Sensitivity Analysis in Photodynamics: How Does the Electronic Structure Control -Stilbene Photodynamics?

The techniques of computational photodynamics are increasingly employed to unravel reaction mechanisms and interpret experiments. However, misinterpretations in nonadiabatic dynamics caused by inaccurate underlying potentials are often difficult to foresee. This work focuses on revealing the systematic errors in the nonadiabatic simulations due to the underlying potentials and suggests a thrifty approach to evaluate the sensitivity of the simulations to the potential.

A stability study of amphotericin B, colistin and tobramycin in a hydrophilic suspension commonly used for selective decontamination of the digestive tract by HPLC and in vitro potency measurements.

Objectives: A suspension for oral use which consists of three non-absorbable antibiotics (amphotericin B, colistin and tobramycin) is often used in clinical practice for the selective decontamination of the digestive tract (SDD) of patients in intensive care. Such a therapy is a preventive tool to minimise the risk of pneumonia and bacteraemia in intubated patients. The administration and the treatment results are controversially discussed.

Purity determination of amphotericin B, colistin sulfate and tobramycin sulfate in a hydrophilic suspension by HPLC.

A suspension comprising of the three antibiotic substances amphotericin B, colistin sulfate and tobramycin sulfate is often used in clinical practice for the selective decontamination of the digestive tract of patients in intensive care. Since no detailed procedures, specifications or stability data are available for manufacturing this suspension, there may be discrepancies regarding formulation and stability of suspensions prepared in different pharmacies. The aim of this work is to develop a standardized formulation and to determine its stability under defined storage conditions.

Development and validation of a rapid stability indicating HPLC-method using monolithic stationary phase and two spectrophotometric methods for determination of antihistaminic acrivastine in capsules.

Simple, rapid and accurate high performance liquid chromatographic (HPLC) and spectrophotometric methods are described for determination of antihistaminic acrivastine in capsules. The first method (method A) is based on accurate, sensitive and stability indicating chromatographic separation method. Chromolith® Performance RP-18e column, a relatively new packing material consisting of monolithic rods of highly porous silica, was used as stationary phase applying isocratic binary mobile phase of ACN and 25 mM NaH2PO4 pH 4.

Evaluation of (S)- and (R)-misonidazole as GPX inhibitors: synthesis, characterization including circular dichroism and in vitro testing on bovine GPx-1.

Racemic misonidazole, a radiosensitizer formally used in radiation therapy of cancer and to date still applied, was once reported to exhibit strong inhibitory effects on mouse glutathione peroxidases (GPX). This appeared to qualify misonidazole as a lead structure for the development of novel GPX inhibitors to cause oxidative stress in chemotherapy-resistant tumors. A unique feature of misonidazole as an inhibitor of GPX is the absence of a thiol functionality.

Intergroup cross-comparison for the evaluation of data-interchangeability from various chromatographic tests.

The recently dramatic increase in the available choices of reversed-phase columns could be an advantage of this mode of separation. However, due to the insufficiency of available information in terms of the exact functionality of these phases and the similarities and differences between these newly introduced and conventional reversed-phase columns, it is now somehow problematic to determine which could be the best column for a given analytical problem. There is no single column that will give us a good separation for all applications.

Analytical power of LLE-HPLC-PDA-MS/MS in drug metabolism studies: identification of new nabumetone metabolites.

Nabumetone is a non-acidic, nonsteroidal anti-inflammatory prodrug. Following oral administration, the prodrug is converted in the liver to 6-methoxy-2-naphthylacetic acid (6-MNA), which was found to be the principal metabolite responsible for the NSAID effect. The pathway of nabumetone transformation to 6-MNA has not been clarified, with no intermediates between nabumetone and 6-MNA having been identified to date.

Spectrophotometric and stability-indicating high-performance liquid chromatographic determinations of terbutaline sulfate.

Spectrophotometric and stability-indicating HPLC procedures are described for determination of terbutaline sulfate in bulk powder and dosage form. The first procedure is based on diazo coupling of the phenolic groups of terbutaline sulfate with fast red B salt in the presence of sodium hydroxide. The colored compound developed in alkaline medium was measured at 475 nm.

Effect of chromatographic conditions on liquid chromatographic chiral separation of terbutaline and salbutamol on Chirobiotic V column.

In this study, a method for enantioseparation of terbutaline and salbutamol was established using Chirobiotic V column as a stationary phase. Polar ionic mode applying mobile phase containing ammonium nitrate in 100% ethanol, pH 5.1 was found to give the best separation.

Comparison of the chromatographic behavior of levofloxacin, ciprofloxacin and moxifloxacin on various HPLC phases.

A simple and rapid HPLC method with UV detection was developed for the separation of ciprofloxacin, levofloxacin and moxifloxacin. Chromatography was carried out using a BDS Hypersil C18 (100 x 4.6 mm, 2.

Selectivity of calixarene-bonded silica phases in HPLC: Description of special characteristics with a multiple term linear equation at different methanol concentrations.

Retention and selectivity characteristics of different calixarene-, resorcinarene- and alkyl-bonded stationary phases are examined by analyzing a set of test solutes covering the main interactions (hydrophobic, steric, ionic, polar) that apply in HPLC. Therefore Dolan and Snyder's multiple term linear equation has been adapted to fit the properties of calixarene-bonded columns. The obtained parameters are used to describe retention and selectivity of the novel Caltrex(®) phases and to elucidate underlying mechanisms of retention.

Characterization of calixarene-bonded stationary phases.

Calixarene-bonded stationary phases received growing interest in HPLC as stationary phases with special retention characteristics and selectivity. The commercially available unsubstituted and p-tert-butyl-substituted Caltrex(®) columns have been intensively studied and characterized in our workgroup. They can be used as reversed phases, yet they support additional interactions.

The role of silver nitrate as additive in non-aqueous capillary electrophoresis.

In this study, effect of use of silver nitrate as additive on non-aqueous capillary electrophoresis (NACE) separations of some structurally related compounds belonging to antidepressants, neuroleptics or sulfonamides, was examined. The presence of silver nitrate was found to enhance these NACE separations. The use of silver nitrate provided a successful method of improving the separations of antidepressants, neuroleptics and sulfonamides.

Description of retention characteristics of calixarene-bonded stationary phases in dependence of the methanol content in the mobile phase.

Calixarene-bonded stationary phases in HPLC are known to support additional interactions compared to conventional alkyl-bonded phases (pi-pi interactions, complex-building interactions). Thus it cannot be presumed that the same mechanisms of retention apply and that retention can be predicted in similar ways. Here 31 solutes of highly various molecular structures have been analysed at different mobile phase compositions (0-98% (v/v) methanol) in order to characterise the chromatographic behaviour of the novel stationary phases and to test the applicability of established models predicting retention factors.

Considerations of the behaviour of C18-chains and calixarenes and their application for determination of stationary phase volume in RP-chromatography.

The volume of stationary phase is extremely important for the estimation of thermodynamic information such as entropy and Gibbs free energy in HPLC. However, the definition of this volume strongly depends on the conditions chosen. In the present mini review the partitioning model of small molecules at low concentrations and methanol as modifier is assumed.

Selectivity of calixarene-bonded silica-phases in HPLC: description of special characteristics with a multiple term linear equation at two different pH-values.

Six different calixarene-bonded phases were characterized by analyzing 36 and 26 solutes at pH 3 and 7, respectively. Dolan and Snyder's multiple term linear equation was used to correlate retention factors k' to parameters of the solutes and columns. The column parameters have been related to molecular properties of the stationary phases and new suggestions were made for the interpretation of steric selectivity.

The effect of achiral calixarenes on chiral separation of propranolol-HCl and brompheniramine maleate in capillary electrophoresis using cyclodextrin as chiral selector.

In this study we have examined the effect of achiral water soluble p-sulfonatocalixarenes (SCX[n]) on chiral separation propranolol-HCl and brompheniramine maleate. Several cyclodextrins (CDs) and cyclodextrin derivatives were examined as chiral selectors applying complete filling technique (CFT) accompanied with the partial filling technique PFT of (SCX[n]) as achiral modifier. Only with hydroxypropyl-beta-cyclodextrin (HP-beta-CD) chiral separation could be achieved.

Comparison of the chromatographic behavior of tricyclic neuroleptics on calixarene-bonded, monolithic and conventional RP-HPLC columns.

The effect of different chromatographic conditions, such as buffer concentration and type of organic modifier, on the retention behavior of nine tricyclic neuroleptics on three different RP-HPLC columns was investigated. Two recently developed columns, calixarene-bonded (CALTREX) AIII) and monolithic (Chromolith) Performance RP-18e) columns, were compared with a conventional RP-C18 HPLC column (LiChrospher). The results showed how the mobile phase conditions had different effects on the analyte retention on these three columns.

Achiral and chiral high-performance liquid chromatographic determination of flubendazole and its metabolites in biomatrices using UV photodiode-array and mass spectrometric detection.

Flubendazole, methyl ester of [5-(4-fluorobenzoyl)-1H-benzimidazol-2-yl]carbamic acid, belongs to the group of benzimidazole anthelmintics, which are widely used in veterinary and human medicine. The phase I flubendazole biotransformation includes a hydrolysis of the carbamoyl methyl moiety accompanied by a decarboxylation (hydrolysed flubendazole) and a carbonyl reduction of flubendazole (reduced flubendazole). Flubendazole is a prochiral drug, hence a racemic mixture is formed during non-stereoselective reductions at the carbonyl group.

Effect of chaotropic mobile phase additives on retention behaviour of beta-blockers on various reversed-phase high-performance liquid chromatography columns.

In this study the effect of type and concentration of chaotropic counter anion in buffered mobile phase on retention behaviour of some beta-blockers was studied. Two types of anions (perchlorate, dihydrogen phosphate) were examined under different concentrations. Further different pH-values for each anion were used to investigate the effect of pH changes on chaotropic behaviour of these anions.

Retention behaviour of beta-blockers in HPLC using a monolithic column.

The chromatographic behaviour of a new HPLC-stationary phase (Chromolith RP-18e) is described for separation of beta-blockers. The effects of the different chromatographic conditions (buffer system, pH value, content of organic modifier, injection volume and flow rate) on the separation behaviour were studied. At higher flow rates the peaks seemed to be more symmetrical than at lower flow rates.

Use of chiral liquid chromatography for the evaluation of stereospecificity in the carbonyl reduction of potential benzo[c]fluorene antineoplastics benfluron and dimefluron in various species.

Benfluron (B) [5-(2-dimethylaminoethoxy)-7H-benzo[c]fluorene-7-one hydrochloride] is a potential antineoplastic agent. In the organism, B undergoes a rapid phase I biotransformation through oxidative and reductive metabolic pathways. The carbonyl reduction of B leads to reduced benfluron, red-B, this is one of the principal pathways for the deactivation of this compound.

The effect of the process variables on the HPLC separation of tricyclic neuroleptics on a calixarene-bonded stationary phase.

The chromatographic behavior of a new HPLC-stationary phase with supramolecular selectors on the basis of calixarenes is described for the separation of nine tricyclic neuroleptics. The effects of different chromatographic conditions (buffer system, pH-value, type and content of organic modifier, injection volume) on the separation of the analytes were studied. Additionally, the effect of structural differences of the neuroleptic analytes was studied.

Capillary electrophoretic separation of enantiomers of amino acids and amino acid derivatives using crown ether and cyclodextrin.

The capillary zone electrophoresis using (+)-18-crown-6-tetracarbonic acid as a chiral selector was a suitable method for the enantiomeric separation of racemates of amino acids and of some amino acid derivatives (esters, dipeptides). The influence of the chemical structure of the compounds on the separation was investigated. After optimization of the separation conditions, baseline separations were obtained for most racemates.

Peak shape improvement of basic analytes in capillary liquid chromatography.

The analysis of bases is of special interest in pharmaceutical research because numerous active substances contain basic functional groups. Capillary and conventional size LC separations of drug substances spiked with potential impurities were compared. In the case of the nonpolar drug levonorgestrel equal separation efficiency was readily attained by both techniques.