Response Surface Methodology for Spectrophotometric Determination of Two ß-Adrenergic Agonists-Terbium Chemosensors in Urine and Pharmaceutical Dosage Forms.

BACKGROUND: According to literature reports, none of the previous methods of analysis had touched the multivariate approach for the quantification of significant factors affecting the interaction of dobutamine or hexoprenaline with Terbium. OBJECTIVE: Two novel ß-adrenergic agonists-lanthanide chemosensors were prepared for the determination of dobutamine and hexoprenaline in their pure and pharmaceutical dosage forms and in urine samples. Fabrication of the two chemosensors was based on their ligand-metal interaction with the lanthanide Terbium. METHODS: A Plackett-Burman Design (PBD) was selected for the screening of four main variables (reaction time, metal volume, pH, and temperature). Applying Response Surface Methodology (RSM), a Central Composite Design (CCD) was executed for the optimization of the significant factors with narrower upper and lower limits. Spectrophotometric technique was exploited for the analysis of the two chemosensors. RESULTS: Maximum absorption was obtained at 299 and 298 nm for dobutamine-terbium and hexoprenaline-terbium complexes, respectively. Only factors that were found to bear significant effects on the formed complexes were promoted to the optimization level. Model verification was carried out, where target results coincided with those at the predicted levels, indicating the efficiency of the two proposed models. Validation of the proposed was implemented and linear ranges were found to be 3.30-13.50 and 1.90-10.00 µg/mL, for dobutamine and hexoprenaline, respectively. CONCLUSIONS: Recovery and relative standard deviation values by application in pure powder, pharmaceutical dosage forms and spiked urine samples indicated high accuracy and reproducibility. Wide-ranging linear values and comparatively low detection limits inferred the effectiveness of the proposed method. HIGHLIGHTS: RSM for optimization of spectrophotometric determination of dobutamine and hexoprenaline ß-adrenergic agonists-lanthanide chemosensors; PBD was used for screening and CCD for optimization of variables affecting the spectrophotometric method; Determination of dobutamine and hexoprenaline in pure powder, pharmaceutical dosage form, and spiked urine samples was accomplished after method validation.

Two new sponge species (Demospongiae: Chalinidae and Suberitidae) isolated from hyperarid mangroves of Qatar with notes on their potential antibacterial bioactivity.

This study presents the taxonomic description of two new sponge species that are intimately associated with the hyperarid mangrove ecosystem of Qatar. The study includes a preliminary evaluation of the sponges' potential bioactivity against pathogens. Chalinula qatari sp. nov. is a fragile thinly encrusting sponge with a vivid maroon colour in life, often with oscular chimneys and commonly recorded on pneumatophores in the intertidal and shallow subtidal zone. Suberites luna sp. nov. is a massive globular-lobate sponge with a greenish-black colour externally and a yellowish orange colour internally, recorded on pneumatophores in the shallow subtidal zone, with large specimens near the seagrass ecosystem that surrounds the mangrove. For both species, a drug extraction protocol and an antibacterial experiment was performed. The extract of Suberites luna sp. nov. was found to be bioactive against recognized pathogens such as Staphylococcus epidermidis, Staphylococcus aureus and Enterococcus faecalis, but no bioactive activity was recorded for Chalinula qatari sp. nov. This study highlights the importance of increasing bioprospecting effort in hyperarid conditions and the importance of combining bioprospecting with taxonomic studies for the identification of novel marine drugs.

Design and optimization of a luminescent Samarium complex of isoprenaline: A chemometric approach based on Factorial design and Box-Behnken response surface methodology.

A chemometrically optimized procedure has been developed for the determination of isoprenaline (ISO) in the parent substance as well as in its respective pharmaceutical preparation. It is worth mentioning that although spectroscopic determination of Isoprenaline metal complexes has been described in literature, yet, no methods for the quantification of Isoprenaline with Samarium nor any other lanthanide metal have been reported. Fractional factorial design (FFD) was implemented in the initial screening procedure of the four designated factors, namely, reaction time (RT), metal volume (MV), pH and temperature (T) followed by Response Surface Methodology (RSM) optimization tool performed by the aid of Box Behnken design (BBD).The proposed techniques are based on a multivariate approach where a complexation reaction between Isoprenaline (ISO) and Samarium III (Sm3+) metal was exploited for the first time to synthesize novel fluorescence and absorbance probes of ISO-Sm. Maximum fluorescence intensity (Y1) as well as maximum absorbance (Y2) of the produced complex were attained at λex/λem = 315/450 and λ 295 nm for spectrofluorimetric and spectrophotometric determinations, respectively, against blank solutions. Using assessment quality tools such as, Pareto charts, normal probability plots and statistical analysis of variance testing (ANOVA), significant factors were successfully indicated (p < 0.05). Furthermore, the proposed methods verified specificity and accuracy for the determination of Isoprenaline in its pure and pharmaceutical preparation using spectrofluorimetric (Technique A) and spectrophotometric (Technique B) techniques, respectively. Linearity was obtained in the range of (0.02-0.50 µg/mL) and (2-12 µg/mL) upon employing both techniques A and B, respectively. Furthermore, limit of detection (LOD) and limit of quantification (LOQ), were found to be 5.1877 ∗ 10-3 µg/mL, 0.01572 µg/mL and 0.5593 µg/mL, 1.6949 µg/mL, upon employing techniques A and B, respectively. Standard addition method was applied for both techniques. The analysis was successfully applied to the assay of pure powder and pharmaceutical dosage forms after which the corresponding mean recoveries were computed and were found to be in the range of 99.546%-100.257% (Technique A) and 99.872%-99.887% (Technique B) with RSD (<1).

Screening and optimization of samarium-assisted complexation for the determination of norfloxacin, levofloxacin and lomefloxacin in their corresponding dosage forms employing spectrofluorimetry.

Multivariate strategy was applied for setting a fluorescent technique for the determination of three fluoroquinolones: norfloxacin (NOR), levofloxacin (LEV) and lomefloxacin (LOM) in their pure powder and dosage forms. Based on their known interaction with lanthanides, and augmented fluorescence intensity obtained by antenna effect at λex/λem = 314/553, 312/553 and 310/556 for NOR, LEV and LOM, respectively, the current research was scrutinized. Four continuous factors were selected for study in the screening step by means of Plackett-Burman Design, where temperature factor was excluded for being non-significant and the other factors as volume of metal ion solution, pH and reaction time were evaluated through Central Composite Design. 3-D surfaces demonstrations and 2-D contour plots designated the factors interactions followed by optimization plots, which defined the best blend for factors conjunction. pH factor was the chief motor force affecting the response as the number of coordinated ligands formed depends on the pH, whereas 1:2 complex is the main species at higher pH values followed by the volume of metal ion solution and ended by little effect of the reaction time. Model verification was monitored, which showed the model superiority for the three fluoroquinolones, where all target points tested were in good agreement with the predicted ones. The linear range for the tested drugs were found to be 0.090-1.280 µg/mL for NOR, 0.068-1.448 µg/mL for LEV and 0.077-1.552 µg/mL in case of LOM, thus approving the suitability of this method for Quality Control testing. Furthermore, applying these conditions to test the fluoroquinolones in their pharmaceuticals was done as well as intra and inter-day effects as to confirm the validity of this technique for routine analysis. Recovery % and RSD were found to be 99.958 ±â€¯0.797, 99.887 ±â€¯0.935 and 100.427 ±â€¯0.698 for NOR, LEV and LOM respectively in their pure powder. While it was calculated to be 100.200 ±â€¯0.785, 100.530 ±â€¯0.396 and 100.620 ±â€¯0.896 for NOR, LEV and LOM in their corresponding dosage forms. This excellent precision and accuracy obtained in results impulse it to be one of the most appropriate methods for further analysis.

Substituted 2-Aminobenzothiazoles Salicylidenes Synthesis and Characterization as Cyanide Sensors in Aqueous Medium.

(E)-2-((benzo[d]thiazol-2-ylimino)methyl)-4-nitrophenol 1 and (E)-2-(((6-methoxybenzo[d]thiazol-2-yl)imino)methyl)-4-nitrophenol 2 were synthesized efficiently under microwave conditions. The structures were confirmed using IR, ¹H NMR, and 13C NMR. UV-vis. Fluorescence investigations demonstrated that 1 and 2 are sensitive and selective sensors for detection of cyanide over all other anions SCN−, AcO−, N3−, H2PO4−, H2AsO4−, F−, Cl−, Br−, and I− in aqueous media. Cyanide induces colorimetric change from pale yellow to dark yellow and from transparent to pale yellow for 1 and 2, respectively. It enhances the absorption at wavelengths 385 nm and 425 nm of 1 and 385 nm and 435 nm of 2. Acidic anions H2PO4− and H2AsO4− displayed significant interference with the interaction of cyanide and sensors 1 and 2. Sensor 1 has lower detection limit (LDL) 1 × 10−6 M, while 2 has LDL 1.35 × 10−6 M.

Plackett-Burman and Box-Behnken designs as chemometric tools for micro-determination of l-Ornithine.

Plackett-Burman (PB) and Box-Behnken (BB) screening and response surface factorial designs were used to evaluate spectrophotometric and spectrofluorimetric approaches for the determination of l-Ornithine (ORN) as per se and in dietary supplements. Both approaches were based on the derivatization of the primary amino group of ORN via Hantzsch condensation reaction producing yellow coloured adducts (dihydrolutidine derivative). The reaction product was determined spectrophotometrically (method A) at λmax=327nm and spectrofluorimetrically (method B) at 480nm (λem) after excitation at 325nm (λex). A multivariate scheme was tailored to investigate the process numerical variables; reaction temperature, heating time, reagent volume, and pH implementing PB as a screening design followed by BB as an optimization strategy. Categorical factors including diluting solvent and sequence of addition were kept invariable. Responses of the reaction systems were the maximum absorbance (Y1) and maximum fluorescence intensity (Y2), correspondingly. Quality tools as well as ANOVA testing, before and after response transformation were used to decide upon the substantial variables. Following the optimization of reaction variables using desirability plots, calibration graphs were found to be rectilinear in the range of 6-14µg/mL and 0.4-1.2µg/mL for methods A and B, respectively. Both methods proved to be sensitive with detection limits (DL) of 337 and 85ng/mL, and quantitation limits (QL) of 1086 and 283ng/mL, for methods A and B, respectively. An interference study was performed using potential foreign species. No significant interference effect was observed on any of the proposed procedures. System performance was addressed following ICH guidelines and considering parameters such as linearity, detection and quantification limits, accuracy and precision, robustness and specificity.