Anomalous X-ray scattering study of local structures in the superionic conducting class (CuI)(0.3)(Cu2O)(0.35)(MoO3)(0.35)

The anomalous X-ray scattering (AXS) method using Cu and Mo K absorption edges has been employed for obtaining the local structural information of superionic conducting glass having the composition (CuI)(0.3)(Cu2O)(0.35)(MoO3)(0.35). The possible atomic arrangements in near-neighbor region of this glass were estimated by coupling the results with the least-squares analysis so as to reproduce two differential intensity profiles for Cu and Mo as well as the ordinary scattering profile. The coordination number of oxygen around Mo is found to be 6.1 at the distance of 0.187 nm. This implies that the MoO6 octahedral unit is a more probable structural entity in the glass rather than MoO4 tetrahedra which has been proposed based on infrared spectroscopy. The pre-peak shoulder observed at about 10 nm(-1) may be attributed to density fluctuation originating from the MoO6 octahedral units connected with the corner sharing linkage, in which the correlation length is about 0.8 nm. The value of the coordination number of I- around Cu+ is estimated as 4.3 at 0.261 nm, suggesting an arrangement similar to that in molten CuI.

Intermolecular complexes of singly linked bisporphyrins with trinitrobenzene

Several covalently linked bisporphyrin systems, free-base (H2P---H2P), hybrid bisporphyrins (Zn---H2P) and Zn(II) dimers (ZnP---ZnP) and their 1:1 molecular complexes with sym 1,3,5-trinitrobenzene have been investigated by optical absorption and emission, and magnetic resonance spectroscopic methods. In these systems, two porphyrin units are linked singly through one of the meso aryl groups via ether linkages of variable length. The bisporphyrins cooperatively bind a molecule of a ?-acceptor; 1,3,5-trinitrobenzene (TNB). The binding constant values vary with interchromophore separation. Maximum binding is observed in the bisporphyrin bearing a two-ether covalent linkage. It is found that TNB quenches the fluorescence of the two porphyrine units in a selective manner. It is suggested that a critical distance between the two porphyrin units is necessary for the observance of maximum cooperative intermolecular binding with an acceptor.

Variational principles in evolution

For a one-locus selection model, Svirezhev introduced an integral variational principle by defining a Lagrangian which remained stationary on the trajectory followed by the population undergoing selection. It is shown here (i) that this principle can be extended to multiple loci in some simple cases and (ii) that the Lagrangian is defined by a straightforward generalization of the one-locus case, but (iii) that in two-locus or more general models there is no straightforward extension of this principle if linkage and epistasis are present. The population trajectories can be constructed as trajectories of steepest ascent in a Riemannian metric space. A general method is formulated to find the metric tensor and the surface-in the metric space on which the trajectories, which characterize the variations in the gene structure of the population, lie. The local optimality principle holds good in such a space. In the special case when all possible linkage disequilibria are zero, the phase point of the n-locus genetic system moves on the surface of the product space of n higher dimensional unit spheres in a certain Riemannian metric space of gene frequencies so that the rate of change of mean fitness is maximum along the trajectory. In the two-locus case the corresponding surface is a hyper-torus.

Synthetic Studies Towards Prismanes - Rearrangements In Some Pentacyclic Precursors And X-Ray Crystal-Structure Of A Novel Heptacyclic Ether

In order to gain access to the heptacyclic tetraone 3, efforts were directed towards the utilisation of the major 'unwanted' [4 + 2]-adduct 11 of tetrachlorodimethoxycyclopentadiene and norbornenobenzoquinone. Epoxides derived from the diol and dimethoxy derivatives of the adduct 11 undergo facile Wagner-Meerwein rearrangement resulting in the required endo, syn, endo stereochemistry as well as methano-bridge functionalisation to deliver 18 and 24, respectively. However, intramolecular ether formation, occurring via the capture of carbocation intermediate with the transannularly poised oxygen functionality, is a more facile process. Attempts to cleave the ether linkage resulted in the formation of a novel transannularly cyclised twisted bowl shape heptacyclic compound 30 and its structure has been established through X-ray crystallography.

Synthesis of path generating flexible-link mechanisms

Flexible-link mechanisms are those linkage mechanisms (or structures) which are capable of motion by virtue of elastic deformation of one or more;links. In such mechanisms a single flexible link; can replace several rigid links and joints resulting in fewer links, fewer pin joints, reduced overall weight and reduced mechanical error. In spite of such clear advantages, contributions toward flexible-link mechanisms remain very scarce. The area of flexible-link mechanisms offers much scope for further exploration. This paper attempts to show the potential of flexible-link mechanisms in accomplishing a kinematic task like path generation. Synthesis of a four-bar mechanism with a flexible rocker for circular and straight line path generation is carried out. Displacement analysis of the structure is carried out using finite element method (FEM) and synthesis is formulated and solved as an optimization problem. Several numerical examples are presented for illustration. Based on the results obtained with these examples, the flexible-link mechanism considered shows good promise for-path generation.

Synthesis, Thermotropic Behavior, and Permeability Properties of Vesicular Membranes Composed of Cationic Mixed-Chain Surfactants

In order to elucidate the role of the linkage region that connects polar headgroups with hydrophobic segments in a lipid monomer, cationic mixed-chain amphiphiles containing acyl and alkyl hydrophobic segments connected at the level of Me(2)N(+) headgroups 2a-d were synthesized. Related dialkyldimethyl-ammonium ion surfactants 1a-e and diacyl systems 3a-c were also synthesized. Despite mismatch in the connector region, amphiphiles 2a-d form bilayer vesicles like their dialkyl and diacyl counterparts, as revealed by electron microscopy. Introduction of an ester connector function between the polar and hydrophobic parts raises the phase transition temperature (T-m), transition enthalpies, and resistance to ion permeation. Consideration of energy minimized conformations points toward the importance of differences in the depth of chain penetration into the putative bilayer.

Macro-economic analysis of forestry options on carbon sequestration in India

The forestry sector provides a number of climate change mitigation options. Apart from this ecological benefit, it has significant social and economic relevance. Implementation of forestry options requires large investments and sustained long-term planning. Thus there is a need for a detailed analysis of forestry options to understand their implications on stock and flow of carbon, required investments, value of forest wealth, contribution to GNP and livelihood, demand management, employment and foreign trade. There is a need to evaluate the additional spending on forestry by analysing the environmental (particularly carbon abatement), social and economic benefits. The biomass needs for India are expected to increase by two to three times by 2020. Depending upon the forest types, ownership patterns and land use patterns, feasible forestry options are identified. It is found among many supply options to be feasible to meet the 'demand based needs' with a mix of management options, species choices and organisational set up. A comparative static framework is used to analyze the macro-economic impacts. Forestry accounts for 1.84% of GNP in India. It is characterized by significant forward industrial linkages and least backward linkage. Forestry generates about 36 million person years of employment annually. India imports Rs. 15 billion worth of forest based materials annually. Implementation of the demand based forestry options can lead to a number of ecological, economic and institutional changes. The notable ones are: enhancement of C stock from 9578 to 17 094 Mt and a net annual C-sequestration from 73 to 149 Mt after accounting for all emissions; a trebling of the output of forestry sector from Rs. 49 billion to Rs. 146 billion annually; an increase in GDP contribution of forestry from Rs. 32 billion to Rs. 105 billion over a period of 35 years; an increase in annual employment level by 23 million person years, emergence of forestry as a net contributor of foreign exchange through trading of forestry products; and an increase in economic value of forest capital stock by Rs. 7260 billion with a cost benefit analysis showing forestry as a profitable option. Implementation of forestry options calls for an understanding of current forest policies and barriers which are analyzed and a number of policy options are suggested. (C) 1997 Elsevier Science B.V.

Syntheses, Transfection Efficacy and Cell Toxicity Properties of Novel Cholesterol-based Gemini Lipids having Hydroxyethyl Head group

We have synthesized five new cholesterol based gemini cationic lipids possessing hydroxyethyl (-CH2CH2OH) function on each head group, which differ in the length of the polymethylene spacer chain. These gemini lipids are important for gene delivery processes as they possess pre-optimized molecular features, e. g., cholesterol backbone, ether linkage and a variable spacer chain between both the headgroups of the gemini lipids. Cationic liposomes were prepared from each of these lipids individually and as a mixture of individual cationic gemini lipid and 1,2-dioleoyl phosphatidylethanolamine (DOPE). Each gemini lipid based formulation induced better transfection activity than that of their monomeric counterpart. One such gemini lipid with a -(CH2)(12)-spacer, HG-12, showed dramatic increase in the mean fluorescence intensity due to the expression of green-fluorescence protein (GFP) in the presence of 10% FBS compared to the conditions where there was no serum. Other gemini lipids retained their gene transfection efficiency without any marked decrease in the presence of serum. The only exception was seen with the gemini with a -(CH2)(3)-spacer, HG-3, which on gene transfection in the presence of 10% FBS lost similar to 70% of its transfection efficiency. Overall the gemini lipid with a -(CH2)(5)-spacer, HG-5, showed the highest transfection activity at N/P (lipid/DNA) ratio of 0.5 and lipid : DOPE molar ratio of 2. Upon comparison of the relevant parameters, e. g., %-transfected cells, the amount of DNA transfected to each cell and %-cell viability all together against Lipofectamine 2000, one of the best commercial transfecting agents, the optimized lipid formulation based on DOPE/HG-5 was found to be comparable. In terms of its ability to induce gene-transfer in the presence of serum and shelf-life DOPE/HG-5 liposome was found to be superior to its commercial counterpart. Confocal imaging analysis confirmed that in the presence of 10% serum using a Lipid : DOPE of 1 : 4 and N/P charge ratio of 0.75 with 1.2 mu g DNA per well, HG-5 is better than Lipofectamine 2000.

The role of lysine-256 in the structure and function of sheep liver recombinant serine hydroxymethyltransferase

The active site lysine residue, K256, involved in Schiffs base linkage with pyridoxal-5'-phosphate (PEP) in sheep liver recombinant serine hydroxymethyltransferase (rSHMT) was changed to glutamine or arginine by site-directed mutagenesis. The purified K256Q and K256R SHMTs had less than 0.1% of catalytic activity with serine and H(4)folate as substrates compared to rSHMT. The mutant enzymes also failed to exhibit the characteristic visible absorbance spectrum (lambda(max) 425 nm) and did not produce the quinonoid intermediate (lambda(max) 495 nm) upon the addition of glycine and H(4)folate. The mutant enzymes were unable to catalyze aldol cleavage of beta-phenylserine and transamination of D-alanine. These results suggested that the mutation of the lysine had resulted in the inability of the enzyme to bind to the cofactor. Therefore, the K256Q SHMT was isolated as a dimer and the K256R SHMT as a mixture of dimers and tetramers which were converted to dimers slowly. On the other hand, rSHMT was stable as a tetramer for several months, further confirming the role of PLP in maintenance of oligomeric structure. The mutant enzymes also failed to exhibit the increased thermal stability upon the addition of serine, normally observed with rSHMT. The enhanced thermal stability has been attributed to a change in conformation of the enzyme from open to closed form leading to reaction specificity. The mutant enzymes were unable to undergo this conformational change probably because of the absence of bound cofactor.

N-6-anisoyladenosine monohydrate

The title compound, C18H19N5O6. H2O, has a syn conformation about the glycosidic bond. Its furanose ring shows a C2'-endo-C3'-exo twist conformation and trans-gauche geometry about the C4'-C5' bond. The angle between the adenine base and the phenyl ring of the anisoyl group is 22.9 degrees. Adenine and anisoyl groups stack along the b axis at a separation of 3.4 Angstrom.

Hyperbranched Polyacetals with Tunable Degradation Rates

We report the first synthesis of hyperbranched polyacetals via a melt transacetalization polymerization process. The process proceeds via the self-condensation of an AB(2) type monomer carrying a hydroxyl group and a dimethylacetal unit; the continuous removal of low boiling methanol drives the equilibrium toward polymer formation. Because of the susceptibility of the acetal linkage to hydrolysis, the polymer degrades readily under mildly acidic conditions to yield the corresponding hydroxyl aldehyde as the primary product. Furthermore, because of the unique topology of hyperbranched structures, the rate of polymer degradation was readily tuned by changing just the nature of the end-groups alone; instead of the dimethylacetal bearing monomer, longer chain dialkylacetals (dibutyl and dihexyl) monomers yielded hyperbranched polymers carrying longer alkyl groups at their molecular periphery. The highly branched topology and the relatively high volume fraction of the terminal alkyl groups resulted in a significant lowering of the ingress rates of the aqueous reagents to the loci of degradation, and consequently the degradation rates of the polymers were dramatically influenced by the hydrophobic nature of the terminal alkyl substituents. The simple synthesis and easy tunability of the degradation rates make these materials fairly attractive candidates for use as degradable scaffolds.

Synthesis of novel cationic lipids with fully or partially non-scissile linkages between the hydrocarbon chains and pseudoglyceryl backbone

Five novel cationic lipids with fully or partially non-scissile linkage regions between the pseudoglyceryl backbone and the hydrocarbon chains have been synthesized. The membrane-forming properties of these new lipids are briefly presented.

Thermal Lipid Order−Disorder Transitions in Mixtures of Cationic Cholesteryl Lipid Analogues and Dipalmitoyl Phosphatidylcholine Membranes

Two types of cationic cholesteryl amphiphiles, one where the headgroup is attached to the steroid by an ester linkage and the second by an ether linkage, were synthesized. A third type of cholesteryl lipid bearing an oligoethylene glycol segment was also prepared. Each of these synthetic lipids generated vesicle-like aggregates with closed inner aqueous compartments from their aqueous suspensions. We examined their interaction with L-α-dipalmitoyl phosphatidylcholine (DPPC) membranes using fluorescence anisotropy, transmission electron microscopy (TEM), and differential scanning calorimetry (DSC). When included in membranes, the synthetic cholesteryl lipids were found to quench the chain motion of the acyl chains of DPPC. This suggests that these cationic cholesteryl derivatives act as filler molecules despite modification at the headgroup level from the molecular structure of natural cholesterol. Careful analyses of DSC and fluorescence anisotropy data suggest that the nature of perturbation induced by each of these cationic cholesterol derivatives is dependent on the details of their molecular structure and provides significant information on the nature of interaction of these derivatives with phospholipid molecules. In general, amphiphiles that support structured water at the interfacial region tend to rigidify the fluid phase more than others. Importantly, these cholesteryl amphiphiles behave less like cholesterol in that their incorporation in DPPC not only abolishes the phase transition but also depresses the phase transition temperature.

Static Balancing of Spring-loaded Planar Revolute-joint Linkages without Auxiliary Links

We present a method to statically balance a general treestructured,planar revolute-joint linkage loaded with linear springs or constant forces without using auxiliary links. The balancing methods currently documented in the literature use extra links; some do not apply when there are spring loads and some are restricted to only two-link serial chains. In our method, we suitably combine any non-zero-free-length load spring with another spring to result in an effective zero-free-length spring load. If a link has a single joint (with the parent link), we give a procedure to attach extra zero-free-length springs to it so that forces and moments are balanced for the link. Another consequence of this attachment is that the constraint force of the joint on the parent link becomes equivalent to a zero-free-length spring load. Hence, conceptually,for the parent link, the joint with its child is removed and replaced with the zero-free-length spring. This feature allows recursive application of this procedure from the end-branches of the tree down to the root, satisfying force and moment balance of all the links in the process. Furthermore, this method can easily be extended to the closed-loop revolute-joint linkages, which is also illustrated in the paper.

Effect of ester chemical structure and peptide bond conformation in fragmentation pathways of differently metal cationized cyclodepsipeptides

Fragmentation behavior of two classes of cyclodepsipeptides, isariins and isaridins, obtained from the fungus Isaria, was investigated in the presence of different metal ions using multistage tandem mass spectrometry (MS(n)) with collision induced dissociation (CID) and validated by NMR spectroscopy. During MS(n) process, both protonated and metal-cationized isariins generated product ions belonging to the identical `b-ion' series, exhibiting initial backbone cleavage explicitly at the beta-ester bond. Fragmentation behavior for the protonated and metal-cationized acyclic methyl ester derivative of isariins was very similar. On the contrary, isaridins during fragmentation produced ions belonging to the `b' or/and the `y' ion series depending on the nature of interacting metal ions, due to initial backbone cleavages at the beta-ester linkage or/and at a specific amide linkage. Interestingly, independent of the nature of the interacting metal ions, the product ions formed from the acyclic methyl ester derivative of isaridins belonged only to the `y-type'. Complementary NMR data showed that, while all metal ions were located around the beta-ester group of isariins, the metal ion interacting sites varied across the backbone for isaridins. Combined MS and NMR data suggest that the different behavior in sequence specific charge-driven fragmentation of isariins and isaridins is predetermined because of the constituent beta-hydroxy acid residue in isariins and the cis peptide bond in isaridins.