With frontal analysis(FA),the dependence of adsorption isotherms of insulin on the composition of mobile phase in reversed phase liquid chromatography (RPLC) has been investigated,This is also a good example to employ the stoichiometric displacement theory (SDT) for ivestigating solute adsorption in physical chemistry.Six kinds of mobile phase in RPLC were employed to study the effects on the elution curves and adsorption isotherms of insulin.the key points of this paper are:(1) the stability of insulin due to delay time after preparing,the organic solvent concentration,the kind and the concentration of ion-pairing agent in mobile phase were found to affect both elution curve and adsorption isotherm very seriously.(2)To obtain a valid and comparable result,the composition of the mobile phase employed in FA must be as same as possible to that in usual RPLC of either analytical scale or preparative purpose.(3)Langmuir Equation and the SDT were employed to imitate these obtained adsorption isotherms.The expression for solute adsorption from solution of the SDT was found to have a better elucidation to the insulin adsorption from mobile phase in RPLC. 相似文献
1H NMR-spectroscopic investigations of the acid catalyzed addition of methanol to dihydrodipyrrinones (Z)-2, (E)-2, and4 show the C-protonation of their enamide parts to be the first and rate determining step forming the key intermediate, the N-acyl-immonium ion N+. Its ability to add nucleophiles diastereoselectively can be used to prepare the adductsl-3 andl-5. Exclusive formation of thelike-isomer can be explained by a stereoelectronically favoured approach of the nucleophile and by the thermodynamically favoured arrangement of the bulky ring substituents. Both explanations are based on low temperature X-ray crystal structure determinations: in the first place, the orientation of the added nucleophile could be found to be nearly parallel to the -plane of the lactam unit and quasi-axial with respect to theenvelope-like conformation of the five-ring lactam; in the second place, the relative orientation of the methoxycarbonyl-metyl-group at C-3 and the pyrrolylmethyl-substituent at C-4 could be found to be atrans-quasi-diequatorial one. 相似文献
The thermal decomposition of some M
2I
HPO3 (M-Li, Na, K) phosphites under nitrogen atmosphere was investigated. A stepwise mechanism of thermal decomposition has been proposed.
Zusammenfassung Es wurde die thermische Zersetzung von Phosphiten M
2I
HPO3 (M-Li, Na, K) in Stickstoffatmosphere untersucht. Die Schritte des Mechanismus der thermischen Zersetzung wurden vorgeschlagen.
A thin film of manganese hexacyanoferrate (MnHCF) was electrochemically formed on a glassy carbon (GC) electrode to prepare a chemically modified electrode (CME). The mechanism of film formation of MnHCF and its growth process were investigated in detail by cyclic voltammetry. The results show that the stoichiometric composition of MnHCF is Mn^ⅢFe^Ⅲ(CN)6, an analogue of prussian yellow. There exist three clear-cut stages in the whole modification process and the last stage is indispensable to the fabrication of homogenized, stable MnHCF film and must last for an appropriate time. The surface morphology of MnHCF/GC electrode was characterized by scanning electron microscopy (SEM), which further verified the effective deposition of MnHCF film on GC. The kinetic constants of MnHCF/GC electrode process were also evaluated. The resulting MnHCF film modified electrode presented good stability and high electrocatalytic activity toward the oxidation of H2O2, indicating that MnHCF film possesses function of catalase and can be expected for analytical purposes. 相似文献
A complete electrochemical study and a novel electroanalytical procedure for bromhexine quantitation are described. Bromhexine in methanol/0.1 mol L−1 Britton–Robinson buffer solution (2.5/97.5) shows an anodic response on glassy carbon electrode between pH 2 and 7.5. By DPV and CV, both peak potential and current peak values were pH-dependent in all the pH range studied. A break at pH 5.5 in EP versus pH plot revealing a protonation–deprotonation (pKa) equilibrium of bromhexine was observed. Spectrophotometrically, an apparent pKa value of 4.3 was also determined.
An electrodic mechanism involving the oxidation of bromhexine via two-electrons and two-protons was proposed. Controlled potential electrolysis followed by HPLC–UV and GC–MS permitted the identification of three oxidation products: N-methylcyclohexanamine, 2-amino-3,5-dibromobenzaldehyde and 2,4,8,10-tetrabromo dibenzo[b,f][1,5] diazocine.
DPV at pH 2 was selected as optimal pH for analytical purposes. Repeatability, reproducibility and selectivity parameters were adequate to quantify bromhexine in pharmaceutical forms. The recovery was 94.50 ± 2.03% and the detection and quantitation limits were 1.4 × 10−5 and 1.6 × 10−5 mol L−1, respectively. Furthermore, the DPV method was applied successfully to individual tablet assay in order to verify the uniformity content of bromhexine. No special treatment of sample were required due to excipients do not interfered with the analytical signal. Finally the method was not time-consuming and less expensive than the HPLC one. 相似文献
The reaction of C2H6with lattice oxygen, O2- (in the absence of gaseous oxygen), or “adsorbedℍ oxygen (in the presence of gaseous oxygen) over NiMoO4 catalysts has been performed and compared to C3H8 activation. The results obtained indicate that adsorbed oxygen exhibits a higher reactivity to C2H6, while lattice oxygen is more reactive relative to C3H8. Kinetic studies of these two reactions in presence of molecular oxygen have indeed shown that the ethane oxidative dehydrogenation
(ODH) is dependent on the oxygen partial pressure, whilst on the contrary propane ODH is not. In order to confirm the presence
of “adsorbed” oxygen for ethane activation, ODH tests have been performed with N2O. On increasing temperature, the O- adsorbed species enhances the mild oxidation of ethane. The activation energy of ethane consumption EC2H6, relative to propane (EC3H8 = 133 kJ/mol) is 145 kJ/mol. A possible mechanism is proposed for the oxidative dehydrogenation of ethane.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
We have studied the rate of 15 reactions of acyl transfer from O-acyl salts of 4-dimethylaminostyryl-4-pyridine N-oxide to 4-morpholinopyridine and 4-dimethylaminopyridine N-oxides in acetonitrile solutions. Analysis of the results based on the Shaik – Pross approach and the Marcus equation shows that if the structure of the acyl group is varied, then the reactivity is determined by such parameters as the resonance interaction in the transition state (B) or the internal barrier (G0) of the reaction. 相似文献
Activation of CO2 at Transition Metal Centres: The Route of the CO2 Reduction at Nikel(0) Moieties A competing reaction in the catalytic cyclooligomerization of hex-3-yne and CO2 at the (TMED)Ni(0)-fragment (TMED = N,N,N′,N′-tetramethylethylendiamine) is the formation of carbon monoxide and (TMED)Ni(CO3). So it is possible to explain the generation of II (TMED)Ni(diethylmalicacidanhydride) and III (a nickel trimer with two (TMED)Ni(CO3) units). Both complexes are characterized by X-ray analysis. The reduction of CO2 to CO most likely proceeds via an intermediate in which two molecules of carbon dioxide are coupled head-to-tail to form a metallacycle. An ab initio scf geometry optimization supports the existence of such an intermediate. 相似文献