Basic Characteristics of Synchrotron Radiation

Many advances have been made in chemical structure research over the past three decades using synchrotron radiation. Synchrotron radiation has a number of unique properties. They include high brightness, high collimation, broad energy spectrum, variable polarization, coherent power, and subnanosecond pulse width. The third-generation storage rings with wiggler and undulator sources and lower electron beam dimensions are delivering over 10¹² times higher brightness than laboratory-based sources. The future of synchrotron sources looks very promising with the development of energy recovery linac sources and free-electron laser sources. These will permit dynamic studies of chemical structure with subpicosecond time resolution. Commensurate with the development of X-ray sources, major progress has occurred in optical schemes to meet the challenging needs of chemical structure research. High-resolution monochromatization and submicron focusing of X rays present new avenues for the future.     

Second‐harmonic response of a series of chiral polyesters: A joint experimental and theoretical study

A series of polyesters with π‐conjugated donor–acceptor segments was synthesized by the condensation of azobenzene‐4,4′‐dicarbonylchloride with 1,4:3,6‐dianhydro‐D‐sorbitol ([α] = + 42.5°) and biphenolic chromophores, bis(4‐hydroxyphenylazo)‐2,2′‐dinitrodiphenylmethane and bis(4‐hydroxyphenylazo)‐2,2′‐dinitrodiphenylsulfone. The polymers were characterized by spectral methods (IR, ultraviolet–visible, and NMR), thermal methods (thermogravimetry and differential scanning calorimetry), wide‐angle X‐ray scattering, and polarimetry. The polymers containing isosorbide units were optically active and crystalline. They exhibited glass‐transition temperature values between 100 and 160 °C and were stable up to 400 °C. The second‐harmonic generation (SHG) efficiency of the polymers was experimentally verified by a powder‐reflection technique with 2‐methyl‐4‐nitroaniline as a reference. The SHG efficiencies of the polymers were compared to those of the chromophores and explained as a function of the percentage of chiral composition. The hyperpolarizability β values were also determined by a two‐level model solvatochromic method and computational methods. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2868–2877, 2002     

Electron-transfer in molecular functional materials

We discuss electron-transfer processes that govern the physics of several materials or systems of interest for advanced applications. The discussion touches upon several topics, ranging from solvatochromism to solvent-induced symmetry breaking, from excitonic to cooperative effects in molecular crystals, from phase transitions to vibrational contributions to the dielectric constant in organic materials, from spectroscopy to molecular transport. In all these diverse systems electron transfer (ET) plays a major role and is discussed with reference to simple models for delocalized charges.     

Microfabricated bioreactor chips for immobilised enzyme assays

A microfabricated device is reported that has been designed to permit the in situ packing of a section of channel with enzyme immobilised onto controlled pore glass (CPG). It is fabricated from glass and polydimethylsiloxane and to prevent dead volumes, has dedicated channels for packing the reactor. The device has the advantage of being simple in design, the flow through enzyme reactor channel being simply a widened section of the analyte channel. The system is suitable for both hydrodynamic and electro-osmotic pumping, and is designed such that when the packing is exhausted it can be repacked. Controlled pore glass provides a reproducible none swelling, high porosity medium onto which the enzyme could be immobilised. The large particle size meant that it was vital to optimise the immobilisation procedure in order to achieve acceptable enzyme activity. The microfabricated device was developed with two enzymes of different molecular masses; alkaline phosphatase and xanthine oxidase. The pore size of the CPG was found to be very important for xanthine oxidase, where the 697 Å pore size (120-200 mesh) CPG was found to give the highest activity (18-20% activity retained after immobilisation). The microfabricated device was used for the assay of p-nitrophenyl phosphate and hypoxanthine with spectrophotometric detection at 405 and 470 nm, respectively. The limits of detection were 5 and 8 μM, respectively.     

Progress on phthalocyanine-conjugated Ag and Au nanoparticles: Synthesis,characterization, and photo-physicochemical properties

Phthalocyanine (Pc) complexes are an important class of dyes with numerous (e.g., biological, photophysical, and analytical) applications. Among the methods used to improve the properties of these complexes, one should mention the introduction of different substituents, variation of the central metal ion, ligand exchange, and conjugation to nanomaterials (e.g., carbon-based nanomaterials and metal nanoparticles (NPs)). This work briefly reviews Pc complex conjugation to Ag and Au NPs, highlights the different NP shapes, and discusses the diversity of conjugation approaches. Moreover, the use of UV–Vis spectroscopy, powder X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, atomic force microscopy, dynamic light scattering and Fourier transform infrared spectroscopy to characterize Pc-NP hybrids is summarized. The effect of conjugation on Pc photo-physicochemical properties (fluorescence, singlet oxygen generation, triplet state formation, and optical limiting behavior) is discussed, and future perspectives for the synthesis and applications of new hybrids are provided.     

Organophosphorus π-conjugated materials: the rise of a new field

The synthesis and electronic properties of new linear organic π-conjugated systems incorporating phosphole rings are described. Well defined α,α′-(phosphole-thiophene) oligomers possess low HOMO-LUMO gaps and their optical and electrochemical properties can be tuned via chemical modifications of the P-atoms. The physical properties of these compounds make them valuable materials for OLED’s. The coordination ability of phosphole-based dipoles has been exploited for the synthesis of efficient multipolar NLO-phores. Lastly, phospholes have been used for the synthesis of assemblies exhibiting through-bond interaction between two π-systems via P-P σ-skeletons.     

Second-order nonlinear optical properties of side-chain liquid crystalline polymers studied by second harmonic generation from thin films

The two independent elements of the second-order nonlinear optical susceptibility tensor of a range of contact poled, donor–acceptor substitued side-chain polymers are reported. The susceptibilities were measured by second harmonic generation from thin films, typically less than 0.5 μm thick, at a fundamental wavelength of 1064 nm. The largest value was χ = 2.64 pm/V which is three times greater than the χ value of KDP and was measured in a nitrobenzylidene side chain, polyhydroxystyrene polymer with an eleven unit alkyl chain spacer attaching the side group to the backbone. Typical susceptibility values obtained were χ～0.3 pm/V and X⁽²⁾₃₃～1 pm/V. The coherence lengths of the materials, which lay in the range 4–12 μm, were measured at 1064 nm by the maker fringe technique using thick, wedge-shaped samples.     

本征导电聚合物的智能性

在化学掺杂或电化学掺杂过程中，性质发生可逆性变化的本征导电聚合物是一种潜在的智能材料，可望实现或部分实现传感、处理和执竽功能，适于制成电机执行器、智能窗、化学分离与释放体系、传感器和非线性光学器件等。     

Doped Sol-Gel Films for Silica-on-Silicon Photonic Components

Further expansion of optical communication systems depends strongly on the development of cheap component technologies for functions such as switching, demultiplexing and amplification. Silica-on-silicon is increasingly recognised as the best approach to low cost integrated optics for such applications, but so far the functionality is limited. The purpose of NODES, a basic research collaboration sponsored by the European Union under the programme ESPRIT, has been to examine the application of sol-gel to a highly functional silica-on-silicon technology. In particular, the project has investigated film processing and characterisation, rare-earth doping for amplification, and semiconductor nanocrystallite doping for nonlinear functions. This paper presents the background and context to this work, summarises the technical results obtained, and discusses requirements and challenges for successful application of sol-gel in photonics.