Additivity of substituent effects on the acidity of alcohols

Using Fourier Transform Ion Cyclotron Resonance Spectrometry, we have determined the gas‐phase acidities (GA) of 1‐phenylethanol, diphenylmethanol and triphenylmethanol. Combining these results with the available experimental data for other alcohols, we obtained three sets of experimental acidities for the families (CH₃)_nC–OH, (CF₃)_nC–OH and Ph_nC–OH (n = 1–3) as well for some other α‐substituted alcohols combining these substituents. GA values for these alcohols were studied at the B3LYP/6‐311 + G(d,p), MP2/6‐311 + G(d,p), G3(MP2) and G3 levels. This allowed the prediction of a number of GA values for other alcohols. We also developed an empirical method for the estimation of these magnitudes and used it to predict the cases wherein simple additivity of substituent effects would break down. Copyright © 2013 John Wiley & Sons, Ltd.     

Effect of interaction between loop bases and ions on stability of G-quadruplex DNA

G-quadruplexes(GQs) are guanine-rich, non-canonical nucleic acid structures that play fundamental roles in biological processes. The topology of GQs is associated with the sequences and lengths of DNA, the types of linking loops, and the associated metal cations. However, our understanding on the basic physical properties of the formation process and the stability of GQs is rather limited. In this work, we employed ab initio, molecular dynamics(MD), and steered MD(SMD)simulations to study the interaction between loop bases and ions, and the effect on the stability of G-quadruplex DNA, the Drude oscillator model was used in MD and SMD simulations as a computationally efficient manner method for modeling electronic polarization in DNA ion solutions. We observed that the binding energy between DNA bases and ions(K⁺/Na⁺)is about the base stacking free energies indicates that there will be a competition among the binding of M⁺-base, H-bonds between bases, and the base-stacking while ions were bound in loop of GQs. Our SMD simulations indicated that the side loop inclined to form the base stacking while the loop sequence was Thy or Ade, and the cross-link loop upon the G-tetrads was not easy to form the base stacking. The base stacking side loop complex K+was found to have a good stabilization synergy. Although a stronger interaction was observed to exist between Cyt and K+, such an interaction was unable to promote the stability of the loop with the sequence Cyt.     

Charge distribution and stability of charged carbon nanotubes

Density-functional calculations of charge distribution on negatively and positively charged nanotubes result in charge density profiles characterized by a significant increase of charge density at the tube ends. These results are in quantitative agreement with classical electrostatic analysis, which assumes constant electrostatic potential on the conductive tube surface. At high charging levels, the tube ends are observed to be unstable due to Coulomb repulsion. By combining ab initio calculations with classical electrostatics, we determine, as a function of tube length and geometry of the tube end, the critical voltage beyond which nanotubes are unstable.     

Charge transfer and stability of NFE random alloys

The stability of random alloys is determined primarily by a balance between the energy of the volume change upon alloy formation (elastic energy), and the charge transfer between atomic cells. The charge transfer in homovalent, nearly free electron alloys was determined by taking the wave function to be that of the free atoms inside the ion cores, and to be plane waves in the interstitial regions. For a given valence, it was possible to establish an electronegativity series based on charge transfer, to determine charge transfer as a function of composition, and to compute the energy of alloy formation. The theory properly accounts for the formation of alloys of the alkali and alkaline earth metals, and shows why so few such alloys form.     

Charge density waves effects on the phonon modes of 1T-TaS2

The effects of lattice distortion driven charge density waves on the 1T polytype of TaS₂ are reported. The results of a raman study of this transition metal dichalcogenide show features consistent with results previously reported using resistivity and electron diffraction techniques. The possibility of the presence of a phason mode in the raman spectra is suggested and the temperature dependence of this mode is fitted to the expected functional form.     

Charge overlap effects dependence on the nature of the interaction

The He-He, He-H(1s), H(1s)-H(1s) and H(1s)-H(2s) interactions are considered as model systems for studying how charge overlap effects in second-order dispersion energies vary as a function of the nature of the interacting species. The non-expanded second-order energy and the corresponding multipole R ^-1 expansions, through all powers of R ^-1, are obtained for each interaction using Unsöld's average energy approximation. The results are used to discuss the limitations of the usefulness of the R ^-1 expansions.     

Cooperativity of tetrel bonds tuned by substituent effects

Substituent effects on cooperativity between N···X and C···X interactions are studied in the 4-Z-Py···XH₃(NC)···XH₃(NC) complexes, where X = C, Si; Z = H, F, OH, CH₃, NH₂, F, NC, CN, NO₂ and Py = pyridine. All N···X and C···X binding distances in the ternary complexes are always shorter than those in the corresponding binary complex. This indicates that the formation of the N···X interaction strengthens C···X bond in these complexes and vice versa. Our results reveal that the strength of N···X and C···X interactions in the ternary complexes considerably depends on the nature of X and Z substituents. For a given aromatic system, the shortening of N···X and C···X distances is more important for SiH₃(NC) complexes than CH₃(NC) counterparts. The mechanism of cooperative effects in the ternary complexes is unveiled by electrostatic potential analyses and natural bond theory.     

Symmetric bifurcated halogen bonds: substituent and cooperative effects

ABSTRACT

The aim of this study is to investigate the geometries, interaction energies and bonding properties of the symmetrical bifurcated halogen bond interactions (BXBs) by means of ab initio calculations. For this purpose, the NCX (X = Cl, Br) molecule is paired with a series of N-formyl formamide (NFF) derivatives (NFF-Z, Z = H, CN, CCH, OH, CH₃ and Li), and the properties of the resulting complexes are studied by molecular electrostatic potential, quantum theory of atoms in molecules, noncovalent interaction index and natural bond orbital analyses. For a fixed NCX molecule, interaction energies increase in the order of Z = Li > CH₃ > H > OH > CCH > CN. We found a strong correlation between the interaction energies of NCX:NFF-Z complexes and molecular electrostatic potential minimum values associated with NFF-Z monomers. Moreover, cooperative effects between BXB and X???N halogen bond interactions are studied in the ternary NCX:NCX:NFF-Z systems. Our results indicate that the strength of BXB interactions in the ternary complexes is enhanced by the presence of X???N bonds. Besides, cooperativity effects tend to increase the covalency of BXBs in these systems.     

Charge transfer effects on the luminescent properties of Eu3+ in oxysulfides

Energy shifts of 4f⁶ states of Eu³⁺ in matrices, and phonon sidebands, linewidths and luminescence decay of Eu³⁺ in Ln₂O₂S (Ln=Lu, Y, Gd and La) have been studied. The charge transfer state (CTS) of Eu³⁺ is described by a model in which a hole is transferred from Eu³⁺ to ligands. Septet states obtained from the 4f⁷(⁸S) + hole configuration of CTS interact with the ⁷F term of the 4f⁶ configuration. This effect causes downward shifts of ⁷F_J states in matrices. Diffuse charge distributions for ⁷F_J states due to the mixing with CTS make the curvatuve of their adiabatic potential curves be smaller than that for ⁵D_J'. Such a difference in the potential curves between ⁷F_J and ⁵D_J' causes broadening of the absorption lines compared with the corresponding emission linewidths in Y₂O₂S. A dynamic Jahn-Teller model is proposed for the concentration-enhanced phonon sidebands accompanying 4f-4f transitions. The vibronics appear only in the excitation spectra and not in the emission spectra. Spectral distributions of the effective density of phonon states are obtained from the observed phonon sidebands for Ln₂O₂S: 5%Eu. The phonon spectra indicate delocalization of the 4f orbitals of Eu³⁺ with increasing the host-cation radius. The observed lifetimes of ⁵D₀ show a decrease in the same order due to decrease in the 4f-CTS mixing.     

An ab initio study on substituent and cooperative effects in bifurcated fluorine bonds

Bifurcated fluorine bond (BFB) interactions are studied in model binary complexes pairing N-formyl formamide derivatives and FX molecules (X = F, CN, NC, CF₃ and CCH) by means of ab initio calculations. The calculated F···O binding distances in these complexes are in the range of 2.813–3.048 Å. The corresponding interaction energies lie in a narrow range, from?2.25 to ?16.49 kJ/mol. The nature of BFBs is analysed by a vast number of methods including molecular electrostatic potential, quantum theory of atoms in molecules, non-covalent interaction index and natural bond orbital methods. According to the energy decomposition analysis, the electrostatic and dispersion effects have a dominant role in the formation of these complexes. The formation of a hydrogen- and lithium-bonding interaction tends to increase the strength of BFBs in the ternary XF:NFF-H:NH₃ and XF:NFF-Li:NH₃ complexes, respectively.     

Charge radii and polarization effects in the oxygen region

When using reasonable monopole polarization charges, it is possible to fit the systematics of charge radii in the oxygen region, if core-excited components are taken into account.     

Self-assembling effects and mechanisms of interchromophore interactions in porphyrin pentads

The directional self-assembly of nanosized, structurally organized pentads that include five tetrapyrrole macrocycles and are based on the two-point coordination interaction of two covalently bound dimers of Zn porphyrins (homo-and heterodimers) with molecules of either the free base or the Cu complex of tetrametapyridyl-substituted porphyrin extra ligand is implemented in methylcyclohexane at 295 K. Using the method of the density functional theory (DFT) in the B3LYP/6-31g(d) approximation, the geometry of the pentad is fully optimized and the main factors that determine its redox properties are determined. The energies of the lowest excited states of the pentad are calculated by the ZINDO/S method, and it is shown that the occurrence of identical molecules in the system facilitates the formation of excitonic states with different contributions from the charge-transfer component. The directional energy transfer and the photoinduced electron transfer, which leads to the formation of a low-lying charge-transfer state (CT state), are studied and the rate constants of these two processes are determined (k _ET ∼ 10¹¹ s⁻¹ and k _PET ≈ (1.8−6.0) × 10⁹ s⁻¹, respectively). The strong effect of the temperature of the solvent on the efficiency of relaxation processes in pentad complexes under study is revealed and studied. Roles played by the low-lying CT state and d-π exchange effects (the Cu-contained pentad) in fluorescence quenching of pentad complexes are determined.     

Charge distribution and covalency effects on mössbauer parameters in KFeS2

In this paper we report the effects of covalency on the Mössbauer Hyperfine parameters in KFeS₂. We emphasize the use of simple bonding schemes and models based on isomer shift calibration, point charge calculations and electronegativity differences in order to determine the ionic character of the atoms in the crystal. The previous Mossbauer spectroscopic work is also extended to liquid nitrogen temperature and it has been shown how the simple concept of electronegativity difference can also account for the order of magnitude of the measured saturation value of magnetic field.     

Humidity effects on the stability of a sandpile

Humidity is well-known to significantly affect the mechanical properties, static as well as dynamic, of granular materials. We present the method of humidification of granular media from an under-saturated vapor that we designed in order to experimentally quantify such moisture-induced effects under accurately-controlled humidity conditions. We report the quantitative measurements of the maximum angle of stability of a pile made of small glass beads, as a function of the relative vapor pressure, up to close to saturation. The results obtained with liquids differing in their wetting properties on glass, namely water and heptane, are presented. It is shown that the wetting properties of the liquid on the grains have a strong influence on the cohesion of the non-saturated granular medium. Received 26 October 1998 and Received in final form 30 March 1999     

Theoretical insight into the substituent effects on linear and nonlinear optical properties of azobenzene‐based chromophores

The linear and nonlinear optical properties of 4 kinds of experimental synthesized azobenzene‐based chromophores were investigated by different density functional theories (DFTs) upon the electronic structures. The structure‐property relationship was studied on each single molecule either in the gas phase or in diethylether and tetrahydrofuran (THF) solutions. The substituent effect on optical properties was revealed by checking the positions of substituent groups, and the influence of dynamic perturbation to the optical nonlinearity was investigated by simulating the experimental excitation. The results revealed that the substituent in the meta‐position of the azobenzene group affects the optical properties more significantly than that in the ortho‐position, which is in agreement with the experimental finding. The modulation of molecular hyperpolarizability of bridge‐substituted azobenzene derived by dynamic perturbation is not recommended because of the reduced dynamic hyperpolarizability relative to the static one. The different functions of the DFT method hardly affect the calculated results, while solvent effects of diethylether and THF solutions are significant on the optical properties, especially for optical nonlinearity. The information derived from the single chromophore may be helpful in the design and preparation of high‐performance nonlinear optical materials in further.     

Substituent effects on the conformational stability of allyl fluorides

By the B3P86/6‐311G(3d,2p) method, remote substituent effects on trans‐YCH?CHCH₂F were investigated by examining their conformational stabilities, molecular geometries, and stereoelectronic interactions in this paper. The cis conformer is favored for Y?H, Cl, Me, Vinyl, CF₃, CN, CHO, and NO₂, whereas the gauche is favored for Y?OMe, OH. A correlation of ΔH with the substituent constants σ⁺(Y) shows that the increasing electron‐withdrawing ability of the substituent Y increases the relative stability of the cis conformer. It was found that the substituent effect on the molecule stabilization energies (relative to CH₂?CHCH₂F) is more significant in the gauche conformers than in the cis conformers. In agreement, molecular structures of the gauche conformers were also observed to vary more significantly with the substitution than those of the cis conformers. By the second‐order perturbation energy (E(2)) in NBO analysis, it was found that the total C₂–C₃ vicinal hyperconjugation is determinant in the enthalpy difference and consequently controls the conformational stability. Further analysis shows that the substituent effect on the C₂–C₃ vicinal hyperconjugations is much higher in the gauche conformers than in the cis conformers. The highly sensitive π_C?C→σ*_{C? F} interaction to the substitution in the gauche conformers, is the leading factor in variation of molecular stability and geometry. Copyright © 2010 John Wiley & Sons, Ltd.     

Dielectrophoretic transients effects on liquid stability

Effects of dielectrophoretic transients on stability ofn-pentane and methyl methacrylate have been experimentally studied. Dielectrophoretic transients have been found to demonstrate anomalous effects in methyl methacrylate. The effects are observed both on the application of electric field and its subsequent turning off to zero and are equal in magnitude and direction during both the operations. Results have been explained on the basis of the body forces acting on the dielectric in presence of a non-uniform electric field and a temperature gradient. Heater surface thermodynamics has been studied under controlled temperature and electric field gradients. A striking feature of the experiment is the application of a high voltage directly on the heater surface making the body force calculations more realistic.     

Combined effects of pressure and temperature on enzyme stability

Abstract

The effect of high temperature and high hydrostatic pressure on the residual hydrolytic activity of a commercial Rhizomucor miehei lipase has been studied. Inactivation at high temperature and/or high pressure was carried out. Under non-denaturing pressure conditions, results showed that pressurisation protects enzymes against thermal deactivation. This is in accordance with previous results obtained with enzymes from mesophilic sources, such as invertase and galactosidases.     

The effects of plasma treatment on the thermal stability of HfO2 thin films

The thermal stability of pure HfO₂ thin films is not high enough to withstand thermal processes, such as S/D activation or post-metal annealing, in modern industrial CMOS production. In addition, plasma nitridation technology has been employed for increasing the dielectric constant of silicon dioxide and preventing boron penetration. In this experiment, atomic layer deposition (ALD) technology was used to deposit HfO₂ thin films and inductively coupled plasma (ICP) technology was used to perform plasma nitridation process. The C-V and J-V characteristics of the nitrided samples were observed to estimate the effect of the nitridation process. According to this study, plasma nitridation process would be an effective method to improve the thermal stability of HfO₂ thin films.