3,5-Bis(2-hydroxyphenyl)-1<Emphasis Type="Italic">H</Emphasis>-1,2,4-triazole based ligands — protonation and metal complex formation

3,5-Bis(2-hydroxyphenyl)-1H-1,2,4-triazole (H₂L^a) and 4-[3,5-bis(2-hydroxyphenyl)-1H-1,2,4-triazol-1-yl]benzoic acid (H₃L^b) have been prepared, and crystal structure of the intermediate 2-(2-hydroxyphenyl)-4H-1,3-benzoxazin-4-one has been determined. Temperature dependent ¹H NMR spectroscopic measurements of H₂L^a indicated dynamic behavior with the equilibrium between the two asymmetric tautomers. For H₃L^b, pD-dependent ¹H NMR spectroscopic measurements showed small but characteristic shifts in the range of 0 ≤ pD ≤ 1, indicative of a triazole nitrogen atom protonation; the corresponding pK _a of 0.98 ± 0.04 was determined by spectrophotometric titrations. (H₂O, 26°C, 1 M KCl/HCl). Formation of [Fe^III(L^a)]⁺ (pH 2.5) and [Fe^III(L^a)₂]⁻ (pH > 6) was verified by UV-Vis spectroscopy. Complex formation of H₃L^b with Al³⁺ and VO²⁺ was investigated by ¹H NMR spectroscopic titration and cyclic voltammetry, respectively. Single crystals of the phenoxo bridged [V^VO(HL^b)(EtO)]₂·2EtOH were characterized by X-ray structural analysis. Dedicated to Professor Milan Melník on the occasion of his 70th birthday     

FOURIER ANALYSIS OF TEMPORAL AND SPATIAL OSCILLATIONS OF TUNNELING CURRENT IN SCANNING TUNNELING MICROSCOPY

Partially oxidized Si(111) surfaces and surfaces of highly oriented pyrolytic graphite (HOPG) were studied by two different ultrahigh vacuum scanning tunneling microscope (UHV-STM) systems and by an STM system working under ambient conditions, respectively. The STM current images of partially oxidized Si(111) surfaces and HOPG surfaces were analyzed by one/two-dimensional fast Fourier transformation (1D-FFT/2D-FFT). The phenomenon of temporal oscillations of tunneling current on the partially oxidized Si(111) surfaces was detected with both UHV-STM systems. Temporal as well as spatial oscillations of tunneling current appeared in highly resolved STM current images of the Si(111) surfaces simultaneously, but both kinds of oscillations could be discriminated according to their different influence on the 2D-FFT spectra of the current images, while varying the scanning range and rate. On clean HOPG surfaces only spatial oscillations of tunneling current induced by the surface structure were observed.     

Recent advances in terahertz imaging

We review recent progress in the field of terahertz “T-ray” imaging. This relatively new imaging technique, based on terahertz time-domain spectroscopy, has the potential to be the first portable far-infrared imaging spectrometer. We give several examples which illustrate the possible applications of this technology, using both the amplitude and phase information contained in the THz waveforms. We describe the latest results in tomographic imaging, in which waveforms reflected from an object can be used to form a three-dimensional representation. Advanced signal processing tools are exploited for the purposes of extracting tomographic results, including spectroscopic information about each reflecting layer of a sample. We also describe the application of optical near-field techniques to the THz imaging system. Substantial improvements in the spatial resolution are demonstrated. Received: 29 January 1999 / Published online: 7 April 1999     

Changes in the Structural Dimensionality of Selenidostannates in Ionic Liquids: Formation,Structures, Stability,and Photoconductivity

In situ transformations of selenidostannate frameworks in ionic liquids (ILs) were initiated by treatment of the starting phase K₂[Sn₂Se₅] and the consecutive reaction products by means of temperature increase and/or amine addition. Along the reaction pathway, the framework dimensionalities of the five involved selenidostannate anions develop from 3D to 1D and back, both in top‐down and bottom‐up style. Addition of ethane‐1,2‐diamine (en) led to the reversion of the 2D→1D step from 2D‐{[Sn₂₄Se₅₆]^16?} to 1D‐{[Sn₆Se₁₄]^4?}. As rationalized by DFT investigations, the 2D anion is thermodynamically favored. Photoconductivity measurements reveal that all samples show Schottky contact behavior with absolute thresholds below 10 V. One of the samples exhibits conductive states within the energy range of visible photons.     

Einige Aspekte der Entwicklung radiometrischer Analysen- und Detektionsverfahren

Die Ausnutzung von Quanten- und Teilchenstrahlung zur Analyse von Stoiffverteilungen und Stoffzusammensetzungen hat im vergangenen Jahrzehnt einen beträctlichen und fast unübersehbaren Umfang angenommen.

Es werden mögliche Schicerpunkie der zukünftigen Anforderungen an solche Analysenverfahren — die sich aus der modernen Forschung und Entvicklung ergeben — aufgezeichnet und die Anwendungsmöglichkeiten und der Entwicklungsstand spezieller Verfahren besprochen. Insbesondere werden Mönlichkeiten der Gesamtbilddurstellung, der Scanning-Verfahren und der Oberflächenuntersuchungen dünnster Schichten und Fragen der Strukluraufklärung, der chemischen Bindungen bzw. Bindungskonfigurationen diskutiert.     

Time-resolved imaging of hydrogel printing via laser-induced forward transfer

In this work, the printing mechanism of an alginate-based hydrogel via laser-induced forward transfer (LIFT) is investigated by spatial and temporal high-resolved stroboscopic imaging. First, the generation of the liquid jet is studied at two different laser fluences in a process without collector slide. Furthermore, the impingement process onto the collector slide at the same fluence levels is observed. With the help of these images the development of the jet is explained. Besides the influences of the collector slide as well as the applied laser fluence on the transfer are demonstrated.     

Analyzing sub-100-μm samples with transmission terahertz time domain spectroscopy

The authors propose a method for the extraction of material parameter and thickness information from sub-100-μm thin samples using non-differential transmission terahertz time domain spectroscopy. The approach relies on an additional Fourier transform of the frequency dependent material parameters to a quasi space regime. In this quasi space, periodic Fabry-Perot oscillations from the frequency domain, which originate from multiple reflections inside the sample, correspond to discrete peaks. By iterative minimization of these peaks, the highly precise thickness information along with the refractive index and absorption coefficient of the sample can be determined. Experimental verification of the approach is also provided.     

Electronic effects of heterocyclic ring systems as evaluated with the aid of 13C and 15N NMR chemical shifts and NBO analysis

The electronic effects of the 5‐ and 6‐membered heterocyclic rings on the C?N? N unit of five different hydrazone derivatives of pyridine‐2‐, ‐3‐ and ‐4‐carbaldehydes, pyrrole‐2‐carbaldehyde, furan‐2‐ and ‐3‐carbaldehydes and thiophene‐2‐ and ‐3‐carbaldehydes have been studied with the aid of ¹³C and ¹⁵N NMR measurements together with the natural bond orbital (NBO) analysis. As model compounds are used the corresponding substituted benzaldehyde derivatives. The polarization of the C?N unit of the hydrazone functionality of the heteroaryl derivatives occurs in an analogous manner with that of phenyl derivatives. The electron‐withdrawing heteroaryl groups destabilize and the electron‐donating groups stabilize the positive charge development at the C?N carbon while the effect on the negative charge development is opposite. The ¹⁵N NMR chemical shift of the C?N and C?N? N nitrogens and the NBO charges at C?N? N unit can be correlated with the replacement substituent constants σ of the heteroaryl groups. ¹³C NMR shifts of the C?N carbon of N,N‐dialkylhydrazones of the heteroarenecarbaldehydes can be correlated with a dual parameter equation possessing the polar substituent constant σ* of the heteroaryl group and the electronegativity of the heteroatom as variables. Copyright © 2008 John Wiley & Sons, Ltd.