On self-interacting oligoribonucleotides. I. Absorption and optical rotatory dispersion of 2′-5′- and 3′-5′-oligoguanylic acids

A series of 2′-5′-oligoguanylic acids are prepared by reacting G(cyclic)p with takadiastase T1 ribonuclease and separating the products chromatographically. The 3′-5′-oligoguanylic acids are obtained by separating the products of alkaline degradation of 3′-5′-poly(G). The optical rotatory dispersion and hypochromism of both 2′-5′- and 3′-5′-oligoguanylic acids are studied at two different pH. The optical rotatory dispersion spectrum of 2′-5′-GpG is significantly different from that of 3′-5′-GpG. The magnitude of rotation of the long-wavelength peak of 2′-5′-GpG is larger than that of 3′-5′-GpG. This finding contradicts the explanation that the extra stability and more intense circular dichroism band of other 3′-5′-dinucleoside monophosphates is due to H-bond formation between 2′-OH and either the base or the phosphate oxygen. The end phosphate group has a marked effect on the spectrum of GpG between 230 and 250 mμ. In addition the optical rotatory dispersion spectra of 2′-5′ exhibit strong pH, temperature, and solvent dependence between 230 and 250 mμ. ΔH and AS for order ⇌ disorder transition is estimated to be 9.7 kcal/mole and 35.2 eu, respectively. The optical rotatory dispersion spectra of guanine-rich oligoribonucleotides, GpGpC, GpGpU, GpGpGpC, and GpGpGpU are compared to the calculated optical rotatory dispersion from the semiempirical expression of Cantor and Tinoco, using measured optical rotatory dispersion of dimers. Contrary to previous studies, agreement is found not at all satisfactory. However, optical rotatory dispersion of 3′-5′-GpGpGpC and GpGpGpU can be estimated from the semiempirical expression, if a next-nearest interaction parameter is introduced empirically. Such interaction parameter can be calculated from the measured properties of trinucleotide sequences like GpGpG, GpGpC, and GpGpU, assuming that only the nearest-neighbor interaction is important. The optical rotatory dispersion of single-stranded poly(G) is also predicted. The importance of syn-anti equilibrium and next-nearest-neighbor interaction in oligoguanylic acids is suggested as a probable explanation.

Influence of Oxide Particle Network Morphology on Ion Solvation and Transport in ``Soggy Sand''Electrolytes

The role of oxide surface chemical composition and solvent on ion solvation and ion transport of ``soggy sand'' electrolytes are discussed here. A ``soggy sand'' electrolyte system comprising dispersions of hydrophilic/hydrophobic functionalized aerosil silica in lithium perchlorate methoxy polyethylene glycol solution was employed for the study. Static and dynamic rheology measurements show formation of an attractive particle network in the case of the composite with unmodified aerosil silica (i.e., with surface silanol groups) as well as composites with hydrophobic alkane groups. While particle network in the composite with hydrophilic aerosil silica (unmodified) were due to hydrogen bonding, hydrophobic aerosil silica particles were held together via van der Waals forces. The network strength in the latter case (i.e., for hydrophobic composites) were weaker compared with the composite with unmodified aerosil silica. Both unmodified silica as well as hydrophobic silica composites displayed solid-like mechanical strength. No enhancement in ionic conductivity compared to the liquid electrolyte was observed in the case of the unmodified silica. This was attributed to the existence of a very strong particle network, which led to the ``expulsion'' of all conducting entities from the interfacial region between adjacent particles. The ionic conductivity for composites with hydrophobic aerosil particles displayed ionic conductivity dependent on the size of the hydrophobic chemical moiety. No spanning attractive particle network was observed for aerosil particles with surfaces modified with stronger hydrophilic groups (than silanol). The composite resembled a sol, and no percolation in ionic conductivity was observed.

Ring-Opening-Induced Toughening of a Low-Permittivity Polymer-Metal Interface

Integrating low dielectric permittivity (low-k) polymers to metals is an exacting fundamental challenge because poor bonding between low-polarizability moieties and metals precludes good interfacial adhesion. Conventional adhesion-enhancing methods such as using intermediary layers are unsuitable for engineering polymer/metal interfaces for many applications because of the collateral increase in dielectric permittivity. Here, we demonstrate a completely new approach without surface treatments or intermediary layers to obtain an excellent interfacial fracture toughness of > 13 J/m(2) in a model system comprising copper. and a cross-linked polycarbosilane with k similar to 2.7 obtained by curing a cyclolinear polycarbosilane in air.Our results suggest that interfacial oxygen catalyzed molecularring-opening and anchoring of the opened ring moieties of the polymer to copper is the main toughening mechanism. This novel approach of realizing adherent low-k polymer/metal structures without intermediary layers by activating metal-anchoring polymer moieties at the interface could be adapted for applications such as device wiring and packaging, and laminates and composites.

Glucose-Triggered Drug Delivery from Borate Mediated Layer-by-Layer Self-Assembly

In this study, we report a novel approach for glucose-triggered anticancer drug delivery from the self-assembly of neutral poly(vinyln alcohol) (PVA) and chitosan. In the present study, we have fabricated multilayer thin film of PVA-borate and chitosan on colloidal particle (MF particle) and monitored the layer-by-layer growth using Zetapotential measurements. Formation of multilayer membrane on MF particle has been further characterized with transmission electron microscopy (TEM) and confocal laser scanning microscopy (CLSM). Subsequently,disintegration of multilayer thin film and microcapsules was observed in presence of glucose. We investigated the disassembly of PVA-borate and chitosan self-assembly under CLSM and atomic force microscopy. These results suggest that this multilayer thin film is very efficient for encapsulation and release of DOX molecules above certain concentration of glucose (25 mM). This glucose-sensitive self-assembly is relevant for the application of anticancer therapeutic drug delivery.

Steroids and related natural products. VIII. Synthesis of oxasteroids

Peroxydisulfuric acid oxidation of testosterone propionate, progesterone, and cholest-4-en-3-one has been shown to yield 3-oxo-17β-hydroxy-4-oxa-5α-androstane (I, after saponification), 3,20-dioxo-4-oxa-5α-pregnane (V) and 3-oxo-4-oxa-5α-cholestane (VII) respectively. Boron trifluoride etherate-lithium aluminum hydride reduction of δ-lactones I, V, and VII led to the corresponding tetrahydropyran derivatives (IIb, VIa, and VIII). Similar reduction of 3β-hydroxy-17-oxo-17a-oxa-D-homo-5α-androstane (XI) gave 3β-hydroxy-17a-oxa-D-homo-5α-androstane (XIIa). Diborane-boron trifluoride etherate was also found to reduce lactones to cyclic ethers, while reduction with diborane gave hemiacetals. Evidence in support of the structures and stereochemistry assigned to the lactones and their unusual reduction products has been summarized. A tentative mechanism is proposed for lactone → ether reduction employing diborane-boron trifluoride etherate.

Fatty acid specificity for the esterification of vitamin A and cholesterol by intestinal and pancreatic enzymes in rats

VITAMIN A and cholesterol esters have been shown to undergo extensive hydrolysis in the lumen of the small intestine during the process of absorption; they are re-esterified to appear in the lymph mostly as esters1,2. However, the vitamin A esters of the lymph, blood and liver of the rat are formed by long-chain fatty acids3 and in the normal rat liver, probably as palmitates4. On the other hand, cholesterol esters are usually made up of poly-unsaturated fatty acids in the lymph and blood of rats5. For the absorption of the two lipid materials, the enzymes of the pancreas have been largely implicated, while not much attention has been paid to the possible role of the mucosal enzymes. From the behaviour of the mucosal enzymes, as presented here, it appears that probably these enzymes play a more important part in the re-esterification of the two lipid materials during their absorption.

An acid method for the volumetric estimation of water-soluble dithiocarbamates

Dithiocarbamates have been estimated previously by reaction with a strong acid, the carbon disulfide evolved being converted into a xanthate and the latter estimated iodimetrically. In the present method, a water-soluble dithiocarbamate is reacted with a decinormal mineral acid and the excess acid is determined to compute the amount of dithiocarbamate present. This method is applicable for the determination of a dithiocarbamate in a mixture containing thiuram disulfide.

Steroids and related natural products. VII. Boron trifluoride etherate-lithium aluminum hydride reduction of smilagenin acetate

Reduction of smilagenin acetate (Va) using a boron trifluoride etherate-lithium aluminum hydride reagent, followed by hydrogen peroxide oxidation and acetylation, was found to yield: 3β-ethoxysmilagenin (Vb), 3β-ethoxydihydrosmilagenin acetate (VIa), dihydrosmilagenin diacetate (VIb), and a complex mixture of partially acetylated products. Similar reaction conditions were employed to convert dihydrodiosgenin (II) to dihydrochlorogenin (III). Boron trifluoride etherate-lithium aluminum hydride reduction of 3β-acetoxy-5α-cholestane and 3β-acetoxy-5α-lanostane (VIIIa) was shown to yield the corresponding 3β-ethoxy (e.g., VIIIb) derivatives.

The Bertele arc

THE electron emission in the cathode spot of arcs has remained an unexplained phenomenon since K. T. Compton1 first directed attention to it. It appears that the arc discharge discovered by H. von Bertele 2 puts this paradox into an even more acute form.

Distribution of coenzyme Q in rat liver cell fractions

COENZYME Q (CoQ), which is widely distributed in animal, plant and microbial sources, has been implicated in electron transport1 and generally assumed to be associated with mitochondria. However, it has also been found in non-mitochondrial fractions of green leaves, although it appears to be concentrated in mitochondria2. A similar distribution has now been demonstrated in rat liver cell fractions.

Colorimetric determination of 2,4-dinitrophenylamino groups by sodium borohydride reduction

When sodium borohydride is added to aqueous solutions of 2,4-dinitrophenylamino acids and related derivatives, an intense red color is formed. Measurement of the red color, with a 420 filter, permits the determination of such compounds in concentrations of 0.01 to 0.06 μmole per ml. with a precision to 2%. The reaction is highly specific-while 2,4-dinitroaniline will react to the test, o-, m-, and p-nitroanilines, 2,4-dinitrophenyl aryl or alkyl ethers, and 2,4-dinitrophenyl-imidazole and pyrrolidine derivatives will not. Heretofore aromatic nitro groups have been considered resistant to attack by sodium borohydride. The method, as developed, is applicable to the evaluation of the degree of substitution of protein amino groups by fluorodinitrobenzene.