The electrocapillarity of polyacrylates

Summary The electrocapillary properties of polyacrylic acid have been studied by two methods. Exploratory measurements have been made of the effect of the polymer on the differential capacity of a mercury drop in 0.1 m sodium perchlorate. They showed that the polymer was strongly adsorbed over a wide range of potentials but that it did not appear to form a monolayer. The surface excess of polymer obtained from drop weight data showed a maximum at very low concentrations and then a decline at higher concentrations. The bulk of the work was carried out by making surface tension measurements, using a sessile mercury drop, in solutions of a fraction of polyacrylic acid (mol. wt. 7.02×10⁴) in potassium chloride at 0.01, 0.1, 0.2, and 0.5 m at 25°C.The data have been used to evaluate the surface excesses of the polymer and of the inorganic ions. The distribution of K⁺ and Cl^– in the electrical double layer and the contact adsorption of Cl^– on the mercury were very little affected by the presence of the polymer. The surface excess of polymer was always found to be greatest at low concentrations, to decrease steeply at first as the concentration was increased and then to decrease more slowly at higher concentrations.Possible explanations of this behaviour are discussed and it is concluded that the rapid decrease is a consequence of molecular weight dispersion and the stronger adsorption of high molecular weight polymer. The slow decrease in surface excess at higher concentrations may be a result of configurational changes of the polymer molecules.Surface pressure data show that, despite this decrease in the surface excess, the surface coverage reaches a high level at very low polymer concentrations and then continues to increase slowly as the concentration of polymer is increased. This apparent contradiction is due to changes in configuration of the adsorbed polymer molecules. At higher bulk concentrations the chain configurations are more compact and each adsorbed molecule makes more contacts with and so occupies a greater area of the mercury surface than at low concentrations.The conclusion is reached that the surface excess of polymer is mostly contained in a layer probably more than 1000 Å thick. It consists of a concentrated and entangled mass of polymer chains. Relatively few of these chains are in contact with the mercury at any istant. The concentration in this surface layer decreases steadily with increasing distance from the mercury surface and it merges without discontinuity into the bulk solution.With 10 figures in 22 details     

Determination of inosine 5′-monophosphate and guanosine 5′-monophosphate in pig feed by capillary zone electrophoresis

A capillary zone clectrophoresis method was developed for the determination of IMP and GIMP, commonly used as flavor enhancers in poultry feed, in a real sample of complex composition. A baseline separation of inosine 5′-monophosphate and guanosine 5′-monophosphate was achieved within 10 min and the other components in the sample did not interfere with the separation. Quantitative results obtained from pig feed samples are presented. The separation conditions and experimental reproducibility are also discussed.     

Stereochemie von Metallocenen, 40. Mitt.

Starting from optically active methylferrocene-- and--carboxylic acids (1 a and1 b) of known absolute configuration and enantiomeric purity about 15 chiral ferrocenes (of each isomeric series— and ) were obtained by suitable ligand transformations. Thereby (almost) all possible chiral combinations of the ligands CH₃, COOH (COO^–), COOCH₃, CN and NH₂ (NH₃ ⁺) were accessible which are necessary for a potential test of approximations of chirality functions for compounds with basic symmetry C_5v. The chiroptical properties of these disubstituted ferrocenes are recorded.Preliminary tests using a shortened Ansatz revealed large discrepancies between calculated () and found [M]_D-values. Possible reasons for this failure are discussed.

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61. Mitt. über Ferrocenderivate

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39. Mitt.:A. Meyer, H. Neudeck undK. Schlögl, Chem. Ber.110, 1403 (1977).

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60. Mitt.:V. Rapi, K. Schlögl undB. Steinitz, J. Organometal. Chem.94, 87 (1975).     

Neue Wege der Analytik durch Kombination der direkten quantitativen Dünnschicht-Chromatographie mit elektronischer Datenverarbeitung

A computer program for direct evaluation of thin-layer chromatograms, which already was described earlier [3] has been tested with a laboratory and some technical formulations of a pesticide. Results have been compared with those obtained by two conventional methods. Mean relative standard deviation calculated from results compiled by electronic data processing (method A) is about 6%, compared to 10% received by graphic method (method C) which is employed by most investigators. In addition, overall time of analysis is 34% higher if graphic method is used. Method A saves time and expense especially in routine analysis because working of the process is easier and may be performed even by assistent personal. The proposed method is suitable for the determination of different active ingredients and impurities even in difficult technical products.     

Oligonucleotide Analogues with Integrated Bases and Backbone. Part 14

The self‐complementary tetrameric propargyl triols 8, 14, 18 , and 21 were synthesized to investigate the duplex formation of self‐complementary, ethynylene‐linked UUAA, AAUU, UAUA, and AUAU analogues with integrated bases and backbone (ONIBs). The linear synthesis is based on repetitive Sonogashira couplings and C‐desilylations (34–72% yield), starting from the monomeric propargyl alcohols 9 and 15 and the iodinated nucleosides 3, 7, 11 , and 13 . Strongly persistent intramolecular H‐bonds from the propargylic OH groups to N(3) of the adenosine units prevent the gg‐type orientation of the ethynyl groups at C(5′). As such, an orientation is required for the formation of cyclic duplexes, this H‐bond prevents the formation of duplexes connected by all four base pairs. However, the central units of the UAUA and AAUU analogues 18 and 14 associate in CDCl₃/(D₆)DMSO 10 : 1 to form a cyclic duplex characterized by reverse Hoogsteen base pairing. The UUAA tetramer 8 forms a cyclic UU homoduplex, while the AUAU tetramer 21 forms only linear associates. Duplex formation of the O‐silylated UUAA and AAUU tetramers is no longer prevented. The self‐complementary UUAA tetramer 22 forms Watson–Crick‐ and Hoogsteen‐type base‐paired cyclic duplexes more readily than the sequence‐isomeric AAUU tetramer 23 , further illustrating the sequence selectivity of duplex formation.     

Analysis and parametric sensitivity of the behavior of overshoots in the concentration of a charged adsorbate in the adsorbed phase of charged adsorbent particles: practical implications for separations of charged solutes

In this work, an analysis of the parametric sensitivity of the overshoot in the concentration of the adsorbate in the adsorbed phase, which occurs under certain conditions during an ion-exchange adsorption process, is presented and used to suggest practical implications of the concentration overshoot phenomenon on operational policies and configurations of chromatographic columns and finite bath adsorption systems. The results presented in this work demonstrate and explain how the development of an overshoot in the concentration of the adsorbate in the adsorbed phase could be enhanced or suppressed by (i) varying the diffusion coefficient, D3, of the adsorbate relative to the diffusion coefficients, D1 and D2, of the cations and anions, respectively, of the background/buffer electrolyte, (ii) altering the initial surface charge density, delta0, of the charged adsorbent particles, (iii) varying the Debye length, lambda, and (iv) changing the initial concentration, Cd3(0), of the adsorbate in the bulk liquid of the finite bath. The influence of the pH and ionic strength, Iinfinity, of the liquid solution on the development of an overshoot in the concentration of the adsorbate in the adsorbed phase is also presented and discussed through the relationships of these parameters to delta0 and lambda, respectively. Furthermore, a detailed explanation of the effects of each parameter on the interplay between the diffusive and electrophoretic molar fluxes, as well as on the structure and functioning of the electrical double layer, which are responsible for the concentration overshoot phenomenon, is presented.     

Zur Kenntnis von Natrium-hexafluoromanganat(III)

Sodium hexafluoromanganate(III) has been synthesized by heating equimolecular quantities of Na₂MnF₅ and NaF in argon atmosphere. The compound is monoclinic witha=5.56 (1) Å,b=5.84 (1) Å,c=8.10 (2) Å, =90.7 (2) andZ=2. It is a high spin complex with _eff and the deformation of the octahedra is evident from its IR-spectra. Two enantiotropic transitions (at 562 and 653°C) and the melting point at 800°C have been observed.

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8. Mitt.: Mh. Chem.106, 483 (1975).     

Discussion on the method for the measurement of the flexural modulus of coupled materials and reasons of the shifts of theQ −1 maxima caused by coupling

Summary When measuringQ ^–1 and the flexural resonance frequency of bars clamped at one end, constituted by a viscoelastic polymeric material glued to a rigid support of modulusE ₁, it is possible to calculate the componentsE ₂ andE ₂ of the complex elastic modulus of the polymeric material examined. In this work the minimum (critical) value of the ratioa=E ₂ /E ₁=a _c and the values of the ratioQ ₂ ^–1/Q ^–1=F ₁ are evaluated beyond which no exact calculation ofE ₂ and ofQ ₂ ^–1 is possible.Within the confidence limits of the linear viscoelasticity theory, these values depend on the accuracy of measurement of both frequency and resonance curve, as well as on the instrument employed, on the operating temperature and on the ratio between the thicknesses of the two coupled materials.In order to keep outside the critical conditions, the most convenient method involves the use of measurements of coupled test-pieces having different ratiosz between their thicknesses and of supports having different modulusE ₁, depending on the field of temperature of the analysis ofE ₂ and tg ₂ concerning and E.P.R. elastomer and a vulcanized cis-1,4 polyisoprene in very wide ranges of temperature comprising the glass transition. Moreover, it is demonstrated by analysis the shift on the temperature axis of the tg maximum of the composite test-piece with respect to the position of the tg maximum of the polymeric material alone.With 11 figures and 1 table