The total synthesis of gambierol

This communication describes the total synthesis of the marine polyether toxin, gambierol. This work couples our iterative C-glycoside/enol ether-olefin metathesis strategy to the subunits with a unique olefin metathesis/carbonyl olefination reaction to bring the subunits together.     

First principle study of adsorption of boron-halogenated system on pristine graphyne

To ensure the possibility of using graphyne as a gas sensor, we have studied the adsorption of boron-halogenated system on pristine graphyne with the help of density functional theory using generalized gradient approximation. Depending on binding energy the most stable orientation, adsorption strength and optimal distance between the above mention molecules and graphyne surface have been determined. The band gap of graphyne slightly increases with the adsorption of the boron-halogenated system. The graphyne system behaves as n-type semiconductor when it interacts with BI₃ and BCl₃ molecules, and it behaves as p-type semiconductor when interaction with BF₃ molecule takes place. Our result reveals that the electronic properties of pristine graphyne are highly influenced by the adsorption of boron-halogenated molecule. We have observed that pristine graphyne has zero electric dipole moment, but with the interaction of boron-halogenated molecule, a significant change in the electric dipole moment takes place. Hence, by measuring the electric dipole moment change, graphyne-based gas sensor can be design for the detection of above-mentioned molecules.     

Development and validation of HPLC method for the resolution of drug intermediates: DL-3-Phenyllactic acid, DL-O-acetyl-3-phenyllactic acid and (+/-)-mexiletine acetamide enantiomers

Sensitive and specific, high-performance liquid chromatography (HPLC) methods have been developed and validated for linearity, accuracy and precision for the quantification of dl-3-phenyllactic acid, dl-O-acetyl-3-phenyllactic acid and (+/-)-mexiletine acetamide enantiomers. Chromatographic separations were performed on a Chiralcel OJ-H column (0.46 mm x 250 mm, 5 microm, Daicel Chemical Industries, Japan) based on cellulose tris-(4-methyl benzoate) chiral stationary phase. The mobile phase consists of hexane and isopropanol (IPA) in the ratio of 90:10 containing 0.1% trifluoroacetic acid (in case of dl-3-phenyllactic acid and dl-O-acetyl-3-phenyllactic acid) and hexane and IPA (95:5) containing 0.1% triethylamine (in case of (+/-)-mexiletine acetamide) and the flow rate was set at 0.5 ml/min at 25 degrees C. The detection was carried out at 261 nm for dl-3-phenyllactic acid and dl-O-acetyl-3-phenyllactic acid and at 254 nm for (+/-)-mexiletine acetamide. The developed methods were utilized for monitoring the progress of lipase catalyzed enantioselective synthesis of O-acetyl-3-phenyllactic acid and mexiletine acetamide from dl-3-phenyllactic acid and (+/-)-mexiletine, respectively.     

LEP constraints on grand unified theories

Recent developments on grand unified theories (GUTs) in the context of the LEP measurements of the coupling constants will be reviewed. The three coupling constants at the electroweak scale have been measured at LEP quite precisely. One can allow these couplings to evolve with energy following the renormalization group equations for the various groups and find out whether all the coupling constants meet at any energy. It was pointed out that the minimalSU (5) grand unified theory fails to satisfy this test. However, various extensions of the theory are still allowed. These extensions include (i) supersymmetricSU (5) GUT, with some arbitrariness in the susy breaking scale arising from the threshold corrections, (ii) non-susySU (5) GUTs with additional fermions as well as Higgs multiplets, which has masses of the order of TeV, and (iii) non-renormalizable effect of gravity with a fine tuned relation among the coupling constants at the unification energy. The LEP results also constrain GUTs with an intermediate symmetry breaking scale. By adjusting the intermediate symmetry breaking scale, one usually can have unification, but these theories get constrained. For example, the left-right symmetric theories coming from GUTs can be broken only at energies higher than about ～ 10¹⁰ GeV. This implies that if right handed gauge bosons are found at energies lower than this scale, then that will rule out the possibility of grand unification. Another recent interesting development on the subject, namely, low energy unification, will be discussed in this context. All the coupling constants are unified at energies of the order of ～ 10⁸ GeV when they are embedded in anSU (15) GUT, with some particular symmetry breaking pattern. But even in this case the results of the intermediate symmetry breaking scale remain unchanged.     

Photochemical activation of a polycarbonate surface for covalent immobilization of a protein ligand

Polycarbonate—a thermostable polymer is activated by a simple and rapid method using a photolinker, 1-fluoro-2-nitro-4-azidobenzene (FNAB) for covalent immobilization of a biomolecule. Horseradish peroxidase (HRP) is used as a model enzyme to check the efficacy of the activated surface. HRP is immobilized on the activated polycarbonate surface without addition of any reagent or catalyst and is found to give 2-2.5-fold increase in absorbance with the substrate as compared to the directly adsorbed enzyme. Photochemical attachment of FNAB to the PC surface is confirmed by X-ray photoelectron spectroscopy (XPS), which shows the presence of nitrogen and fluorine in the ratio of 2:1 in the activated polycarbonate. Disappearance of fluorine peak in the XP spectra of PC bound enzyme further confirms the covalent binding of HRP, through displacement of fluorine moiety of the activated PC by the amino group of the protein. Optimized concentration of the photolinker is found as 6 μmol of FNAB per well and time of photo irradiation is 8 min for activation of a PCR polycarbonate plate. PC bound HRP has shown enhanced thermal and storage stability. Kinetic studies of the immobilized HRP shows improved catalytic activity. The potential application of activated polycarbonate surface includes immobilization of biomolecules for biosensors, immunoassays, and protein and DNA micro-arrays. Due to the stability of the polycarbonate at high temperature, the activated polycarbonate has an advantage for immobilization of thermostable biomolecule such as thermostable enzyme for reaction at elevated temperature.     

A simple and efficient tetradentate Schiff base derived palladium complex for Suzuki–Miyaura reaction in water

A simple and efficient catalytic system based on Pd complex of tetradentate Schiff base ligands is found to be highly active (up to 99% isolated yield) for Suzuki–Miyaura reaction of aryl bromides with arylboronic acids in water at room temperature. Further the scope of this protocol has been extended to the Suzuki–Miyaura cross-coupling reaction of aryl chlorides with arylbronic acids in isopropanol.     

Copper oxide catalyzed domino process for the synthesis of substituted 2H-pyran-2-ones and polyhydroxy coumarin derivatives

An efficient method for the synthesis of substituted 2H-pyran-2-ones and polyhydroxy coumarin derivatives has been developed via CuO-catalyzed C–C bond formation followed by intramolecular cyclization reaction by reacting electron-deficient alkynes with 1,3-diketones and polyhydroxy benzenes, respectively. The domino reaction proceeded smoothly by using commercially available catalysts under reflux in toluene with very good yield.     

New iridoid from aerial parts of Mussaenda roxburghii

A new iridoid, shanzhiol (1), was isolated from the aerial parts of Mussaenda roxburghii. The structure was established by spectroscopic (including 2D NMR) and chemical methods. Shanzhiol (1) showed mild antibacterial activity against both Staphylococcus aureus and Escherichia coli with a MIC of 100 microg/mL by the broth dilution method.     

Generation of 13.9 µm radiation from CO<Subscript>2</Subscript> by cascade lasing or externally applied CO<Subscript>2</Subscript> laser

13.9 μm radiation from the 10⁰0-01¹0 transition can be obtained from a CO₂ laser by saturating the 00⁰1-10⁰0, 10.6 μm transition with an internally generated q-switched pulse or by the application of an external 10.6 μm pulse. Because of Fermi resonance between the symmetric stretch and the bending modes, decay of population from the 10⁰0 level is fast, and such lasers operate at low power and energies. A theoretical model was developed to study such lasers. The results of the calculations indicate that a large-aperture E-beam-sustained discharge is effective for excitation of the cryogenically cooled gain medium, which uses He rich mixture at low pressure. The system is scalable and capable of generating large powers and energies.