The effect of water or salt solution on thin hydrophobic films

Hydrophobic films of polystyrene synthesized in bulk (PS) and by emulsion polymerization in the presence of the cationic surfactant cetyltrimethylammonium bromide (PS-CTAB) or the anionic surfactant sodium dodecyl sulfate (PS-SDS) were characterized by means of ellipsometry, contact angle measurements, and atomic force microscopy. Thin (approximately 65 nm) and thick (approximately 300 nm) films were spin-coated on hydrophilic silicon wafers. PS films presented scarcely tiny holes, while PS-CTAB and PS-SDS films presented holes and protuberances. The former were attributed to dewetting effects and the latter to surfactant clusters. The films were exposed to water or to a 0.1 mol/L NaCl solution for 24 h. Ex situ measurements evidenced strong topographic alterations after the exposure to the fluid. A model based on the diffusion of water (or electrolyte) molecules to the polymer/silcon dioxide interface through holes or defects on the film edges was proposed to explain the appearance of wrinkles and protuberances. In situ ellipsometric measurements were performed and compared with simulations, which considered either a water layer between a polymer and a silcon dioxide layer or an air layer between a polymer and water (medium). In the case of thin PS films, the ellipsometric angles evidenced a very thin (0.5-1.0 nm) air layer between water and the PS films. Upon increasing the PS film thickness, no air layer could be observed by ellipsometry. Regardless of the thickness, the ellipsometric data obtained for PS-CTAB and PS-SDS films did not indicate the presence of an air layer between them and the aqueous media. The dramatic changes in the topography of PS, PS-CTAB, and PS-SDS after immersion in salt solution were explained with proposed models. From a practical point of view, this study is particularly relevant because many hydrophobic polymers are used as substrates for biomedical purposes, where the physiological ionic strength is 0.15 mol/L NaCl.     

Hypervirial analysis of enclosed quantum mechanical systems. IV. Further comments

New formal results regarding the hypervirial analysis of enclosed systems are given. Novel applications are presented and several previous equations are reformulated in a more appropriate form.     

Vibrational study of the metal-adsorbate interaction of phenylacetic acid and alpha-phenylglycine on silver surfaces

Raman and SERS spectra of phenylacetic acid and alpha-phenylglycine on silver sols have been recorded at several concentrations and pH values. The alpha-phenylglycine has been also studied in D(2)O. The respective vibrational assignments have been proposed and the analysis of the SERS spectra has made it possible to conclude that phenylacetic acid links to the metal through its carboxylate group only, while alpha-phenylglycine links also through its amino group. In both cases the aromatic ring seems to be almost perpendicular to the metal surface. On the other hand, the contribution of the charge transfer (CT) mechanism to the enhancement of the SERS spectra has been calculated as well and it is found to be very important in both molecules. The band most enhanced by this mechanism is that of vibration 8a, mainly in alpha-phenylglycine.     

Fluorimetric determination of aflatoxins by flow-injection analysis

Summary A fast and inexpensive fluorimetric method for the determination of total aflatoxins (B₁, B₂, G₁, and G₂) in food of use in screening numerous samples suspectedly containing these substances is proposed. The sensitivity of the method (determination range between 0.5 and 200.0 ng ml^–1) allows these analytes to be detected at concentrations well below legal limits; hence, separation-detection techniques such as HPLC need only be used with samples in which these compounds are found to occur. The method has been applied to maize, peanut and tapioca samples, obtaining average recoveries of 100.9 with deviations of ±5% with respect to 100% recovery.

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Fluorometrische Bestimmung von Aflatoxinen durch Fließinjektionsanalyse

     

Synthesis and pharmacological evaluation of new 16-methyl pregnane derivatives

The pharmacological activity of several new pregnane derivatives 15-19 were determined on gonadectomized male hamster flank organs, seminal vesicles and in vitro conversion of testosterone (T) to dihydrotestosterone (DHT) as 5alpha-reductase inhibitors. Steroids 15-19 decreased the diameter of the pigmented spot in the flank organs as compared to the T treated animals; in this model, steroids 16 and 19 showed a higher activity than the commercially available finasteride 3. Injection of T increased the weight of the seminal vesicles. Compounds 15-19 when injected together with T decreased the weight of the seminal vesicles thus showing an antiandrogenic effect. The trienone 19 exhibited a considerably higher activity than finasteride. Steroids 15-19 inhibited the in vitro metabolism of [3H]T to [3H]DHT in seminal vesicles homogenates of gonadectomized male hamsters. Compounds 18 and 19 showed a much higher antiandrogenic effect than finasteride. This enhancement of the biological activity could probably be attributed to the coplanarity of the steroidal skeleton as previously observed by our group. The high antiandrogenic activity of the epoxy compound 16 is probably the result of the ring opening of the oxiran ring with the nucleophilic part of the enzyme 5alpha-reductase thus leading to a stable adduct with concomitant deactivation of this enzyme.     

Electrochemical Synthesis and Characterization of Nickel(II) Complexes with N‐2‐Pyridyl‐sulfonamide Ligands

Heteroleptic nickel(II) complexes [NiL₂L′] of a series of monoanionic and potentially bidentate N‐2‐pyridyl‐sulfonamide ligands [HL] and 2,2′‐bipyridine or 1,10‐Phenanthroline (L′) have been prepared by electrochemical oxidation of a nickel anode in an acetonitrile solution of the ligands. The complexes have been characterized by microanalysis, IR and electronic spectroscopy, magnetic measurements and LSI mass spectrometry. The crystal structure of [Ni(Ms6mepy)₂(bipy)] has been determined by x‐ray diffraction and shows the metal in an octahedral NiN₆ environment. Octahedral structures are also proposed for the other complexes with the N‐2‐pyridyl‐sulfonamide ligands acting as N,N′ or N, O bidentate systems, depending on the position of the methyl substituent on the pyridine ring.     

Möbius aromaticity in [12]annulene: cis-trans isomerization via twist-coupled bond shifting

Density functional and coupled cluster calculations show that facile thermal configuration change in [12]annulene occurs via a twist-coupled bond-shifting mechanism. The transition state for this process is highly aromatic with M?bius topology. At the CCSD(T)/cc-pVDZ//BH&HLYP/6-311+G** level, the isomerization of tri-trans-[12]annulene 1a (CTCTCT) to its di-trans isomer 2 (CCCTCT) via such a mechanism has a barrier of 18.0 kcal/mol, in good agreement with earlier experiments. Two other aromatic M?bius bond-shifting transition states were located that result in configuration change for other [12]annulene conformers. This mechanism contrasts sharply with diradical configuration change for acyclic polyenes and with planar bond-shifting mechanisms generally assumed for annulenes. This constitutes evidence that neutral M?bius aromatic annulenes play a role in the dynamic processes of neutral [4n]annulenes.     

New versatile route to the synthesis of tetrahydro-beta-carbolines and tetrahydro-pyrano[3,4-b]indoles via an intramolecular Michael addition catalyzed by InBr3

A simple multistep synthetic strategy to 4-substituted 1,2,3,4-tetrahydro-beta-carboline and 1,3,4,9-tetrahydro-pyrano[3,4-b]indole derivatives starting from commercially available indole 2-carboxylic acid (5) is described. The final intramolecular Michael addition promoted by catalytic amount of InBr(3) (5-10 mol %) provided the expected polycyclic compounds in excellent yields (up to 97%) both in anhydrous organic and aqueous media.     

Coordination de la phosphine organo-fer [CpFeIIC6Me5CH2PPh2]+ au RhI et proprietes spectroscopiques,electrochimiques et catalytiques des complexes heterobinucleaires FeII-RhI

The reactions between the phosphine-organoiron [CpFe^II-η⁶-C₆Me₅CH₂PPh₂]⁺ PF₆^? (1) and [RhCl(η⁴-diolefin)(μ-Cl)]₂ in CH₂Cl₂ at reflux give the new heterobinuclear air-stable crystalline complexes [CpFe^II-η⁶-C₆Me₅CH₂)P(Ph)₂Rh(η⁴-diene)Cl]PF₆,(D'*-diene=cyclooctadiene (COD): 65%, 2; trimethylfluorobenzobicyclo[2.2.2]octadiene (Me₃TFB): 48%, 3). Complexes 2 and 3 have been studied by ¹H, ¹³C and ³¹P NMR spectroscopy and they are carbonylated (CO, 1 atm). Cyclic voltammetry experiments with addition of MeOH show electron transfer Fe^IRh^I → Fe^IIRh⁰, the presence of a catalytic wave Fe^I/Fe^II and the possible formation of Rh hydrides. Under normal conditions 2 is a catalyst for hydrogenation of cyclohexene, but it is less efficient than the known mononuclear Rh¹ analogues.     

Twistor holomorphic Lagrangian surfaces in the complex projective and hyperbolic planes

We completely classify all the twistor holomorphic Lagrangian immersions in the complex projective plane ², i.e. those Lagrangian immersions such that their twistor lifts to the twistor space over ² are holomorphic. This classification provides a one-parameter family of examples of Lagrangian spheres in ².Research partially supported by a DGICYT grant No. PB91-0731.