Synthesis of Trilaurin by Developing Pisa Seeds (Actinodaphne hookeri)

The developing seeds of Actinodaphne hookeri were investigated to delineate their ability to synthesize large amounts of trilaurin. Until 88 days after flowering the embryos contained 71% neutral lipids (NL) and 29% phospholipids (PL) and both these components contained C-16:0, C-18:0, C-18:2, and C-18:3 as the major fatty acids (FA). At 102 days after flowering the seeds began to accumulate triacylglycerols (TAG) and to synthesize lauric acid (C-12:0). By 165 days after flowering, when the seeds were mature, they contained about 99% NL and 1% FL. At this stage the TAG contained exclusively C-12:0, while the PL consisted of long-chain fatty acids (LCFA) only. Leaf lipids in contrast did not contain any C-12:0. Experiments on [1-C-14]acetate incorporation into developing seed slices showed that at 88 days after flowering only 4% of the label was in TAG, 1% in diacylglycerols (DAG), and 87% in FL. One hundred two days after flowering seeds incorporated only 2% of the label into TAG, 30% into DAG, and 64% into FL. In contrast at 114 days after flowering 71% of the label was incorporated into TAG, 25% into DAG, and only 2% into FL. Analysis of labeled FA revealed that up to 102 days after flowering it was incorporated only into LCFA, whereas at 114 days after flowering it was incorporated exclusively into C-12:0. Furthermore, 67% of the label in PL at 114 days after flowering was found to be dilaurylglycerophosphate. Analysis of the label in DAG at this stage showed that it was essentially in dilaurin species. These observations indicate the induction of enzymes of Kennedy pathway for the specific synthesis of trilaurin at about 114 days after flowering, Homogenates of seeds (114 days after flowering) incubated with labeled FA in the presence of glycerol-3-phosphate and coenzymes A and ATP incorporated 84% of C-12:0 and 61% of C-14:0, but not C-16:0, C-18:2, and C-18:3, into TAG. In contrast the LCFA were incorporated preferentially into FL. It is concluded that, between 102 and 114 days after flowering, a switch occurs in A. hookeri for the synthesis of C-12:0 and trilaurin which is tissue specific. Since the seed synthesizes exclusively C-12:0 at 114 days after flowering onwards and incorporates specifically into TAG, this system appears to be ideal for identifying the enzymes responsible for medium-chain fatty acid as well as trilaurin synthesis and for exploiting them for genetic engineering. (C) 1994 Academic Press, Inc.

Synthesis, x-ray structure and redox properties of [Ru2(?-O) (?-O2CMe)2(Me2NCH2CH2NH2)2(PPh3)2](ClO4)2

The title complex has been prepared from a reaction of [Ru2O(O22CMe)2 (MeCN)4(PPH3)2](ClO4)2 with N,N-dimethyl-1,2-diaminoethane (dmen) in MeOH. The crystal structure of [Ru2O(O2CMe)2(dmen)2(PPh3)2](ClO4)2.MeOH shows the presence of a [Ru2(mu-O)(mu-O2CMe)2]2+ core. The terminal ligands on each metal are a PPh3 and a bidentate chelating dmen. The Ru-Ru distance and Ru-O-Ru angle in the core are 3.271(2) angstrom and 120.9(4)-degrees. The more electron-donating site of the dmen ligand is bonded at the terminal sites trans to the mu-oxo ligand. The complex displays a visible absorption band at 566 nm (epsilon, 6960 M-1 cm-1) in MeCN and undergoes a nearly reversible one-electron oxidation at 1.02 V and an irreversible reduction at -0.52 V (vs SCE) in MeCN-0.1 M [NBu4n](ClO4).

A single network adaptive critic (SNAC) architecture for optimal control synthesis for a class of nonlinear systems

Even though dynamic programming offers an optimal control solution in a state feedback form, the method is overwhelmed by computational and storage requirements. Approximate dynamic programming implemented with an Adaptive Critic (AC) neural network structure has evolved as a powerful alternative technique that obviates the need for excessive computations and storage requirements in solving optimal control problems. In this paper, an improvement to the AC architecture, called the �Single Network Adaptive Critic (SNAC)� is presented. This approach is applicable to a wide class of nonlinear systems where the optimal control (stationary) equation can be explicitly expressed in terms of the state and costate variables. The selection of this terminology is guided by the fact that it eliminates the use of one neural network (namely the action network) that is part of a typical dual network AC setup. As a consequence, the SNAC architecture offers three potential advantages: a simpler architecture, lesser computational load and elimination of the approximation error associated with the eliminated network. In order to demonstrate these benefits and the control synthesis technique using SNAC, two problems have been solved with the AC and SNAC approaches and their computational performances are compared. One of these problems is a real-life Micro-Electro-Mechanical-system (MEMS) problem, which demonstrates that the SNAC technique is applicable to complex engineering systems.

Total synthesis of (±)-allo-cedrol [Khusiol]

The first total synthesis of (+/-)-allo cedrol 1 is described from the ketone 11 which involves the Lewis acid catalysed rearrangement of the prezizaene analogue 8 as the key step.

Total synthesis of the novel sesquiterpenes of Eremophila georgei Diels

The first stereoselective total synthesis of the natural sesquiterpenes 4 and 5, having the tricyclo[6.2.1.0(1,5)]undecane skeleton with a bridgehead methyl group, is reported via the intermediate 9, which was obtained by the acid catalysed rearrangement of the alcohols 7 and 8.

Application of microwave heating technique for rapid synthesis of ?,?-unsaturated esters

The use of microwave heating technique for the acceleration of ortho ester Claisen rearrangement (a three step transformation) is described. Irradiation of a DMF solution of the allyl alcohol 5, triethyl orthoacetate and propionic acid (catalytic) in an Erlenmeyer flask for 10 minutes in a microwave oven generated the ester 8 in 83% yield. Analogously, ortho ester Claisen rearrangement of a variety of allyl and propargyl alcohols (9, 12-22) were achieved. The formation of the diester 10 from 2-butyne-1,4-diol (9) via the ortho ester Claisen rearrangement of two allyl alcohol moieties (involving sh steps) in 15 minutes, demonstrates the versatility of the microwave heating technique.

Asymmetric synthesis of steroidal Tröger's base analogues. X-Ray molecular structure of methyl 3?,12?-{6H,12H-5,11-methanodibenzo[b,f][1,5]diazocine-2,8-bisacetoxy}-5?-cholan-24-oate

Cyclization of compound 5c in trifluoroacetic acid/hexamethylenetetramine produces Tröger's base analogue 6c in 75% yield with 70% diastereoselectivity.

Constructions of 2D-Metallamacrocycles Using Half-Sandwich Ru-2(II) Precursors: Synthesis, Molecular Structures, and Self-Selection for a Single Linkage Isomer

Coordination-driven self-assembly of oxalato-bridged half-sandwich p-cymene ruthenium complex Ru-2(mu-eta(4)-C2O4)(MeOH)(2)(eta(6)-p-cymene)(2)] (O3SCF3)(2) (1a) with several ditopic donors (L-a-L-d) in methanol affords a series of bi- and tetranuclear metallamacrocycles (2a and 3-5). Similarly, the combination of 2,5-dihydroxy-1,4-benzoquinonato (dhbq)-bridged binuclear complex Ru-2(mu-eta(4)-C6H2O4)(MeOH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1b) with a flexible bidentate amide linker (L-a) in 1:1 molar ratio gave the corresponding tetranuclear complex 2b. All the macrocycles were isolated as their triflate salts in high yields and were fully characterized by various spectroscopic techniques. Finally, the molecular structures of all the assemblies were determined unambiguously by single-crystal X-diffraction analysis. Interestingly, the combination of acceptor 1a or 1b with an unsymmetrical linear ditopic donor L-a results in a self-sorted linkage isomeric (head-to-tail) macrocycle (2a or 2b) despite the possibility of formation of two different isomeric macrocycles (head-to-head or head-to-tail) due to different connectivity of the donor. Molecular structures of the complexes 2a and 2b showed tetranuclear rectangular geometry with dimensions of 5.51 angstrom x 13.29 angstrom for 2a and 7.91 angstrom x 13.46 angstrom for 2b. In both cases, two binuclear Ru-2(II) building blocks are connected by a mu-N-(4-pyridyl)isonicotinamide donor in a head-to-tail fashion. Surprisingly, the macrocycle 2a loses one counteranion and cocrystallizes with monodeprotonated 1,3,5-trihydroxybenzene via strong intermolecular pi-pi stacking and hydrogen bonding. The tweezer complex 3 showed strong fluorescence in solution, and it showed fluorescence sensing toward nitroaromatic compounds. A fluorescence study demonstrated a marked quenching of the initial fluorescence intensity of the macrocycle 3 upon gradual addition of trinitrotoluene and exhibits significant fluorescence quenching response only for nitroaromatic compounds compared to various other aromatic compounds tested.

Enantioselective Synthesis of Possible Diastereomers of Heptadeca-1-ene-4,6-diyne-3,8,9,10-tetrol; Putative Structure of a Conjugated Diyne Natural Product Isolated from Hydrocotyle leucocephala

Enantioselective synthesis of possible diastereomers of heptadeca-1-ene-4,6-diyne-3,8,9,10-tetrol, a structure proposed for the natural product isolated from Hydrocotyle leucocephala is accomplished. The reported spectral data of the natural product did not match those of any of the isomers that were synthesized and established that the structure proposed for the natural product is not correct and requires revision.

Microwave assisted synthesis and UV-Vis spectroscopic studies of silver nanoparticles synthesized using vanillin as a reducing agent

The present investigation explores the adaptability of a microwave assisted route to obtain silver nanoparticles by the reduction of AgNO3 with vanillin, an environmentally benign material. Anionic surfactants such as AOT and SDS were used separately for encapsulating AgNPs and their role was compared. The UV-Visible absorption spectra present a broad SPR band consisting of two peaks suggesting the formation of silver nanoparticle with bimodal size distribution. The TEM image shows particles with spherical and hexagonal morphologies which confirms the results of UV-Vis studies. The anisotropy in the particle morphology can be attributed to the surface oxidation which in turn produces Ag@Ag2O core-shell nanostructures. Thus an intriguing feature of this system is that the obtained colloid is a mixture of AgNPs with and without Ag2O layers. Studies on the influence of pH on the stability of the synthesized nanoparticles revealed that the presence of excess Ag2O layers has a profound influence on it. Ag2O layers can be removed from AgNPs' surface by changing the solution pH to the acidic regime. The present study attests the enhanced ability of AOT in stabilizing the AgNPs in aqueous media. (C) 2011 Elsevier B.V. All rights reserved.

Solvothermal synthesis of Hg1-xCdxTe nanostructures-Their structural and optical properties

This article describes a facile, low-cost, solution-phase approach to the large-scale preparation of Hg1-xCdxTe nanostructures of different shapes such as nanorods, quantum dots, hexagonal cubes of different sizes and different compositions at a growth temperature of 180 degrees C using an air stable Te source by solvothermal technique. The XRD spectrum shows that the crystals are cubic in their basic structure and reveals the variation in lattice constant as a function of composition. The size and morphology of the products were examined by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The formation of irregular shaped particles and few nano-rods in the present synthesis is attributed to the cetyl trimethylammonium bromide (CTAB). The room temperature FTIR absorption and PL studies for a compositon of x = 0.8 gives a band gap of 1.1 eV and a broad emission in NIR region (0.5-0.9 eV) with all bands attributed to surface defects.

Lanthanide Sulfate Frameworks: Synthesis, Structure, and Optical Properties

Layered lanthanide sulfate compounds with three different structures have been prepared and characterized. The compounds C10H10N2] La(SO4)(2)]center dot 2H(2)O (I), C10H10N2] La(SO4)(2)(H2O)(2)](2) (Ha), C10H10N2]Pr(SO4)(2)(H2O)(2)](2) (IIb), C10H10N2]Nd-2(SO4)(4)(H2O)(2)](2) (IIIa), C10H10N2]Sm-2(SO4)(4)(H2O)(2)](2) (IIIb), and C10H10N2]Eu-2(SO4)(4)(H2O)(2)] 2 (IIIC) have anionic lanthanide sulfate layers separated by protonated bipyridine molecules. The layers are formed by the connectivity between the lanthanide polyhedra and sulfate tetrahedra. The formation of a two-dimensional La-O-La layer (la), Pr-O-Pr chains (IIb), and a tetramer cluster (IIIa) is noteworthy. The compounds exhibit honeycomb (I), square (IIa, IIb), and honeycomb (IIIa-IIIc) net arrangements, when the connectivity between the lanthanide ions is considered. Optical studies indicate the observation of characteristic metal-centered emission at room temperature. The Nd compound (IIIa) exhibits a two-photon upconversion behavior.

High-Throughput Study of the Cu(CH3COO)(2)center dot H2O-5-Nitroisophthalic Acid Heterocyclic Ligand System: Synthesis, Structure, Magnetic, and Heterogeneous Catalytic Studies of Three Copper Nitroisophthalates

A high-throughput screening was employed to identify new compounds in Cu(CH3COO)(2)center dot H2O-NIPA-heterocyclic ligand systems. Of the compounds identified, three compounds, Cu-3{(NO2)-C6H3-(COO)(2)}(3)(C3N6H6)] (1), Cu-2(mu(3)-OH)(H2O){(NO2)-C6H3-(COO)(2)}(CN4H)]center dot-(H2O) (II), and Cu-2(mu(3)-OH)(H2O){(NO2)-C6H3-(COO)(2}-)(CN5H2)]center dot 2(H2O) (III), have been isolated as good quality single crystals by employing conventional hydrothermal methods. Three other compounds, Cu-2{(NO2)-C6H3-(COO)(2)}-(CN4H)(H2O) (IIa), Cu-2{(NO2)-C6H3-(COO)(2)}(CN5H2) (IIIa), and Cu-2{(NO2)-C6H3-(COO)(2)}{(CN5H2)(2)}2H(2)O (IIIb), were identified by a combination of elemental analysis, thermogravimetric analysis (TGA), and IR spectroscopic studies, although their structures are yet to be determined. The single crystalline compounds were also characterized by elemental analysis, TGA, IR, UV vis, magnetic, and catalytic studies. The structures of the compounds have paddle wheel (I) and infinite Cu 0(H) Cu chains (II and HI) connected with NLPA and heterocyclic ligands forming two-(II) and three-dimensional (I and III) structures. The bound and lattice water molecules in 11 and 111 could be reversibly removed/inserted without affecting the structure. In the case of II, the removal of water gives rise to a structural transition, but the dehydrated phase reverts back to the original phase on prolonged exposure to atmospheric conditions. Magnetic studies indicate an overall antiferromagnetism in all of the compounds. Lewis acid catalytic studies indicate that compounds II and HI are active for cyanosilylation of imines.

A methodology for spirocyclopentannulation. Stereoselective total synthesis of (+/-)-tochuinyl acetate and (+/-)-dihydrotochuinyl acetate

A methodology based on Claisen rearrangement and Wacker oxidation for the spirocyclopentannulation of ketones, and its application to a highly stereoselective first total synthesis of dihydrotoch

A novel (main chain) (side chain) polymeric peroxide: Synthesis and initiating characteristics of poly(alpha-(tert-butylperoxymethyl)styrene peroxide)

A novel (main chain)-(side chain) vinyl polyperoxide, poly(alpha-(tert-butylperoxymethyl)styrene peroxide) (MCSCPP), an alternating copolymer of alpha-(tert-butylperoxymethyl)styrene (TPMS) and oxygen, has been synthesized by the oxidative polymerization of TPMS. The MCSCPP was characterized by H-1 NMR, C-13 NMR, IR, DSC, EI-MS, and GC-MS studies. The overall activation energy (E(a)) for the degradation of MCSCPP was found to be 27 kcal/mol. Formaldehyde and alpha-(tert-butylperoxy)acetophenone (TPAP) were identified as the primary degradation products of MCSCPP; TPAP was found to undergo further degradation. The side chain peroxy groups were found to be thermally more stable than those in the main chain. Polymerization of styrene in the presence of MCSCPP as initiator, at 80 degrees C, follows classical kinetics. The presence of peroxy segments in the polystyrene chain was confirmed by both H-1 NMR and thermal decomposition studies. Interestingly, unlike other vinyl polyperoxides, the MCSCPP initiator shows an increase in molecular weight with conversion.