New insights into the metal ion–peptide hydroxamate interactions: Metal complexes of primary hydroxamic acid derivatives of common dipeptides in aqueous solution

Complex formation of primary dipeptide hydroxamic acids, L-Ala-L-AlaNHOH and L-Ala-L-SerNHOH, as well as the corresponding Z-protected ones, Z-L-Ala-L-AlaNHOH and Z-L-Ala-L-SerNHOH (Z = benzyloxycarbonyl), with iron(III), aluminium(III), nickel(II), copper(II) and zinc(II) was studied in aqueous solution by pH-potentiometric and spectroscopic (UV–Vis, EPR, CD, ¹H NMR) methods. The exclusive formation of [O,O] chelated hydroxamate complexes was found with iron(III) and aluminium(III) with all the ligands. Formation of linkage isomers with the involvement of either [O,O] hydroxamate or [NH₂,CO] chelates was detected both in the zinc(II)-L-Ala-L-AlaNHOH and -L-Ala-L-SerNHOH systems. Upon increasing the pH, none of these chelating sets are capable of preventing the hydrolysis of the metal ion. The formation of stable complexes was found in the nickel(II) and copper(II) systems above pH ∼ 6 with a [NH₂, N_amide, N_hydrox.] binding mode after deprotonation and coordination of the peptide amide and the hydroxamate group. With an excess of copper(II), the formation of trinuclear [Cu₃H_xL₂]^x+4 type (x = −4 to −6) complexes as the major species was also detected. Blocking the terminal amino group in the Z-protected ligands results in a dramatic decrease of the nickel(II) and zinc(II) binding strengths, and insoluble complexes with copper(II). No indication was found for the role of the hydroxyl group of the serine moiety in metal ion binding.     

Effect of High-Humidity Testing on Material Parameters of Flexible Printed Circuit Board Materials

The tendency of polymers to absorb moisture impairs especially their electrical and mechanical properties. These are important characteristics for printed circuit board (PCB) materials, which should provide mechanical support as well as electrical insulation in many different environments in order to guarantee safe operation for electrical devices. Moreover, the effects of moisture are accelerated at increased temperatures. In this study, three flexible PCB dielectric materials, namely polyimide (PI), fluorinated ethylene-propylene (FEP), and polyethylene terephthalate (PET), were aged over different periods of time in a high-humidity test, in which the temperature was 85°C and relative humidity 85%. After aging, the changes in the structure of the polymers were studied by determining different material parameters such as modulus of elasticity, glass-transition temperature, melting point, coefficient of thermal expansion, water absorption, and crystallinity, and changes in the chemical structure with several techniques including thermomechanical analysis, differential scanning calorimetry, Fourier-transform infrared spectroscopy, moisture analysis, and a precision scale. The results showed that PI was extremely stable under the aging conditions and therefore an excellent choice for electrical applications under harsh conditions. Similarly, FEP proved to be relatively stable under the applied aging conditions. However, its crystallinity increased markedly during aging, and after 6000 h of aging the results indicated oxidation. PET suffered from hydrolysis during the test, leading to its embrittlement after 2000 h of aging.     

Adsorption of d-alaninol on Cu(1 0 0)

Adsorption of d-alaninol on Cu(1 0 0) at room temperature has been investigated by photoelectron spectroscopy in the soft X-ray and VUV energy range and low energy electron diffraction (LEED). d-Alaninol was found by LEED to self-assemble at full coverage; core and valence photoemission spectra are presented at low and full coverage. Chemisorption occurs at room temperature. The bonding at low coverage takes place at the hydroxylic group; at full coverage there is evidence of bonding for both hydroxylic and amino groups.     

Coumarins as Tool Compounds to Aid the Discovery of Selective Function Modulators of Steroid Hormone Binding Proteins

Steroid hormones play an essential role in a wide variety of actions in the body, such as in metabolism, inflammation, initiating and maintaining sexual differentiation and reproduction, immune functions, and stress response. Androgen, aromatase, and sulfatase pathway enzymes and nuclear receptors are responsible for steroid biosynthesis and sensing steroid hormones. Changes in steroid homeostasis are associated with many endocrine diseases. Thus, the discovery and development of novel drug candidates require a detailed understanding of the small molecule structure–activity relationship with enzymes and receptors participating in steroid hormone synthesis, signaling, and metabolism. Here, we show that simple coumarin derivatives can be employed to build cost-efficiently a set of molecules that derive essential features that enable easy discovery of selective and high-affinity molecules to target proteins. In addition, these compounds are also potent tool molecules to study the metabolism of any small molecule.     

Shear localisation in interfacial particle layers and its influence on Lissajous-plots

Interfacial rheological measurements often show in their nonlinear Lissajous-plots rhombus or saddle-like shapes indicating complex local deformation behaviour. A strong interacting silica particle and an almost not interacting clay particle were studied in respect to their interfacial rheological properties. Large amplitude oscillation shear measurements were performed with a bicone geometry and combined with optical measurements, from which particle tracks were calculated. A correlation was found between the appearance of shear localisation and Lissajous-plot shapes. Silica particles showed shear localisation at the bicone edge and rhombic plateaus in the Lissajous-plot, while the shear localisation for the clay particles was observed at the cup’s wall as saddle-like shaped Lissajous-plots     

Superconductivity in hydrogenated carbon nanostructures

We present an application of density functional theory for superconductors to superconductivity in hydrogenated carbon nanotubes and fullerane (hydrogenated fullerene). We show that these systems are chemically similar to graphane (hydrogenated graphene) and like graphane, upon hole doping, develop a strong electron phonon coupling. This could lead to superconducting states with critical temperatures approaching 100 K, however this possibility depends crucially on if and how metallization is achieved.     

Temperature and concentration gradient effects on heat and mass transfer in micropolar fluid

We report here the development of collinear laser spectroscopy (CLS) system at VECC for the study of hyperfine spectrum and isotopic shift of stable and unstable isotopes. The facility is first of its kind in the country allowing measurement of hyperfine splitting of atomic levels using atomic beams. The CLS system is installed downstream of the focal plane of the existing isotope separator online (ISOL) facility at VECC and is recently commissioned by successfully resolving the fluorescence spectrum of the hyperfine levels in \(^{85,87}\)Rb. The atomic beams of Rb were produced by charge exchange of 8 keV Rb ion beam which were produced, extracted and transported to the charge exchange cell using the ion sources, extractor and the beam-line magnets of the ISOL facility. The laser propagating opposite to the ion / atom beam direction was allowed to interact with the atom beam and fluorescence spectrum was recorded. The experimental set-up and the experiment conducted are reported in detail. The measures needed to be carried out for improving the sensitivity to a level necessary for studying short-lived exotic nuclei have also been discussed.     

Evidence for gap anisotropy in CaC6 from directional point-contact spectroscopy

We present the first results of directional point-contact spectroscopy in high-quality CaC6 samples both along the ab plane and in the c-axis direction. The superconducting order parameter Delta(0), obtained by fitting the Andreev-reflection (AR) conductance curves at temperatures down to 400 mK with the single-band 3D Blonder-Tinkham-Klapwijk model, presents two different distributions in the two directions of the main current injection, peaked at 1.35 and 1.71 meV, respectively. By ab initio calculations of the AR conductance spectra, we show that the experimental results are in good agreement with the recent predictions of gap anisotropy in CaC6.     

H- desorption from uracil via metastable electron capture

In this Letter we report an analysis of the quantum dynamics for the scattering of slow electrons off uracil molecules, leading to the formation of a trapped, metastable anionic state at around 9 eV of energy. This resonant state is seen to be capable of describing an anionic molecular precursor which can explain the desorption of the H- species observed in experiments on film deposited uracil samples.     

Self-interaction and strong correlation in DFTB

The density functional based tight-binding (DFTB) method can benefit substantially from a number of developments in density functional theory (DFT) while also providing a simple analytical proving ground for new extensions. This contribution begins by demonstrating the variational nature of charge-self-consistent DFTB (SCC-DFTB), proving the presence of a defined ground-state in this class of methods. Because the ground state of the SCC-DFTB method itself can be qualitatively incorrect for some systems, suitable forms of the recent LDA+U functionals for SCC-DFTB are also presented. This leads to both a new semilocal self-interaction correction scheme and a new physical argument for the choice of parameters in the LDA+U method. The locality of these corrections can only partly repair the HOMO-LUMO gap and chemical potential discontinuity, hence a novel method for introducing this further physics into the method is also presented, leading to exact derivative discontinuities in this theory at low computational cost. The prototypical system NiO is used as an illustration for these developments.