Enantioselective Synthesis of Acyclic Orthogonally Functionalized Compounds Bearing a Quaternary Stereocenter Using Chiral Ammonium Salt Catalysis

We herein report an asymmetric protocol to access a series of orthogonally functionalized acyclic chiral target molecules containing a quaternary stereogenic center by carrying out the enantioselective α-alkylation of novel orthogonally functionalized dioxolane-containing cyanoacetates under chiral ammonium salt catalysis. By using just 1 mol % of Maruoka's spirocyclic ammonium salt catalysts enantioselectivities up to e.r.=97.5 : 2.5 could be achieved and further functional group manipulations of the products were carried out as well.     

Complexes with Atomic Gold Ions: Efficient Bis-Ligand Formation

Complexes of atomic gold with a variety of ligands have been formed by passing helium nanodroplets (HNDs) through two pickup cells containing gold vapor and the vapor of another dopant, namely a rare gas, a diatomic molecule (H₂, N₂, O₂, I₂, P₂), or various polyatomic molecules (H₂O, CO₂, SF₆, C₆H₆, adamantane, imidazole, dicyclopentadiene, and fullerene). The doped HNDs were irradiated by electrons; ensuing cations were identified in a high-resolution mass spectrometer. Anions were detected for benzene, dicyclopentadiene, and fullerene. For most ligands L, the abundance distribution of AuL_n⁺ versus size n displays a remarkable enhancement at n = 2. The propensity towards bis-ligand formation is attributed to the formation of covalent bonds in Au⁺L₂ which adopt a dumbbell structure, L-Au⁺-L, as previously found for L = Xe and C₆₀. Another interesting observation is the effect of gold on the degree of ionization-induced intramolecular fragmentation. For most systems gold enhances the fragmentation, i.e., intramolecular fragmentation in AuL_n⁺ is larger than in pure L_n⁺. Hydrogen, on the other hand, behaves differently, as intramolecular fragmentation in Au(H₂)_n⁺ is weaker than in pure (H₂)_n⁺ by an order of magnitude.     

Local Distortions in a Prototypical Zeolite Framework Containing Double Four-Ring Cages: The Role of Framework Composition and Organic Guests**

Cube-like double four-ring (d4r) cages are among the most frequent building units of zeolites and zeotypes. In materials synthesised in fluoride-containing media, the fluoride anions are preferentially incorporated in these cages. In order to study the impact of framework composition and organic structure-directing agents (OSDAs) on the possible occurrence of local distortions of fluoride-containing d4r cages, density functional theory (DFT) calculations and DFT-based molecular dynamics simulations were performed for AST-type zeotypes, considering four different compositions (SiO₂, GeO₂, AlPO₄, GaPO₄) and two different OSDA cations (tetramethylammonium [TMA] and quinuclidinium [QNU]). All systems except SiO₂-AST show significant deformations, with a pyritohedron-like distortion of the d4r cages occurring in GeO₂- and GaPO₄-AST, and a displacement of the fluoride anions towards one of the corners of the cage in AlPO₄- and GaPO₄-AST. While the distortions occur at random in TMA-containing zeotypes, they exhibit a preferential orientation in systems that incorporate QNU cations. In addition to providing detailed understanding of the local structure of a complex host-guest system on the picosecond timescale, this work indicates the possibility to stabilise ordered distortions through a judicious choice of the OSDA, which might enable a tuning of the material's properties.     

A Novel Carbon Nitride Nanosheets-based Electrochemical Sensor for Determination of Hydroxychloroquine in Pharmaceutical Formulation and Synthetic Urine Samples

This study introduces modified carbon paste electrodes with carbon nitride nanosheets (CNNS) and outlines their application for the determination of hydroxychloroquine sulfate (HCQ) in tablets and synthetic urine samples. CNNS were synthesized by hydrothermal route (200 °C, 10 h) using melamine and citric acid as their precursors. The carbon nitride nanosheets-based electrode (CNNS/E) presented a linear dynamic range for HCQ (LDR), ranging from 10.0 nmol l⁻¹ to 6.92 μmol l⁻¹, and detection (LOD) and quantification limits (LOQ) of 0.16 nmol l⁻¹ and 0.52 nmol l⁻¹, respectively. LOD and LOQ were calculated by the equations: LOD=3(S_d/b), and LOQ=10(S_d/b). The modified sensor presented excellent relative standard deviations for parameters such as repeatability (2.39 % and 1.87 %) and reproducibility (3.22 % and 2.32 %) in HCQ oxidation peaks (1 and 2). The CNNS/E has not shown significant variations in its anodic signal intensity in the presence of some organic and inorganic substances. It is worth bearing in mind that CNNS/E can be easily manufactured and the sensor has the lowest HCQ detection limits reported so far. The proposed sensor was successfully applied for HCQ determination in tablets and synthetic urine, showing good recovery values and an error of 0.60 % about comparative method in tablet samples, assuring the quality of the method.     

Theoretical study of the structural and energetic properties of platinum clusters with up to 60 atoms

Structural Chemistry - Applying a theoretical approach that combines an efficient and fast global optimization based on genetic algorithms (GA) to search in structure space and the parameterized...     

Stretch-coil transition and transport of fibers in cellular flows

It is shown that a slender elastic fiber moving in a Stokesian fluid can be susceptible to a buckling instability--termed the "stretch-coil" instability--when moving in the neighborhood of a hyperbolic stagnation point of the flow. When the stagnation point is part of an extended cellular flow, it is found that immersed fibers can move as random walkers across time-independent closed-streamline flow. It is also found that the flow is segregated into transport regions around hyperbolic stagnation points and their manifolds, and closed entrapment regions around elliptic points.     

Particle-hole symmetry and the Pfaffian state

We show that the particle-hole conjugate of the Pfaffian state-or "anti-Pfaffian" state-is in a different universality class from the Pfaffian state, with different topological order. The two states can be distinguished easily by their edge physics: their edges differ in both their thermal Hall conductance and their tunneling exponents. At the same time, the two states are exactly degenerate in energy for a nu=5/2 quantum Hall system in the idealized limit of zero Landau level mixing. Thus, both are good candidates for the observed sigma_{xy}=5/2(e;{2}/h) quantum Hall plateau.     

Nonlinear spectral-spatial control and localization of supercontinuum radiation

We present the first observation of spatiospectral control and localization of supercontinuum light through the nonlinear interaction of spectral components in extended periodic structures. We use an array of optical waveguides in a LiNbO3 crystal and employ the interplay between diffraction and nonlinearity to dynamically control the output spectrum of the supercontinuum radiation. This effect presents an efficient scheme for optically tunable spectral filtering of supercontinua.     

Ultraviolet properties of maximal supergravity

We argue that recent results in string perturbation theory indicate that the four-graviton amplitude of four-dimensional N=8 supergravity might be ultraviolet finite up to eight loops. We similarly argue that the h-loop M-graviton amplitude might be finite for h<7+M/2.     

Globally enumerating unstable periodic orbits for observed data using symbolic dynamics

The unstable periodic orbits of a chaotic system provide an important skeleton of the dynamics in a chaotic system, but they can be difficult to find from an observed time series. We present a global method for finding periodic orbits based on their symbolic dynamics, which is made possible by several recent methods to find good partitions for symbolic dynamics from observed time series. The symbolic dynamics are approximated by a Markov chain estimated from the sequence using information-theoretical concepts. The chain has a probabilistic graph representation, and the cycles of the graph may be exhaustively enumerated with a classical deterministic algorithm, providing a global, comprehensive list of symbolic names for its periodic orbits. Once the symbolic codes of the periodic orbits are found, the partition is used to localize the orbits back in the original state space. Using the periodic orbits found, we can estimate several quantities of the attractor such as the Lyapunov exponent and topological entropy.