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131.
A novel method has been developed to fabricate the assembly of Au colloidal nanoparticles (NPs) using SiO(2) monomers. The key strategy was the use of a controlled sol-gel procedure including hydrolysis, deposition, and condensation of tetraethyl orthosilicate (TEOS). Namely, the assembly of Au NPs was created by the anisotropic deposition of SiO(2) monomers and subsequent permanent fixing by the growth of a SiO(2) shell. Various assemblies of Au NPs such as dimer, trimer, and pearl-chain morphology were fabricated by systematically changing the concentration and injection speed of TEOS. A longitudinal plasmon resonance band was observed as a result of the assembly of Au NPs and can be tuned from visible to near-infrared by altering the length of pearl-chain morphology. In addition, single Au NP was homogeneously coated with a SiO(2) shell by means of controlling the deposition rate of SiO(2) monomers during a Sto?ber synthesis without the use of a silane coupling agent or bulk polymer as the surface primer to render the Au surface vitreophilic. The Au NPs (mean size 11.4 nm in diameter) were thus encapsulated into SiO(2) beads with a wide range of sizes (from 20 to 50 nm in diameter). These pure SiO(2)-coated Au beads with tunable shell thickness should be crucial for biosensors, particularly as Raman-tag particles. 相似文献
132.
Ishizuka T Sinks LE Song K Hung ST Nayak A Clays K Therien MJ 《Journal of the American Chemical Society》2011,133(9):2884-2896
A series of mono-, bis-, tris-, and tetrakis(porphinato)zinc(II) (PZn)-elaborated ruthenium(II) bis(terpyridine) (Ru) complexes have been synthesized in which an ethyne unit connects the macrocycle meso carbon atom to terpyridyl (tpy) 4-, 4'-, and 4'-positions. These supermolecular chromophores, based on the ruthenium(II) [5-(4'-ethynyl-(2,2';6',2'-terpyridinyl))-10,20-bis(2',6'-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II)-(2,2';6',2'-terpyridine)(2+) bis-hexafluorophosphate (RuPZn) archetype, evince strong mixing of the PZn-based oscillator strength with ruthenium terpyridyl charge resonance bands. Potentiometric and linear absorption spectroscopic data indicate that for structures in which multiple PZn moieties are linked via ethynes to a [Ru(tpy)(2)](2+) core, little electronic coupling is manifest between PZn units, regardless of whether they are located on the same or opposite tpy ligand. Congruent with these experiments, pump-probe transient absorption studies suggest that the individual RuPZn fragments of these structures exhibit, at best, only modest excited-state electronic interactions that derive from factors other than the dipole-dipole interactions of these strong oscillators; this approximate independent character of the component RuPZn oscillators enables fabrication of nonlinear optical (NLO) multipoles with extraordinary hyperpolarizabilities. Dynamic hyperpolarizability (β(λ)) values and depolarization ratios (ρ) were determined from hyper-Rayleigh light scattering (HRS) measurements carried out at an incident irradiation wavelength (λ(inc)) of 1300 nm. The depolarization ratio data provide an experimental measure of chromophore optical symmetry; appropriate coupling of multiple charge-transfer oscillators produces structures having enormous averaged hyperpolarizabilities (β(HRS) values), while evolving the effective chromophore symmetry from purely dipolar (e.g., Ru(tpy)[4-(Zn-porphyrin)ethynyl-tpy](PF(6))(2), β(HRS) = 1280 × 10(-30) esu, ρ = 3.8; Ru(tpy)[4'-(Zn-porphyrin)ethynyl-tpy](PF(6))(2), β(HRS) = 2100 × 10(-30) esu, ρ = 3.8) to octopolar (e.g., Ru[4,4'-bis(Zn-porphyrin)ethynyl-tpy](2)(PF(6))(2), β(HRS) = 1040 × 10(-30) esu, ρ = 1.46) via structural motifs that possess intermediate values of the depolarization ratio. The chromophore design roadmap provided herein gives rise to octopolar supermolecules that feature by far the largest off-diagonal octopolar first hyperpolarizability tensor components ever reported, with the effectively octopolar Ru[4,4'-bis(Zn-porphyrin)ethynyl-tpy](2)(PF(6))(2) possessing a β(HRS) value at 1300 nm more than a factor of 3 larger than that determined for any chromophore having octopolar symmetry examined to date. Because NLO octopoles possess omnidirectional NLO responses while circumventing the electrostatic interactions that drive bulk-phase centrosymmetry for NLO dipoles at high chromophore concentrations, the advent of octopolar NLO chromophores having vastly superior β(HRS) values at technologically important wavelengths will motivate new experimental approaches to achieve acentric order in both bulk-phase and thin film structures. 相似文献
133.
Multiple CdTe quantum dots (QDs) were incorporated in SiO(2) beads using a reverse micelle route (i.e., a water-in-oil emulsion) and a precursor solution of SiO(2)-coated CdTe QDs as the water phase. The QDs in the beads retained their initial photoluminescence efficiency (56%) because they had a thin SiO(2) shell that prevented removal of the ligands from their surface during incorporation. Because of the SiO(2) sol in the precursor solution, the size of the water pools in water-in-oil emulsion increased to 700±320nm compared to 25±5nm when an aqueous CdTe QD solution was used. The size of the beads prepared in the water pools depended strongly on the preparation parameters (water phase injection speed, tetraethyl orthosilicate concentration, reaction time). The beads were easily separated into three size ranges (60±23, 160±40, and 650±200nm) by filtering for further application. 相似文献
134.
Akiko Watanabe Naotoshi Kiyota Tetsuo Yamasaki Kazuhiro Tanda Tatsunori Miyagoe Masanori Sakamoto Masami Otsuka 《Journal of heterocyclic chemistry》2011,48(5):1132-1139
Four isomers of the monomer of peptide nucleic acid (PNA) were derived from (2S,4R)‐4‐hydroxyproline; they had different stereochemistries at the C2 and C4 positions in the pyrrolidine ring. These different backbone conformations corresponding to four different stereochemistries were realized through a combination of inversions at the C2 and the C4 positions in pyrrolidine ring. The obtained backbone frameworks were reacted with N‐benzoyl thymine to give the corresponding PNA monomers. Spectroscopic comparison of the resultant monomers confirmed their stereochemistries. J. Heterocyclic Chem., (2011). 相似文献
135.
Quantum Monte Carlo methods are used to investigate the binding of a positron to the alkali-metal hydrides, XH (X = Na and K). We obtain positron affinities for the NaH and KH molecules of 1.422(10) eV and 2.051(39) eV, respectively. These are considerably larger than the previous results of 1.035 eV and 1.273 eV obtained from multireference single- and double-excitation configuration interaction calculations. Together with our previous results for [LiH;e(+)] [Y. Kita et al., J. Chem. Phys. 131, 134310 (2009)], our study confirms the strong correlation between the positron affinity and dipole moment of alkali-metal hydrides. 相似文献
136.
137.
Kurono N Ohtsuga K Wakabayashi M Kondo T Ooka H Ohkuma T 《The Journal of organic chemistry》2011,76(24):10312-10318
Kinetic resolution of sterically hindered racemic α-tert-alkyl-α-hydroxy esters is performed by enantiomer-selective carbamoylation with the t-Bu-Box-Cu(II) catalyst (Box = bis(oxazoline)). The reaction with 0.5 equiv of n-C(3)H(7)NCO is carried out with a substrate-to-catalyst molar ratio of 500-5000 at -20 to 25 °C. The high enantiomer-discrimination ability of the catalyst achieves an excellent stereoselectivity factor (s = k(fast)/k(slow)) of 261 in the best case. A catalytic cycle for this reaction is proposed. 相似文献
138.
Sugawara S Yoshikawa T Takayanagi T Shiga M Tachikawa M 《The journal of physical chemistry. A》2011,115(42):11486-11494
We have carried out path-integral molecular dynamics simulations for hydrated sulfuric acid clusters to understand acid-dissociation and hydrogen-bonded structural rearrangement processes in these clusters from a quantum mechanical viewpoint. The simulations were performed using the PM6 semiempirical electronic structure level whose parameters were modified on the basis of the specific reaction parameters strategy so that relative energies of optimized structures, as well as water binding energies reproduce ab initio and density-functional theory calculations. We have found that the acid dissociation processes, first and second deprotonation, effectively occur in a hydrated cluster with a specific cluster size. The mechanisms of the proton-transfer processes were analyzed in detail and it was found that the distance between O in sulfuric acid and O in the proton-accepting water is playing an important role. We also found that the water coordination number of the poton-accepting water is important in the proton-transfer processes. 相似文献
139.
A combination of dimethyl sulfoxide (DMSO) and trifluoroacetic anhydride (TFAA) mediates functionalization at the 2α-position of indole derivatives. Carbon and heteroatom nucleophiles were directly introduced via a one-pot procedure in excellent yields. 相似文献
140.
Kidera M Seto Y Takahashi K Enomoto S Kishi S Makita M Nagamatsu T Tanaka T Toda M 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,78(3):1215-1219
We developed a detection technology for vapor forms of chemical warfare agents (CWAs) with an element analysis system using an electron cyclotron resonance ion source. After the vapor sample was introduced directly into the ion source, the molecular material was decomposed into elements using electron cyclotron resonance plasma and ionized. The following CWAs and stimulants were examined: diisopropyl fluorophosphonate (DFP), 2-chloroethylethylsulfide (2CEES), cyanogen chloride (CNCl), and hydrogen cyanide (HCN). The type of chemical warfare agents, specifically, whether it was a nerve agent, blister agent, blood agent, or choking agent, could be determined by measuring the quantities of the monatomic ions or CN(+) using mass spectrometry. It was possible to detect gaseous CWAs that could not be detected by a conventional mass spectrometer. The distribution of electron temperature in the plasma could be closely controlled by adjusting the input power of the microwaves used to generate the electron cyclotron resonance plasma, and the target compounds could be detected as molecular ions or fragment ions, enabling identification of the target agents. 相似文献