A Monte Carlo-quantum mechanics study of the lowest n-pi* and pi-pi* states of uracil in water

The solvatochromic shifts of the n-pi(*) and pi-pi(*) states of uracil in water are analyzed using a combined and sequential Monte Carlo/quantum mechanics (MC/QM) approach. The role of the solute polarization and electronic delocalization into the solvent region are investigated. Electronic polarization of the solute is obtained using the HF/6-31G(d), the polarizable continuum model (PCM) and an iterative procedure using MP2/aug-cc-pVDZ in the MC/QM. The in-water dipole moment of uracil is obtained, respectively, as 5.12 D, 6.12 D and 7.01 +/- 0.05 D. This latter result, corresponding to an increase of 60% with respect to the gas phase value, is used in the classical potential of the MC simulation to obtain statistically uncorrelated configurations for subsequent QM calculations of the ultraviolet-visible absorption spectrum of uracil in water. QM calculations are performed at the time-dependent density-functional theory (TD-DFT) combined with the B3LYP and B3PW91 functionals, multiconfigurational (CASSCF) and the semi-empirical all-valence electron INDO/CIS methods. Using 60 solute-solvent configurations with the explicit inclusion of 200 water molecules the solvatochromic shift is obtained as a blue shift of 0.50 eV for the n-pi(*) state and a red shift of 0.19 eV for the pi-pi(*) state, in good agreement with experimentally-inferred values. These results are compared with TD-DFT results in conjunction with PCM approaches and the importance of solute polarization and wave function delocalization over the solvent region is discussed. Our results suggest that the elusive n-pi(*) state of uracil in water lies around 255 nm hidden by the intense and broad pi-pi(*) transition with a maximum at 260 nm, inverting the relative locations of these states compared to the gas phase. This is further supported by considering the in-water dipole moment changes upon excitation, as obtained from CASSCF calculations.     

Metal speciation dynamics in monodisperse soft colloidal ligand suspensions

A comprehensive theory is presented for the dynamics of metal speciation in monodisperse suspensions of soft spherical particles characterized by a hard core and an ion-permeable shell layer where ligands L are localized. The heterogeneity in the binding site distribution leads to complex formation/dissociation rate constants (denoted as k a (*) and k d (*), respectively) that may substantially differ from their homogeneous solution counterparts (k a and k d). The peculiarities of metal speciation dynamics in soft colloidal ligand dispersions result from the coupling between diffusive transport of free-metal ions M within and around the soft surface layer and the kinetics of ML complex formation/dissociation within the shell component of the particle. The relationship between k a,d (*) and k a,d is derived from the numerical evaluation of the spatial, time-dependent distributions of free and bound metal. For that purpose, the corresponding diffusion equations corrected by the appropriate chemical source term are solved in spherical geometry using a Kuwabara-cell-type representation where the intercellular distance is determined by the volume fraction of soft particles. The numerical study is supported by analytical approaches valid in the short time domain. For dilute dispersions of soft ligand particles, it is shown that the balance between free-metal diffusion within and outside of the shell and the kinetic conversion of M into ML within the particular soft surface layer rapidly establishes a quasi-steady-state regime. For sufficiently long time, chemical equilibrium between the free and bound metal is reached within the reactive particle layer, which corresponds to the true steady-state regime for the system investigated. The analysis reported covers the limiting cases of rigid particles where binding sites are located at the very surface of the particle core (e.g., functionalized latex colloids) and polymeric particles that are devoid of a hard core (e.g., polysaccharide macromolecules, gel particles). For both the transient and quasi-steady-state regimes, the dependence of k a,d (*) on the thickness of the soft surface layer, the radius of the hard core of the particle, and the kinetic rate constants k a,d for homogeneous ligand solutions is thoroughly discussed within the context of dynamic features for colloidal complex systems.     

Self-assembly and morphology of gel networks in l,3:2,4-bis-O-(p-methylbenzylidene)-D-sorbitol/n-dibutylphthalate

We investigated the self-assembling structure of the 1,3:2,4-bis-O-(p-methylbenzylidene)-D-sorbitol (PDTS)/n-dibutylphthalate (DBP) system in the parameter space of temperature T and solute concentration Phi(PDTS). Optical microscopic studies revealed that the phase diagram can be divided into four regions. In region I at high T the system is a homogeneous solution. In region II at lower T and low Phi(PDTS), the system still has fluidity but has microgels having spherulitic texture of PDTS crystallites. Regions III and IV at even lower T but higher Phi(PDTS) are in a gel state. In region III, the PDTS forms volume-filling spherulites due to the solid-liquid phase transition of the saturated PDTS solutions. In region IV at the lowest T, both the liquid-liquid phase-separation process and the solid-liquid transition of the PDTS are involved in the self-assembling processes. In this region a bicontinuous phase-separated structure is first formed by liquid-liquid phase separation via spinodal decomposition (SD). The subsequent solid-liquid transition of the PDTS in the PDTS-rich region forms percolating crystalline fibrils rather than spherulites. The formation of the crystalline fibrils pins further growth of the bicontinuous structure via SD.     

Determination of the melting point of hard spheres from direct coexistence simulation methods

We consider the computation of the coexistence pressure of the liquid-solid transition of a system of hard spheres from direct simulation of the inhomogeneous system formed from liquid and solid phases separated by an interface. Monte Carlo simulations of the interfacial system are performed in three different ensembles. In a first approach, a series of simulations is carried out in the isothermal-isobaric ensemble, where the solid is allowed to relax to its equilibrium crystalline structure, thus avoiding the appearance of artificial stress in the system. Here, the total volume of the system fluctuates due to changes in the three dimensions of the simulation box. In a second approach, we consider simulations of the inhomogeneous system in an isothermal-isobaric ensemble where the normal pressure, as well as the area of the (planar) fluid-solid interface, are kept constant. Now, the total volume of the system fluctuates due to changes in the longitudinal dimension of the simulation box. In both approaches, the coexistence pressure is estimated by monitoring the evolution of the density along several simulations carried out at different pressures. Both routes are seen to provide consistent values of the fluid-solid coexistence pressure, p=11.54(4)k(B)T/sigma(3), which indicates that the error introduced by the use of the standard constant-pressure ensemble for this particular problem is small, provided the systems are sufficiently large. An additional simulation of the interfacial system is conducted in a canonical ensemble where the dimensions of the simulation box are allowed to change subject to the constraint that the total volume is kept fixed. In this approach, the coexistence pressure corresponds to the normal component of the pressure tensor, which can be computed as an appropriate ensemble average in a single simulation. This route yields a value of p=11.54(4)k(B)T/sigma(3). We conclude that the results obtained for the coexistence pressure from direct simulations of the liquid and solid phases in coexistence using different ensembles are mutually consistent and are in excellent agreement with the values obtained from free energy calculations.     

ABA triblock copolyesters composed of poly(l-lactide) A hard blocks: A comparative study of amorphous and crystalline aliphatic polyesters as B soft blocks

In this article, two series of ABA triblock copolyesters composed of poly(l-lactide) A hard blocks and odd-odd aliphatic polyesters as B soft midblock were prepared and compared by various techniques. The results showed that the block structures could be formed without any detectable transesterification, and the composition and molecular weight of the triblock copolyesters could be well controlled by adjusting the feeding ratio of l-lactide monomer to the polyester macroinitiator. It was found that the thermal properties, crystal structure, and spherulitic morphology of the triblock copolyesters depended on the composition and block length. The impact of amorphous and crystalline midblocks on the mechanical properties was compared and discussed. The triblock copolyesters composed of crystalline midblock showed similar ultimate stress and elongation, but higher tensile modulus and yield stress, in comparison with analogous containing amorphous midblock. The triblock copolyester composed of short PLLA hard block and amorphous aliphatic polyester soft midblock displayed typical elastomeric behavior without yield, which is a promising aliphatic polyester thermoplastic elastomer.     

Succession of stacking disorder in hard-sphere crystal under gravity by Monte Carlo simulation

We have performed Monte Carlo simulations of hard spheres under gravity. Vertical boundaries are hard walls, which are well separated with each other. On the other hand, the periodic boundary condition is imposed in the horizontal direction. While we previously reported enhancement of crystallinity as well as crystallization due to gravity, we present here the results that demonstrate the succession of a defect. In case that the crystal formed at the bottom of the system includes kinds of stacking disorders for the (0 0 1) growth, twin band structure develops as mediated by a stacking disorder succeeded in the crystal formed in the fluid region which lies on the bottom crystal. In case that the stacking structure along horizontal direction changes from the (1 1 1) stacking to the (0 0 1) stacking, twin band structure in the (0 0 1) stacking region develops as succeeded in the crystal transformed. The twin band structure also becomes large with its upward growth.     

Kinetics and mechanism of *NO2 reacting with various oxidation states of myoglobin

Nitrogen dioxide ((*)NO(2)) participates in a variety of biological reactions. Of great interest are the reactions of (*)NO(2) with oxymyoglobin and oxyhemoglobin, which are the predominant hemeproteins in biological systems. Although these reactions occur rapidly during the nitrite-catalyzed autoxidation of hemeproteins, their roles in systems producing (*)NO(2) in the presence of these hemeproteins have been greatly underestimated. In the present study, we employed pulse radiolysis to study directly the kinetics and mechanism of the reaction of oxymyoglobin (MbFe(II)O(2)) with (*)NO(2). The rate constant of this reaction was determined to be (4.5 +/- 0.3) x 10(7) M(-1)s(-1), and is among the highest rate constants measured for (*)NO(2) with any biomolecule at pH 7.4. The interconversion among the various oxidation states of myoglobin that is prompted by nitrogen oxide species is remarkable. The reaction of MbFe(II)O(2) with (*)NO(2) forms MbFe(III)OONO(2), which undergoes rapid heterolysis along the O-O bond to yield MbFe(V)=O and NO(3-). The perferryl-myoglobin (MbFe(V)=O) transforms rapidly into the ferryl species that has a radical site on the globin ((*)MbFe(IV)=O). The latter oxidizes another oxymyoglobin (10(4) M(-1)s(-1) < k(17) < 10(7) M(-1)s(-1)) and generates equal amounts of ferrylmyoglobin and metmyoglobin. At much longer times, the ferrylmyoglobin disappears through a relatively slow comproportionation with oxymyoglobin (k(18) = 21.3 +/- 5.3 M(-1)s(-1)). Eventually, each (*)NO(2) radical converts three oxymyoglobin molecules into metmyoglobin. The same intermediate, namely MbFe(III)OONO(2), is also formed via the reaction peroxynitrate (O(2)NOO(-)/O(2)NOOH) with metmyoglobin (k(19) = (4.6 +/- 0.3) x 10(4) M(-1)s(-1)). The reaction of (*)NO(2) with ferrylmyoglobin (k(20) = (1.2 +/- 0.2) x 10(7) M(-1)s(-1)) yields MbFe(III)ONO(2), which in turn dissociates (k(21) = 190 +/- 20 s(-1)) into metmyoglobin and NO(3-). This rate constant was found to be the same as that measured for the decay of the intermediate formed in the reaction of MbFe(II)O(2) with (*)NO, which suggests that MbFe(III)ONO(2) is the intermediate observed in both processes. This conclusion is supported by thermokinetic arguments. The present results suggest that hemeproteins may detoxify (*)NO(2) and thus preempt deleterious processes, such as nitration of proteins. Such a possibility is substantiated by the observation that the reactions of (*)NO(2) with the various oxidation states of myoglobin lead to the formation of metmyoglobin, which, though not functional in the gas transport, is nevertheless nontoxic at physiological pH.     

Thermoresponsive hydrogel of diblock methylcellulose: formation of ribbonlike supramolecular nanostructures by self-assembly

This article provides detailed insight into the thermoresponsive gelation mechanism of industrially produced methylcellulose (MC), highlighting the importance of diblock structure with a hydrophobic sequence of 2,3,6-tri-O-methyl-glucopyranosyl units for this physicochemical property. We show herein, for the first time, that well-defined diblock MC self-assembles thermoresponsively into ribbonlike nanostructures in water. A cryogenic transmission electron microscopy (cryo-TEM) technique was used to detect the ribbonlike nanostructures formed by the diblock copolymers consisting of hydrophilic glucosyl or cellobiosyl and hydrophobic 2,3,6-tri-O-methyl-cellulosyl blocks, methyl β-d-glucopyranosyl-(1→4)-2,3,6-tri-O-methyl-celluloside 1 (G-236MC, DP(n) = 10.7, DS = 2.65), and methyl β-d-glucopyranosyl-(1→4)-β-d-glucopyranosyl-(1→4)-2,3,6-tri-O-methyl-celluloside 2 (GG-236MC, DP(n) = 28.2, DS = 2.75). Rheological measurements revealed that the gel strength of a dispersion of GG-236MC (2, 2.0 wt %) in water at 70 °C was 3.0 times stronger than that of commercial MC SM-8000, although the molecular weight of GG-236MC (2) having M(w) = 8 × 10(3) g/mol was 50 times smaller than that of SM-8000 having M(w) = 4 × 10(5) g/mol. Cryo-TEM observation suggested that the hydrogel formation of the diblock copolymers could be attributed to the entanglement of ribbonlike nanostructures self-assembled by the diblock copolymers in water. The cryo-TEM micrograph of GG-236MC (2) at 5 °C showed rectangularly shaped nanostructures having a thickness from 11 to 24 nm, although G-236MC (1) at 20 °C showed no distinct self-assembled nanostructures. The ribbonlike nanostructures of GG-236MC (2) having a length ranging from 91 to 864 nm and a thickness from 8.5 to 27.1 nm were detected above 20 °C. Small-angle X-ray scattering measurements suggested that the ribbonlike nanostructures of GG-236MC (2) consisted of a bilayer structure with a width of ca. 40 nm. It was likely that GG-236MC (2) molecules were oriented perpendicularly to the long axis of the ribbonlike nanostructure. In addition, wide-angle X-ray scattering measurements revealed that GG-236MC (2) in its hydrogel formed the same crystalline regions as 2,3,6-tri-O-methylcellulose. The influence of the DP of diblock MC with a DS of around 2.7 on the gelation behavior will be discussed.     

甲壳型液晶高分子的一种非寻常热致液晶行为

根据液晶相的稳定性 ,热致性液晶有双向性和单向性之分 .前者在升温和降温过程中都能形成液晶 ,而后者只能在降温过程中形成液晶 .原因是单向性液晶的液晶相不稳定 ,清亮点Ｔｉ 低于熔点Ｔｍ .升温时 ,样品熔融后直接进入各向同性的熔体 ;降温时 ,由于结晶过程的过冷 ,冷结晶温度Ｔｃ 低于Ｔｉ,样品先从各向同性态进入液晶态 ,然后才结晶 .一般情况下 ,如果液晶化合物自身是非晶的 ,所形成的有序结构不会由于冷却而遭到破坏 .最近 ,我们在研究分子量和液晶基元末端长度对甲壳型液晶高分子液晶性影响的时候发现 ,聚 [2 ,5 双 ( 4′ 正己氧基…     

One-electron reduction of superoxide radical-anions by 3-alkylpolyhydroxyflavones in micelles. Effect of antioxidant alkyl chain length on micellar structure and reactivity

In micellar solutions, one-electron reduction of (*)O 2 (-) radical-anions by 3-alkylpolyhydroxyflavones (FnH) with alkyl chains of n = 1, 4, 6, 10 carbons produces phenoxyl radicals ( (*)Fn) identical to those obtained by one-electron oxidation by (*)Br 2 (-) radical-anions or by repair of tryptophan radicals. In cetyltrimethylammonium bromide (CTAB), F1H localizes in the Stern layer, and alkyl chains of other FnH solubilize in the hydrophobic interior, interacting with cetyl tails. This interaction produces more compact micelles with lower intramicellar fluidity, as suggested by the increase in the pseudo-first-order rate constant of (*)Fn formation ( k 1) from approximately 390 s (-1) for n = 1 to 610 s (-1) for n = 10, leading to an intramicellar bimolecular rate constant of 1 x 10 (5) M (-1) s (-1). Additionally, (*)F1 and (*)F4 decay by intermicellar bimolecular reaction (2 k = 20 and 2 x 10 (5) M (-1) s (-1), respectively) whereas other (*)Fn radicals are stable over seconds due to increased localization with regards to the Stern layer. In contrast, the thick uncharged hydrophilic palisade layer and the compact hydrophobic core of Triton X100 micelles are responsible for a much higher microviscosity resulting in a decrease in k 1 from approximately 15.6 s (-1) for n = 1 to 9.6 s (-1) for n = 10.     

Internal state distributions of fragment HCO via S0 and T1 pathways of glyoxal after photolysis in the ultraviolet region

The dynamics of photodissociation of glyoxal (HOC-COH) near the dissociation threshold on the triplet manifold are studied through measurement of distributions of nascent fragment HCO in various internal states. Three rotational levels 1(01) (*), 4(13) (*), and 3(21) (*)+3(22) (*) of vibrational state U (excitation wavelength approximately 394.4 nm, origin at 25,331.865 cm(-1)) of glyoxal in state A (1)A(u) and two other vibrational states at excitation wavelengths 390.33 and 382.65 nm are selected to produce fragment HCO. By means of fluorescence in the transition B (2)A(')-X (2)A(') of HCO, we determined the relative populations of internal states of that fragment. Rotational states of product HCO up to N=26 and K=2 are populated, and bimodal distributions of these rotational states are observed for the photolysis wavelengths used in this work. The high rotational part of the distribution with average energy near values calculated on the basis of the statistical model-phase-space theory is assigned to arise from glyoxal on its S(0) surface, and the low rotational part from the T(1) surface with an exit barrier. After photolysis near the threshold region on the triplet surface, HCO arising from the T(1) state appears to be a major component of products because these rotational levels 1(01) (*), 4(13) (*), and 3(2) (*) of U state selected are gateway states with an enhanced rate of intersystem crossing.     

Electronic and vibrational spectra of the low-lying pisigma* state of 4-dimethylaminobenzonitrile: comparison of theoretical predictions with experiment

Comparison of the TD-BP86cc-pVDZ electronic excitation energies and the CIScc-pVDZ vibrational frequencies of 4-dimethylaminobenzonitrile with the available experimental data indicates that the picosecond transient absorption at about 700 nm, and the excited-state vibration of frequency 1467 cm(-1), belong to the lowest-energy pisigma(CN) (*) state of bent geometry (CCN bond angle of about 120 degrees and a large CN bond distance). Consistent with these assignments, the 1467 cm(-1) Raman band, attributed to the CN stretch, exhibits a large resonance enhancement of intensity when the probe (Raman excitation) wavelength is set to the spectral region of the pisigma(*)<--pisigma(*) absorption. The result corroborates the occurrence of an ultrafast state switch from the initially excited (1)pipi(*) (L(b)) state to the (1)pisigma(*) state of lower energy.     

Insight into selected reactions in low-temperature dimethyl ether combustion from Born-Oppenheimer molecular dynamics

Dimethyl ether is under consideration as an alternative diesel fuel. Its combustion chemistry is as yet ill-characterized. Here we use Born-Oppenheimer molecular dynamics (BOMD) based on DFT-B3LYP forces to investigate the short-time dynamics of selected features of the low-temperature dimethyl ether (DME) oxidation potential energy surface. Along the chain propagation pathway, we run BOMD simulations from the transition state involving the decomposition of (*)CH(2)OCH(2)OOH to two CH(2)=O and an (*)OH radical. We predict that formaldehyde C-O stretch overtones are excited, consistent with laser photolysis experiments. We also predict that O-H overtones are excited for the (*)OH formed from (*)CH(2)OCH(2)OOH dissociation. We also investigate short-time dynamics involved in chain branching. First, we examine the isomerization transition state of (*)OOCH(2)OCH(2)OOH --> HOOCH(2)OCHOOH. The latter species is predicted to be a short-lived metastable radical that decomposes within 500 fs to hydroperoxymethyl formate (HPMF; HOOCH(2)OC(=O)H) and the first (*)OH of chain branching. The dissociation of HOOCH(2)OCHOOH exhibits non-RRKM behavior in its lifetime profile, which may be due to conformational constraints or slow intramolecular vibrational energy transfer (IVR) from the nascent H-O bond to the opposite end of the radical, where O-O scission occurs to form HPMF and (*)OH. In a few trajectories, we see HOOCH(2)OCHOOH recross back to (*)OOCH(2)OCH(2)OOH because the isomerization is endothermic, with only an 8 kcal/mol barrier to recrossing. Therefore, some inhibition of chain-branching may be due to recrossing. Second, trajectories run from the transition state leading to the direct decomposition of HPMF (an important source of the second (*)OH radical in chain branching) to HCO, (*)OH, and HC(=O)OH show that these products can recombine to form many other possible products. These products include CH(2)OO + HC(=O)OH, H(2)O + CO + HC(=O)OH, HC(=O)OH + HC(=O)OH, and HC(=O)C(=O)H + H(2)O, which (save CH(2)OO + HC(=O)OH) are all more thermodynamically stable than the original HCO + (*)OH + HC(=O)OH products. Moreover, the multitude of extra products suggest that standard statistical rate theories cannot completely describe the reaction kinetics of significantly oxygenated compounds such as HPMF. These secondary products consume the second (*)OH required for explosive combustion, suggesting an inhibition of DME fuel combustion is likely.     

Rotation-tunneling analysis of the origin band in the tropolone pi(*)<--pi absorption system

The tunneling-split origin band of the tropolone A (1)B(2)-X (1)A(1) (pi(*)<--pi) absorption system was interrogated under ambient, bulk-gas conditions by exploiting high-resolution degenerate four-wave mixing techniques. The inherent complexity of this spectral region was alleviated by performing polarization-resolved measurements, with judicious selection of transverse characteristics for the incident and detected electromagnetic fields enabling rovibronic transitions to be discriminated according to their attendant changes in rotational angular momentum, DeltaJ. Quantitative simulation of recorded data sets showed the vibrationless level of the electronically excited state to be bifurcated by Delta(0) (A)=19.846(25) cm(-1), representing a factor of 20 increase in proton-transfer efficiency over the corresponding level of the ground electronic state. Spectroscopic parameters extracted for the 0(+) and 0(-) manifolds of A (1)B(2) tropolone yield unexpectedly large values of the inertial defect, DeltaI(0(+) ) (A)=-0.802(86) amu A(2) and DeltaI(0(-) ) (A)=-0.882(89) amu A(2), strongly suggesting that a loss of molecular planarity accompanies the pi(*)<--pi electron promotion. These results, as well as complementary information deduced for interloping hot-band resonances, are discussed in terms of the unique structural and dynamical properties exhibited by tropolone and related proton-transfer species.     

Molecular mobility in amorphous maltose and maltitol from phosphorescence of erythrosin B

We have used phosphorescence from erythrosin B (tetraiodofluorescein) dispersed in amorphous thin films of maltose and maltitol at mole ratios of 0.8:10(4) dye:sugar to monitor the molecular mobility of these matrixes over the temperature range from -25 to over 110 degrees C. Analysis of the emission peak frequency and bandwidth (full width at half-maximum) and time-resolved intensity decay parameters provided information about thermally activated modes of matrix mobility that enhanced the rate of dipolar relaxation around the triplet state and the rate of intersystem crossing to the ground state (k(TS0)). Detectable dipolar relaxation began in the glassy state about 50 degrees C below T(g) in both maltose and maltitol; the relaxation rate, however, while 3-4 orders of magnitude slower than literature values for the beta relaxation determined from dielectric relaxation, had an activation energy only 2-fold smaller. Dipolar relaxation was further enhanced in the melt above T(g); the dipolar relaxation rates in the melt scaled nearly exactly with rates for the alpha relaxation determined from dielectric relaxation. Intensity decays were well fit using a stretched exponential decay function in which the lifetime (tau) and the stretching exponent (beta) were the physically significant parameters. In maltose, the magnitude of k(TS0) was essentially constant in the glass and increased dramatically at the T(g); in maltitol k(TS0) increased moderately at T(g) = -50 degrees C and more dramatically in the melt at T(g) = +20 degrees C. The value of k(TS0) in maltose:maltitol mixtures was significantly smaller than that seen in pure maltose and maltitol, suggesting that specific interactions decreased the mobility of the mixed sugar matrix; this phenomenon was comparable to the antiplasticization seen in mixtures of small molecule plasticizers with synthetic polymers and starch. The extent of inhomogeneous broadening and dynamic heterogeneity were essentially constant in the glass and increased dramatically in maltose and more gradually in maltitol at the glass transition.     

Pyrroles as antioxidants: solvent effects and the nature of the attacking radical on antioxidant activities and mechanisms of pyrroles, dipyrrinones, and bile pigments

The absolute rate constants, k(inh), and stoichiometric factors, n, of pyrroles, 2-methyl-3-ethylcarboxy-4,5-di-p-methoxyphenylpyrrole, 6, 2,3,4,5-tetraphenylpyrrole, 7, and 2,3,4,5-tetra-p-methoxyphenylpyrrole, 8, compared to the phenolic antioxidant, di-tert-butylhydroxyanisole, DBHA, during inhibited oxidation of cumene initiated by AIBN at 30 degrees C gave the relative antioxidant activities (k(inh)) DBHA > 8 > 7 > 6 and n = 2, whereas in styrene, 8 > DBHA. These results are explained by hydrogen atom transfer, HAT, from the N-H of pyrroles to ROO(*) radicals. The k(inh) values in styrene of dimethyl esters of the bile pigments of bilirubin ester (BRDE), of biliverdin ester (BVDE), and of a model compound (dipyrrinone, 1) gave k(inh) in the order pentamethylhydroxychroman (PMHC) > BRDE > 1 > BVDE. These antioxidant activities for BVDE and the model compound, 1, and PMHC dropped dramatically in the presence of methanol due to hydrogen bonding at the pyrrolic N-H group. In contrast the k(inh) of BRDE increased in methanol. We now show that pyrrolic compounds may react by HAT, proton-coupled electron transfer, PCET, or single electron transfer, SET, depending on their structure, the nature of the solvent, and the attacking radical. Compounds BVDE and 1 react by the HAT or PCET pathway (HAT/PCET) in styrene/chlorobenzene with ROO(*) and with the DPPH(*) radical in chlorobenzene according to N-H/N-D kH/kD of 1.6, whereas the DKIE with BRDE was only 1.2 with ROO(*). The antioxidant properties of polypyrroles of the BVDE class and model compounds (e.g., 1) are controlled by intramolecular H bonding which stabilizes an intermediate pyrrolic radical in HAT/PCET. According to kinetic polar solvent effects on the monopyrrole, 8, and BRDE, which gave increased rates in methanol, some pyrrolic structures are also susceptible to SET reactions. This conclusion is supported by some calculated ionization potentials. The antioxidant mechanism for BRDE with peroxyl radicals is described by the PCET reaction. Experiments using the 2,6-di-tert-butyl-4-(4'-methoxyphenyl)phenoxyl radical (DBMP(*)) showed this to be a better radical to monitor HAT activities in stopped-flow kinetics compared to the use of the more popular DPPH(*) radical.     

Multicomponent Self‐Assembly with a Shape‐Persistent N‐Heterotriangulene Macrocycle on Au(111)

Multicomponent network formation by using a shape‐persistent macrocycle ( MC6 ) at the interface between an organic liquid and Au(111) surface is demonstrated. MC6 serves as a versatile building block that can be coadsorbed with a variety of organic molecules based on different types of noncovalent interactions at the liquid–solid interface. Scanning tunneling microscopy (STM) reveals the formation of crystalline bicomponent networks upon codeposition of MC6 with aromatic molecules, such as fullerene (C₆₀) and coronene. Tetracyanoquinodimethane, on the other hand, was found to induce disorder into the MC6 networks by adsorbing on the rim of the macrocycle. Immobilization of MC6 itself was studied in two different noncovalently assembled host networks. MC6 assumed a rather passive role as a guest and simply occupied the host cavities in one network, whereas it induced a structural transition in the other. Finally, the central cavity of MC6 was used to capture C₆₀ in a complex three‐component system. Precise immobilization of organic molecules at discrete locations within multicomponent networks, as demonstrated here, constitutes an important step towards bottom‐up fabrication of functional surface‐based nanostructures.     

Doubled heterogeneous crystal nucleation in sediments of hard sphere binary-mass mixtures

Crystallization during the sedimentation process of a binary colloidal hard spheres mixture is explored by Brownian dynamics computer simulations. The two species are different in buoyant mass but have the same interaction diameter. Starting from a completely mixed system in a finite container, gravity is suddenly turned on, and the crystallization process in the sample is monitored. If the Peclet numbers of the two species are both not too large, crystalline layers are formed at the bottom of the cell. The composition of lighter particles in the sedimented crystal is non-monotonic in the altitude: it is first increasing, then decreasing, and then increasing again. If one Peclet number is large and the other is small, we observe the occurrence of a doubled heterogeneous crystal nucleation process. First, crystalline layers are formed at the bottom container wall which are separated from an amorphous sediment. At the amorphous-fluid interface, a secondary crystal nucleation of layers is identified. This doubled heterogeneous nucleation can be verified in real-space experiments on colloidal mixtures.     

Oxidation potentials of alpha-hydroxyalkyl radicals in acetonitrile obtained by photomodulated voltammetry.

Oxidation potentials, E1/2(ox) of alpha-hydroxyalkyl radicals of the type R(1)R(2)C(*)OH (denoted K(1)H(*)) have been obtained in acetonitrile by photomodulated voltammetry. The values of E1/2(ox) increase as the R(1) and R(2) groups are changed from alkyl to aryl and, in particular, strong electron-withdrawing functionalities such as CN and CF3. Using rate data available in the literature for the pinacol photoexchange reaction K + K(1)H(*) --> KH(*) + K(1), it is found that as the difference in the standard potential of the ketone K, EK degrees and the oxidation potential of K(1)H(*), E1/2(ox), increases there is a modest increase in the exchange rate constant, k(ex). This indicates that even if some charge transfer may occur between the hydroxyalkyl radical and the ketone in the transition state, it is certainly not to the extent of a complete electron transfer. If the exchange reaction is treated as a simple hydrogen atom transfer process within the Marcus model, the intrinsic barrier is found to be 8-13 kcal mol(-1) due to the changes occurring in bonds, hybridizations, and bond angles. Finally, acid dissociation constants for K(1)H(*) are provided by means of a thermochemical cycle.     

An extended multireference study of the electronic states of para-benzyne

A state-averaged, multireference complete active space (CAS) approach was used for the determination of the vertical excitation energies of valence and Rydberg states of para-benzyne. Orbitals were generated with a 10- and 32-state averaged multiconfigurational self-consistent field approach. Electron correlation was included using multireference configuration interaction with singles and doubles, including the Pople correction for size extensivity, multireference averaged quadratic coupled cluster (MR-AQCC), and MR-AQCC based on linear response theory. There is a very high density of electronic states in this diradical system-there are more than 17 states within 7 eV of the ground state including two 3s Rydberg states. All excitations, except 2 (1)A(g), are from the pi system to the sigmasigma(*) system. Of the 32 states characterized, 15 were multiconfigurational, including the ground (1)A(g) state, providing further evidence for the necessity of a multireference approach for p-benzyne. The vertical singlet-triplet splitting was also characterized using a two-state averaged approach. A CAS(2,2) calculation was shown to be inadequate due to interaction with the pi orbitals.