An asymmetric iodolactonization reaction catalyzed by a zinc bis-proline–phenol complex

The intramolecular zinc bis-proline-phenol complex 2a was found to promote enantioselective iodolactonization reactions of both electron-rich and electron-poor 5-aryl-5-hexenoic acids affording δ-iodolactones in good chemical yields with up to 82% enantiomeric excess. The reactions were found to be insensitive to air and moisture, providing an experimentally simple protocol for synthetically useful compounds.     

The Effect of the Molecular Weight of Polyvinylpyrrolidone and the Model Drug on Laser-Induced In Situ Amorphization

Laser radiation has been shown to be a promising approach for in situ amorphization, i.e., drug amorphization inside the final dosage form. Upon exposure to laser radiation, elevated temperatures in the compacts are obtained. At temperatures above the glass transition temperature (T_g) of the polymer, the drug dissolves into the mobile polymer. Hence, the dissolution kinetics are dependent on the viscosity of the polymer, indirectly determined by the molecular weight (M_w) of the polymer, the solubility of the drug in the polymer, the particle size of the drug and the molecular size of the drug. Using compacts containing 30 wt% of the drug celecoxib (CCX), 69.25 wt% of three different M_w of polyvinylpyrrolidone (PVP: PVP12, PVP17 or PVP25), 0.25 wt% plasmonic nanoaggregates (PNs) and 0.5 wt% lubricant, the effect of the polymer M_w on the dissolution kinetics upon exposure to laser radiation was investigated. Furthermore, the effect of the model drug on the dissolution kinetics was investigated using compacts containing 30 wt% of three different drugs (CCX, indomethacin (IND) and naproxen (NAP)), 69.25 wt% PVP12, 0.25 wt% PN and 0.5 wt% lubricant. In perfect correlation to the Noyes–Whitney equation, this study showed that the use of PVP with the lowest viscosity, i.e., the lowest M_w (here PVP12), led to the fastest rate of amorphization compared to PVP17 and PVP25. Furthermore, NAP showed the fastest rate of amorphization, followed by IND and CCX in PVP12 due to its high solubility and small molecular size.     

Towards a nanorisk appraisal framework

The article discusses, in the context of nanotechnology, whether current concepts of chemical risk assessment can be used to assess nanorisk. Nanorisk can be defined from the narrow (eco)toxicological perspective to the broader sense to include societal/cultural impacts or even to the fundamental philosophical level, i.e. questioning societies need for the technology. We outline here the limitations of chemical risk assessment and other recent proposed risk governance paradigms in relation to nanotechnology and nanomaterials, including its inability to include societal risks (ownership, privacy, security, nanodivide,¹ convergence of nano-, bio-, etc.) and metaphysical risk (including the lay persons perspective on the risks of nanotechnology). Finally, we outline the fundamental principles and criteria that an alternative comprehensive framework should be based on.     

A spectral method for elliptic equations: the Neumann problem

Let Ω be an open, simply connected, and bounded region in ℝ ^d , d ≥ 2, and assume its boundary ∂Ω is smooth. Consider solving the elliptic partial differential equation − Δu + γu = f over Ω with a Neumann boundary condition. The problem is converted to an equivalent elliptic problem over the unit ball B, and then a spectral method is given that uses a special polynomial basis. In the case the Neumann problem is uniquely solvable, and with sufficiently smooth problem parameters, the method is shown to have very rapid convergence. Numerical examples illustrate exponential convergence.     

Water Dynamics at Interfaces and Solutes: Disentangling Free Energy and Diffusivity Contributions

The dynamics of single water molecules in bulk and at interfaces is studied by means of molecular dynamics simulations. We use a recently developed stochastic method based on the Fokker-Planck equation to disentangle the contributions of the free energy and diffusivity profiles on the local dynamics. The strong variations found in the diffusivity profiles are crucial for accurately modeling the water kinetics. A comparison of hydrophobic and hydrophilic substrates and solutes yields significant differences in the diffusivities, which can be attributed to the presence of hydrogen bonds.     

Time-resolved photoelectron angular distributions from strong-field ionization of rotating naphthalene molecules

A nanosecond laser pulse confines the spatial orientation of naphthalene in 1D or 3D while a femtosecond kick pulse initiates rotation of the molecular plane around the fixed long axis. Time-dependent photoelectron angular distributions (PADs), resulting from ionization by an intense femtosecond probe pulse, exhibit pronounced changes as the molecular plane rotates. Enhanced 3D alignment, occurring shortly after the kick pulse, provides strongly improved contrast in molecular-frame PADs. Calculations in the strong-field approximation show that the striking structures observed in the PADs originate from nodal planes in occupied valence orbitals.     

Sympathetic cooling in an optically trapped mixture of alkali and spin-singlet atoms

We report on the realization of a stable mixture of ultracold lithium and ytterbium atoms confined in a far-off-resonance optical dipole trap. We observe sympathetic cooling of 6Li by 174Yb and extract the s-wave scattering length magnitude |a(6Li-174Yb)|=(13±3)a0 from the rate of interspecies thermalization. Using forced evaporative cooling of 174Yb, we achieve reduction of the 6Li temperature to below the Fermi temperature, purely through interspecies sympathetic cooling.     

Demultiplexing of OTDM-DPSK signals based on a single semiconductor optical amplifier and optical filtering

We propose and demonstrate the use of a single semiconductor optical amplifier (SOA) and optical filtering to time demultiplex tributaries from an optical time division multiplexing-differential phase shift keying (OTDM-DPSK) signal. The scheme takes advantage of the fact that phase variations added to the target channel by cross-phase modulation from the control signal are effectively subtracted in the differential demodulation scheme employed for DPSK signals. Demultiplexing from 80 to 40 Gbit/s is demonstrated with moderate power penalty using an SOA with recovery time twice as long as the bit period at 80 Gbit/s. Large dynamic ranges for the input power and SOA current are experimentally demonstrated. The scheme is expected to be scalable toward higher bit rates.     

Ultrahigh mobility in polymer field-effect transistors by design

In this article, the design paradigm involving molecular weight, alkyl substituents, and donor-acceptor interaction for the poly[2,6-(4,4-bis-alkyl-4H-cyclopenta[2,1-b;3,4-b']-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (cyclopentadithiophene-benzothiadiazole) donor-acceptor copolymer (CDT-BTZ) toward field-effect transistors (FETs) with ultrahigh mobilities is presented and discussed. It is shown that the molecular weight plays a key role in improving hole mobilities, reaching an exceptionally high value of up to 3.3 cm(2) V(-1) s(-1). Possible explanations for this observation is highlighted in conjunction with thin film morphology and crystallinity. Hereby, it is found that the former does not change, whereas, at the same time, crystallinity improved with ever growing molecular weight. Furthermore, other important structural design factors such as alkyl chain substituents and donor-acceptor interaction between the polymer backbones potentially govern intermolecular stacking distances crucial for charge transport and hence for device performance. In this aspect, for the first time we attempt to shed light onto donor-acceptor interactions between neighboring polymer chains with the help of solid state nuclear magnetic resonance (NMR). On the basis of our results, polymer design principles are inferred that might be of relevance for prospective semiconductors exhibiting hole mobilities even exceeding 3 cm(2) V(-1) s(-1).     

A Stable Silanol Triad in the Zeolite Catalyst SSZ‐70

Nests of three silanol groups are located on the internal pore surface of calcined zeolite SSZ‐70. 2D ¹H double/triple‐quantum single‐quantum correlation NMR experiments enable a rigorous identification of these silanol triad nests. They reveal a close proximity to the structure directing agent (SDA), that is, N,N′‐diisobutyl imidazolium cations, in the as‐synthesized material, in which the defects are negatively charged (silanol dyad plus one charged SiO^? siloxy group) for charge balance. It is inferred that ring strain prevents the condensation of silanol groups upon calcination and removal of the SDA to avoid energetically unfavorable three‐rings. In contrast, tetrad nests, created by boron extraction from B‐SSZ‐70 at various other locations, are not stable and silanol condensation occurs. Infrared spectroscopic investigations of adsorbed pyridine indicate an enhanced acidity of the silanol triads, suggesting important implications in catalysis.