Active transport of Na + and K + through animal cell membranes

The transport of Na⁺ out of the cell and K⁺ into the cell against a concentration gradient is catalyzed by a (Na⁺ + K⁺)-activated ATPase. The way in which the cations pass through the cell membrane has not yet been elucidated. Studies on the ATP hydrolysis revealed a Na⁺-dependent phosphorylation of the enzyme protein; the conformation of the enzyme also appears to change. The energy required for transport of the cations against their concentration gradients is probably provided by K⁺-dependent hydrolysis of the enzyme-bound phosphate. The enzyme can synthesize ATP from inorganic phosphate and ADP on reversal of the cation concentration gradient. By keeping the enzyme in a particular conformation, the cardiac glycoside ouabain specifically inhibits the Na⁺ pump.     

Palladium-catalyzed cascade reaction of alpha,beta-unsaturated sulfones with aryl iodides

Unlike traditionally used acyclic 1,2-disubstituted alkenes, the reaction of alpha,beta-unsaturated phenyl sulfones with aryl iodides under Heck reaction conditions (Pd(OAc)(2) as catalyst, Ag(2)CO(3) as base in DMF at 120 (0)C) takes place mainly by a cascade process, involving one unit of the alkene and three units of the aryl iodide, to afford a substituted 9-phenylsulfonyl-9,10-dihydrophenanthrene. The dominant formation of this 3:1 coupling product, instead of the Heck trisubstituted olefin, shows that aromatic C-H bond activation processes can compete with the usually fast syn beta-hydrogen elimination step in the Heck arylation of an acyclic olefin. The structural scope of this palladium-catalyzed cascade arylation of alpha,beta-unsaturated sulfones has proved to be wide with regard to substitution at the beta-position (alkyl, aryl, or alkenyl substitution), substitution at the sulfone unit (alkyl or phenyl sulfones), and configuration at the CdoublebondC bond (trans or cis). Moreover, although less favored than in the case of the arylation of alpha,beta-unsaturated sulfones, similarly substituted 9,10-dihydrophenanthrenes have also been obtained in the case of alpha,beta-unsaturated phosphine oxides and alpha,beta-unsaturated phosphonate esters. A Pd(0)-Pd(II)-Pd(IV) mechanistic pathway involving the successive formation of highly electrophilic sigma-alkylpalladium intermediates and palladacycles is proposed for this multicomponent arylation.     

Liquid chromatographic determination of aliphatic amines in water using solid support assisted derivatization with 9-fluorenylmethyl chloroformate

Summary A simple and sensitive method has been developed for the liquid chromatographic determination of short-chain aliphatic amines in water. Analytes are retained in solid-phase extraction (SPE) cartridges, and then derivatized by drawing an aliquot of the fluorogeneic reagent 9-fluorenylmethyl chloroformate (FMOC) through the cartridges. After a certain reaction time the derivatives formed are desorbed with acetonitrile. The collected extracts are then chromatographed on a LiChrospher 100 RP₁₈ 125 mm×4 mm i.d., 5 μm, column using an acetonitrile-water gradient. The influence of experimental conditions (SPE material, volume of sample, concentration of FMOC, time of reaction and pH) has been investigated. Optimal results have been obtained with C₁₈ SPE cartridges using a sample volume of 5.0 mL. For derivatization, 0.25 mL aliquots of 25 mM FMOC have been used, the reaction time being only 2 min. The method has been applied to the quantification of several aliphatic amines: methylamine, ethylamine, dimethylamine,n-butylamine,n-pentylamine andn-hexylamine. Under the proposed conditions the percentages of analytes retained plus derivatized were of about 54–107% compared to those obtained with direct solution derivatization. The method provided good reproducibility, linearity and accuracy within the 0.050–1.0 mg L⁻¹ concentration range. The limits of detection were in the 0.25–5.0 μg L⁻¹ range. The utility of the described approach has been tested by analysing tap water, river water and industrial waste water.     

Performance characteristics of suspended particulate reagent-iminodiacetate as a binding agent for diffusive gradients in thin films

The performance characteristics of an alternative binding agent, suspended particulate reagent-iminodiacetate (SPR-IDA), for use with DGT methodology were investigated. The parameters investigated during this study included gel hydration, blank levels, elution factor (f_e), capacity, the effects of pH on the binding of trace metals by DGT. The novel application of this resin for use as a quantitative standard for laser ablation ICP-MS was also evaluated. To further constrain the results for the SPR-IDA binding agent, parallel experiments were performed using resin gel containing Chelex 100, which has been widely reported in the literature. Hydration results showed that the SPR-IDA resin gel reached a stable dimension and weight within ∼30 min and was dimensionally stable for ≤6 months. The measured DGT blanks for the SPR-IDA resin were 0.0023, 0.15, 0.21, 0.0033 and 0.011 ng disc⁻¹ for Co, Ni, Cu, Cd and Pb, respectively. The elution factor differed for the two resin types with the Chelex 100 recoveries slightly lower than previous reports and the SPR-IDA resin showing on average ∼5-9% better recoveries than DGT containing Chelex 100. The measured capacity of DGT discs containing the SPR-IDA binding agent was 0.26 mg Cd, similar to the calculated value of 0.29 mg Cd, indicating the entire resin layer was available for metal uptake.Both resin types performed equally well when deployed in 1 mM NaNO₃ solutions with DGT measurements of ∼100% of direct solution measurements for Co, Ni and Cd. However, DGT measurements of Cu and Pb systematically decreased with increasing solution pH down to ∼50% of solution values at pH 8.0, due to artifacts resulting from colloid formation during the addition of the metals. This was remedied by adding the metals as dilute salt standards and addition of Mg(NO₃)₂ to eliminate adsorption to the container walls. In the latter experiments, DGT measured concentrations of Co, Ni, Cu, Cd and Pb were in agreement with solution concentrations. Deployment of DGT in solutions with increasing concentrations of trace metals yielded linear results, suggesting that quantitative analysis using simplified laser ablation techniques should be possible using this newly characterized SPR-IDA resin gel.     

A Sensitive Spectrophotometric Determination of Nitrite in Water and Soil

A highly sensitive spectrophotometric method for the determination of nitrite in water and soil has been developed. The reaction of nitrite with acidified potassium iodide to liberate iodine which oxidizes leuco‐crystal violet (LCV) to form crystal violet having absorption maxima at 590 nm forms the bases of this method. In aqueous medium the system obeys Beer's law in the range of 0.1 to 1.0 μg per 25 mL (0.004–0.04 ppm), while in an extractive system the range is 0.025–0.25 μg in 100 mL (0.00025–0.0025 ppm). The molar absorptivity and Sandell's sensitivity were found to be 1.54 × 10⁶ 1 mol^?1 cm^?1 and 44 pg cm^?2, respectively.     

SYNTHESIS AND CHARACTERIZATIONS OF NEAR INFRARED ABSORBING POLYMERS

A series of near infrared (NIR) absorbing dinuclear ruthenium dicarbonylhydrazine complexes (DCH-Ru),[{Ru(bpy)_2)_2μ-DCH]~(n ) (where bpy = 2,2'-bipyridinc and n = 2, 3 or 4), were prepared. The DCH-Ru complexes areelectrochromic in the NIR region with a high absorption coefficient at 1550-1600 nm typically over 10000 M~(-1)cm~(-1). DCH-Ru complex polymers with good NIR electrochromic properties were also obtained and processed to make a device foroptical attenuation at a wavelength of 1550 nm. The potential of these DCH-Ru polymers for use in a variable opticalattenuator has been demonstrated with an attenuating power at the 1550-nm telecommunication wavelength over 7.0 dB permicron of polymer film thickness. Other classes of NIR active materials are the pentacenediquinones and the correspondingpoly(ether pentacenediquinone)s. These polymers can be electrochemically reduced to the corresponding semiquinone(radical anion) having NIR absorption within a telecom window (e. g., 1310 nm).     

Divergent synthesis of the tetracyclic ethers of 6-X-7-6 ring systems

Ladder-shaped polyether natural products show diverse biological activities with extreme potency. As the initial phase of detailed SAR studies of bioactive polyethers, we set out to construct structurally simple mimics. This paper details the divergent synthesis of 6-X-7-6 tetracycles (X=7, 8, or 9) starting from a simple 6-membered ether. Key reactions in the synthesis include (i) the direct formation of an O,S-acetal by the coupling of an alcohol with an α-chlorosulfide, (ii) the construction of a 7-membered ring by radical cyclization, and (iii) cyclization to the 7, 8 or 9-membered ring via a ring-closing metathesis reaction. The neutral reaction conditions of our strategy enable the synthesis of a wide variety of substrates. The results of this study can be applied for the rapid construction of artificial polyether compounds with diversified molecular shapes and sizes.     

Preparation and characterization of polypropylene/mesoporous silica nanocomposites with confined polypropylene

Polypropylene (PP)/Ti-MCM-41 nanocomposites were prepared by isospecific propylene polymerization with Ti-MCM-41/Al(i-C₄H₉)₃ catalyst. The cross polarization/magic angle spinning (CP/MAS) ¹³C NMR spectrum of the composite was similar to that of the conventional isotactic PP, and the decrease in the pore volume of Ti-MCM-41 in the nanocomposites, as measured by N₂ adsorption, was consistent with the value calculated from the weight loss in the thermogravimetric analysis (TGA) curve; both these facts attest to propylene polymerization within the mesopores of Ti-MCM-41. Alkali treatment followed by extraction with o-dichlorobenzene allows us to extract the confined PP out of the Ti-MCM-41 mesopores. Although the PP/Ti-MCM-41 nanocomposites do not exhibit a crystalline melting point, the same PP when extracted from the mesopores showed a clear melting point at 154.7 °C; this indicates that the crystallization of PP confined in mesopores is strongly hindered. For the PP polymerized within the confinement, the molecular weight (M_w) and molecular weight distribution (M_w/M_n) were 84,000 and 4.3, respectively; these values were considerably smaller than those of the PP polymerized concurrently outside the Ti-MCM-41 mesopores (M_w = 200,000–450,000, M_w/M_n = 40–75). Therefore, the confinement also has a marked effect on the molecular weight of the PP. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 3324–3332, 2003     

Synthesis and properties of organosoluble poly(amide imide imide)s based on tetraimide dicarboxylic acid condensed from 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride, 4,4′‐oxydianiline,and trimellitic anhydride and various aromatic diamines

A novel tetraimide dicarboxylic acid was synthesized with the ring‐opening addition of 4,4′‐(hexafluoroisopropylidene)diphthalic anhydride, 4,4′‐oxydianiline, and trimellitic anhydride in a 1/2/2 molar ratio in N‐methyl‐2‐pyrrolidone followed by azeotropic condensation to tetraimide dicarboxylic acid. A series of poly(amide imide imide)s (PAIIs) with inherent viscosities of 0.8–1.1 dL/g were prepared from tetraimide dicarboxylic acid with various aromatic diamines by direct polycondensation. Most of the PAIIs were readily soluble in a variety of amide polar solvents and even in less polar m‐cresol and pyridine. Solvent‐cast films had tensile strengths ranging from 99 to 106 MPa, elongations at break ranging from 8 to 13%, and initial moduli ranging from 2.0 to 2.3 GPa. The glass‐transition temperatures of these PAIIs were recorded at 244–276 °C. They had 10% weight losses at temperatures above 520 °C in air or nitrogen atmospheres. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1092–1102, 2002     

Method and algorithm of obtaining the molecular intrinsic characteristic contours (MICCs) of organic molecules

The molecular intrinsic characteristic contour (MICC) is defined as the set of all the classical turning points of electron movement in a molecule. Studies on the MICCs of some medium organic molecules, such as dimethylether, acetone, and some homologues of alkanes, alkenes, and alkynes, as well as the electron density distributions on the MICCs, are shown for the first time. Results show that the MICC is an intrinsic approach to shape and size of a molecule. Unlike the van der Waals hard-sphere model, the MICC is a smooth contour, and it has a clear physical meaning. Detailed investigations on the cross-sections of MICCs have provided a kind of important information about atomic size changing in the process of forming molecules. Studies on electron density distribution on the MICC not only provide a new insight into molecular shape, but also show that the electron density distribution on the boundary surface relates closely with molecular properties and reactivities. For the homologues of alkanes, Rout(H), Dmin, and Dmax (the minimum and maximum of electron density on the MICC), all have very good linear relationships with minus of the molecular ionization potential. This work may serve as a basis for exploring a new reactivity indicator of chemical reactions and for studying molecular shape properties of large organic and biological molecules.