Dip-coating crystallization on a superhydrophobic surface: a million mounted crystals in a 1 cm2 array

Silicon wafers (silicon dioxide surfaces) were patterned by photolithograpy to contain 3 μm (width) × 6 μm (length) × 40 μm (height) staggered rhombus posts in a square array (20 μm center-to-center spacing). These surfaces were hydrophobized using a vapor phase reaction with tridecafluorooctyldimethylchlorosilane and exhibit "superhydrophobicity" (water contact angles of θ(A)/θ(R) = 169°/156°). When a section of a wafer is submerged in and withdrawn from water, the superhydrophobic surface emerges, apparently completely dry. If the same procedure is performed using aqueous sodium chloride as the liquid bath, individual crystals of the salt can be observed on the top of each of the posts. "Dip-coating crystallization" using an aqueous sodium chloride solution of 4.3 M produces crystals with ～1 μm dimensions. A less concentrated solution, 1 M NaCl, renders crystals with ～500 nm dimensions. These experiments suggest that superhydrophobic surfaces that emerge from water and are "apparently completely dry" are, in fact, decorated with micrometer-size (several femtoliters) sessile water drops that rapidly evaporate. This simple technique is useful for preparation of very small liquid drops or puddles (of controlled composition) and for preparation of arrays of controlled size, crystalline substances (dip-coating crystallization).     

Role played by a natural channel on the quality of bordering environment: a chemical assessment

Based on a rational and simple chemical approach, a field-investigation aimed to assess the role played by a natural channel "lama" on the quality of underlying groundwater and neighbouring soils has been carried out. The results have demonstrated that: (a) the stream flowing through the "lama" is mainly made up of treated effluent from a nearby municipal wastewater treatment plant; (b) the occurrence of nitrates in the "lama" is due to rain-washing of nitrogen fertilized agricultural soils bordering on the "lama"; (c) hydraulic connections exist between the lama and the underlying groundwater causing contaminants flowing through the "lama" to reach groundwater within less than one week; (d) compared with the values measured in the "lama", the concentrations of TOC, N-NH4 and N-NO3 in groundwater result: lower, far lower and greater, respectively; (e) agricultural soils bordering on the "lama" result significantly contaminated by halogenated organics.     

Synthesis of desoxyanteridiol,a lanostane analog of a fungal sex hormone

The stereoselective synthesis of a-lactone, (22R)-3-acetoxy-22-hydroxylanosta-8,24(31)-dien-32-oic acid (X), which is the first lanostane analog of the sex hormone ofAchlya aqueous fungi, was carried out by means of 1,3-dipolar addition of nitrile oxides to lanostane olefin (I) through (22R)-isoxazoline (III) as a key intermediate.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 4, pp. 969–972, April, 1991.     

Assembly and incorporation of a CO2Me group into a bridging vinyliminium ligand in a diiron complex

The diiron complex [Fe₂{μ-к¹(O):η¹(C):η³(C)-C(N(Me)(Xyl))C(H)C(Me)C(O)OMe}(μ-CO)(Cp)₂] (2) has been obtained from the diiron bridging vinyliminium [Fe₂{μ-η¹:η³-C(Me)C(H)CN(Me)(Xyl)}(μ-CO)(CO)(Cp)₂][SO₃CF₃] (1; Xyl = 2,5-C₆H₃Me₂) upon treatment with NaH in the presence of CH₂CCMe₂, followed by chromatography on alumina with MeOH as eluent. The reaction consists in the incorporation of a methylcarboxylate unit, assembled from CO and MeO⁻, into the bridging vinyliminium ligand. The resulting complex 2 exhibits a C₄ fragment bridging the two iron centres through the carbonyl oxygen atom and the allylidene moiety.The X-ray molecular structure of 2 has been determined.     

Radical cation of a trimethylenemethane with a nondegenerate ground state

Upon ionization by gamma-irradiation in frozen CFCl(3), or by X-irradiation in an Ar matrix, 2,2,3,3-tetramethylmethylenecyclopropane (MCP-Me4) readily undergoes ring opening to yield the radical cation of 1,1,2,2-tetramethyltrimethylenemethane (TMM-Me4). The hyperfine-coupling constants for TMM-Me4(.+) are (mT) -1.99 (2H), +0.53 (6H), and +0.19 (6H), and the singly occupied orbital closely resembles one of the two degenerate nonbonding pi-MOs (NBMOs) of trimethylenemethane (TMM). Due to the expected effect of the methyl substituents, this "symmetric" NBMO, psi(2+) (b(1)), is energetically favored relative to its "antisymmetric" counterpart, psi(2-) (a(2)), so that the ground state assumes a structure with (2)B(1) symmetry in the C(2v) point group. Calculations show that the ring opening in the primary radical cation MCP-Me4(.+) to yield TMM-Me4(.+) is spontaneous, whereas in the parent system (MCP(.+) --> TMM(.+) a low barrier does exist. In contrast to the previously investigated case of the radical cation of tetramethyleneethane, the "electromer" of TMM-Me4(.+), in which the unpaired electron occupies psi(2-), cannot be attained photochemically.     

Bubble extraction as a preconcentration step in trace elemental analysis: a preliminary study

Summary Surface active properties of dithizone and mercury(II) dithizonate have been analyzed by means of a laboratory apparatus for bubble extraction in view of utilizing it as a preconcentration device. Dependence of extraction efficiency on various parameters has been analyzed. Particularly, the dependence on concentration has been discussed in terms of adsorption isotherm and compared with that of a typical surface-active dye (crystal violet). It has been found that quantitative recovery ( 90%) of mercury, as mercury(II) dithizonate, is obtained from solutions of sufficiently low concentration ( 0.3 g/l).

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Fraktionierextraktion als Anreicherungsstufe in der Spurenelementanalyse. Eine vorläufige Untersuchung

     

Coupling of a sheep anti-T3 IgG to a solid phase for a triiodothyronine radioimmunoassay

Optimal conditions for coupling sheep anti-T₃ IgG to a solid phase are presented. We found that the optimal activation of microcrystalline cellulose was achieved with 0.15M 1,1-carbonyldiimidazol (CDI) in acetone. We also found that using a 25 mg/cm³ anti-T₃ IgG solution, in barbitone buffer 0.05M, pH 8.0, we could get a reasonable yield of coupling and a remaining solution of anti-T₃ IgG (first supernatant) with a suitable concentration (10 mg/cm³) for another coupling. The solid phase anti-T₃ obtained in these two couplings present similar characteristics which make possible their use in a total T₃ RIA.     

Ligand substitution in a transition metal complex: a new type of photocatalytic reaction in a semiconductor

We show that a semiconductor can serve as a photocatalyst for the ligand substitution reaction in coordination compounds of chromium(III). The mechanism of the process includes stages of generation of an electron-hole pair upon action of light quanta with energy equal to (or greater than) the width of the forbidden gap in the semiconductor, capture of the electron from the conduction band by the chromium(III) complex, fast ligand substitution in the chromium(II) complex formed by a solvent molecule, and oxidation of the chromium(II) complex by the hole from the valence band. The reaction of aquation of the complex ions [CrCl₂(H₂O)₄]⁺ proceeds when using the semiconductors (CdS, GaAs), whose conduction band is located in the more negative potential region compared with the standard oxidation-reduction potential of the Cr(III)/Cr(II) pair. We show that the reaction rate is slowed down when electron acceptors (oxygen) and hole acceptors (ethanol) are introduced, which confirms the proposed mechanism.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 26, No. 1, pp. 89–92, January–February, 1990.     

Self-assembly mechanism of a bimetallic europium triple-stranded helicate

We report the self-assembly process of a supramolecular edifice based on the coordination of europium(III) by a ditopic strand L bearing tridentate bis(benzimidazolyl)pyridine subunits. Varying the metal/ligand ratio and using a fruitful combination of electrospray mass spectrometry and absorption spectrophotometry, we characterized three major complexes (EuL(2), Eu(2)L(2), and Eu(2)L(3)) in acetonitrile. Kinetic investigations showed an alternative "braiding" and "keystone" mechanism leading to Eu(2)L(3). The formation mechanism of the dinuclear triple-stranded helicate, which is mainly governed by electrostatic interactions, goes via the "side-by-side" Eu(2)L(2) intermediate. Our thermodynamic and kinetic data allow the prediction of the apparent "magic" self-assembly of Eu(2)L(3) which is fast and efficient only under a strict set of conditions.     

Potential distribution around a charged spherical colloidal particle in a medium containing its counterions and a small amount of added salts

A theory is developed for the potential distribution around a charged spherical colloidal particle carrying ionized groups on the particle surface in a medium containing its counterions (i.e., counterions produced from dissociation of the particle surface groups) and a small amount of added salts on the basis of the theory of Imai and Oosawa. Numerical solutions to the Poisson–Boltzmann equation for the potential distribution are obtained for the case of dilute (but not infinitely dilute) particle suspensions of volume fraction 1 for a1 (where is the Debye–Hückel parameter and a is the particle radius). Here we have taken into account the effects of (i) counterions from the particle surface groups, and (ii) the finite particle volume fraction. These effects, which are usually neglected in the conventional Poisson–Boltzmann equation, are found to be important. It is found that, as in the case of completely salt-free media, there is a certain critical value of the particle charge (which is the same as that for the completely salt-free case). When the particle charge is lower than the critical value, the potential is given by a Coulomb potential. If the particle charge is higher than the critical value, then counterions are accumulated in the vicinity of the particle surface (counterion condensation) and the potential becomes less dependent on the particle charge. The above behaviors can be observed even for the case where the electrolyte concentration is higher than the concentration of counterions from the particle surface groups, if the conditions 1 and a1are both satisfied.     

Wetting of a drop on a sphere

In this work, the equilibrium morphology of a drop on a sphere is analyzed as a function of the contact angle and drop volume experimentally and with analytical effective interfacial energy calculations. Experimentally, a drop on a sphere geometry is realized in an oil bath by placing a water drop on a sphere coated with a dielectric, of which the radii of curvature are comparable with that of the drop. Electrowetting (EW) is used to change the contact angle of the water drop on the sphere. To validate the applicability of EW and the Lippman-Young equation on nonflat surfaces, we systematically investigate the response of the contact angle to the applied voltage (EW response) for various drop volumes and compared the results with the case of a planar surface. The effective interfacial energy of two competing morphologies, namely, the spherically symmetric "completely engulfing" and "partially engulfing" morphologies are calculated analytically. The analytical calculations are then compared to the experimental results to confirm which morphology is energetically more favored for a given contact angle and drop volume. Our findings indicate that the "partially engulfing" morphology is always the energetically more favorable morphology.     

Ideal Conductivity Profile of a Porous Matrix for a Flow-through Porous Electrode with a High Conversion Degree of the Electroactive Component

The possibility of designing an equally accessible, in electric respect ( const), porous electrode (PE) is considered. The design involves creating a special conductivity profile of the solid phase, _s(x), in conditions of considerable variations of current density inside the electrode. A generalized expression for an ideal profile _s(x) at any current distribution is derived, and some concrete solutions for different PE operation modes at the limiting current of the target reaction are obtained. The profiles are exponential over a major fraction of PE and change to hyperbolic at a low conversion degree of the electroactive component. Similarities and differences of the profiles are analyzed. At a high conversion degree, only the exponential profile ensures effective operation of the entire surface of PE and selectivity of the target reaction.     

Isothiouronium-based amphiphilic gold nanoparticles with a colorimetric response to hydrophobic anions in water: a new strategy for fluoride ion detection in the presence of a phenylboronic acid

Gold nanoparticles modified with isothiouronium-derived amphiphile units 1 were prepared by the reduction of with NaBH₄ in the presence of bis(5-(N-(2-(2-methoxyethoxy)ethyl)-N-methyl-S-isothiouronio)pentyl) disulfide 2. The obtained nanoparticles 1 showed a selective coloration for hydrophobic anions in water, possibly due to an anion exchange and subsequent aggregation. On the basis of this observation, the detection of F⁻ in water has been achieved using 3-nitrophenylboronic acid as a mediator at pH 5.5, thereby providing a new strategy for the design of a F⁻ sensory system.     

Spectrophotometric sensor devices working in a raster of a few wavelengths

Commercial UV-VIS-spectrophotometers usually offer a surplus of spectral information with regard to qualitative analytical problems. When measuring in a raster of a few selected wavelengths redundant information can be omitted and the spectrophotometric device can be simplified to a considerable extent. Several raster spectral sensor devices are presented and examples for their application and for the chemometric data evaluation are given. The use of artificial neural network (ANN) software for qualitative classification (raster spectral pattern recognition) and quantitative calibration is shown exemplarily.     

Photometry in a continuous flow system

Summary Sulphate in various environmental samples was determined by measuring the optical absorbance upon reaction with the barium(II) dimethylsulphonazo(III) complex. The measurement took place in a flow-through system. Interferences from phosphate, metal ions and others were eliminated. The results of a turbidimetric measurement, a spectrophotometric measurement with thorin, an automatic titration and the proposed method are compared. The latter allows the determination of sulphate in the range of 1.4–60 mol·l^–1. The standard deviation is 0.3–0.6 mol·l^–1, depending on the type of sample (water) analysed. A determination takes 1.5min.

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Photometric in einem DurchflußsystemBestimmung von Sulphat mit Dimethylsulfonazo(III) in Umweltmaterial mit Hilfe eines Durchflußsystems

Zusammenfassung Sulfat wurde in verschiedenen Umweltproben durch Messung der Extinktion nach Reaktion mit dem Barium(II)-dimethylsulfonazo(III)-komplex im Durchflußsystem bestimmt. Störungen von Phosphat, Metallionen, u.a. wurden beseitigt. Die Ergebnisse einer turbidimetrischen, einer photometrischen, einer automatischen Titration und der vorgeschlagenen Methode werden verglichen. Die Methode ermöglicht die Sulfatbestimmung im Bereich von 1,4–60 mol·l^–1. Die Standardabweichung beträgt 0,3–0,6 mol· l^–1 je nach Typ des Probematerials (Wasser). Eine Bestimmung erfordert 1,5min.

     

Comparing an ionic liquid to a molecular solvent in the cesium cation extraction by a calixarene: a molecular dynamics study of the aqueous interfaces

We report a molecular dynamics (MD) study of the interfacial behavior of key partners involved in the Cs(+) cation extraction by a calix[4]arene-crown-6 host (L), comparing an ionic liquid (IL) to a classical molecular solvent (chloroform) as receiving "oil" phase. The IL is composed of hydrophobic 1-butyl-3-methylimidazolium cations (BMI(+)) and bis(trifluoromethylsulfonyl)imide anions (Tf(2)N(-)) and forms a biphasic system with water. The simulations reveal similarities but also interesting differences between the two types of interfaces. Much longer times are needed to "equilibrate" IL systems, compared to classical liquid mixtures, and there is more intersolvent mixing with the IL than with chloroform, especially concerning the water-in-oil content. There is also some excess of the BMI(+) cations over the Tf(2)N(-) anions in the aqueous phase. Simulations on the Na(+)NO(3)(-) and Cs(+)NO(3)(-) ions show that they sometimes interact at the interface with the IL ions, forming hydrated intimate ion pairs, whereas they are "repelled" by the classical interface. The LCs(+) complex and L ligand also behave differently, depending on the "oil phase". They are better solvated by the IL than by chloroform and thus poorly attracted at the IL interface, whereas they adsorb at the chloroform interface, adopting well-defined amphiphilic orientations. The results are discussed in the context of assisted ion transfer and provide a number of arguments explaining the specificity and efficiency of IL based, compared to classical extraction systems.     

The gamma-radiolysis of HEDTA in a simulated, mixed waste

The -radiolysis of the parent compound N-(2-hydroxyethyl)ethylenediaminetriaceticacid (HEDTA) in a simulant of a Hanford mixed waste, at a -dose of7.5 . 10₆±10% R, yielded 94.4% degradation. HEDTA radiolysisyielded four degradation products: glyoxylic acid, N-( nitroso)iminodiaceticacid (NIDA) and 2 dicarboxylic acids, ethandioic (oxalic) and propandioic(malonic) acids. Glyoxylic acid had been identified in previous studies byour laboratory as N-hydroxymethyl-N-methyliminoacetic acid (HMMIA). Promptedby studies from another laboratory, the chelator fragment previously reportedby our laboratory as N-(methylamine)iminodiacetic acid (MAIDA) is re-identifiedas NIDA. A methylamine moiety previously believed to be present in MAIDA,and several other chelator fragments, as well, has been re-identified as anitroso group.     

Aerogelation Process Simulation by a Cluster-Cluster Aggregation Algorithm

A ballistically-limited cluster-cluster aggregation (BLCA) model was developed to simulate aerogelation processes. In the model, the clusters move along linear paths, in random directions, in a finite box. When two aggregates contact each other, they are combined irreversibly to form a larger aggregate. As expected, the simulations show that the aggregation time is much shorter than that obtained with diffusion-limited cluster-cluster aggregation (DLCA) models. The minimum concentration, c_g, required for gel formation scales as L^D–3, where L is the length of the sides of the box and D is the fractal dimension of the aggregates (D 1.95). For a concentration c larger than c_g, the mean free path of the aggregating clusters, , scales as c^–1.1. The pair correlation function g(r) and its Fourier transform S(q) were determined for the single large aggregates formed at the end of the simulations. These functions indicate that there is a characteristic length which scales as c^1/(D–3). As observed previously for the DLCA model, there is a discrepancy between the fractal dimensions obtained from g(r) and S(q).