Sensing through signal amplification

The naked eye detection of single molecules in a complex mixture is the ultimate detection limit. Since a single molecule is unable to generate a strong enough signal, sensing methodologies able to reach that limit by necessity need to rely on signal amplification. This tutorial review describes various molecular approaches towards signal amplification in which a single analyte molecule affects the properties of a multitude of reporter molecules. Sensing by advanced instrumentation or changes in the physical properties of materials are excluded. The review is divided into four parts (catalysts, macromolecules, metal surfaces and supramolecular aggregates) depending on the species responsible for generating reporter molecules. Although on first sight apparently very diverse in nature, the majority of approaches rely on two key concepts: catalysis and multivalency. The ability of a catalyst to convert a multitude of substrate molecules into product (defined by the turn over number) makes a catalyst an intrinsic signal amplifier in case the chemical conversion of the substrate is accompanied by a measurable change in physical properties. For sensing purposes, catalytic activity must depend on the interaction between the analyte and the catalyst. Sensing using multivalent structures such as polymers and functionalized nanoparticles relies on the ability of a single analyte molecule to affect the properties of a multitude of reporter molecules collected in the multivalent structure. Chemical sensing systems will be discussed with detection limits that indeed go down to a few molecules and can rival the best biological assays. It will be shown that the most sensitive methods rely on a cascade of amplification mechanisms.     

Hydrocarbon ions with triplet ground states

The N.M.R. spectra of meta dichloro and meta dibromo benzenes are analysed in the nematic phase of 4-methoxy benzylidene-4-amino-α-methyl cinnamic acid-n-propyl ester at room temperature.

The direct couplings are found to be of negative sign. The molecules orient preferentially with the aromatic plane along the direction of the magnetic field and the C ₂-symmetry axis perpendicular to it.

The relations between the various direct couplings and the inter-proton distances are reported. The ratio of the distance between the meta protons along the axis perpendicular to the C ₂ symmetry and the ortho protons is determined precisely. The other ratios could not be determined to any reasonable precision. The reasons are discussed.

The angles between the C-H bonds of the equivalent protons and the C-C bonds in both the molecules are determined on the assumption of the C-H bond lengths and the ring geometry of benzene.     

Heuristics and memetic algorithm for the two-dimensional loading capacitated vehicle routing problem with time windows

This work deals with a new combinatorial optimization problem, the two-dimensional loading capacitated vehicle routing problem with time windows which is a realistic extension of the well known vehicle routing problem. The studied problem consists in determining vehicle trips to deliver rectangular objects to a set of customers with known time windows, using a homogeneous fleet of vehicles, while ensuring a feasible loading of each vehicle used. Since it includes NP-hard routing and packing sub-problems, six heuristics are firstly designed to quickly compute good solutions for realistic instances. They are obtained by combining algorithms for the vehicle routing problem with time windows with heuristics for packing rectangles. Then, a Memetic algorithm is developed to improve the heuristic solutions. The quality and the efficiency of the proposed heuristics and metaheuristic are evaluated by adding time windows to a set of 144 instances with 15–255 customers and 15–786 items, designed by Iori et al. (Transport Sci 41:253–264, 2007) for the case without time windows.     

Self-Assembled Multivalent Ag-SR Coordination Polymers with Phosphatase-Like Activity

We show herein the phosphatase-like catalytic activity of coordination polymers obtained after adding Ag⁺-ions to thiols bearing hydrophobic alkyl chains terminated with a 1,4,7-triazacyclononane (TACN) group. The subsequent addition of Zn²⁺ -ions to the self-assembled polymers resulted in the formation of multivalent metal coordination polymers capable of catalysing the transphosphorylation of an RNA-model compound (2-hydroxypropyl-4-nitrophenyl phosphate, HPNPP) with high reactivity. Analysis of a series of metal ions showed that the highest catalytic activity was obtained when Ag⁺-ions were used as the first metal ions to construct the backbone of the coordination polymer through interaction with the -SH group followed by Zn²⁺-ions as the second metal ions complexed by the TACN-macrocycle. Furthermore, it was demonstrated that the catalytic activity could be modulated by changing the length of the hydrophobic alkyl chain.     

Lower and upper bounds for the m-peripatetic vehicle routing problem

The m-Peripatetic Vehicle Routing Problem (m-PVRP) consists in finding a set of routes of minimum total cost over m periods so that two customers are never sequenced consecutively during two different periods. It models for example money transports or cash machines supply, and the aim is to minimize the total cost of the routes chosen. The m-PVRP can be considered as a generalization of two well-known NP-hard problems: the Vehicle Routing Problem (VRP or 1-PVRP) and the m-Peripatetic Salesman Problem (m-PSP). In this paper we discuss some complexity results of the problem before presenting upper and lower bounding procedures. Good results are obtained not only on the m-PVRP in general, but also on the VRP and the m-PSP using classical VRP instances and TSPLIB instances.     

Self-diffusion in gaseous and liquid ethylene

Proton spin echoes at 24 MHz have been used in an accurate study of the self-diffusion coefficient in gaseous and liquid ethylene over a large range of density and temperature. The high temperature data are well described by the corrected Enskog theory. As the temperature is lowered, increasing deviations from the hard sphere behaviour are observed, which are in qualitative agreement with computer simulations on square-well and Lennard-Jones particles.     

Time-resolved in situ XAS study of the preparation of supported gold clusters

Incipient-wetness impregnation of gamma-Al(2)O(3) with HAuCl(4) and subsequent removal of chlorine with NaOH, and deposition-precipitation of HAuCl(4) on TiO(2) at pH 7 resulted in supported Au(3+) species. Time-resolved in situ XAS at the Au L(3) edge showed that the Al(2)O(3)-supported oxidic or hydroxidic species were reduced in hydrogen at 440 K to yield small metallic gold clusters. The Au(3+) precursor decomposed to metallic gold in inert atmosphere at 573 K and in oxidizing atmosphere above 623 K. In all atmospheres, initially small clusters were formed that gradually grew with increasing temperature. The TiO(2)-supported species were considerably less stable. In hydrogen and carbon monoxide, Au(0) clusters of 1 to 1.5 nm were formed at room temperature, which was the lowest temperature studied. In inert and oxidizing atmosphere, the Au(3+) precursor decomposed fully to metallic gold at 530 K, as shown by XAS and temperature-programmed experiments. Large clusters were obtained already in the initial stage of reduction. Residual chlorine inhibited the reduction and led to sintering of the gold clusters. Exposure of the TiO(2)-supported catalyst precursor to light or the X-ray beam led to partial reduction, and STEM showed that storage of the reduced gold clusters under ambient conditions led to agglomeration and bimodal cluster-size distributions.