Chemical reactions in fast atom bombardment mass spectrometry

Examples of various chemical reactions occurring in the matrix or in the selvedge region in fast atom bombardment (FAB) mass spectrometry are discussed. These are categorized as oxidations and reductions; substitutions; clusterings and additions; and sample decomposition or transformation. Some reactions observed showed significant time behaviour and in one case it was possible to determine rate constants. These data suggest that chemical reactions can be accelerated significantly by fast atom bombardment.     

Modulated hydrogen beam study of adsorption-induced desorption of deuterium from Si(100)-3x1:D surfaces

We have studied the kinetic mechanism of the adsorption-induced-desorption (AID) reaction, H+D/Si(100) --> D2. Using a modulated atomic hydrogen beam, two different types of AID reaction are revealed: one is the fast AID reaction occurring only at the beam on-cycles and the other the slow AID reaction occurring even at the beam off-cycles. Both the fast and slow AID reactions show the different dependence on surface temperature Ts, suggesting that their kinetic mechanisms are different. The fast AID reaction overwhelms the slow one in the desorption yield for 300 K < or = Ts < or = 650 K. It proceeds along a first-order kinetics with respect to the incident H flux. Based on the experimental results, both two AID reactions are suggested to occur only on the 3x1 dihydride phase accumulated during surface exposure to H atoms. Possible mechanisms for the AID reactions are discussed.     

Effect of side chains on competing pathways for beta-scission reactions of peptide-backbone alkoxyl radicals

High-level quantum chemistry calculations have been carried out to investigate beta-scission reactions of alkoxyl radicals located at the alpha-carbon of a peptide backbone. This type of alkoxyl radical may undergo three possible beta-scission reactions, namely C-C beta-scission of the backbone, C-N beta-scission of the backbone, and C-R beta-scission of the side chain. We find that the rates for the C-C beta-scission reactions are all very fast, with rate constants of the order 10(12) s(-1) that are essentially independent of the side chain. The C-N beta-scission reactions are all slow, with rate constants that range from 10(-0.7) to 10(-4.5) s(-1). The rates of the C-R beta-scission reactions depend on the side chain and range from moderately fast (10(7) s(-1)) to very fast (10(12) s(-1)). The rates of the C-R beta-scission reactions correlate well with the relative stabilities of the resultant side-chain product radicals (*R), as reflected in calculated radical stabilization energies (RSEs). The order of stabilities for the side-chain fragment radicals for the natural amino acids is found to be Ala < Glu < Gln approximately Leu approximately Met approximately Lys approximately Arg < Asp approximately Ile approximately Asn approximately Val < Ser approximately Thr approximately Cys < Phe approximately Tyr approximately His approximately Trp. We predict that for side-chain C-R beta-scission reactions to effectively compete with the backbone C-C beta-scission reactions, the side-chain fragment radicals would generally need an RSE greater than approximately 30 kJ mol(-1). Thus, the residues that may lead to competitive side-chain beta-scission reactions are Ser, Thr, Cys, Phe, Tyr, His, and Trp.     

Domino Constructions of Pentacyclic Indeno[2,1-c]quinolines and Pyrano[4,3-b]oxepines by [4+1]/[3+2+1]/[5+1] and [4+3] Multiple Cyclizations

New three-component domino reactions have been discovered. The reactions are easy to perform (see scheme; MW=microwave irradiation) and proceed with fast rates, which makes work-up convenient. Most of the multiple stereocenters and the geometry are controlled well. The stereochemistry has been unequivocally determined by X-ray structural analysis.     

Flash chemistry: fast chemical synthesis by using microreactors

This concept article provides a brief outline of the concept of flash chemistry for carrying out extremely fast reactions in organic synthesis by using microreactors. Generation of highly reactive species is one of the key elements of flash chemistry. Another important element of flash chemistry is the control of extremely fast reactions to obtain the desired products selectively. Fast reactions are usually highly exothermic, and heat removal is an important factor in controlling such reactions. Heat transfer occurs very rapidly in microreactors by virtue of a large surface area per unit volume, making precise temperature control possible. Fast reactions often involve highly unstable intermediates, which decompose very quickly, making reaction control difficult. The residence time can be greatly reduced in microreactors, and this feature is quite effective in controlling such reactions. For extremely fast reactions, kinetics often cannot be used because of the lack of homogeneity of the reaction environment when they are conducted in conventional reactors such as flasks. Fast mixing using micromixers solves such problems. The concept of flash chemistry has been successfully applied to various organic reactions including a) highly exothermic reactions that are difficult to control in conventional reactors, b) reactions in which a reactive intermediate easily decomposes in conventional reactors, c) reactions in which undesired byproducts are produced in the subsequent reactions in conventional reactors, and d) reactions whose products easily decompose in conventional reactors. The concept of flash chemistry can be also applied to polymer synthesis. Cationic polymerization can be conducted with an excellent level of molecular-weight control and molecular-weight distribution control.     

A pulse polarograph for the measurement of fast chemical reactions

A fast pulse polarograph suitable for the measurement of fast homogeneous reactions and of electrode reactions is described in detail. The fast charging of the double layer (<10^?5s) is realized either by charge injection or by iR-compensation. The minimum delay time between the charging of the double layer and the measuring of the current is about 7 μs. The applicability of the instrument is demonstrated with the measurement of the dissociation rate of Cd(CN)₄^2?.     

Leveling of reactivity for intramolecular radical substitution reactions in viscous media

A leveling of the reactivity was found for intramolecular radical reactions in substituted 2-oxyphenoxyls in viscous media. A comparison of rate constants in toluene, hexane, pentane, and vaseline oil shows that fast reactions are decelerated more rapidly than slow reactions.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 334–336, February, 1994.     

Product distribution from fast pyrolysis of glucose-based carbohydrates

Carbohydrates are the major constituents of biomass. With the growing interest in utilizing bio-oil obtained from fast pyrolysis of biomass for fuels and chemicals, understanding the carbohydrate pyrolysis behavior has gained particular importance. The chemical composition of the bio-oil is an important consideration for its upstream and/or downstream processing. Though the classification of pyrolysis products into overall tar, char and gaseous fraction has evolved as a standard; detailed knowledge of the chemical constituents that determine the quality of bio-oil has received little attention. Furthermore, the speciation arising from primary and secondary reactions has been rarely distinguished. In this study the product distribution arising from the primary reactions during 500 °C fast pyrolysis of several mono-, di- and polysaccharides is studied with the help of micro-pyrolyzer. The study suggests that levoglucosan and the low molecular weight compounds are formed through competitive pyrolysis reactions rather than sequential pyrolysis reactions. It is also shown that the orientation or the position of glycosidic linkages does not significantly influence the product distribution except with 1,6-linked polysaccharide, which showed considerably less formation of levoglucosan than other polysaccharides.     

Multifluorinated Aryl Azides for the Development of Improved H2S Probes,and Fast Strain‐promoted Azide‐Alkyne Cycloaddition and Staudinger Reactions

The development of advanced bioorthogonal reactions for detection and labeling of biomolecules is significant in chemical biology. Recently, researchers have found that multifluorinated aryl azides hold great potential for the development of improved bioorthogonal reactions. The fluorine atom can be a perfect substituent group because of its properties of excellent electronegativity and small steric hindrance. In this Minireview, we discuss recent developments of improved hydrogen sulfide (H₂S) fluorescence probes, fast strain‐promoted azide‐alkyne cycloaddition (SPAAC) and nonhydrolysis Staudinger reactions based on the use of multifluorinated aryl azides. Additionally, kinetic studies and biological applications of these reactions are also presented.     

Mild and efficient method for the cleavage of benzylidene acetals using HClO4-SiO2 and direct conversion of acetals to acetates

HClO₄-SiO₂ has been used successfully for the deprotection of benzylidene acetals and the direct conversion of benzylidene acetals to the corresponding di-O-acetates. The reactions are very fast and yields are excellent.     

Quasiequilibrium approximation of fast reaction kinetics in stochastic biochemical systems

We address the problem of eliminating fast reaction kinetics in stochastic biochemical systems by employing a quasiequilibrium approximation. We build on two previous methodologies developed by [Haseltine and Rawlings, J. Chem. Phys. 117, 6959 (2002)] and by [Rao and Arkin, J. Chem. Phys. 118, 4999 (2003)]. By following Haseltine and Rawlings, we use the numbers of occurrences of the underlying reactions to characterize the state of a biochemical system. We consider systems that can be effectively partitioned into two distinct subsystems, one that comprises "slow" reactions and one that comprises "fast" reactions. We show that when the probabilities of occurrence of the slow reactions depend at most linearly on the states of the fast reactions, we can effectively eliminate the fast reactions by modifying the probabilities of occurrence of the slow reactions. This modification requires computation of the mean states of the fast reactions, conditioned on the states of the slow reactions. By assuming that within consecutive occurrences of slow reactions, the fast reactions rapidly reach equilibrium, we show that the conditional state means of the fast reactions satisfy a system of at most quadratic equations, subject to linear inequality constraints. We present three examples which allow analytical calculations that clearly illustrate the mathematical steps underlying the proposed approximation and demonstrate the accuracy and effectiveness of our method.     

Amine catalysis in phosphoryl transfer from 2,4-dinitrophenyl phosphate in aprotic and protic solvents

Reactions of tetra-n-butylammonium 2,4-dinitrophenyl hydrogen phosphate, (ArPH)^?(R₄N)⁺, in aprotic and protic solvents, in the absence and in the presence of alcohols or water, ROH, are compared with analogous reactions of the salt in the presence of hindered and unhindered amines, e.g. diisopropylethyl amine and quinuclidine. Similar studies are performed with the acid, ArPH₂, in the presence of variable amounts of amines. The release of phenol and the fate of the phosphorus compounds are followed by ¹H and ³¹P NMR spectrometry. In the absence of free unhindered amine, reactions of the monoanion are relatively slow, sensitive to steric hindrance in the alcohol, and incapable of producing t-butyl phosphate from t-butanol; reactions of the dianion are relatively fast, insensitive to steric hindrance in the alcohol, and produce t-butyl phosphate. In the presence of free unhindered amine, reactions of the monoanion are relatively fast but still sensitive to steric hindrance in the alcohol, and hence do not produce t-butyl phosphate. The intermediate CH(CH₂CH₂)₃⁺NP(O)(OH)O^? is detected in the presence of quinuclidine. Reactions of the dianion in the presence of unhindered amines are analogous to those observed in the presence of hindered amines. The uncatalyzed and the nucleophilic amine-catalyzed reactions of the monoanion are assumed to proceed via oxyphosphorane, P(5), intermediates. The dianion reactions, which are not susceptible to nucleophilic catalysis, are assumed to proceed via the monomeric metaphosphate ion intermediate, PO₃^?. Significant effects related to solvent properties are observed in these reactions.     

1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD) catalyzed Michael reactions

1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD), a bicyclic guanidine base, has been found to be an excellent catalyst for Michael and Michael-type reactions. A wide variety of Michael donors and acceptors can participate in these reactions using 10-20 mol % of TDB. These reactions are mild, fast, easy to perform, produce excellent yields and can occur in several solvents without the need for strictly anhydrous conditions.     

Inteferences in neutron and photon activation analysis

The effect of following interferences was quantitatively assessed in terms of interference factor by irradiating samples together with highly pure reagents at two reactor sites of diferent neutron spectra and fluxes for neutron activation analysis (NAA) and an electron LINAC for photon activation analysis (PAA). The interfering reactions studied are 91) fast neutron-induced reactions, (2) uranium fission (3) (n,γ) reactions of other target elements in NAA, and (4) reactions induced by secondary neutrons in PAA. Corrections for these interferences were successfully applied to the activation analysis of some geological reference rock samples and biological samples.     

A comparison of electrometric and gasometric methods for following autoxidations

Gasometric and electrometric methods for determining oxygen in the study of photosensitized reactions are compared. The oxygen electrode must be calibrated against known solutions similar in composition to the solutions used in the reactions that are studied. The electrode can be used to study initial reaction rates whereas this is impossible for fast reactions with the Warburg apparatus.     

Reactions of fluoronitrobenzenes with MTBD strong base in acetonitrile in the presence of water molecules

Products of the reactions between three fluorinated nitrobenzenes (2,3,4,6-tetrafluoronitrobenzene, mNF4; 2,3,4,5-tetrafluoronitrobenzene, oNF4; pentafluoronitro-benzene, NF5) and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD) in the presence of the water molecules in acetonitrile were isolated and identified by analytical and spectroscopic methods. The reaction products included ortho- and para-substituted nitro-compounds. The kinetics of these reactions is independent of the substrates studied. The rate-determining step of these reactions is the hydrolysis of one ring of the MTBD molecule after the fast formation of the Meisenheimer complex. The mechanism of these reactions and the structures of the products are discussed.     

Copper(II) tetrafluoroborate as a novel and highly efficient catalyst for Michael addition of mercaptans to α,β-unsaturated carbonyl compounds

Copper(II) tetrafluoroborate has been found to be a new and highly efficient catalyst for Michael addition of thiols to α,β-unsaturated carbonyl compounds under solvent-free conditions and in H₂O at room temperature. The reactions are very fast and are completed in 2 min to 1 h affording high yields. The rate of thiol addition was dependent on the steric hindrance at the β-carbon of the α,β-unsaturated carbonyl substrate. In the case of chalcones, the reactions are best carried out in MeOH as solvent.     

Electron-beam initiated crosslinking in poly(N-isopropylacrylamide) aqueous solution

The reactions between the OH, H and e_aq⁻ transients of water radiolysis and a linear poly(N-isopropylacrylamide) were identified by the spectral and kinetic properties of intermediates. The radical responsible for crosslink formation is the isopropyl-centered radical that forms mainly in OH radical attack on the polymer. Below pH 3 this radical undergoes reversible protonation with pK_a≈2.1. The radical decay is composed of fast and slow parts. The initial fast decay is attributed to intramolecular reactions of radicals on the same chain (loop formation), the following slow decay to competition between further intramolecular and intermolecular (H-type crosslinks) termination processes. The differences in the network formation during irradiation of aqueous monomer and polymer solutions are discussed.     

Competitive isomerization and dimerization in co-crystals of 1,1,6,6-tetraphenyl-2,4-hexadiyne-1,6-diol and sorbic acid: a new look at stereochemical requirements for [2+2] dimerization

Competitive [2+2] photodimerization and E-->Z isomerization reactions occur in a co-crystal of 1,1,6,6-tetraphenyl-2,4-hexadiyne-1,6-diol upon irradiation with 325 nm light. At 90 K both reactions are observed, whereas at 280 K the dimerization reaction is very fast and inhibits isomerization as the nature of the chromophore is affected by the reaction. The temperature dependence of the stereospecificity of the dimerization reaction is related to the large sliding motion required to bring the reacting molecules into juxtaposition. The progress of the reactions has been monitored by photocrystallographic methods.     

The electrochemical behaviour of cobalt in alkaline solutions part II. The potentiodynamic response of Co(OH)2 electrodes

The potentiodynamic behaviour of Co(OH)₂ hydroxide electrodes is studied in the potential range related to the appearance of CO(III) and CO(IV) species. The corresponding electrochemical reactions involve relatively fast proton transfer processes occurring at potentials close to those predicted from thermodynamics. Sandwich-type structures of the electrode/film/solution interface are assumed in the interpretation of the processes. They probably include configurational changes of reactants and products participating in the various electrochemical reactions.