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1.
Chemistry ; 29(60): e202301993, 2023 Oct 26.
Artículo en Inglés | MEDLINE | ID: mdl-37581259

RESUMEN

Controlled self-assembly of PtII complexes is key to the development of optical and stimuli-responsive materials, but designing and precisely controlling them is still difficult owing to weak intermolecular interactions. Herein, we report the successful water-vapor-induced assembly of an anionic PtII complex [Pt(CN)2 (ppy)]- (Hppy=2-phenylpyridine) electrostatically loaded onto cationically charged layered double hydroxide (LDH) nanoparticles consisting of Mg2+ and Al3+ ions. When the PtII complexes were densely loaded onto the LDH nanoparticles, the assembly was maintained, even in dilute aqueous media. In the case of sparse loading, the PtII complexes were loaded discretely in the dry state; however, when water vapor was adsorbed, the increased mobility of the PtII complexes led to their assembly on the LDH nanoparticles. The presence of water vapor led to a drastic change in luminescence from green to orange.

2.
Chemistry ; 29(60): e202303224, 2023 Oct 26.
Artículo en Inglés | MEDLINE | ID: mdl-37830449

RESUMEN

Invited for the cover of this issue is the group of Masaki Yoshida and Masako Kato at Hokkaido University/Kwansei Gakuin University. The image depicts the changes in the assembly of PtII complexes with humidity on layered double hydroxide (LDH) nanoparticles, resulting in a drastic emission color change from green to orange. Read the full text of the article at 10.1002/chem.202301993.

3.
Chemistry ; 29(38): e202204002, 2023 Jul 06.
Artículo en Inglés | MEDLINE | ID: mdl-37084044

RESUMEN

A thermoresponsive structural change based on a disilane-bridged bis(pyridine) ligand and CuI is reported. Single-crystal X-ray analysis revealed that there are two polymorphs in the Cu(I) complex: octanuclear copper(I) complex at 20 °C and 1D staircase copper(I) polymer complex at -173 °C. The formation of these polymorphs is due to the flexibility of the ligand. Cu-I bond formation is observed upon cooling the sample from -10 °C to -170 °C. The temperature-induced phase transition progression was clarified by DSC, VT-PXRD, and VT-photoluminescence measurements and indicated a reversible temperature-controlled crystal-to-crystal phase transition. Observation on a VT-stage using a high-speed camera showed crystal cracking during single-crystal to single-crystal transitions between these polymorphic forms.


Asunto(s)
Cobre , Piridinas , Temperatura , Cobre/química , Cristalografía por Rayos X , Ligandos
4.
Inorg Chem ; 62(1): 66-74, 2023 Jan 09.
Artículo en Inglés | MEDLINE | ID: mdl-36543520

RESUMEN

Vapochromic materials that exhibit color/luminescence changes induced by vapor exposure have attracted considerable attention. Herein, we report the grinding- and heating-induced ON-OFF switching of the vapochromic behavior of [Pt(ppyCl2)(Clacac)] (1; ppyCl2 = 2-(3-chlorophenyl)-4-chloropyridinato, Clacac = 3-chloroacetylacetonato). 1 formed yellow and orange polymorphs (1-Y and 1-O), and 1-Y could be converted to 1-Og, which showed a very similar crystal structure but with a broadened X-ray diffraction pattern compared with that of 1-O. Moreover, 1-Og can be reversibly transformed into 1-O via heating and grinding. Notably, 1-Og underwent a N,N-dimethylacetamide vapor-induced transformation to 1-Y, whereas 1-O did not undergo such a transformation. These results indicate the ON-OFF switching of vapochromic behavior induced via grinding and heating. This finding will be beneficial for developing intelligent molecular devices.

5.
Phys Occup Ther Pediatr ; 43(6): 713-724, 2023.
Artículo en Inglés | MEDLINE | ID: mdl-36927329

RESUMEN

AIMS: To investigate the factors that contribute to subjective quality of life (QOL) in adolescents with cerebral palsy (CP). METHODS: We evaluated the subjective QOL in 51 adolescents with CP through interviews using the Japanese version of KIDSCREEN-27 (J-KIDSCREEN-27) and compared the scores with those of 60 typically developing adolescents. Correlations of subjective QOL with age, sex, the levels of functions (gross motor, manipulation, and communication), intelligence, the level of activity of daily living (ADL), and the type of educational support were examined. Thereafter, we investigated the predictors of the subjective QOL by multiple regression analysis. RESULTS: The total QOL scores and individual J-KIDSCREEN-27 domains were not significantly different from those of typically developing adolescents. Sex, manipulation and communication functions, and intelligence had no relationship with subjective QOL. Gross motor function and ADL level negatively correlated with satisfaction with the school environment. Multiple regression analysis revealed that higher age predicts lower psychological well-being, lower gross motor function predicts higher satisfaction with the school environment, and attending schools or classes for special needs predicts higher physical well-being. CONCLUSIONS: Seeking adequate support for mildly affected adolescents attending regular classes will be the key to further improving subjective QOL in adolescents with CP.


Asunto(s)
Parálisis Cerebral , Calidad de Vida , Humanos , Adolescente , Calidad de Vida/psicología , Pueblos del Este de Asia , Padres/psicología , Bienestar Psicológico , Encuestas y Cuestionarios
6.
Chemistry ; 28(32): e202200703, 2022 Jun 07.
Artículo en Inglés | MEDLINE | ID: mdl-35446453

RESUMEN

The vapochromic single-crystal-to-single-crystal (SCSC) transformation of a highly luminescent PtII complex bearing an N-heterocyclic carbene [Pt(CN)2 (tBu-impy)] (tBu-impyH+ =1-tert-butyl-3-(2-pyridyl)-1H-imidazolium) is reported. The trihydrate form of the complex, which exhibits blue 3 MMLCT emission owing to weak Pt⋅⋅⋅Pt interactions, changed its luminescence color from blue to yellowish-green upon the desorption of water molecules while keeping the high emission quantum yield of more than 0.45. Variable-temperature and continuous in-situ tracking of single-crystal X-ray diffraction measurements revealed that the SCSC transformation proceeds reversibly by the release and reabsorption of water molecules, thereby changing the stacked structure slightly. As a result, the dynamics of vapor-induced SCSC transformation were elucidated: that the anhydrous form returned to the original trihydrate form in a two-step process under a water vapor atmosphere. In addition, the PtII complex exhibited a similar SCSC response accompanied by a luminescence color change in the presence of methanol vapor, while being inactive toward ethanol vapor.

7.
Chemistry ; 28(48): e202200716, 2022 Aug 26.
Artículo en Inglés | MEDLINE | ID: mdl-35754004

RESUMEN

A complex comprising one [Re(CO)3 ]+ unit and a phthalocyanine (Pc) ligand (Re1 Pc) is shown to function as a photo-induced CO-releasing molecule (photoCORM) in the presence of O2 and a coordinative solvent under irradiation with red light, which can deeply penetrate living tissues. Transient absorption spectroscopic measurements indicate very short excited-state lifetimes and ultrafast intersystem crossing for Re1 Pc and Re2 Pc, which contains two [Re(CO)3 ]+ units. The excited-state properties are ascribed to efficient spin-orbit coupling and large Franck-Condon factors originating from the complexes' distorted structures, that is, unsymmetric coordination of [Re(CO)3 ]+ unit(s), one of which was confirmed by single-crystal X-ray analysis of a symmetrically substituted Pc with two [Re(CO)3 ]+ units. Re1 Pc represents a promising red-light-driven photoCORM that can be applied in biological environments or therapeutic applications.


Asunto(s)
Renio , Indoles , Isoindoles , Ligandos , Luz , Renio/química
8.
J Org Chem ; 87(14): 8928-8938, 2022 07 15.
Artículo en Inglés | MEDLINE | ID: mdl-35785998

RESUMEN

A series of σ-π extended octamethyltetrasilanes, which have phenothiazine, 9,9-dimethyl-9,10-dihydroacridine, or phenoxazine (1, 2, and 3) groups as donor moieties and thienopyrazine or benzothiadiazole (a and b) groups as acceptor fragments, has been prepared, and their optical properties have been studied as an extension of our work. All six compounds exhibited fluorescence in the solid state with maximum wavelengths centered in the range of 400 and 650 nm upon excitation by a UV lamp. Compound 2b showed apparent dual emission behavior in solution, which depends on solvent polarity, and a reversible photoluminescent change under mechanical and thermal stimuli in the solid state. Quantum chemical calculations suggest the contribution of a quasi-axial conformer of the 9,9-dimethyl-9,10-dihydroacridine moiety in 2b to the dual emission in solution and the mechanofluoroluminescence in the solid state, similarly to 1a. These studies provide new insight into the preparation of disilane-bridged triads capable of responding to multiple stimuli.


Asunto(s)
Luminiscencia , Fluorescencia , Estructura Molecular , Solventes
9.
Inorg Chem ; 61(29): 11095-11102, 2022 Jul 25.
Artículo en Inglés | MEDLINE | ID: mdl-35833492

RESUMEN

To develop highly active H2 evolving dye-sensitized photocatalysts (DSPs) applicable for Z-scheme water splitting, we synthesized a series of Ru(II)-dye-double-layered DSPs, X'-RuCP6-Zr-RuP6@Pt-TiO2 (X'-DSP) with different surface-bound metal cations (X' = Fe2+, Y3+, Zr4+, Hf4+, and Bi3+). In 0.5 M KI aqueous solution, the photocatalytic H2 evolution activity under blue light irradiation (λ = 460 ± 15 nm) increased in the following order: nonmetal-modified DSP, H+-DSP (turn over number for 6 h irradiation = 35.2) < Fe2+-DSP (54.9) ≈ Bi3+-DSP (55.2) < Hf4+-DSP (65.5) ≈ Zr4+-DSP (68.3) ≈ Y3+-DSP (71.5), suggesting that the redox-inactive and highly charged metal cations tend to improve the electron donation from the iodide electron mediator. On the other hand, DSPs having heavy metal cations, Hf4+-DSP (18.4) and Bi3+-DSP (16.6), exhibited better activity under green light irradiation (λ = 530 ± 15 nm) than Zr4+-DSP (15.7) and H+-DSP (7.80), implying the contribution of a heavy atom effect of the surface-bound metal cation to partially allow the spin-forbidden metal-to-ligand charge-transfer excitation.

10.
J Phys Chem A ; 126(42): 7687-7694, 2022 Oct 27.
Artículo en Inglés | MEDLINE | ID: mdl-36259145

RESUMEN

Vapochromic crystals of Ni(II)-quinonoid complexes were theoretically investigated using density functional theory (DFT) calculations. Kato et al. previously reported that the purple crystals of a four-coordinate Ni(II)-quinonoid complex (1P) exhibited vapochromic characteristics upon exposure to methanol gas, resulting in orange crystals of the six-coordinate methanol-bound complex (1O) [Angew. Chem., Int. Ed.2017, 56, 2345-2349]. However, the authors did not characterize the crystal structure of 1P. In the present study, we computationally predicted the crystal structure of 1P by performing a crystal structure search with classical force-field computations followed by optimization using DFT calculations. The simulated powder X-ray diffraction pattern of the DFT-optimized structure agreed with experimental observations, indicating that our predicted crystal structure is reliable. Investigation of the optimized crystal structure of 1P revealed that its color change arose from changes in its 1D-band structure, which consists of Ni 3d orbitals and quinonoid π-orbitals. Intermolecular interactions were weakened upon the binding of methanol to the Ni(II) center in 1O. Consequently, the intermolecular 3d-π interaction in 1P lowered the band gap and induced the red-shifting of the monomeric four-coordinate Ni(II)-quinonoid complex. Meanwhile, the obtained absorption spectrum of 1O closely corresponded to that of the monomeric six-coordinate Ni(II)-quinonoid complex. Our study provides a new strategy for accurately predicting molecular crystal structures and reveals a new insight into vapochromism based on band structure color switching.

11.
Plant J ; 101(5): 1221-1233, 2020 03.
Artículo en Inglés | MEDLINE | ID: mdl-31654577

RESUMEN

Sesame (Sesamum indicum) seeds contain a large number of lignans, phenylpropanoid-related plant specialized metabolites. (+)-Sesamin and (+)-sesamolin are major hydrophobic lignans, whereas (+)-sesaminol primarily accumulates as a water-soluble sesaminol triglucoside (STG) with a sugar chain branched via ß1→2 and ß1→6-O-glucosidic linkages [i.e. (+)-sesaminol 2-O-ß-d-glucosyl-(1→2)-O-ß-d-glucoside-(1→6)-O-ß-d-glucoside]. We previously reported that the 2-O-glucosylation of (+)-sesaminol aglycon and ß1→6-O-glucosylation of (+)-sesaminol 2-O-ß-d-glucoside (SMG) are mediated by UDP-sugar-dependent glucosyltransferases (UGT), UGT71A9 and UGT94D1, respectively. Here we identified a distinct UGT, UGT94AG1, that specifically catalyzes the ß1→2-O-glucosylation of SMG and (+)-sesaminol 2-O-ß-d-glucosyl-(1→6)-O-ß-d-glucoside [termed SDG(ß1→6)]. UGT94AG1 was phylogenetically related to glycoside-specific glycosyltransferases (GGTs) and co-ordinately expressed with UGT71A9 and UGT94D1 in the seeds. The role of UGT94AG1 in STG biosynthesis was further confirmed by identification of a STG-deficient sesame mutant that predominantly accumulates SDG(ß1→6) due to a destructive insertion in the coding sequence of UGT94AG1. We also identified UGT94AA2 as an alternative UGT potentially involved in sugar-sugar ß1→6-O-glucosylation, in addition to UGT94D1, during STG biosynthesis. Yeast two-hybrid assays showed that UGT71A9, UGT94AG1, and UGT94AA2 were found to interact with a membrane-associated P450 enzyme, CYP81Q1 (piperitol/sesamin synthase), suggesting that these UGTs are components of a membrane-bound metabolon for STG biosynthesis. A comparison of kinetic parameters of these UGTs further suggested that the main ß-O-glucosylation sequence of STG biosynthesis is ß1→2-O-glucosylation of SMG by UGT94AG1 followed by UGT94AA2-mediated ß1→6-O-glucosylation. These findings together establish the complete biosynthetic pathway of STG and shed light on the evolvability of regio-selectivity of sequential glucosylations catalyzed by GGTs.


Asunto(s)
Vías Biosintéticas , Glucósidos/metabolismo , Glicosiltransferasas/metabolismo , Lignanos/metabolismo , Sesamum/enzimología , Catálisis , Sistema Enzimático del Citocromo P-450/genética , Sistema Enzimático del Citocromo P-450/metabolismo , Dioxoles/metabolismo , Furanos/metabolismo , Glucosiltransferasas/genética , Glucosiltransferasas/metabolismo , Glicosiltransferasas/genética , Filogenia , Proteínas de Plantas/genética , Proteínas de Plantas/metabolismo , Semillas/química , Semillas/enzimología , Semillas/genética , Sesamum/química , Sesamum/genética
12.
Faraday Discuss ; 225: 184-196, 2021 Feb 01.
Artículo en Inglés | MEDLINE | ID: mdl-33094299

RESUMEN

The luminescent and proton conductive Pt(ii) complex [PtCl(tpy-o-py)]Cl and its HCl adduct [PtCl(tpy-o-pyH)]Cl2 (o-Pt and o-Pt·HCl, respectively; tpy-o-py = 2,2':6',2''-terpyridine-6',2'''-pyridine) were synthesised and their crystal structures, vapochromic behaviour, and proton conduction, were investigated and compared to those of the para isomers [PtCl(tpy-p-py)]Cl and [PtCl(tpy-p-pyH)]Cl2 (p-Pt and p-Pt·HCl, respectively; tpy-p-py = 2,2':6',2''-terpyridine-4',4'''-pyridine). X-ray structure analysis revealed that the intermolecular metallophilic (PtPt) interaction was negligible in o-Pt but effective in o-Pt·HCl. Reversible transformation between o-Pt and o-Pt·HCl coupled with significant colour and luminescence changes was achieved by four different external stimuli, namely: exposure of o-Pt to humid HCl gas to form o-Pt·HCl, heating, exposure to MeOH vapour, and finally drying in air to regenerate the original o-Pt. The intraligand π-π* orange emission observed for o-Pt exhibited negligible dependence on the relative humidity (RH). Conversely, o-Pt·HCl exhibited red metal-metal-to-ligand charge-transfer (MMLCT) phosphorescence at 725 nm, originating from effective intermolecular Pt-Pt interactions, and interesting vapochromic behaviour that was dependent on the RH. Notably, o-Pt·HCl presented higher conductivity than the p-Pt·HCl isomer at RH < 80%. This trend was reversed at RH values > 80%, probably owing to the second water-adsorption-induced transformation of p-Pt·HCl. The cooperative phenomenon between the proton conduction and vapochromic behaviour observed for both o-Pt·HCl and p-Pt·HCl should allow the visualisation of the proton-conducting pathway, without the need for a bulk electrode, via the absorption and emission colours at both macroscopic and microscopic levels.

13.
Chemistry ; 26(70): 16939-16946, 2020 Dec 15.
Artículo en Inglés | MEDLINE | ID: mdl-33067824

RESUMEN

To investigate the effect of the surface structure of dye-sensitized photocatalyst nanoparticles, we prepared three types of RuII -photosensitizer (PS)-double-layered Pt-cocatalyst-loaded TiO2 nanoparticles with different surface structures, Zr-RuCP6 -Zr-RuP6 @N wt %Pt-TiO2 , RuCP6 -Zr-RuP6 @N wt %Pt-TiO2 , and RuCP2 -Zr-RuP6 @N wt %Pt-TiO2 (N=0.2, 1, and 5), and evaluated their photocatalytic H2 evolution activity in the presence of redox-reversible iodide as the electron donor. Although the driving force of the electron injection from I- to the photo-oxidized RuIII PS is comparable, the activity increased in the following order: RuCP2 -Zr-RuP6 @1 wt %Pt-TiO2 < RuCP6 -Zr-RuP6 @1 wt %Pt-TiO2 < Zr-RuCP6 -Zr-RuP6 @1 wt %Pt-TiO2 . The apparent quantum yield of Zr-RuCP6 -Zr-RuP6 @1 wt %Pt-TiO2 in the first hour reached 1 %. Zeta-potential measurements suggest that the surface Zr4+ -phosphate groups attracted I- anions to the nanoparticle-solution interface. Our results indicate that the surface modification of dye-sensitized photocatalysts is a promising approach to enhance photocatalytic activity with various redox mediators.

14.
Chemistry ; 26(24): 5449-5458, 2020 Apr 24.
Artículo en Inglés | MEDLINE | ID: mdl-32086967

RESUMEN

Transition-metal complexes bearing biaryl-2,2'-diyl ligands tend to show intense luminescence. However, difficulties in synthesis have prevented their further functionalization and practical applications. Herein, a series of platinum(II) complexes bearing biaryl-2,2'-diyl ligands, which have never been prepared in air, were synthesized through transmetalation and successive cyclometalation of biarylboronic acids. This approach does not require any air- or moisture-sensitive reagents and features a simple synthesis even in air. The resulting (Et4 N)2 [Pt(m,n-F2 bph)(CN)2 ] (m,n-F2 bph=m,n-difluorobiphenyl-2,2'-diyl) complexes exhibit intense green emissions with high quantum efficiencies of up to 0.80 at 298 K. The emission spectral fitting and variable-temperature emission lifetime measurements indicate that the high quantum efficiency was achieved because of the tight packing structure and strong σ-donating ability of bph.

15.
Inorg Chem ; 59(14): 9511-9520, 2020 Jul 20.
Artículo en Inglés | MEDLINE | ID: mdl-32614600

RESUMEN

As a new environmentally friendly route for synthesizing thermally activated delayed-fluorescence (TADF) Cu(I) complexes, we successfully and quantitatively synthesized strongly emissive Cu(I) coordination polymers [Cu2I2(PR3)2(n,n'-bpy)]∞ (CuIR-n, R = Ph, Tol; n = 3, 4; bpy = bipyridine) via the quick thermal reaction of three starting materials (CuI, PR3, and bpy organic ligands) for 1 h in the absence of a solvent. Powder X-ray diffraction and thermogravimetric analyses revealed that melting of the organic ligands significantly promoted the coordination polymerization reaction, and the stoichiometry of three starting materials was crucial to quantitatively affording CuIR-n. Notably, the photophysical properties of CuIR-n obtained by the thermal reaction were almost the same (emission wavelength, quantum yield, and lifetime) as that obtained by generally used solution reactions, probably because CuIR-n was thermally stable enough to prevent the thermal damage and to improve the crystallinity in the heating process. The emission origin of CuIR-n was assignable to TADF at 298 K and phosphorescence at 77 K originating from the metal-to-ligand charge-transfer excited state effectively mixed with the halide-to-ligand charge transfer ((M+X)LCT) state. Thus, the thermal reaction in the melted ligand could be a promising environmentally friendly method for producing TADF Cu(I) luminophores.

16.
Pathol Int ; 70(7): 422-432, 2020 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-32342600

RESUMEN

Niemann-Pick disease type C (NPC) is a neurovisceral lipid-storage disease. Although NPC patients show lipid storage in anterior horn cells of the spinal cord, little information is available regarding the electron microscopic analyses of the morphologies of intra-endosomal lipid like-materials in the anterior horn cells of NPC patients. In this study, we elucidated the intra-endosomal ultrastructures in spinal anterior horn cells in an NPC patient, as well as in mutant BALB/c NPC1-/- mice with a retroposon insertion in the NPC1 gene. These morphologies were classified into four types: vesicle, multiple concentric sphere (MCS), membrane, and rose flower. The percentages of the composition in the NPC patient and NPC1-/- mice were: vesicle (55.5% and 14.9%), MCS (15.7% and 3.4%), membrane (23.6% and 57.1%), and rose flower (5.2% and 24.6%), respectively. Formation of the intra-endosomal structures could proceed as follows: (i) a vesicle or MCS buds off the endosome into the lumen; (ii) when a vesicle breaks down, a membrane is formed; and (iii) after an MCS breaks down, a rose flower structure is formed. Our new finding in this study is that ultrastructural morphology is the same between the NPC patient and NPC1-/- mice, although there are differences in the composition.


Asunto(s)
Células del Asta Anterior/ultraestructura , Modelos Animales de Enfermedad , Enfermedad de Niemann-Pick Tipo C/patología , Animales , Células del Asta Anterior/patología , Preescolar , Femenino , Humanos , Cuerpos de Inclusión/patología , Cuerpos de Inclusión/ultraestructura , Ratones , Ratones Endogámicos BALB C , Ratones Noqueados , Proteína Niemann-Pick C1/genética , Retroelementos
17.
Neuropathology ; 40(4): 319-327, 2020 Aug.
Artículo en Inglés | MEDLINE | ID: mdl-32236982

RESUMEN

Excessive production of nitric oxide (NO) due to the overinduction of inducible nitric oxide synthase (iNOS) has a severe cytotoxic effect, which may relate to the pathogenesis of neurodegenerative disorders. In this study, we report the novel finding that iNOS is overinduced in a large number of bizarre astrocytes in the white matter of patients with panencephalopathic (PE)-type Creutzfeldt-Jakob disease (CJD). This study was carried out on brain tissue from seven patients with PE-type CJD. As controls, 12 normal individuals and nine patients with cerebral infarction were examined. We identified a large number of bizarre astrocytes in the degenerative cerebral white matter in PE-type CJD. Using immunohistochemistry, only bizarre astrocytes in PE-type CJD showed strong immunoreactivity for both iNOS and superoxide dismutase 1 (SOD1). Ultrastructural examination demonstrated that these bizarre astrocytes contained many free polyribosome-like granules. No significant iNOS immunoreactivity was observed in either the astrocytes of patients with cerebral infarcts or in the normal controls. This study suggests that the iNOS-overexpressing astrocytes, especially iNOS-overexpressing bizarre astrocytes, could play an important role in the development of white matter lesions in PE-type CJD. Our data also suggest that the bizarre astrocytes could be protecting themselves from the cytotoxicity of NO by producing SOD1. These immunohistochemical findings are supported by the ultrastructural observation of numerous polyribosome granules restricted to the cytoplasm of these bizarre astrocytes.


Asunto(s)
Astrocitos/enzimología , Astrocitos/patología , Síndrome de Creutzfeldt-Jakob/enzimología , Síndrome de Creutzfeldt-Jakob/patología , Óxido Nítrico Sintasa de Tipo II/metabolismo , Adulto , Anciano , Astrocitos/ultraestructura , Femenino , Humanos , Inmunohistoquímica , Masculino , Persona de Mediana Edad , Degeneración Nerviosa/patología , Sustancia Blanca/patología , Sustancia Blanca/ultraestructura
18.
Int J Urol ; 27(1): 60-66, 2020 Jan.
Artículo en Inglés | MEDLINE | ID: mdl-31587417

RESUMEN

OBJECTIVES: The aim of the present study was to report on our early experience with hydrogel spacer (SpaceOAR) placement in combination with iodine-125 low-dose-rate brachytherapy for prostate cancer. METHODS: From April 2018, SpaceOAR hydrogel spacer was placed in 100 consecutive patients undergoing iodine-125 low-dose-rate brachytherapy. Complications and the status of the placement were evaluated. Deformation of the prostate by the spacer was examined measuring prostate diameters and evaluating the change from preoperative status. The position of the prostate was similarly examined by evaluating the change in distance between the pubic symphysis and the prostate. Post-plan dosimetric data were compared with 200 patients treated without a spacer. RESULTS: No complications were found during either the intraoperative or perioperative periods. The mean displacement distance of 11.64 mm was created, the mean value before spacer placement was 0.28 mm (P < 0.0001). The change of the prostate diameters showed a positive increase in all directions, with no significant negative change in any one direction. Regarding the change in distance between pubic symphysis and the prostate, no significant shortening trend was observed between the two groups (P = 0.14). Whereas the dosimetric parameters showed means of 0.001 and 0.026 cc for RV150 and RV100 in the spacer group, they were 0.025 and 0.318 cc, respectively, in the non-spacer group, showing a significant decrease in both parameters (P < 0.001). CONCLUSIONS: Prostate deformation secondary to hydrogel placement might adversely affect dosimetric parameters in patients undergoing low-dose-rate brachytherapy. However, a significant reduction in the rectal dose can be adopted without adversely affecting the other parameters related to treatment outcome.


Asunto(s)
Braquiterapia/métodos , Hidrogeles/administración & dosificación , Radioisótopos de Yodo/administración & dosificación , Neoplasias de la Próstata/radioterapia , Anciano , Anciano de 80 o más Años , Humanos , Masculino , Persona de Mediana Edad , Dosificación Radioterapéutica , Estudios Retrospectivos
19.
Angew Chem Int Ed Engl ; 59(42): 18723-18730, 2020 Oct 12.
Artículo en Inglés | MEDLINE | ID: mdl-32666592

RESUMEN

A series of assembled PtII complexes comprising N-heterocyclic carbene and cyanide ligands was constructed using different substituent groups, [Pt(CN)2 (R-impy)] (R-impyH+ =1-alkyl-3-(2-pyridyl)-1H-imidazolium, R=Me (Pt-Me), Et (Pt-Et), i Pr (Pt-i Pr), and t Bu (Pt-t Bu)). All the complexes exhibited highly efficient photoluminescence with an emission quantum yield of 0.51-0.81 in the solid state at room temperature, originating from the triplet metal-metal-to-ligand charge transfer (3 MMLCT) state. Their emission colors cover the entire visible region from red for Pt-Me to blue for Pt-t Bu. Importantly, Pt-t Bu is the first example that exhibits blue 3 MMLCT emission. The 3 MMLCT emission was proved and characterized based on the temperature dependences of the crystal structures and emission properties. The wide-range color tuning of luminescence using the 3 MMLCT emission presents a new strategy of superfine control of the emission color.

20.
Chemistry ; 25(20): 5105-5112, 2019 Apr 05.
Artículo en Inglés | MEDLINE | ID: mdl-30653768

RESUMEN

A new material concept of soft crystals is proposed. Soft crystals respond to gentle stimuli such as vapor exposure and rubbing but maintain their structural order and exhibit remarkable visual changes in their shape, color, and luminescence. Various interesting examples of soft crystals are introduced in the article. By exploring the interesting formation and phase-transition phenomena of soft crystals through interdisciplinary collaboration, new materials having both the characteristics of ordered hard crystals and those of flexible soft matter are expected.

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