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61.
Gyarfas BJ Wiggins B Zosel M Hipps KW 《Langmuir : the ACS journal of surfaces and colloids》2005,21(3):919-923
Scanning tunneling microscopy (STM) is utilized to study the solution-solid interface formed between Au(111) and solutions of coronene in hexanoic, heptanoic, and octanoic acids. In all three cases adsorbed coronene is observed and lays flat on the metal surface. Heptanoic and hexanoic acid solutions produce a hexagonal symmetry monolayer. For the heptanoic and hexanoic cases, dipole-image dipole interactions and H bonding stabilize a surface structure in which 12 acid molecules surround each coronene and produce a coronene spacing of 1.45 nm. In the case of octanoic acid as solvent, the incorporation of the solvent into the monolayer is not as strongly favored. The coronene spacing can range from close-packed (1.2 nm) with no solvent presumed present in the monolayer, to 1.50 nm with up to 12 solvent molecules surrounding each coronene. The close-packed regions have hexagonal symmetry, as do those with the largest (1.5 nm) spacing. Heptanoic acid solutions give the clearest STM images and are associated with the most stable two-component monolayer. The present paper demonstrates that non-covalent interactions at the solution-metal interface can lead to complex multicomponent monolayer structures. 相似文献
62.
Lenghor N Grudpan K Jakmunee J Staggemeier BA Quigley WW Prazen BJ Christian GD Ruzicka J Synovec RE 《Talanta》2003,59(6):1153-1163
A sequential injection analysis (SIA) system is coupled with dynamic surface tension detection (DSTD) for the purpose of studying the interfacial properties of surface-active samples. DSTD is a novel analyzer based upon a growing drop method, utilizing a pressure sensor measurement of drop pressure. The pressure signal depends on the surface tension properties of sample solution drops that grow and detach at the end of a capillary tip. In this work, SIA was used for creating a reagent concentration gradient, and for blending the reagent gradient with a steady-state sample. The sample, consisting of either sodium dodecyl sulfate (SDS) or poly(ethylene glycol) at 1470 g mol−1 (PEG 1470), elutes with a steady-state concentration at the center of the sample plug. Reagents such as Brij®35, tetrabutylammonium (TBA) hydroxide and β-cyclodextrin were introduced as a concentration gradient that begins after the sample plug has reached the steady-state concentration. By blending the reagent concentration gradient with the sample plug using SIA/DSTD, the kinetic surface pressure signal of samples mixed with various reagent concentrations is observed and evaluated in a high throughput fashion. It was found that the SIA/DSTD method consumes lesser reagent and required significantly less analysis time than traditional FIA/DSTD. Four unique chemical systems were studied with regard to how surface activity is influenced, as observed through the surface tension signal: surface activity addition, surface activity reduction due to competition, surface activity enhancement due to ion-pair formation, and surface activity reduction due to bulk phase binding chemistry. 相似文献
63.
The substitution chemistry of TcCl(3)(PPh(3))(2)(CH(3)CN) is rather facile relative to the analogous rhenium complex, since both the chloride and phosphine ligands are easily substituted for various pyridine ligands. Consequently a series of Tc(III) complexes with amine, pyridine, and polypyridyl ligands were prepared and characterized by (1)H NMR and cyclic voltammetry. In addition, the zinc reduction of TcCl(4)(py)(2) in the presence of pyridine results in TcCl(2)(py)(4). Structural and spectroscopic data indicate that this Tc(II) complex exhibits strong metal-pyridine interactions characteristic of low-valent amine complexes of Re(II) and Os(II). For example, a decrease of 0.04 and 0.06 ? is observed for the trans-Tc-N bond length in TcCl(2)(py)(4 )relative to mer-TcCl(3)(pic)(3) and [TcCl(2)(py)(3)(PPh(3))](+), respectively. This ability of pyridine to function both as a strong sigma-donor and moderate pi-acid ligand has resulted in the isolation of technetium complexes in various oxidation states with similar ligand environments. As a result, a structural comparison of [TcCl(2)(py)(3)(PPh(3))](+), TcCl(2)(py)(4), TcCl(tpy)(py)(2), and other known Tc(III) and Tc(II) pyridine complexes is presented. Crystals of [TcCl(2)(py)(3)(PPh(3))]PF(6) are triclinic, with space group P&onemacr;, Z = 2, and lattice parameters a = 12.677(4) ?, b = 13.064(4) ?, c = 13.103(5) ?, alpha = 110.14(3) degrees, beta = 101.12(3) degrees, gamma = 96.61 degrees, V = 1959 ?(3), and R = 0.0615 (R(w) = 0.1148). Crystals of TcCl(2)(py)(4) are tetragonal, with space group I4(1)/acd, Z = 8, and lattice parameters a = 15.641(4) ?, c = 16.845(6) ?, V = 4121 ?(3), and R = 0.0373 (R(w) = 0.0290). Crystals of TcCl(tpy)(py)(2) are orthorhombic, with space group C222(1), Z = 4, and lattice parameters a = 9.359(3) ?, b = 16.088(6) ?, c = 18.367(4) ?, V = 2765 ?(3), and R = 0.0499 (R(w) = 0.0599). 相似文献
64.
Eric E. Boros James B. Thompson Edgar R. Wood O. Bradley McDonald Timothy D. Spitzer Andrea M. Sefler Bryan R. Reep 《Journal of heterocyclic chemistry》2004,41(3):355-358
5‐Methoxy and 5‐anilinopyrido[2,3‐d]pyrimidin‐7(8H)‐ones 2a‐2f were obtained by a tandem Michael addition‐cyclization reaction of methanol and anilines with pyrimidinylpropynoate 5. Methoxy derivative 2a was obtained in 62% yield by treatment of 5 with methanol and potassium carbonate. Anilino derivatives 2b‐2f were prepared in 31–71% yields by reacting 5 with the corresponding anilines in refluxing methanol. This methodology accomplishes Michael‐addition and pyridopyrimidinone ring formation in one‐pot and affords the desired products in reasonable yield without chromatography. Propynoate 5 did not react with 4‐cyanoaniline under these conditions. Reaction of 5 with 2‐aminopyridine gave the unexpected arylpyrido[2,3‐d]pyrimidinone 8 in 58% yield and reaction of 5 with imidazole afforded Michael‐adduct 9 in 69% yield. Compounds 2a and 5 were submicromolar inhibitors of epidermal growth factor receptor (EGFR) tyrosine kinase. 相似文献
65.
The asymmetric Michael addition of glycine imine esters to simple α,β-unsaturated ketones via PTC is investigated. It is found that by employing 1 mol % of a chiral quaternary ammonium salt, derived from α-methylnaphthylamine in conjunction with Cs2CO3, high enantioselectivities can be obtained in conjugate additions involving simple alkylvinylketones. 相似文献
66.
Jun Liu Kelton A. Schleyer Tyrel L. Bryan Changjian Xie Gustavo Seabra Yongmei Xu Arjun Kafle Chao Cui Ying Wang Kunlun Yin Benjamin Fetrow Paul K. P. Henderson Peter Z. Fatland Jian Liu Chenglong Li Hua Guo Lina Cui 《Chemical science》2021,12(1):239
Heparanase (HPA) is a critical enzyme involved in the remodeling of the extracellular matrix (ECM), and its elevated expression has been linked with diseases such as various types of cancer and inflammation. The detection of heparanase enzymatic activity holds tremendous value in the study of the cellular microenvironment, and search of molecular therapeutics targeting heparanase, however, no structurally defined probes are available for the detection of heparanase activity. Here we present the development of the first ultrasensitive fluorogenic small-molecule probe for heparanase enzymatic activity via tuning the electronic effect of the substrate. The probe exhibits a 756-fold fluorescence turn-on response in the presence of human heparanase, allowing one-step detection of heparanase activity in real-time with a picomolar detection limit. The high sensitivity and robustness of the probe are exemplified in a high-throughput screening assay for heparanase inhibitors.Heparanase, a critical enzyme involved in the remodeling of the extracellular matrix, activates a disaccharide probe HADP to give a strong fluorescence signal. 相似文献
67.
Ozonolysis of tetramethylethylene: characterization of cyclic and open-chain oligoperoxidic products
The ozonolysis of tetramethylethylene (TME) in solution to high conversion in nonparticipating solvents at -60 degrees C yields predominantly oligoperoxides. For the first time, these products have been characterized using electrospray ionization mass spectrometry (ESI-MS) under soft ionization conditions. The predominant structure formed in reactions carried out in pentane (up to 2.0 M TME) is shown to be the cyclic hexamer of acetone carbonyl oxide (oligocarbonyl oxide with degree of polymerization, n = 6), but cyclic structures with n up to 19 are observed. A small proportion of the oligoperoxides formed are open-chain compounds with end groups that suggest that chain termination of oligocarbonyl oxides can occur through reaction with either water or hydrogen peroxide. Ozonolysis in dried butyl acetate similarly produces mainly cyclic oligoperoxides. However, ozonolyses carried out in undried butyl acetate yield mainly open-chain oligoperoxides, confirming that propagating carbonyl oxide chains are readily terminated by water. Relative amounts of the open-chain oligomers so-formed suggest that undried butyl acetate contains ca. 0.1% w/w water. The ozonolysis of TME in the participating solvent, methanol, at -60 degrees C yields 2-methoxyprop-2-yl hydroperoxide via reaction of acetone carbonyl oxide with methanol; no oligoperoxidic products are formed in this case. 相似文献
68.
Alpha-fluorosulfonamides were prepared by electrophilic fluorination of tertiary sulfonamides using N-fluorobenzenesulfonimide as fluorinating agent and utilizing the dimethoxybenzyl group (DMB) as a new sulfonamide protecting group. Removal of the DMB group with TFA/CH(2)Cl(2) gave primary and secondary alpha-fluorosulfonamides. 相似文献
69.
Ian Hamerton John R. Jones David C. Povey Gallienus W. Smith John M. Barton 《Journal of chemical crystallography》1992,22(1):101-108
The structure of the title compound (I) was determined by direct methods using MoK diffractometer data, and refined by full-matrix least squares toR=0.066 for 1536 reflections (I3 (I)). The structure shows a central tetrahedral carbon atom surrounded by two methyl and two 3-allyl-4-cyanatophenyl groups. The geometry of the cyanato group in this molecule compares well with those in 2,2-bis(4-cyanatophenyl)isopropylideneII) and 4-chloro-3,5-dimethyl-phenylcyanate (III), the only other examples of organic compounds bearing the cyanato moiety in the Cambridge Crystallographic Database (V.3). 相似文献
70.