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Thomas W Bell

Publications and source records attributed to Thomas W Bell.

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Synthesis and structure-activity relationship studies of CD4 down-modulating cyclotriazadisulfonamide (CADA) analogues.

HIV attachment via the CD4 receptor is an important target for developing novel approaches to HIV chemotherapy. Cyclotriazadisulfonamide (CADA) inhibits HIV at submicromolar levels by specifically down-modulating cell-surface and intracellular CD4. An effective five-step synthesis of CADA in 30% overall yield is reported. This synthesis has also been modified to produce more than 50 analogues. Many tail-group analogues have been made by removing the benzyl tail of CADA and replacing it with various alkyl, acyl, alkoxycarbonyl and aminocarbonyl substituents. A series of sidearm analogues, including two unsymmetrical compounds, have also been prepared by modifying the CADA synthesis, replacing the toluenesulfonyl sidearms with other sulfonyl groups. Testing 30 of these compounds in MT-4 cells shows a wide range of CD4 down-modulation potency, which correlates with ability to inhibit HIV-1. Three-dimensional quantitative structure-activity relationship (3D-QSAR) models were constructed using comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) approaches. The X-ray crystal structures of four compounds, including CADA, show the same major conformation of the central 12-membered ring. The solid-state structure of CADA was energy minimized and used to generate the remaining 29 structures, which were similarly minimized and aligned to produce the 3D-QSAR models. Both models indicate that steric bulk of the tail group, and, to a lesser extent, the sidearms mainly determine CD4 down-modulation potency in this series of compounds.

Anti-HIV Agents↗

Inhibitors of HIV infection via the cellular CD4 receptor.

Recent advances in our understanding of cellular and molecular mechanisms of viral penetration of the target cell have provided the basis for novel chemotherapy and prophylaxis of HIV-1 infections. This knowledge has been successfully applied to the development of inhibitors that target discrete steps of the entry process. Interesting approaches for prevention of HIV-1 entry include the use of small-molecule inhibitors, natural ligands and/or monoclonal antibodies that interfere with gp120/CD4 interaction. Other compounds acting by novel mechanisms have recently been identified as anti-HIV agents and seem worthy of further preclinical development. Of particular interest in this regard are cyclotriazadisulfonamide (CADA) compounds, which down-modulate the cellular receptor, CD4. A series of analogues of 9-benzyl-3-methylene-1,5-di-p-toluenesulfonyl-1,5,9-triazacyclododecane (CADA) has been synthesized and tested for CD4 down-modulation and anti-HIV activity. Some derivatives proved to be highly effective in decreasing cellular CD4 and in acting as HIV entry inhibitors. Three-dimensional quantitative structure-activity relationship (3D-QSAR) studies correlating molecular features with potency have been used to produce a computational model. This model can be used to design more potent CD4 down-modulating drugs for HIV therapy and prophylaxis. This review summarizes the results of recent studies relating to inhibitors of HIV infection via CD4 and discusses the therapeutic potential of targeting this cellular receptor. Special attention is given to our own work on small-molecule HIV entry inhibitors endowed with CD4 down-modulating properties.

Anti-HIV Agents↗

Syntheses, structures, and photoisomerization of (E)- and (Z)-2-tert-butyl-9-(2,2,2-triphenylethylidene)fluorene.

"Sterically geared" 9-(2,2,2-triphenylethylidene)fluorene (1) is of potential interest as a photoactive moiety in molecular devices, and the 2-tert-butyl derivative (6) has been synthesized to investigate photoisomerization. E and Z stereoisomers of 6 were separated and identified by X-ray crystallography. The tert-butyl group does not introduce additional strain, and its close proximity to the trityl group in the Z isomer suggests an attractive van der Waals interaction. The UV spectra of (E)-6 and (Z)-6 are nearly identical, showing absorption bands that are similar to those of fluorene occurring at wavelengths longer than 240 nm. Photoisomerization of 6 was investigated at 266, 280 and 320 nm. Solutions initially containing only (E)-6 or (Z)-6 were irradiated with pulsed laser light, monitoring isomerization by 1H NMR spectroscopy. Negligible photodecomposition was observed when the solutions were agitated by N2 ebullition. Experimental data were fitted to theoretical curves to obtain photoisomerization quantum yields (phi(ZE) and phi(EZ)) ranging from 0.04 to 0.09. This first photoisomerization study of a dibenzofulvene reveals significant quantum yields, despite theoretical prediction of inefficient or negligible isomerization of the parent hydrocarbon, fulvene. Thermal isomerization of 6 at 270 degrees C (t(1/2) = 120 min) was also followed by 1H NMR spectroscopy, resulting in an estimated activation energy (deltaG(double dagger)) of 43 kcal/mol.

Journal Article↗

CADA, a novel CD4-targeted HIV inhibitor, is synergistic with various anti-HIV drugs in vitro.

OBJECTIVE: To evaluate the anti-HIV-1 activity of the cyclotriazadisulfonamide CADA against primary isolates in vitro and the combination of CADA with approved anti-HIV drugs for potential synergy. METHODS: Peripheral blood mononuclear cells (PBMC) were treated with CADA and infected with 16 different clinical isolates. After 8 days of infection, the median inhibitory concentration (IC50) was calculated from the p24 viral antigen content in the supernatant. MT-4 cells were infected with HIV-1NL4.3 and then cultured with CADA or other antiretroviral drugs (i.e., several reverse transcriptase, protease and entry inhibitors), alone and in combination. After 4 days, IC50 was determined for the various drugs in replicate assays. Analysis of combined effects was performed using the median effect principle (CalcuSyn; Biosoft). RESULTS: The entry inhibitor CADA exerted a potent and consistent anti-HIV-1 activity against a wide range of R5, R5/X4 and X4 primary isolates in PBMC. From the two-drug studies, combination indices showed synergy between CADA and reverse transcriptase inhibitors (zidovudine, stavudine, lamivudine, zalcitabine, didanosine, abacavir, tenofovir, nevirapine, delavirdine and efavirenz), and protease inhibitors (lopinavir, saquinavir, indinavir, nelfinavir, amprenavir and ritonavir). In addition, the combination of CADA with the gp41 fusion inhibitor T-20 (enfuvirtide), the CXCR4 antagonist AMD3100 and the gp120-specific interacting plant lectins from Galanthus nivalis (GNA) and Hippeastrum hybrid (HHA) also resulted in a synergistic inhibition. CONCLUSIONS: Compounds that can specifically downmodulate the CD4 receptor in PBMC have broad-spectrum anti-HIV activity against primary isolates and act synergistically when used in conjunction with currently available antiretroviral drugs. They deserve further study as potential candidate anti-HIV drugs.

Anti-HIV Agents↗

Supramolecular optical chemosensors for organic analytes.

Supramolecular optical chemosensors are abiotic molecular devices that bind analytes by noncovalent interactions, producing a change in light absorption or fluorescence. This review summarizes recent progress in the development of such chemosensors for organic analytes based on artificial receptors. Important design considerations, such as analyte affinity, choice of chromophore or fluorophore, binding selectivity, and optical signaling mechanism are briefly discussed. Chemists have fashioned chemosensors from a wide range of molecular structures, including polyalcohols, crown ethers, calixarenes, helicenes, sterically geared tripods, metal complexes, pinwheels, porphyrins, and fused-ring heterocycles. Analytes of interest include amines, carboxylic acids, amino acids, hydroquinones, alkaloids, carbohydrates, peptides, urea and creatinine.

Biosensing Techniques↗

CD4 down-modulating compounds with potent anti-HIV activity.

The use of HAART with double or triple drug combinations has significantly improved the survival of AIDS patients. However, the emergence of virus-drug resistance and both short- and long-term drug-related side effects are among the main reasons for continuing the development of new classes of effective anti-HIV drugs that target the replicative cycle at different sites. In recent years, tremendous progress has been made in understanding HIV-1 entry, a multistep process that comprises viral attachment, coreceptor interactions and fusion. The mechanistic insight gained from these studies has enabled the design of specific agents that can inhibit each step in the HIV entry process. The successful results from clinical trials with enfuvirtide (T-20), the first approved entry inhibitor, indicate that targeting of HIV entry will soon be an important component of antiretroviral therapy and further encourage the development of effective entry inhibitors. In this article the recent developments of therapeutic agents endowed with inhibitory properties against the binding of the HIV envelope glycoprotein gp120 to the CD4 receptor (e.g., PRO 542, BMS-378806, TNX-355, PRO 2000 and CV-N) are briefly outlined. Major focus is placed on the anti-HIV activity of cyclotriazadisulfonamides (CADA), a novel class of compounds with a unique mode of action by down-modulating the CD4 receptor in lymphocytic and monocytic cells.

Animals↗

Syntheses, conformations, and basicities of bicyclic triamines.

The multistep syntheses of several bicyclic triamines are described, all of which have an imbedded 1,5,9-triazacyclododecane ring. In 1,5,9-triazabicyclo[7.3.3]pentadecanes 12, 13, 15, and 16, two nitrogens are bridged by three carbons. The monoprotonated forms of these triamines are highly stabilized by a hydrogen-bonded network involving the bridge and both bridgehead nitrogens, producing a difference of more than 8 pK(a) units in acidities of their monoprotonated and diprotonated forms. The one- and zero-carbon bridges in 1,5,9-triazabicyclo[9.1.1]tridecane (23) and 7-methyl-1,5,9-triazabicyclo[5.5.0]dodecane (39) do not enhance the stabilities of their monoprotonated forms. X-ray crystal structures and computational studies of 12.HI and 16.HI reveal similar, but somewhat weaker, hydrogen-bonded networks, relative to 15.HI. The activation free energies for conformational inversion of 13.HI (14.4 +/- 0.2 kcal/mol), 16.HI (15.0 +/- 0.1 kcal/mol) and 16 (8.8 +/- 0.3 kcal/mol) were measured by variable-temperature (1)H and (13)C NMR spectroscopy. These experimental barriers give an estimate of 6.2 kcal/mol for the strength of the bifurcated hydrogen bond between the bridge nitrogen and cavity proton in 16.HI. Computational studies support the hypothesis that N-inversion occurs in an open conformation, leading to an estimate of 10.32 kcal/mol for the enthalpy of the bifurcated hydrogen bond in 16.HI in the gas phase.

Journal Article↗

The Anti-HIV potency of cyclotriazadisulfonamide analogs is directly correlated with their ability to down-modulate the CD4 receptor.

9-Benzyl-3-methylene-1,5-di-p-toluenesulfonyl-1,5,9-triazacyclododecane (CADA) has been identified as a novel antiviral lead compound with significant anti-human immunodeficiency virus and anti-human herpesvirus 7 activity. Surprisingly, this compound selectively decreased the expression of the CD4 glycoprotein, the primary receptor needed for the entry of both viruses. Herein, we describe the CD4 down-modulating and antiviral potencies of more than 25 CADA derivatives. Flow cytometric evaluation of cellular CD4 receptor expression in T cells demonstrated the specific CD4 down-modulating capacity of the CADA derivatives, with IC(50) values similar to those obtained in the antiviral assays. The close correlation observed between the CD4 down-regulating and anti-HIV potencies of the CADA derivatives further points to CD4 receptor down-modulation as the primary mode of antiviral action for this group of compounds.

Anti-HIV Agents↗

Role of pyridine hydrogen-bonding sites in recognition of basic amino acid side chains.

A series of three, new artificial receptors for guanidinium and ammonium guests has been synthesized. All three receptors have highly preorganized clefts bearing two carboxylate groups. They differ in the number of nitrogen atoms contained in their clefts, as follows: four N atoms in receptor 3, three N atoms in 4, and two nitrogens in 5. Crystallographic studies have produced the solid-state structures of the following guanidinium complexes of each receptor: 3.2CH(3)CH(2)NHC(NH(2))(2)(+), 4.2CH(3)NHC(NH(2))(2)(+), and 5.2C(NH(2))(3)(+). The conformations of the receptor molecules in all three complexes are very similar. N-Alkylguanidinium guests are bound in the clefts of 3 and 4 in similar manners, despite the loss of one hydrogen-bond acceptor nitrogen in 4 and the possible hindrance of the cavity by a CH group. In the guanidinium complex of 5, neither guest enters the cavity containing two CH groups. Complexation studies were conducted in methanol by (1)H NMR titration for several guanidinium and ammonium guests, including derivatives of the amino acids arginine and lysine. Receptor 5 binds all such guests weakly (K(s) < 4000), while 3 binds most guests very strongly (K(s) > 100 000). Receptor 3 is selective for arginine versus lysine, while 4 binds lysine better than does 3. The results generally underscore the importance of receptor preorganization and hydrogen-bonding complementarity in the design of receptors that can serve as probes for biomolecules.

Amino Acids↗

Bond angle versus torsional deformation in an overcrowded alkene: 9-(2,2,2-triphenylethylidene)fluorene.

Competition between bond angle and torsional strain in sterically crowded alkenes generally causes twisting in tetrasubstituted alkenes, while most structurally characterized trisubstituted alkenes are planar. To investigate structural effects of steric repulsion between a planar aromatic ring and a vicinal triphenylmethyl (trityl) group, 9-(2,2,2-triphenylethylidene)fluorene (1 a) was synthesized by reaction of 9-bromomethylenefluorene with triphenylmethyllithium. For comparison with a less strained analogue, 9-ethylidenefluorene (1 b) was prepared by reaction of fluorenone with ethylmagnesium bromide. The X-ray crystal structures show that the difference between bond angles at the 9-fluorenyl carbon atom is much larger for 1 a (12.9 degrees) than 1 b (2.6 degrees). Bond angle and torsional deformations were compared theoretically (HF/6-31+G*) with the tert-butyl analogue (1 c), 1,2,2-tri-tert-butylethene (7), and 2,4,4-trimethyl-2-pentene (8) and crystallographically with six known 1,1-diaryl-2-tert-alkylethenes (2). The trisubstituted alkenes formed three groups with 1) large angle distortion with moderate twisting (1 a, 1 b, and 7), 2) moderate bending with a large range of torsional angles (2), and 3) little bending or twisting (1 b and 8). For the entire series, there appears to be a delicate balance between angle and torsional deformation, but twisting appears to produce smaller relief from steric strain than angle bending. In the crystallographically characterized trisubstituted alkenes, the choice between the two is mainly determined by more subtle packing forces.

Journal Article↗

CADA inhibits human immunodeficiency virus and human herpesvirus 7 replication by down-modulation of the cellular CD4 receptor.

The novel antiviral agent cyclotriazadisulfonamide (CADA) inhibited human immunodeficiency virus (HIV) (IC50, 0.3-3.2 microM) and human herpesvirus 7 (HHV-7) infection (IC50, 0.3-1.5 microM) in T-cell lines and PBMCs. When T-cells were pretreated with CADA for 24 h, they became markedly protected from viral infection. Flow cytometric analysis revealed a significant decrease in the expression of the CD4 glycoprotein, the primary receptor needed for entry of both viruses. Moreover, the antiviral activity of CADA correlated with its ability to down-modulate the CD4 receptor. CADA did not alter the expression of any other cellular receptor (or HIV coreceptor) examined. Time course experiments showed that CD4 down-modulation by CADA differs in mechanism from the effects of aurintricarboxylic acid, which binds directly to CD4, and phorbol myristate acetate, which activates protein kinase C. Further analysis of CD4 mRNA levels suggested that CADA was not involved in the regulation of CD4 expression at a transcriptional level, but very likely at (post) translational levels. This unique mechanism of action makes CADA an important lead in developing new drugs for treatment of AIDS, autoimmune diseases, and inflammatory disorders.

Anti-Infective Agents↗

Circular dichroism readout of sugar recognition in the cleft of a fused-pyridine receptor.

Dicarboxamide host 2 forms 1:1 complexes with n-octyl pyranosides derived from D-glucose, D-mannose, D-galactose, D-fucose, D-lyxose, and D-arabinose. Association constants (K(a)) in the range of 77-940 M(-1) were measured in chloroform by means of induced circular dichroism and fluorescence spectroscopy. Variations in K(a) values correspond qualitatively to expected differences in hydrogen-bonding abilities of guest hydroxyl groups. Induced circular dichroism effects for complexes of saccharides bearing equatorial 3-OH, 4-OH, and 6-OH groups show that the host chromophore is twisted in a P-helical conformation. A structural model is proposed that is also consistent with the results of previous studies involving complexation of dicarboxylic acid 1 with cationic saccharides in methanol.

Anions↗