Simple model of skin formation caused by solvent evaporation in polymer solutions

A simple model is proposed for the skin formation in the evaporation process of a polymer solution at a free surface. In this model the skin is regarded as a gel phase formed near the free surface, and the dynamics is described by a diffusion equation for the polymer concentration with moving boundaries. The equation is solved both analytically and numerically. It is shown that the skin phase appears when the evaporation rate is high or when the initial polymer concentration is high. An analytical expression is given for the criterion for the skin phase to be formed.     

Structural and Electrochemical Comparison of Copper(II) Complexes with Tripodal Ligands

A series of copper(II) complexes with tripodal polypyridylmethylamine ligands, such as tris(2-pyridylmethyl)amine (tpa), ((6-methyl-2-pyridyl)methyl)bis(2-pyridylmethyl)amine (Me(1)tpa), bis((6-methyl-2-pyridyl)methyl)(2-pyridylmethyl)amine (Me(2)tpa), and tris((6-methyl-2-pyridyl)methyl)amine (Me(3)tpa), have been synthesized and characterized by X-ray crystallography. [Cu(H(2)O)(tpa)](ClO(4))(2) (1) crystallized in the monoclinic system, space group P2(1)/a, with a = 15.029(7) ?, b = 9.268(2) ?, c = 17.948(5) ?, beta = 113.80(3) degrees, and Z = 4 (R = 0.061, R(w) = 0.059). [CuCl(Me(1)tpa)]ClO(4) (2) crystallized in the triclinic system, space group P&onemacr;, with a = 13.617(4) ?, b = 14.532(4) ?, c = 12.357(4) ?, alpha = 106.01(3) degrees, beta = 111.96(2) degrees, gamma = 71.61(2) degrees, and Z = 4 (R = 0.054, R(w) = 0.037). [CuCl(Me(2)tpa)]ClO(4) (3) crystallized in the monoclinic system, space group P2(1)/n, with a = 19.650(4) ?, b = 13.528(4) ?, c = 8.55(1) ?, beta = 101.51(5) degrees, and Z = 4 (R = 0.071, R(w) = 0.050). [CuCl(Me(3)tpa)][CuCl(2)(Me(3)tpa)]ClO(4) (4) crystallized in the monoclinic system, space group P2(1)/a, with a = 15.698(6) ?, b = 14.687(7) ?, c = 19.475(4) ?, beta = 97.13(2) degrees, and Z = 4 (R = 0.054, R(w) = 0.038). All the Cu atoms of 1-4 have pentacoordinate geometries with three pyridyl and one tertiary amino nitrogen atoms, and a chloride or aqua oxygen atom. Nitrite ion coordinated to the Cu(II) center of Me(1)tpa, Me(2)tpa, and Me(3)tpa complexes with only oxygen atom to form nitrito adducts. The cyclic voltammograms of [Cu(H(2)O)(Me(n)()tpa)](2+) (n = 0, 1, 2, and 3) in the presence of NO(2)(-) in H(2)O (pH 7.0) revealed that the catalytic activity for the reduction of NO(2)(-) increases in the order Me(3)tpa < Me(2)tpa < Me(1)tpa < tpa complexes.     

Elastic scattering of the conduction electrons by adsorbed hydrogen

The cross section of adsorbed hydrogen for the conduction electrons is evaluated according to the Boltzmann-Fuchs equation, the Greene and Soffer theories for surface scattering of the conduction electrons and to the change of the electrical resistivity due to hydrogen adsorbed on evaporated nickel films obtained experimentally by Suhrmann et al. The calculated cross sections are 2.0 × 10^?15 cm² and 1.8 × 10^?15 cm² at 273°K and 90°K respectively at a low coverage of hydrogen, which are consistent with the theoretical value 3.0 × 10^?15 cm² by Toya and reasonable compared with 0.9 × 10^?15 cm², the cross section of a gaseous hydrogen atom. The cross section decreases with increase of the coverage. This change is considered to be closely related to that of the heat of adsorption.     

Optical properties of semiconductor quantum dots in magnetic fields

Optical properties of semiconductor quantum dots in magnetic fields are reviewed. A theory is described based on a multi-band effective-mass approximation with a nonparabolic conduction electron dispersion, the direct Coulomb interaction, and the electron-hole exchange interaction taken into account. The transition from the quantum-confined Zeeman effect for a weak magnetic field to the quantum-confined Paschen-Back effect to a strong magnetic field is discussed in comparison with atomic spectra in magnetic fields. Experimental results of the optical properties of isolated CuCl, CdSSe, and Si quantum dots in magnetic fields are also discussed in conjunction with the theoretical results.     

Polarization imaging by use of optical scanning holography

Optical Review - Polarization information is useful for various applications such as remote sensing and biomedical imaging. In general, polarization information is obtained using a polarization...     

Synthesis of polymers having photocrosslinkable moieties for second-order nonlinear optics

Second-order non-linear optical polymers having photocrosslinkable moieties were synthesized by cationic polymerization of monomer (I) and monomer (II). The polymerization proceeded rapidly to give linear polymers in high yields. Monomer reactivity ratios were calculated to be r₁ = 0.90 and r₂ = 0.96 (r₁r₂ = 0.86), indicating that these monomers copolymerized through the almost ideal copolymerization mechanism. The photocrosslinking reaction of an equimolar copolymer film underwent the conversion of up to ca. 70% upon irradiation with a 500 W high-presure mercury lamp for 5 min. The electric field induced polar orientation of the chromophores (pendant 4-nitrophenyloxy groups) in a photocrosslinked polymer was stable for more than 10 days. This polymer exhibits a nonlinear coefficient d₃₃ of 5.6 × 10^-10 esu measured at a pumping wavelength of 1064 nm.     

Residue analysis of ethylenethiourea in vegetables by high-performance liquid chromatography with amperometric detection

Summary A method for the residue analysis of ethylenethiourea (ETU) in vegetables by HPLC with amperometric detection was developed. ETU was separated with Nucleosil C₁₈ as stationary phase and methanol-water (5:95, v/v) containing 0.05 mol/l ammonium acetate as eluent. The voltage of the working electrode (glassy carbon) was set at +1150 mV vs. Ag/AgCl. The limit of detection for ETU was found to be 0.3 ng. The method was applied to the determination of trace amounts of ETU in tomatoes and cucumbers. The minimum quantitation level was 0.01 ppm. The method can be performed easily; it is selective and highly sensitive.     

A comparison of new techniques for the detection and quantitative determination of triazine herbicides separated by thin-layer chromatography

Summary A rapid semi-quantitative method for the analysis of triazine herbicides has been developed. Ultra-violet reflectance spectroscopy was used to evaluate the spots directly from the thin-layer chromatogram. About ± 3% accuracy was obtained if the spots were removed and packed into a suitable reflectance cell. A non-destructive detection method also permitted the elution of the spots and subsequent quantitative analysis of the herbicides by means of absorption spectroscopy with an accuracy of ± 1.5%. The sensitivity was about 1g per spot for either technique.

---

Zusammenfassung Ein rasches halbquantitatives Verfahren zur Analyse von Triazin-Herbiziden wurde entwickelt. Die Flecken eines Dünnschichtchromatogramms werden UV-reflexionsspektroskopisch direkt ausgewertet. Etwa ± 3% Genauigkeit sind zu erzielen, wenn die Flecken entnommen und in eine geeignete Reflexionsmeßzelle gebracht werden. Eine nicht destruktive Nachweismethode ermöglicht die Elution der Flecken und die nachfolgende quantitative Bestimmung der Herbizide durch Absorptionsspektroskopie mit einer Genauigkeit von ± 1,5%. Die Empfindlichkeit beträgt in jedem Fall etwa 1g pro Fleck.

---

---

Presented at the 21st International Congress of Pure and Applied Science, Prague, September 1967.     

Evaluation of laser induced breakdown spectroscopy for the determination of macronutrients in plant materials

Laser induced breakdown spectroscopy (LIBS) has become an analytical tool for the direct analysis of a large variety of materials in order to provide qualitative and/or quantitative information. However, there is a lack of information for LIBS analysis of agricultural and environmental samples. In this work a LIBS system has been evaluated for the determination of macronutrients (P, K, Ca, Mg) in pellets of vegetal reference materials. An experimental setup was designed by using a Nd:YAG laser operating at 1064 nm and an Echelle spectrometer with ICCD detector. The plasma temperature was estimated by Boltzmann plots and instrumental parameters such as delay time, lens-to-sample distance and pulse energy were evaluated. Certified reference materials as well as reference materials were used for analytical calibrations of P, K, Ca, and Mg. Most results of the direct analysis of plant samples by LIBS were in reasonable agreement with those obtained by ICP OES after wet acid decomposition.     

Synthesis and properties of a soluble and widely conjugated polyacetylene with anthryl pendant

The metathesis polymerization of an anthrylacetylene bearing an alkyl ester group, 9‐(10‐hexoxycarbonyl)anthrylacetylene ( 1 ), was conducted with various transition‐metal catalysts. A completely soluble black polymer was obtained from 1 in a good yield when W‐based catalysts were employed. The polymerization at a high monomer concentration (1 M) and a high temperature (80 °C) led to the formation of poly( 1 ) with a weight‐average molecular weight of 297 × 10³ in an 80% yield. The use of cocatalysts unexpectedly decreased both the yield and molecular weight of poly( 1 ). Rh‐catalyzed and Mo‐catalyzed polymerizations, however, resulted in poor yields of the polymer. The ultraviolet–visible spectrum of poly( 1 ) showed a significantly redshifted absorption (λ_max = 571) with a cutoff at 780 nm, which verified the very high order of conjugation of the main chain. Poly( 1 ) exhibited the largest third‐order nonlinear optical susceptibility [χ⁽³⁾ (−ω; ω, 0, 0) = − 1.9 × 10⁻¹⁰ esu] among the polymers from the monosubstituted polyacetylenes synthesized so far. The electrical conductivity of poly( 1 ) in an I₂‐doped state was 8.77 × 10⁻⁴ at 293 K. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4717–4723, 2000