One-photon photophysics and two-photon absorption of 4-[9,9-di(2-ethylhexyl)-7-diphenylaminofluoren-2-yl]-2,2':6',2'-terpyridine and their platinum chloride complexes

The synthesis, one-photon photophysics and two-photon absorption (2PA) of three dipolar D-π-A 4-[9,9-di(2-ethylhexyl)-7-diphenylaminofluoren-2-yl]-2,2':6',2'-terpyridine and their platinum chloride complexes with different linkers between the donor and acceptor are reported. All ligands exhibit (1)π,π* transition in the UV and (1)π,π*/(1)ICT (intramolecular charge transfer) transition in the visible regions, while the complexes display a lower-energy (1)π,π*/(1)CT (charge transfer) transition in the visible region in addition to the high-energy (1)π,π* transitions. All ligands and the complexes are emissive at room temperature and 77 K, with the emitting excited state assigned as the mixed (1)π,π* and (1)CT states at RT. Transient absorption from the ligands and the complexes were observed. 2PA was investigated for all ligands and complexes. The two-photon absorption cross-sections (σ(2)) of the complexes (600-2000 GM) measured by Z-scan experiment are much larger than those of their corresponding ligands measured by the two-photon induced fluorescence method. The ligand and the complex with the ethynylene linker show much stronger 2PA than those with the vinylene linker.     

Relation between two-photon absorption and dipolar properties in a series of fluorenyl-based chromophores with electron donating or electron withdrawing substituents

We investigate two-photon absorption (2PA) in a series of fluorenyl-based 9,9-diethyl-2-ethynyl-7-((4-R-phenyl)ethynyl)-9,9a-dihydro-4aH-fluorene chromophores with R being various electron donating (ED) and electron withdrawing (EW) groups. We use wavelength-tunable femtosecond laser pulses to measure the 2PA cross sections in the lowest dipole-allowed transition and show that the substituents with stronger ED or EW character enhance the peak 2PA cross section (up to σ(2) ～ 60-80 GM) while the neutral substituents lead to smaller cross sections, σ(2) < 10 GM. We apply two-level approximation to establish a quantitative relation between the 2PA in the pure electronic transition (0-0) and the corresponding change of the permanent electric dipole moment upon the excitation (Δμ). This relation is elucidated by comparing Δμ values obtained from the 2PA measurements with quantum-chemical calculations and with measurements of solvatochromic shifts in a series of solvents. We show that the calculated Δμ correlate well with the values obtained from the 2PA spectroscopy. The Δμ values obtained from the solvatochromic shifts agree well with the above two methods for the chromophores with neutral or weak EW or ED substituents. On the other hand, stronger EW or ED end groups give much larger Stokes shifts, which lead to an overestimation of the Δμ values. We tentatively attribute this effect to the excitation-induced electronic density change occurring predominantly at the substituent side of the molecule, which causes the effective point dipole associated with the Δμ to interact more strongly with the surrounding solvent.     

In vivo detection of applied electric currents by magnetic resonance imaging

Magnetic resonance imaging is very sensitive to magnetic field variations. This inherent sensitivity can be exploited to measure small electric currents flowing in the human body. This report describes an experiment in which the magnetic fields produced by small currents applied to the forearm of a living subject have been detected in the tissue. It shows how such measurements have been used to measure current density. The suggested technique is used to measure one component of a current density in a saline solution in vitro.     

New families of supermicroporous metal oxides: the link between zeolites and mesoporous materials

Sol-gel hydrolysis reactions in propanol of two or more metal acetates or alkoxides in n-alkylamines have been found to yield porous mixed oxides with the presence of pores largely in the 10-20 A region.     

Gold(I) and platinum(II) complexes with a new diphosphine ligand based on the cyclotriphosphazene platform

A new diphosphine ligand assembled on the cyclotriphosphazene platform forms linear chelate and dimetallic bridged complexes with Au(I) and a cis-chelate complex with Pt(II).     

Interaction of the glycoalkaloid tomatine with DMPC and sterol monolayers studied by surface pressure measurements and Brewster angle microscopy

The interaction of the glycoalkaloid tomatine with monolayers of dimyristoylphosphatidylcholine (DMPC) and cholesterol, as well as other selected sterols, has been investigated using surface pressure measurements at constant area and Brewster angle microscopy (BAM). The interaction of tomatine with sterol monolayers is found to vary with the structure of the sterol. The interaction of tomatine with cholesterol-containing monolayers results in a surface pressure increase accompanied by the appearance of a mottled texture. Morphological changes are observed that suggest the formation of tomatine-cholesterol complexes that aggregate at the water-air interface. No morphology change observable by BAM is observed for monolayers containing epicholesterol, suggesting that the stereochemistry of hydrogen bonding between the sterol and the sugar units on tomatine is of particular significance. Strong interactions are observed with cholestanol- and coprostanol-containing monolayers, and BAM reveals formation of spiked aggregates upon interaction with 7:3 mole ratio DMPC/coprostanol mixed monolayers. More modest surface pressure changes are observed for cholestenone- and epicoprostanol-containing monolayers. A much smaller surface pressure increase is observed when tomatine is injected beneath a pure DMPC monolayer.     

High magnetostriction coefficient of Mn substituted cobalt ferrite sintered from nanocrystalline powders and after magnetic field annealing

Magnetostriction characteristics of Mn substituted cobalt ferrite, CoFe_2?xMn_xO₄ (0 ≤ x ≤ 0.3), sintered from nanocrystalline powders of average particle size of ～4 nm have been studied. Larger value of magnetostriction at lower magnetic field is achieved after substitution of Mn for Fe. The maximum value of magnetostriction coefficient is not much affected and the slope of the magnetostriction is increased with increasing Mn content. Higher maximum value of magnetostriction coefficient (λ) of 234 ppm comparable to that of the unsubstituted composition with larger strain derivative (dλ/dH) is obtained for x = 0.2 in CoFe_2?xMn_xO₄. The magnetostriction coefficient is increased to 262 ppm with further enhancement in the strain derivative after annealing the sintered compact at 300 °C in a magnetic field of 400 kA/m for 30 min.     

Excited-state absorption in a terpyridyl platinum(II) pentynyl complex

The singlet excited-state lifetime of a terpyridyl platinum(II) pentynyl complex was determined to be 268+/-87 ps by fitting femtosecond transient absorption data, the triplet excited-state lifetime was found to be 62 ns by fitting nanosecond transient absorption decay data, and the triplet quantum yield was measured to be 0.16. A ground-state absorption cross section of 2.5 x 10(-19) cm(2) at 532 nm was deduced from UV-vis absorption data. Excited-state absorption cross sections of 3.5 x 10(-17) cm(2) (singlet) and 4.5 x 10(-17) cm(2) (triplet) were obtained by using a five-level dynamic model to fit open-aperture Z scans at picosecond and nanosecond pulse widths and a variety of pulse energies.     

Magnetic and Mössbauer spectroscopic studies of NiZn ferrite nanoparticles synthesized by a combustion method

The properties of nanocrystalline Ni_0.5Zn_0.5Fe₂O₄ synthesized by an auto-combustion method have been investigated by magnetic measurements and Mössbauer spectroscopy. The as-synthesized single phase nanosized ferrite powder is annealed at different temperatures in the range 673–1,273 K to obtain nanoparticles of different sizes. The powders are characterized by powder X-ray diffraction, vibrating sample magnetometer, transmission electron microscopy and Mössbauer spectroscopy. The as-synthesized powder with average particle size of ~9 nm is superparamagnetic. Magnetic transition temperature increases up to 665 K for the nanosized powder as compared to the transition temperature of 548 K for the bulk ferrite. This has been confirmed as due to the abnormal cation distribution, as evidenced from room temperature Mössbauer spectroscopic studies.     

Multi-C−C/C−N-Coupled Light-Emitting Aliphatic Terpolymers: N−H-Functionalized Fluorophore Monomers and High-Performance Applications

To circumvent costly fluorescent labeling, five nonconventional, multifunctional, intrinsically fluorescent aliphatic terpolymers ( 1 – 5 ) have been synthesized by C−C/C−N-coupled, solution polymerization of two non-emissive monomers with protrusions of fluorophore monomers generated in situ. These scalable terpolymers were suitable for sensing and high-performance exclusion of Cu^II, logic function, and bioimaging. The structures of the terpolymers, in situ attachment of fluorescent monomers, aggregation-induced enhanced emission, bioimaging ability, and super adsorption were investigated by ¹H and ¹³C NMR, EPR, FTIR, X-ray photoelectron, UV/Vis, and atomic absorption spectroscopy, thermogravimetric analysis, high-resolution transmission electron microscopy, dynamic light scattering, solid-state fluorescence, fluorescence imaging, and fluorescence lifetime measurements, as well as by isotherm, kinetics, and thermodynamic studies. The geometries and electronic structures of the fluorophores and the absorption and emission properties of the terpolymers were examined by DFT, time-dependent DFT, and natural transition orbital analyses. For 1 , 2 , and 5 , the limits of detection were determined to be 1.03×10⁻⁷, 1.65×10⁻⁷, and 1.77×10⁻⁷ m , respectively, and the maximum adsorption capacities are 1575.21, 1433.70, and 1472.21 mg g⁻¹, respectively.