无外加催化剂条件下的克脑文盖尔缩合反应与溶剂效应的研究

本文报道了无外加催化剂条件下以DMF为溶剂芳香醛与丙二腈或氰基乙酸乙酯进行克脑文盖尔缩合反应, 此法产率较高。讨论了影响溶剂效应的一些因素。     

Spectroscopic characterization of zinc oxide nanorods synthesized by solid-state reaction

Well-crystallized zinc oxide nanorods have been fabricated by single step solid-state reaction using zinc acetate and sodium hydroxide, at room temperature. The sodium lauryl sulfate (SLS) stabilized zinc oxide nanorods were characterized by using X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy and photoluminescence spectroscopy. The X-ray diffraction revealed the wurtzite structure of zinc oxide. The size estimation by XRD and TEM confirmed that the ZnO nanorods are made of single crystals. The growth of zinc oxide crystals into rod shape was found to be closely related to its hexagonal nature. The mass ratio of SLS:ZnO in the nanorods was found to be 1:10 based on the thermogravimetric analysis. Blue shift of photoluminescence emission was noticed in the ZnO nanorods when compared to that of ZnO bulk. FT-IR analysis confirmed the binding of SLS with ZnO nanorods. Apart from ease of preparation, this method has the advantage of eco-friendliness since the solvent and other harmful chemicals were eliminated in the synthesis protocol.     

Microwave assisted solvent free amination of halo-(pyridine or pyrimidine) without transition metal catalyst

A solvent free direct amination of halo-(pyridine or pyrimidine) has been developed in good to high yields under computer-controlled microwave irradiation without transition metal catalyst. This reaction is a solvent and metal free, useful method for coupling of halo-(pyridine or pyrimidine) with pyrrolidine and piperidine derivatives by nucleophilic aromatic substitution (S_NAr).     

Microwave-assisted regioselective addition of P(O)-H bonds to alkenes without added solvent or catalyst

The addition of P(O)-H bonds to alkenes has been accomplished using microwave irradiation in the absence of added solvent and catalyst. In addition to single addition reactions, tandem hydrophosphinylation reactions with alkynes afforded unsymmetrical species such as phosphine oxide-phosphinates. [reaction: see text]     

Formylation without catalyst and solvent at 80 °C

A simple and efficient protocol for N-formylation of aliphatic and heterocyclic amines has been described with formic acid in the absence of catalyst and solvent.     

Microwave-assisted synthesis of diaryl or aryl-alkyl sulfones without catalyst

The microwave-assisted coupling reaction of electrondeficient aryl halides with sulfmic acid salts through SNAr-based addition reactions within 5-30 min. No catalysts were required under our conditions.     

Spectroscopic investigations and physico-chemical characterization of newly synthesized mixed-ligand complexes of 2-methylbenzimidazole with metal ions

Some mixed ligand complexes containing 2-methylbenzimidazole and thiocyanate ion were synthesized. Free ligands and their metal complexes were characterized using elemental analysis, determination of metal, magnetic susceptibility, molar conductivity, infrared, UV-VIS, and (¹H, ¹³C) NMR spectra, and X-ray structure analysis. The results suggest that the Ag(I) complex has linear geometry, Fe(II), Co(II), Ni(II), Cu(II), Zn(II), and Cd(II) have tetrahedral geometry, Pd(II) complex has square planar geometry, VO(IV) square pyramidal geometry, Pb(II) irregular tetrahedral geometry, and that the Cr(III) and Mn(II) complexes have octahedral geometry. The following general formulae were proposed for the prepared complexes: [AgBX], [CrB₃X₃], (HB)₂[MnB₂X₄] · 2B and [MB₂X₂], where B = 2-methylbenzimidazole, HB = 2-methylbenzimidazolium, X = thiocyanate ion, and M = VO(IV), Fe(II), Co(II), Ni(II), Cu(II), Zn(II), Pd(II), Cd(II), and Pb(II). Molar conductance of a 10⁻³ M solution in N,N-dimethyl formamide (DMF) indicates that all the complexes are non-electrolytes except the Mn(II) complex which is an electrolyte because the molar conductivity of its solution in DMF is high.     

Synthesis and properties of halogen- or methyl-containing poly(diphenylacetylene) membranes

Novel diphenylacetylenes with both trimethylsilyl groups and other substituents (R₂C₆H₃CCC₆H₄-p-SiMe₃, R = m,p-Cl,Cl, m,m-Cl,Cl, m,p-Br,Br, m,m-Br,Br, m,p-Me,Me, m,m-Me,Me, 1a–f, respectively) were polymerized with TaCl₅–n-Bu₄Sn to produce solvent-soluble polymers (2a–f). Most polymers (2a–e) had high molecular weight over 1 × 10⁶, and gave free-standing membranes by the solution casting method. Desilylation of these Si-containing polymer membranes was carried out with trifluoroacetic acid (TFA), which afforded solvent-insoluble desilylated polymer membranes (3a–e). According to thermogravimetric analysis (TGA), both Si-containing and desilylated polymers showed high thermal stability (T₀ ≥ 420 °C). The fractional free volume (FFV) of both Si-containing and desilylated polymer membranes (2a–d, 3a–d) were fairly large (ca. 0.27–0.32), while the FFVs of membranes (2e, 3e) were rather small (0.28 and 0.24). The oxygen permeability coefficients (P_O2) of 2a was as high as 5400 barrers, which is the largest among all the poly(diphenylacetylene) derivatives. Polymers 2b–d also exhibited high oxygen permeability, and their desilylated ones 3b–d retained similar high oxygen permeability. On the other hand, the P_O2 values of 2e and 3e were 1200 and 530 barrers, respectively, which are smaller than those of the halogen-containing polymers (2a–d and 3a–d).     

Spectroscopic characterization of porous nanohydroxyapatite synthesized by a novel amino acid soft solution freezing method

In this paper, we have reported a novel method to synthesize nanoporous hydroxyapatite (HAP) powders by freezing organic–inorganic soft solutions. The formation of porous and crystalline HAP nanopowder was achieved via calcining the samples at 600 °C followed by sintering at temperatures ranging from 900 °C to 1100 °C. The samples were analyzed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopic (SEM) techniques. The results showed the formation of a carbon free nanoporous hydroxyapatite powders due to the decomposition of organic template enclosing the precipitated HAP. It was also observed that the rapid grain growth with retainment of pores while the crystallinity of the HAP nanopowder increased with the increase in sintering temperature which is substantiated from the XRD and SEM results. Such organized porous materials can act as a better biomaterial for bone tissue engineering.     

Spectroscopic,thermal and electrochemical characterization of synthesized divalent transition metal complexes with cysteine and 4-substituted thiosemicarbazides

Mixed ligand complexes of Co^II, Ni^II and Cu^II with cysteine and 4-substituted thiosemicarbazides (l ¹–l ³) have been synthesized. The elemental analyses, molar conductance, spectra [electronic, i.r., ¹H-n.m.r., mass] and thermal studies were used to characterize the isolated complexes. Cyclic voltammetry was used to study the electrochemical behaviour of the Ni^II complexes. The i.r. and ¹H-n.m.r. showed that cysteine is deprotonated in the complex and acts as a binegative ligand coordinating through thiol sulphur and COOH groups. Also, thiosemicarbazides act as a bidentate ligand, coordination via NH₂ and (C=S) groups. Square-planar geometry has been proposed for Co^II, Ni^II and Cu^II ternary complexes.     

Spectroscopic characterization of carbon chains in nanostructured tetrahedral carbon films synthesized by femtosecond pulsed laser deposition

A comparative study of carbon bonding states and Raman spectra is reported for amorphous diamondlike carbon films deposited using 120 fs and 30 ns pulsed laser ablation of graphite. The presence of sp(1) chains in femtosecond carbon films is confirmed by the appearance of a broad excitation band at 2000-2200 cm(-1) in UV-Raman spectra. Analysis of Raman spectra indicates that the concentrations of sp(1)-, sp(2)-, and sp(3)-bonded carbon are approximately 6%, approximately 43%, and approximately 51%, respectively, in carbon films prepared by femtosecond laser ablation. Using surface enhanced Raman spectroscopy, specific vibrational frequencies associated with polycumulene, polyyne, and trans-polyacetylene chains have been identified. The present study provides further insight into the composition and structure of tetrahedral carbon films containing both sp(2) clusters and sp(1) chains.     

Spectroscopic investigations of solvent effect on chiral interactions

The spectrophotometric method was used to determine the mechanism of chiral interactions between a known chiral selector, tert-butyl carbamoylated quinine (t-BuCQN), and N-derivative amino acids (DNB-Leu). Results obtained on binding constants, free energy of binding (DeltaG), and difference in free energy of binding (DeltaDeltaG) values seem to suggest that there are three possible types of interactions between DNB-Leu and t-BuCQN: electrostatic interaction between the carboxylate group of the DNB-Leu and the ammonium group of the t-BuCQN, the donor-acceptor charge-transfer type of interaction between the (acceptor) aromatic group of the amino acid and the (donor) aromatic group of the t-BuCQN, and the hydrogen-bonding interaction between the amide group of the DNB-Leu and the carbonyl group of t-BuCQN. The strongest interaction will be observed if all of three interactions are in operation as in the case of DNB-Leu. The electrostatic interaction seems to play the dominant role in the interactions. While the charge-transfer interaction is relatively weaker, it seems, however, to be responsible for enantiomeric selectivity, namely, the closer the electron acceptor dinitrophenyl group is to the electron donor quinoline group, the higher is the enantiomeric selectivity. Specifically, in solvent with high polarity, both donor and acceptor are solvated by solvent molecules, thereby preventing them from being close. As a consequence, the interaction will be weaker and, hence, lower enantiomeric selectivity. Solvation will be less in less polar solvent which, in turn, leads to stronger interaction and higher enantiomeric selectivity.     

Constant-potential pulse polarographic detection in flow-injection analysis without deaeration of solvent or sample

A constat-potential pulse waveform is applicable for the polacographic analysis of buffered solutions (pH ?= 7) of cathodically active metal ions without voltammetric interference from dissolved oxygen. The technique is demonstrated at a dropping mercury electrode for detection of lead(II) and cadmium(II) in a conventional polarographic Cell (ca. 75 ml) as well as for small samples (2 ml) in a flow-injection system. The flow-injection polarographic technique is recommended for higher sample throughout than conventional polagraphy and is demonstrated for an electroless copper plating solution containing about 1.5 × 10^–2 M copper(II).     

Spectroscopic and structural characterization of pascoite

Pascoite mineral having yellow-orange colour of Colorado, USA origin has been characterized by EPR, optical and NIR spectroscopy. The colour dark red-orange to yellow-orange colour of the pascoite indicates that the mineral contain mixed valency of vanadium. The optical spectrum exhibits a number of electronic bands due to presence of VO(II) ions in the mineral. From EPR studies, the parameters of g, A are evaluated and the data confirm that the ion is in distorted octahedron. Optical absorption studies reveal that two sets of VO(II) is in distorted octahedron. The bands in NIR spectra are due to the overtones and combinations of water molecules.     

Influence of solvent on platinum catalyst formation

The adsorption properties of Pt-black reduced in various solvents (water, sulfuric acid, ethanol, alkali, heptane) have been studied. The nature of solvent is shown to influence the catalyst surface formation, the heat of hydrogen adsorption and the ratio of its forms.

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Pt-, : , , , , . , , .

     

Spectroscopic characterization of 2-naphthylcarbene

The 308 nm excimer laser flash photolysis of 2-naphthyldiazomethane produces triplet 2-naphthylcarbene (λ_max = 362 nm) which decays with the observed pseudo-first-order rate constants (k_exptl) of 5.54 ± 0.03 × 10⁶; 3.33 ± 0.4 × 10⁶; 1.64±0.02 × 10⁷; and 3.05±0.4 × 10⁶ s^-1 in n-pentane, 2,2,4-trimethylpentane (2,2,4-TMP), benzene and Freon 113 respectively. In hydrocarbon solvents the observed decay of triplet 2-naphthylcarbene is correlated with the pseudo-first-order growth of the 2-naphthylmethyl radical (λ_max = 378 nm). Direct kinetic measurements of the reaction of triplet 2-naphthylcarbene in 2,2,4-TMP with cyclohexane, styrene, methanol and carbon tetrachloride yielded bimolecular quenching rate constants of 1.48 ± 0.04 × 10⁶;4.33 ± 0.1 × 10⁷;7.25 ± 0.5 × 10⁶; and 3.35 ± 0.07 × 10⁶M^-1S^-1. It is also found that 2-naphthylcarbene reacts with acetonitrile (k_q = 5.28 ± 0.1 × 10⁵ M^-1 s^-1) to form a nitrile ylide intermediate with a λ_max = 372 nm. These results are interpreted in terms of a rapid singlet-triplet 2-naphthylcarbene equilibrium.     

Spectroscopic characterization of natural corals

The FTIR, micro-Raman, NMR, and XPS spectra of 25 different natural corals have been compared. Reflectance and transmission absorbance IR and Raman data have been used as rapid and efficient means of classification of natural corals containing aragonite (non-precious white species), calcite (red, pink, precious white species), and organic material (black protein polymer). The combination of reflectance IR and infrared microscopy could serve as a rapid, non-destructive method for distinguishing natural corals from artificial, fake jewels.     

Spectroscopic characterization of ambers and amber-like materials

Longitudinal acoustic (LA) phonon of Baltic, Dominican and Kuji ambers, amber-like rosin and synthetic acrylic resin has been investigated by means of Brillouin light scattering (BLS) at room temperature. We observed a pair of LA phonon peaks and a broad quasi-elastic scattering peak in backscattering spectra from ambers. The LA phonon frequencies were found to be 16.97–17.11 GHz for Baltic ambers, 17.23–17.68 GHz for Dominican ambers and 17.70–17.97 GHz for Kuji ambers, respectively. We would like to point out that the LA phonon frequency can be a good physical quantity to specify the amber-producing district. We also present a correlation between the BLS spectrum and infrared absorption spectrum of ambers and amber-like materials.     

SAR and pH stability of cyano-substituted epothilones

[formula: see text] 3-Cyano epothilones 15-18 are the only examples of non-hydroxy C-3-substituted analogues. Their tubulin binding affinity and cytotoxicity provide meaningful structure-activity relationship information on the dependence of C-1/C-3 conformation upon activity. 12-Cyano epothilone 24 has improved pH stability over epothilone B, and its activity further supports the hypothesis that C-12 stereochemistry is not critical for tubulin affinity.