Vanadate complexes bearing an imidazolidine-bridged bis(aryloxido) ligand: synthesis and solid state and solution structure

A new imidazolidine-bridged bis(aryloxido) ligand precursor (H(2)L) [H(2)L = 2,2'-(imidazolidine-1,3-diylbis(methylene))bis(4-(1,1,3,3-tetramethylbutyl-2-yl)phenol)] was prepared in a relatively high yield (～60%) via a single-step Mannich condensation of 4-(1,1,3,3-tetramethylbutyl)phenol, ethylenediamine and paraformaldehyde at 2:1:3 molar ratio and characterized by chemical and physical techniques including X-ray crystallography. Reactions of H(2)L with [VO(OEt)(3)] at 1:1 and 1:2 molar ratios in toluene afforded [V(L-κ(3)O,N,N,O)(O)(OEt)] (1) and [V(2)(μ-L-κ(4)O,N,N,O)(μ-OEt)(2)(O)(2)(OEt)(2)] (2), respectively. Alcoholysis of 1 with EtOH enables elimination of one molecule of H(2)L and the formation of 2. Compounds 1 and 2 were characterized by IR and NMR spectroscopy as well as ES-MS experiments. The definitive molecular structure of 2 was provided by a single-crystal analysis and revealed its dinuclear nature, featuring two octahedral vanadium centres bridged by both OEt groups and the L ligand. The (51)V, (1)H and (13)C NMR spectra as well as ES-MS showed that 2 does not stay intact in solution and undergoes dissociation to give 1 and [VO(OEt)(3)].     

Characterization of a novel crown ether-bearing near-infrared heptamethine cyanine dye. A study of fluorescence quenching by lithium

The spectral characteristics of a crown ether-bearing heptamethine cyanine dye (JCM-15C5) and its quenching by lithium ion are reported. The absorbance maximum of the dye is at 776 nm in acetonitrile. This value matches the output of a commercially available laser diode (780 nm), thus making use of such a source practical for excitation. The emission wavelength of the dye in acetonitrile is at 799 nm. It was found that Li⁺ ion selectively quenches the fluorescence intensity of JCM-15C5 by the static quenching mechanism. The Stern-Volmer quenching constant (K_sv) was calculated from the Stern-Volmer plot and found to be 1.17×10⁷ M⁻¹ at room temperature. The detection limit for Li⁺ ion was found to be 7.43×10⁻² ppb. The stability constant (K_s) of the metal-dye complex was determined by fluorometric titration and found to be 5.40×10⁷ M⁻¹.     

Preparation and surface properties of low-density gels synthesized using prepolymerized silica precursors

Properties of silica xerogels and aerogels synthesized using a number of prepolymerized silica precursors were probed by 29Si magic-angle spinning (MAS) NMR spectroscopy, the small-angle X-ray scattering (SAXS) method, the nitrogen adsorption method, and transmission electron microscopy (TEM) to show that xerogels with attractive textural properties can easily be prepared using this type of precursors and the conventional one-step, base procedure. Pore sizes and overall pore volumes in these materials can be notably larger than those in the corresponding materials synthesized using tetraethoxysilane. This positive effect stems from the stronger structure of the polymeric network due to a higher degree of silica condensation on one side and a larger thickness of polymeric chains on the other. The thorough investigations of the fine silica structure demonstrate, however, that the relationship between the microstructure of the silica precursor and the micro- and macrostructures of dry gels is complex and the use of more condensed precursors favors, but does not necessarily ensure, more porous dry materials, under the same reaction conditions. Ethyl silicate 40 may be recommended as a low-cost precursor suitable for applications in this situation.     

Structural characterization of a methylaluminoxane (MAO)-magnesium dichloride cluster: model of MAO grafted onto a MgCl2 support

The study outlines our initial results that contribute to a better understanding of MAO/MgCl2 (MAO=methylaluminoxane) incorporation in the Cp2ZrCl2/MAO/MgCl2 catalytic system, which is currently of global industrial use. We show here that the[Al3(mu3-O)(Me)5]2+ moiety can be trapped by the tetrapodal [Mg3Cl4(thffo)4(THF)]2- macrounit to form a cluster [Al3Mg3(mu3-O)(thffo)4(Me)5Cl4(THF)] (thffo=2-tetrahydrofurfuroxide). From this perspective, this macrounit might be considered as a part of the MgCl2 support surface, which fulfills the requirement of a Al3(mu3-O) core.     

Ligand.Info small-molecule Meta-Database

Ligand.Info is a compilation of various publicly available databases of small molecules. The total size of the Meta-Database is over 1 million entries. The compound records contain calculated three-dimensional coordinates and sometimes information about biological activity. Some molecules have information about FDA drug approving status or about anti-HIV activity. Meta-Database can be downloaded from the http://Ligand.Info web page. The database can also be screened using a Java-based tool. The tool can interactively cluster sets of molecules on the user side and automatically download similar molecules from the server. The application requires the Java Runtime Environment 1.4 or higher, which can be automatically downloaded from Sun Microsystems or Apple Computer and installed during the first use of Ligand.Info on desktop systems, which support Java (Ms Windows, Mac OS, Solaris, and Linux). The Ligand.Info Meta-Database can be used for virtual high-throughput screening of new potential drugs. Presented examples showed that using a known antiviral drug as query the system was able to find others antiviral drugs and inhibitors.     

Photophysics and crystal structure of a europium(III) cryptate incorporating 3,3'-biisoquinoline-2,2'-dioxide

Increased interest in the emission properties of lanthanide(III) (Eu and Tb) complexes containing ultraviolet and visible sensitizers is being driven by the desire to produce efficient and selective luminescent probes of biological structure. Of special interest are cryptates and other macrocyclic chelating ligands that efficiently encapsulate the lanthanide ions. These species also form relatively stable systems and in some cases are well protected from penetration of the first coordination sphere by solvent molecules and counterions. This work describes the X-ray structure and various spectroscopic measurements on a europium cryptate containing 3,3'-biisoquinoline-2,2'-dioxide (biqO2). This cryptate has been previously recognized for special stability and luminescence efficiency. The compound, (Eu:biqO2.2.2)(CF3SO3)3.CH3CN.H2O, forms rhombic crystals with the space group Pbca. Absorption, emission, and excitation spectra at 293, 77, and 4 K as well as luminescence decay time measurements are used to characterize the solid state and solutions. The ligand-to-metal energy-transfer mechanism and thermally activated back-energy-transfer processes are analyzed and compared to previously published results on related Eu(III) cryptate systems. Preliminary results on the use of high liquid pressure to perturb ligand singlet and triplet states and, as a consequence, probe the ligand-metal orbital interactions are also presented.     

An efficient procedure to evaluate long-range coulombic interactions within the framework of the LCAO–CO method for infinite polymers

A very efficient and exact method for calculating the long-range effects in polymers is reported. The method is based on the multipole expansion within the Fock operator, and exact summation up to infinity is carried out. Only a small number of one-electron integrals have to be considered, while in the traditional approach one has to compute a large number of two-electron integrals. Results on LiH model polymer have been obtained with a remarkable accuracy within a negligible computing time.     

An activated trifluoromethyl group as a new synthon for 4,5-dihydro-1H-imidazole and 1,4,5,6-tetrahydropyrimidine systems

Treatment of 4-(trifluoromethyl)benzenamine 1a and 2-(trifluoromethyl)benzamine 1b with lithium 2-aminoethylamide gives 2-(4-aminophenyl)-4,5-dihydro-1H-imidazole 3a and 2-(2-aminophenyl)-4,5-dihydro-1H-imidazole 3b , respectively. Similar reactions of 1a and 1b with lithium 3-aminopropylamide produce the respective 2-(aminophenyl)-1,4,5,6-tetrahydropyrimidines 4a and 4b . 3-(Trifluoromethyl)benzenamine 1c is recovered unchanged from analogous mixtures. The mechanism is discussed.     

Handling and detection of 0.8 amol of a near-infrared cyanine dye by capillary electrophoresis with laser-induced fluorescence detection

We are interested in the detection of DNA adducts and other trace analytes by labeling them with a fluorescent tag followed by use of capillary electrophoresis with laser-induced fluorescence detection (CE-LIF) for high resolution and sensitivity. Towards this goal, here we report the following: (1) synthesis and handling properties of a near-IR, carboxyl-substituted heptamethine cyanine dye; (2) modification of an existing ball lens LIF detector to provide near-LIF detection with excitation at 785 nm for CE; and (3) corresponding handling and detection of as little as 0.8 amol of the dye by enrich-injection of 4.7 microl of 1 x 10(-13) mol/l dye in methanol from an 8-microl volume into a corresponding CE-LIF system. The electrolyte for the separation was methanol-40 mmol/l aqueous sodium borate (98:2, v/v). This finding encourages further exploration of the dye by functionalization of its carboxyl group for chemical labeling purposes.