Elucidating the binding mechanism of thione-containing mercaptopurine and thioguanine drugs to small gold clusters

Density functional theory methods were employed to clarify the adsorption/desorption behaviors of the thione-containing mercaptopurine and thioguanine drugs on the gold surface using both small Au₆ and Au₈ clusters as model reactants. Structural features, thermodynamic parameters, bonding characteristics, and electronic properties of the resulting complexes were investigated using the Perdew–Burke–Ernzerhof (PBE) and LC-BLYP functionals along with correlation-consistent basis sets, namely cc-pVDZ-PP for gold and cc-pVTZ for non-metals. Computed results show that the drug molecules tend to anchor on the gold cluster at the S atom with binding energies around −34 to −40 kcal/mol (in vacuum) and − 28 to −32 kcal/mol (in aqueous solution). As compared to Au₈, Au₆ undergoes a shorter recovery time and a larger change of energy gap that could be converted to an electrical signal for selective detection of the drugs. Furthermore, interactions between the drugs and gold clusters are reversible processes and a drug release mechanism was also proposed. Accordingly, the drugs are able to separate from the gold surface due to either a slight change of pH in tumor cells or the presence of cysteine residues in protein matrices.     

Formation of phosphaethyne dimers: a mechanistic study

High-level ab initio (CCSD(T), CBS-QB3 and CASSCF, CASPT2, MR-ACPF, MR-ACPF-2) and density functional theory (B3LYP) calculations were carried out to study the dimerization of phosphaacetylene or phosphaethyne (HCP). Seventeen low energy closed-shell and five open-shell phosphaacetylene dimers were found on the potential energy surface. Two head-to-head, one head-to-tail and three other dimerization reaction pathways were determined, all with high activation barriers, suggesting that closed-shell minima are usually kinetically stable. An open-shell head-to-head reaction pathway has also been found with moderate initial barrier (95.0 kJ mol(-1)) leading to 1,2- and 1,3-diphosphacyclobutadiene, suggesting that polymerization of HCP and oligomerization of its derivatives have open-shell mechanism. Formation of 1,2-diphosphacyclobutadiene is both thermodynamically and kinetically favored over 1,3-diphosphacyclobutadiene. A head-to-head reaction involving LiBr as a catalyst was also studied. It has been pointed out that LiBr catalyze the closed-shell mechanism. All the four possible reaction channels of this reaction yield 1,4-diphosphatriafulvene with a fairly low activation Gibbs-free energy (44.8 kJ mol(-1)), suggesting that this compound could be synthesized. This finding fully supports the experimental results.     

Methyl and phenyl substitution effects on the proton affinities of hydrides of first and second row elements and substituent effects on the proton affinities of ring carbons in benzene: a DFT study

Theoretical calculations using B3LYP density functional theory (DFT) with the 6-311++G(d,p) basis set have been performed to determine proton affinities (PAs) of a series of H-X compounds and the corresponding methyl- (H(3)C-X) and phenyl- (Ph-X) substituted derivatives with a variety of proton acceptor atoms, such as C, O, N, F, Si, P, S, Cl, etc. Our results illustrate an interesting substituent effect on PAs. The PAs of ring carbon atoms for a series of monosubstituted benzene molecules (Y-C(6)H(5); Y = F, Cl, CH(3), OCH(3), NH(2), PH(2), OH, SH, SiH(3), CN, CF(3), and NO(2)) have also been estimated. Correlations between proton affinities of H-X, H(3)C-X, and Ph-X and substituent effects on the PAs of the ring carbon atoms for a series of monosubstituted benzene molecules have been studied. It has been observed that substituent effects on the PAs of the ring carbon atoms follow a good Hammett-type correlation.     

Electronic structure and properties of some oligomers based on fluorinated 1H-phospholes: n- versus p-type materials

A series of oligothiophenes and novel oligophospholes, consisting of fluorinated and perfluoroarene-substituted structures, were investigated using density functional theory (DFT) methods. The study focused on the geometrical structures and electronic properties. The degree of π-conjugation in the neutral oligomers was probed by different approaches including analysis of predicted Raman spectra. The character of the charge carrier of the new substituted oligomers, either electron (n-type doping) or hole (p-type doping) transport, was predicted by comparing their properties, including the frontier orbital HOMO and LUMO, excitation, and reorganization energies, with those of their non-substituted parent oligomers. The quantum chemical DFT results are consistent with available experimental data on the oligothiophenes for both geometries and conductivity properties. The results strongly suggest that an effective way of designing new materials with n-type conductivity is to introduce electron-withdrawing groups into the oligomer backbone. Calculated results were subsequently obtained for oligomers based on 1H-phospholes, which are predicted to have potentially useful properties as novel semiconductor materials.     

Synthesis and X-ray structure of N-phenyl phenylglyoxamide

The title compound (C₁₄H₁₁NO₂) is monoclinic with a = 13.579(2), b = 5.297(1), c = 16.455(2) Å, = 98.11(2)°, Z = 4, and space group P2₁/n. The significant structural features lie in the two carbonyl groups of the glyoxamide which are oriented antiperiplanar to each other [–163.6(3)°]. The central bond C(1)–C(2) is 1.545(4) Å. The observed conformation is stabilized by intramolecular hydrogen bonds.     

Quantum chemical study of hydrogen abstraction reactions of the ethynyl radical with hydrogen compounds (C2H+HX)

We have theoretically investigated the hydrogen abstraction reactions of ethynyl radical with simple hydrogen compounds, C₂H+HX, using quantum chemical computations. Computations have been performed using the density functional theory with the recently proposed MPW1K functional and the 6-311++G(3df,2p) basis set. An analysis of the resulting energy barriers for hydrogen abstraction reactions has been carried out using the bond dissociation energy of the breaking X–H bond and DFT-based reactivity parameters to rationalize the reaction behavior.     

Mechanism of the oxidation reaction of Cu with N2O via nonadiabatic electron transfer

We treat the present work as an attempt to elucidate the mechanism of the oxidation reaction of the Cu atom by nitrous oxide based on our recent work (Kryachko, E. S.; Vinckier, C.; Nguyen, M. T. J Chem Phys 2001, 114, 7911) on the electron attachment to this molecule. We suggest that the title reaction in its Arrhenius regime occurs via the nonadiabatic electron transfer from Cu to the oxygen atom at the crossing of the potential energy surfaces Cu(4s ²S_1/2) + N₂O(X ¹Σ⁺) and Cu⁺ + N₂O^?, where the latter is linked to the complex N₂O^? originated from the higher‐energy T‐shape N₂O molecule and discovered in the aforementioned work. The calculations performed in the present work using a variety of quantum chemical methods support the proposed model. We also show the existence of other reaction pathways of the title reaction that, we believe, contribute to its non‐Arrhenius behavior observed experimentally at T > 1190 K. © 2002 Wiley Periodicals, Inc. Int J Quantum Chem, 2002     

Polychloroprene. II. Etude comparée de la microstrusture par RMN 1H et 13C. Thermodynamique de propagation des différentes unités structurales

A microstructure analysis of polychloroprenes by ¹H and ¹³C NMR produced slightly different results which, however, are in good agreement. The main uncertainty concerned the assignment of the 1,4-cis and trans head-to-head and tail-to-tail additions. In the (+ 12, +70°C) region of polymerization temperatures the principal addition mode was 1,4. An increase in the polymerization temperature to 70°C increased the abnormal head-to-head, tail-to-tail additions, and 1,4-cis additions (6–7%), and all vinyl structures that were not higher than 2–3% were equally distributed between 1,2 and 3,4. Under the experimental conditions used in this study no isomerized vinyl structures were found. As in all radical polymerizations the influence of temperature on the propagation mechanisms, namely, the addition modes, was relatively weak, but because of the great number of possible addition modes in microstructure—physicomechanical relationships variations in the microstructure must be taken into account. Only ¹H and ¹³C NMR are capable of determining these variations quantitatively.     

Potential energy surfaces, product distributions and thermal rate coefficients of the reaction of O(3P) with C2H4(X1Ag): a comprehensive theoretical study

The potential energy surface for the O((3)P) + C(2)H(4) reaction, which plays an important role in C(2)H(4)/O(2) flames and in hydrocarbon combustion in general, was theoretically reinvestigated using various quantum chemical methods, including G3, CBS-QB3, G2M(CC,MP2), and MRCI. The energy surfaces of both the lowest-lying triplet and singlet electronic states were constructed. The primary product distribution for the multiwell multichannel reaction was then determined by RRKM statistical rate theory and weak-collision master equation analysis using the exact stochastic simulation method. Intersystem crossing of the "hot" CH(2)CH(2)O triplet adduct to the singlet surface, shown to account for about half of the products, was estimated to proceed at a rate of approximately 1.5 x 10(11) s(-1). In addition, the thermal rate coefficients k(O + C(2)H(4)) in the T = 200-2000 K range were computed using multistate transition state theory and fitted by a modified Arrhenius expression as k(T) = 1.69 x 10(-16) x T(1.66) x exp(-331 K/T) . Our computed rates and product distributions agree well with the available experimental results. Product yields are found to show a monotonic dependence on temperature. The major products (with predicted yields at T = 300 K/2000 K) are: CH(3) + CHO (48/37%), H + CH(2)CHO (40/19%), and CH(2)(X(3)B(1)) + H(2)CO (5/29%), whereas H + CH(3)CO, H(2) + H(2)CCO, and CH(4) + CO are all minor (< or =5%).     

Gas chromatography—mass spectrometry analysis of termite defence secretions in the subfamilyNasutitermitinae

Summary Mono- and diterpenoid components of severalNasutitermitinae soldier secretions have been characterised by gas chromatographymass spectrometry. Patterns in monoterpene distribution are useful, but not sufficient for chemotaxonomic purposes without determination of the diterpene distribution. Diterpenoids are structurally complex and can have tetracyclic, tricyclic and bicyclic skeletal structures with various degrees of oxygenation. The relative retention indices for several identified diterpenoid compounds have been determined on OV-1 and OV-17 columns. The amount and distribution of the terpenoid components are useful aids to chemotaxonomy forNasutitermitinae termites.

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Gaschromatographisch-massenspektrometrische Analyse der Verteidigungs-Sekrete der Termiten-Subfamilie Nasutitermitinae

Zusammenfassung Mono- und Diterpenderivate in den Sekreten verschiedenerNasutitermitinae-Soldaten wurden mit Hilfe der Gaschromatographie-Massenspektro-metrie charakterisiert. Verteilungsmuster der Monoterpene sind nützlich, aber für chemotaxonomische Zwecke ohne Bestimmung der Diterpen-Verteilung nicht ausreichend. Diterpenabkömmlinge sind in struktureller Hinsicht komplex und haben tetracyklische, tricyklische und bicyklische Strukturen mit wechselndem Sauerstoffgehalt. Die relativen Retentionsindices für einzelne identifizierte Diterpenabkömmlinge wurden auf OV-1- und OV-17-Säulen bestimmt. Menge und Verteilung der Terpenabkömmlinge sind nützliche Hilfsmittel für die Chemotaxonomie der genannten Termiten.

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Presented at the 8th International Microchemical Symposium, Graz, August 25–30, 1980.