New insights on the active species and mechanism of cytotoxicity of salan-Ti(IV) complexes: a stereochemical study

Following the discovery of cisplatin, much effort has been devoted to the exploration of transition metal complexes as cytotoxic agents. We have recently introduced the highly efficient C(2)-symmetrical salan-Ti(IV) family of complexes, demonstrating high cytotoxicity toward colon and ovarian cells and enhanced hydrolytic stability in mixed organic/water solutions. The effect of stereochemistry is hereby reported, by comparing the cytotoxic activity and hydrolysis of pure enantiomers and their racemic mixture for four complexes of this family with different aromatic substitutions: para-Me, para-Cl, ortho-Cl, and ortho-OMe. These complexes include the trans-diaminocyclohexyl bridge, which enables ligand-to-metal chiral induction to give solely the Δ isomer when starting from the R,R ligand and vice versa. Different activity is obtained for the different stereochemical forms (Δ, Λ, and rac) in two of the four complexes, where for the other two either all forms are inactive or all are highly active. Additionally, where not all are of similar activity, the racemic mixture is the least active of the three. We therefore conclude that the salan ligand is essential for the fruitful biological interaction, which probably involves a chiral cellular target. The activity of the racemate differing from that expected from a simple mixture of enantiomers operating separately may be explained by the involvement of a polynuclear active species, where different metal centers might be of different configurations. This is particularly supported by the different polynuclear products of hydrolysis obtained from an optically pure complex and from the racemic one, as analyzed crystallographically. The former is an all-R,R chiral C(1)-symmetrical homodimer, while the latter is an achiral R,R-S,SC(i)-symmetrical heterodimer obtained through chiral recognition.     

Effect of Cd content on the structural characteristic and some physical properties of Zn1−x Cd x Se

The present work focuses on the structural, optical, and electrical properties of Zn_1?x Cd _x Se (0.1≤x≤0.25) compounds. The compounds were synthesized by solid state reaction. X-ray diffraction (XRD) patterns confirm that the samples have cubic single phase (zinc-blende) crystal structure with space group F-43m. The crystal structural parameters were refined by the Rietveld method using the FullProf program. It was found that the lattice parameters increase linearly with increasing the Cd content and obeys Vegard’s law. The refined values of the crystallite size and the bond lengths increase with increasing the Cd content. The energy band gap of the samples has been calculated and it was found that it decreased as Cd increased. The conductivity of the samples increases with increasing both of composition parameter x and temperature, and showing semiconducting behavior.     

Efficient text fingerprinting via Parikh mapping

We consider the problem of fingerprinting text by sets of symbols. Specifically, if S is a string, of length n, over a finite, ordered alphabet Σ, and S′ is a substring of S, then the fingerprint of S′ is the subset φ of Σ of precisely the symbols appearing in S′. In this paper we show efficient methods of answering various queries on fingerprint statistics. Our preprocessing is done in time O(n|Σ|lognlog|Σ|) and enables answering the following queries:

(1)Given an integer k, compute the number of distinct fingerprints of size k in time O(1).

(2)Given a set φΣ, compute the total number of distinct occurrences in S of substrings with fingerprint φ in time O(|Σ|logn).

     

Vapor phase absorption spectrum of 1-azaindolizine

A vibrationally very rich and sharp spectrum with noticeable rotational fine structure has been recorded for the lowest singlet in-plane polarized transition of 1-azaindolizine with origin at 30030.2 cm^?1. Through Franck-Condon relative intensity calculations, and a knowledge of the ground state fundamentals determined by ir measurements, a very detailed analysis of the spectrum has been achieved. Dependence of the band contours on interference between the allowed and vibronically induced intensity components has been noted. The large linewidths recorded for the second system are considered as possible evidence for the presence of a near-lying ${}^{\mathrm{<mtext>I</mtext>}}\text{nπ}{}^1$ state.     

Optical phonons in PbGa2S4 crystals

Raman scattering of light in a PbGa₂S₄ crystal is studied. The phonon spectrum of this crystal is calculated using factor group analysis for the first time. The number of active modes in the Raman spectrum, their symmetry, and the selection rules are determined. The modes observed in the Raman spectra are identified with the vibrations of the atoms comprising the crystal lattice of the PbGa₂S₄ compound.     

Transfer-printing of highly aligned DNA nanowires

We developed a simple method of reproducibly creating highly aligned DNA nanowires without any surface modifications or special equipment. Stretched DNA molecules initially present on the PDMS sheet were transferred onto another surface using transfer-printing (TP). Fluorescent microscopic and atomic force microscopic images revealed that many DNA molecules were highly aligned on surfaces after TP. Furthermore, it was also possible to realize the two-dimensional assembly of DNA nanowires by repeating TP.     

Reactions with 3,6‐diaminothieno[2,3‐b]‐pyridines: Synthesis and characterization of several new fused pyridine heterocycles

6‐Aminopyridine‐2(1H)thiones 1 reacting with α‐halo‐compounds 2a–c afforded the alkylthiopyridine derivatives 3a–c which in turn cyclized to the corresponding thieno[2,3‐b]pyridine derivatives 4a–c . Several thieno[2,3‐b]pyridine derivatives 7, 16, 19 , pyrido[3′,2′:4,5]thieno[3,2‐d]pyrimidine derivatives 6a,b, 11a–c, 21 and pyrido[3′,2′:4,5]thieno[3,2‐c]pyridazine derivatives 13, 17 were prepared starting from compounds 4a–c . © 2007 Wiley Periodicals, Inc. Heteroatom Chem 18:405–413, 2007; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20313     

Reactions with dimethylformamide‐dimethylacetal: Synthesis and reactions of several new pyridine and pyrazolo[3,4‐b]pyridine derivatives

6‐Aminopyridine‐2(1H)‐thiones 1a,b reacted with dimethylformamide‐dimethylacetal (DMF‐DMA) to give the corresponding 6‐{[(N,N‐dimethylamino)methylene]amino}pyridine derivatives 2a,b . The latter compounds reacted with hydrazine hydrate to afford the 3,6‐diamino‐1H‐pyrazolo[3,4‐b]pyridine derivative 4 and 3‐amino‐5‐hydrazino‐1H‐pyrazolo[4′,3′:5,6]pyrido[2,3‐d]pyrimidine derivative 7 , respectively. Compound 4 condensed with DMF‐DMA to yield the 3,6‐bis{[(N,N‐dimethylamino)methylene]amino}‐1H‐pyrazolo[3,4‐b]pyridine derivative 10 , which reacted with malononitrile to give the corresponding pyridopyrazolopyrimidine derivative 15 . © 2007 Wiley Periodicals, Inc. Heteroatom Chem 18:399–404, 2007; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20312