Atomistic understanding of the C·T mismatched DNA base pair tautomerization via the DPT: QM and QTAIM computational approaches

It was established that the cytosine·thymine (C·T) mismatched DNA base pair with cis‐oriented N1H glycosidic bonds has propeller‐like structure (|N3C4C4N3| = 38.4°), which is stabilized by three specific intermolecular interactions–two antiparallel N4H…O4 (5.19 kcal mol^?1) and N3H…N3 (6.33 kcal mol^?1) H‐bonds and a van der Waals (vdW) contact O2…O2 (0.32 kcal mol^?1). The C·T base mispair is thermodynamically stable structure (ΔG_int = ?1.54 kcal mol^?1) and even slightly more stable than the A·T Watson–Crick DNA base pair (ΔG_int = ?1.43 kcal mol^?1) at the room temperature. It was shown that the C·T ? C*·T* tautomerization via the double proton transfer (DPT) is assisted by the O2…O2 vdW contact along the entire range of the intrinsic reaction coordinate (IRC). The positive value of the Grunenberg's compliance constants (31.186, 30.265, and 22.166 Å/mdyn for the C·T, C*·T*, and TS_{C·T ? C*·T*}, respectively) proves that the O2…O2 vdW contact is a stabilizing interaction. Based on the sweeps of the H‐bond energies, it was found that the N4H…O4/O4H…N4, and N3H…N3 H‐bonds in the C·T and C*·T* base pairs are anticooperative and weaken each other, whereas the middle N3H…N3 H‐bond and the O2…O2 vdW contact are cooperative and mutually reinforce each other. It was found that the tautomerization of the C·T base mispair through the DPT is concerted and asynchronous reaction that proceeds via the TS_{C·T ? C*·T*} stabilized by the loosened N4? H? O4 covalent bridge, N3H…N3 H‐bond (9.67 kcal mol^?1) and O2…O2 vdW contact (0.41 kcal mol^?1). The nine key points, describing the evolution of the C·T ? C*·T* tautomerization via the DPT, were detected and completely investigated along the IRC. The C*·T* mispair was revealed to be the dynamically unstable structure with a lifetime 2.13·× 10^?13 s. In this case, as for the A·T Watson–Crick DNA base pair, activates the mechanism of the quantum protection of the C·T DNA base mispair from its spontaneous mutagenic tautomerization through the DPT. © 2013 Wiley Periodicals, Inc.     

The accuracy of some formulae for the interconversion of creep and stress-relaxation data

The accuracy of the approximation formulaeJ (t) ~ 1/G (t) andd lnJ (t)/d lnt ~ —d lnG (t)/d lnt, which interconnect stress-relaxation modulusG (t) and creep complianceJ (t) and their double logarithmic rates are investigated. For glassy polymers, the errors in the first formula are less than 1–2%, and in the second, they are generally in the order of a few percent, too. Similar estimates can also be found for the real parts of the analogous complex functionsJ ^* () andG ^* ().     

3-d Model for strain ordering in steel: I Static effects

We present a spring-defect model in 3-dimensions to describe the connection between elastic distortion and interstitial carbon ordering associated with phase transition from a body centred cubic (BCC) to body centered tetragonal (BCT) structure in BCC metals such as α-iron. The presence or the absence of the carbon is modelled in terms of a pseudo spinŝ=+1or -l.An Ising interaction between carbon atoms is recovered after eliminating the lattice degrees of freedom, which is longranged. The coupling between the spin and lattice degrees of freedom allows for a systematic study of ferroelasticity and the variation of the lattice parameter with carbon concentration. The mean field results for the paraelastic to ferroelastic transition, lattice parameter and static compliance are presented. The significant feature of this calculation is not only a derivation of the defect-defect interaction, but also an explicit calculation of the strain dipole tensor associated with each defect, from a microscopic model.     

Calculation of discrete relaxation modulus and creep compliance

Müntz theorems from classical approximation theory are used to lay the mathematical foundations for discrete spectral representations of the relaxation modulus and creep conpliance. Algorithms that can automatically generate nonnegative discrete relaxation and retardation strengths are formulated by using the nonnegative least square method. Received: 30 September 1998 Accepted: 20 May 1999     

Minimum value assured by a method to determine gold in alloys by using laser-induced breakdown spectroscopy and partial least-squares calibration model

A procedure for estimating the minimum value assured by an analytical method has been developed. It is applied to the determination of gold in jewellery alloys by means of a recently proposed spectroscopy technique. The laser-induced breakdown spectroscopic data of 17 gold alloys, with gold concentration ranging between 50 and 100% were used as calibration set for carrying out the partial least-squares regression (PLS). Ninety alloys, with known gold concentration, were used to evaluate the method’s accuracy. Finally, the minimum guaranteed value of the gold content was analysed, taking into account the values for gold hallmark in Spanish regulations.     

ENVIRONMENTAL COMPLIANCE AND OPTIMAL OIL AND GAS EXPLOITATION

This paper examines the impacts of environmental regulations on firms in the oil and gas industry. A model is developed using optimal control theory, which extends the existing models by incorporating the environmental compliance costs into the exploration and production stages. An approach for measuring the cumulative impacts of these regulations on the firm's exploration and production is presented. The results indicate that rising environmental compliance costs lead to reductions in investment and production, and the alteration of investment and production profiles. This implies that less resources will be developed and associated economic benefit will decline. Therefore, it is vital for policy makers to consider carefully whether the perceived environmental benefits derived from these regulations justify associated compliance costs.     

Ophthalmic Glucose Monitoring Using Disposable Contact Lenses—A Review

We have developed a range of disposable and colorless tear glucose sensing contact lenses, using off-the-shelf lenses embedded with new water soluble, highly fluorescent and glucose sensitive boronic acid containing fluorophores. The new lenses are readily able to track tear glucose levels and therefore blood glucose levels, which are ideally suited for potential use by diabetics. The fluorescence responses from the lenses can be monitored using simple excitation and emission detection devices. The novelty of our approach is two fold. Firstly, the notion of sensing extremely low glucose concentrations in tears, which track blood levels, by our contact lens approach, and secondly, the unique compatibility of our new glucose signaling probes with the internal mildly acidic contact lens environment. The new lenses are therefore ideal for the non-invasive and continuous monitoring of tear glucose, with about 15-min response time, and a measured shelf life in excess of 3 months. In this review article, we show that fluorescence based signaling using plastic disposable lenses, which have already been industrially optimized with regard to vision correction and oxygen/analyte permeability etc, may a notable alternative to invasive and random finger pricking, the most widely used glucose monitoring technology by diabetics.     

Cumulative solutions of nonlinear longitudinal vibration in isotropic solid bars

Based on the strain invariant relationship and taking the high-order elastic energy into account, a nonlinear wave equation is derived, in which the excitation, linear damping, and the other nonlinear terms are regarded as the first-order correction to the linear wave equation. To solve the equation, the biggest challenge is that the secular terms exist not only in the fundamental wave equation but also in the harmonic wave equation （unlike the Duffing oscillator, where they exist only in the fundamental wave equation）. In order to overcome this difficulty and to obtain a steady periodic solution by the perturbation technique, the following procedures are taken： （i） for the fundamental wave equation, the secular term is eliminated and therefore a frequency response equation is obtained; （ii） for the harmonics, the cumulative solutions are sought by the Lagrange variation parameter method. It is shown by the results obtained that the second- and higher-order harmonic waves exist in a vibrating bar, of which the amplitude increases linearly with the distance from the source when its length is much more than the wavelength; the shift of the resonant peak and the amplitudes of the harmonic waves depend closely on nonlinear coefficients; there are similarities to a certain extent among the amplitudes of the odd- （or even-） order harmonics, based on which the nonlinear coefficients can be determined by varying the strain and measuring the amplitudes of the harmonic waves in different locations.     

Long-term behavior of mineral-filled polymer composites modeled by discrete spectra

A discrete spectra transformation technique is used for the processing and analysis of long-term stress relaxation and creep compliance data of mineral-filled polymer composites. A non-linear regression simultaneously adjusts the parameters of N discrete relaxation or retardation spectra. For small N the solution is insensitive to the choice of regression starting value sets. From the relaxation time spectrum a corresponding discrete retardation spectrum and creep compliance can be calculated using the Laplace transform and vice versa. The analysis of long-term (more than 1200 days) both relaxation and retardation experimental data demonstrates the applicability of the transformation technique. Comparisons of the experimental and calculated spectra are given. The influence of the filler amount is demonstrated.