[Regorafenib and Trifluridine and Tipiracil Hydrochloride Can Potentially Improve the Survival Time for Patients with Advanced or Recurrent Colorectal Cancer].

Regorafenib and trifluridine and tipiracil hydrochloride(TFTD)have been recently used for the treatment of advanced or recurrent colorectal cancer during or after the third-line therapy. These drugs are expected to prolong survival. The progression- free survival period associated with each drug in clinical trials is known to be less than 2 months. However, reports on the overall survival in the sequential therapy with these drugs have been limited. In our institution, sequential therapy using regorafenib and TFTD has achieved longer median survival time(MST)than the previously reported. The MST with monotherapy and sequential therapy was 37 and 45 months, respectively. We currently have a patient who has not had cancer progression for 3 years and 6 months with monotherapy. Regorafenib and TFTD can potentially improve the survival time beyond our observations on monotherapy when used at the appropriate time and with a thorough understanding of their adverse effects.

Intercalation of a surfactant with a long polyfluoroalkyl chain into a clay mineral: unique orientation of polyfluoroalkyl groups in clay layers.

Eight novel polyfluorinated surfactants (C(n)F(2n+1)CONH(CH2)2 N(+)(CH3)2C16H33 Br(-); abbreviated as CnF-S, where n = 1, 2, 3, 4, 5, 6, 8, 10) were synthesized and their intercalation into cation-exchangeable clay was investigated. All of the polyfluorinated surfactants intercalated in amounts exceeding the cation exchange capacity (CEC) of the clay. The C4F-S and C5F-S surfactants exhibited intercalation up to 480% of the CEC as a saturated adsorption limit. On the basis of X-ray analysis, CnF-S surfactants intercalated between clay nanosheets to form a bilayer structure in which the surfactant molecules tilt at an angle of ∼60° with respect to the clay surface. The saturated adsorption limits and layer distances differed between surfactants with short (n = 1, 2) and long (n = 3-10) perfluoroalkyl chains. For long-chain surfactants, their saturated adsorption limits were independent of the perfluoroalkyl chain length and the layer distances systematically increased with increasing perfluoroalkyl chain length. These results suggest that the microscopic orientation differed between the short and long chains. X-ray analysis showed that the long-chain surfactants orient the perfluoroalkyl chains at a tilt of 41 ± 5° with respect to the clay layer. This value was in good agreement with polarized IR measurements of 42 ± 2° for this angle.

Mesoporous TiO2 core-shell spheres composed of nanocrystals with exposed high-energy facets: facile synthesis and formation mechanism.

A facile new method that combines electrospray and hydrothermal treatment is used to prepare mesoporous core-shell TiO(2) spheres with high specific surface areas and high pore volumes. Interestingly, the resulting TiO(2) spheres are composed of anatase TiO(2) nanocrystals with exposed step-like {001} and smooth {010} facets. The percentage of exposed {001} facets can be adjusted by changing the experimental parameters used in the electrospray and hydrothermal treatment processes, such as the contents of poly(N-vinyl-2-pyrrolidone) and acetic acid. The combination of high specific surface area (>100 m(2) g(-1)), high pore volume (>0.30 cm(3) g(-1)), useful pore size (10-15 nm), spherical core-shell structure, and exposed high energy facets makes these TiO(2) spheres an important candidate for use in many photoelectrochemical applications. The formation mechanism of the mesoporous TiO(2) spheres is also studied. The great advantage of this method is that interesting and complicated mesoporous superstructures can be prepared using electrospray technology.

Antireflection and self-cleaning properties of a moth-eye-like surface coated with TiO2 particles.

Poly(ethylene terephthalate) (PET) films with a moth-eye-like surface are coated with TiO(2) particles to form self-cleaning antireflective films. The use of a TiO(2) suspension of high concentration to coat the PET surface produces a thicker TiO(2) layer with smaller pores, whereas a low concentration of a TiO(2) suspension gives a thinner layer of TiO(2) with larger pores. The PET films coated with TiO(2) particles exhibit a high transmittance of 76-95% and almost no absorption in the range of 400-800 nm. The PET films coated with a TiO(2) suspension with a concentration of ≥2 vol % exhibit superhydrophilicity after irradiation with UV light. After irradiation, the superhydrophilic nature is retained for at least 18 days. The TiO(2)-coated PET films showed the ability to decompose methylene blue under UV irradiation.

Photoinduced electron transfer between the anionic porphyrins and viologens in titania nanosheets and monodisperse mesoporous silica hybrid films.

Photoinduced electron transfer between an anionic porphyrin derivative (tetrakis(p-carboxyphenyl)porphyrin; H(2)TCPP(4-)) and an electron accepting methyl viologen (MV(2+)) was investigated in two different nanoscale configurations, i.e., layered titania nanosheet (TNS) photocatalysts and ammonium-functionalized monodisperse mesoporous silica (AMMSS) particles. Cationic MV(2+) intercalated within the TNS interlayers while anionic H(2)TCPP(4-) was accommodated within AMMSS nanocavities to form (MV(2+)-TNS)/(H(2)TCPP(4-)-AMMSS) hybrid films. Upon irradiation with UV light and excitation of the TNS in the (MV(2+)-TNS)/(H(2)TCPP(4-)-AMMSS) hybrid films, the consumption of H(2)TCPP(4-) and the formation of a one-electron reduced MV(2+) (MV(+·)) were simultaneously observed. No consumption of H(2)TCPP(4-) was observed when an electrically insulating poly(styrene) (PS) was also introduced at the interface. These results suggest that photoinduced electron transfer occurred at the interface between the TNS and the AMMSS.

Stacked-structure-dependent photoelectrochemical properties of CdS nanoparticle/layered double hydroxide (LDH) nanosheet multilayer films prepared by layer-by-layer accumulation.

Inorganic multilayer films were prepared by layer-by-layer accumulation of positively charged layered double hydroxide (LDH) nanosheets and negatively charged CdS nanoparticles of different sizes. Nanoparticles were densely immobilized on LDH sheets to form a monolayer without coalescence into larger particles. The absorbance and photoluminescence intensity of immobilized CdS particles were enlarged with an increase in the accumulation number of the film. Hybrid films produced by accumulation of both monolayers of CdS particles (diameter: 5 nm) and those of smaller CdS particles (2.1 nm) exhibited characteristic photoluminescence spectra indicating the efficient energy transfer of photogenerated excitons from nanoparticle layers of smaller CdS particles to those of larger ones. LDH/CdS multilayers deposited on an F-doped SnO(2) (FTO) electrode behaved as an n-type semiconductor photoelectrode in an acetonitrile solution regardless of the size of the CdS particles immobilized, but their efficiency for photocurrent generation was greatly dependent on the stacked structure of the films. Accumulation of CdS particles of 2.1 nm in diameter on pre-coated LDH/CdS layers of 5 nm-sized CdS particles on FTO remarkably enhanced the photocurrent intensity in comparison to that in the case of accumulation of these two kinds of CdS particles in the opposite sequence. These observations can be explained by photoinduced electron transfer and energy transfer along with the band gap gradient in the films.

Photo-induced electron migrations in the nano-cavities of mesoporous silica sensitized by a cationic porphyrin dye.

Photo-induced redox reactions in a hybrid film of a cationic porphyrin dye (H2TMPyP) accommodated within a transparent mesoporous silica (MPS) film spin-coated on an FTO electrode have been investigated for such applications as the construction of efficient solar energy storage devices and novel light-stimulated sensors. In this system, anodic and cathodic photocurrents were observed under bias voltages of +0.3 V and -0.4 V, respectively. The action spectrum of the photocurrents corresponded well with the absorbance of the H2TMPyP molecules in the visible light region. Control experiments showed no photocurrents for the mesoporous silica without H2TMPyP. Our investigations showed that the H2TMPyP molecules function not only as a sensitizer but also as a mediator for electron migrations within mesoporous nano-cavities.

Reversible redox processes of poly(anilines) in layered semiconductor niobate films under alternate UV-vis light illumination.

The synthesis of polyaniline (PANI) with semiconducting layered niobate (NbO) to form PANI/NbO hybrid materials and their reversible color change under a unique redox process under the influence of UV and/or visible light have been investigated. The in-situ polymerization of anilinium chlorides (ANI) packed in a regular orientation in a bilayer structure within the NbO interlayers led to PANI/NbO hybrid powders by heat treatment using (NH(4))(2)S(2)O(8) as the catalyst. The resulting PANI of these hybrids showed the characteristics of a fully oxidized quinoid form, i.e., pernigranine (PG). The PANI/NbO suspension in H(2)O was cast on a glass substrate to form a PANI/NbO film after evaporation of the water with a good parallel orientation of the NbO layers against the glass substrate. Upon UV light irradiation in the presence of a reductant such as MeOH, the violet-colored PANI (PG) polymers within the NbO interlayers were reduced by the NbO-induced photocatalytic reactions and led to a colorless PANI, i.e., leucoemeraldine (LE). Moreover, the resulting colorless PANI/NbO films reverted back to a blue-colored PANI, i.e., emeraldine (EM), due to oxidation by the surrounding O(2) gas. The PANI/NbO hybrid films were able to retain repetitive and reversible photoinduced patterning for over 50 cycles under such alternate UV and visible light irradiation.

Photochemical electron transfer through [corrected] the interface of hybrid films of titania nano-sheets and mono-dispersed spherical mesoporous silica particles.

Photochemical Electron Transfer (ET) between an organic dye, the porphyrin derivative TMPyP, and an electron acceptor, methyl viologen MV2+, have been investigated at the interface of two different inorganic films, i.e., layered titania nano-sheets (TNS) and a monolayer film of spherical and mono-dispersed mesoporous silica (sMPS) particles (ca. 0.5 microm). TMPyP ions were intercalated within the sMPS nano-cavities to form (TMPyP-sMPS) while MV2+ ions were intercalated into the TNS interlayers to form (MV2+-TNS). The (TMPyP-sMPS) and (MV2+-TNS) films were then stacked on a silica substrate in this order to form a (MV2+-TNS)/(TMPyP-sMPS) film and, upon UV light irradiation, ET could be induced. However, when this film was stacked inversely, i.e., for the (TMPyP-sMPS)/(MV2+-TNS) films on a silica substrate, no photoinduced ET were observed. Interestingly, however, even for this photo-inactive inversely stacked film, ET could be generated by inserting a gold vapor-deposited layer between the (MV2+-TNS) and (TMPyP-sMPS) films. The conjugation conditions at the interface of the inversely stacked (TMPyP-sMPS)/(MV2+-TNS) hybrid film were, thus, confirmed to strongly affect the photoinduced electron transfers and their efficiencies.

Zinc chelation and photofluorochromic behavior of spironaphthoxazine intercalated into hydrophobically modified montmorillonite.

Spironaphthoxazine (SNO) and Zn2+ were intercalated into montmorillonite interlayers hydrophobically modified by the alkyltrimethylammonium cation during UV light irradiation. The fluorescence spectra of the montmorillonite composites were observed to vary with an increase in the UV and visible light irradiation times. These composites exhibited two types of fluorescence emissions: F1, which originates from a new species, Xs, which is different from SNO (ring-closed form) and merocyanine (MC; ring-open form), and F2, which originates from the MC-Zn complex. With increasing UV light irradiation time, the F1 intensities decreased, whereas the F2 intensities increased. Xs, which is an intermediate species between SNO and MC, was transformed into MC and then coordinated with Zn2+ (i.e., MC-Zn complex) during the UV light irradiation. The reaction rate of the formation of the MC-Zn complex decreased for the hydrophobically modified montmorillonite due to a longer alkyl chain. The retrieval changes in the F1 and F2 intensities were observed with an increasing visible light irradiation time, implying the dissociation of the MC-Zn complex into Xs and Zn2+. The dissociation especially occurred for the hydrophobically modified montmorillonite with a longer alkyl chain. The formation and disappearance of Xs and the MC-Zn complex obeyed first-order kinetics, and therefore the interconversion between Xs and MC could be regarded as the rate-determining step of the whole reaction during the UV and visible light irradiations. The photoinduced reactions of the SNO species and Zn2+ were profoundly affected by the physicochemical environment provided by the clay interlayers. It is concluded that the present photoreactions can be controlled not only by the amounts of the intercalated SNO species and Zn2+, but also by the hydrophobic environment created by the surfactant molecules.

Layered double hydroxide hybrids with dicetylphosphate.

Dicetyl phosphate (DCP) ions incorporated into layered double hydroxide (LDH) clays to form a DCP/LDH hybrid were prepared and structurally characterized by X-ray diffraction analysis, scanning electron microscopy, thermogravimetry, and differential thermal analyses. DCP was concluded not only to form well-aligned bilayer structures along the vertical axis of the LDH layers but also to be arranged in a distorted hexagonal packing orientation in the lateral planes within the DCP/LDH hybrid interlayers.

Odd-even effect of the methylene chain number in the template polymerization of alpha,beta-diacetylenecarboxylates incorporated in layered double hydroxide clay.

The present investigation reports on the significant differences observed in the efficiency of the polymerization depending on the odd- or even-numbered methylene chains of diacetylenecarboxylates, CH3(CH2)(m-1)C[triple bond]C-C[triple bond]C(CH2)(n-1)CO2- (mono-[m,n]), incorporated in layered double hydroxide (LDH) clay. Upon gamma-ray irradiation of the diacetylenecarboxylates, or mono-[m,n], in LDH clay, polymer hybrids or poly-[m,n]/LDH, which exhibited coloring from light orange to violet, were obtained. The color of the poly-[m,n]/LDH hybrids was strongly dependent on the extent of the polymerization degrees. Moreover, the polymerization degrees were controlled by the number of methylene spacers n between the carboxyl and diacetylene groups. An odd-numbered n for the methylene chain of mono-[m,n] was found to be the determining factor in the efficient polymerization of these self-assembling aggregates within the interlayers of LDH clay.

Photoinduced one-electron reduction of MV2+ in titania nanosheets using porphyrin in mesoporous silica thin films.

Composite films of a meso-(tetramethylpyridinium)porphyrin (TMPyP) hybrid incorporated in mesoporous silica (MPS) and cast on a methyl viologen (MV2+)/titania nanosheet hybrid were synthesized and a light-induced charge separation between the two could be observed. These composite thin films were able to initiate a one-electron reduction of the MV2+ ions accompanied by the simultaneous decomposition of the TMPyP organic dye within the mesoporous silica channels.

Reversible color changes in lamella hybrids of poly(diacetylenecarboxylates) incorporated in layered double hydroxide nanosheets.

The present study is an investigation of a reversible thermal color change induced in lamella hybrids of poly(diacetylenecarboxylates) incorporated in layered double hydroxide (LDH) nanosheets. These poly-[m,n]/LDH hybrids prepared by the photo- or gamma-ray-induced polymerization of diacetylenecarboxylates, i.e., CH(3)(CH(2))(m)()(-)(1)CC-CC(CH(2))(n)()(-)(1)CO(2)(-) (mono-[m,n]), and intercalated in LDH lamella sheets, were observed to develop colors ranging from yellow to blue. The change in color was found to depend greatly on the alkyl carbon numbers of the mono-[m,n] (m,n = 10,11; 5,11; 10,5; 16,1) values. Moreover, the conformational alignment of the mono-[m,n] within the LDH was observed to be a crucial factor in color development, which was greatly affected by the intercalation degrees and extent of poly(ene-yne) linkage elongation of the polymers. For the poly-[m,n]/LDH hybrids investigated, a reversible color change was found to occur repeatedly and remarkably for the poly-[10,11]/LDH hybrid. This color change occurred at temperatures between ca. 20 and 80 degrees C back and forth from purple red to bright orange, in stark contrast to the irreversible color change for poly-[10,11] without LDH. Moreover, DSC and Raman spectroscopic studies of the LDH hybrids showed that the thermochromic temperature corresponded to the phase transition temperature of 80 degrees C. XRD analysis also indicated that the poly-[m,n]/LDH hybrid could retain its lamella structure during such thermochromic color changes, enabling conformational recovery in the polymer chains by a cooling down of the hybrids to temperatures lower than the transition temperature, while the nonhybrid poly-[10,11] powders exhibited an irreversible color change at 60 degrees C, above which the polymer powder turned amorphous.

Novel soft chemical method for optically transparent Ru(bpy)3-K4Nb6O17 thin film.

A unique guest-guest ion exchange method was developed for preparing a thin film of a nano-layered K(4)Nb(6)O(17).3H(2)O that possesses both (1) optical transparency and (2) ion-exchangeability under ambient conditions without calcination at high temperature. An optically transparent Ru(bpy)(3)(2+)-K(4)Nb(6)O(17) hybrid thin film, a photoresponsive electrode, was successfully prepared by the guest-guest exchange method by use of the intercalation compound MV(2+)-K(4)Nb(6)O(17) as a precursor. The optically transparent Ru(bpy)(3)(2+)-K(4)Nb(6)O(17) hybrid thin films have been characterized by X-ray diffraction, SEM, AFM, IR, and UV spectroscopies, as well as elemental analysis. The electrochemical behavior of the ITO/Ru(bpy)(3)(2+)-K(4)Nb(6)O(17) hybrid thin film electrode was studied; it also exhibits swift photoresponse in the visible region.

Luminescence properties of rhodamine 6G intercalated in surfactant/clay hybrid thin solid films.

To develop the solid-state laser oscillator based on laser dye compounds, the incorporation of rhodamine 6G (R6G, a laser dye) in cetyltrimethylammonium (CTA+) cationic surfactant/montmorillonite clay hybrid (HpC) thin solid films was investigated. The R6G/HpC samples were prepared by immersing the HpC films into a R6G aqueous solution with various concentration. X-ray diffraction patterns of the films of HpC, measured before and after the intercalation of R6G, proved the coexistence of both the dye and surfactant in clay interlayer spaces. All prepared thin films exhibited luminescence. It indicates that CTA+ molecules play a role as a partial suppressor of the aggregation of R6G molecules which prevents fluorescence. Moreover, the luminescence property of the present thin films was observed to be dependent on the co-intercalated degree of R6G molecules, indicating that the R6G intercalating in HpC interlayer space molecules exist as two or more luminescence species in the clay interlayer space.

Reversible light-driven structural changes between the mono- and bilayer stacking alignments in 4-octadecyloxystilbazolium arylcarboxylate films.

The present investigation deals with the light-driven morphological changes in multilamella films of N-methyl-4-octadecyloxystilbazolium arylcarboxylates (C18OStz+X-) cast on glass slides. The results of XRD analysis show a photostimulated layer expansion and shrinkage of the stacked thin films along the c-axis under alternative illumination at >350 and 254 nm, respectively. It was revealed that such lamellar changes could be switched either way by a reversible transformation between the mono- and bilayer units in these stacked multilamella films. Moreover, such controlled structural adjustments in the alignment could be initiated by the photocyclodimerization of the stilbazolium moieties of the arylcarboxylate salts; i.e., a monolayer-to-bilayer transformation could be induced at a stage of only 10% cyclodimer formation. The photoinduced patterning on the surface of the films was also analyzed by SEM and fluorescence microscopic investigations.

Surface tension and its temperature coefficient of molten tin determined with the sessile drop method at different oxygen partial pressures.

The surface tension of molten tin has been determined by the sessile drop method at temperatures ranging from 523 to 1033 K and in the oxygen partial pressure (P(O(2))) range from 2.85 x 10(-19) to 8.56 x 10(-6) MPa, and its dependence on temperature and oxygen partial pressure has been analyzed. At P(O(2))=2.85 x 10(-19) and 1.06 x 10(-15) MPa, the surface tension decreases linearly with the increase of temperature and its temperature coefficients are -0.151 and -0.094 mN m(-1) K(-1), respectively. However, at high P(O(2)) (3.17 x 10(-10), 8.56 x 10(-6) MPa), the surface tension increases with the temperature near the melting point (505 K) and decreases above 723 K. The surface tension decrease with increasing P(O(2)) is much larger near the melting point than at temperatures above 823 K. The contact angle between the molten tin and the alumina substrate is 158-173 degrees, and the wettability is poor.