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101.
The effect of pressure on the dissociation constant of hydrofluoric acid was determined by using the indicator technique at 25°C at an ionic strength of 0.1m over a pressure range of 1 to 2000 atm. A value of 3.14 for pK
a
*
at I =0 was obtained by extrapolation to zero ionic strength at 1 atm. The pressure dependence yielded a partial molar volume change of –9.6 cm3-mol–1 and a compressibility change of — 35×10–3 cm3-mol–1 –atm–1 for the dissociation. The dependence of ionic strength on the association constant K
A
*
of NaF was studied at 25°C and 1 atm. Extrapolation to I=0 yielded a pK
A
*
of –0.78. The pressure dependence of K
A
*
gave a change of volume of 3.26 cm3-mol–1 and a change in compressibility of 6×10–3 cm3-mol–1-atm–1 for the formation of the ion pair. 相似文献
102.
Abstract— Acetone-sensitized photoinactivation and subsequent in vivo photoreactivation of tobacco mosaic virus (TMV) and potato virus X (PVX) ribonucleic acids (RNA's) were demonstrated. The photoreactivable sectors were comparable to those obtained for the same RNA's irradiated at 253·7 nm. Only dimers were detected in these RNA's. Irradiation of E. coli rRNA at a higher dose indicated that photoreversible pyrimidine dimers were the main photoproducts detected in the sensitized reaction, whereas pyrimidine hydrates were formed only in negligible amounts. These results have led us to conclude that photoreversible pyrimidine dimers constitute both a lethal and photorepairable type of lesion in u.v.-damaged viral RNA. 相似文献
103.
The heteronuclear metal clusters [H3MRu4(CO)12(PPh3)] and [MFe3(μ-COMe)(CO)10(PPh3)] (M = Cu, Ag or Au) have been prepared; the gold-tetraruthenium cluster has a different metal core geometry to that adopted by the copper and silver analogues, whereas all three iron-Group IB mixed-metal clusters have the same geometry. 相似文献
104.
The fused heterocycle 4-(phenylsulfonyl)-4H-furo[3,4-b]indole, which is an indole-2,3-quinodimethane synthetic analogue, is prepared in five steps from indole in 46% yield. A similar sequence is used to synthesize C-3 derivatives (3-methyl, 3-phenyl, and 3-heptyl). Thus, indole-3-carbaldehyde (1) is protected as the N-phenylsulfonyl derivative 2 and converted to the ethylene acetal 6. Lithiation at C-2 followed by treatment with an aldehyde affords the expected hydroxy acetals 7 and 8. Exposure to acid effects cyclization to the furoindoles 5 and 9. Furthermore, C-1 lithiation of furo[3,4-b]indole 9c followed by treatment with methyl iodide affords disubstituted furo[3,4-b]indole 10. 相似文献
105.
106.
We demonstrate all-optical fibre switches, including soliton-dragging logic gates, soliton-interaction gates and soliton-trapping AND-gates, that have the potential of operating up to speeds of 0.2 Tbps. Solitons in fibres are attractive for ultrafast timedomain switching because they avoid pulse distortion during propagation and because they exhibit particle-like properties. Soliton-dragging logic gates satisfy all requirements for a digital optical processor and having switching energies approaching 1 pJ. In addition, soliton-dragging logic gates are one example of a more general timedomain chirp switch architecture in which a dispersive delay line acts as a lever-arm to reduce the switching energy. Soliton-interaction gates are based on elastic collisions between solitons and illustrate that solitons can be used to implement conservative, billiard-ball logic operations. Soliton-trapping AND-gates are sensitive to the timing of the input pulses and display on/off contrast ratios greater than 201. The soliton-trapping AND-gate can serve as the final stage in an all-optical system and as the interface to electronics. These ultrafast gates may prove advantageous in applications where the switch bandwidth limits the performance of the system 相似文献
107.
We use the lace expansion to study the standard self-avoiding walk in thed-dimensional hypercubic lattice, ford5. We prove that the numberc
n ofn-step self-avoiding walks satisfiesc
n
~A
n
, where is the connective constant (i.e. =1), and that the mean square displacement is asymptotically linear in the number of steps (i.e.v=1/2). A bound is obtained forc
n(x), the number ofn-step self-avoiding walks ending atx. The correlation length is shown to diverge asymptotically like (––Z)1/2. The critical two-point function is shown to decay at least as fast as x–2, and its Fourier transform is shown to be asymptotic to a multiple ofk
–2 ask0 (i.e. =0). We also prove that the scaling limit is Gaussian, in the sense of convergence in distribution to Brownian motion. The infinite self-avoiding walk is constructed. In this paper we prove these results assuming convergence of the lace expansion. The convergence of the lace expansion is proved in a companion paper.Supported by the Nishina Memorial Foundation and NSF grant PHY-8896163.Supported by NSERC grant A9351 相似文献
108.
Summary This paper introduces a mathematical framework within which a wide variety of known and new inequalities can be viewed from a common perspective. Probability and expectation inequalities of the following types are considered: (a)P(ZA) P(ZA) for some class of setsA, (b)k(Z)k(Z) for some class of functionsk, and (c)l(Z)k(Z) for some class of pairs of functionsl andk. It is shown, sometimes using explicit constructions ofZ andZ, that, in several cases, (a) (b) (c); included here are cases of normal and elliptically contoured distributions. A case where (a) (b) (c) is studied and is expressed in terms ofn monotone functions for (some of) which integral representations are obtained. Also, necessary and sufficient conditions for (c) are given.Research supported by the Air Force Office of Scientific Research under Grants AFOSR-75-2796 and AFOSR-80-0080Research supported by the National Science Foundation under Grants MCS78-01240 and MCS81-00748 相似文献
109.
Macleod C McKiernan GJ Guthrie EJ Farrugia LJ Hamprecht DW Macritchie J Hartley RC 《The Journal of organic chemistry》2003,68(2):387-401
Titanium(IV) benzylidenes bearing a masked oxygen or nitrogen nucleophile in the ortho position were generated from thioacetals, using low-valent titanocene complex, Cp2Ti[P(OEt)3]2. Methylene acetal, alkyl ether, silyl ether, fluoro, tertiary amino, and N-alkyl, N-benzyl, N-prenyl, and N-silyl tert-butyl carbamate groups were tolerated in the titanium alkylidene reagents (Schrock carbenes). Aryl-chlorine bonds were stable to the titanium benzylidene functionality, but there was poor chemoselectivity for the reduction of the thioacetal in the presence of an aryl chloride. The titanium benzylidenes converted Merrifield and Wang resin-bound esters into enol ethers. The oxygen nucleophile was masked as a TMS ether, and when the resin-bound enol ethers bearing this ortho substituent were treated with 1% TFA in dichloromethane, benzofurans were released from resin in high yields. The chameleon catch strategy ensured excellent purity. In a similar way, N-alkylated and N-silylated tert-butyl carbamates were used for the synthesis of N-alkyl and N-Boc indoles, respectively. These traceless solid-phase syntheses of heterocycles are believed to involve postcleavage modification rather than cyclative termination. 相似文献
110.
The new compound Ta(4)SI(11) has been prepared by direct reaction of the elements at 430 degrees C for 2 weeks in evacuated Pyrex ampules and characterized by single-crystal X-ray diffraction, X-ray photoelectron spectroscopy, magnetic susceptibility measurements, and semiempirical electronic structure calculations. Ta(4)SI(11) crystallizes with orthorhombic symmetry in space group Pmmn; a = 16.135(3) A, b = 3.813(1) A, c = 8.131(2) A, and Z = 1. The disordered structure involves two crystallographically distinct sites for Ta atoms, both of which are 50% occupied as well as a bridging anion site that is 50% S and 50% I. Magnetic susceptibility above 100 K gives micro (eff) = 1.53 micro (B) to suggest one unpaired electron per formula unit. X-ray photoelectron spectroscopy and extended Hückel calculations suggest that the structure consists of Ta(3) triangles and "isolated" Ta atoms, leading to the formulation (Ta(3))(9+)(Ta(4+))(S(2)(-))(I(-))(11) and we hypothesize that each Ta(3) is capped by a sulfur atom. 相似文献