Keggin-type Bronsted dodecatungstophosphoric acid: a quasi homogenous and reusable catalyst system for liquid phase Beckmann rearrangement

A variety of ketoximes, prepared from corresponding ketones, undergo Beckmann rearrangement using H₃PW₁₂O₄₀ (DTPA) in acetonitrile under reflux to yield N-substituted amides and lactams in good to excellent yields (72–96%). The present method provides an efficient, clean, eco-friendly, and simple synthesis. The catalyst is cheap, moisture tolerant, recoverable, and reusable without much loss of its activity.     

Effects of active muscle contraction on whiplash injury

The objective of this work is to develop a finite element model of active human skeletal muscle, which can mimic its contraction behaviour. The model is then used to analyse the effects of active muscle contraction into occupant kinematics and injuries during rear-end collision. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Clam‐like Cyclotricatechylene‐based Capsules: Identifying the Roles of Protonation State and Guests as well as the Drivers for Stability and (Anti‐)Cooperativity

Cyclotricatechylene (ctcH₆) is a bowl‐shaped macrocyclic compound that can be used as a building block for self‐assembled capsules. ctcH₆ and its derivatives in various protonation states – here collectively labeled as CTC – form dimers that resemble the shape of a clam. These clam‐shaped entities have been studied experimentally by Abrahams, Robson, and co‐workers [B. F. Abrahams, N. J. FitzGerald, T. A. Hudson, R. Robson and T. Waters, Angew. Chem. Int. Ed. 2009 , 48, 3129–3132] where the capsules acted as an excellent host for large alkali‐metal cations. In this study, we present a detailed analysis based on accurate dispersion‐corrected Density Functional Theory approaches that reveals the factors that stabilise such CTC‐based capsules at different protonation states and their interaction with various encapsulated guests. Our results show that the capsules’ overall stability results as an interplay of hydrogen bonding, London dispersion, and electrostatic effects. The most stable capsules with group‐1 and group‐2 cations as guests contain only six phenolic hydrogens, as opposed to the maximum possible number of twelve. Inclusion of larger alkali‐metal cations is favoured due to larger London‐dispersion contributions. Cations are favoured as guests over isoelectronic neutral species, as the resulting host‐guest complexes experience additional stability due to cooperative effects. In fact, using the latter to drive the formation of specific capsules could be used in future strategies aimed at synthesising similar aggregates; our results provide an insightful understanding and useful guidance for such future endeavours.     

Functionalized Tricyclic Cytosine Analogues Provide Nucleoside Fluorophores with Improved Photophysical Properties and a Range of Solvent Sensitivities

Tricyclic cytosines (tC and tC^O frameworks) have emerged as a unique class of fluorescent nucleobase analogues that minimally perturb the structure of B‐form DNA and that are not quenched in duplex nucleic acids. Systematic derivatization of these frameworks is a likely approach to improve on and diversify photophysical properties, but has not so far been examined. Synthetic methods were refined to improve on tolerance for electron‐donating and electron‐withdrawing groups, resulting in a series of eight new, fluorescent cytidine analogues. Photophysical studies show that substitution of the framework results in a pattern of effects largely consistent across tC and tC^O and provides nucleoside fluorophores that are brighter than either parent. Moreover, a range of solvent sensitivities is observed, offering promise that this family of probes can be extended to new applications that require reporting on the local environment.     

Tuning the morphology of gold clusters by substrate doping

The morphology of small metal clusters can have a big impact on their electronic, magnetic, and chemical properties. This has been shown earlier, for example, for Au(20) clusters on MgO(001), where planar and tetrahedral geometries are possible for the gold atoms. While the planar geometry is more desirable for catalytic applications, it is disfavored in the usual situation. While earlier suggestions that have been made for tilting this balance in favor of the planar isomer are of considerable fundamental interest, they do not easily lend themselves to practical applications. Here, we suggest a conceptually simple but practicable way of achieving the same goal: viz., by doping the MgO substrate with Al atoms. We show, by performing density functional theory calculations, that this stabilizes the planar over the tetrahedral arrangement by an energy difference that is linearly proportional to the dopant concentration and is insensitive to the position of the dopant atom. The charge transferred to the Au cluster also depends monotonically on the doping concentration. This work is of interest for possible applications in the field of gold nanocatalysis.     

Unified scaling behavior of physical properties of clays in alcohol solutions

This paper reports observation of universal scaling of physical properties of clay particles, Laponite (aspect ratio=30) (L) and Na Montmorillonite (MMT, aspect ratio=200), in aqueous alcohol solutions (methanol, ethanol and 1-propanol) with solvent polarity, defined through reaction field factor f(OH)(?(0),n)=[(?(0) - 1/?(0) + 2) - (n(2) - 1/n(2) + 2)], at room temperature (20°C). Here, ?(0) and n are the static dielectric constant and refractive index of the solvent concerned. Physical properties (Z) such as zeta potential, effective aggregate size, viscosity and surface tension scaled with the relative solvent polarity as Z～δf(α); δf=(f(w)(?(0),n) - f(OH)(?(0),n)), where f(w)(?(0),n) is the reaction field factor for water, Z is the normalized physical property, and α is its characteristic scaling exponent. The value of this exponent was found to be invariant of aspect ratio of the clay but dependent on the solvent polarity only.     

Quark matter properties and fluctuations of conserved charges in (2+1)-flavored quark model

In this study, the susceptibilities of conserved charges, baryon number, charge number, and strangeness number at zero and low values of chemical potential are presented. Taylor series expansion was used to obtain results for the three-flavor Polyakov quark meson (PQM) model and the Polyakov loop extended chiral quark mean-field (PCQMF) model. Mean-field approximation was used to study quark matter with the inclusion of the isospin chemical potential, as well as the vector interactions. The effects of isospin chemical potential and vector-interactions on phase diagrams were analyzed. A comparative analysis of the two models was completed. Fluctuations of the conserved charges were enhanced in the transition temperature regime and hence provided information about the critical end point (CEP). Susceptibilities of conserved quantities were calculated by using the Taylor series method. Enhancement of fluctuations in the transition temperature neighborhood provided a clear signature of a quantum chromodynamics (QCD) critical-point.     

Instrumental detection limit and sensitivity of K and L shell X‐ray emission lines of 17Cl, 37Rb,and 38Sr elements using PC‐WDXRF spectrometer

This work was aimed to improve the instrumental detection limit and sensitivity of ₁₇Cl, ₃₇Rb, and ₃₈Sr elements present in solid samples by using the advanced polychromatic wavelength dispersive X‐ray fluorescence spectrometry method. Instrumental measuring parameters, as well as study of calibration curves of K and L shell spectral lines, were evaluated to select the best conditions for ₁₇Cl, ₃₇Rb, and ₃₈Sr quantification. From the results, it was observed that the detection limits of the Rb Kα and Sr Kα spectral lines were lower than those of the Kβ_1,3 and Lα spectral lines. From the calibration curves, it was concluded that Kα spectral lines are more suitable than Kβ_1,3 and Lα lines to identify the traces of ₁₇Cl, ₃₇Rb, and ₃₈Sr elements in different types of solid samples.     

Multi-wavelength generation using a bismuth-based EDF and Brillouin effect in a linear cavity configuration

The generation of a multiple wavelength source using a bismuth-based erbium-doped fiber (Bi-EDF) in a linear cavity configuration is demonstrated. The configuration uses a pair of optical circulators at the input and output ends of the cavity to form a resonator for multi-wavelength generation in conjunction with optical couplers to inject the Brillouin pump (BP) and to tap the output at the two ends. The Brillouin erbium fiber laser (BEFL) comb with a 2.15 m of Bi-EDF has a wavelength spacing of 0.09 nm and operates in long-wavelength (L-) band region. A stable output laser comb of 50 lines is obtained at a BP of 1568.2 nm and 5 dBm and two 1480 nm pumps at 120 mW. The injected BP wavelength and power as well as the 1480 nm pump powers have a great effect on the number of lines and output power of the BEFL. This configuration is compact due to the use of the significantly shorter Bi-EDF as the linear gain medium, and can be made more compact by replacing the single-mode fiber with highly non-linear fibers such as holey fibers.