Methods and approaches for determination and enantioseparation of (RS)‐propranolol

Propranolol, a β‐adrenergic receptor antagonist, is a chiral compound that is marketed as a racemate, but only the (S)‐(?)‐enantiomer is responsible for the β‐adrenoceptor blocking activity. Different chromatographic methods have been applied for separation and determination of enantiomers of (RS)‐propranolol. In this article a review is presented on different liquid chromatographic methods used for enantioseparation of (RS)‐propranolol, using both HPLC and TLC. In addition, some aspects of enantioseparation under achiral phases of liquid chromatography have been briefly mentioned.     

A novel approach for enantioseparation as applied to (RS)‐etodolac from pharmaceutical formulations: LC MS and density functional theory support for confirmation of diastereomers so separated

In the present studies formation of diastereomers of (RS)‐etodolac was confirmed using LC‐MS when [M + H]⁺ or [M]⁺ were recorded for the diastereomers. The lowest energy optimized structures of two diastereomers were drawn, which confirmed the three‐dimensional geometry of the diastereomers. This supports the optimized analytical separation conditions. In addition, separation of diastereomers was successful using a C₁₈ column and a binary mixture of methanol and triethyl ammonium phosphate buffer of pH 4.5 (80:20, v/v) as mobile phase at a flow rate of 1 mL min^?1 and UV detection at 223 nm. The separation method was validated as per International Conference on Harmonization guidelines. (RS)‐Etodolac was isolated from commercial tablets and purified and characterized to be used as racemic standard. Three pairs of diastereomers were synthesized using enantiomerically pure amines, namely, (R)‐(+)‐α‐methyl benzyl amine, (S)‐(?)‐α,4‐dimethylbenzylamine and (R)‐(?)‐1‐cyclohexylethylamine. Derivatization reactions were carried out under conditions of stirring at room temperature (30 °C for 2 h) as well as under microwave irradiation (MWI), and the two types of diastereomers were compared. Reaction conditions for derivatization were optimized with respect to mole ratio of chiral derivatizing agent and (RS)‐etodolac and MWI time. No racemization was observed throughout the study. Copyright © 2015 John Wiley & Sons, Ltd.     

$$E^{2} SR^{2}$$ E 2 S R 2 : An acknowledgement-based mobile sink routing protocol with rechargeable sensors for wireless sensor networks

Wireless Networks - The advances in hardware manufacturing technologies and wireless communications enabled the evolution of tiny, multi-functional, low-power and resource constrained sensor nodes...     

Hybrid area exploration–based mobility‐assisted localization with sectored antenna in wireless sensor networks

In common practice, sensor nodes are randomly deployed in wireless sensor network (WSN); hence, location information of sensor node is crucial in WSN applications. Localization of sensor nodes performed using a fast area exploration mechanism facilitates precise location‐based sensing and communication. In the proposed localization scheme, the mobile anchor (MA) nodes integrated with localization and directional antenna modules are employed to assist in localizing the static nodes. The use of directional antennas evades trilateration or multilateration techniques for localizing static nodes thereby resulting in lower communication and computational overhead. To facilitate faster area coverage, in this paper, we propose a hybrid of max‐gain and cost‐utility–based frontier (HMF) area exploration method for MA node's mobility. The simulations for the proposed HMF area exploration–based localization scheme are carried out in the Cooja simulator. The paper also proposes additional enhancements to the Cooja simulator to provide directional and sectored antenna support. This additional support allows the user with the flexibility to feed radiation pattern of any antenna obtained either from simulated data of the antenna design simulator, ie, high frequency structure simulator (HFSS) or measured data of the vector network analyzer (VNA). The simulation results show that the proposed localization scheme exhibits minimal delay, energy consumption, and communication overhead compared with other area exploration–based localization schemes. The proof of concept for the proposed localization scheme is implemented using Berkeley motes and customized MA nodes mounted with indigenously designed radio frequency (RF) switch feed network and sectored antenna.     

Separation and identification of enzymatically prepared dephosphorylated products of myo‐inositolhexakisphosphate using LC‐MS

LC‐MS technique described here is a new way for the separation and direct determination of UV–Vis insensitive inositol phosphates (InsP₂‐InsP₆). This circumvents the need of radioisotopic labeling and post‐column derivatization techniques. The method involves separation of various enzymatically dephosphorylated derivatives of InsP₆ on C₁₈‐column using MeOH/H₂O (30:70 v/v) and their identification using electron spray ionization MS in positive ion mode (+pESI‐MS). The LC‐MS studies revealed that the purified phytase from Aspergillus niger van Teighem hydrolyzes InsP₆ in a sequential manner leading to InsP₂ (InsP₂·2Na, t_R 4.4–4.54 min, base peak m/z 382.9) as the end product.     

Microwave-assisted synthesis of near-infrared fluorescent sphingosine derivatives

Microwave-assisted synthesis of near-infrared fluorescent sphingosine derivatives is described, and the utility of the probes demonstrated by co-localization studies with visible wavelength fluorescent sphingosine derivatives.     

Direct enantiomeric TLC resolution of dl-penicillamine using (R)-mandelic acid and l-tartaric acid as chiral impregnating reagents and as chiral mobile phase additive

DL-Penicillamine has been resolved into its enantiomers by normal-phase TLC using L-tartaric acid as chiral impregnating reagent as well as chiral mobile phase additive, while (R)-mandelic acid has been found to be successful as a chiral impregnating reagent. The solvent system acetonitrile-methanol-water (5:1:1, v/v) was found to be successful when L-tartaric acid was used as impregnating agent while the solvent combination acetonitrile-methanol-(0.5% l-tartaric acid in water, pH 5)-glacial acetic acid (7:1:1.1:0.7, v/v) was successful as mobile phase as it contained L-tartaric acid as the chiral additive. (R)-mandelic acid was successful as chiral impregnating reagent with ethyl acetate-methanol-water (3:1:1, v/v), as the mobile phase. The effects of concentration of chiral selectors, temperature and pH were examined on enantiomeric resolution. The spots were detected with iodine vapors and the detection limits were found to be 0.12 microg for each enantiomer of penicillamine with L-tartaric acid, under both the conditions, and 0.11 microg with (R)-mandelic acid.     

Synthesis of succinimidyl-(S)-naproxen ester and its application for indirect enantioresolution of penicillamine by reversed-phase high-performance liquid chromatography

Synthesis of N-succinimidyl-(S)-2-(6-methoxynaphth-2-yl) propionate was carried out by the reaction of (S)-naproxen with N-hydroxysuccinimide in the presence of dicyclohexyl carbodiimide. It was characterized and was used as a chiral derivatizing reagent, under mild conditions, to form diastereomers of dl-penicillamine which were resolved by reversed-phase high-performance liquid chromatography using triethyl ammonium phosphate buffer (pH 4.0, 5mM)-acetonitrile (linear gradient (30min) of acetonitrile from 30 to 70%). Excellent separation was achieved with gradient mobile phase. The detection limit was at pmol level.     

Photosynthetic,Biochemical and Secondary Metabolite Changes in a Medicinal Plant Chlorophytum borivillianum (Safed musli) against Low and High Doses of UV-B Radiation

Plants are inevitably grown in presence of sunlight, therefore bound to be exposed to natural UV-B radiation. Several studies have already been conducted with UV-B and medicinal plants and only few studies showed dose dependent variation. The present study aims to find out the variations and adaptation in Chlorophytum borivillianum under two different doses of UV-B radiation; ambient + low (3.2 kJm⁻² d⁻¹) and high (7.2 kJm⁻² d⁻¹) UV-B dose, denoted as LD and HD, respectively. Reduction in photosynthetic rate was higher at HD, while plants receiving LD displayed nonsignificant variation. During vegetative and reproductive stage, significant reduction (P ≤ 0.001) in stomatal conductance was obtained when exposed to HD-eUV-B. F_v/F_m showed more reductions in HD-eUV-B (12.6%) followed by LD-eUV-B (7.9%). Low and high doses of UV-B enhanced the anthocyanin content but the increase was significant in HD, indicates epidermal protection strategy by the plants. Under LD-eUV-B, the content of saponin, a major phytochemical constituent was enhanced by 26%. Phytochemical analysis of roots revealed reduction mostly in fatty acid components whereas the steroidal components (stigmasterol and sarsasapogenin) showed enhancement in response to LD. The study suggests the importance of LD-eUV-B in the stimulation of medicinal compounds in C. borivillianum.     

Direct TLC Resolution of (±)-Ketamine and (±)-Lisinopril by Use of (+)-Tartaric Acid or (−)-Mandelic Acid as Impregnating Reagents or Mobile Phase Additives. Isolation of the Enantiomers

Direct resolution of the enantiomers of the racemic drugs ketamine and lisinopril has been achieved by TLC. Enantiomerically pure tartaric acid and mandelic acid were used as chiral impregnating reagents and as mobile phase additives. When (?)-mandelic acid was used as chiral impregnating reagent use of ethyl acetate–methanol–water 3:1:1 (v/v) as mobile phase enabled successful resolution of the enantiomers of both compounds. For lisinopril, the mobile phase acetonitrile–methanol–water–dichloromethane 7:1:1:0.5 (v/v) was successful when (+)-tartaric acid was used as impregnating agent. When (+)-tartaric acid was used as mobile phase additive the mobile phase acetonitrile–methanol–(+)-tartaric acid (0.5% in water, pH 5)–glacial acetic acid 7:1:1.1:0.7 (v/v) enabled successful resolution of the enantiomers of lisinopril. The effects on resolution of temperature, pH, and the amount of chiral selector were also studied. The separated enantiomers were isolated and identified. Spots were detected with iodine vapour. LODs were 0.25 and 0.27 μg for each enantiomer of ketamine with (+)-tartaric acid and (?)-mandelic acid, respectively, whereas for lisinopril LODs were 0.14 and 0.16 μg for each enantiomer with (+)-tartaric acid (both conditions) and (?)-mandelic acid, respectively.