Equilibrium Studies of Binary and Ternary Complexes Involving Tricine and Some Selected α-Amino Acids

Summary. The formation equilibria for the binary complexes of Co^II, Ni^II, Cu^II, Zn^II, Cd^II, Mn^II, Pb^II, Th^IV, UO₂^II, and Ce^III with tricine and for the ternary complexes involving some -amino acids (glycine, -alanine, proline, serine, asparagine, and aspartic acid) were investigated using pH-metric technique. The formation of binary and ternary complexes was inferred from the pH-metric titration curves. It was deduced that tricine acts as a primary ligand in the ternary complexes involving the monocarboxylic amino acids (glycine, -alanine, proline, serine, and asparagine), whereas it behaves as a secondary ligand in the ternary systems containing the dicarboxylic aspartic acid. The ternary complex formation was found to take place in a stepwise manner. The stability constants of the complexes formed in aqueous solutions were determined potentiometrically under the experimental conditions (t=25°C, I=0.1moldm^–3 NaNO₃). The order of stability of the ternary complexes in terms of the nature of the amino acids is investigated and discussed. The values of log K for the ternary complexes have been evaluated and discussed. Evaluation of the effects of ionic strength and temperature of the medium on the stability of the ternary system M^II-tricine--alanine (M^II=Co^II, Ni^II, and Cu^II) has been studied. The thermodynamic parameters were calculated and discussed.     

New HPLC method to detect individual opioids (heroin and tramadol) and their metabolites in the blood of rats on combination treatment

Drug abuse is both an age-old and a constantly evolving problem in society. Trends in illicit drug use are highly fluid, with new formulations increasing in popularity. For this reason, methods for illicit drug detection and analysis need to be continually updated so they remain useful and relevant. A recent trend in street heroin production has seen it diluted with large amounts of tramadol in addition to the classical diluents such as acetaminophen and caffeine. This study describes a sensitive, simple and accurate high-performance liquid chromatographic method with ultraviolet detection for the simultaneous detection of heroin, 6-acetylmorphine, morphine, tramadol and O-desmethyltramadol in the blood of rats using a liquid-liquid back-extraction method. The separation was performed on LichroCART RP-18e with particle size of 5 μm (250 × 4.6 mm) with mobile phase acetonitrile-50 mM KH(2)PO(4) buffer, pH 7.1, using a gradient mode with a 1.0 mL/min flow rate. The calibration curves were linear in the concentration ranges 0.25-100 and 0.1-100 μg/mL for morphine and other analytes, respectively. Recovery values for the substances ranged between 59 and 83%. This technique was successfully used in pharmacokinetic studies measuring 6-acetylmorphine, morphine, tramadol and O-desmethyltramadol in the blood of rats intraperitoneally treated with a blend of 10 mg/kg heroin and 70 mg/kg tramadol. This technique shows promise for analysis of confiscated street heroin.     

Synthesis,Reactions, and Anticancer Activity of Some 1,3,4-Thiadiazole/Thiadiazine Derivatives of Carbazole

A novel method for the synthesis of 1,3,4-thiadiazole and 1,3,4-thiadiazine derivatives bearing a carbazole moiety is described. Carbazole was transformed into carbazole-9-thiocarbohydrazide in two steps. This compound was allowed to react with various electrophiles to yield 1,3,4-thiadiazole derivatives. The reaction with bifunctional electrophiles led to 1,3,4-thiadiazines. 2-(Carbazol-9-yl)-5,6-dihydro-4H-1,3,4-thiadiazin-5-one reacted with piperidine and formaldehyde to yield the 4-(piperidin-1-ylmethyl) derivative. The reaction with aromatic aldehydes led to the corresponding 6-arylidene derivatives, which were transformed into pyrimidino[4,5-e]-1,3,4-thiadiazines and pyrazolo[3,4-e]-1,3,4-thiadiazines by a reaction with guanidine, acetamidine, or phenylhydrazine, respectively. Structures of the products were confirmed by ¹H NMR, ¹³C NMR, IR, and mass spectrometric measurements. Selected examples of products were screened for anticancer activity.     

Epoxy-amine multimethacrylic prepolymers,kinetic and structural studies

Epoxy-amine methacrylated prepolymers are prepared in a 1-step synthesis by the reaction of Bisphenol A diglycidyl ether, glycidyl methacrylate, and different diamines. The adaptation of these reactions to production processes with a reduced reaction time requires a kinetic control and the use of efficient catalysts. The comparative kinetic treatment of the epoxy-amine reaction in the frame of Horie's and Rozenberg's kinetic schemes have been made. Cases where an efficient acid catalyst is used are also examined. Structural studies of these reactions established the occurrence of a Michael amine/double bond addition, when some amines are used. © 1995 John Wiley & Sons, Inc.     

Pyranoxanthones from Calophyllum Inophyllum

Phytochemical investigation of the stem bark of Calophyllum inophyllum resulted in the isolation of a new dipyrenoxanthone, calophinone ( 1 ), together with four related xanthones ( 2–5 ). Identification of the isolated compounds was achieved through intensive studies of their spectral data, especially 2D NMR.     

Uranium removal from nitric acid raffinate solution by solvent immobilized PVC cement

The present work deals with uranium removal from a nitric acid raffinate (waste) solution using prepared solvent (tri-butyl phosphate, TBP) immobilizing PVC cement (SIC) as a suitable adsorbent. The studied relevant factors affecting uranium adsorption onto SIC adsorbent involved; contact time, solution molarity, initial uranium concentration and temperature. The obtained adsorption isotherm of uranium onto the SIC adsorbent was fitted to Langmuir, Freundlich and Dubinin–Radushkviech (D–R) adsorption models. The results showed that the obtained equilibrium data fitted well the Langmuir isotherm. Additionally, it was found that the adsorption process obeys the pseudo second-order kinetic model. On the other hand, the calculated theoretical capacity of our prepared SIC adsorbent reached about 17 g U/kg SIC. Uranium adsorption from the studied raffinate solution was carried out applying the attained optimum conditions. The obtained data showed that 58.4 mg U/5 g SIC were adsorbed. However, using of 2 M HNO₃ solution as an eluent, 93 (54.3 mg U) from the adsorbed amount were eluted.     

Low temperature pyrolysis of carboxymethylcellulose

Unlike the common high temperature pyrolysis of carboxymethylcellulose (CMC) targeting activated carbon, this study investigates the pyrolytic behaviour of plain CMC at low temperatures ranging between 260 and 300 °C. Preliminary experiments were conducted using differential scanning calorimetry to define the temperature range necessary for the process. Low-temperature pyrolysis was then simulated using thermogravimetric analysis under inert atmosphere. Investigations reveal that a minimum holding temperature of 260 °C is required for an isothermal process, at which pyrolysis is terminated after around 26 min. Increasing exposure temperature reduces pyrolysis time. Within the range of the investigated sample and CMC particle size, no significant effects could be measured regarding the decomposition behaviour. The resulting char was further analysed using X-ray diffraction and Fourier transform infrared spectroscopy. Visual inspection was conducted using scanning electron microscopy. Upon pyrolysis, originally longitudinally shaped CMC was found to be converted into spherical particles of functionalised amorphous carbon with an average particle size of 41 µm.     

Development and validation of spectrophotometric, TLC and HPLC methods for the determination of lamotrigine in presence of its impurity

Three reliable, rapid and selective methods have been developed and validated for the determination of lamotrigine in the presence of its impurity, 2,3-dichlorobenzoic acid. The first method is spectrophotometric method using p-chloranilic acid forming a colored product with lambda(max) 519+/-2 nm. All variables affecting the reaction have been investigated and the conditions were optimized. Beer's law was obeyed over a concentration range of 10-200 microg ml(-1) with mean accuracy 100.13+/-0.44%. The molar ratio of the formed ion-association complex is found to be 1 : 1 as deduced by Job's method. The conditional stability constant (K(f)), standard free energy (DeltaG), molar absorptivity(epsilon), and sensitivity index were evaluated. The second method is based on TLC separation of the cited drug (Rf=0.75+/-0.01) from its impurity (Rf=0.23+/-0.01) followed by densitometric measurement of the intact drug spots at 275 nm. The separation was carried on silica gel plates using ethyl acetate : methanol : ammonia 35% (17 : 2 : 1 v/v/v) as a mobile phase. The linearity range was 0.5-10 microg/spot with mean accuracy 99.99+/-1.33%. The third method is accurate and sensitive stability-indicating HPLC method based on separation of lamotrigine from its impurity on a reversed phase C(18) column, using a mobile phase of acetonitrile : methanol : 0.01 M potassium orthophosphate (pH 6.7+/-0.1) (30 : 20 : 50 v/v/v) at ambient temperature 25+/-5 degrees C and UV detection at 275 nm in an overall analysis time of about 6 min., based on peak area. The injection repeatability, intraday and interday repeatability were calculated. The procedure provided a linear response over the concentration range 1-12 microg ml(-1) with mean accuracy of 99.50+/-1.30%. The proposed methods were successfully applied for the determination of lamotrigine in bulk powder, in dosage form and in presence of its impurity. The results obtained were analyzed by ANOVA to assess that no significant difference between each of the three methods and the reported one. The validation was performed according to USP guidelines.     

Tasumatrols P – T,Five New Taxoids from Taxus sumatrana

The phytochemical investigation of the more polar fractions from the leaves and twigs of Taxus sumatrana (Taxaceae) afforded five new taxane diterpene esters, tasumatrols P–T ( 1 – 5 ) possessing an 11(15→1),11(10→9)‐diabeotaxane skeleton. Compounds 1, 4 , and 5 contain an α‐hydroxy group at C(14), while 3 has no OH group at either C(13) or C(14). Compound 2 is a natural 4,5‐acetonide derivative, while 4 has an unusual spiro‐connected 2‐hydroxy‐2‐phenyl‐1,3‐dioxolane ring. Ten known taxoids, were also isolated in the course of the chromatographic fractionation. Five additional new O‐acetyl derivatives 3a, 4a, 4b, 5a , and 5b were prepared from the taxanes 3 – 5 . The structures of all new compounds were established on the basis of their spectroscopic analyses. Compound 1 showed mild cytotoxic activity against human Hela and Daoy tumor cells.     

Four New Briarane Diterpenoids from the Gorgonian Coral Junceella fragilis

Chemical investigation of the gorgonian coral Junceella fragilis, collected by scuba diving in Taiwan, resulted in the isolation of four new briarane‐type diterpenoids, frajunolides A–D ( 1 – 4 ), along with three known briaranes. Their structures were elucidated on the basis of spectroscopic studies, especially 1‐ and 2D‐NMR as well as HR‐MS experiments. The inhibitory effect of all isolated metabolites towards superoxide‐anion generation and elastase release by human neutrophils in response to formylmethionyl‐leucyl‐phenylalanine/dihydrocytochalasin B (FMLP/CB) was evaluated.