed as an intermediate which undergoes a nucleophilic substitution with cysteine. Both FFT-S-Cys and MFT-S-Cys are odourless but produce strong aroma when tasted in aqueous solutions, supposedly induced by ? -lyases from the oral microflora. The perceived aromas resemble those of the corresponding aroma-active thiols 2-furfurylthiol (FFT) and 2-methyl-3-furanthiol (MFT) which smell coffee-like and meaty, respectively. PMID:23790889

Cerny, Christoph; Guntz-Dubini, Renée



Formation of early and advanced Maillard reaction products correlates to the ripening of cheese.  


The present study deals with the characterization of the ripening of cheese. A traditional German acid curd cheese was ripened under defined conditions at elevated temperature, and protein and amino acid modifications were investigated. Degree of proteolysis and analysis of early [Amadori compound furosine (6)] and advanced [N(?)-carboxymethyllysine (4), N(?)-carboxyethyllysine (5)] Maillard reaction products confirmed the maturation to proceed from the rind to the core of the cheese. Whereas 6 was decreased, 4 and 5 increased over time. Deeper insight into the Maillard reaction during the ripening of cheese was achieved by the determination of selected ?-dicarbonyl compounds. Especially methylglyoxal (2) showed a characteristic behavior during storage of the acid curd cheese. Decrease of this reactive structure was directly correlated to the formation of 5. To extend the results of experimental ripening to commercial cheeses, different aged Gouda types were investigated. Maturation times of the samples ranged from 6 to 8 weeks (young) to more than 1 year (aged). Again, increase of 5 and decrease of 2 were able to describe the ripening of this rennet coagulated cheese. Therefore, both chemical parameters are potent markers to characterize the degree of maturation, independent of coagulation. PMID:22224825

Spanneberg, Robert; Salzwedel, Grit; Glomb, Marcus A



Efficient and directed peptide bond formation in the gas phase via ion/ion reactions  

PubMed Central

Amide linkages are among the most important chemical bonds in living systems, constituting the connections between amino acids in peptides and proteins. We demonstrate the controlled formation of amide bonds between amino acids or peptides in the gas phase using ion/ion reactions in a mass spectrometer. Individual amino acids or peptides can be prepared as reagents by (i) incorporating gas phase–labile protecting groups to silence otherwise reactive functional groups, such as the N terminus; (ii) converting the carboxyl groups to the active ester of N-hydroxysuccinimide; and (iii) incorporating a charge site. Protonation renders basic sites (nucleophiles) unreactive toward the N-hydroxysuccinimide ester reagents, resulting in sites with the greatest gas phase basicities being, in large part, unreactive. The N-terminal amines of most naturally occurring amino acids have lower gas phase basicities than the side chains of the basic amino acids (i.e., those of histidine, lysine, or arginine). Therefore, reagents may be directed to the N terminus of an existing “anchor” peptide to form an amide bond by protonating the anchor peptide’s basic residues, while leaving the N-terminal amine unprotonated and therefore reactive. Reaction efficiencies of greater than 30% have been observed. We propose this method as a step toward the controlled synthesis of peptides in the gas phase. PMID:24474750

McGee, William M.; McLuckey, Scott A.



Formation and stability of lanthanide complexes and their encapsulation into polymeric microspheres  

SciTech Connect

The complexation of lanthanides (Ln) with dicarbonyl compounds (acetylacetone, acac; ethyl acetoacetate; 3-ethyl-2,4-pentanedione; 2,4-hexanedione; 3-methyl-2,4-pentanedione; and diethyl malonate) was investigated using a potentiometric titration technique. The ability of a dicarbonyl compound to complex with the lanthanide elements was greatly dependent on its pK{sub a} and on the pH of the titrated solution. Selected lanthanide complexes (Ln complexes) were incorporated into spherical poly(L-lactic acid)(PLA) matrices and irradiated in a nuclear reactor with neutrons to produce short-lived high-energy {Beta}-particle-emitting radioisotopes. The lanthanides investigated (Ho, Dy, Sm, and La) were chosen on the basis of their physical and nuclear properties. A transition element (Re) was also studied. The small decrease in the ionic radii of the lanthanides with increasing atomic number led to (a) greater ability to extract and complex from an aqueous solution with complexing agents, (b) larger formation and stability constants for the Ln complexes, (c) increased solubility of the Ln complexes in chloroform, and (d) increase in the maximum percent incorporation of the stable lanthanides in PLA spheres. Ho(aca) was found to be the most promising candidate of the complexes studied on the basis of the above observations and due to the favorable physical properties of {sup 165}Ho and nuclear properties of {sup 166}Ho. 21 refs., 5 figs., 4 tabs.

Mumper, R.J.; Jay, M. [Univ. of Kentucky, Lexington, KY (United States)



Geminin Inhibits a Late Step in the Formation of Human Pre-replicative Complexes*  

PubMed Central

The initial step in initiation of eukaryotic DNA replication involves the assembly of pre-replicative complexes (pre-RCs) at origins of replication during the G1 phase of the cell cycle. In metazoans initiation is inhibited by the regulatory factor Geminin. We have purified the human pre-RC proteins, studied their interactions in vitro with each other and with origin DNA, and analyzed the effects of HsGeminin on formation of DNA-protein complexes. The formation of an initial complex containing the human origin recognition complex (HsORC), HsCdt1, HsCdc6, and origin DNA is cooperative, involving all possible binary interactions among the components. Maximal association of HsMCM2–7, a component of the replicative helicase, requires HsORC, HsCdc6, HsCdt1, and ATP, and is driven by interactions of HsCdt1 and HsCdc6 with multiple HsMCM2–7 subunits. Formation of stable complexes, resistant to high salt, requires ATP hydrolysis. In the absence of HsMCM proteins, HsGeminin inhibits the association of HsCdt1 with DNA or with HsORC-HsCdc6-DNA complexes. However, HsGeminin does not inhibit recruitment of HsMCM2–7 to DNA to form complexes containing all of the pre-RC proteins. In fact, HsGeminin itself is a component of such complexes, and interacts directly with the HsMcm3 and HsMcm5 subunits of HsMCM2–7, as well as with HsCdt1. Although HsGeminin does not prevent the initial formation of DNA-protein complexes containing the pre-RC proteins, it strongly inhibits the formation of stable pre-RCs that are resistant to high salt. We suggest that bound HsGeminin prevents transition of the pre-RC to a state that is competent for initiation of DNA replication. PMID:25231993

Wu, Min; Lu, Wenyan; Santos, Ruth E.; Frattini, Mark G.; Kelly, Thomas J.



Enantioselective three-component Kabachnik-Fields reaction catalyzed by chiral scandium(III)-N,N'-dioxide complexes.  


The N,N'-dioxide-Sc(III) complex has been applied in the three-component Kabachnik-Fields reaction of aldehydes, 2-aminophenol, and diphenyl phosphite, giving the corresponding alpha-amino phosphonates in good yields with high enantioselectivities (up to 87% ee). The direct Kabachnik-Fields reaction proceeded with extremely high reactivity under mild reaction conditions and could be used for large-scale synthesis of the alpha-amino phosphonates. PMID:19226133

Zhou, Xin; Shang, Deju; Zhang, Qi; Lin, Lili; Liu, Xiaohua; Feng, Xiaoming



Sodium ferric gluconate complex in hemodialysis patients. II. Adverse reactions in iron dextran-sensitive and dextran-tolerant patients  

Microsoft Academic Search

Sodium ferric gluconate complex in hemodialysis patients. II. Adverse reactions in iron dextran-sensitive and dextran-tolerant patients.BackgroundIron dextran administration is associated with a high incidence of adverse reactions including anaphylaxis and death. Although dextran, rather than iron, is believed to be the cause of these reactions, it is not known whether iron dextran-sensitive patients can be safely administered another form of

Daniel W Coyne; Franklin N Adkinson; Allen R Nissenson; Steven Fishbane; Rajiv Agarwal; Joseph W Eschbach; Beckie Michael; Vaughn Folkert; Daniel Batlle; J Richard Trout; Naomi Dahl; Pamela Myirski; Jur Strobos; David G Warnock



Formation of carriers in Ti-oxide thin films by substitution reactions  

SciTech Connect

Conductive Ti-oxide thin films are produced using a reactive sputtering and post-annealing process. The lowest resistivity of Ti-oxide thin films (2.30 x 10{sup -2}{Omega}-cm) can be achieved after annealing for 1 h at 400 deg. C in ambient O{sub 2}. Additionally, the Hall measurement results indicate that the carrier concentration increases during the initial 1-h annealing process before decreasing during subsequent annealing. By curve fitting the O{sub ls} core-level peaks in the x ray photoelectron spectroscopy (XPS) spectrum of the annealed Ti-oxide thin films, we found that the oxygen (O) vacancy concentration monotonically increases with annealing time, which differs from the behavior of the carrier concentration regarding annealing time. This means that the O-vacancy mechanism alone cannot explain the formation of carriers in Ti-oxide thin films. By curve-fitting core-level Ti peaks in the XPS spectrum of annealed Ti-oxide thin films, a Ti{sup 3+}-to-Ti{sup 4+} substitution reaction in the TiO{sub 2} phase of the Ti-oxide thin film after annealing plays the dominant role in the formation of conduction carriers. Instead of the O-vacancy mechanism, the Ti{sup 3+}-to-Ti{sup 4+} substitution mechanism can explain the concentration of carriers in Ti-oxide thin films following annealing.

Liu, Y. S.; Lin, Y. H.; Wei, Y. S.; Liu, C. Y. [Department of Chemical and Materials Engineering, National Central University, Jhong-Li, Taiwan (China)



Formation of carcinogenic 4(5)-methylimidazole in Maillard reaction systems.  


4(5)-Methylimidazole has received the attention of federal and state regulatory agencies because of its carcinogenicity and common presence in foods and beverages. In the present study, the formation of 4(5)-methylimidazole in Maillard reaction model systems consisting of D-glucose/NH(3), L-rhamnose/NH(3), methylglyoxal/NH(3), and methylglyoxal/formaldehyde/NH(3) was investigated. 4(5)-Methylimidazole was formed at levels ranging from 0.49 to 0.71 mg/mL in the d-glucose/NH(3) model system. The formation of 4(5)-methylimidazole was slightly higher in the L-rhamnose/NH(3) system (0.91 mg/mL) than in the d-glucose/NH(3) system (0.71 mg/mL) under the conditions used in the present study. A methylglyoxal/NH(3) system produced significantly higher levels of 4(5)-methylimidazole (5.70 mg/mL), suggesting that methylglyoxal is an important precursor of 4(5)-methylimidazole. Ammonolysis of methylglyoxal, which is one of the glucose degradation products, was proposed to form formamide, which subsequently reacted with 2-aminopropanal (?-aminocarbonyl intermediate) formed from methylglyoxal to give 4- or 5-methylimidazole. The levels of 4(5)-methylimidazole found in commercial cola soft drinks range from 0.30 ?g/mL (brand 3) to 0.36 ?g/mL (brands 1 and 5). PMID:21186780

Moon, Joon-Kwan; Shibamoto, Takayuki



Lethal synergism between organic and inorganic wood preservatives via formation of an unusual lipophilic ternary complex  

SciTech Connect

We have shown previously that exposing bacteria to wood preservatives pentachlorophenol (PCP) and copper-containing compounds together causes synergistic toxicity. However, it is not clear whether these findings also hold true in mammalian cells; and if so, what is the underlying molecular mechanism? Here we show that PCP and a model copper complex bis-(1,10-phenanthroline) cupric (Cu(OP){sub 2}), could also induce synergistic cytotoxicity in human liver cells. By the single crystal X-ray diffraction and atomic absorption spectroscopy assay, the synergism was found to be mainly due to the formation of a lipophilic ternary complex with unusual structural and composition characteristics and subsequent enhanced cellular copper uptake, which markedly promoted cellular reactive oxygen species (ROS) production, leading to apoptosis by decreasing mitochondrial membrane potential, increasing pro-apoptotic protein expression, releasing cytochrome c from mitochondria and activating caspase-3, and -9. Analogous results were observed with other polychlorinated phenols (PCPs) and Cu(OP){sub 2}. Synergistic cytotoxicity could be induced by PCP/Cu(OP){sub 2} via formation of an unusual lipophilic complex in HepG2 cells. The formation of ternary complexes with similar lipophilic character could be of relevance as a general mechanism of toxicity, which should be taken into consideration especially when evaluating the toxicity of environmental pollutants found at currently-considered non- or sub-toxic concentrations. -- Highlights: ? The combination of PCP/Cu(OP){sub 2} induces synergistic cytotoxicity in HepG2 cells. ? The synergism is mainly due to forming a lipophilic ternary complex between them. ? The formation of lipophilic ternary complex enhances cellular copper uptake. ? PCP/Cu(OP){sub 2} stimulates the cellular ROS production. ? The ROS promoted by PCP/Cu(OP){sub 2} induces mitochondria-dependent apoptosis.

Sheng, Zhi-Guo; Li, Yan; Fan, Rui-Mei; Chao, Xi-Juan [State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Science, Chinese Academy of Sciences, Beijing 100085 (China)] [State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Science, Chinese Academy of Sciences, Beijing 100085 (China); Zhu, Ben-Zhan, E-mail: [State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Science, Chinese Academy of Sciences, Beijing 100085 (China) [State Key Laboratory of Environmental Chemistry and Ecotoxicology, Research Center for Eco-Environmental Science, Chinese Academy of Sciences, Beijing 100085 (China); Linus Pauling Institute, Oregon State University, Corvallis, OR 97331 (United States)



Open complex formation around a lesion during nucleotide excision repair provides a structure for cleavage by human XPG protein.  

PubMed Central

Human XPG nuclease makes the 3' incision during nucleotide excision repair of DNA. The enzyme cleaves model DNA bubble structures specifically near the junction of unpaired DNA with a duplex region. It is not yet known, however, whether an unpaired structure is an intermediate during actual DNA repair. We find here that XPG requires opening of >5 bp for efficient cleavage. To seek direct evidence for formation of an open structure around a lesion in DNA during a nucleotide excision repair reaction in vitro, KMnO4 footprinting experiments were performed on a damaged DNA molecule bearing a uniquely placed cisplatin adduct. An unwound open complex spanning approximately 25 nucleotides was observed that extended to the positions of 5' and 3' incision sites and was dependent on XPA protein and on ATP. Opening during repair occurred prior to strand incision by XPG. PMID:9034344

Evans, E; Fellows, J; Coffer, A; Wood, R D



Substitutionality of nitrogen atoms and formation of nitrogen complexes and point defects in GaPN alloys  

NASA Astrophysics Data System (ADS)

Nitrogen substitution and formation of point defects in GaP(1-x)Nx layers (x ranging from 0.01 to 0.04) grown on GaP substrates are characterized by channelling Rutherford backscattering, nuclear reaction analysis and positron annihilation spectroscopy measurements. It is observed that the substitutionality of nitrogen into GaP decreases from a value of 0.91 to that of <0.1 with increasing nitrogen content from x = 1.7% to x = 4.0%. In addition to substitutional nitrogen atoms, GaPN layers have nitrogen interstitials, nitrogen clusters and defect complexes composed of multiple nitrogen atoms. Positron annihilation spectroscopy of GaPN layer shows positron trapping not only in vacancies but also trapping due to nitrogen clusters. In addition, the footprint of different nitrogen cluster states and point defects is observed in temperature dependent photoluminescence measurements.

Jussila, H.; Yu, K. M.; Kujala, J.; Tuomisto, F.; Nagarajan, S.; Lemettinen, J.; Huhtio, T.; Tuomi, T. O.; Lipsanen, H.; Sopanen, M.



Americium(iii) and europium(iii) complex formation with lactate at elevated temperatures studied by spectroscopy and quantum chemical calculations.  


Thermodynamic parameters for the complex formation of Am(iii) and Eu(iii) with lactate were determined with UV-vis and time-resolved laser-induced fluorescence spectroscopy (TRLFS) in a temperature range between 25 and 70 °C. The reaction enthalpy decreased with increasing ionic strength. ATR FT-IR and NMR spectroscopy in combination with density functional theory (DFT) calculations revealed structural details of the Eu(iii) lactate 1?:?1 complex: a chelating coordination mode of the lactate with a monodentate binding carboxylate group and the hydroxyl group being deprotonated. PMID:24828353

Barkleit, Astrid; Kretzschmar, Jerome; Tsushima, Satoru; Acker, Margret



Pattern formation in reaction-diffusion systems: From spiral waves to turbulence  

NASA Astrophysics Data System (ADS)

Almost all systems we encounter in nature possess some sort of form or structure. In many cases, the structures arise from an initially unstructured state without the action of an agent that predetermines the pattern. Such self-organized structures emerge from cooperative interactions among the constituents of the system and often exhibit properties that are distinct from those of their constituent elements or molecules. For example, chemical waves in reaction-diffusion systems are at the core of a huge variety of physical, chemical, and biological processes. In (quasi) two-dimensional situations, spiral wave patterns are especially prevalent and determine the characteristics of processes such as surface catalytic oxidation reactions, contraction of the heart muscle, and various signaling mechanisms in biological systems. In this talk, I will review and discuss recent theoretical and experimental results regarding the dynamics, properties and stability of spiral waves and their three-dimensional analog (scroll waves). Special emphasis will be given to synchronization defect lines which generically arise in complex-oscillatory media, and the phenomenon of defect-mediated turbulence or filament turbulence where the dynamics of a pattern is dominated by the rapid motion, nucleation, and annihilation of spirals or scroll waves, respectively. The latter is of direct relevance in the context of ventricular fibrillation - a turbulent electrical wave activity that destroys the coherent contraction of the ventricular muscle and its main pumping function leading to sudden cardiac death.

Davidsen, Joern



Reactions of nitroplatinum complexes. 1. sup 15 N and sup 195 Pt NMR spectra of platinum(II) nitrite complexes  

SciTech Connect

{sup 15}N and {sup 195}Pt NMR spectra have been used to characterize the products of reaction of Pt({sup 15}NO{sub 2}){sub 4}{sup 2{minus}} with sulfamic acid, Pt({sup 15}NO{sub 2}){sub 3}(H{sub 2}O){sup {minus}} and cis-Pt({sup 15}NO{sub 2}){sub 2}(H{sub 2}O){sub 2}, and the hydroxo complexes Pt({sup 15}No{sub 2}){sub 2}(OH){sub 2}{sup 2{minus}} derived from them by deprotonation. At intermediate pH values, the dinitro complexes rapidly form the hydroxo-bridged compounds ({l brace}Pt({sup 15}NO{sub 2}){sub 2}({mu}-OH){r brace}){sup n{minus}} (n = 2,3). The acid dissociation constant for Pt({sup 15}BO{sub 2}){sub 3}(H{sub 2}O){sup {minus}} (pK{sub a} 5.32) was determined from the variation with pH of {delta}{sub N} for nitro ligands cis to water/hydroxide. {sup 15}N and {sup 195}Pt NMR parameters were obtained for the series Pt({sup 15}NO{sub 2}){sub 3}Z{sup m{minus}}. These changes in these parameters as Z was changed correlated with those in the series Pt({sup 15}NH{sub 3}){sub 3}Z{sup n+}. {delta}{sub N} and J(Pt-N) values are much more sensitive to change in the ligand Z for the nitro ligand trans to Z than for that cis to Z. 44 refs., 3 figs., 3 tabs.

Appleton, T.G.; Barnham, K.J.; Hall, J.R.; Mathieson, M.T. (Univ. of Queensland, Brisbane (Australia))



Unprecedented formation of a doubly bridged ?-peroxo-?-pyrazolyldicarboxylato-dicobalt(III) complex  

Microsoft Academic Search

The reaction of an aqueous solution containing Co(ClO4)2, di(2-pyridymethyl)amine (DPA) and 3,5-pyrazole dicarboxylate anion (Hpzdc2?) afforded the unprecedented diamagnetic dicobalt(III)-peroxo complex [Co2(DPA)2(?-pzdc)(?-?1:?1-O2)]ClO4·3H2O (1) where the pyrazole group was fully deprotonated. The complex was structurally characterized by IR and UV–vis spectroscopy. X-ray crystal structure of 1 reveals the existence of the doubly bridged nature of cis-?-?1:?1-peroxo (end-on) and the dicarboxylato pyrazole.

Febee R. Louka; Lam T. Nguyen; Jörg H. Albering; Franz A. Mautner; Salah S. Massoud


Improved methods for calculating formation constants for nucleotide--cation complexes.  


Two data reduction methods that can be used to calculate formation constants for nucleotide-cation complexes are described. Both methods are used to analyze data obtained by an anion-exchange resin method, and either method can improve the accuracy of the calculated formation constants by more than 50%. The key to this significant improvement in accuracy is the realization that the equation for the mathematical model describing such systems is always nonlinear in terms of the formation constants and, in the general case, is higher order in the cation concentration. There are two major reasons for the improved quality of the results associated with the new model. First, successive linear extrapolations are eliminated, and error propagation is reduced. Second, all of the data are used for the simultaneous calculation of all formation constants, and the uncertainty due to random experimental errors is minimized. PMID:6859527

Clary, L G; Voige, W H; Leary, J J



Bis(pentamethylcyclopentadienyl) ytterbium: Electron-transfer reactions with organotransition metal complexes  

SciTech Connect

The divalent lanthanide complex, (Me{sub 5}C{sub 5}){sub 2}Yb, reacts with methylcopper to produce the base-free, ytterbium-methyl complex, (Me{sub 5}C{sub 5}){sub 2}YbMe. This product forms a asymmetric, methyl-bridged dimer in the solid state. The bulky alkyl complex, (Me{sub 5}C{sub 5}){sub 2}YbCH(SiMe{sub 3}){sub 2}, displays similar chemistry to (Me{sub 5}C{sub 5}){sub 2}YbMe, but at a reduced reaction rate due to the limited accessibility of the metal in (Me{sub 5}C{sub 5}){sub 2}YbCH(SiMe{sub 3}){sub 2}. Copper and silver halide salts react with (Me{sub 5}C{sub 5}){sub 2}V to produce the trivalent halide derivatives, (Me{sub 5}C{sub 5}){sub 2}VX (X + F, Cl, Br, I). The chloride complex, (Me{sub 5}C{sub 5}){sub 2}VCl, reacts with lithium reagents to form the phenyl and borohydride species. Nitrous oxide transfers an oxygen atom to (Me{sub 5}C{sub 5}){sub 2}V producing the vanadium-oxo complex, (Me{sub 5}Ce{sub 5}){sub 2}VO. The trivalent titanium species, (Me{sub 5}C{sub 5}){sub 2}TiX (X = Cl, Br, Me, BH{sub 4}), form bimetallic coordination complexes with (Me{sub 5}C{sub 5}){sub 2}Yb. The magnetic behavior of the products indicates that electron transfer has not occurred. The solid state structures of the chloride and bromide complexes show unusual bend angles for the halide bridges between ytterbium and titanium. A model based on frontier orbital theory has been proposed to account for the bending behavior in these species. The bimetallic methyl complex contains a linear methyl bridge between ytterbium and titanium.

Matsunaga, P.T.



Phosphonato complexes of platinum(II): kinetics of formation and phosphorus-31 NMR characterization studies  

Microsoft Academic Search

Reactions of cis-diamminedichloroplatinum(II) with phosphonoformic acid (PFA), phosphonoacetic acid (PAA), and methylenediphosphonic acid (MDP) yield various phosphonatoplatinum(II) chelates which were characterized by phosphorus-31 NMR spectroscopy. The P-31 resonances for the chelates appear at 6-12 ppm downfield as compared to the uncomplexed ligands. All complexes exhibit monoprotic acidic behavior in the pH range 2-10. The chemical shift-pH profiles yielded acidity constants,

L. L. Slavin; R. N. Bose



Salen-complex-mediated formation of cyclic carbonates by cycloaddition of CO2 to epoxides.  


Metal complexes of salen ligands are an important class of compounds, and they have been widely studied in the past. Among their successful catalytic applications, the synthesis of cyclic carbonates by the coupling reaction of epoxides with CO(2) has received increased attention; this is mostly due to the importance of using a greenhouse gas as a feedstock for the synthesis of useful molecules. Herein the most relevant past and present research surrounding this topic is presented. PMID:20957709

Decortes, Antonello; Castilla, Ana M; Kleij, Arjan W



Synthesis and structures of doubly-bridged dicyclopentadienyl dinuclear rhenium complexes, and their photochemical reactions with aromatic halides in benzene.  


Reaction of the doubly-bridged biscyclopentadienes (C5H4(EMe2))(C5H4(SiMe2)) (E = Si(), or C()) with Re2(CO)10 in refluxing mesitylene gave the corresponding dirhenium carbonyl complexes [(?(5)-C5H3)2(EMe2)(SiMe2)][Re(CO)3]2 (trans- and cis-), and the desilylated products [(?(5)-C5H4)2(EMe2)][Re(CO)3]2 (). Photolysis of trans- with a series of aryl halides in benzene results in the formation of biphenyl, together with the corresponding rhenium dihalide complexes trans-[(?(5)-C5H3)2(EMe2)(SiMe2)][Re(CO)3][Re(CO)2X2] (X = Cl, Br, I) (, , , or ) and trans-[(?(5)-C5H3)2(EMe2)(SiMe2)][Re(CO)2X2]2 (, , or ). Additional experiments indicate that one phenyl ring in the resulting biphenyl comes from aryl halides and the other phenyl ring comes from the solvent benzene. However, photolysis of trans- with benzyl chloride and n-hexyl chloride in benzene afforded the corresponding bibenzyl and n-dodecane, as well as the rhenium dichlorides and . In addition, complex trans- can also activate the C-F bond on C6F6 to form the pentafluorophenyl rhenium fluoride trans-[(?(5)-C5H3)2(SiMe2)2][Re(CO)3][Re(CO)2(C6F5)F] (). Molecular structures of cis-, cis-, trans-, , , , , , and determined by X-ray diffraction are also presented. PMID:25274024

Zhu, Bolin; Huang, Xinwei; Hao, Xiaoting



Large Ground-State Entropy Changes for Hydrogen Atom Transfer Reactions of Iron Complexes  

PubMed Central

Reported herein are the hydrogen atom transfer (HAT) reactions of two closely related dicationic iron tris ?-diimine complexes. FeII(H2bip) (iron(II) tris[2,2?-bi-1,4,5,6-tetra-hydropyrimidine]diperchlorate) and FeII(H2bim) (iron(II) tris[2,2?-bi-2-imidazoline]diperchlorate) both transfer H• to TEMPO (2,2,6,6-tetramethyl-1-piperidinoxyl) to yield the hydroxylamine, TEMPO-H, and the respective deprotonated iron(III) species, FeIII(Hbip) or FeIII(Hbim). The ground-state thermodynamic parameters in MeCN were determined for both systems using both static and kinetic measurements. For FeII(H2bip) + TEMPO: ?G° = ?0.3 ± 0.2 kcal mol?1, ?H° =?9.4 ± 0.6 kcal mol?1, ?S° = ?30 ± 2 cal mol?1 K?1. For FeII(H2bim) + TEMPO: ?G° = 5.0 ± 0.2 kcal mol?1, ?H° = ?4.1 ± 0.9 kcal mol?1, ?S° = ?30 ± 3 cal mol?1 K?1. The large entropy changes for these reactions, |T?S°| = 9 kcal mol?1 at 298 K, are exceptions to the traditional assumption that ?S° ? 0 for simple HAT reactions. Various studies indicate that hydrogen-bonding, solvent effects, ion-pairing, and iron spin-equilibria do not make major contributions to the observed ?S°HAT. Instead, this effect arises primarily from changes in vibrational entropy upon oxidation of the iron center. Measurement of the electron transfer half-reaction entropy, |?S° Fe(H2bim)/ET| = 29 ± 3 cal mol?1 K?1, is consistent with a vibrational origin. This conclusion is supported by UHF/6-31G* calculations on the simplified reaction [FeII(H2N=CHCH=NH2)2(H2bim)]2+•••ONH2 ? [FeII(H2N=CHCH=NH2)2(Hbim)]2+•••HONH2. The discovery that ?S°HAT can deviate significantly from zero has important implications on the study of HAT and proton-coupled electron transfer (PCET) reactions. For instance, these results indicate that free energies, rather than enthalpies, should be used to estimate the driving force for HAT when transition metal centers are involved. PMID:17402735

Mader, Elizabeth A.; Davidson, Ernest R.



Mechanism and kinetics for the formation of uranium mononitride by the reaction of uranium dioxide with carbon and nitrogen  

Microsoft Academic Search

The mechanism and kinetics of UN formation by reaction of a pellet of mixed UOâ and C with Nâ were studied for temperatures of 1420 to 1750°C. The reaction followed the first-order rate equation; the activation energy was 83 kcal\\/mol. Only UN\\/sub 1-x\\/C\\/sub x\\/ was produced. The lattice parameter variation of UN\\/sub 1-x\\/C\\/sub x\\/ had a minimum and a maximum




Product formation from the gas-phase reactions of OH radicals and O 3 with a series of monoterpenes  

Microsoft Academic Search

The formation yields of nine carbonyl products are reported from the gas-phase OH radical-initiated reactions (in the presence of NOx) and the O3 reactions with seven monoterpenes. The products were identified using GC\\/MS and GC-FTIR and quantified by GC-FID analyses of samples collected on Tenax solid adsorbent cartridges. The identities of products from camphene, limonene and ß-pinene were confirmed by

Hannele Hakola; Janet Arey; Sara M. Aschmann; Roger Atkinson



Chiral BINOL-derived phosphoric acids: privileged Brønsted acid organocatalysts for C-C bond formation reactions.  


BINOL-derived phosphoric acids have emerged during the last five years as powerful chiral Brønsted acid catalysts in many enantioselective processes. The most successful transformations carried out with chiral BINOL phosphates include C-C bond formation reactions. The recent advances have been reviewed in this article with a focus being placed on hydrocyanations, aldol-type, Mannich, Friedel-Crafts, aza-ene-type, Diels-Alder, as well as cascade and multi-component reactions. PMID:20820680

Zamfir, Alexandru; Schenker, Sebastian; Freund, Matthias; Tsogoeva, Svetlana B



Topoisomerase II? promotes activation of RNA polymerase I transcription by facilitating pre-initiation complex formation  

PubMed Central

Type II DNA topoisomerases catalyse DNA double-strand cleavage, passage and re-ligation to effect topological changes. There is considerable interest in elucidating topoisomerase II roles, particularly as these proteins are targets for anti-cancer drugs. Here we uncover a role for topoisomerase II? in RNA polymerase I-directed ribosomal RNA gene transcription, which drives cell growth and proliferation and is upregulated in cancer cells. Our data suggest that topoisomerase II? is a component of the initiation-competent RNA polymerase I? complex and interacts directly with RNA polymerase I-associated transcription factor RRN3, which targets the polymerase to promoter-bound SL1 in pre-initiation complex formation. In cells, activation of rDNA transcription is reduced by inhibition or depletion of topoisomerase II, and this is accompanied by reduced transient double-strand DNA cleavage in the rDNA-promoter region and reduced pre-initiation complex formation. We propose that topoisomerase II? functions in RNA polymerase I transcription to produce topological changes at the rDNA promoter that facilitate efficient de novo pre-initiation complex formation. PMID:23511463

Ray, Swagat; Panova, Tatiana; Miller, Gail; Volkov, Arsen; Porter, Andrew C. G.; Russell, Jackie; Panov, Konstantin I.; Zomerdijk, Joost C. B. M.



Age Differences in Reaction Time and Attention in a National Telephone Sample of Adults: Education, Sex, and Task Complexity Matter  

ERIC Educational Resources Information Center

This study demonstrated effects of age, education, and sex on complex reaction time in a large national sample (N = 3,616) with a wide range in age (32-85) and education. Participants completed speeded auditory tasks (from the MIDUS [Midlife in the U.S.] Stop and Go Switch Task) by telephone. Complexity ranged from a simple repeated task to an…

Tun, Patricia A.; Lachman, Margie E.



Structural and Spectroscopic Properties of a Reaction Center Complex from the Chlorosome-Lacking Filamentous Anoxygenic Phototrophic Bacterium Roseiflexus castenholzii  

Microsoft Academic Search

The photochemical reaction center (RC) complex of Roseiflexus castenholzii, which belongs to the filamentous anoxygenic phototrophic bacteria (green filamentous bacteria) but lacks chlorosomes, was isolated and char- acterized. The genes coding for the subunits of the RC and the light-harvesting proteins were also cloned and sequenced. The RC complex was composed of L, M, and cytochrome subunits. The cytochrome subunit

Mitsunori Yamada; Hui Zhang; Satoshi Hanada; Kenji V. P. Nagashima; Keizo Shimada; Katsumi Matsuura



Formation of host-guest complexes of ?-cyclodextrin and perfluorooctanoic acid.  


Structural characterization and dynamic properties of solid-state inclusion complexes of ?-cyclodextrin (?-CD) with perfluorooctanoic acid (PFOA) were investigated by (19)F/(13)C solid-state and (19)F/(1)H solution NMR spectroscopy. The complexes in the solid state were prepared using dissolution and slow cool methods, where thermal analyses (DSC and TGA), PXRD, and FT-IR results provided complementary support that inclusion complexes were formed between ?-CD and PFOA with variable stoichiometry and inclusion geometry. (19)F DP (direct polarization) and (13)C CP (cross-polarization) with magic-angle spinning (MAS) solids NMR, along with (19)F/(1)H solution NMR were used to characterize the complexes in the solid and solution phases, respectively. The dynamics of the guest molecules in the inclusion complexes (ICs) were studied using variable temperature (VT) (19)F DP/MAS NMR experiments in the solid state. The guest molecules were observed to be in several different molecular environments, providing strong evidence of variable host-guest stoichiometry and inclusion geometry, in accordance with the preparation method of the complex and the conformational preference of PFOA. It was concluded from PXRD that ?-CD and PFOA form inclusion complexes with "channel-type" structures. Variable spin rate (VSR) (19)F DP/MAS NMR was used to assess the phase purity of the complexes, and it was revealed that slow cooling resulted in relatively pure phases. In the solution state, (1)H and (19)F NMR complexation-induced chemical shifts (CISs) of ?-CD and PFOA, respectively, provided strong support for the formation of 1:1 and 2:1 ?-CD/PFOA inclusion complexes. The dynamics of the guest molecule in the ?-CD/PFOA complexes in D(2)O solutions were probed using VT (19)F NMR and revealed some guest conformational and exchange dynamics as a function of temperature and the relative concentrations of the host and guest. PMID:21688796

Karoyo, Abdalla H; Borisov, Alex S; Wilson, Lee D; Hazendonk, Paul



Carbon dioxide sequestration via olivine carbonation: Examining the formation of reaction products  

NASA Astrophysics Data System (ADS)

Due to its abundance and natural ability to sequester CO2, olivine has been proposed as one mineral that could be used in the control of CO2 emissions into the atmosphere (Metz, 2005). Large scale peridotite deposits found in locations such as the Western Gneiss Region in Norway could provide in-situ sites for sequestration or the raw materials for ex-situ mineral carbonation. Determining the conditions under which magnesite (MgCO3) forms most efficiently is crucial to conduct a cost effective process. Understanding the development of secondary minerals is particularly important for in-situ methods as these phases can form passivating layers and affect the host rock porosity. The final solution of flow-through experiments conducted at alkaline pH have been shown to be supersaturated with respect to talc and chrysotile (Giammer et al., 2005), although these phases were not found to have precipitated the formation of a passivating, amorphous silica layer has been observed on reacted olivine surfaces (Bearat et al., 2006). By studying magnesite and other products produced during the carbonation of olivine within Teflon lined steel autoclaves we have begun to form a more comprehensive understanding of how these reactions would proceed during sequestration processes. We have performed batch experiments using carbonated saline solutions in the presence of air or gaseous CO2 from 80 to 200 Ë? C. X-ray powder diffraction was used to identify magnesite within the reaction products. Crystals of magnesite up to 20 m in diameter can be observed on olivine grain surfaces with scanning electron microscopy. Secondary reaction products formed a platy layer on olivine surfaces in reactions above 160 Ë? C and below pH 12. Energy dispersive X-ray analysis of the platy layer revealed an increase in Fe concentration. The macroscopically observable red colouration of the reaction products and Raman spectroscopy indicate that hematite is present in these layers. For experiments with a duration of 4 weeks, lizardite has also been identified using X-ray powder diffraction. The Mg/Si ratio obtained from energy dispersive X-ray analysis of the secondary phases from shorter period experiments indicates that lizardite may also be present. However, the components of these platy layers are closely associated and too low in concentration to be distinguishable with X-ray diffraction analysis. We have not observed the precipitation of talc or chrysotile phases in any of our experiments. Amorphous silica has also not been identified in any of the reaction rims. Higher temperature experiments and those with an initial solution slightly undersaturated with respect to magnesite produced well formed carbonate crystals. The presence of CO2 above the solution did not affect the final magnesite crystal shape but did increase the rate of precipitation. References: Bearat H., McKelvy M. J., Chizmeshya A. V. G., Gormley D., Nunez R., Carpenter R. W., Squires K. and Wolf G. H. (2006), Environ. Sci. Technol., 40 4802-4808. Giammar D. E., Bruant R. G. and Peters C. A. (2005), Chem. Geol., 217 257-276. Metz B. D. O., de Coninck H., Loos M. and Meyer L. (2005), IPCC Special Report on Carbon Dioxide Capture and Storage, Cambridge University Press.

King, H. E.; Plümper, O.; Putnis, A.



Enzyme-polyelectrolyte complex: Salt effects on the reaction of urease with polyallylamine  

NASA Astrophysics Data System (ADS)

The effects of inorganic mono- and divalent salts of different types on how the cation polyelectrolyte polyallylamine hydrochloride (PAA) binds with the oligomer enzyme urease were studied. It was shown that in solutions of the monovalent salts NaCl, KCl, and NH4Cl, polyelectrolyte-protein complexes formed by electrostatic interactions, which decreased monotonically as the salt concentrations increased according to the classic law of statistical physics, correlating the Debye radius with the ionic strength of the solution. In solutions of the divalent salts Na2SO4 and (NH4)2SO4, the efficiency of the formation of the polyelectrolyte-protein complexes changed abruptly (the enzyme was drastically activated) at low salt concentrations (˜0.6-0.8 mM), which was not consistent with the classic theory of charge interactions in solutions with different ionic strengths. Turbidimetric titration at different salt concentrations in the given range revealed a high aggregative ability for sulfates and low ability for chlorides. It was concluded that the anomalies in the concentration dependence of the enzyme activity and aggregative ability were related to the formation of stable bonds PAA to the divalent SO{4/2-} anion, which increased drastically when the ratio of anion concentration to the number of positively charged PAA monomers in solution reached 1: 2.

Tikhonenko, S. A.; Saburova, E. A.; Durdenko, E. N.; Sukhorukov, B. I.



Case report: adverse granulomatous reaction (Granuloma formation) and pseudomonas superinfection after lip augmentation by the new filler DermaLive®  

Microsoft Academic Search

In recent years, there has been a huge increase of injectable filler materials on the aesthetic market to correct wrinkles,\\u000a aging lines, or volume deficits in the face. Despite their nontoxicity and low immunologic reactivity, they can induce a foreign\\u000a body reaction and formation of inflammatory nodules or granulomas. We report a case of severe complications with granuloma\\u000a formation and

Birgit Weyand; Henrik Menke



Aryl formate as bifunctional reagent: applications in palladium-catalyzed carbonylative coupling reactions using in situ generated CO.  


After decades of development, carbonylation reactions have become one of the most powerful tools in modern organic synthesis. However, the requirement of CO gas limits the applications of such reactions. Reported herein is a versatile and practical protocol for carbonylative reactions which rely on the cooperation of phenyl formate and nonaflate, and the generation of CO in situ. This protocol has a high functionalgroup tolerance and could be applied in carbonylations with C, N, and, O nucleophiles. The corresponding amides, alkynones, furanones, and aryl benzoates were synthesized in good yields. PMID:24677435

Li, Haoquan; Neumann, Helfried; Beller, Matthias; Wu, Xiao-Feng



Ambiguities in the rate of oxygen formation during stellar helium burning in the 12C(?,?) reaction  

NASA Astrophysics Data System (ADS)

The rate of oxygen formation determines the C/O ratio during stellar helium burning. It is the single most important nuclear input in stellar evolution theory, including the evolution of type II and type Ia supernova. However, the low-energy cross section of the fusion of 4He +12C, denoted as the 12C(?,?)16O reaction, still remains uncertain. I analyze and critically review the most recent measurements of complete angular distributions of the outgoing ? rays at very low energies (Ec.m.?1.0 MeV). My analysis of the angular distributions measured with the EUROGAM/GANDI arrays leads to considerably larger error bars than have been published, which excludes them from the current sample of “world data.” I show that the current sample of “world data” of the measured E2 cross-section factors below 1.7 MeV cluster into two distinct groups that lead to two distinct extrapolations: SE2(300)?60 or SE2(300)?154 keVb. There is a discrepancy between the measured E1-E2 phase difference (?12) and unitarity as required by the Watson theorem, which suggests systematic problem(s) in some of the measured ?-ray angular distributions. The ambiguity of the extrapolated SE2(300) together with the previously observed ambiguity of SE1(300) (approximately 80 or 10 keVb) must be resolved by future measurements of complete and detailed angular distributions of the 12C(?,?) reaction at very low energies (Ec.m.?1.0 MeV).

Gai, Moshe



Immunomodulatory Gene Therapy Prevents Antibody Formation and Lethal Hypersensitivity Reactions in Murine Pompe Disease  

PubMed Central

Infantile Pompe disease progresses to a lethal cardiomyopathy in absence of effective treatment. Enzyme-replacement therapy (ERT) with recombinant human acid ?-glucosidase (rhGAA) has been effective in most patients with Pompe disease, but efficacy was reduced by high-titer antibody responses. Immunomodulatory gene therapy with a low dose adeno-associated virus (AAV) vector (2 × 1010 particles) containing a liver-specific regulatory cassette significantly lowered immunoglobin G (IgG), IgG1, and IgE antibodies to GAA in Pompe disease mice, when compared with mock-treated mice (P < 0.05). AAV-LSPhGAApA had the same effect on GAA-antibody production whether it was given prior to, following, or simultaneously with the initial GAA injection. Mice given AAV-LSPhGAApA had significantly less decrease in body temperature (P < 0.001) and lower anaphylactic scores (P < 0.01) following the GAA challenge. Mouse mast cell protease-1 (MMCP-1) followed the pattern associated with hypersensitivity reactions (P < 0.05). Regulatory T cells (Treg) were demonstrated to play a role in the tolerance induced by gene therapy as depletion of Treg led to an increase in GAA-specific IgG (P < 0.001). Treg depleted mice were challenged with GAA and had significantly stronger allergic reactions than mice given gene therapy without subsequent Treg depletion (temperature: P < 0.01; symptoms: P < 0.05). Ubiquitous GAA expression failed to prevent antibody formation. Thus, immunomodulatory gene therapy could provide adjunctive therapy in lysosomal storage disorders treated by enzyme replacement. PMID:19690517

Sun, Baodong; Kulis, Michael D; Young, Sarah P; Hobeika, Amy C; Li, Songtao; Bird, Andrew; Zhang, Haoyue; Li, Yifan; Clay, Timothy M; Burks, Wesley; Kishnani, Priya S; Koeberl, Dwight D



Formation of multiple focal spots using a high NA lens with a complex spiral phase mask  

NASA Astrophysics Data System (ADS)

The formation of a transversally polarized beam by transmitting a tightly focused double-ring-shaped azimuthally polarized beam through a complex spiral phase mask and high numerical aperture lens is presented based on vector diffraction theory. The generation of transversally polarized focal spot segment splitting and multiple focal spots is illustrated numerically. Moreover, we found that a properly designed complex spiral phase mask can move the focal spots along the optical axis in the z direction. Therefore, one can achieve a focal segment of two, three or multiple completely transversely polarized focal spots, which finds applications in optical trapping and in material processing technologies.

Lalithambigai, K.; Anbarasan, P. M.; Rajesh, K. B.



On the Silver Effect and the Formation of Chloride-Bridged Digold Complexes  

PubMed Central

Abstraction of chloride anion from Au(I) complexes such as JohnPhosAuCl in noncoordinating solvents with 1 equiv of a silver salt, or even larger amounts, leads to the formation of chloride-bridged dinuclear gold(I) complexes, irrespective of the counteranion, which are substantially less reactive as catalysts. This incomplete removal of chloride ligand could lead to false negative results when using the in situ generation of the gold(I) active species by silver-promoted chloride abstraction. PMID:24195441



Multinuclear complex formation between Ca(II) and gluconate ions in hyperalkaline solutions.  


Alkaline solutions containing polyhydroxy carboxylates and Ca(II) are typical in cementitious radioactive waste repositories. Gluconate (Gluc(-)) is a structural and functional representative of these sugar carboxylates. In the current study, the structure and equilibria of complexes forming in such strongly alkaline solutions containing Ca(2+) and gluconate have been studied. It was found that Gluc(-) significantly increases the solubility of portlandite (Ca(OH)2(s)) under these conditions and Ca(2+) complexes of unexpectedly high stability are formed. The mononuclear (CaGluc(+) and [CaGlucOH](0)) complexes were found to be minor species, and predominant multinuclear complexes were identified. The formation of the neutral [Ca2Gluc(OH)3](0) (log ?213 = 8.03) and [Ca3Gluc2(OH)4](0) (log ?324 = 12.39) has been proven via H2/Pt-electrode potentiometric measurements and was confirmed via XAS, (1)H NMR, ESI-MS, conductometry, and freezing-point depression experiments. The binding sites of Gluc(-) were identified from multinuclear NMR measurements. Besides the carboxylate group, the O atoms on the second and third carbon atoms were proved to be the most probable sites for Ca(2+) binding. The suggested structure of the trinuclear complex was deduced from ab initio calculations. These observations are of relevance in the thermodynamic modeling of radioactive waste repositories, where the predominance of the binuclear Ca(2+) complex, which is a precursor of various high-stability ternary complexes with actinides, is demonstrated. PMID:24865662

Pallagi, Attila; Bajnóczi, Éva G; Canton, Sophie E; Bolin, Trudy; Peintler, Gábor; Kutus, Bence; Kele, Zoltán; Pálinkó, István; Sipos, Pál



Change in Protein Flexibility Upon Complex Formation: Analysis of Ras-Raf Using Molecular Dynamics and a  

E-print Network

Change in Protein Flexibility Upon Complex Formation: Analysis of Ras-Raf Using Molecular Dynamics Changes in flexibility upon pro- tein­protein complex formation of H-Ras and the Ras-binding domain of C time of about one second, FIRST identifies flexible and rigid regions in a single, static three


Synthesis of molybdenum imido alkylidene complexes and some reactions involving acyclic olefins  

SciTech Connect

The reaction between Mo(C-t-Bu)(dme)Cl{sub 3} (dme = 1,2-dimethoxyethane) and Me{sub 3}SiNHAr (Ar = 2,6-diisopropylphenyl) yields Mo(C-t-Bu)(NHAr)Cl{sub 2}(dme) (1), which upon treatment with a catalytic amount of NEt{sub 3} is transformed into Mo(CH-t-Bu)(NAr)Cl{sub 2}(dme) (2). Complexes of the type Mo(CH-t-Bu)(NAr)(OR){sub 2} (OR = OCMe(CF{sub 3}){sub 2}, OCMe{sub 2}(CF{sub 3}), O-t-Bu, or OAr) have been prepared from 2. Complexes of the type Mo(C-t-Bu)(NHAr)(OR){sub 2} (OR = OCMe(CF{sub 3}){sub 2} or OAr) have been prepared from 1, but they cannot be transformed into Mo(CH-t-Bu)(NAr)(OR){sub 2} complexes. A precursor to imido alkylidene complexes that is related to 2 has been prepared by the sequence MoO{sub 2} {yields} MoO{sub 2}Cl{sub 2} {yields} Mo(NAr){sub 2}Cl{sub 2} {yields} Mo(NAr){sub 2}(CH{sub 2}R{prime}){sub 2} {yields} Mo(CHR{prime})(NAr)(OTf){sub 2}(dme) (R{prime} = t-Bu or CMe{sub 2}Ph; OTf = OSO{sub 2}CF{sub 3}). Mo(CH-t-Bu)(NAr)(OTf){sub 2}(dme) crystallizes in the space group P{anti 1} with a = 17.543 {angstrom}, b = 19.008 {angstrom}, c = 9.711 {angstrom}, {alpha} = 91.91{degree}, {beta} = 99.30{degree}, {gamma} = 87.27{degree}, Z = 4, M{sub r} = 729.60, V = 3,191.1 {angstrom}{sup 3}, {rho}(calcd) = 1.518 g cm{sup {minus}3}.

Schrock, R.R.; Murdzek, J.S.; Bazan, G.C.; Robbins, J.; DiMare, M.; O'Regan, M. (Massachusetts Institute of Technology, Cambridge (USA))



Secondary organic aerosol formation from gasoline vehicle emissions in a new mobile environmental reaction chamber  

NASA Astrophysics Data System (ADS)

We present a new mobile environmental reaction chamber for the simulation of the atmospheric aging of different emission sources without limitation from the instruments or facilities available at any single site. Photochemistry is simulated using a set of 40 UV lights (total power 4 KW). Characterisation of the emission spectrum of these lights shows that atmospheric aging of emissions may be simulated over a range of temperatures (-7 to 25 °C). A photolysis rate of NO2, JNO2, of (8.0 ± 0.7) × 10-3 s-1 was determined at 25 °C. We demonstrate the utility of this new system by presenting results on the aging (OH = 12 × 106 cm-3 h) of emissions from a modern (Euro 5) gasoline car operated during a driving cycle (New European Driving Cycle, NEDC) on a chassis dynamometer in a vehicle test cell. Emissions from the entire NEDC were sampled and aged in the chamber. Total organic aerosol (OA; primary organic aerosol (POA) emission + secondary organic aerosol (SOA) formation) was (369.8-397.5)10-3 g kg-1 fuel, or (13.2-15.4) × 10-3 g km-1, after aging, with aged OA/POA in the range 9-15. A thorough investigation of the composition of the gas phase emissions suggests that the observed SOA is from previously unconsidered precursors and processes. This large enhancement in particulate matter mass from gasoline vehicle aerosol emissions due to SOA formation, if it occurs across a wider range of gasoline vehicles, would have significant implications for our understanding of the contribution of on-road gasoline vehicles to ambient aerosols.

Platt, S. M.; El Haddad, I.; Zardini, A. A.; Clairotte, M.; Astorga, C.; Wolf, R.; Slowik, J. G.; Temime-Roussel, B.; Marchand, N.; Ježek, I.; Drinovec, L.; Mo?nik, G.; Möhler, O.; Richter, R.; Barmet, P.; Bianchi, F.; Baltensperger, U.; Prévôt, A. S. H.



Measured rates of fluoride/metal association correlate with rates of superoxide/metal reactions for Fe(III)EDTA(H2O)- and related complexes.  


The effects of 10 paramagnetic metal complexes (Fe(III)EDTA(H2O)-, Fe(III)EDTA(OH)2-, Fe(III)PDTA-, Fe(III)DTPA2-, Fe(III)2O(TTHA)2-, Fe(III)(CN)6(3-), Mn(II)EDTA(H2O)2-, Mn(II)PDTA2-, Mn(II)beta-EDDADP2-, and Mn(II)PO4(-)) on F- ion 19F NMR transverse relaxation rates (R2 = 1/T2) were studied in aqueous solutions as a function of temperature. Consistent with efficient relaxation requiring formation of a metal/F- bond, only the substitution inert complexes Fe(III)(CN)6(3-) and Fe(III)EDTA(OH)2- had no measured effect on T2 relaxation of the F- 19F resonance. For the remaining eight complexes, kinetic parameters (apparent second-order rate constants and activation enthalpies) for metal/F- association were determined from the dependence of the observed relaxation enhancements on complex concentration and temperature. Apparent metal/F- association rate constants for these complexes (k(app,F-)) spanned 5 orders of magnitude. In addition, we measured the rates at which O2*- reacts with Fe(III)PDTA-, Mn(II)EDTA(H2O)2-, Mn(II)PDTA2-, and Mn(II)beta-EDDADP2- by pulse radiolysis. Although no intermediate is observed during the reduction of Fe(III)PDTA- by O2*-, each of the Mn(II) complexes reacts with formation of a transient intermediate presumed to form via ligand exchange. These reactivity patterns are consistent with literature precedents for similar complexes. With these data, both k(app,O2-) and k(app,F-) are available for each of the eight reactive complexes. A plot of log(k(app,O2-)) versus log(k(app,F-)) for these eight showed a linear correlation with a slope approximately 1. This correlation suggests that rapid metal/O2*- reactions of these complexes occur via an inner-sphere mechanism whereas formation of an intermediate coordination complex limits the overall rate. This hypothesis is also supported by the very low rates at which the substitution inert complexes (Fe(III)(CN)6(3-) and Fe(III)EDTA(OH)2-) are reduced by O2*-. These results suggest that F- 19F NMR relaxation can be used to predict the reactivities of other Fe(III) complexes toward reduction by O2*-, a key step in the biological production of reactive oxygen species. PMID:18186636

Summers, Jack S; Baker, Joseph B; Meyerstein, Dan; Mizrahi, Amir; Zilbermann, Israel; Cohen, Haim; Wilson, Christopher M; Jones, Jamie R



Electrochemistry and spectroelectrochemistry of indium(III) porphyrins. Reactions of five-coordinate ionic complexes  

SciTech Connect

The electrochemistry and spectroelectrochemistry of In(III) tetraphenyl- and octaethylporphyrins were investigated in nonaqueous media. Counterions on the In(III) complexes were either Cl/sup -/ or ClO/sub 4//sup -/. Each oxidized and reduced species was characterized by UV-visible spectroscopy, and ESR spectra were obtained for each of the generated cation and anion radicals. Singly oxidized species gave rise to ESR spectra with values of g approx. = 2.00 but with values of that varied between 16.8 and 221 G depending upon the nature of the porphyrin ring and the composition of the solvent-supporting electrolyte systems. Analysis of the ESR data indicated ..pi..-ring-centered reactions with a small amount of spin density residing upon the metal. 23 references, 6 figures, 5 tables.

Kadish, K.M.; Cornillion, J.L.; Cocolios, P.; Tabard, A.; Guilard, R.



Formation of gels and complexes by pairwise interacting P. G. Higgs and R. C. Ball  

E-print Network

3285 Formation of gels and complexes by pairwise interacting polymers P. G. Higgs and R. C. Ball réseaux 2014 par exemple, des zones de jonction en double hélice dans les gels de biopolymère, ou à l maximum si le nombre de liaisons à l'équilibre est grand. Ceci suggère la possibilité d'existence de gels

Boyer, Edmond


Formation and annihilation of H-point defect complexes in quenched Si doped with C  

Microsoft Academic Search

We investigated the formation and annihilation of H-point defect complexes formed in C-doped Si by heating at high temperatures followed by quenching in hydrogen gas. Specimens of C-doped Si were sealed in quartz capsules together with hydrogen (H) gas, at pressure 0.8-1.5 atm at high temperature, and were heated at high temperature for 1 h followed by quenching in water.

Naoki Fukata; Masashi Suezawa