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71.
A practical stereoselective synthesis of cytotoxic anhydrophytosphingosine pachastrissamine (jaspine B) was achieved in 48% overall yield from D-(-)-tartaric acid. Key features of the sequence include the diastereoselective formation of a tetrol with three contiguous chiral centers, which was further elaborated to pachastrissamine. The synthetic route is operationally simple, diastereoselective and is amenable for the synthesis of a number of analogues of pachastrissamine. 相似文献
72.
The exchange part of the usual Hartree-Fock potential in the unrestricted Hartree-Fock (UHF) theory is suitablyaveraged to construct an, average one-electron model Hamiltonian which generates a set of spin-restricted one-electron orbitals in
a self-consistent manner. These orbitals are then used to calculate the electronic energy of the open-shell system by using
the proper functional form for the energy which handles the exchange terms correctly. The eigenvalues ofF
av can be used for calculating either the spin-polarised or spin-averaged ionisation potentials of different orbitals at theKoopmans’ theorem level of approximation. Comparison ofE
ac with the UHF-energy shows thatE
UHF<E
ac in each case revealing some kind of an upper bound nature ofE
ac. An approximate variational argument is given. Relationship of our model with the hyper-Hartree-Fock theory of slater is
explored and the general problem of eliminating ‘self-interaction’ terms in average Fock-operator based theories is discussed. 相似文献
73.
Synthesis of Some Novel Bisisoxazolidine Derivatives from Glyoxal‐derived Bisnitrones via Simultaneous Double Cycloaddition Reactions in Water 下载免费PDF全文
Simultaneous double 1,3‐dipolar cycloaddition reactions of glyoxal‐derived bisnitrones have been described in water. Significant rate acceleration and improved yields of exclusively diastereoselective and regioselective bisisoxazolidines in water have been observed at room temperature in a short reaction time compared with conventional solvents. 相似文献
74.
AK Parchur AI Prasad AA Ansari SB Rai RS Ningthoujam 《Dalton transactions (Cambridge, England : 2003)》2012,41(36):11032-11045
Tb(3+)-doped CaMoO(4) (Tb(3+) = 1, 3, 5, 7, 10, 15 and 20 atom%) core and core-shell nanoparticles have been prepared by urea hydrolysis in ethylene glycol (EG) as capping agent as well as reaction medium at low temperature ~150 °C. As-prepared samples were annealed at 500 and 900 °C for 4 h to eliminate unwanted hydrocarbons and/or H(2)O present in the sample and to improve crystallinity. The synthesised nanophosphors show tetragonal phase structure. The crystallite size of as-prepared sample is found to be ~18 nm. The luminescence intensity of the (5)D(4) → (7)F(5) transition at 547 nm of Tb(3+) is much higher than that of the (5)D(4) → (7)F(6) transition at 492 nm. 900 °C annealed samples show the highest luminescence intensity. The intensity ratio R (I[(5)D(4) → (7)F(6)]/I[(5)D(4) → (7)F(5)]) lies between 0.3-0.6 for as-prepared, 500 and 900 °C annealed samples. The luminescence decay of (5)D(4) level under 355 nm excitation shows biexponential behaviour indicating availability of Tb(3+) ions on surface and core regions of particle; whereas, contribution of Mo-O charge transfer to lifetime is obtained under 250 nm excitation. The CIE coordinates of as-prepared, 500 and 900 °C annealed 5 atom% Tb(3+)-doped CaMoO(4) samples under 250 nm excitation are (0.28, 0.32), (0.22, 0.28) and (0.25, 0.52), respectively. The dispersed particles in polar medium and its polymer film show green light emission. The luminescence intensity is improved significantly after core-shell formation due to extent of decrease of non-radiative rates arising from surface dangling bonds and capping agent. Quantum yields of as-prepared samples of 1, 5 and 7 atom% Tb(3+)-doped CaMoO(4) samples are found to be 10, 3 and 2, respectively. 相似文献
75.
Structures of three dialkyl tartrates, namely, dimethyl tartrate, diethyl tartrate, and diisopropyl tartrate, in CCl4, dimethyl sulfoxide (DMSO)/DMSO-d6, and H2O/D2O solvents have been investigated using vibrational absorption (VA), vibrational circular dichroism (VCD), and optical rotatory dispersion (ORD). VA, VCD, and ORD spectra are found to be dependent on the solvent used. Density functional theory (DFT) calculations are used to interpret the experimental data in CCl4 and DMSO. The trans-COOR conformer with hydrogen bonding between the OH group and the C=O group attached to the same chiral carbon is dominant for dialkyl tartrates both in vacuum and in CCl4. The experimental VA, VCD, and ORD data of dialkyl-D-tartrates in CCl4 correlated well with those predicted for dimethyl-(S,S)-tartrate molecule as both isolated and solvated in CCl4. In DMSO solvent, dialkyl tartrate molecules favor formation of intermolecular hydrogen bonding with DMSO molecules. Clusters of dimethyl-(S,S)-tartrate, with one molecule of dimethyl-(S,S)-tartrate hydrogen bonded to two DMSO molecules, are used for the DFT calculations. A trans-COOR cluster and a trans-H cluster are needed to obtain a reasonable agreement between the predicted and experimental data of dimethyl tartrate in DMSO solvent. VA, VCD, and optical rotations are also measured for dialkyl tartrate-cyclodextrin complexes. It is noted that these properties are barely affected by complexation of dialkyl tartrates with cyclodextrins, indicating weak interaction between tartrates and cyclodextrin. Binding constants of alpha-CD and beta-CD with diethyl L-tartrate in both H2O and DMSO have been determined using isothermal titration calorimetry technique. The smaller binding constants (less than 100) confirmed the weak interaction between tartrates and cyclodextrin in the solution state. 相似文献
76.
A general strategy is developed for the stereoselective synthesis of C-substituted morpholine derivatives using intramolecular reductive etherification reaction. The method is extended to the first stereoselective total synthesis of (±)-chelonin C. 相似文献
77.
Nerium odorum, Linn. (Apocynaceae) is an important evergreen shrub. It is heat, salinity and drought tolerant. Plants with milky sap have medicinal value, mainly cardenolides, flavonoids and terpenes. It is used for wastewater purification and for restoration of riparian woodlands. In view of these facts, the study was conducted for micropropagation of N. odorum. Murashige and Skoog (MS) media supplemented with different concentrations (0.5–10.0 mg/l) of 1-naphthaleneacetic acid (NAA), 2,4-dichlorophenoxyacetic acid (2,4-D), 6-benzylaminopurine (BAP) and kinetin (Kin) were used singly and in combinations. Among all the growth hormones, 2,4-D was the best for callus induction (75 % in stem and 79 % in leaf) and in combination 2,4-D and BAP (78 % in stem and 81 % in leaf). The day of callus induction started from the 19th to the 37th day. This variation is due to the differences in culture conditions and the age of explants. The fresh and dry weight and moisture content showed good growth of callus, which is used in further studies of alkaloid production. Micropropagation of this plant allows the production of clones at a fast rate and in continuous manner. This work can lead to the development of an efficient protocol for callus induction and other issues. 相似文献
78.
The coagulation of positively charged sol of hydrous ferric oxide of different average sizes for potassium sulphate has been studied in the presence of glucose and urea which stabilise the sol. The degree of stabilisation increases with the fineness of dispersed particles. It has been concluded that the adhesive tendency of the surface of dispersed particles decreases in the presence of said non-electrolytes leading to a decrease in the frequency of collisions resulting in stabilisation. The stability ratioW increases in the presence of glucose and urea for the same amount of the coagulant.
Zusammenfassung Die Koagulation positiv geladener Sole von wäßrigem Ferrioxid verschiedener mittlerer Partikelgrößen mit Kaliumsulfat wird in Gegenwart von Glykose und Harnstoff, die beide das Sol stabilisieren, untersucht. Der Grad der Stabilisierung hängt von der Teilchengröße ab. Es wird geschlossen, daß die Adhäsionstendenz der Oberflächen der dispergierten Partikel in Gegenwart besagter Nichtelektrolyte abnimmt und so zur Abnahme der Kollisionshäufigkeit und damit zur Stabilisierung führt. Das StabilisierungsverhältnisW wächst in Anwesenheit von Glykose und Harnstoff für gleiche Beträge des Koagulators.相似文献
79.
A quantitative, computer processed spectroscopic study, using photon counting, on the first excited triplet and singlet states of dilute isotopic mixed crystals of naphthalene at 2 K is presented for C10H8; 1-DC10H7; 2-DC10H7; 1,4-D2C10H6; 1,4,5-D3C10H5; 1,4,5,8-D4C10H4; 1,2,4,5,8-D5C10H3; a β-D4C10H4 and a β2-D6C10H2 as guests in C10D8 host crystals (and, for comparison, also for the same guests in a durene host crystal). The guest—host relative polarization Rashba formula has been verified quantitatively, and, as an added bonus, the elusive polarization ratio of the pure naphthalene crystal singlet Davydov components has been found to be 80 ± 20 (b/a), which is in poor agreement with the transition octupole—transition octupole model. The experimental guest energies and their concomitant quasiresonance shifts for bound singlet states (as well as the occurrences of unbound states) are in excellent quantitative agreement (about 1 cm?1) with those calculated using a Green's function formalism based on the ideal mixed crystal approximation and on a restricted Frenkel type dispersion relation derived from resonance pairs. The same Green's function also accounts quantitatively (within 10%) for the guest singlet state exciton localizations (guest excitation amplitudes). The triplet exciton state reveals an orientational site splitting (about 0.7 cm?1) for the 0—0 transition of the I-DC10H7 guest in C10D8 host. The order of the α and β substituted deuteronaphthalenes in the triplet state is reversed from that of the singlet state. The last two observations are related to the different nature of the lowest Π-Π* singlet and triplet states of naphthalene. 相似文献
80.
Abstract— The order of inhibition of the photooxidation of chlorophyll a in ethanol and ethanol-benzene is as follows: β-carotene, α-tocopherol, benzoquinone, DABCO, menadione, cholesterol and KI. The quenching of singlet oxygen by β-carotene occurs by a collisional quenching mechanism with a diffusion-controlled rate of 1.7 × 1010 M -1 s-1 . Photodecomposition of Chi a is faster in ethanol-D2 O than in ethanol-H2 O. Photoirradiation (660 nm) of the peridinin-Chl a -protein complex, a photosynthetic light-harvesting pigment isolated from marine dinoflagellates, did not show any photo-decomposition of its Chi a in H2 O or D2 O, even after an extended period (12 h) of irradiation. However, the carotenoid, peridinin, in the photosynthetic antenna pigment was photobleached (ca. 10%) during the irradiation. We conclude that the singlet oxygen formed as a result of the Chi photosensitization is immediately quenched by the low-lying triplet state of four peridinin molecules (per Chl a ) bound within the same protein crevice. The carotenoid thus effectively protects Chl a from photodynamic damage, providing a direct proof for the protective role of carotenoids in the photosynthetic pigment complex. 相似文献