UVB-induced photodamage to phycobilisomes of Synechococcus sp. PCC 7942

The effect of UVB irradiation on the phycobilisomes (PBSs) of Synechococcus sp. PCC 7942 cells was studied. The sucrose density-gradient-isolated PBSs from in vivo UVB-treated (280–320 nm) cells showed a strong decrease in β-phycocyanin (βPC) and -phycocyanin (PC) polypeptides. In addition to a decrease in the linker polypeptides LCM 75 (linker connecting the core to the thylakoid membranes), LR 33 (linker in the rod structure), LRC 31.5 (linker connecting the rod to the core) and LRC 29. In vitro UVB treatment of gradient-isolated intact PBSs for 1 h had no effect on any of the constituent polypeptides, and only after 2 h was a degradation of LCM 75 and LR 33 and a decrease in βPC evident. Further investigation of phycobiliproteins (4 h of UVB irradiation) using polyclonal antibody directed against purified whole PBSs revealed that, in vivo, there was a gradual decline in the levels of LCM 75, LR 33, LRC 31.5, LRC 29, βPC and PC.     

Label Free Colorimetric Biosensing Using Nanoparticles

In this review article, we discuss a class of biosensors that exploit the change in the colorimetric properties of noble metal nanoparticles in response to biomolecular binding at their surface. Several sensor fabrication techniques as well as sensor configurations are discussed with an emphasis on their strengths and limitations. We conclude by presenting the future prospects and challenges for the successful transition of this technology from the laboratory to a commercial product.     

Using path sampling to build better Markovian state models: predicting the folding rate and mechanism of a tryptophan zipper beta hairpin

We propose an efficient method for the prediction of protein folding rate constants and mechanisms. We use molecular dynamics simulation data to build Markovian state models (MSMs), discrete representations of the pathways sampled. Using these MSMs, we can quickly calculate the folding probability (P(fold)) and mean first passage time of all the sampled points. In addition, we provide techniques for evaluating these values under perturbed conditions without expensive recomputations. To demonstrate this method on a challenging system, we apply these techniques to a two-dimensional model energy landscape and the folding of a tryptophan zipper beta hairpin.     

Comparing the structural topology of integral and peripheral membrane proteins utilizing electron paramagnetic resonance spectroscopy

The alignment of membrane proteins provides pertinent structural and dynamic information. Structural topology data gleaned from such studies can be used to determine the functional mechanisms associated with a wide variety of integral membrane proteins. In this communication, we successfully demonstrate, for the first time, the determination of the structural topology and helical tilt of an antimicrobial peptide magainin 2 using aligned X-band spin-label EPR spectroscopic techniques. This novel comparison unlocks many possibilities utilizing EPR spectroscopy to probe antimicrobial peptide topologies with increased sensitivity and may also give further clues to elucidate their corresponding mechanisms.     

Liquid-Phase and Solventless Oxidation of Cyclohexane,Benzene, and Other Hydrocarbons by Cerium(IV) Catalyzed by Iridium(III) in Acidic Medium

Oxidation of some hydrocarbons dissolved in acetic acid by cerium(IV) sulphate at 100 °C in the presence of traces of iridium(III) chloride (catalyst-substrate 1:56818 to 151515) in the solution phase resulted in good to excellent yields of corresponding carbonyl compounds. In the cases of cyclohexane and benzene, 44% and 51.8% yields of corresponding carbonyl compounds were obtained, whereas in other cases, yield ranged from 34.9 to 99.8%. Yield decreased when reactions were performed in a microwave oven by adsorbing reactants (except acetic acid) on alumina. Decrease in the yield was probably due to the high temperature generated during the course of the reaction, resulting in the loss of organics from evaporation. Conditions were optimized for the highest yields under ambient conditions.     

Simultaneous quantification of centchroman and its 7-demethylated metabolite in rat dried blood spot samples using LC-MS/MS

An approach has been developed for the quantitative determination of concentrations of centchroman ( I), a nonsteroidal once‐a‐week oral contraceptive, and its major metabolite (7‐desmethyl centchroman, II) using dried blood spots (DBS) on paper, rather than conventional plasma samples. The assay employed simple solvent extraction of the DBS sample circle (6 mm) requiring small blood volumes (30 μL) followed by reversed‐phase HPLC separation, combined with multiple reaction monitoring mass spectrometric detection. The calibration plot in matrix using d ‐trans‐hydroxy chroman as internal standard (IS) was linear (r² = 0.998) over ranges of 1.5–240 and 4.5–720 ng/mL for I and II, respectively. The recoveries of both I and II were always >60% with quantification limits (signal‐to‐noise ratio = 10) of 1.5 and 4.5 ng/mL for I and II, respectively. The intra‐day and inter‐day precision (%RSD) and accuracy (%bias) variations in blood spots for both I and II were better than 13%. Moreover, both I and II were stable in DBS for at least 3 months when stored at room temperature. The developed method was successfully applied to the pharmacokinetic interaction study after oral administration of centchroman with and without co‐administration of carbamazepine in female Sprague–Dawley rats using serial sampling and results were comparable with the plasma concentrations reported earlier. Copyright © 2011 John Wiley & Sons, Ltd.     

Oxidations with IBX: benzyl halides to carbonyl compounds, and the one-pot conversion of olefins to 1,2-diketones

A variety of benzyl halides were converted to the corresponding aldehydes/ketones in respectable yields by IBX in DMSO at 65 °C. The bromohydrin reaction of olefins using NBS-H₂O in DMSO can be nicely adapted to IBX-mediated oxidation of benzyl halides in such a way that olefins are converted to the corresponding 1,2-diketones in good isolated yields in one-pot.     

Allylpalladium (II) complexes with dichalcogenoimidodiphosphinate ligands: Synthesis, structure, spectroscopy and their transformation into palladium chalcogenides

The synthesis, characterization and thermal behavior of new monomeric allylpalladium (II) complexes with dichalcogenoamidodiphosphinate anions are reported. The complexes [R = H, R′ = Prⁱ, E = S (1a); R = H, R′ = Prⁱ, E = Se (1b); R = H, R′ = Ph, E = S (1c); R = H, R′ = Ph, E = Se (1d); R = Me, R′ = Prⁱ, E = S (2a); R = Me, R′ = Prⁱ, E = Se (2b); R = Me, R′ = Ph, E = S (2c); R = Me, R′ = Ph, E = Se (2d)] have been prepared by room temperature reaction of [Pd(η³-CH₂C(R)CH₂)(acac)] (acac = acetylacetonate) with dichalcogenoimidodiphosphinic acids in acetonitrile solution. The complexes have been characterized by multinuclear NMR (¹H, ¹³C{¹H}, ³¹P{¹H}, ⁷⁷Se{¹H}), FT-IR and elemental analyses. The crystal structures of complexes 1a, 1d and 2d have been reported and they consist of a six-membered PdE₂P₂N ring (E = S for 1a and Se for 1d and 2d) and an allyl group, C₃H₄R(R = H for 1a and 1d and Me for 2d). Thermogravimetric studies have been carried out for few representative complexes. The complexes thermally decompose in argon atmosphere to leave a residue of palladium chalcogenides, which have been characterized by PXRD, SEM and EDS.     

Cycloadditions of 1H-1,3-Benzazaphospholes with o-Chloranil

NH-Functional 1H-1,3-benzazaphospholes 1a–1c and o-chloranil (tetrachloro-o-benzoquinone - TCBQ) undergo rapid [1+4]-cycloaddition in a 1:2 molar ratio to give 2a – 2c as high-melting zwitterionic σ⁶λ⁵-phosphorus compounds. In the case of 2a the yield is high (rel. to TCBQ) even if the reactants were used in a 1:0.5 molar ratio. For the 2-tert-butyl-substituted compounds 2b and 2c the yields were significantly lower, in part by unidentified byproducts. Addition of excess TCBQ to crude 2c containing unconverted 1c did not increase but strongly decrease the amount of 2c . Crystallization and XRD analysis led to detection of a minor side or consecutive product 3c , formally corresponding to P=C bond cleavage and [1+4] cycloaddition of three equivalents TCBQ, two at the phosphinidene and one at the carbene end. NMR spectroscopic data of 2a – 2c including conclusive ¹³C data for 2a give evidence of the structures of the new compounds.