Nonlinear optical properties in calix[n]arenes: orientation effects of monomers

We investigate the nonlinear optical (NLO) polarizations for various geometric arrangements of the dipolar chromophores in a calix[n]arene geometry. The interactions were studied by using (HF)3 as model compounds both in parallel and frustrated orientations. The interdipolar angle between the monomer molecules is varied so that many different arrangements of the dipoles can be realized which is associated with the opening up of the calix[n]arene rings. Quantum-chemical calculations at both ab initio and semiempirical levels, show that the all-parallel arrangement of the dipoles exhibit the maximum magnitude for the nonlinear optical coefficients at small interdipolar angles for all interdipolar distances. In the frustrated orientations however, the NLO response is maximum at large interdipolar angles corresponding to the flattened calix[n]arene rings. The role of hydrogen bonding in stabilizing these assemblies in various conformations has been investigated. Crystallographic database analysis for calix[3]arenes shows that optical properties in real molecular systems can be modeled based on our simple interaction theory.     

Blood Coagulation and Living Tissue Sterilization by Floating-Electrode Dielectric Barrier Discharge in Air

Thermal plasma discharges have been widely used in the past for treatment of living human and animal tissue. However, extensive thermal damage and tissue desiccation occurs due to extreme temperatures. Some solutions have been offered where the temperature is lowered by short current pulses, addition of noble gases, or significant decrease in the size of treatment electrodes. We propose a method of direct treatment of living tissue that occurs at room temperature and pressure without visible or microscopic tissue damage. The presented Floating-Electrode Dielectric Barrier Discharge plasma is proven electrically safe to human subjects and our results show no gross (visual) or histological (microscopic) damage to skin samples in minutes, complete tissue sterilization from skin flora in seconds, and blood clot formation in seconds of electric plasma treatment. We also observe significant hastening of blood clot formation via electric plasma induced catalysis of “natural” processes occurring in human blood. A model describing these processes is offered.An erratum to this article can be found at     

Odd-even oscillations in first hyperpolarizability of dipolar chromophores: role of conformations of spacers

Quantum chemical calculations on the linear and nonlinear electric polarizabilities of dipolar molecules separated by the alkyl spacers have been performed on O(2)N-Ph-N=N-Ph-(CH(2))(n)-Ph-N=N-Ph-NO(2), n = 1-12. These molecules exhibit a very strong odd-even behavior in the first hyperpolarizabilities (beta), with large (small) beta for n = odd (n = even). Such odd-even oscillations have been reported experimentally on similar systems, but the origin of such phenomena remains unclear. We propose it to be due to the role of the conformational orientation of the intervening alkyl spacers that leads to eclipsed orientation (parallel) of the dipoles for n = odd chains while staggered orientation (antiparallel) for n = even chains. The energy difference between the two extreme angular forms is approximately 6-8 kcal/mol, clearly more than the thermal fluctuations at room temperature. These conformational orientations will be preserved, leading to different packing arrangements at the macroscopic scale. We believe that it is this interaction at the molecular scale that controls such a macromolecular property.     

New examples of metalloaromatic Al-clusters: (Al4M4)Fe(CO)3 (M = Li, Na and K) and (Al4M4)2Ni: rationalization for possible synthesis

Ab initio calculations reveal that all-metal antiaromatic molecules like Al4M4 (M = Li, Na and K) can be stabilized in half sandwich (Al4M4)Fe(CO)3 and full sandwich (Al4M4)2Ni complexes. The formation of the full sandwich complex [(Al4M4)2Ni] from its organometallic precursor depends on the stability of the organic-inorganic hybrid (C4H4)Ni(Al4Li4).     

Aromatic superclusters from all-metal aromatic and antiaromatic monomers, [Al4]2- and [Al4]4-

Calculations on the structures of dimers of all-metal aromatic and anti-aromatic molecules such as (Al4(2-)) and (Al4(4-)) reveal that, unlike their organic counterparts such as benzene and cyclobutadiene which form pi-stacked complexes, these molecules form new clusters with no reminiscence of the original units. These clusters have a very large binding energy and can be further stabilized through charge-balance by counterions and solvents.     

Lithium silicate nanosheets with excellent capture capacity and kinetics with unprecedented stability for high-temperature CO2 capture

An excessive amount of CO₂ is the leading cause of climate change, and hence, its reduction in the Earth''s atmosphere is critical to stop further degradation of the environment. Although a large body of work has been carried out for post-combustion low-temperature CO₂ capture, there are very few high temperature pre-combustion CO₂ capture processes. Lithium silicate (Li₄SiO₄), one of the best known high-temperature CO₂ capture sorbents, has two main challenges, moderate capture kinetics and poor sorbent stability. In this work, we have designed and synthesized lithium silicate nanosheets (LSNs), which showed high CO₂ capture capacity (35.3 wt% CO₂ capture using 60% CO₂ feed gas, close to the theoretical value) with ultra-fast kinetics and enhanced stability at 650 °C. Due to the nanosheet morphology of the LSNs, they provided a good external surface for CO₂ adsorption at every Li-site, yielding excellent CO₂ capture capacity. The nanosheet morphology of the LSNs allowed efficient CO₂ diffusion to ensure reaction with the entire sheet as well as providing extremely fast CO₂ capture kinetics (0.22 g g⁻¹ min⁻¹). Conventional lithium silicates are known to rapidly lose their capture capacity and kinetics within the first few cycles due to thick carbonate shell formation and also due to the sintering of sorbent particles; however, the LSNs were stable for at least 200 cycles without any loss in their capture capacity or kinetics. The LSNs neither formed a carbonate shell nor underwent sintering, allowing efficient adsorption–desorption cycling. We also proposed a new mechanism, a mixed-phase model, to explain the unique CO₂ capture behavior of the LSNs, using detailed (i) kinetics experiments for both adsorption and desorption steps, (ii) in situ diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy measurements, (iii) depth-profiling X-ray photoelectron spectroscopy (XPS) of the sorbent after CO₂ capture and (iv) theoretical investigation through systematic electronic structure calculations within the framework of density functional theory (DFT) formalism.

Capturing CO₂ before its release. Lithium silicate nanosheets showed high CO₂ capture capacity (35.3 wt%) with ultra-fast kinetics (0.22 g g⁻¹ min⁻¹) and enhanced stability at 650 °C for at least 200 cycles, due to mixed-phase-model of CO₂ capture.     

Understanding the Influence of Donor-Acceptor Diazo Compounds on the Catalyst Efficiency of B(C6F5)3 Towards Carbene Formation

Diazo compounds have been largely used as carbene precursors for carbene transfer reactions in a variety of functionalization reactions. However, the ease of carbene generation from the corresponding diazo compounds depends upon the electron donating/withdrawing substituents either side of the diazo functionality. These groups strongly impact the ease of N₂ release. Recently, tris(pentafluorophenyl)borane [B(C₆F₅)₃] has been shown to be an alternative transition metal-free catalyst for carbene transfer reactions. Herein, a density functional theory (DFT) study on the generation of carbene species from α-aryl α-diazocarbonyl compounds using catalytic amounts of B(C₆F₅)₃ is reported. The significant finding is that the efficiency of the catalyst depends directly on the nature of the substituents on both the aryl ring and the carbonyl group of the substrate. In some cases, the boron catalyst has negligible effect on the ease of the carbene formation, while in other cases there is a dramatic reduction in the activation energy of the reaction. This direct dependence is not commonly observed in catalysis and this finding opens the way for intelligent design of this and other similar catalytic reactions.     

Rational Design of Biaxial Tensile Strain for Boosting Electronic and Ionic Conductivities of Na2MnSiO4 for Rechargeable Sodium-Ion Batteries

Using first-principles calculations, biaxial tensile (ϵ=2 and 4 %) and compressive (ϵ=−2 and −4 %) straining of Na₂MnSiO₄ lattices resulted into radial distance cut offs of 1.65 and 2 Å, respectively, in the first and second nearest neighbors shell from the center. The Si−O and Mn−O bonds with prominent probability density peaks validated structural stability. Wide-band gap of 2.35 (ϵ=0 %) and 2.54 eV (ϵ=−4 %), and narrow bandgap of 2.24 eV (ϵ=+4 %) estimated with stronger coupling of p–d σ bond than that of the p–d π bond, mainly contributed from the oxygen p-state and manganese d-state. Na⁺-ion diffusivity was found to be enhanced by three orders of magnitude as the applied biaxial strain changed from compressive to tensile. According to the findings, the rational design of biaxial strain would improve the ionic and electronic conductivity of Na₂MnSiO₄ cathode materials for advanced rechargeable sodium-ion batteries.     

Cooperative interactions in supramolecular aggregates: linear and nonlinear responses in calix[4]arenes.

The linear and nonlinear optical polarizabilities of donor-acceptor (D-pi-A) chromophores in confined geometries of calix[4]arenes are investigated through a model for interacting polar-polarizable molecules. Both the linear polarizability (alpha) and the first hyperpolarizability (beta) decrease with increasing the interdipolar angle, as expected in the oriented-gas picture. However, within the polar-polarizable model we predict deviations from the additive result, irrespective of the interdipolar angle. Depending on the nature of the chromophore, electrostatic intermolecular interactions between polar and polarizable chromophores lead to cooperative damping or enhancement of the optical responses. Specifically, for chromophores whose ground state is dominated by the neutral D-pi-A structure both alpha and beta are suppressed with respect to the prediction of the oriented-gas model, whereas the opposite holds true for chromophores whose ground state is dominated by the zwitterionic D(+)-pi-A(-). These results explain recent experimental data on a calix[4]arene functionalized with a donor-acceptor dye for nonlinear optical applications. Density functional theory calculations on the relevant crystal structure further support our interpretation.     

Precise frequency measurements of atomic transitions by use of a Rb-stabilized resonator

We demonstrate a technique for frequency measurements of atomic transitions with a precision of 30 kHz. The frequency is measured with a ring-cavity resonator whose length is calibrated against a reference laser locked to the D2 line of 87Rb, the frequency of which is known with 10-kHz accuracy. We have used this method to measure the hyperfine structure in the 5P(3/2) state of 85Rb. We obtain precise values for the hyperfine constants, A = 25.041(6) MHz and B = 26.013(25) MHz, and a value of 77.992(20) MHz for the isotope shift in the D2 line.