CHEMISTRY

 

 

Publication Record

 

Al-Ghoul, M. 2000. Dynamics and dissipation of externally forced system. Physical Chemistry Chemical Physics 2:3773.

———. 2001. Generalized hydrodynamic theory of shock waves: Mach number dependence of inverse shock width for nitrogen gas. Physical Review Letters 86:4294.

Haddadin, M. J., M. J. Kurth, and M. M. Olmstead. 2000. One step synthesis of new heterocyclic azacyanines. Tetrahedron Letter 41:5613.

 

Haung, K. S., M. J. Haddadin, M. M. Olmstead, and M. J. Kurth. 2001. Synthesis and reactions of heterocyclic azacyanines (dedicated to Professor Costas H. Issidorides on the occasion of his Eightieth birthday). Journal of Organic Chemistry 66:1310.

Kortz, U. 2000. Polyoxometalate-diphosphate complexes. 5. The cigar-shaped 30-molybdob]ispyrophosphate: Structure of (N(C4H9)4)2H9[{(P2O7) Mo15O45}2 [PMo12O40]. Inorganic Chemistry 39:623.

———. 2000. Polyoxometalate-diphosphate complexes. 6. Possible intermediates in the molybdate-catalyzed hydrolysis of pyrophosphate. Structure of hexamolybdopyrophosphate, [(O3POPO3)Mo6O18(H2O)4]4-. Inorganic Chemistry 39:625.

 

Kortz, U., and M. H. Dickman*. 2000. Cadmium copper tetrachloride tetrahydrate. Acta Crystallographica C56:265.

 

Kortz, U., S. Isber, M. H. Dickman*, and D. Ravot*. 2000. Sandwich-type silicotungstates: Structure and magnetic properties of the dimeric polyoxoanions [{SiM2W9O34(H2O)}2]12- (M = Mn2+, Cu2+, Zn2+). Inorganic Chemistry 39:2915.

Kortz, U., Y. P. Jeannin*, A. Tιzι*, G. Hervι*, and S. Isber. 1999. A novel dimeric Ni-substituted beta-keggin silicotungstate: Structure and magnetic properties of K12 [{β-SiNi2W10O36(OH)2(H2O)}2]·20H2O. Inorganic Chemistry 38:3670.

Kortz, U., and S. Matta. 2001. Novel, triangular Mn-substituted undecatungstosilicate, [(SiW11MnO39)3]18-. Inorganic Chemistry 40:815.

 

Kortz, U., A. Tιzι*, and G. Hervι*. 1999. A Cubane-substituted Polyoxoanion: Structure and Magnetic Properties of Cs2[H2PW9Ni4O34(OH)3(H2O)6]· 5H2O. Inorganic Chemistry.

Nazer, M. Z., and M. J. Haddadin. 2000. Reactions of TCU with 0-Nitrobenzaldehye. Heterocycles 53 (10):2221.

Panjarian, S., and R. Sultan. 2001. Crystal selection and Liesegang banding in dynamic precipitate systems. Collection of the Czechoslovak Chemical Communications 66:514–541.

Sammelson, R. E., M. M. Olmstead, M. J. Haddadin, and M. J. Kurth. 2000. 1, 2, 4, 5-tetrazines as oxidant and reactant with DBU: An unexpected formation of novel fused tetraheterocyclic azepine. Journal of Organic Chemistry 65:9265.

Sultan, R. F., N. K. Al-Kassem, A. A. H. Sultan, and N. M. Salem. 2000. Periodic trends in precipitate patterning schemes involving two salts. Physical Chemistry Chemical Physics (PCCP) 2:3155–3162.

Sultan, R., and R. Halabieh. 2000. Effect of an electric field on propagating Co(OH)2 liesegang patterns. Chemical Physics Letters 332:331–338.

Sultan, R., and S. Jaafar. 1999. Static and swinging chemical waves in a two-interface dynamics on a ring. Physical Chemistry Chemical Physics (PCCP) 1:4931–4936.

 

 

 

Abstracts, Conferences, and Proceedings

 

Al-Ghoul, M. March 2000. Shock waves in monatomic gases: A continuum theory. The international conference on research trends in science and technology, Beirut, Lebanon.

———. June 2001. Generalized hydrodynamic theory of shock waves in nitrogen gas. Dynamics Days Europe 2001, Dresden, Germany.

Assaf-Diab, M., M. J. Haddadin, and H. Ghali-Mouhtaseb. April 2001. Quinoxaline 1,4-dioxides after epithelial cell proliferation via changes in transforming growth factors expression. 5th Middle East Oncology Congress, Beirut, Lebanon.

———. April 2001. Quinoxaline 1,4-dioxides a new class of hypoxia-selective drugs. 5th Middle East Oncology Congress, Beirut, Lebanon.

Kortz, U. October 1999. Novel structures in transition metal-substituted polyoxometalate chemistry. Polyoxometalates: From Topology to Industrial Applications, Bielefeld, Germany.

———. August 2000. Synthesis and characterization of novel transition metal-substituted silicotungstates. 220th American Chemical Society National Meeting, Washington, DC, USA.

Kurth, M. J., R. E. Sammelson, K. S. Haung, and M. J. Haddadin. April 2001. Solution and solid phase synthesis of unsymmetrical azacyanines. The 221st National Meeting of American Chemical Society, San Diego, California, USA.

Nazer, M. Z., S. Abu Eid, M. J. Haddadin, and M. T. Kurth. April 2001. Tandem cycloaddition, retrocycloaddition reaction:Formation of a diazadioxabicyclononene system. The 221st National Meeting of the American Chemical Society, April 1-5, 2001, San Diego, California, USA.

Sultan, R., and Sh. Panjarian. August 2000. Crystal selection and liesegang banding in dynamic precipitate systems. Gordon Research Conference/Oscillations and Dynamic Instabilities in Chemical Systems, Bristol, Rhode Island, USA.

———. August 2000. Propagating fronts in 2D Cr(OH)3 precipitate systems in gelled media. Gordon Research Conference/Oscillations and Dynamic Instabilities in Chemical Systems, Bristol, Rhode Island, USA.

 

 

Miscellaneous

 

Kortz, U. September 2000. Novel structures in polyoxometalate chemistry. Georgetown University, Department of Chemistry, Washington, DC, USA.

 

 

Graduate Theses and Projects

 

Abou Ghali, F. June 2001. Synthesis of novel, transition metal-substituted polyoxotungstates, [M4(H2O)10(ί-XW9O33)2]n- ( X = AsIII, SbIII, SeIV, TeIV; M = Mn2+, Co2+, Ni2+, Zn2+, Cd2+, Hg2+, Cr3+, V5+). U. Kortz.

Khalil, L. June 2001. Synthesis of dimeric, transition metal-substituted arsenotungstates, [M4(H2O)2(B-alpha-AsW9O34)2]10- (M = Mn2+, Co2+, Ni2+, Cu2+). U. Kortz.

 

 

Research Projects

 

Dissipation and efficiency in a biochemical oscillator

We study the dissipation and the efficiency of a biochemical oscillator driven by periodic signals and by noise. Such systems are described by stochastic differential equations which, in this work, are solved numerically or semi-analytically. Entropy production is used as a criterion for dissipation. Al-Ghoul, M.

Supported by AUB

 

Shock waves in diatomic gases

We developed a continuum hydrodynamic theory of shock waves which yields shock structures (shock widths) for supersonic waves in a diatomic gas. The theory is based on the Boltzmann-Curtiss kinetic equation, which is solved using the modified moment method. The results are in excellent agreement with experiments. Al-Ghoul, M. (PL), and Byung Chan (EU).

Supported by URB and National Science and Engineering Research Council of Canada

Completed or in progress at AUB

 


Mathematical and numerical modeling of a precipitate system

We modeled a complex precipitate system that exhibits Liesegang patterns using a set of reaction-diffusion equations. The model is then solved numerically, and the results are compared with experiments. An excellent agreement was found. Al-Ghoul, M. (PL), and R. Sultan.

Supported by URB
Completed or in progress at AUB

 

Synthesis of biodegradable macromolecular drug delivery vehicles

 

The goal of our research is to develop new approaches to increase the circulation of anticancer agents in the body while minimizing their side effects.  A number of these agents, when complexed or attached to a biodegradable macromolecular moiety, can be delivered systemically.  These complexes have relatively high molecular weights and are not easily excreted by the kidney.  The initial high molecular weight of the polymer can be exploited to facilitate site-specific accumulation of anticancer agents in solid tumors via the enhanced permeability and retention (EPR) effect.  The enhanced permeability of the microvascular within solid tumors allows the passage of high molecular weight conjugates that are restricted to normal tissue.  Drugs are then released slowly from the macromolecular drug carrier at the desired site.  This approach could potentially be used to deliver multiple agents and could be useful in preventing the development of multi-drug resistance (MDR). Bouhadir, K.

Supported by URB
Completed or in progress at AUB

 

Quinoxalin 1,4- dioxides as hypoxia selective therapeutic agents

 

Number of quinoxaline 1,4-dioxides have been found to be effective hypoxia selective agents with 2- benzyl-3-phenyl-6, 7-dichloro quinoxaline 1,4-dioxide being the most effective. One paper is in the press, another was submitted recently; and a third is in the last phase of being written up. Ghali-Mouhtaseb, H. U., M. J. Haddadin, and M. Diab-Assaf.

Supported by AUB
Completed or in progress at AUB

 

Synthesis of water-soluble quinoxaline 1,4-dioxides

 

For the purpose of a more efficient drug delivery, the synthesis of water-soluble quinoxaline 1,4-dioxides is in its initial stage. It is planned to have this work as the M.S. thesis of Mr. Roland Bou Chedid. Haddadin, M. J.

Supported by AUB and potentially University of California, Davis
Completed or in progress at AUB and possibly University of California, Davis

 

Volta metric measurements of some Azacyanines

 

The redox potetials of a number of Azacyanines will be determined for the first time. Some preliminary results are at hand and more are planned for. Haddadin, M. J. and L. Halaoui.

Supported by AUB
Completed or in progress at AUB

 

Synthesis and reactions of azacyanines

 

A continuation of this project in collaboration with Professor Mark J. Kurth of the University of California at Davis is being pursued. New azacyanines have been prepared, and their reactions are being studied. Two papers have been published (see Publication Record below) and more are in preparation. Haddadin, M. J., and M. J. Kurth.

Supported by AUB and University of California, Davis
Completed or in progress at AUB and University of California, Davis


Reactions of 0-nitrobenzaldehyde with TCU: Formation of heterocyclic clefts

 

As a continuation of our previous work on the synthesis of heterocyclic clefts, we investigated the reactions of 0-nitrobenzaldehyde with TCU and isolated and identified, with X-Ray structural confirmation, eight new derivatives. One paper was published and the second is ready for submission for publication. Other products will be pursued further. Haddadin, M. J., and M. Z. Nazer.

Supported by AUB and University of Jordan
Completed or in progress at AUB and University of Jordan

 

Interaction of ethylenediphosphonate with tungstate, molybdate and vanadate

The anionic, ditetrahedral heterogroup, ethylenediphosphonate, (O3PCH2CH2PO3)4-, was reacted in an aqueous medium with tungstate, WO42-, molybdate, MoO42-, and vanadate, VO43-, respectively, at a variety of ratios and at different pH. The reactions were monitored by 31P-NMR (at Georgetown University), and it was apparent that compounds were formed, but until now, it has not been possible to isolate and crystallize a pure product. This work is still in progress. Kortz, U. (PL).

Supported by URB
Completed or in progress at AUB

 

Interaction of phosphonocarboxylates with tungstate, molybdate and vanadate

The interaction of three phosphonocarboxylates, (O3P(CH2)nCOOH)2- (n = 0, 1, 2), with tungstate, WO42-, and molybdate, MoO42-, were studied by 31P-NMR. As expected, there is an indication that novel polyoxometalates are formed. Currently, attempts are being made to crystallize these compounds so that structural characterization by single-crystal X-ray diffraction becomes possible.  Kortz, U. (PL).

Supported by URB
Completed or in progress at AUB

 

Interaction of the dilacunary gamma-decatungstophosphate, [gamma-PW10O36]7-, with first-row transition metals

We were able to synthesize and also crystallize products by reacting [-PW10O36]7- with a variety of transition metal ions, e.g., Fe3+, Co2+, Ni2+, and Zn2+. Last summer, while at Georgetown University working on a Long-Term Faculty Development Grant, I used single-crystal X-ray crystallography to collect data sets on different crystalline samples. Unfortunately, it turned out that the respective transition metals were incorporated in the well-known Keggin ion, most likely corresponding to the formula [PW10M2O40]11- or [PW11MO40]7- (M = Co2+, Zn2+, Ni2+). Elemental analysis for the cobalt derivative indicates that the latter formula is correct. However, it is still possible that a mixture of rotational isomers (e.g., [-PW11CoO40]7- vs. [-PW11CoO40]7-) is present. Crystals of the Co2+ containing product are of sufficient size for single-crystal electron paramagnetic resonance (EPR). This technique could perhaps allow us to determine if indeed two or more different isomers are present. Kortz, U. (PL).

Supported by URB
Completed or in progress at AUB

 

Introduction of second and third-row transition metals in lacunary heteropolyanions

We were able to synthesize a very interesting ruthenium-substituted polyoxotungstate. A detailed study of its catalytic properties (redox, electrocatalysis) is currently under way.
Furthermore, we have obtained nice results by working with first-row transition metals. It has been possible to synthesize and crystallize a large number of products by interaction of first-row transition metals with a variety of lacunary polyoxometalates. Structural characterization of the solid was done by single-crystal X-ray crystallography. The solution properties of some species were studied by 183W-NMR spectroscopy. Kortz, U. (PL).

Supported by URB
Completed or in progress at AUB

 

Synthesis of transition metal substituted molybdopyrophosphate heteropolyanions

It was attempted to introduce first-row transition metals (e.g. Ni) in-between the two half-units of the 30-molybdobispyrophosphate during the synthesis of the polyanion (in situ), but so far without success. On the other hand, it might be possible to synthesize a lacunary version of the 30-molybdobispyrophosphate. e.g., by loss of a Mo3O6 cap through controlled action of strong base. This will be further investigated this coming summer at Georgetown University by using 31P-NMR. Kortz, U. (PL).

Supported by URB
Completed or in progress at AUB

 

The interaction of dinuclear and trinuclear heterogroups with tungstate, molybdate, and vanadate

During the summers of 1998 and 1999, I worked in the laboratory of Prof. M. T. Pope at Georgetown University, and I reacted the two tritetrahedral heterogroups, namely, tripolyphosphate, (O3POPO3PO3)4-, and nitrilotrismethylenephosphonate, {N(CH2PO3)3}6-, with tungstate, WO42-, molybdate, MoO42-, and vanadate, VO43-, respectively, at a variety of ratios and at different pH. The reactions were monitored by 31P-NMR, and it was apparent that a variety of products formed, but until now, it has not been possible to isolate and crystallize a pure product. This work is still in progress.


However, I was able to obtain nice results for the interaction of diphosphate, (O3POPO3)4-, and molybdate. I synthesized the hexamolybdopyrophosphate, [(O3POPO3)Mo6O18(H2O)4]4-, and I was able to determine its structure in the solid state by single-crystal X-ray crystallography. This compound is the first example of a structurally characterized molybdopyrophosphate, synthesized in an aqueous solution.  Kortz, U. (PL).

Supported by URB
Completed or in progress at AUB

 

Cycloaddition reactions of symmetrical tetrazines; formation of a new heterocyclic system

 

The reaction of 3,5-diphenyl tetrazine with aldahydes with only one proton on the carbon alpha to the carbonyl group gave a host of products, the most interesting of which is the isolation and the X-Ray confirmation of the a new heterocyclic system: Diazadioxabicyclonoene. These results were orally presented at the 221st National Meeting of the American Chemical Society in San Diego, April 1-5, 2001. More work is in progress in collaboration with Professor Musa Z. Nazer of the University of Jordan and Professor Mark J. Kurth of the University of California at Davis. Nazer, M. Z., M. J. Haddadin, and M. J. Kurth.

Supported by AUB, University of Jordan, and University of California, Davis
Completed or in progress at AUB, University of Jordan, and University of California, Davis

 

Front propagation in patterned precipitation I: Simulation of a migrating Co(OH)2 Liesegang pattern

The propagation of a stratum of Co(OH)2 Liesegang bands is simulated using the
model of Muller and Polezhaev. The experimentally-observed results were
reproduced. Paper in press (The Journal of  Physical Chemistry). Sultan, R., and M. Al-Ghoul.

 

Supported by URB
Completed or in progress at AUB

 

Liesegang banding and the particle size distribution

A Liesegang pattern is a stratification of parallel bands that appear when two co-precipitate ions inter-diffuse in a gel. In some cases, the bands are themselves composed of tiny particles of different sizes. We study the particle size distribution in a cobalt oxinate precipitate system. The sizes of the particles are measured in every band, and the average particle size and the number of particles within a given band are determined. The measurement and count are repeated by image analysis of an enlarged picture of each separate band. Then, the average particle size and the number of bands are plotted versus band number. As the band number increases, the system is shown to evolve toward a state of fewer and larger particles, thus directly verifying the Ostwald ripening phenomenon. We look for other possible trends by exploring the various conditions under which the pattern is prepared. Sultan, R. (PL), and M. Al-Ghoul.

Supported by URB

Completed or in progress at AUB

 

Fractal structures in lead fluoride precipitate systems

Tree-like aggregates (dendrites) have been reported in a variety of precipitate systems. We here explored different routes for the growth of dendrites of PbF2 in Liesegang-type and some other experiments. The latter include interdiffusion of co-precipitates in microslides, evaporation, and infiltration of electrolyte through cracks, thus simulating geochemical fractals. Images of the various patterns obtained are analyzed, and their fractal dimensions are determined. A comparison between the properties of the patterns obtained through the different routes is finally made. Sultan, R. (PL), and L. Mandalian (RA).

Supported by URB
Completed or in progress at AUB

 

Propagating fronts in 2D Cr(OH)3  precipitate systems in gelled media

The propagation of a circular Cr(OH)3 precipitate ring in 2D is studied, and the velocities are measured at different concentrations. The effect of an electric field on the propagation is investigated. Interesting deformations in the ring are obtained when the field is applied in a non-uniform manner. Paper in press (Physica D). Sultan, R. (PL), and Sh. Panjarian (RA).

Supported by URB
Completed or in progress at AUB

 

Effect of competitive complex formation on patterning and front propagation in periodic precipitation

The Co(OH)2 Liesegang pattern (from Co2+ and NH4OH) propagates in space via periodic band formation ahead due to precipitation and band disappearance at the tail due to dissolution in excess NH4OH. Ni2+ (which competes with Co2+ for complex formation with ammonia) was introduced into the system, resulting in many interesting observations: slowing down of the propagation, decrease in the number of bands, and increase in the spacing between them. At high concentrations of Ni2+, only a uniform precipitate zone was observed. The difference in the distance of last band in the system with nickel relative to that without nickel attained at a fixed time (89 hours) was found to oscillate as the initial concentration of NH4OH is varied. It was shown that the concentration of intermediate NH4+ is a precursor for those oscillations. Project completed and paper being written. Sultan, R. (PL), and Z. Shreif (undergraduate student).

Supported by URB
Completed or in progress at AUB