Slow-light enhanced optical detection in liquid-infiltrated photonic crystals

Slow-light enhanced optical detection in liquid-infiltrated photonic crystals is theoretically studied. Using a scattering-matrix approach and the Wigner–Smith delay time concept, we show that optical absorbance benefits both from slow-light phenomena as well as a high filling factor of the energy residing in the liquid. Utilizing strongly dispersive photonic crystal structures, we numerically demonstrate how liquid-infiltrated photonic crystals facilitate enhanced light–matter interactions, by potentially up to an order of magnitude. The proposed concept provides strong opportunities for improving existing miniaturized absorbance cells for optical detection in lab-on-a-chip systems.     

Growth and long-run stability

This paper analyses the implications of persistent growth upon the stability properties of dynamic models. Besides the traditional concept of asymptotic stability, new stability criteria-strong/weak absolute, strong/weak relative, strong/weak logarithmic stability-are introduced, and global stability conditions for satisfying these criteria are stated for general first-order autonomous differential equations. The conflict between rapidity of growth and the degree of stability is demonstrated. Economic applications of the stability theorems are illustrated within the growth models of Harrod and Solow.     

Synthetic protocols and building blocks for molecular electronics

Simple and readily accessible aryl bromides are useful building blocks for thiol end-capped molecular wires. Thus, 4-bromophenyl tert-butyl sulfide and 1-bromo-4-(methoxymethyl)benzene serve as precursors for a variety of oligo(phenylenevinylene) and oligo(phenyleneethynylene) wires via efficient synthetic transformations as presented in this paper.     

A rigid linker-scaffold for solid-phase synthesis of dimeric pharmacophores

Bifunctional linker-scaffolds (compounds 1-3) were designed to meet several criteria for solid-phase syntheses of bivalent ligands. They have two amine-functionalized arms that can be differentially protected. Elaboration of these arms could give ligand-pharmacophore dimers wherein the two active components are held reasonably rigidly at around 10 A separation. Their bifunctional design also enables reactions of libraries with libraries to amplify diversity in a truly combinatorial fashion. Molecules 1-3 are also designed so that cleavage of the linker liberates the scaffold entity into solution under conditions that create only byproducts that should not interfere with biological assays. Thus they contain 2-nitrobenzene sulfonamide components that cleave in the presence of good nucleophiles. In the event, the linker-scaffolds 1-3 were prepared (Schemes 1 and 2). The N-benzyl system 2 was shown to have good stability to the types of conditions that might be used to functionalize the scaffold arms and to be sufficiently labile to the cleavage nucleophile (vide infra). The nucleophiles generally used to cleave nitrobenzene sulfonamides either generate undesirable byproducts (thiophenol or alkane thiols) or proved to be insufficiently reactive for the required solid-phase transformations (n-propylamine). However, sodium sulfide was investigated as a new alternative and shown to be a highly reactive cleavage agent that gives only volatile byproducts and sodium hydroxide. It is suggested that sodium sulfide is a highly desirable nucleophile for cleavage of 2-nitrobenzene sulfonamides, in general. The linker-scaffolds 1-3 were used to prepare a small library of bivalent ligands targeted to a protein receptor having charged cavities separated by approximately 10 A. These systems were made from guanidine, pyridinium, carboxylic acid, and sulfonic acid constituents (Tables 1 and 2).     

Selective Halogen-Lithium Exchange Reaction of Bromine-Substituted 25,26,27,28-Tetrapropoxycalix[4]arene

Methods are described for the selective bromine-lithium exchange reaction of bromine-substituted calix[4]arenes with either n-BuLi or t-BuLi in THF. Quenching of the lithiated calix[4]arenes with MeOH, D(2)O, CH(3)SSCH(3), B(OCH(3))(3), DMF, or CO(2) as electrophiles resulted in 5-monosubstituted, 5,17-disubstituted, or 5,11,17,23-tetrasubstituted calix[4]arenes with H, D, SCH(3), B(OH)(2), CHO, or COOH functionalities.     

Mono‐ and Bis(pyrrolo)tetrathiafulvalene Derivatives Tethered to C60: Synthesis,Photophysical Studies,and Self‐Assembled Monolayers

A series of mono‐ (MPTTF) and bis(pyrrolo)tetrathiafulvalene (BPTTF) derivatives tethered to one or two C₆₀ moieties was synthesized and characterized. The synthetic strategy for these dumbbell‐shaped compounds was based on a 1,3‐dipolar cycloaddition reaction between aldehyde‐functionalized MPTTF/BPTTF derivatives, two different tailor‐made amino acids, and C₆₀. Electronic communication between the MPTTF/BPTTF units and the C₆₀ moieties was studied by a variety of techniques including cyclic voltammetry and absorption spectroscopy. These solution‐based studies indicated no observable electronic communication between the MPTTF/BPTTF units and the C₆₀ moieties. In addition, femtosecond and nanosecond transient absorption spectroscopy revealed, rather surprisingly, that no charge transfer from the MPTTF/BPTTF units to the C₆₀ moieties takes place on excitation of the fullerene moiety. Finally, it was shown that the MPTTF–C₆₀ and C₆₀–BPTTF‐C₆₀ dyad and triad molecules formed self‐assembled monolayers on a Au(111) surface by anchoring to C₆₀.     

Solar Thermal Energy Storage in a Photochromic Macrocycle

The conversion and efficient storage of solar energy is recognized to hold significant potential with regard to future energy solutions. Molecular solar thermal batteries based on photochromic systems exemplify one possible technology able to harness and apply this potential. Herein is described the synthesis of a macrocycle based on a dimer of the dihydroazulene/vinylheptafulvene (DHA/VHF) photo/thermal couple. By taking advantage of conformational strain, this DHA–DHA macrocycle presents an improved ability to absorb and store incident light energy in chemical bonds (VHF–VHF). A stepwise energy release over two sequential ring‐closing reactions (VHF→DHA) combines the advantages of an initially fast discharge, hypothetically addressing immediate energy consumption needs, followed by a slow process for consistent, long‐term use. This exemplifies another step forward in the molecular engineering and design of functional organic materials towards solar thermal energy storage and release.