An Efficient Synthesis of [(Tosylamino)alkyl]naphthalenols by Nucleophilic Addition of Naphthalen‐2‐ol with N‐Tosyl Imines Using Boron Trifluoride Etherate as Catalyst

[(Tosylamino)alkyl]naphthalenols have efficiently been synthesized by nucleophilic addition of naphthalen‐2‐ol with N‐tosyl imines (derived from both aromatic and aliphatic aldehydes) in the presence of BF₃?OEt₂ as a catalyst at room temperature. The products are formed within 5–9 h in high yields (72–91%).     

HPLC-FLD for the simultaneous determination of primary and secondary amino acids from complex biological sample by pre-column derivatization

A rapid, sensitive, and reproducible pre-column derivatisation procedure has been established for the simultaneous determination of 20 amino acids by high-performance liquid chromatography using fluorescence detection. The amino acids were derivatized using o-phthalaldehyde and 9-fluorenylmethyl-chloroformate reagents. The optimal conditions for simultaneous separation and detection of both primary and secondary amino acids were investigated. The developed method has several advantages, namely automated pre-column derivatization, short analysis time with optimal separation, a simple and economical mobile phase, high level of precision for peak area and retention time, and higher sensitivity with more reliability of peak identification. The biological media development is the key parameter for macromolecule drug discovery. Biological media amino acids in three consecutive discovery batches were determined and the results showed a good agreement with hypothetical value. The method appears suitable for application to measure biological media amino acids at various stages of macromolecule drug discovery.     

Geometry and quadratic nonlinearity of charge transfer complexes in solution: a theoretical study

In this paper, we have computed the quadratic nonlinear optical (NLO) properties of a class of weak charge transfer (CT) complexes. These weak complexes are formed when the methyl substituted benzenes (donors) are added to strong acceptors like chloranil (CHL) or di-chloro-di-cyano benzoquinone (DDQ) in chloroform or in dichloromethane. The formation of such complexes is manifested by the presence of a broad absorption maximum in the visible range of the spectrum where neither the donor nor the acceptor absorbs. The appearance of this visible band is due to CT interactions, which result in strong NLO responses. We have employed the semiempirical intermediate neglect of differential overlap (INDO∕S) Hamiltonian to calculate the energy levels of these CT complexes using single and double configuration interaction (SDCI). The solvent effects are taken into account by using the self-consistent reaction field (SCRF) scheme. The geometry of the complex is obtained by exploring different relative molecular geometries by rotating the acceptor with respect to the fixed donor about three different axes. The theoretical geometry that best fits the experimental energy gaps, β(HRS) and macroscopic depolarization ratios is taken to be the most probable geometry of the complex. Our studies show that the most probable geometry of these complexes in solution is the parallel displaced structure with a significant twist in some cases.     

Total synthesis of (+)-erogorgiaene using lithiation-borylation methodology, and stereoselective synthesis of each of its diastereoisomers

A short (8 steps) synthesis of (+)-erogorgiaene in 44% overall yield from p-methylacetophenone is described. Key steps include lithiation/borylation-protodeboronation to build up the molecule and control the stereochemistry at C1 and C4. The C11 stereochemistry was similarly set up by using lithiation/borylation methodology. The use of a mixed, unhindered borane in the lithiation/borylation reaction proved critical to success in the reaction of the tetralone-derived carbamate to control the C4 stereochemistry. The power of the reagent controlled methodology is illustrated in the stereocontrolled synthesis of all of the diastereomers of (+)-erogorgiaene.     

Synthesis of glycosylthiols and reactivity studies

The acid-catalyzed reaction of 1,2-anhydro-3,4,6-tri-O-benzyl-α-d-glucopyranose (7) as glycosyl donor with bis-trimethylsilyl sulfide as acceptor affords the α-thiol. Hence, this sterically hindered S-nucleophile as acceptor should provide with O-glycosyl trichloroacetimidates as glycosyl donors that have nonparticipating groups at C-2, glycosylthiols with the thiol group in axial position. This was confirmed for various donors (4, 16-19) with the exception of the corresponding mannosyl donor (20). However, powerful participating groups at C-2 of the donor (23-28) governed the anomeric selectivity.     

Synthesis of α-glycosyl thiols by stereospecific ring-opening of 1,6-anhydrosugars

Treatment of 1,6-anhydrosugars with commercially available bis(trimethylsilyl) sulfide in the presence of trimethylsilyl triflate led to the formation of α-glycosyl thiols. All the reactions were highly stereoselective and afforded the α-glycosyl thiols in good to excellent yields. By this procedure, a variety of 1,6-anhydrosugars, differing in their sugar units, glycosidic linkages, and protecting group pattern, were converted smoothly into the corresponding α-glycosyl thiols, which could be of great utility in thioglycoside chemistry. It is noteworthy that 1,6-anhydrosugars carrying the 2-O-acyl group and 1,6-anhydrosugar-containing oligosaccharides could also be ring-opened stereospecifically under the same conditions to give rise to the corresponding 1-thiosugars in high yields. Thus, a very concise and efficient access to α-glycosyl thiols of great value was established.     

Relative performance of a vibratory energy harvester in mono- and bi-stable potentials

Motivated by the need for broadband vibratory energy harvesting, many research studies have recently proposed energy harvesters with nonlinear characteristics. Based on the shape of their potential function, such devices are classified as either mono- or bi-stable energy harvesters. This paper aims to investigate the relative performance of these two classes under similar excitations and electric loading conditions. To achieve this goal, an energy harvester consisting of a clamped-clamped piezoelectric beam bi-morph is considered. The shape of the harvester's potential function is altered by applying a static compressive axial load at one end of the beam. This permits operation in the mono-stable (pre-buckling) and bi-stable (post-buckling) configurations. For the purpose of performance comparison, the axial load is used to tune the harvester's oscillation frequencies around the static equilibria such that they have equal values in the mono- and bi-stable configurations. The harvester is subjected to harmonic base excitations of different magnitudes and a slowly varying frequency spanning a wide band around the tuned oscillation frequency. The output voltage measured across a purely resistive load is compared over the frequency range considered. Two cases are discussed; the first compares the performance when the bi-stable harvester has deep potential wells, while the second treats a bi-stable harvester with shallow wells. Both numerical and experimental results demonstrate the essential role that the potential shape plays in conjunction with the base acceleration to determine whether the bi-stable harvester can outperform the mono-stable one and for what range of frequencies. Results also illustrate that, for a bi-stable harvester with shallow potential wells, super-harmonic resonances can activate the inter-well dynamics even for a small base acceleration, thereby producing large voltages in the low frequency range.     

Wigner distribution of elliptical quantum optical vortex

We calculate the Wigner quasiprobability distribution function of the quantum elliptical vortex in elliptical beam (EEV), produced by coupling squeezed coherent states of two modes. The coupling between the two modes is performed by using beam splitter (BS) or a dual channel directional coupler (DCDC). The quantum interference due to the coupling between the two modes promises the generation of controlled entanglement for quantum computation and quantum tomography.     

Streamer-Like Electrical Discharges in Water: Part I. Fundamental Mechanisms

Electrical discharge plasma formed in liquid water is under intensive investigation for many possible applications in biomedical, environmental and chemical engineering as well as for general scientific issues in plasma chemistry and other engineering applications. The subject of pulsed breakdown of water has additionally begun to assume importance due to growing interest in decontamination, purification of water containing chemical impurities and industrial sludge, and also in the emerging area of bio-electrics. This review paper focuses on the plasma physics (Part I) and chemistry of electrical discharges in liquid water and the chemical effects of plasmas on the degradation of organic molecules (Part II). This part discusses dielectric liquid breakdown and its mechanisms, streamer propagation and the effect of electrode polarity on streamer dynamics.     

ALOHA: a novel probability fusion approach for scoring multi-parameter drug-likeness during the lead optimization stage of drug discovery

Automated lead optimization helper application (ALOHA) is a novel fitness scoring approach for small molecule lead optimization. ALOHA employs a series of generalized Bayesian models trained from public and proprietary pharmacokinetic, absorption, distribution, metabolism, and excretion, and toxicology data to determine regions of chemical space that are likely to have excellent drug-like properties. The input to ALOHA is a list of molecules, and the output is a set of individual probabilities as well as an overall probability that each of the molecules will pass a panel of user selected assays. In addition to providing a summary of how and when to apply ALOHA, this paper will discuss the validation of ALOHA’s Bayesian models and probability fusion approach. Most notably, ALOHA is demonstrated to discriminate between members of the same chemical series with strong statistical significance, suggesting that ALOHA can be used effectively to select compound candidates for synthesis and progression at the lead optimization stage of drug discovery.