scholarly journals Determination of the preferred reaction pathway of acetophenone on Si(001) using photoelectron diffraction.

Author(s):  
Paula Laborda Lalaguna ◽  
Holly Hedgeland ◽  
Paul Ryan ◽  
Oliver Warschkow ◽  
Matthias Muntwiler ◽  
...  
Author(s):  
John Ross ◽  
Igor Schreiber ◽  
Marcel O. Vlad

In a chemical system with many chemical species several questions can be asked: what species react with other species: in what temporal order: and with what results? These questions have been asked for over one hundred years about simple and complex chemical systems, and the answers constitute the macroscopic reaction mechanism. In Determination of Complex Reaction Mechanisms authors John Ross, Igor Schreiber, and Marcel Vlad present several systematic approaches for obtaining information on the causal connectivity of chemical species, on correlations of chemical species, on the reaction pathway, and on the reaction mechanism. Basic pulse theory is demonstrated and tested in an experiment on glycolysis. In a second approach, measurements on time series of concentrations are used to construct correlation functions and a theory is developed which shows that from these functions information may be inferred on the reaction pathway, the reaction mechanism, and the centers of control in that mechanism. A third approach is based on application of genetic algorithm methods to the study of the evolutionary development of a reaction mechanism, to the attainment given goals in a mechanism, and to the determination of a reaction mechanism and rate coefficients by comparison with experiment. Responses of non-linear systems to pulses or other perturbations are analyzed, and mechanisms of oscillatory reactions are presented in detail. The concluding chapters give an introduction to bioinformatics and statistical methods for determining reaction mechanisms.


2000 ◽  
Vol 62 (3) ◽  
pp. 1635-1638 ◽  
Author(s):  
M. E. Dávila ◽  
S. L. Molodtsov ◽  
M. C. Asensio ◽  
C. Laubschat

1994 ◽  
Vol 73 (26) ◽  
pp. 3548-3551 ◽  
Author(s):  
M. Zharnikov ◽  
M. Weinelt ◽  
P. Zebisch ◽  
M. Stichler ◽  
H. -P. Steinrück

2009 ◽  
Vol 15 (2) ◽  
pp. 69-76 ◽  
Author(s):  
S.M. Al-Ghannam ◽  
A.M. Al-Olyan

A sensitive spectrophotometric method was developed for the determination of some 1,4-dihydropyridine compounds namely, nicardipine and isradipine either in pure form or in pharmaceutical preparations. The method is based on the reduction of nicardipine and isradipine with zinc powder and calcium chloride followed by further reduction with sodium pentacyanoaminoferrate (II) to give violet and red products having the absorbance maximum at 546 and 539 nm with nicardipine and isradipine, respectively. Beer's law was obeyed over the concentration range 8.0-180 ?g/ml with the detection limit of 1.67 ?g/ml for nicardipine and 8.0-110 ?g/ml with the detection limit of 1.748 ?g/ml for isradipine. The analytical parameters and their effects on the reported methods were investigated. The molar absorptivity, quantization limit, standard deviation of intercept (Sa), standard deviation of slope (Sb) and standard deviation of the residuals (Sy/x) were calculated. The composition of the result compounds were found 1:1 for nicardipine and 1:2 for isradipine by Job's method and the conditional stability constant (Kf) and the free energy changes (?G) were calculated for compounds formed. The proposed method was applied successfully for the determination of nicardipine and isradipine in their dosage forms. The results obtained were in good agreement with those obtained using the reference or official methods. A proposal of the reaction pathway was presented.


2019 ◽  
Vol 12 (1) ◽  
pp. 108-118 ◽  
Author(s):  
Martin Michalík ◽  
Ján Rimarčík ◽  
Vladimír Lukeš ◽  
Erik Klein

Abstract Very recently, a report on the antioxidant activity of flavonoids has appeared, where authors concluded that Hydrogen Atom Transfer mechanism represents the thermodynamically preferred mechanism in polar media (https://doi.org/10.1016/j.foodres.2018.11.018). Unfortunately, serious errors in the theoretical part of the paper led to incorrect conclusions. For six flavonols (galangin, kaempferol, quercetin, morin, myricetin, and fisetin), reaction enthalpies related to three mechanisms of the primary antioxidant action were computed. Based on the obtained results, the role of intramolecular hydrogen bonds (IHB) in the thermodynamics of the antioxidant effect is presented. Calculations and the role of solvation enthalpies of proton and electron in the determination of thermodynamically preferred mechanism is also briefly explained and discussed. The obtained results are in accordance with published works considering the Sequential Proton-Loss Electron-Transfer thermodynamically preferred reaction pathway.


2008 ◽  
Vol 6 (2) ◽  
pp. 222-228 ◽  
Author(s):  
Sheikha Al-Ghannam ◽  
Abeer Al-Olyan

AbstractA simple and highly sensitive spectrofluorometric method was developed for the determination of some 1,4-dihydropyridine compounds namely, nicardipine, nifedipine and isradipine in pharmaceutical preparations and biological fluids. The method is based on the reduction of nicardipine, nifedipine and isradipine with Zn/HCl and measuring the fluorescence intensity obtained (λem/λex) at 460/364, 450/393 and 446/360 nm, respectively. The factors affecting the development of the fluorophore and its stability were studied and optimized. The effect of some surfactants such as β-cyclodextrin (βCD), carboxymethylcelullose (CMC), sodium dodecyl sulphate (SDS) and triton X-100, on the fluorescence intensity was studied. The fluorescence intensity-concentration plots of nicardipine, nifedipine and isradipine were rectilinear over the ranges 0.4–6.0, 0.2–4.0 and 0.1–9.0 μg ml−1 with detection limits of 0.0028, 0.017 and 0.016 μg ml−1, respectively. The proposed method was successfully applied to commercial tablets containing the compounds; the percentage recovery agreed well with those obtained using the official methods. The method was further extended to the in vitro determination of the compounds in spiked human plasma and urine samples. A proposal of the reduction reaction pathway was postulated.


2001 ◽  
Vol 84 (4) ◽  
pp. 1017-1024 ◽  
Author(s):  
Ekram M Hassan ◽  
Fathalla Belal ◽  
Omar A Al-Deeb ◽  
Nasr Y Khalil

Abstract A highly sensitive and specific method is proposed for the determination of vigabatrin (I) and gabapentin (II) in their dosage forms and spiked human plasma. The method is based on coupling the drugs with 4-chloro-7-nitrobenzo-2-oxa-1,3-diazole in borate buffer at pH 7.1 and measuring the resulting fluorescence at 532 nm after excitation at 465 nm. The fluorescence intensity was a linear function of the concentration of the drugs over the ranges of 1.3–6.5 and 1.7–8.5 μg/mL for I and II, respectively. Minimum detectability values were 0.54 μg/mL (4.2 × 10−6M) and 0.97 μg/mL (5.7 × 10−6M) for I and II, respectively, under the described conditions. The proposed method was successfully applied to the determination of the 2 drugs in their dosage forms, and the percent recoveries ± standard deviation (SD) were 104.53 ± 1.2 and 100.00 ± 1.32 of the label claim for I and II, respectively. The method was further applied to the determination of vigabatrin in spiked plasma samples. The percent recovery ± SD was 101.58 ± 2.68. Interference from endogenous α-amino acids was overcome through selective complexation with freshly prepared Cu(OH)2. The interference likely to be encountered from co-administered drugs, such as carbamazepine, cimetidine, clonazepam, clopazam, phenobarbital, valproic acid, and lamotrigine, was also studied. A reaction pathway is suggested.


1999 ◽  
Vol 06 (06) ◽  
pp. 1201-1206 ◽  
Author(s):  
A. VERDINI ◽  
M. SAMBI ◽  
F. BRUNO ◽  
D. CVETKO ◽  
M. DELLA NEGRA ◽  
...  

A new method to determine the surface relaxation by means 0 of photoelectron diffraction (PED) from an s-core level has been applied to the (1 × 1)- TiO 2(110) surface. Complete 2π solid angle PED patterns for both oxygen 1s and titanium 3s core level peak intensities have been measured at the ALOISA beamline (Elettra Synchrotron, Italy) in two different photon polarization/electron detection geometrical configurations: one with the photon polarization vector parallel to the surface normal (TM polarization) and the other with the photon polarization vector perpendicular to the surface normal (TE polarization). In the latter case the PED sensitivity to the vertical spacing is enhanced. Because forward scattering is suppressed on the node of the primary wave along the surface normal, the relative weight of the distance-sensitive higher order interference fringes is enhanced. The opposite occurs for the TM polarization, which enhances the PED sensitivity to lateral spacing at grazing emission angles. The experimental PED patterns are compared with the theoretical simulations calculated for the relaxed and unrelaxed TiO 2(110) surface. The results prove the feasibility of the method and the adequacy of the PED technique to the studies of relaxation phenomena at crystal surfaces.


2001 ◽  
Vol 63 (11) ◽  
Author(s):  
L. Petaccia ◽  
L. Floreano ◽  
M. Benes ◽  
D. Cvetko ◽  
A. Goldoni ◽  
...  

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