Manipulating the surface properties of polyacrylamide with nitrogen plasma

Polyacrylamide (PAL) was physically adsorbed onto a hydroxylated silicon surface to form a uniform PAL film and the up-top PAL thin film was treated by nitrogen (N₂) plasma for surface modification. The atomic composition of the modified surface of the PAL film adsorbed on silicon substrate was analyzed with Fourier Transform Infrared Spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The surface energy of PAL film was calculated from the data of contact angle of three-probe liquid. The FTIR results show an increase of peak intensity at 1214 cm⁻¹ (NH₂ stretch vibration) after the nitrogen plasma treatment, which confirms that the nitrogen was grafted to the PAL surface in the process of N₂-plasma treatment. The XPS results show that the ratio of relative intensity of N1s to O1s increases with increasing the plasma treatment time, which further affirms the formation of the amine groups on the PAL surface after the nitrogen plasma treatment. The surface tension increases with increasing the plasma grafting time. However, the surface energy decreases rapidly at the early stage when stored in air and approaches to an equilibrium value. It suggests that some physically-adsorbed ions and alkyl radicals on PAL surface can rapidly lose their activities. The increase of the surface tension of the plasma treated PLA films is due to the amine groups covalently grafted to PAL surface.     

Chiral base route to functionalised cyclopentenyl amines: formal synthesis of the cyclopentene core of nucleoside Q

A chiral base route to a range of highly functionalised amino cyclopentenes has been developed. The key asymmetric step involved the chiral lithium amide base-mediated rearrangement of a protected trans-4-hydroxy cyclopentene oxide to give an allylic alcohol (88% ee). Subsequent Overman rearrangement gave a protected trans-1,2-aminocyclopentenol whereas Mitsunobu substitution with BocNHNs gave a protected cis-amino cyclopentenol. Both are proven intermediates for natural product synthesis. The protected cis-aminocyclopentenol was transformed in a few steps into a precursor of the cyclopentene core of nucleoside Q, a natural product whose deficiency in animals is related to tumour growth.     

N–N2 state to state vibrational-relaxation and dissociation rates based on quasiclassical calculations

Interpolation formulas are presented to reproduce the rate coefficients for vibrational–translational energy exchange and dissociation for the N + N₂ collision process. The original data have been obtained by quasiclassical method in a detailed way, including the effect of molecular rotation. The fitting procedure results are compared with original data and the related error is evaluated. Comparison with global experimental dissociation results is also presented.     

Vicarious nucleophilic substitution in enamine derivatives of 1-hydroxynaphthalene-2,4-dicarbaldehyde

The reaction of aromatic amines with highly stable Schiff base enamines formed from an alkyl amine and 1-hydroxynaphthalene-2,4-dicarbaldehyde resulted in nucleophilic substitution of the alkyl amine with the aromatic amine in ethyl alcohol at room temperature within 1-2 min. This reactivity, regioselectivity and formation of stable derivatives are due to extra stabilization through extended conjugation in these systems.     

Synthesis and structural characterization of ferrocene-based bis(pyrazol-1-yl)borate ligands: FcB(Me)pz2K, Fc2Bpz2K, and 1,1′-fc[B(Me)pz2]2K2 (Fc: ferrocenyl, fc: ferrocenylene, pz: pyrazolyl)

Reaction of the ferrocenyl(dimethylamino)boranes FcB(Me)NMe₂, Fc₂BNMe₂, and 1,1′-fc[B(Me)NMe₂]₂ with 1:1 mixtures of pyrazole and potassium pyrazolide in refluxing THF gave the potassium salts of the ferrocene-based bis(pyrazol-1-yl)borate ligands FcB(Me)pz₂K, Fc₂Bpz₂K, and 1,1′-fc[B(Me)pz₂]₂K₂ in good yield (Fc: ferrocenyl, fc: ferrocenylene, pz: pyrazolyl). In the solid state, FcB(Me)pz₂K and Fc₂Bpz₂K form centrosymmetric dimers with short K?Cp contacts suggesting an η⁵ coordination mode of the potassium ion. The crystal lattice of the ditopic ligand 1,1′-fc[B(Me)pz₂]₂K₂ consists of coordination polymer strands featuring essentially the same structural motif that has been observed for the monotopic derivatives. All three scorpionate ligands are thus promising building blocks for the preparation of ferrocene-containing multiple-decker sandwich complexes.     

Influence of conjugated nitrogenous bases on the spectra and structure of mixed-ligand nickel(II) chelates containing β-diones

The infrared and electronic excitation spectra of a series of new nickel(II) chelates containing an-diimine (or nitrogenous base, enR) and the anion of a-dione (1,3-ketoenol or 1,3-ketoester,H) were obtained in the solid state and in solution. The composition and the overall structure of the new chelates in the solid state depends on ligand concentration, the substituents within the-dionato moiety and the counterion present. The IR and electronic excitation spectra of [Ni(enR)₂ ]NO₃ and [Ni(enR)(O₂NO)] indicate, in conjunction with other physicochemical measurements, bidentate coordination of the ligands, while the spectral shifts reveal replacement of the (O,O)nitrato group by basic solvents. The existence of the nickel(II) in an octahedral environment is confirmed by an X-ray structure analysis of [Ni(dpamH)₂acac]NO₃ · CH₃OH (monoclinic, space groupP2_l/n, a=17.296(1),b=7.462(1),c=21.604(3) å,=95.65(1),Z=4, R=0.0534,Rw=0.0600), where dpamH denotes the 2,2-dipyridylamine.     

Structure and protonation of some indolizine derivatives studied by ab initio MO calculations

Some gauge invariant atomic orbitals-coupled-perturbed Hartree-Fock (GIAO-CPHF) calculations were performed for seven indolizine derivatives and their monoprotonated forms. Chemical shift, molecular geometry, and charge distribution data are reported for each molecule. The calculations support the results of nuclear magnetic resonance (NMR) spectroscopy measurements showing that protonation occurs preferentially at N1. The good agreement between the calculated and observed ¹³C and ¹⁵N chemical shifts show that such calculations can be used for chemical shift assignment purposes. Cation structures and probable sites for electrophilic reaction or second protonation are also discussed.     

Computing global minima to polynomial optimization problems using Gröbner bases

The local optimality conditions to polynomial optimization problems are a set of polynomial equations (plus some inequality conditions). With the recent techniques of Gröbner bases one can find all solutions to such systems, and hence also find global optima. We give a short survey of these methods. We also apply them to a set of problems termed with exact solutions unknown in the problem sets of Hock and Schittkowski. To these problems we give exact solutions.     

Molar heat capacities and volumes of transfer of cytosine,thymine, caffeine and 1,3-diethylthymine to aqueous solutions of glycyl-glycine and L-α-alanyl-L-α-alanine at 25°C

Densities and specific heat capacities of ternary aqueous systems containing dipeptides (glycyl-glycine or L--alanyl-L--alanine) and nucleic acid bases (cytosine or thymine) or their alkyl derivatives (1,3-diethylthymine or caffeine) were determined at 25°C by flow calorimetry and flow densimetry. The partial molar volumes and heat capacities of transfer at infinite dilution of the different nucleic acid bases from water to water+dipeptide solutions were obtained therefrom. Except for the case of the transfer of cytosine to aqueous glycyl-glycine solutions where a small positive dependence of the transfer quantities was observed with the dipeptide concentration, the values of the heat capacities of transfer were in general low, positive or negative, depending on the compensation of hydrophobic-hydrophilic interactions between the dipeptide and the base. The volumes of transfer of most of the bases are very small, within the limit of the experimental error.     

Synthesis of alkylN-(α-amidomethyl)glycinates from glycine esters,aroylamides, and formaldehyde

A one-step synthesis of alkylN-(-amidomethyl)glycinates from glycine esters or their salts, formaldehyde, and aroylamides was developed. The effect of the structure of the amide component and the reaction conditions on the yields of the products was investigated.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1078–1080, June, 1994.