Ionic liquids as novel guests for cucurbit[6]uril in neutral water

Cucurbit[6]uril was dissolved through encapsulation of an imidazolium-based ionic liquid guest in a pure water environment and the dissolution ability could be tuned by augmenting the imidazolium structure.     

Pulsed flow modulation comprehensive two-dimensional gas chromatography

Pulsed flow modulation (PFM) is based on higher flow rate time compression of the first GC column effluent, which prior to the injection into the second column is stored for a few seconds in a standard fused silica wide bore transfer line. We constructed the PFM device with two standard 1/16 in. brass compression fittings with the insertion of the two columns inside the wide bore 0.53 mm i.d. fused silica storage transfer line for the elimination of dead volumes. This simple arrangement provides a combination of flexibility in the length of the sample storage transfer line hence comprehensive two-dimensional gas chromatography (GC x GC) cycle time, inert sample path and full elimination of cooling gas consumption. A record short second column injection time of 20 ms is demonstrated. Practical injection times are the sample collection time (such as 4s) divided by the second to first column flow rate ratio (such as 20/0.7), which is typically around 150 ms. Due to the low cost of the device it can also be considered for use with non comprehensive time segmented GC x GC to remove a few accidental coelutions. PFM-GCxGC excels with high second column capacity due to the use of 0.32 mm i.d. columns with high flow rates as the second dimension GC x GC column. As a result, PFM-GCxGC can have up to two orders of magnitude higher second column sample capacity and linear dynamic range for improved reduction of adverse matrix interference effects due to column overloading.     

Surface‐Bound Cucurbit[8]uril Catenanes on Magnetic Nanoparticles Exhibiting Molecular Recognition

We demonstrate the preparation of surface‐bound cucurbit[8]uril (CB[8]) catenanes on silica nanoparticles (NPs), where CB[8] was employed as a tethered supramolecular “handcuff” to selectively capture target guest molecules. In this catenane, CB[8] was threaded onto a methyl viologen (MV²⁺) axle and immobilized onto silica NPs. The formation of CB[8] catenanes on NPs were confirmed by UV/Vis titration experiments and lithographic characterization, demonstrating a high density of CB[8] on the silica NPs surface, 0.56 nm^?2. This CB[8] catenane system exhibits specific molecular recognition towards certain aromatic molecules such as perylene bis(diimide), naphthol and aromatic amino acids, and thus it can act as a nanoscale molecular receptor for target guests. Furthermore, we also demonstrate its use as an efficient and recyclable nano‐platform for peptide separation. By embedding magnetic NPs inside silica NPs, separation could be achieved by simply applying an external magnetic field. Moreover, the peptides captured by the catenanes could be released by reversible single‐electron reduction of MV²⁺. The entire process demonstrated high recoverability.     

Outer approximation methods for solving variational inequalities in Hilbert space

In this paper, we study variational inequalities in a real Hilbert space, which are governed by a strongly monotone and Lipschitz continuous operator F over a closed and convex set C. We assume that the set C can be outerly approximated by the fixed point sets of a sequence of certain quasi-nonexpansive operators called cutters. We propose an iterative method, the main idea of which is to project at each step onto a particular half-space constructed using the input data. Our approach is based on a method presented by Fukushima in 1986, which has recently been extended by several authors. In the present paper, we establish strong convergence in Hilbert space. We emphasize that to the best of our knowledge, Fukushima’s method has so far been considered only in the Euclidean setting with different conditions on F. We provide several examples for the case where C is the common fixed point set of a finite number of cutters with numerical illustrations of our theoretical results.     

<Emphasis Type="Italic">M</Emphasis>-slenderness

Analogues of Nunke’s theorem are proved which characterize variants of slenderness. For a bounded monotone subgroup M of ? ^ω , a torsion-free reduced abelian group G is M-slender if, and only if, there is no monomorphism from M into G. It is consistent relative to ordinary set theory (ZFC) that if M ≠ ? ^ω is an unbounded monotone subgroup of ? ^ω , then a torsion-free reduced abelian group G is M-slender if, and only if, there is no monomorphism from M into G.     

X-ray structure and DFT study of C1-C60(CF3)12. A high-energy, kinetically-stable isomer prepared at 500 degrees C

The title compound, prepared from C(60) and CF(3)I at 500 degrees C, exhibits an unusual fullerene(X)12 addition pattern that is 40 kJ mol(-1) less stable than the previously reported C(60)(CF(3))12 isomer.     

Electron ionization LC‐MS with supersonic molecular beams—the new concept,benefits and applications

A new type of electron ionization LC‐MS with supersonic molecular beams (EI‐LC‐MS with SMB) is described. This system and its operational methods are based on pneumatic spray formation of the LC liquid flow in a heated spray vaporization chamber, full sample thermal vaporization and subsequent electron ionization of vibrationally cold molecules in supersonic molecular beams. The vaporized sample compounds are transferred into a supersonic nozzle via a flow restrictor capillary. Consequently, while the pneumatic spray is formed and vaporized at above atmospheric pressure the supersonic nozzle backing pressure is about 0.15 Bar for the formation of supersonic molecular beams with vibrationally cold sample molecules without cluster formation with the solvent vapor. The sample compounds are ionized in a fly‐though EI ion source as vibrationally cold molecules in the SMB, resulting in ‘Cold EI’ (EI of vibrationally cold molecules) mass spectra that exhibit the standard EI fragments combined with enhanced molecular ions. We evaluated the EI‐LC‐MS with SMB system and demonstrated its effectiveness in NIST library sample identification which is complemented with the availability of enhanced molecular ions. The EI‐LC‐MS with SMB system is characterized by linear response of five orders of magnitude and uniform compound independent response including for non‐polar compounds. This feature improves sample quantitation that can be approximated without compound specific calibration. Cold EI, like EI, is free from ion suppression and/or enhancement effects (that plague ESI and/or APCI) which facilitate faster LC separation because full separation is not essential. The absence of ion suppression effects enables the exploration of fast flow injection MS‐MS as an alternative to lengthy LC‐MS analysis. These features are demonstrated in a few examples, and the analysis of the main ingredients of Cannabis on a few Cannabis flower extracts is demonstrated. Finally, the advantages of EI‐LC‐MS with SMB are listed and discussed. Copyright © 2015 John Wiley & Sons, Ltd.     

Hybrid Supramolecular and Colloidal Hydrogels that Bridge Multiple Length Scales

Hybrid nanocomposites were constructed based on colloidal nanofibrillar hydrogels with interpenetrating supramolecular hydrogels, displaying enhanced rheological yield strain and a synergistic improvement in storage modulus. The supramolecular hydrogel consists of naphthyl‐functionalized hydroxyethyl cellulose and a cationic polystyrene derivative decorated with methylviologen moieties, physically cross‐linked with cucurbit[8]uril macrocyclic hosts. Fast exchange kinetics within the supramolecular system are enabled by reversible cross‐linking through the binding of the naphthyl and viologen guests. The colloidal hydrogel consists of nanofibrillated cellulose that combines a mechanically strong nanofiber skeleton with a lateral fibrillar diameter of a few nanometers. The two networks interact through hydroxyethyl cellulose adsorption to the nanofibrillated cellulose surfaces. This work shows methods to bridge the length scales of molecular and colloidal hybrid hydrogels, resulting in synergy between reinforcement and dynamics.     

The geometric phase in nonlinear frequency conversion

The geometric phase of light has been demonstrated in various platforms of the linear optical regime, raising interest both for fundamental science as well as applications, such as flat optical elements. Recently, the concept of geometric phases has been extended to nonlinear optics, following advances in engineering both bulk nonlinear photonic crystals and nonlinear metasurfaces. These new technologies offer a great promise of applications for nonlinear manipulation of light. In this review, we cover the recent theoretical and experimental advances in the field of geometric phases accompanying nonlinear frequency conversion. We first consider the case of bulk nonlinear photonic crystals, in which the interaction between propagating waves is quasi-phase-matched, with an engineerable geometric phase accumulated by the light. Nonlinear photonic crystals can offer efficient and robust frequency conversion in both the linearized and fully-nonlinear regimes of interaction, and allow for several applications including adiabatic mode conversion, electromagnetic nonreciprocity and novel topological effects for light. We then cover the rapidly-growing field of nonlinear Pancharatnam-Berry metasurfaces, which allow the simultaneous nonlinear generation and shaping of light by using ultrathin optical elements with subwavelength phase and amplitude resolution. We discuss the macroscopic selection rules that depend on the rotational symmetry of the constituent meta-atoms, the order of the harmonic generations, and the change in circular polarization. Continuous geometric phase gradients allow the steering of light beams and shaping of their spatial modes. More complex designs perform nonlinear imaging and multiplex nonlinear holograms, where the functionality is varied according to the generated harmonic order and polarization. Recent advancements in the fabrication of three dimensional nonlinear photonic crystals, as well as the pursuit of quantum light sources based on nonlinear metasurfaces, offer exciting new possibilities for novel nonlinear optical applications based on geometric phases.