Methyltrioctylammonium Chloride as a Separation Solvent for Binary Mixtures: Evaluation Based on Experimental Activity Coefficients

An ammonium based ionic liquid (methyltrioctylammonium chloride) [N8 8 8 1] [Cl] was investigated as an extraction potential solvent for volatile organic solvents (in this regard, solutes), which includes alkenes, alkanes, ketones, alkynes, aromatic hydrocarbons, tetrahydrofuran (THF), alcohols, thiophene, water and acetonitrile based on the experimental activity coefficients at infinite THF measurements were conducted by the use of gas-liquid chromatography at four different temperatures (313.15 to 343.15) K. Experimental data of activity coefficients obtained across the examined temperatures were used in order to calculate the physicochemical properties at infinite dilution such as partial molar excess enthalpy, Gibbs free energy and entropy term. Capacity and selectivity data for selected petrochemical extraction problems (heptane/thiophene, heptane/benzene, cyclohaxane/cyclohexene, hexane/toluene, hexane/hexene) were computed from activity coefficients data and compared to the literature values with other ionic liquids. Evaluation of activity coefficients at infinite dilution expands the knowledge and provides a good understanding related to the interactions between the ionic liquid and the investigated compounds.

Characterization of Penicillin V Acid and Its Related Compounds by HPLC

Background: 'Penicillin V' is a narrow, bactericidal antibiotic of the beta-lactam family of the naturally occurring penicillin group. It is limited to infections due to the germs defined as sensitive. The objective of this work was to identify and to characterize Penicillin V acid and its related compounds by High-performance liquid chromatography (HPLC). Methods: Firstly phenoxymethylpenicillin was identified by an infrared absorption. The organoleptic characteristics, pH, and determination of water content were also studied. The dosage of Penicillin V acid active substance and the determination of its related compounds were carried on waters HPLC, equipped with a UV detector at 254 nm and Discovery HS C18 column (250 mm X 4.6 mm X 5 µm) which is maintained at room temperature. The flow rate was about 1 ml per min. A mixture of water, acetonitrile and acetic acid (65:35:01) was used as mobile phase for phenoxyacetic acid ‘impurity B' and a mixture of water, acetonitrile and acetic acid (650:150:5.75) for the assay and 4-hydroxypenicillin V 'impurity D'. Results: The identification of Penicillin V acid active substance and the evaluation of its chemical quality showed conformity with USP 35th edition. The Penicillin V acid content in the raw material is equal to 1692.22 UI/mg. The percentage content of phenoxyacetic acid and 4-hydroxypenicillin V was respectively: 0.035% and 0.323%. Conclusion: Through these results, we can conclude that the Penicillin V acid active substance tested is of good physicochemical quality.

Development and Validation of a HPLC Method for 6-Gingerol and 6-Shogaol in Joint Pain Relief Gel Containing Ginger (Zingiber officinale)

High Performance Liquid Chromatography (HPLC) method was developed and validated for simultaneous estimation of 6-Gingerol(6G) and 6-Shogaol(6S) in joint pain relief gel containing ginger extract. The chromatographic separation was achieved by using C18 column, 150 x 4.6mm i.d., 5μ Luna, mobile phase containing acetonitrile and water (gradient elution). The flow rate was 1.0 ml/min and the absorbance was monitored at 282 nm. The proposed method was validated in terms of the analytical parameters such as specificity, accuracy, precision, linearity, range, limit of detection (LOD), limit of quantification (LOQ), and determined based on the International Conference on Harmonization (ICH) guidelines. The linearity ranges of 6G and 6S were obtained over 20- 60 and 6-18 μg/ml respectively. Good linearity was observed over the above-mentioned range with linear regression equation Y= 11016x- 23778 for 6G and Y = 19276x-19604 for 6S (x is concentration of analytes in μg/ml and Y is peak area). The value of correlation coefficient was found to be 0.9994 for both markers. The limit of detection (LOD) and limit of quantification (LOQ) for 6G were 0.8567 and 2.8555 μg/ml and for 6S were 0.3672 and 1.2238 μg/ml respectively. The recovery range for 6G and 6S were found to be 91.57 to 102.36 % and 84.73 to 92.85 % for all three spiked levels. The RSD values from repeated extractions for 6G and 6S were 3.43 and 3.09% respectively. The validation of developed method on precision, accuracy, specificity, linearity, and range were also performed with well-accepted results.

Recovery of Acetonitrile from Aqueous Solutions by Extractive Distillation–Effect of Entrainer

The aim of this work was to apply extractive distillation for acetonitrile removal from water solutions, to validate thermodynamic criterion based on excess Gibbs energy to entrainer selection process for acetonitrile – water mixture separation and show its potential efficiency at isothermal conditions as well as at isobaric (conditions of real distillation process), to simulate and analyze an extractive distillation process with chosen entrainers: optimize amount of trays and feeds, entrainer/original mixture and reflux ratios. Equimolar composition of the feed stream was chosen for the process, comparison of the energy consumptions was carried out. Glycerol was suggested as the most energetically and ecologically suitable entrainer.

Development and Validation of a UPLC Method for the Determination of Albendazole Residues on Pharmaceutical Manufacturing Equipment Surfaces

In Pharmaceutical industries, it is very important to remove drug residues from the equipment and areas used. The cleaning procedure must be validated, so special attention must be devoted to the methods used for analysis of trace amounts of drugs. A rapid, sensitive and specific reverse phase ultra performance liquid chromatographic (UPLC) method was developed for the quantitative determination of Albendazole in cleaning validation swab samples. The method was validated using an ACQUITY HSS C18, 50 x 2.1mm, 1.8μ column with a isocratic mobile phase containing a mixture of 1.36g of Potassium dihydrogenphosphate in 1000mL MilliQ water, 2mL of triethylamine and pH adjusted to 2.3 ± 0.05 with ortho-phosphoric acid, Acetonitrile and Methanol (50:40:10 v/v). The flow rate of the mobile phase was 0.5 mL min-1 with a column temperature of 350C and detection wavelength at 254nm using PDA detector. The injection volume was 2µl. Cotton swabs, moisten with acetonitrile were used to remove any residue of drug from stainless steel, teflon, rubber and silicon plates which mimic the production equipment surface and the mean extraction-recovery was found to be 91.8. The selected chromatographic condition was found to effectively elute Albendazole with retention time of 0.67min. The proposed method was found to be linear over the range of 0.2 to 150µg/mL and correlation coefficient obtained is 0.9992. The proposed method was found to be accurate, precise, reproducible and specific and it can also be used for routine quality control analysis of these drugs in biological samples either alone or in combined pharmaceutical dosage forms.

New Simultaneous High Performance Liquid Chromatographic Method for Determination of NSAIDs and Opioid Analgesics in Advanced Drug Delivery Systems and Human Plasma

A new and cost effective RP-HPLC method was developed and validated for simultaneous analysis of non steroidal anti inflammatory dugs Diclofenac sodium (DFS), Flurbiprofen (FLP) and an opioid analgesic Tramadol (TMD) in advanced drug delivery systems (Liposome and Microcapsules), marketed brands and human plasma. Isocratic system was employed for the flow of mobile phase consisting of 10 mM sodium dihydrogen phosphate buffer and acetonitrile in molar ratio of 67: 33 with adjusted pH of 3.2. The stationary phase was hypersil ODS column (C18, 250×4.6 mm i.d., 5 μm) with controlled temperature of 30 C°. DFS in liposomes, microcapsules and marketed drug products was determined in range of 99.76-99.84%. FLP and TMD in microcapsules and brands formulation were 99.78 - 99.94 % and 99.80 - 99.82 %, respectively. Single step liquid-liquid extraction procedure using combination of acetonitrile and trichloroacetic acid (TCA) as protein precipitating agent was employed. The detection limits (at S/N ratio 3) of quality control solutions and plasma samples were 10, 20, and 20 ng/ml for DFS, FLP and TMD, respectively. The Assay was acceptable in linear dynamic range. All other validation parameters were found in limits of FDA and ICH method validation guidelines. The proposed method is sensitive, accurate and precise and could be applicable for routine analysis in pharmaceutical industry as well as in human plasma samples for bioequivalence and pharmacokinetics studies.

Validation and Application of a New Optimized RP-HPLC-Fluorescent Detection Method for Norfloxacin

A new reverse phase-high performance liquid chromatography (RP-HPLC) method with fluorescent detector (FLD) was developed and optimized for Norfloxacin determination in human plasma. Mobile phase specifications, extraction method and excitation and emission wavelengths were varied for optimization. HPLC system contained a reverse phase C18 (5 μm, 4.6 mm×150 mm) column with FLD operated at excitation 330 nm and emission 440 nm. The optimized mobile phase consisted of 14% acetonitrile in buffer solution. The aqueous phase was prepared by mixing 2g of citric acid, 2g sodium acetate and 1 ml of triethylamine in 1 L of Milli-Q water was run at a flow rate of 1.2 mL/min. The standard curve was linear for the range tested (0.156–20 μg/mL) and the coefficient of determination was 0.9978. Aceclofenac sodium was used as internal standard. A detection limit of 0.078 μg/mL was achieved. Run time was set at 10 minutes because retention time of norfloxacin was 0.99 min. which shows the rapidness of this method of analysis. The present assay showed good accuracy, precision and sensitivity for Norfloxacin determination in human plasma with a new internal standard and can be applied pharmacokinetic evaluation of Norfloxacin tablets after oral administration in human.

Development of Molecular Imprinted Polymers (MIPs) for the Selective Removal of Carbamazepine from Aqueous Solution

The occurrence and removal of trace organic contaminants in the aquatic environment has become a focus of environmental concern. For the selective removal of carbamazepine from loaded waters molecularly imprinted polymers (MIPs) were synthesized with carbamazepine as template. Parameters varied were the type of monomer, crosslinker, and porogen, the ratio of starting materials, and the synthesis temperature. Best results were obtained with a template to crosslinker ratio of 1:20, toluene as porogen, and methacrylic acid (MAA) as monomer. MIPs were then capable to recover carbamazepine by 93% from a 10-5 M landfill leachate solution containing also caffeine and salicylic acid. By comparison, carbamazepine recoveries of 75% were achieved using a nonimprinted polymer (NIP) synthesized under the same conditions, but without template. In landfill leachate containing solutions carbamazepine was adsorbed by 93-96% compared with an uptake of 73% by activated carbon. The best solvent for desorption was acetonitrile, with which the amount of solvent necessary and dilution with water was tested. Selected MIPs were tested for their reusability and showed good results for at least five cycles. Adsorption isotherms were prepared with carbamazepine solutions in the concentration range of 0.01 M to 5*10-6 M. The heterogeneity index showed a more homogenous binding site distribution.

High Performance Liquid Chromatographic Method for Determination of Colistin Sulfate and its Application in Medicated Premixand Animal Feed

The aim of the present study was to develop and validate an inexpensive and simple high performance liquid chromatographic (HPLC) method for the determination of colistin sulfate. Separation of colistin sulfate was achieved on a ZORBAX Eclipse XDB-C18 column using UV detection at λ=215 nm. The mobile phase was 30 mM sulfate buffer (pH 2.5):acetonitrile(76:24). An excellent linearity (r2=0.998) was found in the concentration range of 25 - 400 μg/mL. Intra- day and inter-day precisions of method (%RSD, n=3) were less than 7.9%.The developed and validated method was applied to determination of the content of colistin sulfate in medicated premix and animal feed sample.The recovery of colistin from animal feed was satisfactorily ranged from 90.92 to 93.77%. The results demonstrated that the HPLC method developed in this work is appropriate for direct determination of colistin sulfate in commercial medicated premixes and animal feed.

Removal of Chromium from Aqueous Solution using Synthesized Polyaniline in Acetonitrile

Absorptive characteristics of polyaniline synthesized in mixture of water and acetonitrile in 50/50 volume ratio was studied. Synthesized polyaniline in powder shape is used as an adsorbent to remove toxic hexavalent chromium from aqueous solutions. Experiments were conducted in batch mode with different variables such as agitation time, solution pH and initial concentration of hexavalent chromium. Removal mechanism is the combination of surface adsorption and reduction. The equilibrium time for removal of Cr(T) and Cr(VI) was about 2 and 10 minutes respectively. The optimum pH for total chromium removal occurred at pH 7 and maximum hexavalent chromium removal took place under acidic condition at pH 3. Investigating the isothermal characteristics showed that the equilibrium adsorption data fitted both Freundlich-s and Langmuir-s isotherms. The maximum adsorption of chromium was calculated 36.1 mg/g for polyaniline

Pervasiveness of Aflatoxin in Peanuts Growing in the Area of Pothohar, Pakistan

Mycotoxin (aflatoxins) contamination of peanuts is a great concern for human health. A total of 72 samples of unripe, roasted, and salty peanuts were collected randomly from Pothohar plateau of Pakistan for the assessment of aflatoxin. Samples were dried, ground and extracted by acetonitrile (84%). The filtered extracts were cleaned up by MycoSep-226 and analyzed by high performance liquid chromatography with flourescence detector. Quantification limit of Aflatoxin was 1 μg/kg and 70% Recovery was observed in spiked samples in the range 1–10 μg/kg. The screening of mycotoxins indicated that aflatoxins were present in most of the samples being detected in 82%, in concentrations from 14.25 μg/kg to 98.80 μg/kg. Optimal conditions for mycotoxin production and fungal growth are frequently found in the crop fields as well as in store houses. Human exposure of such toxin can be controlled by pointed out such awareness and implemented the regulations.

Effect of Chloroform on Aerobic Biodegradation of Organic Solvents in Pharmaceutical Wastewater

In this study, cometabolic biodegradation of chloroform was experimented with mixed cultures in the presence of various organic solvents like methanol, ethanol, isopropanol, acetone, acetonitrile and toluene as these are predominant discharges in pharmaceutical industries. Toluene and acetone showed higher specific chloroform degradation rate when compared to other compounds. Cometabolic degradation of chloroform was further confirmed by observation of free chloride ions in the medium. An extended Haldane model, incorporating the inhibition due to chloroform and the competitive inhibition between primary substrates, was developed to predict the biodegradation of primary substrates, cometabolic degradation of chloroform and the biomass growth. The proposed model is based on the use of biokinetic parameters obtained from single substrate degradation studies. The model was able to satisfactorily predict the experimental results of ternary and quaternary mixtures. The proposed model can be used for predicting the performance of bioreactors treating discharges from pharmaceutical industries.

Determination of Penicillins Residues in Livestock and Marine Products by LC/MS/MS

Multi-residue analysis method for penicillins was developed and validated in bovine muscle, chicken, milk, and flatfish. Detection was based on liquid chromatography tandem mass spectrometry (LC/MS/MS). The developed method was validated for specificity, precision, recovery, and linearity. The analytes were extracted with 80% acetonitrile and clean-up by a single reversed-phase solid-phase extraction step. Six penicillins presented recoveries higher than 76% with the exception of Amoxicillin (59.7%). Relative standard deviations (RSDs) were not more than 10%. LOQs values ranged from 0.1 and to 4.5 ug/kg. The method was applied to 128 real samples. Benzylpenicillin was detected in 15 samples and Cloxacillin was detected in 7 samples. Oxacillin was detected in 2 samples. But the detected levels were under the MRL levels for penicillins in samples.