New ionic phosphite ligands: synthesis and application in asymmetric Rh-catalyzed hydrogenation

A series of chiral ionic phosphite-type ligands bearing pyridinium and imidazolium fragments were prepared. Testing of these ligands in Rh-catalyzed asymmetric hydrogenation of dimethyl itaconate and methyl 2-acetamidoacrylate resulted in 95% ee of the products with 100% conversion of the reactants.     

Synthesis and immobilization of molecular switches onto titaniumdioxide nanowires

The precursor [Fe^III(L)Cl (L = N,N′-bis(2′-hydroxy-3′-methyl-benzyliden)-1,7-diamino-4-azaheptane) is combined with [Mo(CN)₈]^4? yields a star shaped nona-nuclear cluster, [Mo^IV{(CN)Fe^III(L)}₈]Cl₄. This Fe₈Mo molecule is a high-spin system at room temperature. On cooling to 20 K some of the iron(III) centres in the molybdenum(IV)-star switch to the low-spin state as proven by Mössbauer spectroscopy. This molecule was deposited on TiO₂ nanowires by electrostatic interactions between the cluster cations and the surface functionalized titanium oxide nanowire. The synthesis and surface binding of the multistable molecular switch was demonstrated using IR and UV–Vis spectroscopy (high-resolution) transmission electron microscopy ((HR)TEM) and Mössbauer spectroscopy. High- and low-temperature Mössbauer spectra indicate that the spin state transition of the free cluster molecules is preserved after surface binding. The above results emphasize the possibility of fabricating molecule-based low-dimensional structures by using traditional bottom-up approaches based on the electrostatic interaction between the cluster cations and polymer functionalized nanowires. These results can be generalized for the application to both charged and non-charged molecules.     

Spectroscopic Properties of Amine‐substituted Analogues of Firefly Luciferin and Oxyluciferin

Spectroscopic and photophysical properties of firefly luciferin and oxyluciferin analogues with an amine substituent (NH₂, NHMe and NMe₂) at the C6' position were studied based on absorption and fluorescence measurements. Their π‐electronic properties were investigated by DFT and TD‐DFT calculations. These compounds showed fluorescence solvatochromism with good quantum yields. An increase in the electron‐donating strength of the substituent led to the bathochromic shift of the fluorescence maximum. The fluorescence maxima of the luciferin analogues and the corresponding oxyluciferin analogues in a solvent were well correlated with each other. Based on the obtained data, the polarity of a luciferase active site was explained. As a result, the maximum wavelength of bioluminescence for a luciferin analogue was readily predicted by measuring the photoluminescence of the luciferin analogue in place of that of the corresponding oxyluciferin analogue.     

Thermodynamic characteristics of the adsorption of 1,3,4-oxadiazoles and 1,2,4,5-tetrazines from methanol and water–methanol solutions onto hypercrosslinked polystyrene

Russian Journal of Physical Chemistry A - The thermodynamic characteristics of the adsorption of several 1,3,4-oxadiazoles and 1,2,4,5- tetrazines from methanol and water-methanol solutions onto...     

Methyl methacrylate particles with amino groups on the surface: Colloid stability and sorption of biologically active substances

The present article investigates the influence of dispersion medium on the aggregate stability of cross-linked poly-(methyl methacrylate) particles on the surface layer of which aliphatic amino groups are localized. It is shown that particle size depends on the ionic strength of dispersion medium. The research determines the optimal content of cross-linked agent, ethylene glycol dimetharylate that results in the formation of cationic particles being stable in saline. Particle modification is performed by bovine serum albumin and luminophore fluorescein 5(6)-isothiocyanate. Protein sorption is observed not to influence luminescent properties of the particles. It is also determined that due to the aggregate stability of particles obtained from 5?wt% of ethylene glycol dimethacrylate in saline, the monodispersity and the absence of inversion of zeta potential in wide pH range is retained, such particles may be considered as perspective carriers of biologically active substances.     

Biomimetic membranes with aqueous nano channels but without proteins: impedance of impregnated cellulose ester filters

Earlier we have shown that many important properties of ionic aqueous channels in biological membranes can be imitated using simple biomimetic membranes. These membranes are composed of mixed cellulose ester-based filters, impregnated with isopropyl myristate or other esters of fatty acids, and can be used for high-throughput drug screening. If the membrane separates two aqueous solutions, combination of relatively hydrophilic polymer support with immobilized carboxylic groups results in the formation of thin aqueous layers covering inner surface of the pores, while the pore volume is filled by lipid-like substances. Because of these aqueous layers biomimetic membranes even without proteins have a cation/anion ion selectivity and specific (per unit of thickness) electrical properties, which are similar to typical properties of biological membranes. Here we describe frequency-dependent impedance of the isopropyl myristate-impregnated biomimetic membranes in the 4-electrode arrangement and present the results as Bode and Nyquist diagrams. When the membranes are placed in deionized water, it is possible to observe three different dispersion processes in the frequency range 0.1 Hz to 30 kHz. Only one dispersion is observed in 5 mM KH(2)PO(4) solution. It is suggested that these three dispersion features are determined by (a) conductivity in aqueous structures/channels, formed near the internal walls of the filter pores at high frequencies, (b) dielectric properties of the whole membrane at medium frequencies, determined by polymer support, aqueous layers and impregnating oil, and, finally, (c) by the processes in hydrated liquid crystal structures formed in pores by impregnating oil in contact with water at low frequencies.     

1H NMR cryoporosimetry of swollen hypercrosslinked polymers

The porous structure of two laboratory samples of hypercrosslinked polystyrene networks with a crosslinking degree of 200%, the commercial hypercrosslinked sorbent MN-270 (Purolite Int.), and macroporous polystyrene sorbents Amberlite XAD-4 and Amberlite XAD-1600 were investigated by means of ¹H NMR cryoporosimetry. It was determined that the signal intensity of benzol, dioxane, dichloroethane and water protons previously frozen in polymer pores increases during solvent melt. Dependencies of the integral proton signal intensities on the sample temperature obtained in various solvents are discussed in terms of sample micropore accessibility and solvent—polystyrene interaction energy. Pore dimensions are estimated using the melting temperature value of ice according to the Gibbs—Thomson equation. We conclude that the obtained distribution curves reveal all hypercrosslinked polymers to be mainly microporous with diameter distribution maxima around 10 Å. It is shown that along with pores 120 Å in diameter, XAD-4 has a considerable amount of micropores. In contrast, XAD-1600 is ranged as a mesoporous sorbent.     

Isomorphous substitutions of rare earth elements for calcium in synthetic hydroxyapatites

Polycrystalline hydroxyapatites Ca(10-x)REE(x)(PO(4))(6)(OH)(2-x)O(x) were synthesized and studied by X-ray powder diffraction, infrared absorption, diffuse-reflectance spectroscopy, and thermogravimetry. The solubility limits x(max) of rare earth elements (REE) in Ca hydroxyapatites decreases with an increasing REE atomic number from x(max) = 2.00 for La, Pr, and Nd to x(max) = 0.20 for Yb at 1100 °C. Refinements of X-ray diffraction patterns by the Rietveld method show that REE atoms substitute for Ca preferentially at the Ca(2) sites of the apatite structure. The substitution decreases the Ca(2)-O(4) atomic distances in the calcium coordination polyhedra and increases the Ca(2)-O(1,2,3) distances. This observation shows that interatomic distances depend not only on radii of the ions involved in the substitution but also on their charges.     

Push-pull nitrile ligands exhibit specific hydration patterns

The reaction between K[PtCl(3)(Me(2)SO)] or prepared in this work cis- and trans-[PtCl(2)(NCNR(2))(Me(2)SO)] (R(2) = Me(2), 1; C(4)H(8)O, 2; C(5)H(10) 3) with an excess of NCNR(2) in water gives the cationic bischelate [Pt{κ(2)-N,N'-NH=C(NMe(2))OC(NMe(2))=NH}(2)](2+) (4(2+)) and the monochelates [PtCl{κ(2)-N,O-NH=C(NR(2))NC(NR(2))=O}(Me(2)SO)] (R(2) = C(4)H(8)O, 5; C(5)H(10), 6). Complex 4(2+) was released from the reaction mixture as 4·[PtCl(3)(Me(2)SO)](2)·(H(2)O)(2) or it was precipitated as 4·[A](2) (A = pic, 4·[pic](2); PF(6), 4·[PF(6)](2); BPh(4), 4·[BPh(4)](2)·(NH(2)CONMe(2))) by addition of picric acid, NaPF(6), or NaBPh(4), respectively, to the filtrate obtained after separation of 4·[PtCl(3)(Me(2)SO)](2)·(H(2)O)(2). In 2, the dialkylcyanamide ligand undergoes bond cleavage giving the known trans-[PtCl(2){N(H)C(4)H(8)O}(Me(2)SO)] (trans-7). All complexes were characterized by elemental analyses (C, H, N), high resolution ESI-MS, IR, (1)H and (13)C{(1)H} NMR spectroscopic techniques, including 2D NMR correlation experiments ((1)H,(1)H-COSY, (1)H,(13)C-HMQC/(1)H,(13)C HSQC, (1)H,(13)C-HMBC, and (1)H,(1)H-NOESY). The structures of cis-1, cis-3, 4·[PtCl(3)(Me(2)SO)](2)·(H(2)O)(2), 4·[BPh(4)](2)·(NH(2)CONMe(2)) and 5 were determined by a single-crystal X-ray diffraction.     

Palladium-catalyzed allylic substitution assisted by 1,3,2-diazaphospholidine derivatives of (<Emphasis Type="Italic">R,R</Emphasis>)-<Emphasis Type="Italic">N</Emphasis>-naphthyltartarimide

P,P-Bidentate diamidophosphite ligands containing the (3R,4R)-3,4-dioxy-1-(1-naphthyl)pyrrolidine-2,5-dione framework and 1,3,2-diazaphospholidine rings with the stereogenic P atoms were obtained. The use of these ligands provides up to 85% ee in Pd-catalyzed asymmetric amination of (E)-1,3-diphenylallyl acetate and up to 95% ee in its asymmetric alkylation with dimethyl malonate.