New sesterterpenes from Madagascan Lendenfeldia sponges

A new furanoterpene designated dehydrofurodendin and nine scalarane sesterterpenes of which four are new, were isolated from two different species of Madagascan sponges of the genus Lendenfeldia, both of which seem to be yet undescribed. The structure of the compounds was elucidated by interpretation of 1D and 2D NMR data. Dehydrofurodendin was found to be a potent inhibitor of HIV-1 RT. Several of the isolated scalaranes exhibited cyctotoxicity against several human tumor cells.     

Patterns in Hydrogen Bonding: Functionality and Graph Set Analysis in Crystals

Whereas much of organic chemistry has classically dealt with the preparation and study of the properties of individual molecules, an increasingly significant portion of the activity in chemical research involves understanding and utilizing the nature of the interactions between molecules. Two representative areas of this evolution are supramolecular chemistry and molecular recognition. The interactions between molecules are governed by intermolecular forces whose energetic and geometric properties are much less well understood than those of classical chemical bonds between atoms. Among the strongest of these interactions, however, are hydrogen bonds, whose directional properties are better understood on the local level (that is, for a single hydrogen bond) than many other types of non-bonded interactions. Nevertheless, the means by which to characterize, understand, and predict the consequences of many hydrogen bonds among molecules, and the resulting formation of molecular aggregates (on the microscopic scale) or crystals (on the macroscopic scale) has remained largely enigmatic. One of the most promising systematic approaches to resolving this enigma was initially developed by the late M. C. Etter, who applied graph theory to recognize, and then utilize, patterns of hydrogen bonding for the understanding and design of molecular crystals. In working with Etter's original ideas the power and potential utility of this approach on one hand, and on the other, the need to develop and extend the initial Etter formalism was generally recognized. It with that latter purpose that we originally undertook the present review.     

Side chain thermotropic liquid crystalline polysulfone obtained from polysulfone udel by chemical modification

Polysulfone udel was chemically functionalized with chloromethylene functional groups via the chloromethylation reaction. A new azomethine dimesogen containing one phenolic hydroxyl functional group was recently synthesized and proved to exhibit a large nematic mesophase range in the liquid state. Further reaction of the dimesogen with the functionalized polysulfone using a transquaternization reaction led to new polysulfones bearing pendant rigid dimesogenic units--no spacer being involved in the chemical design of the polymer. The polymers were characterized by IR, ¹H NMR spectroscopy techniques, and their thermotropic liquid crystallinity behaviour was studied by optical polarizing microscopy (PLM) and DSC measurements. Enantiotropic nematic mesophases were observed under the PLM. A dependence of the melting temperature on the degree of substitution was noticed.     

Photoinactivation of hepatitis A virus by synthetic porphyrins

Porphyrins are photosensitizers and may be applicable in situations where viral inactivation is required, as for in vitro inactivation of nonenveloped viruses in blood components or in other aqueous media. No study has examined the efficacy of porphyrin inactivation on human pathogens such as hepatitis A virus (HAV) in plasma or other liquids. Experiments were conducted to evaluate the effect of synthetic porphyrins on HAV in porphyrin-containing human plasma and phosphate-buffered saline exposed to long-wavelength (365 nm) UV light. Inactivation of bacteriophage MS2 (MS2) also was determined in some trials. Solutions containing cationic, anionic or amphiphilic porphyrins irradiated with an average light dose of 4.3 J/cm(2) for 90 min resulted in >3 log(10) (>99.9%) to >4 log(10) (>99.99%) inactivation of both HAV and MS2. Viral inactivation may have been greater than observed because the limits of detection of the assay had been reached. Under ambient lighting conditions, none of the porphyrins was mutagenic in the Ames assay and only the congener with the longest chain-length, tetrakis (N-[n-hexadecyl]-4-pyridiniumyl) porphyrin, was appreciably toxic to mammalian cells. Disinfection by photoactivated synthetic porphyrins therefore can offer an effective and relatively safe approach to removal of nonenveloped viruses from aqueous media.     

Self-recognition, structure, stability, and guest affinity of pyrogallol[4]arene and resorcin[4]arene capsules in solution

In the present study, we used diffusion NMR to probe the structures and characteristics of the products obtained from the self-assembly of resorcin[4]arenes 1a and 1b and pyrogallol[4]arenes 2a and 2b in CDCl(3) solutions. It was found that all four molecules self-assemble into hexameric capsules. The hexameric capsules of pyrogallol[4]arenes 2a and 2b were found to be more stable than the capsules of resorcin[4]arenes 1a and 1b in polar media. We also studied the role of water molecules in the self-assembly of the different capsules and found that water molecules are part of the hexameric capsules of resorcin[4]arenes 1a and 1b but not in the capsules of pyrogallol[4]arenes 2a and 2b. It was found that the self-assembly process between the resorcin[4]arenes and pyrogallol[4]arenes proceeds with self-recognition. When mixing two macrocycles of different types in a chloroform solution, no heterohexamers are formed, only the capsule constructed from the same macrocycle is detected. However, when two resorcin[4]arenes (i.e., 1a and 1b) or two pyrogallol[4]arenes (i.e., 2a and 2b) are mixed, heterohexamers are formed over time. In addition, we found that resorcin[4]arenes and pyrogallol[4]arenes differ significantly in their guest affinity. The capsules of 1a and 1b can accommodate both the tertiary alkylamines and their respective ammonium salts, while the capsules of 2a and 2b encapsulate only the neutral tertiary alkylamines.     

Synthesis of chlorinated and non-chlorinated biphenyl-2,3- and 3,4-catechols and their [2H3]-isotopomers

A synthetic scheme is described for chlorinated biphenyl-2,3- and 3,4-catechols to be used as standards for structural assignment of metabolites and protein adducts of 2,2',5,5'-tetrachlorobiphenyl in which both rings retain chlorine substituents. The scheme has general applicability to the synthesis of chlorinated biphenyl catechols. Dimethyl catechol ethers are coupled to dichloroaniline via the Cadogan reaction to give a library of isomers, followed by demethylation of the ethers with BBr3 to yield the target catechols. Separation of pure isomers is accomplished by TLC or HPLC prior to or following demethylation, depending on the isomer mixture. [2H3]-Isotopomers are generated using 2,5-dichloroaniline-d3 as the starting arylamine in the coupling reaction. The dichloroaniline-d3 hydrochloride is obtained as the sole product from nitration of p-dichlorobenzene-d4 followed by Pd/C-catalyzed hydrogenation under strongly acidic conditions. This hydrogenation procedure provides a simple and convenient approach to selective reduction of aryl nitro groups in the presence of halogen ring substituents.     

The role of water molecules in a resorcinarene capsule as probed by NMR diffusion measurements

[structure: see text] NMR diffusion measurements were used to probe the role of water molecules in a resorcinarene capsule in a CDCl(3) solution. It was found that the water/resorcinarene ratio affects both the chemical shift and the diffusion coefficient of the water molecules. From the NMR diffusion measurements we could conclude that the major species in the chloroform solution is the hexamer having eight water molecules that are in fast exchange, on the NMR time scale, with the bulk water.