Ethanol and aqueous extracts of the different parts of Piper sarmentosum were analysed by HPLC for marker compounds to standardise these extracts. The standardised extracts were investigated for antioxidant activity (beta-carotene linoleate model and DPPH model), anti-TB activity (microplate tetrazolium assay), and estimation of total phenolic and amide contents. The extracts of the different parts exhibited different antioxidant activity, phenolic and amide contents (p < 0.01). The ethanol extracts exhibited better antioxidant activity as compared to the aqueous extracts. The leaf ethanol extract was further investigated for dose response relationship and its EC(50) was found to be 38 microg mL(-1). All the extracts have exhibited anti-TB activity with MIC/MBC 12.5 microg mL(-1). The leaf methanol extract was fractionated and the ethyl acetate fraction exhibited anti-TB activity with MIC/MBC 3.12 microg mL(-1) while MIC/MBC of isoniazid (INH) was found to be 0.5 microg mL(-1). A positive correlation was found between antioxidant activity and total polyphenols, flavonoids and amides, in the beta-carotene linoleate model (p = 0.05) and in the DPPH model (p = 0.01). The analytical method was found to have linearity >0.9922, coefficient of variance <5% and accuracy 95.5 +/- 5 to 96.9 +/- 5. This plant possesses promising antioxidant as well as anti-TB properties.
A capillary electrophoretic (CE) method for the baseline separation of the enantiomers of primaquine diphosphate (PQ) and quinocide (QC) (a major contaminant) in pharmaceutical formulations is proposed. Both components were separated under the following conditions: 50 mm tris phosphate buffer (pH 3.0) containing 15 mm hydroxypropyl-gamma-cyclodextrin (HP-gamma-CD) as background electrolyte; applied voltage, 16 kV; capillary temperature, 25 degrees C; detection wavelength, 254 nm; hydrostatic injection, 10 s. The separations were conducted using a 35 cm length and 50 microm i.d. uncoated fused silica capillary column. Under the optimized conditions, the components were successfully separated in about 5 min. Intraday precision of migration time and corrected peak areas when expressed as relative standard deviation ranged from 0.17 to 0.45 and 2.60 to 3.94%, respectively, while the interday precision ranged from 2.59 to 4.20 and 3.15 to 4.21%, respectively. After the validation exercise, the proposed method was applied for the determination of QC impurity in PQ formulations.
The liquid-phase adsorption of phenol onto coconut shell-based activated carbon, CS850A was investigated for its equilibrium studies and kinetic modeling. Coconut shell was converted into high quality activated carbon through physiochemical activation at 850 degrees C under the influence of CO(2) flow. Beforehand, the coconut shell was carbonized at 700 degrees C and the resulted char was impregnated with KOH at 1:1 weight ratio. In order to evaluate the performance of CS850A, a series of batch adsorption experiments were conducted with initial phenol concentrations ranging from 100 to 500 mg l(-1), adsorbent loading of 0.2g and the adsorption process was maintained at 30+/-1 degrees C. The adsorption isotherms were in conformation to both Langmuir and Freundlich isotherm models. Chemical reaction was found to be a rate-controlling parameter to this phenol-CS850A batch adsorption system due to strong agreement with the pseudo-second-order kinetic model. Adsorption capacity for CS850A was found to be 205.8 mg g(-1).
Seven new indole alkaloids of the Aspidosperma type, jerantinines A-G (1-7), were isolated from a leaf extract of the Malayan Tabernaemontana corymbosa. The structures were established using NMR and MS analysis. Five of the alkaloids isolated and two derivatives (1-5, 8, 9) displayed pronounced in vitro cytotoxicity against human KB cells (IC50 < 1 microg/mL).
Two seco-tabersonine alkaloids, jerantiphyllines A and B, in addition to a tabersonine hydroxyindolenine, jerantinine H, and a recently reported vincamine alkaloid 7, were isolated from the leaf extract of the Malayan Tabernaemontana corymbosa and the structures were established using NMR and MS analysis. Biomimetic conversion of jerantinines A and E to their respective vincamine and 16-epivincamine derivatives were also carried out.
Oligostilbenoids are polyphenols that are widely distributed in nature with multifaceted biological activities. To achieve biomimetic synthesis of unnatural derivatives, we subjected three resveratrol analogues to oligomerization by means of one-electron oxidants. Upon varying the metal oxidant (AgOAc, CuBr(2), FeCl(3)6 H(2)O, FeCl(3)6 H(2)O/NaI, PbO(2), VOF(3)), the solvent (over the whole range of polarities), and the oxygenated substitution pattern of the starting material, stilbenoid oligomers with totally different carbon skeletons were obtained. Here we propose to explain the determinism of the type of skeleton produced with the aid of hard and soft acid/base concepts in conjunction with the solvating properties of the solvents and the preferred alignment by the effect of pi stacking.
The continuous adsorption of lead ions from aqueous solution on commercial, granular, unpretreated palm shell activated carbon (PSAC) was studied. Effect of pH, flow rates and presence of complexing agents (malonic and boric acids) were examined. The breakthrough period was longer at pH 5 indicating higher adsorption capacity of lead ions at higher pH. Increase of the flow rate, expectedly, resulted in the faster saturation of the carbon bed. Presence of complexing agents did not improve adsorption uptake of lead ions. However, presence of malonic acid resulted in smoother pH stabilization of solution compared to single lead and lead with boric acid systems. The results on continuous adsorption of lead were applied to the model proposed by Wang et al. [Y.-H. Wang, S.-H. Lin, R.-S. Juang, Removal of heavy metals ions from aqueous solutions using various low-cost adsorbents, J. Hazard. Mater. B 102 (2003) 291-302]. The agreement between experimental and modelled breakthrough curves was satisfactory at both pHs.
Silica supported iron catalyst was prepared from rice husk ash (RHA) via the sol-gel technique using an aqueous solution of iron(III) salt in 3.0 M HNO3. The sample was dried at 110 degrees C and labeled as RHA-Fe. A sample of RHA-Fe was calcined at 700 degrees C for 5 h and labeled as RHA-Fe700. X-ray diffraction spectrogram showed that both RHA-Fe and RHA-Fe700 were amorphous. The SEM/EDX results showed that the metal was present as agglomerates and the Fe ions were not homogeneously distributed in RHA-Fe but RHA-Fe700 was shown to be homogeneous. The specific surface areas for RHA-Fe and RHA-Fe700 were determined by BET nitrogen adsorption studies and found to be 87.4 and 55.8 m(2) g(-1), respectively. Both catalysts showed high activity in the reaction between toluene and benzyl chloride. The mono-substituted benzyltoluene was the major product and both catalysts yielded more than 92% of the product. The GC showed that both the ortho- and para-substituted monoisomers were present in about equal quantities. The minor products consisting of 16 di-substituted isomers were also observed in the GC-MS spectra of both catalytic products. The catalyst was found to be reusable without loss of activity and with no leaching of the metal.
The process for the production of biodegradable plastic material (polyhydroxyalkanoates, PHAs) from microbial cells by mixed-bacterial cultivation using readily available waste (renewable resources) is the main consideration nowadays. These observations have shown impressive results typically under high carbon fraction, COD/N and COD/P (usually described as nutrient-limiting conditions) and warmest temperature (moderate condition). Therefore, the aim of this work is predominantly to select mixed cultures under high storage responded by cultivation on a substrate - non limited in a single batch reactor with shortest period for feeding and to characterize their storage response by using specific and kinetics determination. In that case, the selected-fixed temperature is 30 degrees C to establish tropical conditions. During the accumulated steady-state period, the cell growth was inhibited by high PHA content within the cells because of the carbon reserve consumption. From the experiments, there is no doubt about the PHA accumulation even at high carbon fraction ratio. Apparently, the best accumulation occurred at carbon fraction, 160 +/- 7.97 g COD/g N (PHAmean, = 44.54% of dried cells). Unfortunately, the highest PHA productivity was achieved at the high carbon fraction, 560 +/- 1.62 g COD/g N (0.152 +/- 0.17 g/l. min). Overall results showed that with high carbon fraction induced to the cultivation, the PO4 and NO3 can remove up to 20% in single cultivation.
Oil palm empty fruit bunch (EFB) fibers were employed to remove dyes from aqueous solutions via adsorption approaches. The EFB fibers were modified using citric acid (CA) and polyethylenimine (PEI) to produce anionic and cationic adsorbents, respectively. The CA modified EFB fibers (CA-EFB) and PEI-modified EFB fibers (PEI-EFB) were used to study the efficiency in removing cationic methylene blue (MB) and anionic phenol red (PR) from aqueous solutions, respectively, at different pHs, temperatures and initial dye concentrations. The adsorption data for MB on the CA-EFB fitted the Langmuir isotherm, while the adsorption of PR on the PEI-EFB fitted the Freundlich isotherm, suggesting a monolayer and heterogeneous adsorption behavior of the adsorption processes, respectively. Both modified fibers can be regenerated up to seven adsorption/desorption cycles while still providing as least 70% of the initial adsorption capacity.
ZnS and CdS nanoparticles were prepared by a simple microwave irradiation method under mild conditions. The obtained nanoparticles were characterized by XRD, TEM and EDX. The results indicated that high purity of nanosized ZnS and CdS was successfully obtained with cubic and hexagonal crystalline structures, respectively. The band gap energies of ZnS and CdS nanoparticles were estimated using UV-visible absorption spectra to be about 4.22 and 2.64 eV, respectively. Photocatalytic degradation of methylene blue was carried out using physical mixtures of ZnS and CdS nanoparticles under a 500-W halogen lamp of visible light irradiation. The residual concentration of methylene blue solution was monitored using UV-visible absorption spectrometry. From the study of the variation in composition of ZnS:CdS, a composition of 1:4 (by weight) was found to be very efficient for degradation of methylene blue. In this case the degradation efficiency of the photocatalyst nanoparticles after 6 h irradiation time was about 73% with a reaction rate of 3.61 × 10-3 min-1. Higher degradation efficiency and reaction rate were achieved by increasing the amount of photocatalyst and initial pH of the solution.
Palm empty fruit bunch ash (EFB-ash) was used as a natural catalyst, rich in potassium to enhance the CO2 gasification reactivity of palm shell char (PS-char). Various EFB-ash loadings (ranging from 0 to 12.5wt.%) were implemented to improve the reactivity of PS-char during CO2 gasification studies using thermogravimetric analysis. The achieved results explored that the highest gasification reactivity was devoted to 10% EFB-ash loaded char. The SEM-EDS and XRD analyses further confirmed the successful loading of EFB-ash on PS-char which contributed to promoting the gasification reactivity of char. Random pore model was applied to determine the kinetic parameters in catalytic gasification of char at various temperatures of 800-900°C. The dependence of char reaction rate on gasification temperature resulted in a straight line in Arrhenius-type plot, from which the activation energy of 158.75kJ/mol was obtained for the catalytic char gasification.
In this study, zinc oxide (ZnO) nanorod arrays were synthesized using a simple hydrothermal reaction on ZnO seeds/n-silicon substrate. Several parameters were studied, including the heat-treatment temperature to produce ZnO seeds, zinc nitrate concentration, pH of hydrothermal reaction solution, and hydrothermal reaction time. The optimum heat-treatment temperature to produce uniform nanosized ZnO seeds was 400°C. The nanorod dimensions depended on the hydrothermal reaction parameters. The optimum hydrothermal reaction parameters to produce blunt tip-like nanorods (770 nm long and 80 nm in top diameter) were 0.1 M zinc nitrate, pH 7, and 4 h of growth duration. Phase analysis studies showed that all ZnO nanorods exhibited a strong (002) peak. Thus, the ZnO nanorods grew in a c-axis preferred orientation. A strong ultraviolet (UV) emission peak was observed for ZnO nanorods grown under optimized parameters with a low, deep-level emission peak, which indicated high optical property and crystallinity of the nanorods. The produced ZnO nanorods were also tested for their UV-sensing properties. All samples responded to UV light but with different sensing characteristics. Such different responses could be attributed to the high surface-to-volume ratio of the nanorods that correlated with the final ZnO nanorods morphology formed at different synthesis parameters. The sample grown using optimum synthesis parameters showed the highest responsivity of 0.024 A/W for UV light at 375 nm under a 3 V bias.
A novel glassy carbon electrode (GCE) modified with a composite film of poly (4-vinylpyridine) (P4VP) and multiwalled carbon nanotubes (P4VP/MWCNT GCE) was used for the voltammetric determination of paracetamol (PCT). This novel electrode displayed a combined effect of P4VP and MWCNT on the electro-oxidation of PCT in a solution of phosphate buffer at pH 7. Hence, conducting properties of P4VP along with the remarkable physical properties of MWCNTs might have combined effects in enhancing the kinetics of PCT oxidation. The P4VP/MWCNT GCE has also demonstrated excellent electrochemical activity toward PCT oxidation compared to that with bare GCE and MWCNT GCE. The anodic peak currents of PCT on the P4VP/MWCNT GCE were about 300 fold higher than that of the non-modified electrodes. By applying differential pulse voltammetry technique under optimized experimental conditions, a good linear ratio of oxidation peak currents and concentrations of PCT over the range of 0.02-450 μM with a limit of detection of 1.69 nM were achieved. This novel electrode was stable for more than 60 days and reproducible responses were obtained at 99% of the initial current of PCT without any influence of physiologically common interferences such as ascorbic acid and uric acid. The application of this electrode to determine PCT in tablets and urine samples was proposed.
A new dibenzotetraaza[14]annulene bearing two 3,3-dimethylindolenine fragments at the meso positions (LH(2)), has been synthesized through a nontemplate method. X-ray crystallography shows that the whole molecule is planar. The basicity of the indolenine ring permits the macrocycle to be protonated external to the core and form LH(4)(2+)·2Cl(-). Yet another structural modification having strong C-H···π interactions was found in the chloroform solvate of LH(2). The latter two modifications are accompanied by a degree of nonplanar distortion. The antiaromatic core of the macrocycle can accommodate a number of metal ions, Mn(III), Fe(III), Co(II), Ni(II) and Cu(II), to form complexes of [Mn(L)Br], [Mn(L)Cl], [Fe(LH(2))Cl(2)](+)·Cl(-), [Co(L)], [Ni(L)], and [Cu(L)]. In addition, the reaction of LH(2) with the larger Pd(II) ion leads to the formation of [Pd(2)(LH(2))(2)(OAc)(4)] wherein the macrocycle acts as a semiflexible ditopic ligand to coordinate pairs of metal ions via its indolenine N atoms into dinuclear metallocycles. The compounds LH(2), [Co(L)], and [Ni(L)] are isostructural and feature close π-stacking as well as linear chain arrangements in the case of the metal complexes. Variable temperature magnetic susceptibility measurements showed thermally induced paramagnetism in [Ni(L)].
The separation of enantiomers is one of the important fields of modern analytical chemistry, especially for agrochemical and pharmaceutical products because the stereochemistry has a significant influence on the biological activities of compounds. Cyclodextrin-modified micellar electrokinetic chromatography (CD-MEKC) has become an important capillary electrophoresis mode for enantioseparations. Here, we describe an example of a CD-MEKC method using hydroxypropyl-γ-cyclodextrin as chiral selector and sodium dodecyl sulfate as micellar solution for enantioseparation of triazole fungicides and the drug econazole.
Fibres from oil palm empty fruit bunches, generated in large quantities by palm oil mills, were processed into self-adhesive carbon grains (SACG). Untreated and KOH-treated SACG were converted without binder into green monolith prior to N2-carbonisation and CO2-activation to produce highly porous binderless carbon monolith electrodes for supercapacitor applications. Characterisation of the pore structure of the electrodes revealed a significant advantage from combining the chemical and physical activation processes. The electrochemical measurements of the supercapacitor cells fabricated using these electrodes, using cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge-discharge techniques consistently found that approximately 3h of activation time, achieved via a multi-step heating profile, produced electrodes with a high surface area of 1704m(2)g(-1) and a total pore volume of 0.889cm(3)g(-1), corresponding to high values for the specific capacitance, specific energy and specific power of 150Fg(-1), 4.297Whkg(-1) and 173Wkg(-1), respectively.
Dapivirine, formerly known as TMC 120, is a poorly-water soluble anti-HIV drug, currently being developed as a vaginal microbicide. The clinical use of this drug has been limited due to its poor solubility. The aim of this study was to design solid dispersion systems of Dapivirine to improve its solubility. Solid dispersions were prepared by solvent and fusion methods. Dapivirine release from the solid dispersion system was determined by conducting in-vitro dissolution studies. The physicochemical characteristics of the drug and its formulation were studied using Differential Scanning Calorimetry (DSC), powder X-ray Diffraction (XRD), Fourier-transform Infrared Spectroscopy (FTIR) and Scanning Electron Microscopy (SEM). A significant improvement in drug dissolution rate was observed with the solid dispersion systems. XRD, SEM and DSC results indicated the transformation of pure Dapivirine which exists in crystalline form into an amorphous form in selected solid dispersion formulations. FTIR and HPLC analysis confirmed the absence of drug-excipient interactions. Solid dispersion systems can be used to improve the dissolution rate of Dapivirine. This improvement could be attributed to the reduction or absence of drug crystallinity, existence of drug particles in an amorphous form and improved wettability of the drug.
The effects of organic solvents and their binary mixture in the glucose functionalization of bacterial poly-3-hydroxyalkanoates catalyzed by Lecitase™ Ultra were studied. Equal volume binary mixture of DMSO and chloroform with moderate polarity was more effective for the enzyme catalyzed synthesis of the carbohydrate polymer at ≈38.2 (±0.8)% reactant conversion as compared to the mono-phasic and other binary solvents studied. The apparent reaction rate constant as a function of medium water activity (aw) was observed to increase with increasing solvent polarity, with optimum aw of 0.2, 0.4 and 0.7 (±0.1) observed in hydrophilic DMSO, binary mixture DMSO:isooctane and hydrophobic isooctane, respectively. Molecular sieve loading between 13 to 15gL(-1) (±0.2) and reaction temperature between 40 to 50°C were found optimal. Functionalized PHA polymer showed potential characteristics and biodegradability.
The application of supercritical fluid chromatography (SFC) coupled with a UV variable-wavelength detector to isolate the minor components (carotenes, vitamin E, sterols, and squalene) in crude palm oil (CPO) and the residual oil from palm-pressed fiber is reported. SFC is a good technique for the isolation and analysis of these compounds from the sources mentioned. The carotenes, vitamin E, sterols, and squalene were isolated in less than 20 min. The individual vitamin E isomers present in palm oil were also isolated into their respective components, alpha-tocopherol, alpha-tocotrienol, gamma-tocopherol, gamma-tocotrienol, and delta-tocotrienol. Calibration of all the minor components of palm as well as the individual components of palm vitamin E was carried out and was found to be comparable to those analyzed by other established analytical methods.