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991.
Reaction of copper(II) salts with n-alkylsulfonate anions yields light blue lamellar Cu(C(n)H(2n + 1)SO3)2 x zH2O displaying distinct (mono/bi-layer) chain packing with increasing alkyl chain lengths. This may be attributed to the amphiphilic nature of the surfactants, i.e., the hydrophilic sulfonate head groups, mediating the coordination, and H-bonding interactions, and the hydrophobic alkyl chains. 相似文献
992.
Gloria C. Lin Maria L. Tsoukas Margaret S. Lee Salvador González Chitralada Vibhagool R. Rox Anderson Nikiforos Kollias 《Photochemistry and photobiology》1998,68(4):575-583
In an ideal world, photodynamic therapy (PDT) of abnormal tissue would reliably spare the surrounding normal tissue. Normal tissue responses set the limits for light and drug dosimetry. The threshold fluence for necrosis (TFN) was measured in normal skin following intravenous infusion with a photosensitizer, benzoporphyrin derivative monoacid ring A (BPD-MA) Verteporfin as a function of drug dose (0.25-2.0 mg/kg), wavelength of irradiation (458 and 690 nm) and time interval (0–5h) between drug administration and irradiation. The BPD-MA levels were measured in plasma and skin tissue to elucidate the relationship between TFN, drug kinetics and biodistribution. The PDT response of normal skin was highly reproducible. The TFN for 458 and 690 nm wavelengths was nearly identical and the estimated quantum efficiency for skin response was equal at these two wavelengths. Skin phototoxicity, quantified in terms of 1/ TFN, closely correlated with the plasma pharmacokinetics rather than the tissue pharmacokinetics and was quadratically dependent on the plasma drug concentration regardless of the administered drug dose or time interval between drug and light exposure. This study strongly suggests that noninvasive measurements of the circulating drug level at the time of light treatment will be important for setting optimal light dosimetry for PDT with liposomal BPD-MA, a vascular photosensitizer. 相似文献
993.
Intramolecular proton transfer equilibria of acetamide and methyl carbamate have been studied by AMI MO calculations, and the results are compared with those of the MNDO method. It was found that the two semi- empirical methods predict essentially the same proton transfer mechanism, but MNDO tends to overestimate the activation barriers. Participation of one solvate vater in the proton transfer led to a considerable lovering of the activation barrier, by nearly the same amount, in both methods. One notable conflict between the two methods was that the methoxy-O-protonated form of methyl carbamate, in the gas phase, can be a local energy minimum with MNDO, whereas it leads to dissociation into two species Instead of an optimized structure with AM1. It was concluded that the MNDO method can be useful for this type of process, especially when one is interested in the relative activation barriers only. 相似文献
994.
Ronald G. Sutherland Adam Pirko Choi Chuck Lee Stanley H. Simonsen Vincent M. Lynch 《Journal of heterocyclic chemistry》1988,25(6):1911-1916
Synthesis of the heterocyclic skeletons of some biologically active compounds from (η6-o-dichlorobenzene)(η5-cyclopentadienyrl)iron hexafluorophosphate in a two step procedure is described. Cyclopentadienyliron hexafluorophosphate complexes of 1,4-benzodioxino[2,3-b]pyridine, 1,4-benzoxathiino[3,2-b]pyridine, 10H-pyrido[3,2-b]benzoxazine, benzo[b]naphtho[2,3-e][1,4]dioxin, 4-methylbenzo[b]benzopyran-2-one[7,6-e][1,4]dioxin and benzo[b]anthracen-9,10-diono[1,2-e][1,4]dioxin were isolated and characterized. Upon pyrolytic sublimation of these complexes the free heterocycles were obtained and characterized. (η6-1,4-Benzoxathiino[3,2-b]pyridine)(η5-cyclopentadienyl)iron hexafluorophosphate crystalizes in the orthothombic system, space group Pbca; the dihedral angle between the planes of outer rings was found to be 176.8 (1). 相似文献
995.
J. Charalambous M. J. Frazer R. K. Lee A. H. Qureshi F. B. Taylor 《Journal of mass spectrometry : JMS》1971,5(10):1169-1178
The main fragmentation of the compounds MX3-noxn (oxH=8-quinolinol. n = 3; M=AL, Ga, In, Sc, Cr or Fe. n = 2; M=In or Fe; X=Cl or Br. InIox2. n = 1; M=AL, In or Fe; X= Cl or Br) involves loss of X and intact ox. radicals. The comparative abundances of the fragments are primarily related to the common oxidation states of the metals. For example, all the Mox3 compounds show the ions [Mox3]+ and [Mox2]+. The ions [Mox]+ and [M]+ are present when M=Ga, In, Cr or Fe but for the elements with only one oxidation state (Al or Sc) [M]+ is absent and [Mox]+ has only very low abundance. When M= Cr or Fe metal-containing ions arising from loss of species such as CO, H2O, HX, C2H2, H and OH by fragmentation of the ox ligand are also present; this behaviour is rationalised in terms of the ability of these metals to undergo a unit change in oxidation state. When n=1 the ions [MXox2]+ and [Mox2]+ and when n= 2 the ions [MX2ox]+ and [Mox3]+ are present; these ions arise by ionization and fragmentation of species formed by redistribution reactions in the mass spectrometer. 相似文献
996.
997.
This study investigated the relaxation behaviors of octadecylamine (ODA), stearic acid (SA), and SA/ODA mixed monolayers at the air/water interface. Area relaxations of monolayers at constant surface pressure were studied by a nucleation and growth mechanism and by direct observation using a Brewster angle microscope (BAM). The results showed that ODA and SA monolayers exhibit different characteristics in the area loss and in the BAM morphology. In the initial relaxation stage, SA monolayer illustrates a more stable characteristic than ODA. But at the later stage, the area loss of SA monolayer increases more quickly than that for ODA due to significant nucleation and growth of 3D aggregates. The BAM results demonstrated that 3D aggregates of large scale domains are likely to form on a SA monolayer even when the area loss is insignificant. On the contrary, only dotlike aggregates of low density were found on the ODA monolayer when relaxation is carried out at higher surface pressure. The relaxation behavior of SA monolayer can be described by the Vollhardt model. However, the relaxation of ODA monolayer does not follow the nucleation model described by Vollhard but can reasonably be attributed to the effect of dissolution. For the SA/ODA mixed monolayers, the relaxation behaviors in the initial and final stages follow different mechanisms, which is attributed to the formation of distinct phases as observed from the BAM. This result also implied that SA and ODA are not completely miscible to be a homogeneous phase. Phases of various compositions were formed in the mixed monolayers, and thus, the relaxation mechanism was shifted during the relaxation process as dominated by different relaxation behaviors of various phases. 相似文献
998.
Ju‐Yeon Lee Eun‐Ju Park 《Journal of polymer science. Part A, Polymer chemistry》2002,40(11):1742-1748
Methyl 3,4‐di‐(2′‐hydroxyethoxy)benzylidenecyanoacetate ( 3 ) was prepared by hydrolysis of methyl 3,4‐di‐(2′‐vinyloxyethoxy)benzylidenecyanoacetate ( 2 ). Diol 3 was condensed with 2,4‐toluenediisocyanate, 3,3′‐dimethoxy‐4,4′‐biphenylenediisocyanate, and 1,6‐hexamethylenediisocyanate to yield polyurethanes 4 – 6 containing the nonlinear optical chromophore 3,4‐dioxybenzylidenecyanoacetate. The resulting polyurethanes 4 – 6 were soluble in common organic solvents such as acetone and dimethylformamide. Polymers 4 – 6 indicated thermal stability up to 300 °C in thermogravimetric thermograms with glass‐transition temperature values obtained from differential scanning calorimetric thermograms in the range of 78–102 °C. The second‐harmonic generation coefficients (d33) of the poled polymer films were around 6.9 × 10?9 esu. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1742–1748, 2002 相似文献
999.
Luo QH Howell RC Dankova M Bartis J Williams CW Horrocks WD Young VG Rheingold AL Francesconi LC Antonio MR 《Inorganic chemistry》2001,40(8):1894-1901
The alpha-1 and alpha-2 isomers of the monovacant Wells-Dawson heteropolyoxoanion [P(2)W(17)O(61)](10-) are complexants of trivalent rare-earth (RE) ions and serve to stabilize otherwise reactive tetravalent lanthanide (Ln) and actinide (An) ions in aqueous solution. Aspects of the bonding of Ln ions with alpha-1-[P(2)W(17)O(61)](10-) and alpha-2-[P(2)W(17)O(61)](10-) were investigated to address issues of complex formation and stability. We present structural insights about the Ln(III) coordination environment and hydration in two types of stoichiometric complexes, [Ln(alpha-1-P(2)W(17)O(61))](7-) and [Ln(alpha-2-X(2)W(17)O(61))(2)](17-) (for Ln identical with Sm, Eu, Lu; X identical with P, As). The crystal and molecular structures of [(H(2)O)(4)Lu(alpha-1-P(2)W(17)O(61))](7-) (1) and [Lu(alpha-2-P(2)W(17)O(61))(2)](17-) (2) were solved and refined through use of single-crystal X-ray diffraction. The crystallographic results are supported with corresponding insights from XAFS (X-ray absorption fine structure) for a series of nine solid-state complexes as well as from optical luminescence spectroscopy of the Eu(III) analogues in aqueous solution. All the Ln ions are eight-coordinate with oxygen atoms in a square antiprism arrangement. For the 1:1 stoichiometric Ln/alpha-1-[P(2)W(17)O(61)](10-) complexes, the Ln ions are bound to four O atoms of the lacunary polyoxometalate framework in addition to four O atoms from solvent (water) molecules as [(H(2)O)(4)Ln(alpha-1-P(2)W(17)O(61))](7-). This structure (1) is the first of its kind for any metal complex of alpha-1-[P(2)W(17)O(61)](10-), and the data indicate that the general stoichiometry [(H(2)O)(4)Ln(alpha-1-P(2)W(17)O(61))](7-) is maintained throughout the lanthanide series. For the 1:2 stoichiometric Ln/alpha-2-[X(2)W(17)O(61)](10-) complexes, no water molecules are in the Ln-O(8) coordination sphere. The Ln ions are bound to eight O atoms-four from each of two heteropolyanions-as [Ln(alpha-2-X(2)W(17)O(61))(2)](17-). The average Ln-O interatomic distances decrease across the lanthanide series, consistent with the decreasing Ln ionic radius. 相似文献
1000.
C. S. Lee Wayne W. Y. Lau S. Y. Lee S. H. Goh 《Journal of polymer science. Part A, Polymer chemistry》1992,30(6):983-988
Copolymers of 2,2,6,6-tetramethylpiperidinyl methacrylate (TPMA) with styrene (S) and with methyl methacrylate (MMA) were synthesized using AIBN as initiator. S–TPMA copolymers from feed ranging from 0.10–0.80 mole fractions TPMA and MMA-TPMA copolymers from feed of 0.04–0.85 mole fractions TPMA were used in the determination of monomer reactivity ratios r1, r2. Four different methods were employed in the calculations of r1 and r2 and all calculated results were in good agreement with each other. The structure of S–TPMA copolymers was inferred to be of an alternating nature while that of MMA–TPMA copolymers was random. Both copolymers are potential hindered amine light stabilizers (HALS) and are expected to be less extractable from, and more compatible with, polystyrene and poly(methyl methacrylate) base polymers. 相似文献