Photoluminescence of americium(III) in aqueous and organic solutions

The influence of different solvents on Am³⁺·sold photoluminescen has been studied. A great increase of luminescence lifetime in deuterated DMSO compared with water was found. The sensitization of americium(III) photoluminescence by energy transfer from ligand (TTA or nalidixic acid) was realized for the first time. The photoluminescence of AmW₁₀ O₃₆ ^9– was discovered and some of its characteristics were measured. The use of photoluminescence for investigation of americium complex formation in solutions was demonstrated.     

Magneto-optical enhancement by plasmon excitations in nanoparticle/metal structures

Coupling magnetic materials to plasmonic structures provides a pathway to dramatically increase the magneto-optical response of the resulting composite architecture. Although such optical enhancement has been demonstrated in a variety of systems, some basic aspects are scarcely known. In particular, reflectance/transmission modulations and electromagnetic field intensification, both triggered by plasmon excitations, can contribute to the magneto-optical enhancement. However, a quantitative evaluation of the impact of both factors on the magneto-optical response is lacking. To address this issue, we have measured magneto-optical Kerr spectra on corrugated gold/dielectric interfaces with magnetic (nickel and iron oxide) nanoparticles. We find that the magneto-optical activity is enhanced by up to an order of magnitude for wavelengths that are correlated to the excitation of propagating or localized surface plasmons. Our work sheds light on the fundamental principles for the observed optical response and demonstrates that the outstanding magneto-optical performance is originated by the increase of the polarization conversion efficiency, whereas the contribution of reflectance modulations is negligible.     

General spin structures of organic radicals

Changes of spin structures in the course of chemical reactions have been investigated on the basis of the Heisenberg model, asseming two different exchange integrals. It is found that an axial spin structure changes to another axial spin structure passing through the torsional structure such as the triangular spin arrangement in the cyclic three-electron system. The spin structures of odd polyenic cyclic radicals and the tetrahedral H₄ radical are also torsional spin arrangements.     

Fermi resonance interface modes in organic multilayer structures

Due to intermolecular anharmonicity a new type of vibrational as well as electronic excitation arises in the vicinity of the interface of two organic crystals for which the condition of Fermi resonance (2ω₁ ≈ ω₂) takes place, where ω₁ and ω₂ are eigenfrequencies of contacting crystals.     

Octahedral tilting in MM'X4 metal-oxide organic layer structures

Three metal-oxide organic frameworks have been synthesized and characterized: vanadium 1,4-benzenedicarboxylate, V2O2F0.6(OH)1.4(BDC).0.4H 2O (1); indium 1,4-benzenedicarboxylate, In 2F2.2(OH)1.8(BDC).1.6H2O (2); and aluminum 1,4-benzenedicarboxylate Al2F3(OH)(BDC) (3). The three-dimensional structures of 1, 2, and 3 have the same framework topology as the previously reported vanadium (III) 1,4-benzenedicarboxylate, VIII2(OH)2F2(BDC). The frameworks consist of inorganic layers constructed from corner sharing ML 6 octahedra (M=V, In, Al and L=OH, F) linked by BDC ligands. The structures are related to a general class of perovskite-related layer structures with composition MM'X4. The layers show characteristic distortions that can be related to tilting of the ML 6 octahedra. In particular the structure of 1 consists of O-V distances that strongly alternate along the b axis. The electronic consequences of this distortion then create a tilting of the 1,4-benzenedicarboxylate ligand about the a axis. Crystal data: 1, orthorhombic, space group Pmna, a=7.101(2) A, b=3.8416(11) A, c=20.570(6) A; 2, orthorhombic, space group Cmcm, a=7.490(4) A, b=21.803(1) A, c=8.154(4) A; 3, monoclinic, space group P2(1)/m, a=10.7569(8) A, b=6.7615(3) A, c=7.1291(3) A, beta=76.02(1) degrees.     

Photoluminescence enhancement of PEG-modified YAG:Ce3+ nanocrystal phosphor prepared by glycothermal method

Y3Al5O12:Ce3+ (YAG:Ce3+) nanocrystals were synthesized in 1,4-butylene glycol (BG) with and without poly(ethylene glycol) (PEG) by the glycothermal method. The internal quantum efficiency of the photoluminescence (PL) corresponding to the 5d --> 4f transition of Ce3+ in the YAG:Ce3+ nanocrystal increased from 21.3 to 37.9% by addition of PEG, while no appreciable change in the primary particle size, the crystallite size, and the lattice distortion was recognized by transmission electron microscopy and X-ray diffractometry. The thermogravimetry-differential thermal analysis, Fourier transform infrared absorption spectroscopy and 1H --> 13C cross-polarization magic angle spinning nuclear magnetic resonance (CP-MAS NMR) confirmed the preferential coordination of PEG to the YAG:Ce3+ nanocrystal. 27Al single-pulse excitation MAS NMR reveals that the ratio of the 4-fold coordination site to the 6-fold coordination site increased from 0.53 to 0.72 by addition of PEG. We conclude that the surface modification of the YAG:Ce3+ nanocrystal by PEG induces the surface passivation, the prevention of the oxidation of Ce3+ to Ce4+, the promotion of the incorporation of Ce3+ into YAG and the local structural rearrangement, resulting in the PL enhancement.     

Photoluminescence from C60-coupled porous structures formed on Fe+-implanted silicon

111-oriented p-type Si wafer with a resistivity of 1-5 Omega cm was implanted with Fe+ and then annealed at 1100 degrees C in N2 for 60 min, followed by anodization in a solution of HF to form porous structure with beta-FeSi2 nanocrystallites. Photoluminescence (PL) spectral measurements show that a strong PL peak appears in the range of 610-670 nm. The position of the PL peak remains unchanged, but its intensity increases with the storage time in air until about three months and then saturates. C60 molecules were chemically coupled on the porous structure through a kind of silane coupling agent to form a nanocomposite. It is revealed that the stable PL peak monotonically shifts to a pinning wavelength at 570 nm. Experimental results from PL, PL excitation, Raman scattering, and x-ray diffraction measurements clearly show that the pinned PL originates from optical transition in C60-related defect states, whereas the photoexcited carriers occur in the beta-FeSi2 nanocrystallites formed during anodization. This work opens a new way to tailor nanometer environment for seeking optimal luminescent properties.     

Novel ice structures in carbon nanopores: pressure enhancement effect of confinement

We report experimental results on the structure and melting behavior of ice confined in multi-walled carbon nanotubes and ordered mesoporous carbon CMK-3, which is the carbon replica of a SBA-15 silica template. The silica template has cylindrical mesopores with micropores connecting the walls of neighboring mesopores. The structure of the carbon replica material CMK-3 consists of carbon rods connected by smaller side-branches, with quasi-cylindrical mesopores of average pore size 4.9 nm and micropores of 0.6 nm. Neutron diffraction and differential scanning calorimetry have been used to determine the structure of the confined ice and the solid-liquid transition temperature. The results are compared with the behavior of water in multi-walled carbon nanotubes of inner diameters of 2.4 nm and 4 nm studied by the same methods. For D(2)O in CMK-3 we find evidence of the existence of nanocrystals of cubic ice and ice IX; the diffraction results also suggest the presence of ice VIII, although this is less conclusive. We find evidence of cubic ice in the case of the carbon nanotubes. For bulk water these crystal forms only occur at temperatures below 170 K in the case of cubic ice, and at pressures of hundreds or thousands of MPa in the case of ice VIII and IX. These phases appear to be stabilized by the confinement.     

Fluorescence lifetime enhancement of organic chromophores attached to gold nanoparticles

We present for the first time experimental evidence of fluorescence lifetime enhancement of organic chromophores attached to metal nanospheres via radiative decay engineering. The hybrid system (HS) was a modified "diconjugated" molecular probe, 4-acetamido-4'-maleimidylstilbene-2,2'-dithiol (AMDT), covalently bound to the surface of 5-nm-diameter Au nanospheres by its two sulfur atoms, at a distance d < 1 nm and with its molecular axis parallel to the surface of the nanoparticle surface. We measured a fluorescence lifetime increase of a factor of 2 at room temperature (tau(AMDT) = (4.32 +/- 0.10) ns and tau(HS) = (8.73 +/- 0.23) ns) and a factor of 3.4 at 4.2 K (tau(AMDT) = (2.64 +/- 0.07) ns and tau(HS) = (7.96 +/- 0.14) ns). We also found that the fluorescence quantum yield of this hybrid system is not reduced, proof of a weak energy transfer between the molecular probe and the nanoparticle. These results demonstrate that a molecular dipole oriented parallel to the metal surface tends to be reduced by the coupling with its image.     

Optical enhancement effects of plasmonic nanostructures on organic photovoltaic cells

In this article, the optical enhancement effects of plasmonic nanostructures on OPV cells were reviewed as an effective way to resolve the mismatch problems between the short exciton diffusion length in organic semiconductors (around 10 nm) and the large thickness required to fully absorb sunlight (e.g. hundreds of nanometers). Especially, the performances of OPVs with plasmonic nanoparticles in photoactive and buffer layers and with periodic nanostructures were investigated. Furthermore, nanoimprint lithography-based nanofabrication processes that can easily control the dimension and uniformity of structures for large-area and uniform plasmonic nanostructures were demonstrated.     

Electronic spectra and structures of organic π-systems

The variable integrals method II presented in the preceding paper, which needs no guess work in choosing a set of parameters to calculate the electronic spectra of molecules and contains no arbitrary adjusting parameters, is applied to various kinds of nitrogen- or oxygen-containing heteroatomic molecules in order to check the applicability of this method. At the same time the variable integrals method I, a simplified method of the variable integrals method II, is also applied to the same systems and some sulphur-containing molecules. The both methods give similar results and the agreement between theory and experiment is satisfactory.

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Zusammenfassung Die in der vorangehenden Arbeit dargestellte II. Methode variabler Integrale benötigt zur Auswahl eines Parametersatzes zur Berechnung von Molekülspektren keine Abschätzungen oder willkürliche Parameteradjustierungen. Sie wird in der vorliegenden Arbeit auf eine Reihe von Stickstoff oder Sauerstoff enthaltenden Heterocyclen angewendet, um ihre Leistungsfähigkeit zu untersuchen. Die Ergebnisse sind mit denjenigen, die mit der ähnlichen I. Methode variabler Integrale gewonnen wurden, vergleichbar. Zusätzlich werden mit der letzteren Methode einige Schwefel enthaltene Heterozyklen behandelt. Die Übereinstimmung von Theorie und Experiment ist zufriedenstellend.

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Partly presented at the 21st Annual Meeting of the Chemical Society of Japan, Osaka, April, 1968.

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The calculation has been carried out on a HITAC 5020 computer at the computation centre of the University of Tokyo.     

Electronic spectra and structures of organic π-systems

Semiempirical SCFMO calculations have been carried out on heterocyclic -systems such as benzoxazole, benzotriazole, -pyrone, pyridonimine, pyridonemethide, benzothiazole and so on. A new modification of the Wolfsberg-Helmholz formula has been introduced in the evaluation of the core resonance integrals. The calculated transition energies are in good agreement with the experimental data.The calculation has been carried out on a HITAC 5020 computer at the computation centre of the University of Tokyo.     

Characteristic polynomials of organic polymers and periodic structures

It is shown that the Frame's method (also, Le Verrier-Faddeev's method) for characteristic polynomials of chemical graphs can be extended to periodic graphs and structures. The finite periodic structures are represented by cyclic structures in the Born-von Kárman boundary condition which leads to complex matrices. In this article we demonstrate that our earlier computer program (based on Frame's method) can be extended to these periodic networks. The characteristic polynomials of several lattices such as polydiacetylenes, one-dimensional triangular, square, and hexagonal lattices are obtained. These polynomials can be obtained with very little computer time using this method.     

Flow‐modulated targeted signal enhancement for volatile organic compounds

Comprehensive two‐dimensional gas chromatography is a technique that is becoming more widespread within the analytical community, especially in the separation of complex mixtures. Modulation in comprehensive two‐dimensional gas chromatography can be achieved by manipulating temperature or flow and offers many advantages such as increased separation power, but one underutilized advantage is increased detectability due to the reduction of peak width from the use of a modulator. A flow modulator was used to selectively target analytes for increased detectability with a standard flame ionization detector operated at 100 Hz, without the need for cryogens or advanced modulation software. By the collection of the entire peak volume followed by peak transfer rather than further separation, an increase of 12 times in peak height and detectability was realized for the analytes tested using an internal loop modulator configuration. An external loop flow modulator configuration allowed for more volatile analytes (with k < 5), and demonstrated an analyte detectability enhancement factor of at least 6. The collection loop size can be readily increased with an external loop configuration to accommodate for these naturally broader peaks. This novel flow modulated targeted signal enhancement approach was applied to industrially significant analyses like the analysis of methanol in a hydrocarbon streams. Methanol was detected at 7 ppb with a conventional flame ionization detector and without the need for pre‐concentration.     

应用表面等离激元提高有机发光器件效率的研究进展

表面等离激元（SPP）存在于金属和介质界面,是光场和金属表面自由电子相互作用而产生的电子集体振荡行为.一方面,由于在金属纳米颗粒表面会形成局域的SPP震荡（LSP）,可以调控金属表面附近分子的发光性质,因此,很多研究者尝试在有机电致发光器件（OLED）中引入金属纳米颗粒,利用LSP改善OLED器件性能;另一方面,在传统发光器件中,由于金属表面等离激元的波矢量和自由光波的波矢量不匹配,无法辐射成自由光波,最终只能以热能的形式耗散掉.通过改变金属表面形貌,如附加光栅结构等方法,使得SPP的能量能够耦合成自由光,从而提高发光器件的外量子效率.利用SPP来提高有机发光器件的效率,已经引起广泛的关注,本文着重综述以下两个方面的工作：一是采用金属纳米颗粒的LSP提高荧光分子辐射跃迁的几率,从而提升发光器件的内量子效率;二是利用有序或无序光栅结构使得SPP与自由光的波矢匹配来提高器件的耦合出光,从而提升外量子效率.     

Some factors in membrane structures on permselectivity for organic liquid mixtures

Control of permselectivity based on the structure of the microphase separation of graft copolymer membranes, improvement of ethanolpermselectivity by surface modification of polymer membranes, and enhancement of ethanol-permselectivity with improvements in the membrane separation technique for aqueous ethanol solutions are discussed.     

Comparison of conventional and inverted structures in fullerene-free organic solar cells

A n-type small molecule DC-IDT2 F, with 4,4,9,9-tetrakis(4-hexylphenyl)-indaceno[1,2-b:5,6-b]dithiophene as a central building block, furan as π-bridges, and 1,1-dicyanomethylene-3-indanone as end acceptor groups,was synthesized and used as an electron acceptor in solution-processed organic solar cells(OSCs). DC-IDT2 F exhibited good thermal stability, broad and strong absorption in 500–850 nm, a narrow bandgap of 1.54 e V,LUMO of –3.88 eV, HOMO of –5.44 eV and an electron mobility of 6.5 × 10–4cm2/(V·s). DC-IDT2F-based OSCs with conventional and inverted structures exhibited power conversion efficiencies of 2.26 and 3.08%, respectively. The effect of vertical phase separation and morphology of the active layer on the device performance in the two structures was studied.