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1.
Chemistry ; 30(8): e202303159, 2024 Feb 07.
Artículo en Inglés | MEDLINE | ID: mdl-38018377

RESUMEN

Phosphine periodic mesoporous organosilicas (R-P-PMO-TMS: R=Ph, tBu), which possess electron-donating alkyl substituents on the phosphorus atom, were synthesized using bifunctional compounds with alkoxysilyl- and phosphino groups, bis[3-(triethoxysilyl)propyl]phenylphosphine borane (1 a) and bis[3-(triethoxysilyl)propyl]-tert-butylphosphine borane (1 b). Immobilization of Pd(0) species was performed to give R-P-Pd-PMO-TMS: R=Ph (2 a), tBu (3 a), respectively. The Pd(0) immobilized 2 a and 3 a were applicable as catalysts for Suzuki-Miyaura cross-coupling reactions of aryl chlorides with phenylboronic acid. It was revealed that 3 a bearing more electron-donating tBu groups exhibited higher catalytic activity. Various functional groups including both electron withdrawing and donating substituents were compatible in the system. The recyclability of 3 a was examined to support its moderate utility for the recycle use.

2.
ChemSusChem ; 16(20): e202300679, 2023 Oct 20.
Artículo en Inglés | MEDLINE | ID: mdl-37474453

RESUMEN

Metal complexes inspired by carbonic anhydrase (CA), which is a metalloenzyme containing Zn(II), have been investigated as alternatives for CO2 fixation systems operating under ambient temperature and pressure conditions. In this study, we designed a trinuclear Zn(II) cryptate complex (Zn3 L) and demonstrated rapid CO2 fixation with carbonation of CO2 using Zn3 L. The CO2 fixation performance of Zn3 L surpassed that of a standard CO2 absorbent, KOH(aq) solution, under conditions of the same solute concentration. In addition, the reaction achieved operation without support addition of base, which has been often required in systems of CA-inspired complexes. Fixed CO2 was released by protonating polyazacryptate ligand (L) and breaking the complex structure, and deprotonation of L induced the reconstruction of Zn3 L, allowing it to refix CO2 . This reaction mechanism was proposed based on the analysis of operando extended X-ray absorption fine structure spectroscopy. Zn3 L also demonstrated the ability to capture dilute CO2 from air, and the volume of CO2 captured by Zn3 L was approximately 2.6 times that captured by the KOH(aq) solution. Our Zn3 L exhibited three valuable properties: rapid CO2 fixation without a base, reversibility, and ability to capture dilute CO2 ; thus Zn3 L is a promising candidate as CO2 fixatives.

3.
J Agric Food Chem ; 71(12): 5006-5015, 2023 Mar 29.
Artículo en Inglés | MEDLINE | ID: mdl-36896812

RESUMEN

Simple and rapid screening of agrochemicals greatly contributes to food and environmental safety. Matrix-free laser desorption/ionization mass spectrometry (LDI-MS) is an effective tool for high-throughput analysis of low-molecular-weight compounds. In this study, we report a UV-laser-absorbing organosilica film for the sensitive detection of various sulfonylurea herbicides using LDI-MS. Organosilica films with fluoroalkyl groups on the organic part are fabricated, followed by additional modification of the silica moiety with a fluoroalkyl coupling agent to cover the film surface with hydrophobic fluoroalkyl groups. Nanoimprinting is conducted to impart nanostructures on the film surface to enhance the LDI performance. The fabricated nanostructured organosilica films accomplish sensitive detection of cyclosulfamuron and azimsulfuron at concentrations as low as 1 fmol µL-1. The applicability of the nanostructured organosilica films is confirmed by the recovery of cyclosulfamuron and ethametsulfuron-methyl from pea sprouts (Pisum sativum) hydroponically grown in herbicide-spiked water at concentrations of 0.5 ppm.


Asunto(s)
Fluorocarburos , Nanoestructuras , Espectrometría de Masa por Láser de Matriz Asistida de Ionización Desorción/métodos , Espectrofotometría , Nanoestructuras/química , Rayos Láser
4.
ACS Appl Mater Interfaces ; 14(3): 3716-3725, 2022 Jan 26.
Artículo en Inglés | MEDLINE | ID: mdl-34978407

RESUMEN

The rapid detection of biomolecules greatly contributes to health management, clinical diagnosis, and prevention of diseases. Mass spectrometry (MS) is effective for detecting and analyzing various molecules at high throughput. However, there are problems with the MS analysis of biological samples, including complicated separation operations and essential pretreatments. In this study, a nanostructured organosilica substrate for laser desorption/ionization mass spectrometry (LDI-MS) is designed and synthesized to detect peptides and small proteins efficiently and rapidly. The surface functionality of the substrate is tuned by perfluoroalkyl/alkylamide groups mixed at a molecular level. This contributes to both lowering the surface free energy and introducing weak anchoring sites for peptides and proteins. Analyte molecules applied onto the substrate are homogeneously distributed and readily desorbed by the laser irradiation. The organosilica substrate enables the efficient LDI of various compounds, including peptides, small proteins, phospholipids, and drugs. An amyloid ß protein fragment, which is known as a biomarker for Alzheimer's disease, is detectable at 0.05 fmol µL-1. The detection of the amyloid ß at 0.2 fmol µL-1 is also confirmed in the presence of blood components. Nanostructured organosilica substrates incorporating a molecular-level surface design have the potential to enable easy detection of a wide range of biomolecules.


Asunto(s)
Amidas/química , Péptidos beta-Amiloides/análisis , Materiales Biocompatibles/química , Fluorocarburos/química , Ensayo de Materiales , Tamaño de la Partícula , Porosidad , Espectrometría de Masa por Láser de Matriz Asistida de Ionización Desorción , Propiedades de Superficie
5.
Langmuir ; 37(21): 6397-6405, 2021 Jun 01.
Artículo en Inglés | MEDLINE | ID: mdl-34002607

RESUMEN

Laser desorption/ionization mass spectrometry (LDI-MS) assisted by solid substrates is useful for the facile and rapid analysis of low-molecular-weight compounds. The LDI performance of solid substrates depends on not only a surface morphology but also the surface functionalities dominating the surface-analyte interactions. In this study, we propose a hybrid surface design for LDI substrates, realizing both weak surface-analyte interaction and homogeneous distribution of analytes. The hybrid surface consisted of a mixture of fluoroalkylsilane (FAS), SiO2, and TiO2 and was formed on organosilica substrates containing UV-laser-absorbing naphthalimide moieties. To investigate the surface interactions, the hybrid surface as well as conventional hydrophobic surfaces treated with FAS only were prepared on flat organosilica films. Contact angle measurements and surface free energy analysis showed that the hybrid surface exhibited the highest hydrophobicity, while the contribution of the polar and hydrogen bonding terms in the surface free energy was clearly observed. The organosilica film with the hybrid surface demonstrated significant LDI performance for the detection of biorelated compounds (e.g., peptides, phospholipids, and medicines), and a high detection ability was particularly observed for peptides. The substrate surface promoted the desorption/ionization of analytes through a low surface free energy and uniform distribution of the analytes due to the interactive sites. The hybrid surface design was then applied to a nanostructured organosilica substrate consisting of a base film and a nanoparticle layer. The signal intensity of a peptide was further improved approximately 3-fold owing to the increased surface area of the nanostructured substrate, and the limit of detection reached the subfemtomole order. Our hybrid surface design is expected to improve the LDI performance of various nanostructured solid substrates.

6.
Gan To Kagaku Ryoho ; 48(1): 69-71, 2021 Jan.
Artículo en Japonés | MEDLINE | ID: mdl-33468726

RESUMEN

A 63-year-old woman who underwent breast cancer surgery 9 years ago visited our hospital with palpitations. Laboratory examination revealed severe anemia and thrombocytopenia. Positron emission tomography-computed tomography(PET- CT)demonstrated fluorodeoxyglucose(FDG)uptake at several vertebrae, including the pelvis, ribs, and sternum. Accordingly, bone marrow aspiration cytology was performed and atypical large cells were confirmed. After the diagnosis of disseminated carcinomatosis caused by multiple bone metastases from breast cancer, capecitabine monotherapy was started. At 6 months after the diagnosis, the anemia and thrombocytopenia improved to within normal limits. FDG uptake of multiple bones also improved according to PET-CT. Capecitabine administration was stopped at 30 months due to cancer progression. Chemotherapy with docetaxel, epirubicin, cyclophosphamide(EC), and vinorelbine was alternately continued after capecitabine; nevertheless, the cancer progressed gradually. She died at 62 months without either anemia or thrombocytopenia.


Asunto(s)
Neoplasias de la Mama , Neoplasias Peritoneales , Médula Ósea , Neoplasias de la Mama/tratamiento farmacológico , Capecitabina , Femenino , Fluorodesoxiglucosa F18 , Humanos , Persona de Mediana Edad , Tomografía Computarizada por Tomografía de Emisión de Positrones
7.
Nanoscale ; 12(41): 21146-21154, 2020 Oct 29.
Artículo en Inglés | MEDLINE | ID: mdl-32672778

RESUMEN

Nanoimprinting methods have been used widely to prepare various patterned or nanostructured thin films from inorganic or organic components. However, the accumulation of large functional aromatic groups in covalently crosslinked nanoimprints is challenging, due to the difficulty in controlling the fluidity and reactivity of the precursor films. In this work, nanoimprinting of naphthalimide-silica sol-gel films results in vertically oriented nanoporous structures consisting of covalently crosslinked UV-absorbing frameworks. The nanoimprinted films demonstrate potential as robust analytical substrates for laser desorption/ionization mass spectrometry (LDI-MS). The sol-gel polycondensation behavior of the precursors is examined using 29Si NMR spectroscopy to determine reaction conditions suitable for nanoimprinting. The inorganic-organic hybrid frameworks containing a high density of naphthalimide groups exhibit small volume shrinkage during the polycondensation reactions, which leads to desired nanoimprinting. Various bio-related compounds on the order of picomole to femtomole quantities are detectable by LDI-MS measurements using the nanoimprinted substrates. To improve their user-friendliness and signal intensity in LDI-MS analysis, the nanoimprinted substrates are patterned with surface-modified silica nanoparticles. The direct formation of surface nanostructures by nanoimprinting of functional organosilica films may open a new path to developing optically and electronically functional materials, thereby widening their utility.

8.
Support Care Cancer ; 28(6): 2761-2768, 2020 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-31724073

RESUMEN

PURPOSE: Several studies have analyzed late complications associated with totally implantable venous access ports (TIVAP) implantation via the internal jugular vein (IJV); however, the reported results are inconclusive. The aim of the study is to elucidate the characteristics and risk factors of late complications associated with TIVAP implantation via the IJV. METHODS: The study included 482 patients who underwent TIVAP implantation for long-term chemotherapy and/or nutritional support between April 2012 and December 2017. Most patients (95.2%) had malignant diseases. Events requiring TIVAP removal were defined as TIVAP-related complications. RESULTS: The median TIVAP and global follow-ups were 319 days (IQR 152-661) and 218,971 catheter days, respectively. The 3-year cumulative TIVAP availability rate was 70%. There were 44 complications (incidence of 9.1%; 0.201 complications/1000 catheter days). Infectious, catheter-related, and port-related complications occurred in 21, 14, and 9 patients, respectively with infectious complications occurring earlier and more frequently than catheter- and port-related complications. Multivariate analysis revealed that age < 65 years and presence of non-gastrointestinal diseases were significant unfavorable factors for TIVAP-related complications. Patients with 1 and 2 of these factors had an elevated risk (2.2 and 5.4 times, respectively) compared with those without. CONCLUSIONS: Among the late complications associated with TIVAP implantation via the IJV, infectious complications occur earlier and more frequently than catheter- and port-related complications. Patients with an age < 65 years and having non-gastrointestinal diseases have a significantly high risk of TIVAP-related complications.


Asunto(s)
Infecciones Relacionadas con Catéteres/epidemiología , Cateterismo Venoso Central/efectos adversos , Catéteres de Permanencia/efectos adversos , Catéteres Venosos Centrales/efectos adversos , Venas Yugulares/fisiopatología , Adulto , Anciano , Anciano de 80 o más Años , Antineoplásicos/administración & dosificación , Antineoplásicos/uso terapéutico , Bacterias/clasificación , Bacterias/aislamiento & purificación , Femenino , Humanos , Incidencia , Masculino , Persona de Mediana Edad , Neoplasias/terapia , Adulto Joven
9.
Clin J Gastroenterol ; 12(6): 642-649, 2019 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-30972710

RESUMEN

Splenic cysts are rare and tend to have elevated tumor markers, of which carbohydrate antigen (CA) 19-9 is the most frequently elevated. Therefore, splenic cysts with elevated serum carcinoembryonic antigen (CEA) levels and without CA19-9 elevation are extremely rare. A 26-year-old woman presented with sudden upper abdominal pain while sleeping. Contrast-enhanced computed tomography (CT) showed an 85-mm simple splenic cyst in the upper pole and a moderate amount of ascites around the spleen. The serum levels of CEA, but not CA19-9, were elevated. Spontaneous rupture of a splenic cyst was diagnosed. We performed elective laparoscopic unroofing. The histological findings revealed a stratified squamous epithelium on the inner surface of the cystic wall. On immunohistochemical examination, the squamous epithelium was found to be positive for cytokeratin (CK)7, negative for calretinin, and positive for CEA. The histological diagnosis was an epidermoid cyst. Three months after the operation, the elevated serum tumor marker levels of CEA were normalized. Splenic cysts with high levels of CEA and low levels of CA19-9 are extremely rare. Laparoscopic unroofing is a useful operative procedure for ruptured splenic cysts with elevated levels of serum tumor markers.


Asunto(s)
Antígeno Carcinoembrionario/metabolismo , Quiste Epidérmico/cirugía , Laparoscopía , Esplenectomía , Enfermedades del Bazo/cirugía , Rotura del Bazo/cirugía , Dolor Abdominal , Adulto , Biomarcadores/metabolismo , Antígeno CA-19-9/metabolismo , Procedimientos Quirúrgicos Electivos , Quiste Epidérmico/sangre , Femenino , Humanos , Enfermedades del Bazo/sangre , Rotura del Bazo/sangre , Tomografía Computarizada por Rayos X
10.
Chemistry ; 24(15): 3846-3853, 2018 Mar 12.
Artículo en Inglés | MEDLINE | ID: mdl-29333628

RESUMEN

This paper describes the physicochemical properties of a rhenium (Re) complex [Re(bpy)(CO)3 Cl] immobilized on a bipyridine-periodic mesoporous organosilica (BPy-PMO) acting as a solid support. The immobilized Re complex generated a metal-to-ligand charge transfer absorption band at 400 nm. This wavelength is longer than that exhibited by Re(bpy)(CO)3 Cl in the polar solvent acetonitrile (371 nm) and is almost equal to that in nonpolar toluene (403 nm). The photocatalytic activity of this heterogeneous Re complex was lower than that of a homogeneous Re complex due to the reduced phosphorescence lifetime resulting from immobilization. However, the catalytic activity was enhanced by the co-immobilization of the ruthenium (Ru) photosensitizer [Ru(bpy)3 ]2+ on the PMO pore surfaces. Quantum chemical calculations suggest that electron transfer between the Ru and Re complexes occurs through interactions between the molecular orbitals in the pore walls. These results should have applications to the design of efficient heterogeneous CO2 reduction photocatalysis systems.

11.
Chemistry ; 23(43): 10301-10309, 2017 Aug 01.
Artículo en Inglés | MEDLINE | ID: mdl-28467639

RESUMEN

A periodic mesoporous organosilica (PMO) containing 2,2'-bipyridine (bpy) ligands within the framework (BPy-PMO) has great potential for designing novel catalysts by modifying metal complexes. A photosensitizing site (Ru(PS)) was introduced by treating cis-[Ru(bpy)2 (dimethylsulfoxide)Cl]Cl with BPy-PMO. Then a catalytic site (Ru(Cat)) was brought in Ru(PS)x -BPy-PMO by reaction with a ruthenium polymer [Ru(CO)2 Cl2 ]n . The stepwise modification of BPy-PMO successfully affords a novel photocatalyst Ru(PS)x -Ru(Cat)y -BPy-PMO. The molar fractions (x, y) of Ru(PS) and Ru(Cat) were determined by energy dispersive X-ray (EDX) measurement and quantification of the amount of CO emitted in the photo-decarbonylation of Ru(Cat), respectively. Photochemical CO2 reduction (λex >430 nm) by Ru(PS)x -Ru(Cat)y -BPy-PMO in a CO2 -saturated N,N-dimethylacetamide/water solution containing 1-benzyl-1,4-dihydronicotinamide catalytically produced CO and formate. The total turnover frequency of CO and formate reached more than 162 h-1 on x=0.11 and y=0.0055. The product selectivity (CO/formate) became large when the ratio of Ru(PS)-to-Ru(Cat) (x/y) was increased. The photocatalysts can be recycled at least three times without losing their catalytic activity, demonstrating that the Ru(PS) and Ru(Cat) units were strongly immobilized on the BPy-PMO framework.

12.
Gan To Kagaku Ryoho ; 44(13): 2101-2103, 2017 Dec.
Artículo en Japonés | MEDLINE | ID: mdl-29361626

RESUMEN

A 62-year-old woman received chemotherapy for breast cancer with bone metastasis and malignant pleural and pericardial effusion. She was examined by imaging for progressive cognitive impairment and headache. Enhanced MRI findings showed multiple solid tumors on brain surface, and brain perfusion scintigraphy showed blood flow decrease in both parietal lobes. She was diagnosed with secondary dementia due to leptomeningeal metastases of breast cancer, and whole brain external irradiation was performed(30 Gy/15 Fr). After treatment, multiple tumors were decreased in size and her cognitive impair- ment was improved.


Asunto(s)
Neoplasias Encefálicas/radioterapia , Neoplasias de la Mama/patología , Demencia/etiología , Neoplasias Meníngeas/radioterapia , Neoplasias Encefálicas/diagnóstico por imagen , Neoplasias Encefálicas/secundario , Femenino , Humanos , Imagen por Resonancia Magnética , Neoplasias Meníngeas/diagnóstico por imagen , Neoplasias Meníngeas/secundario , Persona de Mediana Edad
13.
Angew Chem Int Ed Engl ; 55(28): 7943-7, 2016 07 04.
Artículo en Inglés | MEDLINE | ID: mdl-27168492

RESUMEN

Heterogenization of metal-complex catalysts for water oxidation without loss of their catalytic activity is important for the development of devices simulating photosynthesis. In this study, efficient heterogeneous iridium complexes for water oxidation were prepared using bipyridine-bridged periodic mesoporous organosilica (BPy-PMO) as a solid chelating ligand. The BPy-PMO-based iridium catalysts (Ir-BPy-PMO) were prepared by postsynthetic metalation of BPy-PMO and characterized through physicochemical analyses. The Ir-BPy-PMOs showed high catalytic activity for water oxidation. The turnover frequency (TOF) values for Ir-BPy-PMOs were one order of magnitude higher than those of conventional heterogeneous iridium catalysts. The reusability and stability of Ir-BPy-PMO were also examined, and detailed characterization was conducted using powder X-ray diffraction, nitrogen adsorption, (13) C DD MAS NMR spectroscopy, TEM, and XAFS methods.

14.
Nagoya J Med Sci ; 78(1): 79-88, 2016 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-27019529

RESUMEN

A rapid and reliable test for detection of complicated appendicitis would be useful when deciding whether emergency surgery is required. We investigated the clinical usefulness of procalcitonin for identifying acute complicated appendicitis. We retrospectively analyzed 63 patients aged ≥15 years who underwent appendectomy without receiving antibiotics before admission and had preoperative data on the plasma procalcitonin level (PCT), body temperature (BT), white blood cell count (WBC), neutrophil / lymphocyte ratio (N/L ratio), and C-reactive protein level (CRP). Patients were classified into 3 groups: group A (inflammatory cell infiltration of the appendix with intact mural architecture), group B (inflammatory cell infiltration with destruction of mural architecture, but without abscess or perforation), and group C (macroscopic abscess and/or perforation). For identifying destruction of mural architecture, the diagnostic accuracy of PCT was similar to that of BT or CRP. However, the diagnostic accuracy of PCT was highest among the five inflammatory indices for identifying abscess and/or perforation, with the positive predictive value of PCT for abscess and/or perforation being higher than that of CRP (73% vs. 48%). Univariate analysis of the predictors of abscess and/or perforation revealed that a plasma PCT level ≥0.46 ng/mL had the highest odds ratio (30.3 [95% confidence interval: 6.5-140.5] versus PCT <0.46 ng/mL). These findings indicate that procalcitonin is a useful marker of acute appendicitis with abscess and/or perforation.


Asunto(s)
Apendicitis , Adolescente , Adulto , Anciano , Biomarcadores , Proteína C-Reactiva , Calcitonina , Péptido Relacionado con Gen de Calcitonina , Femenino , Humanos , Recuento de Leucocitos , Masculino , Persona de Mediana Edad , Precursores de Proteínas , Estudios Retrospectivos
15.
Breast Cancer ; 23(5): 701-5, 2016 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-26206720

RESUMEN

BACKGROUND: Postmastectomy chest wall irradiation is recommended for high-risk breast cancer patients, such as those with ≥4 positive nodes. Irradiation is performed sequentially rather than concurrently with chemotherapy. However, the 5-year locoregional recurrence-free survival was statistically better in the concurrent method in node-positive patients in a prior study. The benefit of concurrent chemoradiotherapy for postmastectomy breast cancer patients is uncertain. Vinorelbine is often used as concurrent chemoradiotherapy for non-small cell lung cancer in Japan and has antitumor activity in breast cancer as well. Thus, we planned this dose-finding study of concurrent vinorelbine and radiation therapy in high-risk postmastectomy breast cancer patients. METHODS: High-risk postmastectomy breast cancer patients were recruited. Patients received weekly vinorelbine administered concurrently with radiation therapy. The radiation dose was 50 Gy in 25 fractions over 5 weeks. Vinorelbine was administered weekly without a break, so the maximum number of vinorelbine cycles was five. A 3 + 3 dose-escalation design was used for determining maximal tolerable dose, recommended dose and safety. RESULTS: A total of 10 patients were enrolled in cohorts of 10 and 15 mg/m(2). Dose-limiting toxicity was observed in one case in 10 mg/m(2) and two cases in 15 mg/m(2). Therefore, the maximal tolerable dose was defined at 15 mg/m(2) and the recommended dose was determined at 10 mg/m(2). The main adverse events included radiation dermatitis and neutropenia. Recurrence was observed in one patient with a median follow-up of 40 months. CONCLUSIONS: Concurrent vinorelbine and radiation therapy has a manageable safety profile at 10 mg/m(2) in high-risk postmastectomy breast cancer patients.


Asunto(s)
Antineoplásicos Fitogénicos/uso terapéutico , Neoplasias de la Mama/tratamiento farmacológico , Neoplasias de la Mama/radioterapia , Vinblastina/análogos & derivados , Adulto , Anciano , Antineoplásicos Fitogénicos/administración & dosificación , Antineoplásicos Fitogénicos/efectos adversos , Neoplasias de la Mama/patología , Neoplasias de la Mama/cirugía , Quimioradioterapia/efectos adversos , Quimioradioterapia/métodos , Esquema de Medicación , Femenino , Humanos , Mastectomía , Dosis Máxima Tolerada , Persona de Mediana Edad , Resultado del Tratamiento , Vinblastina/administración & dosificación , Vinblastina/efectos adversos , Vinblastina/uso terapéutico , Vinorelbina
16.
ChemSusChem ; 8(3): 439-42, 2015 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-25524162

RESUMEN

A photocatalytic system for CO2 reduction exhibiting visible-light harvesting was developed by preparing a hybrid consisting of a supramolecular metal complex as photocatalyst and periodic mesoporous organosilica (PMO) as light harvester. A Ru(II) Re(I) binuclear complex (RuRe) with methylphosphonic acid anchor groups was adsorbed on acridone or methylacridone embedded in the walls of PMO mesochannels to yield the hybrid structure. The embedded organic groups absorbed visible light, and the excitation energy was funneled to the Ru units. The energy accumulation was followed by electron transfer and catalytic reduction of CO2 to CO on the Re unit. The light harvesting of these hybrids enhanced the photocatalytic CO evolution rate by a factor of up to ten compared with that of RuRe adsorbed on mesoporous silica without a light harvester.


Asunto(s)
Dióxido de Carbono/química , Luz , Compuestos de Organosilicio/química , Renio/química , Rutenio/química , Acridinas/química , Acridonas , Adsorción , Catálisis , Modelos Moleculares , Conformación Molecular , Oxidación-Reducción , Porosidad
17.
Chemistry ; 20(29): 9130-6, 2014 Jul 14.
Artículo en Inglés | MEDLINE | ID: mdl-24890840

RESUMEN

An organic-based photocatalysis system for water oxidation, with visible-light harvesting antennae, was constructed using periodic mesoporous organosilica (PMO). PMO containing acridone groups in the framework (Acd-PMO), a visible-light harvesting antenna, was supported with [Ru(II)(bpy)3(2+)] complex (bpy = 2,2'-bipyridyl) coupled with iridium oxide (IrO(x)) particles in the mesochannels as photosensitizer and catalyst, respectively. Acd-PMO absorbed visible light and funneled the light energy into the Ru complex in the mesochannels through excitation energy transfer. The excited state of Ru complex is oxidatively quenched by a sacrificial oxidant (Na2S2O8) to form Ru(3+) species. The Ru(3+) species extracts an electron from IrO(x) to oxidize water for oxygen production. The reaction quantum yield was 0.34 %, which was improved to 0.68 or 1.2 % by the modifications of PMO. A unique sequence of reactions mimicking natural photosystem II, 1) light-harvesting, 2) charge separation, and 3) oxygen generation, were realized for the first time by using the light-harvesting PMO.


Asunto(s)
Acridinas/química , Luz , Oxígeno/química , Fármacos Fotosensibilizantes/química , Dióxido de Silicio/química , Agua/química , 2,2'-Dipiridil/química , Acridonas , Catálisis , Iridio/química , Oxidación-Reducción , Porosidad , Rutenio/química
18.
J Am Chem Soc ; 136(10): 4003-11, 2014 Mar 12.
Artículo en Inglés | MEDLINE | ID: mdl-24571655

RESUMEN

Synthesis of a solid chelating ligand for the formation of efficient heterogeneous catalysts is highly desired in the fields of organic transformation and solar energy conversion. Here, we report the surfactant-directed self-assembly of a novel periodic mesoporous organosilica (PMO) containing 2,2'-bipyridine (bpy) ligands within the framework (BPy-PMO) from a newly synthesized organosilane precursor [(i-PrO)3Si-C10H6N2-Si(Oi-Pr)3] without addition of any other silane precursors. BPy-PMO had a unique pore-wall structure in which bipyridine groups were densely and regularly packed and exposed on the surface. The high coordination ability to metals was also preserved. Various bipyridine-based metal complexes were prepared using BPy-PMO as a solid chelating ligand such as Ru(bpy)2(BPy-PMO), Ir(ppy)2(BPy-PMO) (ppy = 2-phenylpyridine), Ir(cod)(OMe)(BPy-PMO) (cod = 1,5-cyclooctadiene), Re(CO)3Cl(BPy-PMO), and Pd(OAc)2(BPy-PMO). BPy-PMO showed excellent ligand properties for heterogeneous Ir-catalyzed direct C-H borylation of arenes, resulting in superior activity, durability, and recyclability to the homogeneous analogous Ir catalyst. An efficient photocatalytic hydrogen evolution system was also constructed by integration of a Ru-complex as a photosensitizer and platinum as a catalyst on the pore surface of BPy-PMO without any electron relay molecules. These results demonstrate the great potential of BPy-PMO as a solid chelating ligand and a useful integration platform for construction of efficient molecular-based heterogeneous catalysis systems.

19.
Surg Today ; 44(12): 2255-62, 2014 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-24554374

RESUMEN

PURPOSE: Tension-free mesh repair of adult inguinal hernias has become a standard procedure, but there have been few comparisons of the postoperative outcome after hernia repair using the Prolene Hernia System (PHS) vs. the Mesh Plug (MP) method in a large number of patients from a single institution. METHODS: We reviewed the medical records of patients to investigate the short- and long-term outcomes of the different types of hernia repair. Late symptoms were evaluated by questionnaire. A total of 1,141 repairs performed from 1999 to 2008 (PHS in 957 and MP in 184 repairs) were evaluated. RESULTS: There were 93 early postoperative complications (8.2%). A subcutaneous hematoma was found more frequently after MP repair compared with after PHS repair (3.8 vs. 1.3%, P = 0.013). Seven hundred and ten patients (62.2%) could be followed up for more than 2 years. Recurrence was detected in 14 patients with PHS repair and two patients with MP repair (1.5 vs. 1.1%, P = 0.956). Wound infections occurred in three patients (0.3%) with PHS repair vs. none with MP repair (P > 0.999). Patients with PHS and MP repair showed no significant differences in the long-term wound pain. CONCLUSIONS: The recurrence and wound infection rates were similar after hernia repair using the PHS and MP methods. Patients undergoing PHS repair developed fewer subcutaneous hematomas. An older age (≥65 years) was a significant independent risk factor for recurrence.


Asunto(s)
Hernia Inguinal/cirugía , Herniorrafia/métodos , Adolescente , Adulto , Factores de Edad , Anciano , Enfermedades del Tejido Conjuntivo/epidemiología , Femenino , Hematoma/epidemiología , Humanos , Masculino , Persona de Mediana Edad , Complicaciones Posoperatorias/epidemiología , Recurrencia , Factores de Riesgo , Tejido Subcutáneo , Mallas Quirúrgicas , Infección de la Herida Quirúrgica/epidemiología , Encuestas y Cuestionarios , Factores de Tiempo , Resultado del Tratamiento , Adulto Joven
20.
Nagoya J Med Sci ; 75(1-2): 147-52, 2013 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-23544279

RESUMEN

A 67-year-old man fell from the second floor of his home and was impaled on an iron pipe used for a garden stake. The pipe was 2 cm in diameter and had entered his left buttock to his anus. A plain abdominal X-ray film showed that the tip of the pipe was located in front of the 4th lumbar vertebra, so the penetration distance was 30 cm. An emergency operation was performed for hemorrhagic shock. Laparotomy revealed massive intra-abdominal bleeding, injuries of the sigmoid and transverse mesocolon, superior rectal artery, and the first part of the duodenum. Because of suspected lower rectal injury, division of the upper rectum, closure of the rectal stump, and sigmoidostomy were performed. Gauze packing into the pelvic cavity was performed for uncontrollable bleeding. All the gauze was postoperatively removed from the drain wound without laparotomy. Six months after the operation, he underwent a second operation including anastomosis of the descending colon and lower rectum, which allowed him to live a normal daily life.


Asunto(s)
Accidentes por Caídas , Nalgas/lesiones , Hemorragia/etiología , Heridas Penetrantes/etiología , Anciano , Nalgas/diagnóstico por imagen , Nalgas/cirugía , Colon/lesiones , Procedimientos Quirúrgicos del Sistema Digestivo , Duodeno/lesiones , Hemorragia/diagnóstico por imagen , Hemorragia/cirugía , Técnicas Hemostáticas , Humanos , Perforación Intestinal/etiología , Masculino , Choque Hemorrágico/etiología , Tomografía Computarizada por Rayos X , Resultado del Tratamiento , Heridas Penetrantes/diagnóstico por imagen , Heridas Penetrantes/cirugía
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