NMR studies of chloroform@cryptophane-A and chloroform@bis-cryptophane inclusion complexes oriented in thermotropic liquid crystals

Oriented inclusion complexes of chloroform@cryptophane-A and chloroform@bis-cryptophane were prepared using a nematic thermotropic liquid crystal (ZLI 1132), and the alignment and magnetic resonance properties of these host-guest systems were studied via (13)C NMR of the labeled guests. Large (1)H-(13)C dipolar splittings for (13)CHCl(3) guests indicated significantly enhanced (approximately 2-fold) ordering for the trapped vs. free ligands under all conditions studied, with similar ordering observed for the two complexes-despite significant differences in size and motional freedom between the hosts. For each environment, variable-temperature studies permitted the sign and magnitude of the order parameter for chloroform's C-H bond to be independently determined from the (13)C chemical shift anisotropy (CSA) shifts (via the gradient method) and the restored (1)H-(13)C dipolar couplings. In both systems, the results are consistent with overall alignment of the complexes such that the cage principal axis lies roughly perpendicular to the LC director.     

Bisignate resonance Raman optical activity: a pseudo breakdown of the single electronic state model of RROA?

Raman optical activity (ROA) spectra were calculated for a set of conformers of astaxanthin, which is a non‐rigid molecule exhibiting strong resonance enhancement in the visible range. Single electronic state theory of the Resonance ROA (RROA) predicts the spectrum to be monosigned. For astaxanthin, it appeared that some of the conformers exhibit different sign of the bands than the other conformers. As a result, the conformer population averaged spectrum of astaxanthin can exhibit both signs of the bands, or be monosigned depending on which conformers are dominating, that reflects a departure from the single electronic state approximation. Moreover, use of different basis sets and/or density functional theory (DFT) functionals results in different conformer populations, thus yielding again either monosigned ROA spectrum or with bands of both signs. Consequences of these two findings for the astaxanthin RROA spectrum are discussed. Copyright © 2014 John Wiley & Sons, Ltd.     

Modeling of particle transport and combustion phenomena in a large-scale circulating fluidized bed boiler using a hybrid Euler-Lagrange approach

The constantly developing fiuidized combustion technology has become competitive with a conventional pulverized coal （PC） combustion. Circulating fluidized bed （CFB） boilers can be a good alternative to PC boilers due to their robustness and lower sensitivity to the fuel quality. However, appropriate engineering tools that can be used to model and optimize the construction and operating parameters of a CFB boiler still require development. This paper presents the application of a relatively novel hybrid Euler-Lagrange approach to model the dense gas-solid flow combined with a combustion process in a large-scale indus- trial CFB boiler. In this work, this complex flow has been resolved by applying the ANSYS FLUENT 14.0 commercial computational fluid dynamics （CFD） code. To accurately resolve the multiphase flow, the original CFD code has been extended by additional user-defined functions. These functions were used to control the boiler mass load, particle recirculation process （simplified boiler geometry）, and interphase hydrodynamic properties. This work was split into two parts. In the first part, which is referred to as pseudo combustion, the combustion process was not directly simulated. Instead, the effect of the chemi- cal reactions was simulated by modifying the density of the continuous phase so that it corresponded to the mean temperature and composition of the flue gases, In this stage, the particle transport was simu- lated using the standard Euler-Euler and novel hybrid Euler-Lagrange approaches, The obtained results were compared against measured data, and both models were compared to each other. In the second part, the numerical model was enhanced by including the chemistry and physics of combustion. To the best of the authors＇ knowledge, the use of the hybrid Euler-Lagrange approach to model combustion is a new engineering application of this model, In this work, the combustion process was modeled for air-fuel combustion. The simulation results were compared with experimental data.     

Comparison of the standard Euler-Euler and hybrid Euler-Lagrange approaches for modeling particle transport in a pilot-scale circulating fluidized bed

Particle transport phenomena in small-scale circulating fiuidized beds （CFB） can be simulated using the Euler-Euler, discrete element method, and Euler-Lagrange approaches. In this work, a hybrid Euler-Lagrange model known as the dense discrete phase model （DDPM）, which has common roots with the multiphase particle-in-cell model, was applied in simulating particle transport within a mid-sized experimental CFB facility. Implementation of the DDPM into the commercial ANSYS Fluent CFD package is relatively young in comparison with the granular Eulerian model. For that reason, validation of the DDPM approach against experimental data is still required and is addressed in this paper. Additional difficulties encountered in modeling fluidization processes are connected with long calculation times. To reduce times, the complete boiler models are simplified to include just the combustion chamber. Such simplifications introduce errors in the predicted solid distribution in the boiler. To investigate the conse- quences of model reduction, simulations were made using the simplified and complete pilot geometries and compared with experimental data. All simulations were performed using the ANSYSFLUENT 14.0 package. A set of user defined functions were used in the hybrid DDPM and Euler-Euler approaches to recirculate solid particles.     

Solvent effects on electron-driven proton-transfer processes: adenine-thymine base pairs

Time-Dependent Density Functional Theory (TD-DFT) computations, with M05-2X and PBE0 functionals, have been employed for a detailed study of the Electron-Driven Proton-Transfer (PT) processes in an Adenine-Thymine Watson-Crick Base Pair in the gas phase and in solution, with the bulk solvent described by the polarizable continuum model. In the gas phase, TD-DFT computations predict that the Adenine → Thymine Charge Transfer (CT) excited state undergoes a barrierless PT reaction, in agreement with CC2 computations (S. Perun, A. Sobolewski, W. Domcke, J. Phys. Chem. A, 2006, 110, 9031.). The good agreement between the TD-DFT approach and CC2 results validates the former for the studies of excited state properties, excited state proton transfer reaction, and deactivation mechanisms in the DNA base pairs. Next, it is shown that inclusion of solvent effects significantly influences the possibility of both barrier-less excited state proton transfer and radiation-less deactivation through conical intersection with the ground state, affecting the energy of the CT excited state in the Franck-Condon region, the energy barrier associated to the PT process and the energy gap with the ground electronic state. These findings clearly indicate that environmental effects, with a special attention to proper treatment of dynamical solvation effects, have to be included for reliable computational analysis of photophysical and photochemical processes occurring in condensed phases.     

The effect of point mutation on the equilibrium structural fluctuations of ferric Myoglobin

The ultrafast equilibrium fluctuations of the Fe(III)-NO complex of a single point mutation of Myoglobin (H64Q) have been studied using Fourier Transform 2D-IR spectroscopy. Comparison with data from wild type Myoglobin (wt-Mb) shows the presence of two conformational substates of the mutant haem pocket where only one exists in the wild type form. One of the substates of the mutant exhibits an almost identical NO stretching frequency and spectral diffusion dynamics to wt-Mb while the other is distinctly different in both respects. The remarkably contrasting dynamics are largely attributable to interactions between the NO ligand and a nearby distal side chain which provides a basis for understanding the roles of these side chains in other ferric haem proteins.     

Luminescent Di‐ and Polynuclear Organometallic Gold(I)–Metal (Au2, {Au2Ag}n and {Au2Cu}n) Compounds Containing Bidentate Phosphanes as Active Antimicrobial Agents

The reaction of new dinuclear gold(I) organometallic complexes containing mesityl ligands and bridging bidentate phosphanes [Au₂(mes)₂(μ‐LL)] (LL=dppe: 1,2‐bis(diphenylphosphano)ethane 1 a , and water‐soluble dppy: 1,2‐bis(di‐3‐pyridylphosphano)ethane 1 b ) with Ag⁺ and Cu⁺ lead to the formation of a family of heterometallic clusters with mesityl bridging ligands of the general formula [Au₂M(μ‐mes)₂(μ‐LL)][A] (M=Ag, A=ClO₄^?, LL=dppe 2 a , dppy 2 b ; M=Ag, A=SO₃CF₃^?, LL=dppe 3 a , dppy 3 b ; M=Cu, A=PF₆^?, LL=dppe 4 a , dppy 4 b ). The new compounds were characterized by different spectroscopic techniques and mass spectrometry The crystal structures of [Au₂(mes)₂(μ‐dppy)] ( 1 b ) and [Au₂Ag(μ‐mes)₂(μ‐dppe)][SO₃CF₃] ( 3 a ) were determined by a single‐crystal X‐ray diffraction study. 3 a in solid state is not a cyclic trinuclear Au₂Ag derivative but it gives an open polymeric structure instead, with the {Au₂(μ‐dppe)} fragments “linked” by {Ag(μ‐mes)₂} units. The very short distances of 2.7559(6) Å (Au? Ag) and 2.9229(8) Å (Au? Au) are indicative of gold–silver (metallophilic) and aurophilic interactions. A systematic study of their luminescence properties revealed that all compounds are brightly luminescent in solid state, at room temperature (RT) and at 77 K, or in frozen DMSO solutions with lifetimes in the microsecond range and probably due to the self‐aggregation of [Au₂M(μ‐mes)₂(μ‐LL)]⁺ units (M=Ag or Cu; LL=dppe or dppy) into an extended chain structure, through Au? Au and/or Au? M metallophilic interactions, as that observed for 3 a . In solid state the heterometallic Au₂M complexes with dppe ( 2 a – 4 a ) show a shift of emission maxima (from ca. 430 to the range of 520‐540 nm) as compared to the parent dinuclear organometallic product 1 a while the complexes with dppy ( 2 b–4 b ) display a more moderate shift (505 for 1 b to a max of 563 nm for 4 b ). More importantly, compound [Au₂Ag(μ‐mes)₂(μ‐dppy)]ClO₄ ( 2 b ) resulted luminescent in diluted DMSO solution at room temperature. Previously reported compound [Au₂Cl₂(μ‐LL)] (LL dppy 5 b ) was also studied for comparative purposes. The antimicrobial activity of 1–5 and Ag[A] (A=ClO₄^?, SO₃CF₃^?) against Gram‐positive and Gram‐negative bacteria and yeast was evaluated. Most tested compounds displayed moderate to high antibacterial activity while heteronuclear Au₂M derivatives with dppe ( 2 a – 4 a ) were the more active (minimum inhibitory concentration 10 to 1 μg mL^?1). Compounds containing silver were ten times more active to Gram‐negative bacteria than the parent dinuclear compound 1 a or silver salts. Au₂Ag compounds with dppy ( 2 b , 3 b ) were also potent against fungi.     

Search for the standard model Higgs boson in the diphoton decay channel with 4.9 fb(-1) of pp collision data at √s=7 TeV with ATLAS

A search for the standard model Higgs boson is performed in the diphoton decay channel. The data used correspond to an integrated luminosity of 4.9 fb(-1) collected with the ATLAS detector at the Large Hadron Collider in proton-proton collisions at a center-of-mass energy of √s=7 TeV. In the diphoton mass range 110-150 GeV, the largest excess with respect to the background-only hypothesis is observed at 126.5 GeV, with a local significance of 2.8 standard deviations. Taking the look-elsewhere effect into account in the range 110-150 GeV, this significance becomes 1.5 standard deviations. The standard model Higgs boson is excluded at 95% confidence level in the mass ranges of 113-115 GeV and 134.5-136 GeV.     

Search for scalar bottom quark pair production with the ATLAS detector in pp collisions at sqrt[s]=7 TeV

The results of a search for pair production of the scalar partners of bottom quarks in 2.05 fb(-1) of pp collisions at sqrt[s]=7 TeV using the ATLAS experiment are reported. Scalar bottom quarks are searched for in events with large missing transverse momentum and two jets in the final state, where both jets are identified as originating from a bottom quark. In an R-parity conserving minimal supersymmetric scenario, assuming that the scalar bottom quark decays exclusively into a bottom quark and a neutralino, 95% confidence-level upper limits are obtained in the b(1) - χ(1)(0) mass plane such that for neutralino masses below 60 GeV scalar bottom masses up to 390 GeV are excluded.     

The effect of mechanical activation on the thermal reactions of P2O5–Al2O3–Fe2O3–Na2O phosphate glasses

The effect of mechanical activation on the structure and thermal reactions of glasses has been studied on the example of Na–Al–Fe phosphate glasses. These glasses are used in nuclear technology for immobilization of radioactive waste. The glasses were activated by grinding in a planetary mill. Mechanical activation causes a decrease of the T _g temperature as well as of the glass crystallization temperature. The type of crystalline phases formed and the quantitative proportions between them are changing. Analysis of inter-atomic interactions in the structure of glass was applied to explain the observed regularities governing the crystallization of the activated glasses.