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1.
K. P. Madhusudanan Shubhra Mittal Susheel Durani R. S. Kapil 《Journal of mass spectrometry : JMS》1985,20(5):323-326
Stereospecific adduct ion formation has been observed in the chemical ionization mass spectra (positive and negative) of certain E- and Z-1,2,3-triaryl-2-propen-1-ones. The Z isomers are found to give higher relative abundances of adduct ions than the E isomers. This has been interpreted in terms of the differences in the proton affinities of the isomers originating from their different degrees of enone resonance. Halide ion (CI? and Br?) attachment spectra of these compounds also show stereochemical differences in the relative abundances of [M]?˙ and [M+halide]? ions, though the effect is not as pronounced as in the case of the positive ion spectra. 相似文献
2.
Quantitative correlations between kinetic parameters (energy of activation, E), procedural factors (sample mass, m, and heating rate, φ) and the dependent variables (the temperature of inception of reaction, Ti, and temperature Tα at which a constant fraction α has decomposed) have been derived for differential thermal analysis (DTA) and differential scanning calorimetry (DSC). The relations have the same form as those derived from earlier TG studies. The dependent variables Ti and Tα are related to m, φ and E by the equations where C3 and C2 are constants, and where C4 and C5 are constants for a given α. The variation of C5 with α is given by C5 = a + b α where a and b are constants. The equations are applicable to TG, DTA and DSC. 相似文献
3.
K. P. Madhusudanan Mohan Prasad Shri Nivas Rastogi D. Fraisse 《Journal of mass spectrometry : JMS》1985,20(11):680-684
The nucleophilic substitution reaction under NH3 chemical ionization (CI) conditions in cis- and trans-1,2-dihydroxybenzosuberans (1–4) has been studied with the help of ND3 CI and metastable data. The results indicate that in the parent diols 1 (cis) and 2 (trans), the substitution ion [MsH]+, is produced mainly by the loss of H2O from the [MNH4]+ ion (SNi reaction) while in their 7-methoxy derivatives 3 and 4, the ion-molecule reaction between [M? OH]+ and NH3 seems to be the major pathway for the formation of [MsH]+. The substitution ion from 1 and 2 and the [MH]+ ion from trans-1-amino-2-hydroxybenzosuberan give similar collision-induced dissociation mass-analysed ion kinetic energy spectra. Interestingly, their diacetates do not undergo the substitution reaction. 相似文献
4.
A study of the chemical ionization (CI) and collisional activation (CA) spectra of a number of α, β-unsaturated nitriles has revealed that the even-electron ions such as [MH]+ and [MNH4]+ produced under chemical ionization undergo decomposition by radical losses also. This results in the formation of M +˙ ions from both [MH]+ and [MNH4]+ ions. In the halogenated molecules losses of X˙ and HX compete with losses of H˙ and HCN. Elimination of X˙ from [MH]+ is highly favoured in the bromoderivative. The dinitriles undergo a substitution reaction in which one of the CN groups is replaced with a hydrogen radical and the resulting mononitrile is ionized leading to [M ? CN + 2H]+ under CI(CH4) or [M ? CN + H + NH4] and [M ? CN + H + N2H7]+ under CI(NH3) conditions. 相似文献
5.
K. P. Madhusudanan Rashmi Srivastava D. K. Kulshreshtha D. Fraisse 《Journal of mass spectrometry : JMS》1987,22(6):368-372
Substitution of amino for hydroxyl groups in certain sesquiterpene alcohols has been studied by chemical ionization mass spectrometry using ammonia and ammouia-d3 as the reagent gases, and by mass-analysed ion kinetic energy spectrometry and collision-induced decomposition mass-analysed ion kinetic energy measurements. Depending upon the source conditions and the nature of the substrates, both SNi and SN1 mechanisms have been found to operate. No evidence is obtained for an SN2 mechanism in these compounds. In centdarol and isocentdarol, addition of NH3 to the double bond, followed by elimination of H2O, also contributes to the substitution process. Attack of [NH4]+ on the epoxide function, followed by loss of H2O, appears to lead to the substitution ions in epoxycentdarol, epoxyisocentdarol and epoxyhimachalol. 相似文献
6.
Madhusudanan KP 《Journal of mass spectrometry : JMS》2003,38(4):409-416
Multiple lithium exchange is observed during electrospray ionization of alpha-, beta- and gamma-cyclodextrins from aqueous methanolic solution containing LiOH. Apart from [M + Li](+) and [M + nLi - (n - 1)H](+) ions, abundant multiply lithiated doubly charged ions corresponding to [M + nLi - (n - 2)H](2+) ions were observed. At least six lithium exchanges in alpha-cyclodextrin, seven in beta-cyclodextrin and eight in gamma-cyclodextrin were noted. The propensity of multiply lithiated doubly charged ions is much less in the open-ended maltoheptaose. It appears that during droplet or cluster formation and subsequent desolvation, LiOH trapped in the cavity of cyclodextrin reacts to form multiply lithiated ions. The singly charged [M + Li](+) and doubly charged [M + 2Li](2+) ions fragment by glycosidic cleavages, giving B series of ions, whereas the multiply lithiated ions fragment by cross ring cleavages ((2, 4)A or (O, 2)X) followed by glycosidic cleavage. From the tandem mass spectra, it appears that a maximum of two lithium exchanges occur in one sugar unit in these cyclodextrins. 相似文献
7.
Beena Mathew P. M. Madhusudanan V. N. Rajasekharan Pillai 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(10):1781-1800
Abstract Amino groups were incorporated into polyacrylamides with 2?20 mol% of crosslinking agents by transamidation with ethylenediamine. Divinylbenzene, N,Nv′-methylene-bis-acrylamide, and tetraethyleneglycol diacrylate were used as the crosslinking agents. The complexation of these resins, which contain ligand functions in different macromolecular structural environments, was investigated with Cu(II) ions. The Cu(II) uptake of these different resins was correlated with the molecular character and degree of crosslinking in the polymer matrix. The time course and kinetics of complexation depend on the nature of the crosslinking agent in the polymer matrix. The swelling behavior of the uncomplexed and complexed resins, structural characteristics, and thermal decomposition behavior were followed by IR, EPR, and thermal analysis. The swelling characteristics of the complexed resins are lower than those of the uncomplexed resins. Complexation resulted in shifting of the IR absorptions. The EPR parameters depend on the nature of crosslinking and are in agreement with the distorted tetragonal geometry of the Cu(II) complexes. The thermal decomposition behavior also depends on the nature and the degree of crosslinking in the polymer matrix. 相似文献
8.
Clusters of galaxies are excellent probes of cosmic structure and evolution. X-ray studies of clusters provide some of their
key parameters, viz., temperature of the hot intra-cluster gas, its metallicity, X-ray luminosity and surface brightness giving
mass distribution and mass-flow rate in the case of cooling flows. X-ray measurements for a large sample of clusters have
lead to estimates of the total gravitating mass in them, which can be compared to the virial masses derived from dynamical
considerations and gravitational lensing in some of them. X-ray derived total masses are consistent with masses obtained from
the other methods after the effects due to the presence of cooling flows are taken into account in the analyses. Estimated
virial masses, lack of evolution in X-ray properties, and detection of several very hot clusters at high redshifts indicate
a Universe with a low value (≤ 0.3) for the Ω parameter. 相似文献
9.
K. P. Madhusudanan S. B. Katti S. A. N. Hashmi 《Journal of mass spectrometry : JMS》1993,28(9):970-976
The collision-induced decompositions of the [M – H]? and [M + Li]+ ions of a few dinucleoside phenylphosphonates were studied using fast atom bombardment and linked scanning at constant B/E. Deprotonation takes place on the base or sugar moieties. The [M – H]? ion decomposes mainly by cleavage on either side of the phosphonate linkage, leading to the formation of mononucleotide fragment ions and also by cleavage of the basesugar bond. Rupture of the 3′-phosphonate bond is preferred. Unlike the normal charged nucleotides, these neutral nucleotides do not eliminate a neutral base from the [M – H]? ion. However, the mononucleotide fragment ions which can have the charge on the phosphorus oxygen eliminate neutral bases by charge-remote fragmentation. The 4,4′-dimethoxytrityl (DMT)-protected nucleotides show the additional fragmentation of loss of DMT. Li+ attachment can occur at several sites in the molecule. As observed for the [M – H]? ion, the major cleavage occurs on either side of the phosphonate bond in the fully deprotected nucleotides, cleavage of the ester bond on C(3′) being preferred. Cleavage of the 5′-phosphonate bond is not observed in the DMT-protected nucleotides. Many of the fragmentations observed can be explained as arising from charge-remote reactions. 相似文献
10.