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151.
Jayabharathi J Thanikachalam V Perumal MV Srinivasan N 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,79(1):236-244
Novel donor imidazole derivative, 2-(1-phenyl-1H-imidazo [4,5-f][1,10]phenanthrolin-2-yl)-phenol (PIPP) was screened as highly sensitive chemisensor for transition metal ions and it can be used as a "multi-way" optically switchable material. Solvatochromic effects on the fluorescence behaviour of PIPP were studied in different solvents. The fluorescence of PIPP was highly sensitive to both the polarity as well as protic nature of the solvent. Fluorescence (Forster) resonance energy transfer (FRET) process from PIPP to a potent bioactive indoloquinolizine molecule was studied and it is argued that long-range dipole-dipole interaction is operating for the energy transfer mechanism. The energy transfer efficiency (E) and the distance between the acceptor and the donor (r(0)) have been determined. 相似文献
152.
Umamahesh Balijapalli Sathishkumar Munusamy Karthikeyan Natesan Sundaramoorthy 《合成通讯》2014,44(7):943-953
Acetic acid–promoted, one-pot synthesis of tetrahydropyridines has been developed under metal-catalyst-free conditions via a tandem reaction. High atom economy, good yield, simple procedure, no expensive column chromatography, shorter reaction time, and metal-free and mild reaction conditions are some of the important features of this protocol. The current methodology provides an alternative approach for not only highly substituted tetrahydropyridines (THPs) but also fully substituted tetrahydropyridines (FTHPs) in moderate to good yields. The plausible mechanism for the formation of THPs was greatly promoted by the H+ ion coming from acetic acid.
[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.] 相似文献
153.
In this paper, we have analyzed a one parameter family of hp-discontinuous Galerkin methods for strongly nonlinear elliptic boundary value problems with Dirichlet boundary conditions. These methods depend on the values of the parameter , where θ = + 1 corresponds to the nonsymmetric and θ = −1 corresponds to the symmetric interior penalty methods when and f(u,∇u) = −f, that is, for the Poisson problem. The error estimate in the broken H
1 norm, which is optimal in h (mesh size) and suboptimal in p (degree of approximation) is derived using piecewise polynomials of degree p ≥ 2, when the solution . In the case of linear elliptic problems also, this estimate is optimal in h and suboptimal in p. Further, optimal error estimate in the L
2 norm when θ = −1 is derived. Numerical experiments are presented to illustrate the theoretical results.
Supported by DST-DAAD (PPP-05) project. 相似文献
154.
In this paper, an -local discontinuous Galerkin method is applied to a class of quasilinear elliptic boundary value problems which are of nonmonotone type. On -quasiuniform meshes, using the Brouwer fixed point theorem, it is shown that the discrete problem has a solution, and then using Lipschitz continuity of the discrete solution map, uniqueness is also proved. A priori error estimates in broken norm and norm which are optimal in , suboptimal in are derived. These results are exactly the same as in the case of linear elliptic boundary value problems. Numerical experiments are provided to illustrate the theoretical results.
155.
Ganeshan Sivanandhan Muthukrishnan Arun Subramanian Mayavan Manoharan Rajesh Murugaraj Jeyaraj Gnanajothi Kapil Dev Markandan Manickavasagam Natesan Selvaraj Andy Ganapathi 《Applied biochemistry and biotechnology》2012,168(3):681-696
Adventitious root cultures derived from leaf derived callus of Withania somnifera (L.) Dunal were treated with methyl jasmonate and salicylic acid independently. Biomass accumulation, culture age, elicitation period, and culture duration were optimized for higher withanolides production in the two best-responding varieties collected from Kolli hills (Eastern Ghats) and Cumbum (Western Ghats) of Tamil Nadu, India. Between the two elicitors, salicylic acid (SA) improved the production of major withanolides (withanolide A, withanolide B, withaferin A, and withanone) as well as minor constituents (12-deoxy withastramonolide, withanoside V, and withanoside IV) in the Kolli hills variety. Treatment of root biomass (11.70?g FW) on 30-day-old adventitious root cultures with 150???M SA for 4?h elicitor exposure period resulted in the production of 64.65?mg?g?l dry weight (DW) withanolide A (48-fold), 33.74?mg?g?l DW withanolide B (29-fold), 17.47?mg?g?l DW withaferin A (20-fold), 42.88?mg?g?l DW withanone (37-fold), 5.34?mg?g?l DW 12-deoxy withastramonolide (nine fold), 7.23?mg?g?l DW withanoside V (seven fold), and 9.45?mg?g?l DW withanoside IV (nine fold) after 10?days of elicitation (40th day of culture) when compared to untreated cultures. This is the first report on the use of elicitation strategy on the significant improvement in withanolides production in the adventitious root cultures of W. somnifera. 相似文献
156.
[(η(6)-C(10)H(14))RuCl(μ-Cl)](2) (η(6)-C(10)H(14) = η(6)-p-cymene) was subjected to a bridge-splitting reaction with N,N',N'-triarylguanidines, (ArNH)(2)C═NAr, in toluene at ambient temperature to afford [(η(6)-C(10)H(14))RuCl{κ(2)(N,N')((ArN)(2)C-N(H)Ar)}] (Ar = C(6)H(4)Me-4 (1), C(6)H(4)(OMe)-2 (2), C(6)H(4)Me-2 (3), and C(6)H(3)Me(2)-2,4 (4)) in high yield with a view aimed at understanding the influence of substituent(s) on the aryl rings of the guanidine upon the solid-state structure, solution behavior, and reactivity pattern of the products. Complexes 1-3 upon reaction with NaN(3) in ethanol at ambient temperature afforded [(η(6)-C(10)H(14))RuN(3){κ(2)(N,N')((ArN)(2)C-N(H)Ar)}] (Ar = C(6)H(4)Me-4 (5), C(6)H(4)(OMe)-2 (6), and C(6)H(4)Me-2 (7)) in high yield. [3 + 2] cycloaddition reaction of 5-7 with RO(O)C-C≡C-C(O)OR (R = Et (DEAD) and Me (DMAD)) (diethylacetylenedicarboxylate, DEAD; dimethylacetylenedicarboxylate, DMAD) in CH(2)Cl(2) at ambient temperature afforded [(η(6)-C(10)H(14))Ru{N(3)C(2)(C(O)OR)(2)}{κ(2)(N,N')((ArN)(2)C-N(H)Ar)}]·xH(2)O (x = 1, R = Et, Ar = C(6)H(4)Me-4 (8·H(2)O); x = 0, R = Me, Ar = C(6)H(4)(OMe)-2 (9), and C(6)H(4)Me-2 (10)) in moderate yield. The molecular structures of 1-6, 8·H(2)O, and 10 were determined by single crystal X-ray diffraction data. The ruthenium atom in the aforementioned complexes revealed pseudo octahedral "three legged piano stool" geometry. The guanidinate ligand in 2, 3, and 6 revealed syn-syn conformation and that in 4, and 10 revealed syn-anti conformation, and the conformational difference was rationalized on the basis of subtle differences in the stereochemistry of the coordinated nitrogen atoms caused by the aryl moiety in 3 and 4 or steric overload caused by the substituents around the ruthenium atom in 10. The bonding pattern of the CN(3) unit of the guanidinate ligand in the new complexes was explained by invoking n-π conjugation involving the interaction of the NHAr/N(coord)Ar lone pair with C═Nπ* orbital of the imine unit. Complexes 1, 2, 5, 6, 8·H(2)O, and 9 were shown to exist as a single isomer in solution as revealed by NMR data, and this was ascribed to a fast C-N(H)Ar bond rotation caused by a less bulky aryl moiety in these complexes. In contrast, 3 and 10 were shown to exist as a mixture of three and five isomers in about 1:1:1 and 1·0:1·2:2·7:3·5:6·9 ratios, respectively in solution as revealed by a VT (1)H NMR, (1)H-(1)H COSY in conjunction with DEPT-90 (13)C NMR data measured at 233 K in the case of 3. The multiple number of isomers in solution was ascribed to the restricted C-N(H)(o-tolyl) bond rotation caused by the bulky o-tolyl substituent in 3 or the aforementioned restricted C-NH(o-tolyl) bond rotation as well as the restricted ruthenium-arene(centroid) bond rotation caused by the substituents around the ruthenium atom in 10. 相似文献
157.
Reddy PT Quevillon S Gan Z Forbes N Leek DM Arya P 《Journal of combinatorial chemistry》2006,8(6):856-871
With the goal of developing a modular approach leading to different indoline alkaloid natural-product-like tricyclic derivatives having an unsaturated lactam (see compounds 13, 14, and 16), an aminoindoline-based bicyclic scaffold 10 was obtained from 9. The selective deprotection of the indoline NTeoc or benzylic NHAlloc in compound 10, followed by N-acryloylation and then subjection to a ring-closing metathesis reaction, successfully led to obtaining two different architectures (13/14 and 16) having an unsaturated lactam functionality. This modular solution-phase methodology was then developed on solid phase. To achieve this objective, the aminoindoline bicyclic scaffold having an additional hydroxyl group could be immobilized onto the solid support using alkylsilyl linker-based polystyrene macrobeads, giving 18. By applying a ring-closing metathesis approach, 20 (tricyclic derivative with seven-membered-ring unsaturated lactam) and 23 (tricyclic derivative with eight-membered-ring unsaturated lactam) were then obtained from 18 in a number of steps. 相似文献
158.
Kárpáti T Veszprémi T Thirupathi N Liu X Wang Z Ellern A Nyulászi L Verkade JG 《Journal of the American Chemical Society》2006,128(5):1500-1512
The synthesis and the crystal and molecular structure of N(CH(2)CH(2)NMe)(3)P=CH(2) is reported. The P-N(ax) distance is rather long in N(CH(2)CH(2)NMe)(3)P=CH(2). The ylide N(CH(2)CH(2)NMe)(3)P=CH(2) proved to be a stronger proton acceptor than proazaphosphatrane N(CH(2)CH(2)NMe)(3)P, since it was shown to deprotonate N(CH(2)CH(2)NMe)(3)PH(+). The extremely strong basicity of the ylide is in accordance with its low ionization energy (6.3 eV), which is the lowest in the presently investigated series N(CH(2)CH(2)NMe)(3)P=E (E: CH(2), NH, lone pair, O and S), and to the best of our knowledge it is the smallest value observed for a non-conjugated phosphorus ylide. Computations reveal the existence of two bond strech isomers, and the stabilization of the phosphorus centered cation by electron donation from the equatorial and the axial nitrogens. Similar stabilizing effects operate in the case of protonation of E. A fine balance of these different interactions determines the P-N(ax) distance, which is thus very sensitive to the level of the theory applied. According to the quantum mechanical calculations, methyl substitution at the equatorial nitrogens flattens the pyramidality of this atom, increasing its electron donor capability. As a consequence, the PN(ax) distance in the short-transannular bonded protonated systems and the radical cations is longer by about 0.5 A in the N(eq)(Me) than in the N(eq)(H) systems. Accordingly, isodesmic reaction energies show that a stabilization of about 25 and 10 kcal/mol is attributable to the formation of the transannular bond in case of N(eq)(H) and the experimentally realizable N(eq)(Me) species, respectively. 相似文献
159.
B. Sunil Kumar N. Srinivasulu R. H. Udupi B. Rajitha Y. Thirupathi Reddy P. Narsimha Reddy P. S. Kumar 《Journal of heterocyclic chemistry》2006,43(6):1691-1693
Three component coupling of one pot reaction which servers as the most convenient route to the synthesis of benzopyran derivatives using the TiCl4 catalyst (10 mol %) under solvent free conditions is described. The procedure offers a systematic method with a number of advantages including operational simplicity, neat reactions, reduced reaction time, high yields of products and applicability to large scale reactions. 相似文献
160.
A unified a posteriori error analysis is derived in extension of Carstensen (Numer Math 100:617–637, 2005) and Carstensen
and Hu (J Numer Math 107(3):473–502, 2007) for a wide range of discontinuous Galerkin (dG) finite element methods (FEM), applied
to the Laplace, Stokes, and Lamé equations. Two abstract assumptions (A1) and (A2) guarantee the reliability of explicit residual-based
computable error estimators. The edge jumps are recast via lifting operators to make arguments already established for nonconforming
finite element methods available. The resulting reliable error estimate is applied to 16 representative dG FEMs from the literature.
The estimate recovers known results as well as provides new bounds to a number of schemes.
C. Carstensen and M. Jensen supported by the DFG Research Center MATHEON “Mathematics for key technologies” in Berlin and
the Hausdorff Institute of Mathematics in Bonn, Germany.
C. Carstensen, T. Gudi, and M. Jensen supported by DST-DAAD (PPP-05) project no. 32307481. 相似文献