Multiparametric microsensor chips for screening applications

The identification of drug targets for pharmaceutical screening can be greatly accelerated by gene databases and expression studies. The identification of leading compounds from growing libraries is realized by high throughput screening platforms. Subsequently, for optimization and validation of identified leading compounds studies of their functionality have to be carried out, and just these functionality tests are a limiting factor. A rigorous preselection of identified compounds by in vitro cellular screening is necessary prior to using the drug candidates for the further time consuming and expensive stage, e.g. in animal models. Our efforts are focused to the parallel development, adaptation and integration of different microelectronic sensors into miniaturized biochips for a multiparametric, functional on-line analysis of living cells in physiologically environments. Parallel and on-line acquisition of data related to different cellular targets is required for advanced stages of drug screening and for economizing animal tests.     

Dielectric relaxation of polystyrene with side-chain- and chain-end-labels

Polystyrenes with different concentrations of side groups with cyano groups were prepared and complex dielectric constants were measured in the range of the glass transition temperature and the frequency range of 10^–2–10⁷ Hz.The GPC and DSC measurements showed that the molecular weight of these polystyrenes was about 10500 g/mole and the glass transition temperatures were 89.5°C for all samples.The dielectric relaxation spectra obtained for the side group polystyrene labels and also the chain-end polystyrene labels prepared before [9] were analyzed to find out the degree of coupling of the chain-end and side-group labels with the cooperative reorientation of the polymeric matrix. The analysis of the spectra was carried out using the analysis method developed by Mansour and Stoll [6].The results obtained showed that both end- and side-group labels are strongly coupled with the segmental reorientation and relax with relaxation times longer than that of the segments.The value of logf _m = (logf _m(label)) – logf _m(matrix)) was obtained from the recently designed comparison diagram suggested by Mansour and Stoll [6, 14]. The value of logf _m depends on the label length in the case of chain-end labels.It was surprising to find that the side groups relax slower than the segments by only 0.9 decades. These results obtained implied that the label relaxes through a multistep relaxation mechanism of the side and end groups and not through a diffusion mechanism of the whole chain. In addition, the effective lengths of the relaxing units were determined using the empirical equation obtained before in the case of rodlike molecules in polyisoprene [7].     

Enthalpies of solution and of crystallization of lithium nitrate and of lithium nitrate trihydrate in water at 25°C

The enthalpies of crystallization of LiNO₃ and LiNO₃–3H₂O from aqueous solutions at 25°C, measured by a calorimetric method and determined from the previously published data on the concentration dependence of the enthalpy of solution, are reported. The results are compared with the values obtained from the concentration dependences of the activity coefficients and from the temperature dependences of the solubilities. The enthalpy of solution at infinite dilution and the enthalpy of hydration are given.     

Destabilized carbenium ions: Secondary and tertiary α-carbomethoxybenzyl cations

The secondary α-carbomethoxybenzyl cations a and the tertiary α-carbomethoxybenzyl cations d have been generated by electron impact-induced fragmentation from appropriately α-substituted methyl phenylacetate and 2-phenylpropionates 1–4. The ions a and d are further examples of destabilized carbenium ions with a push–pull substitution at the carbenium ion centre. The characteristic reaction of these ions is a rearrangement by a 1,2-shift of the methoxy group concomitant to the elimination of CO. This rearrangement reaction is associated with a very large and non-statistical kinetic energy release (a : T ₅₀ = 570 meV; d : T ₅₀ = 760 meV), which is attributed to tight transition states along the reaction coordinates corresponding to the three-membered cyclic oxonium ions b and h, respectively. The tertiary ion d can be distinguished from its more stable isomers f and g by the mass-analysed ion kinetic energy and collisional activation spectra. The investigation of specifically deuterated analogues of ions d and g reveals an isomerization of d to g via a species protonated at the phenyl group but no equilibration between d and g. This isomerization exhibits a large isotope effect for the hydrogen transfer, indicating similar energy barriers for the isomerization and for the CO elimination of d.     

Sedimentation of dissolved macromolecules in the vicinity of the consolute point 1. Strictly binary systems and kinetic considerations

This paper analyzes the effect of gravity on polymer solutions near the consolute point. Calculations are carried out for monodisperse polystyrene in cyclohexane using the Flory-Huggins expression with a concentration-dependent interaction parameter for the free energy of mixing. Depending on molecular weight and distance to the demixing temperature, the influence of gravity leads to non-negligible gradients of the volume fraction in the one-phase region as well as in the two-phase region. In particular, the effect of gravity on the measurement of the coexistence curve in a finite sample is calculated explicitly.In contrast to theory, experiments show that the concentration remains constant throughout the sample over a period of days as long as the system is kept in the homogenous region. Pronounced concentration gradients, however, are established in the twophase region within approximately one day. These findings are discussed with respect to sedimentation kinetics in terms of the droplet model of critical fluids.     

Neue Oxoterbate(IV) mit Lithium Rb2Li14[Tb3O14] und Li6Tb2O7

New Oxoterbates(IV) with Lithium: On Rb₂Li₁₄[Tb₃O₁₄] and Li₆Tb₂O₇ For the first time we prepared Rb₂Li₁₄[Tb₃O₁₄] as yellow single crystals from Li₈TbO₆ and Rb₂O (Tb:Rb = 1:2) [Ag-cylinder, 500°C, 30 d, then Au-tube, 700°C, 27 d]. The structure refinement [652 I₀ (h kl), four circle diffractometer Philips PW 1100, ω-scan, MoKα, R = 4.69%, R_w = 3.24%, absorption considered, Immm with a = 1 283.07(10), b = 790.87(7), c = 736.87(7)pm, Z = 2, d_x = 4.30 g · cm^?3] confirms that it is isotypic with K₂Li₁₄[Pb₃O₁₄]. Furthermore we got for the first time Li₆Tb₂O₇ as a bright yellow compound from Li₂O₂ and “Tb₄O₇*” [(Li:Tb = 3.4:1), Au-ube, 750°C, 13 d (powder), 850°C 22 d (single crystals)] and by thermal decomposition of Rb₂Li₁₄[Tb₃O₁₄] (Au-tube, 850°C, 25 d). Powder and single crystal data [1 327 I₀ (h kl), four circle diffractometer PW 1100, ω-scan, AgKα, R = 9.38%, R_w = 5.23%, absorption not considered, P2₁/a, a = 1 056.30(10), b = 613.50(4), c = 546.56(5) pm, β = 109.668(7)°, Z = 2, d_x = 4.67 g · cm^?3 d_pyc = 4.53 g · cm^?3] reveal a new type of structure that may be deduced by the NaCl-type of structure. The Madelung Part of Lattice Energy, MAPLE, Effective Coordination Numbers, ECoN, these via Mean Fictive Ionic Radii, MEFIR, are calculated and discussed.     

Neues über Oxouranate: Über α-Li6UO6. Mit einer Bemerkung über β-Li6UO6

New Investigations about Oxo Uranates: On α-Li₆UO₆. With a Remark about β-Li₆UO₆ The crystal structure of transparent, bright yellow single crystals of α-Li₆UO₆ has been determined. [a = 838.07(5), c = 738.34(7) pm; d_pyk = 4.02, d_x = 4.17 g · cm^?3; space group R3 ; Z = 3; R = 3.17%, R_w = 3.06%; 408 symmetry independent I₀(hkl); AgKα fourcircle diffractometer Philips PW 1100]. The structure is dominated by a threedimensional framwork of “hollow spaces”, built up by 12 O^2? (and 12 Li⁺). The Madelung Part of Lattice Energy, MAPLE, is calculated and discussed.     

Zn2+-dependent peptide nucleic acids probes

Binding of bis-picolylamine-naphthalene diimide-peptide nucleic acid conjugates to complementary DNA is strongly dependent upon Zn2+; ultimately, hybridization is switched ON in the presence muM Zn2+.     

A new route to achiral and chiral 1,2-bis(phosphino)ethanes, 1-arsino-2-phosphinoethanes, and 1,3-bis(phosphino)propanes and the molecular structure and catalytic activity of some rhodium(I) complexes derived thereof

A series of unsymmetrical 1,2-bis(phosphino)ethanes R(2)PCH(2)CH(2)PR'(2) and 1-arsino-2-phosphinoethanes R(2)AsCH(2)CH(2)PR'(2) mainly with bulky substituents R and R' were prepared from the cyclic sulfate by stepwise cleavage of the carbon-oxygen bonds by LiPR(2) and LiPR'(2) or LiAsR(2) and LiPR'(2), respectively. Analogously, racemic mixtures of R(2)PCH(2)CH(Me)PPh(2)(R =iPr, Cy ) as well as the enantiomers (R)-, (R)- and (R)-tBu(2)PCH(2)CH(Me)PPh(2)(R)- were obtained from the corresponding unsymmetrical cyclic sulfates and (S)-. On a similar route, the racemates of the 1,3-bis(phosphino)propanes R(2)PCH(2)CH(2)CH(Me)PPh(2)(R =iPr, tBu ), optically pure (R)- and (S,S)-iPr(2)PCH(Me)CH(2)CH(Me)PPh(2)(S,S)- were prepared. The reaction of [[RhCl([small eta](4)-C(8)H(12))](2)] with chelating ligands L-L, where L-L is R(2)PCH(2)P(men)(2)(R =iPr, Ph; men =(1S,2R,5S)-menthyl), Cy(2)AsCH(2)P(men)(2), or (R)-, (R)-, (R)-, (R)- and (S,S)-, in the presence of AgPF(6), gave the complexes [Rh(eta(4)-C(8)H(12))(L-L)]PF(6) which were used as pre-catalysts in the hydrogenation of the methyl ester of alpha-acetamidocinnamic acid (ACM). Depending on L-L, the solvent, the temperature and the pressure of H(2), optical yields of up to 69% ee were achieved. For two of the rhodium complexes, and, the molecular structures were determined by X-ray crystallography.