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11.
Felix Franks 《Journal of solution chemistry》1995,24(11):1093-1097
At a recent meeting of the International Symposium on Solution Chemistry I presented a paper dealing with aqueous solutions in which water was present not in excess but as one component of a supersaturated solution with polyhydroxy compounds. In response to a request from the Editor of this Journal I have submitted this article in which I outline my general interest in the subject and its importance as a new direction for solution chemists. 相似文献
12.
Amyes TL Diver ST Richard JP Rivas FM Toth K 《Journal of the American Chemical Society》2004,126(13):4366-4374
We report second-order rate constants kDO (M-1 s-1) for exchange for deuterium of the C(2)-proton of a series of simple imidazolium cations to give the corresponding singlet imidazol-2-yl carbenes in D2O at 25 degrees C and I = 1.0 (KCl). Evidence is presented that the reverse protonation of imidazol-2-yl carbenes by solvent water is limited by solvent reorganization and occurs with a rate constant of kHOH = kreorg = 10(11) s-1. The data were used to calculate reliable carbon acid pK(a)s for ionization of imidazolium cations at C(2) to give the corresponding singlet imidazol-2-yl carbenes in water: pKa = 23.8 for the imidazolium cation, pKa = 23.0 for the 1,3-dimethylimidazolium cation, pKa = 21.6 for the 1,3-dimethylbenzimidazolium cation, and pKa = 21.2 for the 1,3-bis-((S)-1-phenylethyl)benzimidazolium cation. The data also provide the thermodynamic driving force for a 1,2-hydrogen shift at a singlet carbene: K12 = 5 x 10(16) for rearrangement of the parent imidazol-2-yl carbene to give neutral imidazole in water at 298 K, which corresponds to a favorable Gibbs free energy change of 23 kcal/mol. We present a simple rationale for the observed substituent effects on the thermodynamic stability of N-heterocyclic carbenes relative to a variety of neutral and cationic derivatives that emphasizes the importance of the choice of reference reaction when assessing the stability of N-heterocyclic carbenes. 相似文献
13.
Islangulov RR Kozlov DV Castellano FN 《Chemical communications (Cambridge, England)》2005,(30):3776-3778
Selective low energy excitation of the metal-to-ligand charge transfer (MLCT) transition in [Ru(dmb)(3)](2+)(dmb = 4,4'-dimethyl-2,2'-bipyridine) in the presence of anthracene or 9,10-diphenylanthracene yields easily visualized upconverted singlet fluorescence resulting from triplet-triplet annihilation at low excitation power. 相似文献
14.
David R. Elmaleh Felix E. Granchelli John L. Neumeyer 《Journal of heterocyclic chemistry》1979,16(1):87-92
The synthesis of three new racemic aporphine alkaloids ( 1b, 1c and 2 ) is reported and these alkaloids are fully characterized. The method of synthesis involved either a Bischler-Napieralski-Psehorr sequence or a Reissert alkylation-Pschorr cyclization route. The Pschorr cyclization also gave the morphinandienones 7a and 7b , respectively. 相似文献
15.
16.
Lakshman MK Ngassa FN Bae S Buchanan DG Hahn HG Mah H 《The Journal of organic chemistry》2003,68(15):6020-6030
Single-electron oxidation of the carcinogenic hydrocarbon benzo[a]pyrene (BaP) is thought to result in a radical cation intermediate and this species has been proposed to cause alkylation at the nitrogens of the purine nucleobases. Although several different nucleoside adducts have been isolated as arising from this mode of metabolic activation, there are no selective, total syntheses of the stable exocyclic amino group adducts formed by the single-electron oxidation of any hydrocarbon with the purine 2'-deoxynucleosides to date. In this paper we disclose the synthesis of the model adducts N(6)-(1-pyrenyl)-2'-deoxyadenosine and N(2)-(1-pyrenyl)-2'-deoxyguanosine as well as the first synthesis of the carcinogen-linked nucleoside derivatives N(6)-(6-benzo[a]pyrenyl)-2'-deoxyadenosine and N(2)-(6-benzo[a]pyrenyl)-2'-deoxyguanosine via a palladium-mediated C-N bond formation. Two different coupling strategies were attempted: coupling of an aryl bromide with a suitably protected nucleoside and the coupling of an arylamine with a suitable halonucleoside. The former had somewhat limited applicability in that only N(6)-(1-pyrenyl)-2'-deoxyadenosine was prepared by this method; on the other hand, the latter was more general. However, there are noteworthy differences in the amination reactions at the C-6 and C-2 positions. Reactions at the C-6 resulted in the competing formation of a 1:2 amine-nucleoside adduct in addition to the desired monoaryl nucleoside. Such a dimer formation was not observed at the C-2. The C-2 adducts, however, displayed an interesting conformational behavior. 相似文献
17.
Figueroa FL Nygård C Ekelund N Gómez I 《Journal of photochemistry and photobiology. B, Biology》2003,72(1-3):35-44
The effect of different wavebands of artificial UV (UVB and UVA) and photosynthetically active radiation (PAR) was assessed in two species of the genus Ulva, U. olivascens and U. rotundata, from southern Spain in order to test for possible differences in acclimation of photosynthesis. Both species share similar morphology but are subject to different light environments: U. rotundata is an estuarine alga, inhabiting subtidal locations, while U. olivascens is an intertidal, sun-adapted organism. Algae were exposed to three different UV conditions, PAR+UVA+UVB, PAR+UVA and PAR for 7 d. Short-term exposure (6 h) was also carried out, using two PAR levels, 150 and 700 micromolm(-2)s(-1). Pigment contents and photosynthesis vs. irradiance curves from oxygen evolution were used to contrast sun- and shade adaptation between these species. O2-based net photosynthesis (Pmax) and PAM-chlorophyll fluorescence (optimal quantum yield, Fv/Fm) were used as parameters to evaluate photoinhibition of photosynthesis in the experiments. The results underline different photobiological characteristics among species: the subtidal U. rotundata had higher contents of pigments (Chl a, Chl b and carotenoids) than the sun-adapted U. olivascens, which resulted in higher thallus absorptance and P-I parameters characterized by higher photosynthetic efficiency at limiting irradiances (alpha) and lower saturating points for photosynthesis (Ek). After 7 d exposure, photoinhibition of Fv/Fm was close to 40-45% in both species. Differences between UV treatments were seen in U. rotundata after 5 d and after 7 d in U. olivascens, in which PAR+UVA impaired strongly photosynthesis (80%). Such patterns were correlated with a progressive decrease in pigment contents, specially chlorophylls. In short-term (6 h) exposures, combinations of UVA+UVB and high PAR level resulted in high rates of photoinhibition of chlorophyll fluorescence (68-92%) in U. rotundata, whereas in U. olivascens photoinhibition ranged between 42% and 53%. Photoinhibition under low PAR combined to UV radiation was lower than observed under high PAR. Net O2-Pmax revealed similar response among the species, with maximal photoinhibition rates close to 60% in algae incubated under high PAR+UVA+UVB. In the case of UV exposure in combination with low PAR, the highest photoinhibition rates were measured in U. rotundata. 相似文献
18.
Felix H. Cano Concha Foces-Foces Manuel Bernabe Jesus Jimenez-Barbero Manuel Martin-Lomas Soledad Penades-Ullate 《Tetrahedron》1985,41(18):3875-3886
X-Ray and 1H N.M.R. studies on pyranoid rings 1,2--fused to dioxolane rings in acetylated -gluco- and --galactopyranose derivatives demonstrate that the configuration of the dioxolane ring influences the conformation of the pyranoid ring in the -gluco but not in the -galactopyranose series. The crystal structure of 3,4,6-tri--acetyl-1,2--(R)--(l-cyano-ethylidene)-α--glucopyranose () and 3,4,6-tri--acetyl-1,2--()-(1-cyano-ethylidene)-α--galactopyranose ()have been determined by X-ray analysis. Lattice parameters for are a=20.6021 (11), b=8.0438 (2), c=5.5541 (1) Å and β= 95.588 (3)° for a cell with P21 symmetry. These parameters for are a=20.3361 (7), b=10.0907 (2), c=18.9115 (5) Å, β =112.399 (2)°, C2, with two crystallographycally independent molecules. The conformation of the pyranoid ring in both compounds can be described as flattened 4C1 and that of the dioxolane ring as distorted E1. The importance of the torsion angles for describing problems of configuration is remarked and the use of relative configurational angles is stressed. The 1H N.M.R. spectra of and and 3,4,6-tri--acetyl-1,2-O-(S)- and (R)-ethylidene-α--glucopyranose ( and ), 3,4,6-tri-O-acetyl--1,2-O-(S)- and ()-ethylidene-α--galactopyranose ( and ), and 3,4,6-tri--acetyl-1,2--()-and ()-benzylidene-α--glucopyranose ( and ) have been analyzed by using iterative computer methods and N.O.E. measurements. The results indicate that the major solution conformation of the pyranoid ring of the derivatives in the -gluco series , and may be described as flattened 4C1 and that of and as 25. The major solution conformation of the pyranoid ring in all compounds in the -galacto series (,,,) may be described as flattened 41. 相似文献
19.
Christine GozeDenis V. Kozlov Felix N. CastellanoRaymond Ziessel 《Tetrahedron letters》2003,44(48):8713-8716
The synthesis of novel ruthenium(II) bipyridine or terpyridine complexes bearing an increasing number of pyrene or toluyl moieties is described. The ruthenium complexes are constructed in a first step with ligands bearing the required bromine functions, followed in a second step by stepwise grafting of 1-ethynylpyrene or 4-ethynyltoluene promoted by Pd(0). A complex bearing a protected triethylsilylacetylene function was also prepared. In situ deprotection of this function with K2CO3 and cross-coupling with 1-bromopyrene afforded a soluble complex in which two pyrene moieties are linearly linked via ethynyl spacers to one of the bipyridine ligands. These highly coloured complexes exhibit well defined absorption and emission properties in solution at both rt and 77 K. 相似文献
20.
Lewis R. Thomas-Hargreaves Marcus J. Giansiracusa Matthew Gregson Emanuele Zanda Felix O'Donnell Ashley J. Wooles Nicholas F. Chilton Stephen T. Liddle 《Chemical science》2021,12(11):3911
Treatment of the new methanediide–methanide complex [Dy(SCS)(SCSH)(THF)] (1Dy, SCS = {C(PPh2S)2}2−) with alkali metal alkyls and auxillary ethers produces the bis-methanediide complexes [Dy(SCS)2][Dy(SCS)2(K(DME)2)2] (2Dy), [Dy(SCS)2][Na(DME)3] (3Dy) and [Dy(SCS)2][K(2,2,2-cryptand)] (4Dy). For further comparisons, the bis-methanediide complex [Dy(NCN)2][K(DB18C6)(THF)(toluene)] (5Dy, NCN = {C(PPh2NSiMe3)2}2−, DB18C6 = dibenzo-18-crown-6 ether) was prepared. Magnetic susceptibility experiments reveal slow relaxation of the magnetisation for 2Dy–5Dy, with open magnetic hysteresis up to 14, 12, 15, and 12 K, respectively (∼14 Oe s−1). Fitting the alternating current magnetic susceptibility data for 2Dy–5Dy gives energy barriers to magnetic relaxation (Ueff) of 1069(129)/1160(21), 1015(32), 1109(70), and 757(39) K, respectively, thus 2Dy–4Dy join a privileged group of SMMs with Ueff values of ∼1000 K and greater with magnetic hysteresis at temperatures >10 K. These structurally similar Dy-components permit systematic correlation of the effects of axial and equatorial ligand fields on single-molecule magnet performance. For 2Dy–4Dy, the Dy-components can be grouped into 2Dy–cation/4Dy and 2Dy–anion/3Dy, where the former have almost linear C Dy C units with short average Dy C distances, and the latter have more bent C Dy C units with longer average Dy C bonds. Both Ueff and hysteresis temperature are superior for the former pair compared to the latter pair as predicted, supporting the hypothesis that a more linear axial ligand field with shorter M–L distances produces enhanced SMM properties. Comparison with 5Dy demonstrates unusually clear-cut examples of: (i) weakening the equatorial ligand field results in enhancement of the SMM performance of a monometallic system; (ii) a positive correlation between Ueff barrier and axial linearity in structurally comparable systems.Studies on equatorial donor and C Dy C angle variation effects on energy barriers to the slow relaxation of magnetisation are reported. 相似文献