Crystal supramolecularity in 2,2′-iminodipyridinium tetrahalometallate(II) salts: Supramolecular motifs that control tetrahedral halometallate solid state structures

N⁺–H$?$Br–M and (π)C–H$?$Br–M hydrogen bond synthons have been exploited in the crystallization of a series of 2,2′-iminodipyridinium(2+) dication (hereafter 2,2′-imdipyH₂), (C₁₀H₁₁N₃)[MX₄] salts (M = Co and Hg; X = Cl and Br) and 2,2′-iminodipyridinium(1+) cation (hereafter 2,2′-imdipyH), (C₁₀H₁₀N₃)₂[MX₄] salts (M = Co, Hg; X = Cl and Br). Intermolecular interactions and crystal supramolecularity adopted in these structures were analyzed and compared with reported similar structures, (C₁₀H₁₁N₃)[CuCl₄] and (C₁₀H₁₀N₃)₂[CoCl₄]. In these salts only one structural form for the halometallate species is observed namely mononuclear tetrahedral. The crystal supramolecularity in the (2,2′-imdipyH₂)[MX₄] series corresponds to three distinct structural motifs: Parallel ribbons of infinitely connected cyclic dimers of two dications and two anions found in the isomorphous salts of [CoCl₄]^2? and [CuCl₄]^2?; and cyclic dimer hearing-bone packing motif found in the isomorphous dication salts of [CoBr₄]^2? and [HgBr₄]^2?. Infinitely helical layers based on alternating $?$anion$?$two stacked cations $?$anion$?$ two stacked cations$?$ are found in the isomorphous salts of (2,2′-imdipyH)₂[CoCl₄] and (2,2′-imdipyH)₂[HgBr₄].     

Elliptic problems with nonlinear terms depending on the gradient and singular on the boundary

In this paper we consider the problem

(P)     

Zwitterionic-type hydrophilic interaction nano-liquid chromatography of complex and high mannose glycans coupled with electrospray ionisation high resolution time of flight mass spectrometry

In this study we describe a new method for rapid and sensitive analysis of reduced high mannose and complex glycans using zwitterionic-type hydrophilic interaction nano-liquid chromatography (nano ZIC-HILIC, 75 μm I.D.×150 mm) coupled with high resolution nanoelectrospray ionisation time of flight mass spectrometry (nano ESI-TOF-MS). The retention of neutral glycans increases with increasing molecular weight and is higher for high mannose glycans than for complex-type glycans. The selectivity of ZIC-HILIC for sialylated glycans differs from that for the neutral glycans and is believed to involve electrostatic repulsion; therefore, charged glycans are eluted earlier than neutral glycans with comparable molecular weight. Due to the improved sensitivity achieved by employing a ZIC-HILIC nano-column, a range of less common complex glycans has been studied and the high resolution mass spectrometry enabled confirmation of glycan composition for the proposed structures. Good sensitivity for glycans was achieved without prior fluorescent labelling, and the time of the analysis was significantly reduced compared to the separation of glycans on a conventional-size column. The proposed method offers a fast and sensitive approach for glycan profiling applied to analysis of biopharmaceuticals.     

Detection of fentanyl in binary mixtures with cocaine by use of surface-enhanced Raman spectroscopy

Abstract

The ongoing epidemic pertaining to overdose deaths has been attributed to the synthetic opioid fentanyl due to its use as an adulterant in other, less potent drugs of abuse. Detection of low quantities of fentanyl would, therefore, be extremely useful in a forensic science laboratory. While Raman spectroscopy is particularly effective at distinguishing between classes of drugs, weak signatures can prove difficult when dealing with microscopic samples. Surface-enhanced Raman scattering spectroscopy provides the enhancement necessary to make Raman a viable approach for the detection of small amounts of fentanyl. This work explores the use of a paper-based substrate loaded with silver nanoparticles for the recovery of small quantities of fentanyl in cocaine, where it was identified at a lower limit of 500?ng (～65?ppm) in mixtures. Linear relationships were investigated between intensity and concentration for diagnostic peaks associated with fentanyl and cocaine, which in turn sheds light on the attenuation of the enhancement intensity as a result of competitive binding to silver nanoparticles. This work demonstrates a potentially simple and qualitative pathway for the forensic analysis of fentanyl as an adulterant in cocaine.     

Intersections of finitely generated clones

We answer negatively the following question asked by Stanley Burris: Is the intersection of two finitely generated clones always finitely generated?     

Comparison of ion chromatography and capillary electrophoresis for the determination of inorganic ions

The techniques of ion chromatography and capillary electrophoresis are compared as analytical methods for the determination of inorganic anions and cations. Comparison is made in the areas of stage of development, separation efficiency, separation selectivity, analytical performance parameters, method development procedures, applications, strenghts and weaknesses, and future directions. It is shown that the two techniques are complementary rather than competitive, especially with regard to their separation selectivities and the type of applications to which they are most suited.     

Monotone trajectories of differential inclusions and functional differential inclusions with memory

The paper gives a necessary and sufficient condition for the existence of monotone trajectories to differential inclusionsdx/dt ∈S[x(t)] defined on a locally compact subsetX ofR ^p, the monotonicity being related to a given preorder onX. This result is then extended to functional differential inclusions with memory which are the multivalued case to retarded functional differential equations. We give a similar necessary and sufficient condition for the existence of trajectories which reach a given closed set at timet=0 and stay in it with the monotonicity property fort≧0.     

Upper bounds for the forwarding indices of communication networks

The decision version of the forwarding index problem is, given a connected graph G and an integer ξ, to find a way of connecting each ordered pair of vertices by a path so that every vertex is an internal point of at most such paths. The optimization version of the problem is to find the smallest ξ for which a routing of this kind exists. Such a problem arises in the design of communication networks and distributed architectures. A model of parallel computation is represented by a network of processors, or machines processing and forwarding (synchronous) messages to each other, subject to physical constraints bearing on either the number of messages that can be processed by a single machine or the number of messages that can be sent through a connection. It was in this context that the problem was first introduced by Chung et al. (IEEE Trans. Inform. Theory 33 (1987) 224). The aim of this paper is to establish upper bounds for the optimal ξ as a function of the connectivity of the graph.