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PubMed2002

OCBBCO: a neutral molecule with some boron-boron triple bond character.

Molecules that contain boron-boron multiple bonds are extremely rare due to the electron-deficient nature of boron. Here we report experimental and theoretical evidence of a neutral OCBBCO molecule with some boron-boron triple bond character. The molecule was produced and unambiguously characterized by matrix isolation infrared spectroscopy. Quantum chemical calculations indicate that the molecule has a linear singlet ground state with a very short boron-boron bond length.

Journal Article↗
PubMed2004

Inhibitors of ADP-ribosylating bacterial toxins based on oxacarbenium ion character at their transition states.

The bacterial exotoxins, cholera toxin (CT), pertussis toxin (PT), and diphtheria toxin (DT), interfere with specific host proteins to cause tissue damage for their respective infections. The common toxic mechanism for these agents is mono-ADP-ribosylation of specific amino acids in G(s)(alpha), G(i)(alpha), and eEF-2 proteins, respectively, by the catalytic A chains of the toxins (CTA, PTA, and DTA). In the absence of acceptor proteins, these toxins also act as NAD(+)-N-ribosyl hydrolases. The transition-state structures for NAD(+) hydrolysis and ADP-ribosylation reactions have oxacarbenium ion character in the ribose. We designed and synthesized analogues of NAD(+) to resemble their oxacarbenium ion transition states. Inhibitors with oxacarbenium mimics replacing the NMN-ribosyl group of NAD(+) show 200-620-fold increased affinity in the hydrolytic and N-ribosyl transferase reactions catalyzed by CTA. These analogues are also inhibitors for the hydrolysis of NAD(+) by PTA with K(i) values of 24-40 microM, but bind with similar affinity to the NAD(+) substrates. Inhibition of the NAD(+) hydrolysis and ADP-ribosyl transferase reactions of DTA gave K(i) values from 19 to 48 microM. Catalytic rate enhancements by the bacterial exotoxins are small, and thus transition-state analogues cannot capture large energies of activation. In the cases of DTA and PTA, analogues known to resemble the transition states bind with approximately the same affinity as substrates. Transition-state analogue interrogation of the bacterial toxins indicates that CTA gains catalytic efficiency from modest transition-state stabilization, but DTA and PTA catalyze ADP-ribosyl transferase reactions more from ground-state destabilization. pH dependence of inhibitor action indicated that both neutral and cationic forms of transition-state analogues bind to DTA with similar affinity. The origin of this similarity is proposed to reside in the cationic nature of NAD(+) both as substrate and at the transition state.

Adenosine Diphosphate↗
PubMed2004

14-electron disilene palladium complex having strong pi-complex character.

The first 14-electron disilene palladium complex eta2-[tetrakis(tert-butyldimethylsilyl)disilene](tricyclohexylphosphine)palladium (4) was synthesized. In the solid state, complex 4 has one tricyclohexylphosphine ligand bound unsymmetrically to the palladium center in regard to the eta2-disilene moiety. The elongation of the Si-Si bond length from that of the corresponding free disilene (3.2%) and the bent back angles of the disilene moiety (4.41 degrees and 9.65 degrees ) for 4 were much smaller than those for the corresponding 16-electron eta2-disilene complex (Me3P)2Pd[tetrakis(tert-butyldimethylsilyl)disilene] (4.6% and 27.2 degrees , respectively). Complex 4 is regarded as the complex having the strongest pi-complex character among the known disilene complexes. Highly symmetric NMR spectra were observed for 4; central Si1 and Si2 nuclei were equivalent and appeared as a doublet with 2J(29Si-31P) of 19 Hz, indicating facile flipping of the phosphine ligand in the Pd-Si-Si plane.

Journal Article↗
PubMed2004

Nucleophilic character of a charge neutral, high oxidation state d0 zirconium trimethylenemethane complex.

The nucleophilic character of a charge neutral, high oxidation d0 zirconium trimethylenemethane (TMM) class of compound of general structure Cp*Zr(TMM)[N(R1)C(Me)N(R2)], 1a (R1 = R2 = i-Pr) and 1b (R1 = t-Bu, R2 = Et), is presented through documentation of its reactivity with a range of alkyl and silyl halides and triflates, including unactivated ones such as ethyl triflate. These results should contribute to efforts directed toward expanding the synthetic chemist's toolbox of synthetic methods for the construction of complex organic molecules.

Journal Article↗
PubMed2004

Definitive evidence for the contribution of biradical character in a closed-shell molecule, derivative of 1,4-bis-(4,5-diphenylimidazol-2-ylidene)cyclohexa-2,5-diene.

This study provides conclusive proof that the thermally excited open-shell state with biradical character is contributing to the ground state of a closed-shell molecule, tF-BDPI-2Y, where four hydrogen atoms at the central phenylene ring are substituted with four fluorine atoms of 1,4-bis-(4,5-diphenylimidazol-2-ylidene)cyclohexa-2,5-diene (BDPI-2Y). A small increase in the population of biradical species of tF-BDPI-2Y results in the formation of the dimer form by the radical recombination reaction. Controlling the equilibrium between a closed-shell diamagnetic-quinoid state and an open-shell paramagnetic-biradical state will provide significant progress in the field of pi-conjugated delocalized biradical chemistry.

Journal Article↗
PubMed2005

Reactions of the heavier group 14 element alkyne analogues Ar'EEAr' (Ar' = C6H3-2,6(C6H3-2,6-Pri2)2; E = Ge, Sn) with unsaturated molecules: probing the character of the EE multiple bonds.

Reactions of the alkyne analogues Ar'EEAr' (Ar' = C6H3-2,6(C6H3-2,6-Pr(i)2)2; E = Ge (1); Sn (2)) with unsaturated molecules are described. Reaction of 1 and 2 with azobenzene afforded the new hydrazine derivatives Ar'E{(Ph)NN(Ph)}EAr' (E = Ge (3); Sn (4)). Treatment of 1 with Me3SiN3 gave the cyclic singlet diradicaloid Ar'Ge{mu2-(NSiMe3)}2GeAr' (5), whereas 2 afforded the monoimide bridged Ar'Sn{mu2-N(SiMe3)}SnAr' (6). Reaction of 1 with t-BuNC or PhCN yielded the adduct Ar'GeGe(CNBu(t))Ar' (7) or the ring compound (8). In contrast, the tin compound 2 did not react with either t-BuNC or PhCN. Treatment of 1 with N2CH(SiMe3) generated Ar'Ge{mu2-CH(SiMe3)}{mu2:eta2-N2CH(SiMe3)}{mu2-N2CH(SiMe3)}GeAr' (9) which contains ligands in three different bridging modes and no Ge-Ge bonding. Reaction of 1 with an excess of N(2)O gave a germanium peroxo species Ar'(HO)Ge(mu2-O)(mu2:eta2-O2)Ge(OH)Ar' (10) which features a ring. Oxidation of 1 by tetracyanoethylene (TCNE) led to cleavage of the Ge-Ge bond and formation of a large multiring system of formula Ar'Ge3+{(TCNE)2-}3{(GeAr')+}3. The digermyne 1 also reacted with 1 equiv of PhCPh to give the 1,2-digermacyclobutadiene 12, which has a ring, and with Me(3)SiCCH or PhCC-CCPh to activate a flanking C6H3-2,6-Pr(i)2 ring and give the tricyclic products 13 and 14. The "distannyne" 2 did not react with these acetylenes. Overall, the experiments showed that 1 is highly reactive toward unsaturated molecules, whereas the corresponding tin congener 2 is much less reactive. A possible explanation of the reactivity differences in terms of the extent of the singlet diradical character of the Ge-Ge and Sn-Sn bonds is discussed.

Journal Article↗
PubMed2006

Ab initio quantum chemistry calculations on the electronic structure of heavier alkyne congeners: diradical character and reactivity.

The electronic structure of the heavier congeners of alkynes has been studied with emphasis on characterizing their extent of diradical character. Four orbitals play a crucial role in determining the electronic structure in planar trans-bent geometries. Two are associated with an out-of-plane pi interaction, pi and pi, and two are associated with in-plane interactions and/or in-plane lone pairs, LP(n-) and LP(n+). The ordering of these orbitals can change depending upon geometry. One extreme, corresponding to the local minimum for Si-Si and Ge-Ge, is a diradicaloid multiple-bonding configuration where LP and pi are nominally occupied. Another extreme, corresponding to a local minimum for Sn-Sn, is a relatively closed-shell single-bond configuration where LP and LP are nominally occupied. This ordering leads to predicted bond shortening upon excitation from singlet to triplet state. For the heavier elements, there appears to be very little energy penalty for large geometric distortions that convert from one ordering to the other on the singlet surface. The implications of these results with respect to experimental observations are discussed.

Journal Article↗
PubMed2006

Semiconductor surface-induced 1,3-hydrogen shift: the role of covalent vs zwitterionic character.

X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) are used to compare the reaction of 1,2-cyclohexanedione (1,2-CHD) with Si(001) and diamond(001) surface dimers under ultra-high-vacuum conditions. 1,2-CHD is known to undergo a keto-enol tautomerization, with the monoenol being the primary equilibrium species in the solid and gas phases. XPS and FTIR data demonstrate that 1,2-CHD reacts with diamond(001) through the OH group of the monoenol, resulting in only one O atom being bonded to the surface. In contrast, XPS and FTIR data suggest that both oxygen atoms in the 1,2-CHD molecule bond via Si-O-C linkages to the Si(001) surface dimer, and that the molecule undergoes an intramolecular 1,3-H shift. While the Si(001) and diamond(001) surfaces are both comprised of surface dimers, the diamond(001) dimer is symmetric, with little charge separation, whereas the Si(001) dimer is tilted and exhibits zwitterionic character. The different reaction products that are observed when clean Si(001) and diamond(001) surfaces are exposed to 1,2-CHD demonstrate the importance of charge separation in promoting a 1,3-H shift and provide new mechanistic insights that may be applicable to a variety of organic reactions.

Journal Article↗
PubMed2006

Synthesis and biradicaloid character of doubly linked corrole dimers.

Directly linked corrole dimer 1, which has a planar cyclooctatetraene in its core, has been synthesized from 2-borylcorrole in excellent yield. 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) oxidation of 1 provides its oxidized form 4, which has two NH protons in each corrole core. Dicorrole 4 and its Zn(II) complex 6 exhibit broad electronic absorption spectra, and magnetic measurement has revealed their biradicaloid character.

Journal Article↗
PubMed2006

Sweetener/sweetness-induced changes in flavor perception and flavor release of fruity and green character in beverages.

Green leaf volatile (GLV) mixtures, commercial orange flavors, and commercial strawberry flavors were applied to beverage bases in which concentrations of citric acid as well as a sweetener (sucrose or aspartame/acesulfame-K) were varied. Sensory profiling showed that flavor-specific fruity character increased as perceptible sweetness increased, independent of whether the sweetness resulted from sucrose (a change from 9 to 12 Brix) or aspartame/acesulfame-K (a change from 0.2 to 0.4 Brix). Sweetness was affected only by the tastants in the base and not by the flavors, although flavor-specific interactions between sweetener type and sweetener level occurred. Flavor release from the sucrose bases was compared to flavor release from bases containing aspartame/acesulfame-K by static headspace measurements and by MS-Nose measurements using an artificial throat. These measurements showed greater flavor volatility from bases having low Brix (fewer soluble solids). This negative Brix effect was also evident in the sensory data for perception of some GLV green notes. The headspace data could not support a positive Brix effect, the typical salting out, which would correspond to the observed perceptual enhancement of fruity notes.

Aspartame↗
PubMed2001

1-[2-methoxy-5-(3-phenylpropyl)]-2-aminopropane unexpectedly shows 5-HT(2A) serotonin receptor affinity and antagonist character.

Certain phenylethylamines, such as 1-(4-bromo-2,5-dimethoxyphenyl)-2-aminopropane (DOB; 1a), are high-affinity 5-HT(2) agonists. Previous structure-affinity studies have concluded that both the 2,5-dimethoxy substitution pattern and the nature of substituents at the 4-position are important determinants of high affinity. We recently demonstrated that replacement of the bromo group of DOB with a 3-(phenyl)propyl substituent results in retention of affinity and that, counter to established structure-affinity relationships, the 2,5-dimethoxy substitution pattern is no longer a requirement for the binding. The present investigation extends these findings by examining a series of analogues, 3, lacking a 5-methoxy group. It was additionally found that shifting the phenylalkyl substituent from the 4- to the 5-position (e.g., 4i) also results in retention of affinity. For example, 1-(2-methoxy-5-(3-phenylpropyl)-2-aminopropane (6; the alpha-methyl derivative of 4i) binds at 5-HT(2A) receptors with high affinity (K(i) = 13 nM) and possesses 5-HT(2A) antagonist character. Thus, not only is the 2,5-dimethoxy substitution pattern not a requirement for the binding of certain phenylethylamines at 5-HT(2A) receptors, the presence of a 4-position substituent (previously thought to serve as a modulator of affinity of DOB-like agents) is also not required. Striking differences in the 5-HT(2A) binding requirements of the present compounds as compared to DOB-like agents suggest multiple substituent-dependent modes of binding.

3T3 Cells↗
PubMed2001

Thianthrene 5-oxide as a probe for the electronic character of oxygen-transfer reactions: re-interpretation of experiments required.

The electronic character of oxidants, i.e., whether they attack substrates in an electrophilic or nucleophilic way, has extensively been investigated using thianthrene 5-oxide (SSO) as probe. The SSO molecule has a sulfide group, which is attacked by electrophilic oxidants, and a sulfoxide moiety, which is oxidized by nucleophilic oxidants. This density-functional study has been carried out in order to gain insight into the origin of the chemo- and stereoselectivity of SSO oxidation. It has been found that the endo and exo stereoisomers of the thianthrene oxides interconvert via ring-inversion with moderate energy barriers. Thus, the stereoselectivity of SSO oxidation has to be interpreted with caution. Furthermore, a topological electron-density analysis of thianthrene 5-oxide reveals that there is an area of charge depletion at the sulfoxide group. The location of this area indicates that the attack of nucleophilic oxidants on SSO is sterically hindered. Therefore, the SSO probe makes oxidants such as dioxiranes appear to be more electrophilic than they actually are.

Journal Article↗
PubMed2006

On gas phase alpha-effects. 1. The gas-phase manifestation and potential SET character.

The possibility of a gas-phase alpha-effect has been explored for the methyl transfer from methyl formate to hydroxide, hydroperoxide, and ethoxide by computing barrier heights at the HF/6-311++G(2df,2p) level of theory. The alpha-nucleophile (hydroperoxide) is found to have a lower barrier than the gas-phase-acidity-matched normal nucleophile (ethoxide) by 3.6 kcal/mol, offering evidence for a gas phase alpha-effect. A Shi-Boyd analysis for these reactions indicates that there is more single-electron-transfer character in the hydroperoxide transition state than for either hydroxide or ethoxide, further bolstering the existence of a gas-phase alpha-effect and the appropriateness of the Hoz model for the alpha-effect.

Journal Article↗
PubMed2005

Marked variations of dissociation energy and H-bond character of the guanine-cytosine base pair induced by one-electron oxidation and Li+ cation coupling.

The variation of dissociation energy and H-bond character of the G-C cation and the Li-GC cation have been investigated by employing density functional theory (B3LYP) with the 6-31+G* basis set. The one-electron oxidation and the coupling of Li(+) to the guanine-cytosine base pair can strengthen the interaction between guanine and cytosine. The interaction of the cation Li(+) with guanine is attractive and is attributed to the polarization of the H-bonds between G-C that enhances G-C interaction. The cooperativity of the three H-bonds in the GC and Li-GC cations is different from that in the neutral GC base pair. The proton-transfer process between N(1) of the guanine and N(3) of the cytosine can occur in the GC cation and the Li-GC cation. The geometries of the transition state are out of plane, especially for the transition state of the Li-GC cation. The analysis of the activation energy for the proton-transfer process shows that the GC(+) before and after proton transfer can exist simultaneously in the gas phase, but for the Li-GC(+) system, the Li-GC(+) without proton transfer is the dominating species in the gas phase.

Base Pairing↗
PubMed2005

Reassessment of the binary, ternary, and quaternary interactions in mixed electrolytes from thermodynamic quantities: The systems with uncommon ions containing hydrophobic character.

Accurate estimates of the binary, ternary, and quaternary interactions in aqueous ionic mixtures with uncommon ions with hydrophobic character are presented. For this purpose, the values of the excess Gibbs free energy of mixing, Delta m G(E), obtained from our earlier isopiestic osmotic coefficients (Kumar, A. J. Phys. Chem. B2003, 107, 2808) for the mixtures of NaCl with four guanidinium (Gn+) salts-CH3COOGn, GnNO3, GnClO4, and Gn2SO4-are analyzed with the help of the method developed by Leifer and Wigent. The methodology of Leifer and Wigent is based on the equations of Scatchard-Rush-Johnson and Friedman's cluster integral expansion theory. The Scatchard-Rush-Johnson theory explicitly considers the quaternary and higher-order ionic interactions in the mixtures as compared to the specific ion interaction theory of Pitzer, which accounts for binary and ternary interactions only. The contributions due to binary, ternary, and quaternary interaction terms to total Delta m G(E) are estimated and discussed critically. Also, the interaction between the same two cations, for example, Gn+ - Gn+, is estimated and found significant, which otherwise cannot be obtained by the use of Pitzer's theory. The information obtained from the analysis of Delta(m)G(E) is also supported by the newly measured excess volumes of mixing, Delta m V(E), at 298.15 K. The individual contributions of the binary, ternary, and quaternary interaction terms to total Delta m V(E) are described. The binary, ternary, and quaternary interaction terms for both Delta m G(E) and Delta m V(E) are analyzed in terms of Friedman's cluster integral expansion theory.

Journal Article↗
PubMed2005

A DFT study of the pericyclic/pseudopericyclic character of cycloaddition reactions of ethylene and formaldehyde to buta-1,3-dien-1-one and derivatives.

Cycloaddition reactions of ethylene and formaldehyde to buta-1,3-dien-1-one and derivatives were studied by performing a density functional theory study with the 6-31+G* basis set. Reactants, products, and transition states for each reaction were localized, and the path connecting reactants and products was also obtained. Magnetic properties were evaluated along the reaction path to elucidate the characteristics of the reactions studied. Also, a natural bond orbital analysis was performed to study the orbital interactions in the transition states. Calculations indicate that all reactions are pericyclic except three cases, which are pseudopericyclic reactions. In the latter, transition states are almost planar, and magnetic properties do not reveal aromatization enhancement in their transition states. Also, though the participation of lone pairs diminish the pericyclic character of the reactions, sometimes this participation is not enough to generate a change to a pseudopericyclic path. Overall, magnetic properties reveal as a good criterion to elucidate the characteristics of the reactions studied, though a combined application of several criteria is recommended.

Journal Article↗
PubMed2005

The charge-transfer character of the S0 --> S2 transition in the carotenoid peridinin is revealed by Stark spectroscopy.

Peridinin, the carotenoid in the peridinin chlorophyll a protein (PCP), was studied by Stark (electroabsorption) spectroscopy to determine the change in electrostatic properties produced on excitation within the absorption band, in methyl tetrahydrofuran (MeTHF) versus ethylene glycol (EG), at 77 K. Strikingly, a large change in the permanent dipole moment (|Deltamu|) was found between the ground state, S(0) (1(1)A(g)(-)), and the Franck-Condon region of the S(2) (1(1)B(u)(+)) excited state, in both MeTHF (22 D) and EG (approximately 27 D), thus revealing the previously unknown charge transfer (CT) character of this pi-pi transition in peridinin. Such a large |Deltamu| produced on excitation, we suggest, facilitates the bending of the lactone moiety, toward which charge transfer occurs, and the subsequent formation of the previously identified intramolecular CT (ICT) state at lower energy. This unexpectedly large S(2) dipole moment, which has not been predicted even from high-level electronic structure calculations, is supported by calculating the shift of the peridinin absorption band as a function of solvent polarity, using the experimentally derived result. Overall, the photoinduced charge transfer uncovered here is expected to affect the excited-state reactivity of peridinin and, within the protein, be important for efficient energy transfer from the carotenoid S(2) and S(1)/ICT states to the chlorophylls in PCP.

Journal Article↗
PubMed2005

Effect of Laponite and a nonionic polymer on the absorption character of cationic dye solutions.

The effect of Laponite and an amphiphilic triblock copolymer of poly(ethylene oxide) (PEO)-poly(propylene oxide) (PPO)-poly(ethylene oxide) (PEO) (PEO(99)-PPO(65)-PEO(99), and labeled F127) on the absorption character of two cationic dyes, methylene blue and toluidine blue O, was studied and interpreted in terms of the changing state of aggregation of the dye molecules. The combined effect of the polymer and Laponite on dye absorption was significantly different from their individual influences. Specifically, the presence of Laponite resulted in an increase in monomer population by dispersing the dye on the silicate surface. The presence of F127 also resulted in an increase in the dye monomer population, although to a smaller extent. The combined effect of the polymer and Laponite was an increase in the dimer or aggregate populations attributed to the competition of F127 with the dye molecules for the silicate surface.

Journal Article↗