A hetero-stranded double helix composed of m-diethynylbenzene-based complementary molecular strands stabilized by amidinium-carboxylate salt bridges

A hetero-stranded double helix with a controlled helix sense was designed and synthesized from an optically active dimeric amidine and its complementary achiral dicarboxylic acid strand with conjugated m-diethynylbenzene backbones, being stabilized by the salt bridges.     

Synthesis of complementary double-stranded helical oligomers through chiral and achiral amidinium-carboxylate salt bridges and chiral amplification in their double-helix formation

A series of complementary molecular strands from 2-mer to 5-mer that are composed of m-terphenyl units bearing chiral/achiral amidine or achiral carboxyl groups linked via Pt(II) acetylide complexes were synthesized by sequential stepwise reactions, and their chiroptical properties on the double-helix formation were investigated by circular dichroism (CD) and (1)H NMR spectroscopies. In CHCl(3), the "all-chiral" amidine strands consisting of (R)- or (S)-amidine units formed preferred-handed double helices with the complementary achiral carboxylic acid strands through the amidinium-carboxylate salt bridges, resulting in characteristic induced CDs in the Pt(II) acetylide complex regions, indicating that the chiral substituents on the amidine units biased a helical sense preference. The Cotton effect patterns and intensities were highly dependent on the molecular lengths. The complementary double-helix formation was also explored using the chiral/achiral amidine strands with different sequences in which a chiral amidine unit was introduced at the center (center-chiral) or a terminus (edge-chiral) of the amidine strands. The effect of the sequences of the chiral and achiral amidine units on the amplification of chirality (the "sergeants and soldiers" effect) in the double-helix formation was investigated by comparing the CD intensities with those of the corresponding all-chiral amidine double helices with the same molecular lengths. Variable-temperature CD experiments of the all-chiral and chiral/achiral amidine duplexes demonstrated that the Pt(II)-linked complementary duplexes are dynamic and their chiroptical properties including the chirality transfer from the chiral amidine unit to the achiral amidine ones are significantly affected by the molecular lengths, sequences, and temperatures. On the basis of the above results together with molecular dynamics simulation results, key structural features of the Pt(II)-linked oligomer duplexes and the effect of the chiral/achiral amidine sequences on the amplification of chirality are discussed.     

Supramolecular porphyrin assemblies through amidinium-carboxylate salt bridges and fast intra-ensemble excited energy transfer

Well‐defined supramolecular assemblies of Zn and free‐base porphyrins are constructed through the formation of amidinium–carboxylate salt bridges. A one‐to‐one donor–acceptor pair and a four‐to‐one antenna‐type assembly are investigated. The steady‐state and time‐resolved fluorescence measurements unequivocally showed that efficient singlet–singlet excited energy transfer from the Zn–porphyrin complex to the free‐base porphyrin takes place in these assemblies. Indeed, the observed energy‐transfer rates in both types of assemblies are much faster than those the Förster mechanism would suggest, implying the involvement of an intermolecular through‐bond mechanism.     

Thermodynamic stabilities of semiconductor electrodes

The application of the Pourbaix diagram to the prediction and understanding of the thermodynamic stability of semiconductor materials is discussed. With the aid of flat band potential information, the thermodynamic stability of semiconductor materials under various operating conditions, types of electrodes (n- or p-) to be used, conversion efficiencies, types of redox couples to be chosen for a given semiconductor electrode material, and the proper operating pH region can be determined. It is shown from the available information that all the semiconductor materials examined, i.e., CdS, CdSe, CdTe, and GaP may be unstable with respect to anodic dissolution and that p-type electrodes may be successfully used as photocathodes for the photoassisted electrolysis of water to hydrogen. GaAs is shown to be unstable with respect to both anodic and cathodic dissolution.     

Further test of the isolated pentagon rule: Thermodynamic and kinetic stabilities of C84 fullerene isomers

Thermodynamic and kinetic stabilities of 73 C₈₄ fullerene isomers were estimated from the MM3 heats of formation and the recently defined bond resonance energies (BREs), respectively. The BRE represents the contribution of a given π bond in a molecule to the topological resonance energy (TRE). All π bonds shared by two pentagons turned out to be highly reactive without exceptions. C₈₄ fullerene isomers with such π bonds must be incapable of survival during harsh synthetic processes. Thus, the isolated pentagon rule (IPR) proved to be applicable to such large fullerene cages. For sufficiently large fullerenes like C₈₄, some isolated-pentagon isomers are also predicted to be very unstable with highly antiaromatic π bonds. © 1996 by John Wiley & Sons, Inc.     

Photoresponsive double-stranded helices composed of complementary strands

A photoresponsive single-handed double helical supramolecule composed of complementary strands bearing azobenzene moieties underwent a reversible trans-cis-isomerization regulated by photoirradiation, resulting in a change in its molecular length.     

Ylide及其相应自由基的热力学稳定性研究

本文首次测定了三苯基胂、三丁基磷和二丁基碲系列Ylide的前体化合物中α-C-H键在二甲亚砜(DMSO)溶液中的pKA和气相中的均裂键能(BDE)。通过这些结构相似的Ylide相应性质的类比, 对有关的碳负离子和碳自由基的热力学稳定性以及磷Ylide中P-C键的属性及其对磷Ylide性质的影响从构效关系的更深层次进行了讨论。     

Molecular design and synthesis of artificial double helices

This account describes novel artificial double helices recently developed by our group. We have designed and synthesized the double helices consisting of two complementary, m-terphenyl-based strands that are intertwined through chiral amidinium-carboxylate salt bridges. Due to the chiral substituents on the amidine groups, the double helices adopted an excess one-handed helical conformation in solution as well as in the solid state. By extending the modular strategy, we have synthesized double helices bearing Pt(II) linkers, which underwent the double helix-to-double helix transformations through the chemical reactions of the Pt(II) complex moieties. In addition, artificial double-stranded metallosupramolecular helical polymers were constructed by combining the salt bridges and metal coordination. In contrast to the design-oriented double helices based on salt bridges, we have serendipitously developed a spiroborate-based double helicate bearing oligophenol strands. The optical resolution of the helicate was successfully attained by a diastereomeric salt formation. We have also unexpectedly found that oligoresorcinols consisting of a very simple repeating unit self-assemble into double helices with the aid of aromatic interactions in water. Furthermore, a bias in the twist sense of the double helices can be achieved by incorporating chiral substituents at both ends of the strands.     

Quantitative comparison of kinetic stabilities of metallomacrocycle-based rotaxanes

Four mononuclear metallomacrocycles with identical cavities but different transition metals (Os(VI), Pd(II), Pt(II), and Re(I)) were prepared. With these metallomacrocycles, the corresponding rotaxanes 2-Os, 2-Pd, 2-Pt, and 2-Re were self-assembled by hydrogen-bonding interactions. The kinetic stabilities of the rotaxanes were determined quantitatively and compared with each other by (1)H NMR spectroscopic techniques, including two-dimensional exchange spectroscopy (2D-EXSY) experiments. The activation free energies (DeltaG( not equal )) for the exchange between the rotaxanes 2-Os, 2-Pd and 2-Pt and their free components were determined to be 15.5, 16.0, and 16.4 kcal mol(-1), respectively. These magnitudes imply that the rotaxanes 2-Os, 2-Pd and 2-Pt are kinetically labile at room temperature and exist only as equilibrium mixtures with free components in solution. In contrast, the rotaxane 2-Re is kinetically stable enough to be isolated in pure form by silica gel chromatography under ordinary laboratory conditions. However, at higher temperatures (>60 degrees C) 2-Re was slowly disassembled into its components until the equilibrium was established. The rate constants were measured at three different temperatures, and the Eyring plot yielded the activation enthalpy DeltaH(not equal)=35 kcal mol(-1) and the activation entropy DeltaS(not equal)=27 eu for the disassembly of the rotaxane 2-Re in Cl(2)CDCDCl(2). These thermodynamic parameters gave the activation free energy DeltaG(not equal)(off)=27.1 kcal mol(-1) at 25 degrees C. Consequently, 2-Re is one example of a novel metallomacrocycle-based rotaxane that contains a coordination bond with enough strength to allow both for isolation in pure form around room temperature and for self-assembly at higher temperatures.     

Hydrolysis on transition metal oxide clusters and the stabilities of M-O-M bridges

Water addition to molecular single, double and triple M-O-M bridges (M = Sc, Ti, V, Cr, and Mn) were considered, and the stabilities toward stepwise hydrolysis of the oxygen bridges were studied by means of quantum chemistry. The M-O bond distances for the studied systems were compared to experiment for demonstration of the applicability of the B3LYP functional to the investigated systems. While substantial exothermicities were found for the hydrolysis of double and triple M-O-M bridges, addition of water to a single bridge was generally found to be slightly endothermic. The lack of enthalpy drive for the (OH)yOxM-O-MOx(OH)y + H2O-->2MOx-1(OH)y+2 reaction was taken to suggest that entropy increase and the formation of mononuclear water complexe, would be decisive factors for the dissociation. A mechanism was proposed for the observed erosion of the protective chromium oxide scale on high-temperature alloys at elevated temperatures and high humidities, based on the formation of CrO2(OH)2(g).     

Thermodynamic and kinetic behaviour of salicylsalicylic acid

The thermal behaviour of salicylsalicylic acid (CAS number 552-94-3) was studied by differential scanning calorimetry (DSC). The endothermic melting peak and the fingerprint of the glass transition were characterised at a heating rate of 10°C min^-1. The melting peak showed an onset at T _on = 144°C (417 K) and a maximum intensity at T _max = 152°C (425 K), while the onset of the glass transition signal was at T _on = 6°C. The melting enthalpy was found to be Δ_mH = 28.9±0.3 kJ mol^-1, and the heat capacity jump at the glass transition was ΔC _P = 108.1±0.1 J K^-1mol^-1. The study of the influence of the heating rate on the temperature location of the glass transition signal by DSC, allowed the determination of the activation energy at the glass transition temperature (245 kJ mol^-1), and the calculation of the fragility index of salicyl salicylate (m = 45). Finally, the standard molar enthalpy of formation of crystalline monoclinic salicylsalicylic acid at T = 298.15 K, was determined as Δ_fH_m ^o(C₁₄H₁₀O₅, cr) = - (837.6±3.3) kJ mol^-1, by combustion calorimetry. This revised version was published online in August 2006 with corrections to the Cover Date.     

Thermodynamic and kinetic aspects of fat crystallization

Naturally occurring fats are multi-component mixtures of triacylglycerols (TAGs), which are triesters of fatty acids with glycerol, and of which there are many chemically distinct compounds. Due to the importance of fats to the food and consumer products industries, fat crystallization has been studied for many years and many intricate features of TAG interactions, complicated by polymorphism, have been identified. The melting and crystallization properties of triacylglycerols are very sensitive to even small differences in fatty acid composition and position within the TAG molecule which cause steric hindrance. Differences of fatty acid chain length within a TAG lead to packing imperfections, and differences in chain lengths between different TAG molecules lead to a loss of intersolubility in the solid phase. The degree of saturation is hugely important as the presence of a double bond in a fatty acid chain causes rigid kinks in the fatty acid chains that produce huge disruption to packing structures with the result that TAGs containing double bonds have much lower melting points than completely saturated TAGs. All of these effects are more pronounced in the most stable polymorphic forms, which require the most efficient molecular packing. The crystallization of fats is complicated not just by polymorphism, but also because it usually occurs from a multi-component melt rather than from a solvent which is more common in other industrial crystallizations. This renders the conventional treatment of crystallization as a result of supersaturation somewhat meaningless. Most studies in the literature consequently quantify crystallization driving forces using the concept of supercooling below a distinct melting point. However whilst this is theoretically valid for a single component system, it can only at best represent a rough approximation for natural fat systems, which display a range of melting points. This paper reviews the latest attempts to describe the sometimes complex phase equilibria of fats using fundamental relationships for chemical potential that have so far been applied to individual species in melts of unary, binary and ternary systems. These can then be used to provide a framework for quantifying the true crystallization driving forces of individual components within a multi-component melt. These are directly related to nucleation and growth rates, and are also important in the prediction of polymorphic occurrence, crystal morphology and surface roughness. The methods currently used to evaluate induction time, nucleation rate and overall crystallization rate data are also briefly described. However, mechanistic explanations for much of the observed crystallization behaviour of TAG mixtures remain unresolved.     

Thermodynamic and kinetic size limit of nanowire growth

The universal models of nucleation thermodynamics and growth kinetics were established for nanowire growth upon metal-catalyst-assisted thermal chemical vapor transport on the basis of vapor-liquid-solid (VLS) mechanism. The thermodynamic and kinetic size limit of nanowire growth was deduced from the proposed model. Theoretical predictions are in agreement with experimental data.     

Ab initio calculations of silicon-halogen-silicon double bridges

Summary Structure and stability of molecular clusters modelling halogen (F, Cl) double bridges between silicon atoms, H₃SiF₂SiH₃ (1), H₃SiF₂SiF₃ (2), H₃SiCl₂SiH₃ (3), and H₃SiCl₂ SiCl₃ (4), have been investigated by an ab initio pseudopotential method. Asymmetrical bridges Si-X...Si with one strong Si-X bond and one weak Si...X bonding interaction (X=F, Cl) result from the geometry optimization using the LP-31 G basis set. Dissociation energy calculations using the MP2/LP-31G*//LP-31G procedure and considering the basis set superposition error provide a decrease of stability of the structures in the order2>4>3>1. The results are discussed with respect to formation and decomposition of halogenated reaction overlayers formed during the etching of silicon by halogen atoms.

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Ab-Initio-Berechnungen von Silizium-Halogen-Silizium-Doppelbrücken

Zusammenfassung Struktur und Stabilität von molekularen Clustern, die Halogen(F, Cl)-Doppelbrücken zwischen Siliziumatomen modellieren, H₃SiF₂SiH₃ (1), H₃SiF₂SiF₃ (2), H₃SiCl₂SiH₃ (3) und H₃SiCl₂SiCl₃ (4), werden mittels eines Ab-Initio-Pseudopotentialverfahrens untersucht. Bei der Geometrieoptimierung unter Verwendung des LP-31 G-Basissatzes ergeben sich asymmetrische Brücken Si-X...Si mit einer starken Si-X-Bindung und einer schwachen bindenden Si...X-Wechselwirkung (X=F, Cl). Dissoziationsenergieberechnungen durch das MP2/LP-31 G*//LP-31 G-Verfahren unter Berücksichtigung des Basissatzüberlagerungsfehlers liefert eine abnehmende Stabilität der Cluster in der Reihenfolge2>4>3>1. Die Resultate werden im Zusammenhang mit der Bildung und dem Zerfall von halogenierten Reaktionsschichen, welche während des reaktiven Ätzens von Silizium mit Halogenatomen gebildet werden, diskutiert.

     

Kinetic stabilities of double,tetra-, and hexarosette hydrogen-bonded assemblies

A study of the kinetic stabilities of hydrogen-bonded double, tetra-, and hexarosette assemblies, comprising 36, 72, and 108 hydrogen bonds, respectively, is described. The kinetic stabilities are measured using both chiral amplification and racemization experiments. The chiral amplification studies show that solvent polarity and temperature strongly affect the kinetic stabilities of these hydrogen-bonded assemblies. For example, the activation energy for the dissociation of a tetramelamine from a tetrarosette assembly, a process that involves the breakage of 24 hydrogen bonds, was determined at 98.7 +/- 16.6 kJ mol(-1) in chloroform and 172.8 +/- 11.3 kJ mol(-1) in benzene. Moreover, racemization studies with enantiomerically enriched assemblies reveal a strong dependence of the kinetic stability on the number and strength of the hydrogen bonds involved in assembly formation. The half-lives for double, tetra-, and hexarosette assemblies were found to be 8.4 min, 5.5 h, and 150 h in chloroform at 50 degrees C, respectively. For higher generations of these types of assemblies, the kinetic stabilities become so high that they can no longer measured in a direct manner.     

Germanium-Iodine System,Thermodynamic Study assessment and complementary experiments

Literature thermodynamic data (enthalpies, entropies, and heat capacities) of the condensed species GeI₄(s)(I) and GeI₂(s) are revised. Entropies and heat capacities of the gaseous species GeI₄(g), GeI₂(g), and GeI(g) are calculated by the R.R.H.O. method. Published experimental investigations of the equilibria: GeI₄(l) ? GeI₄(g), GeI₄(s) ? GeI₄(g), 2 GeI₂ ? Ge(s) + GeI₄(g), GeI₄ ? GeI₂(g) + I₂(g), GeI₂(s) ? GeI₂(g) and Ge(s) + GeI₄(g) ? 2 GeI₂(g) are discussed. In addition, new measurements of the total pressure above the saturation ranges of the GeI₄(l) and for the reaction: Ge(s) + GeI₄(l) ? 2 GeI₂(g) are performed. Enthalpies of formation of GeI₄(g) and GeI(g) are deduced. Enthalpy of formation of GeI(g) is estimated from the evolution of the dissociation energy D°(Ge? X) (X = Cl, Br, I) against the Z atomic number and from the spectroscopic constants of this molecule. In conclusion a self consistent set of thermodynamic data concerning the germanium-iodine system is proposed.     

Ultrafast excited-state deactivation and energy transfer in guanine-cytosine DNA double helices

The DNA double helix poly(dGdC).poly(dGdC) is studied by fluorescence upconversion spectroscopy with femtosecond resolution. It is shown that the excited-state relaxation of the duplex is faster than that of the monomeric components dGMP and dCMP. This contrasts with the behavior of duplexes composed exclusively of adenine-thymine base pairs, for which an overall lengthening of the fluorescence lifetimes with respect to that of an equimolar mixture of dAMP and TMP was reported previously. Despite the difference in the excited-state deactivation rate between the two types of duplexes, the signature of ultrafast energy transfer is present in both of them. It is attested by the decrease of fluorescence anisotropy decay of the duplexes on the subpicosecond time scale, where molecular motions are inhibited, and is corroborated by the fact that their steady-state fluorescence spectra do not change with the excitation wavelength. Energy transfer involves excited states delocalized over at least two bases, whose existence is revealed by the UV absorption spectrum of the duplex, clearly different from that of an equimolar spectrum of dGMP and dCMP.