Mercury-mercurous acetate indicator electrode for potentiometric titrations in anhydrous acetic acid

The authors describe a metallic mercury electrode covered with a mercurous acetate coating, its preparation, its use as an indicator electrode in anhydrous acetic acid neutralization titrations and its properties as compared with other electrodes used for the same purpose.     

A novel copolymerizable surfactant and its application based on concentrated emulsion polymerization

A three-arm copolymerizable surfactant (surfmer) which possesses (1) a side chain terminated with a double bond and (2) a double bond in the hydrophobic moiety was synthesized. Because, one of the double bonds was located at the end of the side chain, the hydrophilicity of the surfmer was not affected in a major way by its copolymerization with the monomer. In addition, because of its three-arm structure, its self-polymerization was greatly inhibited, but not its capability for copolymerization. The surfmer was employed to prepare polystyrene particles of uniform size via the concentrated emulsion polymerization.     

A microscopic model for the fluctuations of local field and spontaneous emission of single molecules in disordered media.

We develop a microscopic model to describe the observed temporal fluctuations of the fluorescence lifetime of single molecules embedded in a polymer at room temperature. The model represents the fluorescent probe and the macromolecular matrix on the sites of a cubic lattice and introduces voids in the matrix to account for its mobility. We generalize Lorentz's approach to dielectrics by considering three domains of electrostatic interaction of the probe molecule with its nanoenvironment: (1) the probe molecule with its elongated shape and its specific polarizability, (2) the first few solvent shells with their discrete structure and their inhomogeneity, (3) the remainder of the solvent at larger distances, treated as a continuous dielectric. The model is validated by comparing its outcome for homogeneous systems with those of existing theories. When realistic inhomogeneities are introduced, the model correctly explains the observed fluctuations of the lifetimes of single molecules. Such a comparison is only possible with single-molecule observations, which provide a new access to local field effects.     

2,2'-Dimercaptodiethylsulphide: A potential analytical reagent

The compound 2,2'-dimercaptodiethylsulphide has been investigated with regard to the stability of its solutions to air oxidation, its acid strength, its reactivity towards metal ions, the nature of its Ni(II) and Pd(II) complexes in solution, and its applicability to the determination of small amounts of Ni(II) and Pd(II). Studies on the Ni(II) complex extend the work reported previously by others and are not in complete accord with it. The results presented show that 2,2'-dimercaptodiethylsulphide is a promising analytical reagent.     

Emulsion polymerization of vinyl acetate using a polymerizable surfactant. I. Kinetic studies

A polymerizable surfactant, sodium dodecyl allyl sulfosuccinate (TREM LF-40; Henkel) and its nonpolymerizable counterpart were used in comparative studies of the emulsion polymerization of vinyl acetate. The conversion-time behavior differed for the two surfactants; the TREM LF-40 showed a decrease in the polymerization rate with increasing concentration while its hydrogenated derivative showed the opposite behavior, the rate increasing with increasing surfactant. Particle size analysis revealed a decreasing particle size with increasing surfactant concentration for both series of reactions. An explanation for the seemingly ambiguous results obtained for the polymerizable surfactant was sought by examining the reactivity of its vinyl group in copolymerization with vinyl acetate and its allylic group in a chain transfer reaction. The results suggest that both the copolymerization and chain transfer reactions can lead to the observed reduction in polymerization rate with increasing TREM LF-40 concentration. © 1992 John Wiley & Sons, Inc.     

A highly selective charge transfer fluoroionophore for Cu2+

A dual fluorescent charge transfer fluoroionophore (1) with its ionophore incorporated in the electron acceptor was developed and was found to show a highly selective fluorescent response to Cu2+ with a dramatic enhancement in its CT emission.     

Study of 7-azaindole in its first four singlet states

The molecular structure and properties of 7-azaindole in its first four singlet states were studied with a view to improving current understanding of the photophysical behavior of its C(2h) dimer. This dimer, which exhibits a double proton transfer via its two hydrogen bonds upon electronic excitation, has for 35 years been used as a model for the photophysical behavior of DNA base pairs. Electronic excitation of 7-azaindole simultaneously increases its acidity and basicity; these changes facilitate a concerted mechanism for the double proton transfer in the dimer. In this work, we found the acidity and basicity changes to occur only in its first pi,pi(*) excited singlet state.     

A highly selective fluorescent probe for Sn based on a new photochromic diarylethene with a phenol-containing Schiff base unit

A novel diarylethene with a phenol-containing Schiff base unit was successfully synthesized and its multi-responsive photoswitching property was investigated by the stimulation of base/acid and light. The diarylethene showed not only normal photochromism by photoirradiation, but also abnormal photochromism by base and light stimuli. By the stimulation of sodium hydroxide, the absorption maximum of its open-ring isomer showed extraordinarily large redshift of 60 nm, accompanied with a notable color change from colorless to yellow. Subsequent irradiation with 297 nm light further caused a dramatic change in its structure transformation from the deprotonated open-ring isomer to the original closed-ring isomer. Similarly, its deprotonated closed-ring isomer returned to its original open-ring isomer upon irradiation with appropriate visible light. Its deprotonated forms could be restored by the stimulation of hydrochloric acid. Moreover, the diarylethene could be served as a fluorescence probe for recognition of Sn²⁺ with high selectivity.     

Studies of asymmetry of diffusion permeability of nanocomposite ion-exchange membranes: Model of charge density of fixed groups linear by membrane thickness

A new model of a fine-porous membrane with a linear distribution of charges of its fixed groups along its depth is suggested in the work to explain the effect of asymmetry of diffusion permeability of perfluorinated MF-4SK membranes surface-modified by polyaniline. The model allowed better describing the experimental data for the synthesized nanocomposite MF-4SK/PANI membranes than the earlier developed model of a bilayer membrane with constant fixed charge densities in layers, which points to its feasilibity.     

Cryoscopy on sulfuric acid solutions of a heterocyclic polymer (BBB) and related compounds

Cryoscopic measurements have been carried out on solutions in sulfuric acid of a heterocyclic polymer, its monomers, and certain of its oligomers. The polymer, BBB, is prepared by the polycondensation of 1,4,5,8-naphthalenetetracarboxylic acid (NTC) with 3,3′-diaminobenzidine (DAB). The results show that the polymer, its oligomers and one of its monomers, DAB, are all extensively protonated in sulfuric acid, whereas its other monomer is not. The degree of protonation appears to be greater for the polymer than for its low molecular weight oligomers.     

Synthesis and thermolysis of a Diels-Alder adduct of pentacene and thiophosgene

Pentacene has excellent semi-conducting properties but its practical use in organic thin film transistors (OTFTs) gives rise to a lot of problems caused by its sensitivity to oxygen and its very low solubility. In order to solve the problems involved in the use of pentacene, we have synthesized a Diels-Alder adduct of pentacene with thiophosgene.     

Rapid and highly selective chromogenic detection of nerve agents with a cleft-shaped host

A new chromogenic protocol has been developed for rapid and selective detection of nerve agents like tabun. The chemsensor displayed a drastic color change from its colorless solution to yellow instantaneously with an 89 nm bathochromic shift. No inference of other chemical warfare agents and its mimics was observed either with the naked-eye or by UV-Vis spectroscopy. The development of a portable chemosensor kit for tabun demonstrates its practical application in real-time monitoring.     

聚己内酯在药物载体方面的研究进展

聚己内酯(poly-ε-caprolactone,PCL)是一种人工合成的聚酯类高分子材料,对人体无毒,具有良好的生物相容性、生物可降解性和无免疫原性。PCL还对其它聚合物具有良好的相容性,可以制备出多种性能优良的共聚物或共混物,因此PCL及其共聚物、共混物作为药物载体的研究受到国内外研究者的高度重视。此外,PCL因其在人体中的降解过程十分缓慢可作为药物控释材料,目前已经获得美国FDA的批准。本文将从聚己内酯的合成与改性及其各剂型在药物载体方面的研究进展进行综述。     

A new water-soluble near-neutral ratiometric fluorescent pH indicator

Donor-pi-acceptor fluorene derivative 1c is a near-neutral pH indicator whose pKa of approximately 7.0 was determined by both absorption and fluorescence methods. 1c satisfies important criteria for a sensitive ratiomeric fluorescent pH indicator with a distinctive isoemissive point, good dispersion in cell cytosol, and low cytotoxicity. Furthermore, its 2PA cross section of 100 GM in its neutral form suggests its potential in two-photon fluorescence imaging applications.     

Synthesis of steroidal thiadiazoles from steroidal ketones

Syntheses of steroidal heterocycles containing a five-membered N,S- heterocycle attached at the 6,7 positions of the B ring are reported. 5Alpha-cholestane-6-one (1), its 3beta-acetoxy- (2) and 3beta-chloro- (3) analogues reacted with semicarbazide and aqueous sodium acetate in refluxing ethanol to yield 5alpha-cholestan-6-one-semicarbazone 1a and its 3-beta-acetoxy and 3beta-chloro derivatives 2a and 3a, respectively. The reactions of 1a, 2a and 3a with thionyl chloride in dichloromethane at low temperature afforded the cyclized thiadiazole 4 and its 3beta-acetoxy- and 3beta-chloro analogues 5 and 6 in good yields.     

Die Rolle des Aerosols im Klimasystem

Atmospheric aerosol particles cause one of the largest uncertainties in estimates of human influence on climate – a good reason to take a closer look at the atmospheric life cycle of the aerosols and its effects. Besides a number of primary and secondary natural aerosol sources we need to consider since the beginning of industrialisation strong manmade particle sources. During its residence in the atmosphere the aerosol interacts in many physical and chemical ways with other atmospheric trace substances, most importantly with water vapor and its liquid and solid phases. Through its direct effect on solar and thermal radiation and through its influence on clouds the atmospheric aerosol exerts a climate forcing. To data we cannot predict the ensuing climate response because of our limited understanding of essential atmospheric processes and of the many possible feedbacks within the climate system. However, already our present knowledge of the role of the atmospheric aerosol in the climate system makes strictly global views of anthropogenic climate changes questionable.     

125 Years of Chemistry in the Mirror of “Angewandte”

This Review investigates the development of Angewandte Chemie since the founding of the journal in 1887 and analyzes how its content reflects the changes in chemical research over these 125 years. Although Angewandte Chemie was originally founded as a journal for applied (“angewandte”)—technical and analytical—chemistry, numerous review articles and abstracts published even in its first 50 years enable the milestones in chemical research in a much broader sense to be traced nicely. With the introduction of the International Edition in 1962, the author base, which had until then been primarily limited to German‐speaking countries, became increasingly international, and the journal experienced impressive growth. Today, with its attractive layout, successful mix of articles, and high impact factor, Angewandte Chemie covers chemical research around the world in its full breadth, with its many achievements and future challenges.     

Interplay between an elusive 4-(isopropylamino)imidazol-2-ylidene and its isolable mesoionic tautomer, and associated reactivities

An elusive free 4-(isopropylamino)imidazol-2-ylidene is engaged in a tautomeric equilibrium with its mesoionic tautomer, 4-(isopropylamido)imidazolium, which displays the typical reactivity of a cyclic diaminocarbene; once coordinated to a Rh(I) centre, it undergoes a smooth 4e(-) oxidation of its backbone to yield an amido-amidino-carbene, a weak electron donor viable only in its complexed form.     

Non equilibrium thermodynamics and the city: a new approach to urban studies

A city can be conceived as a complex self-adaptive system. The multiple interactions among its structural elements and dynamic agents, its organization on multiple time-space scales, its exchanges with the external context, its irreversible dynamics, are signs of complexity. Some concepts from the evolutionary thermodynamics, such us the theory of dissipative structures, could be extended to the city in order to investigate its behaviour. This theoretical framework suggests to analyze the city in terms of entropy and negentropy production. An emergy analysis (spelled with an "m") of an urban region is presented in order to investigate how cities maintain their organization (and decrease their entropy) by virtue of constant energy inflows from the external environment. As a result, a non-homogeneous spatial pattern of emergy density is shown as an attempt to investigate the multiple relations and energy exchanges that take place in an urban region. This approach to urban studies introduces a new energy-based vision to understand cities.