CdSe and CdSe/CdS nanorod solids

We demonstrate the self-organization of CdSe nanorods into nematic, smectic, and crystalline solids. Layered colloidal crystals of CdSe nanorods grow by slow destabilization of a nanocrystal solution upon allowing the diffusion of a nonsolvent into the colloidal solution of nanocrystals. The colloidal crystals of nanorods show characteristic birefringence, which we assign to specific spherulite-like texture of each nanorod assembly. To demonstrate the general character of nanorod self-assembly technique, CdSe/CdS heterostructure nanorods were organized into highly luminescent superlattices.     

Synthesis of 3-hexahelicenol and its transformation to 3-hexahelicenylamines,diphenylphosphine, methyl carboxylate,and dimethylthiocarbamate

A nonphotochemical synthetic route to 3-hexahelicenol is reported. It involves a key [2+2+2] cycloisomerization of CH(3)O-substituted triyne that is readily available from 1-methoxy-3-methylbenzene and 1-bromo-2-(bromomethyl)naphthalene. Further functional group transformations led to 3-CO(2)CH(3), 3-NH(2), 3-PPh(2), and 3-SC(O)N(CH(3))(2) substituted hexahelicenes.     

Azadepsipeptides: synthesis and evaluation of a novel class of peptidomimetics

A general route to azadepsipeptides, a new class of pseudopeptides, has been established. The methodology was applied to the synthesis of a bis-aza analogue of the antiparasitic cyclooctadepsipeptide PF1022A. Comparison of the X-ray crystal structures of natural PF1022A (8) and the chimeric aza analogue 9 revealed that the introduction of nitrogen in the backbone of PF1022A results in almost complete conservation of the 3D structure with only minor deviations at the new nitrogen positions.     

High resolution electrospray and electrospray tandem mass spectra of rotenone and its isoxazoline cycloadducts

An evaluation of the gas-phase ion chemistry of rotenone (1) by electrospray ionisation (ESI) mass spectrometry (MS) and tandem mass spectrometry (MS2) is presented, aiming at providing tools for its determination in natural and biological matrices. The behaviour of its cycloadducts with benzonitrile-N-oxide (2) and 2,4,6-trimethylbenzonitrile-N-oxide (3) was also evaluated and the MS data thus obtained have provided evidence into the mechanism of formation of the key product ion at m/z 192 which can be considered a marker in the MS and MS2 spectra of rotenone and its derivatives.     

A New Family of Nonstoichiometric Layered Rare-Earth Tin Antimonides, RESn(x)()Sb(2) (RE = La, Ce, Pr, Nd, Sm): Crystal Structure of LaSn(0.75)Sb(2)

A new class of nonstoichiometric layered ternary rare-earth tin antimonides, RESn(x)()Sb(2) (RE = La, Ce, Pr, Nd, Sm), has been synthesized through reaction of the elements at 950 degrees C. In the lanthanum series LaSn(x)()Sb(2), tin can be incorporated from a maximum content of x approximately 0.7 or 0.8 to as low as x approximately 0.10. The structure of lanthanum tin diantimonide with the maximum tin content, LaSn(0.75)Sb(2), has been determined by single-crystal X-ray diffraction methods. It crystallizes in the orthorhombic space group -Cmcm with a = 4.2425(5) ?, b = 23.121(2) ?, c = 4.5053(6) ?, and Z = 4. The isostructural rare-earth analogues were characterized by powder X-ray diffraction. The structure of LaSn(0.75)Sb(2) comprises layers of composition "LaSb(2)" in which La atoms are coordinated by Sb atoms in a square-antiprismatic geometry. Between these layers reside chains of Sn atoms distributed over three crystallographically independent sites, each partially occupied at about 20%. The structure of LaSn(0.75)Sb(2) can be regarded as resulting from the excision of RE-Sb and Sb-Sb bonds in the related structures of binary rare-earth diantimonides, RESb(2), and then intercalation of Sn atoms between layers.     

Structure-activity study of intact porcine motilin

Biologically important sites on intact porcine motilin (pMTL) were explored using its partial peptides. The partial peptides were synthesized using Fmoc (9-fluorenylmethyloxycarbonyl) solid phase methodology, and tested for the binding activity to motilin receptor and the smooth muscle contractile activity. The results were as follows: important residues for the contractile activity were found to be Phe1, Ile4, and Tyr7, and an open space existed beyond the N-terminus between motilin and its receptor. On the model of interaction between motilin and motilin receptor evolved from these results, the three points of interaction, due to Phe1, Ile4, and Tyr7, and the presence of an open space were expected. The motilin agonist and antagonist, designed on this model, will help the inquiry into motilin associated diseases.     

pH-Metric determination of acid numbers in petroleum oils without titration

A new pH-metric method without titration has been developed for determination of acid numbers lower than 0.1 mg (KOH) g(-1) (oil) in petroleum oils such as White, Transformer and Basic oils. The method is based on rapid and complete extraction of acids from an oil test portion into the novel reagent and measurement of the conditional pH in the ;oil-reagent' mixture by a glass electrode. The method has a quantitation limit equal to 1x10(-3) mg (KOH) g(-1) (oil), uses non-toxic reagents, is not time and labor consuming, and is cheap and simple for automation.     

Spectrophotometric determination of the stability constants of HgCl(-)3 and HgCl(2-)4 in aqueous ethanol

The stability constants of HgCl(-)(3) and HgCl(2-)(4) in 60% aqueous ethanol (v/v) were determined by spectroscopy at 25 degrees and constant ionic strength and acidity; beta(1) was 3 +/- 1 and beta(2) 9 +/-3.     

Protective effects of cyanidin-3-O-beta-glucopyranoside against UVA-induced oxidative stress in human keratinocytes

Ultraviolet-A (UVA) radiation causes significant oxidative stress because it leads to the generation of reactive oxygen species (ROS), leading to extensive cellular damage and eventual cell death either by apoptosis or necrosis. We evaluated the protective effects of cyanidin-3-O-beta-glucopyranoside (C-3-G) against UVA-induced apoptosis and DNA fragmentation in a human keratinocyte cell line (HaCaT). Treatment of HaCaT cells with C-3-G before UVA irradiation inhibited the formation of apoptotic cells (61%) and DNA fragmentation (54%). We also investigated antioxidant properties of C-3-G in HaCaT cells against ROS formation at apoptotic doses of UVA; C-3-G inhibited hydrogen peroxide (H2O2) release (an indicator of cellular ROS formation) after UVA irradiation. Further confirmation of the potential of C-3-G to counteract UVA-induced ROS formation comes from our demonstration of its ability to enhance the resistance of HaCaT cells to the apoptotic effects of both H2O2 and the superoxide anion (O2*-), two ROS involved in UVA-oxidative stress. Furthermore, in terms of Trolox Equivalent Antioxidant Activity, C-3-G treatment led to a greater increase in antioxidant activity in the membrane-enriched fraction than in the cytosol (55% vs 19%). The protective effects against UVA-induced ROS formation can be attributed to the higher membrane levels of C-3-G incorporation. These encouraging in vitro results support further research into C-3-G (and other anthocyanins) as novel agents for skin photoprotection.     

Novel RPLC stationary phases for lipophilicity measurement: solvatochromic analysis of retention mechanisms for neutral and basic compounds

An RPLC was developed to rapidly determine lipophilicity of neutral and basic compounds using three base deactivated RPLC stationary phases particularly designed for the analysis of basic compounds, namely, Supelcosil ABZ(+)Plus, Discovery RP Amide C16, and Zorbax Extend C18. The work consisted of three sets of experiments. In the first log kw values of neutral compounds were extrapolated using hydroorganic mobile phases at different compositions. Good correlation between log kw and log Poct indicated that the method was appropriate for these supports, without adding a silanol masking agent. In the second set of experiments, isocratic log k values of neutral and basic compounds were measured with three different mobile phases. The best estimation of lipophilicity was obtained for neutral and basic compounds when the secondary interactions were strongly reduced (i. e., when basic compounds were under their neutral form). In the third set of experiments, isocratic retention factors of basic compounds (in their neutral form) were measured with a high-pH mobile phase, on a chemically stable support (Zorbax Extend C18). Under these chromatographic conditions, correlation between the isocratic retention factors and log Poct (log D10.5) for basic compounds was similar to that for neutral compounds.