Enhanced collective optical response of vast numbers of silver nanoparticles assembled on a microbead

We investigated the optical response of a huge number of silver nanoparticles (AgNPs) densely assembled on an organic microsphere, i.e., AgNP-fixed bead, under the collective phenomena of localized surface plasmons. For this purpose, various optical properties of such a AgNP-fixed bead were analyzed in aqueous solution by dark-field optical microscopy and laser Raman microscopy. In particular, in comparison with the optical spectrum of single AgNPs, significant spectral broadening and redshift were observed due to plasmonic superradiance with decreasing interparticle distance to the subnanoscale when using small binder molecules in the AgNP-fixed bead. Furthermore, we observed surface-enhanced Raman scattering and clarified the sensitivity of the signal intensity to the size of the binder molecules between the AgNPs, which can be explained based on optical response theory using a discrete integral with spherical cells. These results and discussion provide a guiding principle for broadband plasmonic light absorbers and for highly sensitive detection of small molecules and nanoscale biomaterials based on vast numbers of nanogaps produced by a bottom-up self-assembly process.     

Intramolecular Benzyne–Phenolate [4+2] Cycloadditions

An intramolecular benzyne–phenolate [4+2] cycloaddition is reported. Benzyne precursors, having vicinal halogen‐sulfonate functionalities, linked with a phenol(ate) by various tether groups undergo efficient intramolecular [4+2] cycloaddition by treatment with either Ph₃MgLi or nBuLi for halogen–metal exchange to form various benzobarrelenes.     

Spin-crossover in cobalt(II) compounds containing terpyridine and its derivatives

In this review article we discuss the unique and novel magnetic properties for the cobalt(II) compounds with a variety of terpy derivatives including substituents at the 4-position. These are also compared with the unsubstituted terpy cobalt(II) complex. Since the first SCO cobalt(II) complex with terpy ligand was reported, this system has been widely studied. SCO cobalt(II) complexes possessing terpy or OH-terpy ligand reveal incomplete or gradual SCO behavior. The pyterpy-appended cobalt(II) complex shows SCO depending on the guest molecules involved. Cobalt(II) complexes with long-alkylated terpy ligands, [Co(Cn-terpy)₂](BF₄)₂ (n = 16, 14 and 12) have been synthesized and some were characterized by single crystal X-ray analysis. Furthermore, variable-temperature magnetic susceptibility indicated that the non-solvated compounds [Co(Cn-terpy)₂](BF₄)₂ (n = 16, 14 and 12) exhibit “reverse spin transition” phenomenon with wide thermal hysteresis around room temperature. In addition, the solvated compound [Co(C12-terpy)₂](BF₄)₂·EtOH·0.5H₂O shows “re-entrant SCO” behavior. The long alkyl chains in SCO cobalt(II) complexes can lead to novel physical properties resulting from a synergetic effect between SCO and response of the flexibility toward external stimuli.     

Gelation process of amylose-DMSO-water system

Amylose gel is obtained by cooling amylose aqueous solution at a certain cooling rate. In order to clarify the gelation process of amylose in the mixed solvent of water and DMSO, the characteristics of turbidity and dynamic viscoelasticity of the solution as a function of temperature have been studied by optical and rheological methods, respectively. Accordingly, cloud temperature (Tc) at which the aggregation of amylose occurs, and gelation temperature (Tgel) at which the elasticity began to appear were obtained. Tc and Tgel were strongly dependent on cooling rate, and these values shifted to higher temperatures with decreasing cooling rate. However, there was difference between Tc and Tgel, and Tc was higher than Tgel, indicating the gelation process occurs in two stages.     

Photo-switchable spin-crossover iron(III) compound based on intermolecular interactions

Iron(III) spin-crossover compounds, [Fe(qnal)₂]CF₃SO₃·MeOH (1·MeOH) and [Fe(qnal)₂]CF₃SO₃·acetone (1·acetone) were prepared and their spin transition properties were characterized by magnetic susceptibility measurement, Mössbauer spectroscopy and single crystal analysis. Two iron(III) compounds exhibited abrupt spin transition with thermal hysteresis loop (T _1/2?? = 115 K and T _1/2?? = 104 K for 1·MeOH, and T _1/2?? = 133 K and T _1/2?? = 130 K for 1·acetone). Single crystal analysis revealed both of the structures in high-spin (HS) and low-spin (LS) states for 1·acetone. The difference of bond length between the HS and LS states for 1·acetone was ~0.10 Å, which was corresponding to that of typical iron(III) SCO compounds. Specially, it showed strong intermolecular interactions by ???C?? stacking formed between the neighbor complexes leading to 2-D sheet. Both 1·MeOH and 1·acetone exhibited LIESST effect when it was illuminated at 1000 nm. We also confirmed that the introduction of strong intermolecular interactions, such as ???C?? stacking, can play an important role in LIESST effect.     

Fluorinated monomer–styrene copolymer latex particles: I. kinetic studies in a soap-free aqueous medium

Soap-free emulsion copolymerization of 2, 2, 2-trifluoroethyl acrylate (3FEA) with styrene was carried out by using potassium persulfate as an initiator, and the effects of the weight fraction of 3FEA in the monomer feed on the kinetics and the particle size were investigated. Monomer conversions were followed by a gravimetric method, revealing that the overall polymerization rate increased exponentially with an increase in the weight fraction of 3FEA. According to dynamic light scattering measurement, the final particle size was found to decrease with an increase in the weight fraction of 3FEA. The number of particles for 3FEA homopolymerization was roughly twice as large as that at the fraction of 0.9, although both fractions had the almost same polymerization rates. These results indicate that soap-free emulsion homopolymerization of 3FEA would proceed not only inside the polymer particles but also in the aqueous phase throughout the polymerization.     

Important role of the 3-mercaptopropionamide moiety in glutathione: promoting effect on decomposition of the adduct of glutathione with the oxoammonium ion of TEMPO

Cyclic voltammetry of TEMPO in aqueous 0.1 M NaOH in the presence of glutathione (GSH) or cysteine (Cys) indicated the following points: (i) Both of the thiols rapidly formed adducts 3 with oxoammonium ion 1 anodically generated from TEMPO. (ii) 3 generated from GSH entered a succeeding reaction that generated N-oxide anion 2- (the reduced TEMPO). (iii) 3 produced from Cys remained intact over the time scale of voltammetry. A structural feature of GSH was considered to contribute to the observed behavior of this tripeptide. Possible structural features were evaluated by screening various thiols on the basis of whether they provided GSH-like voltammetric results. The 3-mercaptopropionamide group with an amide hydrogen in GSH was determined to be responsible for the observed difference between GSH and Cys. The likely function is to transform 3 from GSH into a 5-imino-1,2-oxathiolane intermediate, thereby releasing 2-. Product analysis for reactions of model thiols representing GSH and Cys with 1 provided support for this argument and suggested that the reaction of GSH or Cys with 1 would produce the corresponding disulfides, regardless of whether a five-membered ring intermediate was formed. The proposed function of the 3-mercaptopropionamide moiety of GSH may provide useful insight for the molecular design of exogenous thiol compounds as novel drugs for the treatment of GSH-depletion-related disorders.     

Noise-Limitations of Coherence Imaging Based on Wavefront Folding Interferometry

Noise-limitations of the coherence imaging system based on the wavefront folding interferometer are studied. The signal-to-noise ratio SNR in two kinds of noise-limiting cases, the photon-noise-limit and the detector-noise-limit, is derived and are compared with the experimental results. The experimental demonstration is conducted using a wavefront folding interferometer and a single slit that provides the light source. An ensemble of ten sets of data are measured under the same conditions and the statistics of the retrieved images are computed from them. It is verified that the experimental results generally agree with the theoretical expectations.