The first platinum(IV) complexes involving aromatic cytokinins or cyclin-dependent kinase inhibitors derived from 6-benzylaminopurine: X-ray structures of

A series of Pt(IV) complexes with cytokinins or CDK-inhibitors derived from 6-benzylaminopurine (Bap) of the composition [Pt^IV(LH⁺)Cl₅] (1–14), where LH⁺ stands for protonated form of the Bap derivative (1–12), Boh = 6-(benzylamino)-2-[(3-hydroxypropyl)amino]-9-isopropylpurine, bohemine (13) and Ros = 6-(benzylamino)-2-[(1-hydroxymethylpropyl)amino]-9-isopropylpurine, roscovitine (14), have been prepared.They have been fully characterized by microanalysis, conductivity, FT-IR, ¹H, ¹³C, ¹⁵N and ¹⁹⁵Pt NMR and ES+ mass spectroscopy.It has been found that the cytokinin molecule is coordinated via N9 atom to platinum(IV) and N1, N7-protonated in case of complexes 1–12, and N7 coordinated and N1-protonated in case of complexes with CDK inhibitors (13 and 14).Predicted molecular geometries of the complexes have been supported by DFT calculations at the B3LYP level with the 6-311+G^**/LANL2DZ and aug-cc-pVDZ/LANL2DZ basis sets.All of the compounds have been tested in vitro for their cytotoxicity against four human cancer cell lines: malignant melanoma (G361), osteogenic sarcoma (HOS), chronic myelogenous erythroleukemia (K562) and breast adenocarcinoma (MCF7).The best result has been achieved for complex 14, where IC₅₀ = 17 μM against K562. The molecular structures of two ionic pair compounds have been determined by a single crystal X-ray analysis.     

Pd-induced ordering of 2D Pt nanoarrays on phosphonated calix[4]arenes stabilised graphenes

p-Phosphonic acid calix[4]arenes render high stability to exfoliated graphenes in water. These calix[4]arenes modified graphenes can be used as highly effective substrates to nucleate ultra-small Pd nanoparticles, which in turn serve as galvanic reaction templates for the generation of high density 2D arrays of Pt nanoparticles.     

Electrochemistry, spectroscopy, and electrogenerated chemiluminescence of some star-shaped truxene-oligofluorene compounds

We report electrochemical studies, spectroscopy, and electrogenerated chemiluminescence (ECL) of four monodisperse star-shaped truxene core-oligofluorene compounds (T1-T4). All oligomers produced stable radical anions and radical cations and showed blue ECL by ion annihilation with an intensity that could be seen with the naked eye. ECL spectra showed that all ECL emissions were at the same position as the fluorescence emission, except for T1, the compound with the shortest fluorene arms that produced some longer wavelength emission in addition to that seen in the fluorescence spectrum. When tetra-n-butylammonium oxalate was used as a coreactant for T1, the emission was much weaker than that in ion annihilation with the same long-wavelength emission observed, making it unlikely that this emission can be ascribed to excimer formation. The ECL intensity of T4 was about 80% of the common blue ECL emitter, 9,10-diphenylanthracene (DPA), under similar conditions.     

Comprehensive structural studies of 2',3'-difluorinated nucleosides: comparison of theory, solution, and solid state

The conformations of three 2',3'-difluoro uridine nucleosides were studied by X-ray crystallography, NMR spectroscopy, and ab initio calculations in an attempt to define the roles that the two vicinal fluorine atoms play in the puckering preferences of the furanose ring. Two of the compounds examined contained fluorine atoms in either the arabino or xylo dispositions at C2' and C3' of a 2',3'-dideoxyuridine system. The third compound also incorporated fluorine atoms in the xylo configuration on the furanose ring but was substituted with a 6-azauracil base in place of uracil. A battery of NMR experiments in D 2O solution was used to identify conformational preferences primarily from coupling constant and NOE data. Both (1)H and (19)F NMR data were used to ascertain the preferred sugar pucker of the furanose ring through the use of the program PSEUROT. Compound-dependent parameters used in the PSEUROT calculations were newly derived from complete sets of conformations calculated from high-level ab initio methods. The solution and theoretical data were compared to the conformations of each molecule in the solid state. It was shown that both gauche and antiperiplanar effects may be operative to maintain a pseudodiaxial arrangement of the C2' and C3' vicinal fluorine atoms. These data, along with previously reported data by us and others concerning monofluorinated nucleoside conformations, were used to propose a model of how fluorine influences different aspects of nucleoside conformations.     

Modifying metal nanoparticle placement on carbon supports using an aerosol-based process, with application to the environmental remediation of chlorinated hydrocarbons

A facile aerosol-based process (ABP) is developed to vary the placement of iron nanoparticles on the external surface of carbon microspheres or within the interior. This is accomplished through the competitive mechanisms of sucrose carbonization and the precipitation of soluble iron salts, in an aerosol droplet passing through a high temperature heating zone. At lower aerosolization temperatures, carbonization occurs first leading to iron salt precipitation on the external surface, while at higher temperatures interior placement occurs through concurrent iron salt precipitation and sucrose carbonization. The resulting composites are highly conducive to the reductive dechlorination of compounds such as trichloroethylene (TCE) as the carbon support is a strong adsorbent, and zerovalent iron effectively reduces TCE to innocuous gases such as ethane. Since both iron and carbon are widely used catalysts and catalyst supports, the simple process of modifying iron placement has significant potential applications in heterogeneous catalysis.     

Multidimensional Franck-Condon simulations of photodetachment spectra for the formate-water cluster anion: investigating H atom transfer along the HCOOH+OH reaction coordinate

A new multidimensional Franck-Condon (FC) simulation methodology was applied to an anionic-neutral cluster transition for the first time to investigate the use of photodetachment spectroscopy of the HCOO(-).H(2)O anion as a means to study the HCOO.H(2)O and HCOOH.OH neutral clusters. For the HCOO(-).H(2)O to HCOO.H(2)O transition, vibrationally resolved simulated spectra were obtained across the threshold detachment region, indicating that photodetachment spectroscopy of the respective anionic cluster should provide detailed structural information on the bifurcated HCOO.H(2)O neutral cluster. The simulations predict that the photodetachment spectra should display prominent progressions of both the intermolecular stretch and the in-plane OCO bending mode. In contrast, for the HCOO(-).H(2)O to HCOOH.OH transition, the vibronic FC simulations resulted in transitions with negligible intensities, despite the fact that the geometries of the respective anionic and neutral systems were similar. The low FC intensities were traced to the large off-diagonal elements of the Duschinsky matrix for this transition, which arise due to the considerable differences in the vibrational wave functions following hydrogen transfer.     

Spatial hydration maps and dynamics of naphthalene in ambient and supercritical water

The hydration structures and dynamics of naphthalene in aqueous solution are examined using molecular-dynamics simulations. The simulations are performed at several state points along the coexistence curve of water up to the critical point, and above the critical point with the density fixed at 0.3 g/cm(3). Spatial maps of local atomic pair-density are presented which show a detailed picture of the hydration shell around a bicyclic aromatic structure. The self-diffusion coefficient of naphthalene is also calculated. It is shown that water molecules tend to form pi-type complexes with the two aromatic regions of naphthalene, where water acts as the H-bond donor. At ambient conditions, the hydration shell of naphthalene is comprised, on average, of about 39 water molecules. Within this shell, two water molecules can be identified as pi-coordinating, forming close to one H-bond to the aromatic rings. With increasing temperature, the hydration of naphthalene changes dramatically, leading to the disappearance of the pi-coordination near the critical point.     

Application of associative neural networks for prediction of lipophilicity in ALOGPS 2.1 program

This article provides a systematic study of several important parameters of the Associative Neural Network (ASNN), such as the number of networks in the ensemble, distance measures, neighbor functions, selection of smoothing parameters, and strategies for the user-training feature of the algorithm. The performance of the different methods is assessed with several training/test sets used to predict lipophilicity of chemical compounds. The Spearman rank-order correlation coefficient and Parzen-window regression methods provide the best performance of the algorithm. If additional user data is available, an improved prediction of lipophilicity of chemicals up to 2-5 times can be calculated when the appropriate smoothing parameters for the neural network are selected. The detected best combinations of parameters and strategies are implemented in the ALOGPS 2.1 program that is publicly available at http://www.vcclab.org/lab/alogps.     

Affinity cryogel monoliths for screening for optimal separation conditions and chromatographic separation of cells

Suitable conditions for separating cells using a chromatographic procedure were evaluated in parallel chromatography on minicolumns. A 96-hole minicolumn plate filled with cryogel monoliths (18.8 mm x 7.1 mm ?) with immobilized concanavalin A was used. Chromatographic columns (113 mm x 7.1 mm ?) were used for chromatographic resolution of a mixture of Saccharomyces cerevisiae and Escherichia coli cells. Separation of a cell mixture containing equal amounts of cells of both types performed in a column format under the determined optimal conditions, resulted in a quantitative capture of applied S. cerevisiae cells, while E. coli passed through the column. Bound S. cerevisiae cells were released by flow-induced detachment and by compression of the adsorbent in the presence of 0.3 M methyl alpha-D-manno-pyranoside. The flowthrough and the eluted fractions were analyzed by plate counting and by registering metabolic activity of S. cerevisiae cells in the eluted fractions after capturing on ConA-cryogel monoliths in a 96-minicolumn plate format. The flowthrough fraction contained E. coli cells with nearly 100% purity, whereas the fraction eluted by compression of the adsorbent contained viable S. cerevisiae cells with 95% purity. Thus, an efficient chromatographic separation of cells was achieved using affinity cryogel column.     

Electronic interactions in a new pi-extended tetrathiafulvalene dimer

The first pi-extended tetrathiafulvalene (exTTF) dimer in which the two exTTF units are covalently connected by 1,3-dithiole rings has been obtained in a multistep synthetic procedure involving the Ullmann cross-coupling reaction by using copper(I) thiophene-2-carboxylate (CuTC). The electronic spectrum reveals a significant electronic interaction between the exTTF units. The electrochemical study carried out by cyclic voltammetry in solution and in thin-layer conditions, and the electrochemical simulation and spectroelectrochemical (SEC) measurements confirm the electronic communication and show that the oxidation of dimer 14 occurs as two consecutive 2 e(-) processes D(0)-D(0)-->D(2+)-D(0)-->D(2+)-D(2+). Theoretical calculations, performed at the B3P86/6-31G* level, confirm the experimental findings and predict that 14(2+) exists as a delocalized D(.+)-D(.+) species in the gas phase and as a localized D(2+)-D(0) species in solution (CH(3)CN or CH(2)Cl(2)). Oxidation of 14(2+) forms the tetracation 14(4+) which is constituted by two aromatic anthracene units bearing four aromatic, almost orthogonal 1,3-dithiolium cations.