A catalytic homo-Nazarov cyclization protocol for the synthesis of heteroaromatic ring-fused cyclohexanones

A general protocol for the catalytic homo-Nazarov cyclization of cyclopropyl heteroaryl ketones has been developed, which employs indium triflate as the promoter. A range of heteroaromatic ring-fused cyclohexanones was synthesized in 56-91% yield using this protocol. An example of a tandem cyclopropanation/homo-Nazarov cyclization is also reported in which the one-pot yield is greater than the overall yield of the two individual steps.     

Simultaneous separation and identification of limonoids from citrus using liquid chromatography-collision-induced dissociation mass spectra

Limonoids are considered as potential cancer chemopreventive agents and are widely distributed in the Citrus genus as aglycones and glucosides. In the present study, reversed-phase HPLC coupled with CID mass spectra was developed for the simultaneous separation and identification of aglycones and glucosides of limonoids from citrus. Five aglycones such as limonin, deacetyl nomilin, ichangin, isolimonoic acid and nomilin were identified by positive ion CID MS/MS, whereas five glucosides, viz. limonin glucoside, isoobacunoic acid glucoside, obacunone glucoside, deacetyl nomilinic acid glucoside and nomilinic acid glucoside were analyzed by negative ion CID mass spectra. The developed method was successfully applied to complex citrus samples for the separation and identification of aglycones and glucosides. Citrus seeds were extracted with methanol and partially purified and analyzed by LC-CID mass spectra. The separation was achieved by C-18 column; eight limonoids were identified by comparing the retention times and mass spectral fragmentation. To the best of our knowledge, this is the first report on the identification of citrus limonoids using CID technique.     

Xanthate based radical cascade toward multicomponent formation of pyrrolopyrimidines

A short sequential synthesis of pyrrolidino- pyridines and pyrimidines illustrates the potential of combining Ugi-Smiles couplings with radical tin-free processes.     

Site specific interaction between ZnO nanoparticles and tryptophan: a first principles quantum mechanical study

First principles density functional theory calculations are performed on tryptophan-ZnO nanoparticles complex in order to study site specific interactions between tryptophan and ZnO. The calculated results find the salt bridge structure involving the -COOH group and ZnO cluster to be energetically more favorable than other interacting sites, such as indole and amine groups in tryptophan. The interaction between tryptophan and ZnO appears to be mediated by both ionic and hydrogen bonds. The calculated molecular orbital energy levels and charge distributions suggest non-radiative energy transfer from an excited state of tryptophan to states associated with ZnO, which may lead to a reduction in the emission intensity assigned to the π-π* transition of the indole functional group of tryptophan.     

Synthesis, structure and efficient electroluminescence of a heteroleptic dipyridylamido/bis(pyridylphenyl)iridium(III) complex

A neutral 2,2'-dipyridylamido (dpa)-supported bis(cyclometalated) iridium(III) complex [Ir(ppy)(2)(dpa)] (ppy = o-(2-pyridyl)phenyl) has been synthesized and structurally characterized for the first time, which emits green electroluminescence with high current efficiency (123.5 cd A(-1)) and high power efficiency (43.2 lm W(-1)).     

Indirect identification of continuous-time delay systems from step responses

In this paper, an indirect identification scheme is proposed for identifying the parameters of the continuous-time first-order plus time delay (FOPTD) model and the second-order plus time delay (SOPTD) model from step responses. Unlike the existing direct identification scheme, which identifies the parameters of the continuous-time FOPTD and SOPTD models directly from the continuous-time step response data, the proposed indirect scheme is to pre-identify discrete-time FOPTD and SOPTD models from the discretized continuous-time step response input–output data, then convert the obtained discrete-time models to the desirable continuous-time models. The proposed method is then extended to identify the afore-mentioned models from the step responses of the systems contaminated with input noise and constant output disturbance. The proposed simple alternative method exhibits good estimation performances in both the time domain and the frequency domain. Illustrative examples are presented to demonstrate the effectiveness of the proposed scheme.     

An integer linear programming-based heuristic for scheduling heterogeneous,part-time service employees

Scheduling of heterogeneous, part-time, service employees with limited availability is especially challenging because employees have different availability and skills, and work different total work hours in a planning period, e.g., a week. The constraints typically are to meet employee requirements during each hour in a planning period with shifts which have a minimum & maximum length, and do not exceed 5 work days per week for each employee. The objectives typically are to minimize over staffing and to meet the target total work hours for each employee during the planning period. We decompose this problem into (a) determining good shifts and then (b) assigning the good shifts to employees, and use a set of small integer linear programs to solve each part. We apply this method to the data given in a reference paper and compare our results. Also, several random problems are generated and solved to verify the robustness of our solution method.     

Optimization of two-dimensional gas chromatography time-of-flight mass spectrometry for separation and estimation of the residues of 160 pesticides and 25 persistent organic pollutants in grape and wine

Two-dimensional gas chromatography (GC × GC) coupled with time-of-flight mass spectrometric (TOFMS) method was optimized for simultaneous analysis of 160 pesticides, 12 dioxin-like polychlorinated biphenyls (PCBs), 12 polyaromatic hydrocarbons (PAHs) and bisphenol A in grape and wine. GC × GC–TOFMS could separate all the 185 analytes within 38 min with >85% NIST library-based mass spectral confirmations. The matrix effect quantified as the ratio of the slope of matrix-matched to solvent calibrations was within 0.5–1.5 for most analytes. LOQ of most of the analytes was ≤10 μg/L with nine exceptions having LOQs of 12.5–25 μg/L. Recoveries ranged between 70 and 120% with <20% expanded uncertainties for 151 and 148 compounds in grape and wine, respectively, with intra-laboratory Horwitz ratio <0.2 for all analytes. The method was evaluated in the incurred grape samples where residues of cypermethrin, permethrin, chlorpyriphos, metalaxyl and etophenprox were detected at below MRL.