Preparation of highly stable organic steps with a fullerene-based molecule

We report the formation of highly stable Langmuir-Blodgett (LB) organic steps made with a hexa-adduct fullerene-based amphiphile. This amphiphile forms films of excellent quality, with a very low roughness, that are structurally stable: X-ray reflectivity spectra recorded on fresh and 12-month-old samples are undiscernible. Such a behavior contrasts with that of more traditional amphiphiles, which are unfortunately well-known for their instability in time. The stability of the films stems, among others, from the spheroidal shape of the constitutive molecules. These experiments show that it is possible to circumvent the major drawback of LB films and to prepare materials more suited for applications. We show that the LB film prepared with this fullerene derivative can successfully be used as thickness gauges for atomic force microscopy or light microscopy studies.     

Controlled electrochemical synthesis of polypyrrole nanoparticle thin film and its redox transition to a highly conductive and stable polypyrrole variant

We demonstrated here a unique method to produce a highly stable and conductive polypyrrole (PPY) nanoparticle film. The procedure entails controlling the redox switching and the electrochemical synthesis of PPY. PPY was synthesized at a very low forming potential or reaction rate in nonaqueous CH2Cl2 solvent to promote the PPY nanoparticle formation. Then its property was further optimized by first electrochemically reducing it at a hydrogen evolution potential in a neutral 0.1 M NaClO4, then in a slightly acidic 0.05 M asparagine electrolyte. The PPY nanoparticle thin film was characterized by AFM, UV-vis and EQCM. The procedures described here have proven to be reproducible. The data provided by the EQCM shows a reversible doping and undoping mechanism of asparagine indicating the presence of a highly conductive PPY variant. Both UV-vis and electrochemical characterization suggest that the PPY film made using our approach has excellent redox activity as well as high stability when characterized in asparagine solution. The reversible doping and undoping of asparagine during redox switching shows great potential of these PPY nanoparticle films as biological membranes for a broad range of biological applications.     

Preparation and characterization of highly stable lipid nanoparticles with amorphous core of tuneable viscosity

Lipid nanoparticles (LNP) have been designed based on low cost and human-use approved excipients, and manufactured by an easy, robust, and up-scalable process. Fluid colloidal dispersions or gel viscous formulations of highly stable nanoparticles (more than 12 month stability is achieved for some formulations) can be obtained. Their physicochemical properties are studied by Dynamic Light Scattering, Differential Scanning Calorimetry, and NMR. The results picture nanoparticles with a non-crystalline core, which viscosity can be finely tuned by the lipid composition and the temperature. A design of experiments has been used to investigate the limits of the system colloidal stability. The impact of core and surfactant weight fractions have been explored both experimentally and using the design of experiments. The versatility of this physicochemical system could open the way to a wide range of future pharmaceutical applications.     

Preparation of chiral cholestanofluorene and its electron-rich derivatives for isolation of a stable cation-radical salt

A simple and practical synthesis of a variety of chiral fluorene derivatives is described where a cholestane moiety is attached to the carbon 9 of the fluorene ring system from readily available starting materials. An appropriately substituted fluorene derivative (i.e., R = OMe) forms a highly colored (chiral) cation-radical that can be isolated as robust hexachloroantimonate salt. Interestingly, the simplest cholestanofluorene (i.e., R = H) can also be transformed into a dibromo derivative (i.e., R = Br), a precursor to the (poly)cholestanofluorenes where the cholestane moieties will serve not only as groups that impart chirality but also allow them to be soluble in common organic solvents. The details of these works are described.     

Hydrotrope and hydrotrope-solubilization action of penicillin-K in CTAB/n-C5H11OH/H2O system

Penicillin potassium salt (penicillin-K) is found to show hydrotrope action, which can increase the solubility of cationic surfactant CTAB in water. Penicillin-K also shows hydrotrope-solubilization action, which makes the W/O and O/W microemulsion more stable and increases the solubilized amount of n-C₅H₁₁OH in O/W microemulsion and that of water in W/O microemulsion for CTAB/n-C₅H₁₁OH/H₂O system. However, in this system, the presence of penicillin-K can decrease the stability of the lamellar liquid crystal phase due to its structure change to bicontinuous, which are proved by the mechanism of its hydrotrope-solubilization action.     

Preparation of chiral, highly functionalized cyclopentanes and its application to the synthesis of prostaglandin E1

This paper describes the preparation of the polyfunctionalized cyclopentane ((+/-)-5) by silica gel-catalyzed air-oxidation, and its kinetic resolution by means of microbial reduction with Rhodotorula rubra to afford optically pure (-)-5 (greater than 99% ee). Starting with (-)-5, a new route to prostaglandin E1 was established.     

Characterization of a kinetically stable, highly ordered, octameric form of lithium tert-butoxide and its implications regarding aggregate formation

The controlled reaction of molecular oxygen with hydrocarbon solutions of tBuLi results in the unexpected formation of the octameric species [(tBuOLi)8], 18. Single-crystal X-ray diffraction studies indicate that the connectivity within 18 corresponds with the fusion of two face-opened tetrameric cubanes. Cryoscopic studies establish the stability of the octamer in benzene solution, but heating results in aggregate rearrangement to the commonly found prismatic hexameric form, 16. Theoretical calculations confirm that the hexameric form is the thermodynamically favored aggregate.     

Preparation and evaluation of a hydrolytically stable amide-embedded stationary phase

We have developed a new hydrolytically stable amide-embedded stationary phase via a simple and effective synthetic method. The preparation of the new phase involves the synthesis of multifunctional silane ligands and the surface modification of porous silica particles via multiple attachments of these ligands to the silica surface. A hydrolytically stable coating was produced as a result of multiple covalent linkages formed between silane ligands and the silica surface, and cross-linking between adjacent ligands. The resulting amide-embedded stationary phase showed excellent hydrolytic stability over a wide pH range. Like other existing amide-embedded columns, this new stationary phase exhibits higher retention for polar compounds and different selectivity as compared to conventional C18 columns. The new phase is compatible with 100% aqueous mobile phases, and also provides high column efficiency and good peak shapes for both acidic and basic compounds.     

Synthesis of a highly thermally stable octupolar polyimide for nonlinear optics

A new polyimide with covalently incorporated 4,4'-bis-(dialkylaminostyryl)-2,2'-bipyridine chromophores is described which allows the synthesis of the corresponding NLO octupolar metallo-polymer.     

Folding of a stable DNA motif involves a highly cooperative network of interactions

Hairpins are structural elements that play important roles in the folding and function of RNA and DNA. The extent of cooperativity in folding is an important aspect of the RNA folding problem. We reasoned that an investigation into the origin of cooperativity might be best carried out on a stable nucleic acid system with a limited number of interactions, such as a stable DNA hairpin loop. The stable d(cGNAg) hairpin loop motif (closing base pair in lower case; loop in upper case; N = A, C, G, or T) is stabilized through only three interactions: two loop-loop hydrogen bonds in a sheared GA base pair and a loop-closing base pair interaction. Herein, we investigate this network of interactions and test whether the loop-loop and loop-closing base pair interactions communicate. Thermodynamic measurements of nucleotide analogue substituted oligonucleotides were used to probe the additivity of the interactions. On the basis of double mutant cycles, all interactions were found to be nonadditive and interdependent, suggesting that loop-loop and loop-closing base pair interactions form in a highly cooperative manner. When double mutant cycles were repeated in the absence of the other interaction, nonadditivity was significantly reduced suggesting that coupling is indirect and requires all three interactions in order to be optimal. A cooperative network of interactions helps explain the structural and energetic bases of stability in certain DNA hairpins and paves the way for similar studies in more complex nucleic acid systems.     

Structural and energetic consequences of expanding a highly cooperative stable DNA hairpin loop

Many hairpin loops are expanded versions of smaller, stable ones. Herein we investigate the extent to which the energetics and structure of d(cGNAg) hairpin loops will tolerate sequence variation. Changing the closing base pair from CG to GC was found to completely eliminate loop-loop interactions; in contrast, expanding the loop at the 3'-end resulted in similar energetics and nonadditivity parameters as the parent loop, suggesting that loop-loop interactions remain intact and highly coupled upon expansion. Together, these data suggest that the CG closing base pair forms an essential platform upon which a stable d(GNA) hairpin loop can fold and that this loop can undergo 3'-expansion with little effect to its structure or energetics.     

Preparation of a stable injection solution of barvinkan hydrochloride

Summary A method has been developed for obtaining a stable 1% injection solution of barvinkan hydrochloride with the aid of a complex stabilizer.Institute of the Chemistry of Plant Substances, Academy of Sciences of the Uzbek SSR, Tashkent. Translated from Khimiya Prirodnykh Soedinenii, No. 5, pp. 601–603, September–October, 1978.     

Facile subsequently light-induced route to highly efficient and stable sunlight-driven Ag-AgBr plasmonic photocatalyst

In this paper, we successfully fabricate a stable and highly efficient direct sunlight plasmonic photocatalyst Ag-AgBr through a facile hydrothermal and subsequently sunlight-induced route. The diffuse reflectance spectra of Ag-AgBr indicate strong absorption in both UV and visible light region. The obtained photocatalyst shows excellent sunlight-driven photocatalytic performance. It can decompose organic dye within several minutes under direct sunlight irradiation and maintain a high level even though used five times. In addition, both the scanning electron microscopy images and X-ray photoelectron spectroscopy dates reveal the as-prepared photocatalyst to be very stable. Moreover, the mechanism suggests that the high photocatalytic activity and excellent stability result from the super sensitivity of AgBr to light, the surface plasmon resonance of Ag nanoparticles in the region of visible light, and the complexation between Ag(+) and nitrogen atom. Thus, the facile preparation and super performance of Ag-AgBr will make it available to utilize sunlight efficiently to remove organic pollutants, destroy bacteria, and so forth.     

A highly stable short alpha-helix constrained by a main-chain hydrogen-bond surrogate

Herein we describe a strategy for the preparation of artificial alpha-helices involving replacement of one of the main-chain hydrogen bonds with a covalent linkage. To mimic the C=O...H-N hydrogen bond as closely as possible, we envisioned a covalent bond of the type C=X-Y-N, where X and Y are two carbon atoms connected through an olefin metathesis reaction. Our results demonstrate that the replacement of a hydrogen bond between the i and i + 4 residues at the N-terminus of a short peptide with a carbon-carbon bond results in a highly stable constrained alpha-helix at physiological conditions as indicated by CD and NMR spectroscopies. The advantage of this strategy is that it allows access to short alpha-helices with strict preservation of molecular recognition surfaces required for biomolecular interactions.