Wetting kinetics of oil mixtures on fluorinated model cellulose surfaces

The wetting of two different model cellulose surfaces has been studied; a regenerated cellulose (RG) surface prepared by spin-coating, and a novel multilayer film of poly(ethyleneimine) and a carboxymethylated microfibrillated cellulose (MFC). The cellulose films were characterized in detail using atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). AFM indicates smooth and continuous films on a nanometer scale and the RMS roughness of the RG cellulose and MFC surfaces was determined to be 3 and 6 nm, respectively. The cellulose films were modified by coating with various amounts of an anionic fluorosurfactant, perfluorooctadecanoic acid, or covalently modified with pentadecafluorooctanyl chloride. The fluorinated cellulose films were used to follow the spreading mechanisms of three different oil mixtures. The viscosity and surface tension of the oils were found to be essential parameters governing the spreading kinetics on these surfaces. XPS and dispersive surface energy measurements were made on the cellulose films coated with perfluorooctadecanoic acid. A strong correlation was found between the surface concentration of fluorine, the dispersive surface energy and the contact angle of castor oil on the surface. A dispersive surface energy less than 18 mN/m was required in order for the cellulose surface to be non-wetting (theta e>90 degrees ) by castor oil.     

Use of absorbent materials in on-line coupled reversed-phase liquid chromatography-gas chromatography via the through oven transfer adsorption desorption interface

The use of absorbents as retaining materials in the through oven transfer adsorption desorption interface (TOTAD) of an on-line coupled reversed-phase liquid chromatography-gas chromatography system (RPLC-GC) is proposed for the first time. A comparative study of an adsorbent (Tenax TA) and two absorbents, namely polydimethylsiloxane and poly(50% phenyl/50% methylsiloxane) is performed to establish the best experimental conditions for the automated and simultaneous determination of 15 organophosphorus and organochlorine pesticide residues in olive oil. The proposed method provides satisfactory repeatability (RSDs lower, in general, than 8.5%) and sensitivity (limits of detection ranging from 0.6 to 81.9 microg/L) for the investigated compounds.     

Insight into the mechanism of diazocompounds transformation catalyzed by hetero cuboidal clusters [Mo3CuQ4(MeBPE)3X4]+, (Q = S,Se; X = Cl,Br): The catalytically active species

Two enantiomerically pure trinuclear compounds of formula (P)-[Mo₃S₄{(R,R)-Me–BPE}₃Br₃]Br and (P)-[Mo₃Se₄{(R,R)-Me–BPE}₃Cl₃]Cl, (P)-1b.Br and (P)-1c.Cl, respectively, have been synthesized in a good yield and a stereospecific manner by excision of polymeric [Mo₃Q₇X₄]_n (Q = S or Se, X = Cl or Br) phases with (R,R)-Me–BPE{1,2-bis[(2R,5R)-2,5-(dimethylphospholan-1-yl)]ethane}. They have been transformed into chiral hetereo cuboidal compounds [Mo₃S₄{(R,R)-Me–BPE}₃Br₃]PF₆, (P)-2b.PF₆, and [Mo₃Se₄{(R,R)-Me–BPE}₃Cl₃]PF₆, (P)-2c.PF₆, by reaction with copper salts. All these compounds have been characterized by ³¹P NMR, IR, UV–Vis, mass spectrometry, elemental analysis, and chiral dichroism. The catalytic potential of tetranuclear cuboidal compounds has been assessed in the paradigm intermolecular cyclopropanation reaction of styrene with ethyl diazoacetate. Results are compared with those obtained for the analogue [Mo₃S₄{(R,R)-Me–BPE}₃Cl₃]PF₆, (P)-2a.PF₆. The catalytic data demonstrate that the Se derivative (P)-2c.PF₆ is less reactive than the S analogues, but it leads to a similar product distribution as the sulfide analogue (P)-2a.PF₆. By contrast, exchange of chlorine by the bulky bromine gives rise to a catalyst which makes the carbene dimerization more competitive. These data agree with temporal breaking of one of the Cu–Q bonds to generate an active catalytic species.     

Slow Movements of Bio-Inspired Limbs

Slow and accurate finger and limb movements are essential to daily activities, but the underlying mechanics is relatively unexplored. Here, we develop a mathematical framework to examine slow movements of tendon-driven limbs that are produced by modulating the tendons’ stiffness parameters. Slow limb movements are driftless in the sense that movement stops when actuations stop. We demonstrate, in the context of a planar tendon-driven system representing a finger, that the control of stiffness suffices to produce stable and accurate limb postures and quasi-static (slow) transitions among them. We prove, however, that stable postures are achievable only when tendons are pretensioned, i.e., they cannot become slack. Our results further indicate that a non-smoothness in slow movements arises because the precision with which individual stiffnesses need to be altered changes substantially throughout the limb’s motion.     

UV-induced reduction of Ag<Superscript>+</Superscript> by diazene sulphonates: new method of metallisation of surfaces

The metallisation of surfaces would be technologically very simple if it were possible to use the properties of the substances that decompose upon UV irradiation and produce species with a strong redox potential. In this work, diazene sulphonates are presented as possible reducing agents for Ag⁺ in aqueous solutions and in thin solid layers. The photo-formation of Ag^m+_n clusters in the presence of diazene sulphonates in solutions was investigated via UV-VIS spectroscopy. Significant differences were observed in the electrical properties of surfaces after photo reduction; these occurred without any additional reducing agent.     

Alkyl glycosides as potential anti-<Emphasis Type="Italic">Candida albicans</Emphasis> growth agents

Candida infections are becoming increasingly prevalent and many clinical isolates are resistant to common azole derivatives treatment. Accordingly, the capacity of a series of 19 alkyl glycosides, mainly mannosides and glucosides but also a cellobioside with aglycone chain-length from C-6 to C-20, to inhibit the growth of laboratory and clinically isolated strains of Candida albicans, was investigated. The study showed that only glycosides with the C-10 and C-12 aglycones were effective growth inhibitors of both types of Candida, strains, whose metabolic activity was also significantly reduced as revealed by an XTT assay.     

Diazene sulphonate as a cross-linking agent for polymers with pendant triarylamine hole-conducting units

Diazene sulphonates are readily available compounds which are soluble in water and polar solvents. They strongly absorb the UV-VIS light and they decompose under UV irradiation via radical or ionic intermediates. These properties render them valuable, e.g. for analytical purposes and for photo-printing. In this presentation, it will be demonstrated that polymers with a pendant diazene sulphonate function as cross-linking agents and with pendant aromatic amines as hole-transporters can be considered as useful materials for organic light-emitting device (OLED) technology.     

Kinetically Controlled Sequential Growth of Surface‐Grafted Chiral Supramolecular Copolymers

We report a facile strategy to grow supramolecular copolymers on Au surfaces by successively exposing a surface‐anchored monomer to solutions of oppositely charged peptide comonomers. Charge regulation on the active chain end of the polymer sufficiently slows down the kinetics of the self‐assembly process to produce kinetically trapped copolymers at near‐neutral pH. We thereby achieve architectural control at three levels: The β‐sheet sequences direct the polymerization away from the surface, the height of the supramolecular copolymer brushes is well‐controlled by the stepwise nature of the alternating copolymer growth, and 2D spatial resolution is realized by using micropatterned initiating monomers. The programmable nature of the resulting architectures renders this concept attractive for the development of customized biomaterials or chiral interfaces for optoelectronics and sensor applications.     

Determination of 1-methylhistidine and 3-methylhistidine by capillary and chip electrophoresis with contactless conductivity detection

CE with capacitively coupled contactless detection (C4D) was used to determine 3-methylhistidine (3-MH) and 1-methylhistidine (1-MH). The C4D response to 3-MH was studied in a BGE consisting of 500 mM acetic acid and ammonia at varying concentration and the results were compared with the theory. Complete separation of a model mixture of 3-MH, 1-MH, and histidine (His) was attained in two optimized BGEs, one containing 500 mM HAc, 20 mM NH4OH, and 0.1 % m/v hydroxyethylcellulose (HEC), pH 3.4 (I) and the other consisting of 100 mM morpholinoethanesulfonic acid (MES), 25 mM LiOH, and 0.1 % m/v HEC, pH 5.5 (II). These optimized BGEs were tested in CE/C4D analyses of urine. Promising results were obtained for separation and determination of 3-MH, 1-MH, and His on a silicon microchip, using aluminum strips as the C4D electrodes; the three analytes were baseline-separated within less than 30 s with a separation channel effective length of 38 mm. The LOD were satisfactory and amounted to 26.4 microM for 3-MH and 18.3 microM for 1-MH.