Novel multicellular prokaryote discovered next to an underground stream.

A diversity of prokaryotes currently exhibit multicellularity with different generation mechanisms in a variety of contexts of ecology on Earth. In the present study, we report a new type of multicellular bacterium, HS-3, isolated from an underground stream. HS-3 self-organizes its filamentous cells into a layer-structured colony with the properties of a nematic liquid crystal. After maturation, the colony starts to form a semi-closed sphere accommodating clusters of coccobacillus daughter cells and selectively releases them upon contact with water. This is the first report that shows that a liquid-crystal status of cells can support the prokaryotic multicellular behavior. Importantly, the observed behavior of HS-3 suggests that the recurrent intermittent exposure of colonies to water flow in the cave might have been the ecological context that cultivated the evolutionary transition from unicellular to multicellular life. This is the new extant model that underpins theories regarding a role of ecological context in the emergence of multicellularity.

In Situ Observation of Desorption and Direct Electron Transfer Reaction of Cytochrome c on Bare ITO Electrode with Electrochemical Slab Optical Waveguide Spectroscopy.

Cyclic voltammograms (CVs) of cytochrome c (cytc) on the bare ITO were measured with every 10 times of the continuous the solution exchange (SE) processes at the same time of slab optical waveguide (SOWG) spectral observation, and it was proved that direct electron transfer (DET) reaction functionality of cytc adsorbed on the bare ITO electrode was kept after 100 times SE processes. The existence of three kinds of cytc molecules which were weakly adsorbed, strongly adsorbed and immobilized on the bare ITO electrode below a monolayer coverage was indicated from the change in the Soret band absorbance at 408 nm due to the desorption reaction of cytc with In Situ observation by electrochemically controlled SOWG spectroscopy. As the actual procedure, 100 times of the SE process in the SOWG cell by hands induced the gradual decrease of the absorbance due to cytc desorption, and with every 10 times of the SE process SOWG absorption spectra were obtained. The SOWG absorbance decay curve was well fitted with two components exponential equation depending on the SE process numbers showing that around 31.6% of the cytc molecules adsorbed on bare ITO electrode were finally immobilized.

Vinylpyrroles: solid-state structures and aggregation-induced emission properties.

An aggregation-induced emission chromophore, vinylpyrrole, was prepared from a formylpyrrole derivative, Meldrum's acid, and 1,3-dimethylbarbituric acid. The optical properties of the chromophore both in the solution and solid states were investigated by UV-vis and fluorescence spectroscopy. Single crystal X-ray diffraction measurements revealed that the dimethylbarbituric acid adduct formed a J-aggregate in the solid and resulted in higher fluorescence quantum yield compared to the Meldrum's acid adduct. Emission enhancement was found to occur by the restriction of molecular rotation in the solid state.

Synthesis, Crystal Structure, and Photoluminescent Properties of 3,3',4,4'-Tetraethyl-5,5'-divinyl-2,2'-bipyrrole Derivatives.

Photoluminescent divinylbipyrroles were synthesized from 3,3',4,4'-tetraetyl-2,2'-bipyrrole-5,5'-dicarboxaldehyde and activated methylene compounds via aldol condensation. For mechanistic clarity, molecular structures of Meldrum's acid- and 1,3-dimethylbarbituric acid-derived divinylbipyrroles were determined by single-crystal X-ray diffraction. Photoluminescent properties of the synthesized divinylbipyrroles in dichloromethane were found to be dependent on the presence of electron withdrawing groups at the vinylic terminal. The divinylbipyrroles derived from malononitrile, Meldrum's acid, and 1,3-dimethylbarbituric acid showed fluorescent peaks at 553, 576, and 602 nm respectively. Computational studies indicated that the alkyl substituents on the bipyrrole 3 and 3' positions increased energy level of the highest occupied molecular orbital (HOMO) compared to the unsubstituted derivatives and provided rationale for the bathochromic shift of the ultraviolet-visible (UV-Vis) spectra compared to the previously reported analogs.

In situ Observation of Desorption Reaction of Cytochrome c from Solid/Liquid Interfaces with Slab Optical Waveguide Spectroscopy.

An automated solution exchange (SE) mechanism has been introduced to slab optical waveguide spectroscopy to estimate the protein immobilizing ability of a slab optical waveguide (SOWG) surface. In each SE process, SOWG spectral change in absorbance at peak position of cytochrome c (cyt.c) Soret band at 409 nm was observed to analyze the desorption ratio of cyt.c adsorbed on SOWG surface. Continuous SE processes for 100 times have successfully brought us a kind of master desorption curve of cyt.c, which was well fitted by a double exponential equation, indicating the existence of three kinds of adsorbed states, including weakly adsorbed, strongly adsorbed, and immobilized cyt.c. The present results showed that around 30 times SE processes were enough to anticipate the ratio of desorbed and immobilized amounts of cyt.c adsorbed on SOWG surface.

Efficient Upconversion by Highly Water-Soluble Cationic Sensitizer and Emitter in Aqueous Solutions with DNA.

Highly water-soluble cationic palladium porphyrin as a sensitizer and 9,10-bis(4-trimethylammoniumphenyl)anthracene as an emitter were newly synthesized. They were shown to be bound and immobilized in DNA double helix assembly from absorption, fluorescence, phosphorescence, and circular dichroism spectra. Upon excitation at 532 nm in deaerated aqueous solutions, they showed weak blue upconversion fluorescence, the efficiency of which increased dramatically in the presence of DNA. The threshold power density between the second-order and first-order power dependence of upconversion fluorescence decreased to less than a half upon addition of DNA. The emitter triplet lifetime estimated from time dependences of upconversion fluorescence at low power ns pulsed laser was found to considerably increase in the presence of DNA. From these results, DNA was concluded to work effectively in concentrating both sensitizer and emitter and in migrating excited triplet states, resulting in efficient upconversion.

Fluorescence properties of pyrene derivative aggregates formed in polymer matrix depending on concentration.

We investigated the fluorescence properties of dye aggregates formed in a poly(vinylalcohol) (PVA) matrix by phase separation. Trimethyl-(2-oxo-2-pyrene-1-yl-ethyl)-ammonium bromide (PyAm) was used as a fluorescent dye molecule. The size of PyAm aggregates in the PVA thin films were increased with increasing dye concentration, which was confirmed by atomic force microscope (AFM) measurements. The fluorescence spectra of PyAm in the PVA film at a lower concentration of 0.001 mol% only showed the monomer emission. The fluorescence peak shifted to the red with increasing dye concentration, which was assigned to a dimer or excimer-like emission. Changes in the fluorescence spectra relate to the formation of aggregates in the films. The fluorescence anisotropy decay time constant increases with increasing PyAm concentration up to the order of 100 ps. It is suggested that the exciton efficiently diffuses within the aggregates, and then was trapped at the dimer sites. We also demonstrated the application for gas sensing of nitroaromatics: 2,4-dinitrotoulene (DNT) based on the fluorescence quenching by the photoinduced electron transfer. The quenching efficiency of PyAm fluorescence reached about 43% under concentration of 2.0 mol%. The fluorescence intensity efficiently quenched at the dimer or excimer-like band. These results indicated that the efficient fluorescence quenching increases the reaction probability between PyAm and DNT by the exciton diffusion in the aggregates, called "amplified quenching". The nano-sized aggregates of PyAm formed in the PVA films are responsible for high sensitivity as an artificial fluorescent chemosensor for vapors of the nitroaromatics.

Relaxation behavior of poly(methyl methacrylate) at a water interface.

The relaxation behavior of poly(methyl methacrylate) (PMMA), spin-coated on a silicon wafer, at the water interface was examined by lateral force microscopy as a function of temperature and scanning rate. Even in water, the lateral force peak which was assigned to the segmental motion of PMMA plasticized by water molecules was clearly observed in the temperature domain. The apparent activation energy for the plasticized alpha(a)-relaxation process was much smaller than those for the original alpha(a)-relaxation processes at the intact surface and in the bulk. The depth profile of the glass transition temperature (T(g)) of the PMMA film in water was obtained, showing that T(g) decreases with proximity to the water phase. The T(g) depression observed here was best explained in terms of the water content of the film, rather than a confinement effect.

The photophysics of selectively metallated arrays of quinoxaline-fused tetraarylporphyrins.

A comprehensive study of the photophysical interactions occurring in tris-porphyrin and tetrakis-porphyrin arrays and has been undertaken. The arrays consist of porphyrins with quinoxaline units fused at the beta,beta'-pyrrolic faces of the macrocycle. The linkage geometry is such that these arrays resemble the arrangement of chromophores that constitute natural photosynthetic reaction centres (PRCs). Selective metallation of the terminal chromophores of the arrays with Zn(II) and Au(III) allows directional electron and energy transfer processes to occur. The results show that excitation at any chromophore of the arrays leads to efficient charge transfer across the length of the arrays, distances of 35 and 50 A for and , respectively. Charge recombination is several orders of magnitude slower in both cases. The excellent performance of these arrays is attributed in part to the use of quinoxalinoporphyrins. Linked appropriately, pi-system-fused porphyrins can exhibit strong electronic communication in the excited state, whilst being effectively insulated in the ground state. As such, arrays of these porphyrins might find use as components of photovoltaic devices.

Excited-state relaxation process of free-base and oxovanadium naphthalocyanine in near-infrared region.

Excited-state relaxation process of free-base and oxovanadium naphthalocyanine (H(2)Nc and VONc) in solutions and in polymer films was studied by transient absorption measurements. In polymer films only H-aggregate was observed with H(2)Nc with increasing its weight fraction, whereas VONc formed both H- and J-type aggregates. The transient absorption of singlet excited-state of H(2)Nc and VONc in toluene solution decayed with time constant of 250 +/- 30 and 12 +/- 2 ps, respectively. The relaxation from singlet excited state of H(2)Nc and VONc in toluene solution is governed by the IC and ISC, respectively. The central metal ion, VO(2+), acceralated the ISC by the spin-orbital coupling due to unpaired electron. The excited-state relaxation in polymer films differed from that in toluene solution, which originates from the exciton-exciton annihilation process. The excitation power dependence of the excited-state dynamics and weight ratio dependence of absorption spectrum suggests that the aggregation of VONcs contributes to faster decay from the singlet excited-state. The excition-exciton annihilation occurs more efficiently in VONc system compared with H(2)Nc system. The dipole-dipole interaction depending on the aggregated structure controls excited-state relaxation processes in polymer films. This is mainly due to the differences in the transition dipole moment between H- and J-type aggregates. The ultrafast deactivation of VONc in polymer films can be applied to all-optical ultrafast modulation in the optical telecommunication wavelength region.

Interfacial mobility of polymers on inorganic solids.

The segmental mobility of a typical amorphous polymer, polystyrene, at the interfaces with solid substrates was noninvasively examined by fluorescence lifetime measurements using evanescent wave excitation in conjunction with coarse-grained molecular dynamics simulation. The glass transition temperature (T(g)) was discernibly higher at the interface than in the internal bulk region. Measurements at different incident angles of excitation pulses revealed that T(g) became higher closer to the interface. The gradient became more marked with an increasing difference in the free energy at the interface between the polymer and solid substrate. The T(g) value at the interface decreased with decreasing molecular weight. However, the decrement for the interfacial T(g) was not as much as that for the bulk T(g), due to the restriction of chain end portions by the substrate. Finally, it was observed that when a film became thinner than 50 nm, the depressed mobility at the interface coupled with the enhanced mobility induced by the presence of the surface. The experimental and simulation results were in good accord with each other.

Interfacial width in polymer bilayer films prepared by double-spin-coating and flotation methods.

A spin-coating method with the aid of selective solvents has been used to construct multilayer structures for organic devices under the assumption that the solvents do not invade a preformed structure. To confirm the assumption, we examined the interfacial width (lambda(i)) of model polymer bilayers, composed of polystyrene and perdeuterated poly(methyl methacrylate), prepared by spin-coating and flotation methods. Neutron reflectivity measurements revealed that the lambda(i) value was larger for the spin-coating method than for the flotation method. These results cast doubt on the validity of the assumption. This knowledge should be kept in mind when this method is applied to construct multilayer structures.

Time-resolved studies of energy transfer from meso-tetrakis(N-methylpyridinium-4-yl)- porphyrin to 3,3'-diethyl-2,2'-thiatricarbocyanine iodide along deoxyribonucleic acid Chain.

The excitation energy transfer from meso-tetrakis(N-methylpyridinium-4-yl)porphyrin (TMPyP) to 3,3'-diethyl-2,2'-thiatricarbocyanine iodide (DTTCI) along the deoxyribonucleic acid (DNA) double strand was investigated by the steady-state absorption and fluorescence measurements and time-resolved fluorescence measurements. The steady-state fluorescence spectra showed that the near-infrared fluorescence of DTTCI was strongly enhanced up to 86 times due to the energy transfer from the excited TMPyP molecule in DNA buffer solution. Furthermore, we elucidated the mechanism of fluorescence quenching and enhancement by the direct observation of energy transfer using the time-resolved measurements. The fluorescence quenching of TMPyP chiefly consists of a static component due to the formation of complex and dynamic components due to the excitation energy transfer. In a heterogeneous one-dimensional system such as a DNA chain, it was proved that the energy transfer process only carries out within the critical distance based on the Förster theory and within a threshold value estimated from the modified Stern-Volmer equation. The present results showed that DNA chain is one of the most powerful tools for nanoassemblies and will give a novel concepts of material design.

Nonsolvents cause swelling at the interface with poly(methyl methacrylate) films.

Density profiles of a perdeuterated poly(methyl methacrylate) (dPMMA) film spin-coated on a substrate in water, hexane, and methanol, which are "nonsolvents" for dPMMA, were examined along the direction normal to the interface by specular neutron reflectivity (NR). The interfaces of dPMMA with the liquids were diffuse in comparison with the pristine interface with air; the interfacial width with water was thicker than that with hexane. Interestingly, in water, the dPMMA film was composed of a swollen layer and the interior region, which also contained water, in addition to the diffused layer. The interface of dPMMA with hexane was sharper than that with water. Although there were slight indications of a swollen layer for the dPMMA in hexane, the solvent molecules did not penetrate significantly into the film. On the other hand, in methanol, the whole region of the dPMMA film was strikingly swollen. To conserve mass, the swelling of the film by the nonsolvents is accompanied by an increase in the film thickness. The change in the film thickness estimated by NR was in excellent accord with the results of direct observations using atomic force microscopy (AFM). The modulus of dPMMA in the vicinity of the interfaces with liquids was also examined on the basis of force-distance curves measured by AFM. The modulus decreased closer to the outermost region of the film. The extent to which the modulus decreased in the interfacial region was consistent with the amount of liquid sorbed into the film.

Kinetics of photoinduced e to z isomerization of azobenzene in polystyrene films: thickness, molecular weight and temperature effects.

E to Z (trans-->cis) photoisomerization of azobenzene (Az) chromophores tagged to polystyrene (PS) in thin films was studied as functions of thickness, PS molecular weight, and temperature, using the change in absorption at 336 nm arising from the Az E isomer remaining upon ultraviolet light irradiation at 350+/-5 nm. The photoisomerization in solid films exhibited fast and slow modes. The fractional amount of the fast mode (I1) started to increase with decreasing film thickness once the films were thinner than a threshold value. This was explained in terms of a surface layer in which the photoisomerization reaction proceeds quickly, the effect of which becomes more noticeable with decreasing thickness due to a larger surface to volume ratio. The thickness dependence of the I1 fraction was insensitive to the molecular weight of the PS used. The thickness of the surface layer, estimated through a layer model analysis, increased with rising temperature up to 298 K. Interestingly, the surface layer markedly thickened at temperatures at which the molecular motion of PS is on a relatively small scale, namely, at the gamma and beta relaxation temperatures.

Variable-temperature independently driven four-tip scanning tunneling microscope.

The authors have developed an ultrahigh vacuum (UHV) variable-temperature four-tip scanning tunneling microscope (STM), operating from room temperature down to 7 K, combined with a scanning electron microscope (SEM). Four STM tips are mechanically and electrically independent and capable of positioning in arbitrary configurations in nanometer precision. An integrated controller system for both of the multitip STM and SEM with a single computer has also been developed, which enables the four tips to operate either for STM imaging independently and for four-point probe (4PP) conductivity measurements cooperatively. Atomic-resolution STM images of graphite were obtained simultaneously by the four tips. Conductivity measurements by 4PP method were also performed at various temperatures with the four tips in square arrangement with direct contact to the sample surface.

Enhanced lasing properties of dissymmetric Eu(III) complex with bidentate phosphine ligands.

The luminescent and lasing properties of Eu(III) complexes were enhanced by using an dissymmetric Eu(III) complex. The photophysical properties (the emission spectral shapes, the emission lifetimes, the emission quantum yields, and the stimulated emission cross section (SEC)) were found to be dependent on the geometrical structures of Eu(III) complexes. The geometrical structures of Eu(III) complexes were determined by X-ray single crystal analyses. The symmetrical group of Eu(hfa)3(BIPHEPO) (tris(hexafluoroacetylacetonato)europium(III) 1,1'-biphenyl-2,2'-diylbis(diphenylphosphine oxide)) was found to be C1, which was more dissymmetric than Eu(hfa)3(TPPO)2 (tris(hexafluoroacetylacetonato)europium(III) 1,2-phenylenebis(diphenylphosphine oxide): C2 symmetry) and Eu(hfa)3(OPPO)2 (tris(hexafluoroacetylacetonato)europium(III) 1,2-phenylenebis(diphenylphosphine oxide): C2 symmetry). The analytical data were supported by Judd-Ofelt analysis. The most dissymmetrical Eu(III) complex, Eu(hfa)3(BIPHEPO), showed large electron transition probability and large SEC (4.64 x 10(-20) cm2). The SEC of Eu(hfa)3(BIPHEPO) was superior to even the values of Nd-glass laser for practical use (1.6-4.5 x 10(-20) cm2). The lasing properties of Eu(III) complexes in polymer thin film were measured by photopumping of a Nd:YAG laser (355 nm). The threshold energy of lasing oscillation was found to be 0.05 mJ. The increasing rate of the lasing intensity of Eu(hfa)3(BIPHEPO) as a function of the excitation energy was much larger than that of Eu(hfa)3(TPPO)2 and Eu(hfa)3(OPPO)2. The dissymmetrical structure of Eu(hfa)3(BIPHEPO) promoted the enhancement of the lasing property.

Highly sensitive detection of transient absorption in dye-doped ultrathin polymer films by the TiO(2)/K(+) composite optical waveguide method upon pulsed laser excitation.

A composite optical waveguide (OWG) composed of a 10-18nm thick titanium dioxide (TiO(2)) film sputtered on a conventional K(+)-doped optical waveguide was first applied to detect transient absorption of organic dyes in ultrathin polymer films upon excitation with ns laser. The thickness of the TiO(2) film considerably affected the relative sensitivity of the composite OWG. The composite OWG with 10nm thick TiO(2) gave much stronger transient absorption for 30-415nm thick polymer films containing organic dyes than that with 18nm TiO(2). Transient absorption of phthalocyanine and spiropyran in 20-135nm thick polymer films was detected 3-20 times more sensitively by the composite OWG with 10nm TiO(2) than the conventional K(+)-doped OWG which showed a 150-fold sensitivity as compared with the usual normal incidence method. The relative sensitivity of the composite waveguide was also affected by the thickness and refractive index of polymers.