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1.
Langmuir ; 40(8): 4489-4495, 2024 Feb 27.
Artículo en Inglés | MEDLINE | ID: mdl-38369881

RESUMEN

The efficient removal of radioactive iodine from an aqueous solution is largely dependent on the adsorbent materials employed. In this work, we report a calix[4]pyrrole-based nanofilm and its application for the rapid removal of iodine from water. The nanofilm was synthesized through a confined dynamic condensation of tetra hydrazide calix[4]pyrrole with 1,3,5-tri-(4-formylphenyl) aldehyde at the air/dimethyl sulfoxide (DMSO) interface. The thickness of the obtained nanofilm is ∼35 nm, enabling fast mass transfer and a high ratio of accessible binding sites for iodine. The pseudo-second-order rate constant of the nanofilm for iodine is ∼0.061 g g-1 min-1, 3 orders of magnitude higher than most reported adsorbent materials. Flow-through nanofiltration tests demonstrated that the nanofilm has an adsorption capacity of 1.48 g g-1, a high removal efficiency, and good reusability. The mechanism study revealed that the moieties of Schiff base, pyrrole, and aromatic rings play a key role for binding iodine. We believe this work provides not only a new strategy for the efficient removal of radioactive iodine from water but also new ideas for designing efficient iodine adsorbents.

2.
Small ; 19(9): e2205501, 2023 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-36538755

RESUMEN

The shape and morphology modulations of covalent organic frameworks (COFs) are both difficult, but are of significance to tackle to realize high-performance and practical applications. Here, a two-step method is reported that separates the phase separation and crystallization processes for the shape-controlled synthesis of COFs. The insight into the polymerization-induced phase separation (PIPS) allows for the flexible shaping of COFs into column, rod, film and others, as well as for constructing hierarchically porous structure. The as-synthesized COF monoliths are crack-free, no powder detaching, and show 214 MPa of compressive modulus. The resulting good permeability and mechanical flexibility enable COF films to apply for flow-through adsorption and extraction of pollutants at high flow rates. This work successfully resolves the contradiction between PIPS and crystallization, offering a general approach for scalable production of COFs with desired shapes, sizes, and morphologies.

3.
Molecules ; 28(5)2023 Mar 01.
Artículo en Inglés | MEDLINE | ID: mdl-36903549

RESUMEN

Copper serves as a vital microelement which is widely present in the biosystem, functioning as multi-enzyme active site, including oxidative stress, lipid oxidation and energy metabolism, where oxidation and reduction characteristics are both beneficial and lethal to cells. Since tumor tissue has a higher demand for copper and is more susceptible to copper homeostasis, copper may modulate cancer cell survival through reactive oxygen species (ROS) excessive accumulation, proteasome inhibition and anti-angiogenesis. Therefore, intracellular copper has attracted great interest that multifunctional copper-based nanomaterials can be exploited in cancer diagnostics and antitumor therapy. Therefore, this review explains the potential mechanisms of copper-associated cell death and investigates the effectiveness of multifunctional copper-based biomaterials in the field of antitumor therapy.


Asunto(s)
Nanoestructuras , Neoplasias , Humanos , Cobre/química , Neoplasias/tratamiento farmacológico , Estrés Oxidativo , Especies Reactivas de Oxígeno/metabolismo
4.
Gynecol Oncol ; 166(3): 606-613, 2022 09.
Artículo en Inglés | MEDLINE | ID: mdl-35868881

RESUMEN

Concomitant chemoradiotherapy is the standard treatment for locally advanced cervical cancer. Pelvic irradiation is commonly recommended for patients with negative para-aortic lymph nodes(PALNs). However, owing to the development of imaging-guided brachytherapy, distant failure has become the main failure pattern. The PALNs are a vital site of distant metastasis, and the para-aortic region may contain occult microscopic metastases that are barely detected owing to imaging technology restriction. The prognostic of patients who experienced PALN failure is dismal. Typically, there are four ways to decrease PALN failure. First, surgical staging can be performed to assess the occurrence of metastasis in the para-aortic region; however, the application of surgical staging is decreasing owing to controversial survival benefits and accompanying complications of surgery. Second, regular imaging surveillance and timely salvage of early recurrences could reduce PALN failure. Third, better systemic adjuvant therapy could be recommended since it has enormous potential to reduce distant metastases and improve overall survival. Fourth, performing prophylactic extended-field irradiation (EFI), including pelvic and para-aortic region irradiation, can sterilize occult microscopic metastases in the para-aortic region and improve survival. Prior investigations have revealed that prophylactic EFI could reduce PALN failure as well as distant metastasis and present the benefit of survival. Yet, owing to the serious morbidity induced by enlarged irradiation field in the era of conventional irradiation techniques, further research on EFI is stagnated. Nowadays, with the development of new technologies, intensity modulated radiation therapy can deliver a higher dose to tumors with acceptable toxicity. Prophylactic EFI regained attention. However, the inclusion criteria of prophylactic EFI in existing studies reveal great discrepancies. Thus, it is urgent to precisely identify indications for better survival and lower complications in patients with cervical cancer. In this review, we identify indications and summary guidelines for prophylactic EFI, which may provide a foundation for further trials and clinical applications.


Asunto(s)
Braquiterapia , Radioterapia de Intensidad Modulada , Neoplasias del Cuello Uterino , Quimioradioterapia , Femenino , Humanos , Ganglios Linfáticos/patología , Estadificación de Neoplasias , Neoplasias del Cuello Uterino/tratamiento farmacológico , Neoplasias del Cuello Uterino/radioterapia
5.
Anal Chem ; 93(48): 16051-16058, 2021 12 07.
Artículo en Inglés | MEDLINE | ID: mdl-34806871

RESUMEN

Non-methane hydrocarbons (NMHCs) can serve as precursors of ozone and photochemical smog, and hence their highly efficient detection is of great importance for air quality monitoring. Here, we synthesized a new fluorescent perylene bisimide (PBI)-cored metallacycle complex through coordination-driven self-assembly and used it for the production of a fluorescent film sensor. The unique rectangular structure of the developed fluorophore endows the sensor with enhanced sensing performance and discriminability to n-alkanes (C5-10). Specifically, the experimental detection limits for n-pentane, n-hexane, and n-decane are 39, 7, and 1.4 mg/m3, respectively, and the corresponding linear ranges are from 39 to 2546, 7 to 1745, and 1.4 to 85 mg/m3, respectively. Moreover, the sensing is fully reversible. In tandem with a gas chromatographic separation system, the film sensor showed comparable detection ability for the n-alkanes with a commercial flame ionization detector (FID), while the film sensor needs no hydrogen; it occupies a much smaller size (30 × 30 × 44 mm3) and consumes less energy (0.215 W). Further studies demonstrated that the developed sensor can be used for on-site and real-time quantification of NHMCs, laying the foundation for developing into a portable detector.


Asunto(s)
Imidas , Perileno , Ionización de Llama , Colorantes Fluorescentes , Perileno/análogos & derivados
6.
Anal Chem ; 93(18): 7094-7101, 2021 05 11.
Artículo en Inglés | MEDLINE | ID: mdl-33905230

RESUMEN

Although it is widely used in industry and food products, formic acid can be dangerous owing to its corrosive properties. Accurate determination of formic acid would not only benefit its qualified uses but also be an effective way to avoid corrosion or injury from inhalation, swallowing, or touching. Herein, we present a nanofilm-based fluorescent sensor for formic acid vapor detection with a wide response range, fast response speed, and high sensitivity and selectivity. The nanofilm was synthesized at a humid air/dimethyl sulfoxide (DMSO) interface through dynamic covalent condensation between two typically designed building blocks, de-tert-butyl calix[4]arene-tetrahydrazide (CATH) and 4,4',4″,4‴-(ethene-1,1,2,2-tetrayl)tetra-benzaldehyde (ETBA). The as-prepared nanofilm is uniform, flexible, fluorescent, and photochemically stable. The thickness and fluorescence intensity of the nanofilm can be facilely adjusted by varying the concentration of the building blocks and the sensing performance of the nanofilm can be optimized accordingly. Based on the nanofilm, a fluorescent sensor with a wide response range (4.4 ppt-4400 ppm) for real-time and online detection of formic acid vapor was built. With the sensor, a trace amount (0.01%) of formic acid in petroleum ether (60-90 °C) can be detected within 3 s. Besides, fluorescence quenching of the nanofilm by formic acid vapor can be visualized. It is believed that the sensor based on the nanofilm would find real-life applications in corrosion and injury prevention from formic acid.


Asunto(s)
Formiatos , Gases , Espectrometría de Fluorescencia
7.
Mol Cell Biochem ; 476(2): 757-765, 2021 Feb.
Artículo en Inglés | MEDLINE | ID: mdl-33099745

RESUMEN

Human papillomavirus (HPV) infection is related to cancer growth of vaginal, cervical, vulva, penile, anogenital, and non-genital oropharyngeal sites. HPV, as a sexually transmitted virus, infects all sexes similarly but with more significant pathological risks in women. This accounts for high mortality due to late detection and poor prognosis. The initial development and eventual progress of this cancer type depend entirely on three main oncogenes E5, E6 and E7, constitutively expressed to lead to carcinogenesis. Despite an opportunity for pharmacological therapy, there is still a shortage of medical treatment that may remove HPV from infected lesions. This study offers a concise summary of the nature of the issue and the current status of work on potential lead molecules and therapeutic approaches that show the capacity of HPV therapies to counteract the roles of deregulation of E5, E6, and E7.


Asunto(s)
Interferones/uso terapéutico , Papillomaviridae/patogenicidad , Infecciones por Papillomavirus/complicaciones , Neoplasias del Cuello Uterino/tratamiento farmacológico , Zinc/uso terapéutico , Antivirales/uso terapéutico , Quimioterapia Combinada , Femenino , Humanos , Papillomaviridae/aislamiento & purificación , Infecciones por Papillomavirus/tratamiento farmacológico , Infecciones por Papillomavirus/patología , Infecciones por Papillomavirus/virología , Oligoelementos/uso terapéutico , Neoplasias del Cuello Uterino/metabolismo , Neoplasias del Cuello Uterino/patología , Neoplasias del Cuello Uterino/virología
8.
Environ Sci Technol ; 55(1): 385-392, 2021 01 05.
Artículo en Inglés | MEDLINE | ID: mdl-33284617

RESUMEN

N-Nitrosamine disinfection byproducts (DBPs) are a health concern because they are probable human carcinogens. Complex organic nitrogenous compounds, nitrosamine precursors, are largely unidentified in source water. Using stable isotopic labeling-enhanced nontargeted analysis, we identified a natural product N-heterocyclic amine 1-methyl-1,2,3,4-tetrahydro-ß-carboline-3-carboxylic acid (MTCCA) in source water. Interestingly, we discovered that chloramination of MTCCA-containing water could produce four nitrosamines: methylethylnitrosamine, N-nitrosopyrrolidine, N-nitrosoanatabine, and N-nitrosoanabasine. Computational modeling and experimental results helped explain potential pathways of nitrosamines generated from chloramination of MTCCA. Further investigations confirmed widespread occurrence of MTCCA in source water and wastewater. Its concentration ranged from high in upstream creeks (23.2-332.2 ng L-1) to low in the river (5.7-37.6 ng L-1) during the 2020 spring runoffs, indicating that sources of MTCCA came from creeks around farms. Analysis of wastewater before and after ultraviolet, as well as microfiltration with subsequent ozonation treatments, showed increased MTCCA after treatments, demonstrating a difficulty to degrade and remove MTCCA in water. This study discovered the extensive presence of MTCCA in source water and wastewater, suggesting that natural N-heterocyclic compounds may serve as a new source of nitrosamine precursors.


Asunto(s)
Agua Potable , Compuestos Heterocíclicos , Nitrosaminas , Contaminantes Químicos del Agua , Purificación del Agua , Desinfección , Humanos , Aguas Residuales , Agua , Contaminantes Químicos del Agua/análisis
9.
Anal Chem ; 91(5): 3659-3666, 2019 03 05.
Artículo en Inglés | MEDLINE | ID: mdl-30758947

RESUMEN

We report a new material of a composite silica monolith nested in sponge (SiMNS) and demonstrate an application in the trace analysis of environmental contaminants in water. SiMNS is prepared through sponge absorption of a hydrolyzed mixture of siloxanes and in situ gel formation within the pores. Images obtained using scanning electron microscopy show that the silica and sponge skeletons are mutually nested in SiMNS. This nested composite structure of SiMNS enhances the mechanical flexibility of the material, allowing for reproducible production of desirable sizes and shapes for solid phase extraction (SPE) cartridges without the need to use frits. Functionalization of SiMNS provides appropriate SPE options for selective and efficient extraction of specific contaminants. SPE cartridges packed with functionalized SiMNS-SO3Na have high extraction capacity, good stability in the pH range of 2 to 11, and efficient enrichment of dipeptides in water. Extraction of six dipeptides from water using these new SiMNS-SO3Na SPE cartridges followed by HPLC-MS/MS analysis results in improved method detection limits (MDLs) of 0.02-1.3 ng/L and method quantification limits (MQLs) of 0.05-4.3 ng/L. Successful identification and quantification of three dipeptides, Tyr-Gly, Phe-Gly, and Tyr-Ala, from raw water demonstrates a useful application of the new SPE materials for environmental analysis of trace contaminants. On the basis of this work, a range of functionalized SiMNS materials can be produced and tailored for various environmental and exposomic analyses.


Asunto(s)
Monitoreo del Ambiente/métodos , Dióxido de Silicio/química , Extracción en Fase Sólida/métodos , Contaminantes Químicos del Agua/análisis , Adsorción , Dipéptidos/aislamiento & purificación , Geles , Siloxanos
10.
Anal Chem ; 91(20): 13213-13221, 2019 10 15.
Artículo en Inglés | MEDLINE | ID: mdl-31498582

RESUMEN

We report a new combinatorial approach of stable isotopic labeling (SIL)-solid phase extraction (SPE)-liquid chromatography-tandem high-resolution mass spectrometry (LC-HRMS/MS) for identification of amino-containing contaminants at trace levels in source water. The new SIL method requires small amounts of formaldehyde (CH2O) and deuterated formaldehyde (CD2O) to efficiently label ng/L amino compounds in 1 L of water and improves SPE recovery, enabling environmental analysis of trace amino-compounds. Isotopically methylated components were confirmed using LC-MS/MS based on their retention times, and characteristic isotope patterns of the molecular and product ions. Using the characteristic isotope patterns, we established a data prioritization process to identify the amino compounds in thousands of mass peaks in raw data. Analysis of a labeled authentic source water detected 8952 m/z peaks and tentatively identified 154 amino compounds. Our SIL-methylation prioritization approach effectively reduced the complexity of data. Manual spectrum interpretation identified 77 of the 154 components as amino acids and peptides. We confirmed 8 of the 77 compounds using commercially available standards to demonstrate the feasibility and reliability of our SIL-SPE-LC-HRMS/MS method for environmental analysis of trace amino-containing contaminants. The method can efficiently identify amino-precursors in source water, enabling other studies of nitrogenous disinfection byproduct formation.


Asunto(s)
Aminas/análisis , Marcaje Isotópico/métodos , Contaminantes Químicos del Agua/análisis , Aminas/química , Cromatografía Liquida , Deuterio/química , Formaldehído/química , Metilación , Extracción en Fase Sólida , Espectrometría de Masas en Tándem , Contaminantes Químicos del Agua/química
11.
Biochem Biophys Res Commun ; 519(4): 812-818, 2019 11 19.
Artículo en Inglés | MEDLINE | ID: mdl-31558316

RESUMEN

Due to TRAIL's explicit cancer cell-selectivity, the current study aimed to explore novel agents that sensitized cancer cell for TRAIL-induced apoptosis while sparing normal cell. In this study, we found that TRAIL could induce PARP-1 cleavage and apoptosis in colon cancer HCT116 cell, but HT-29 cell was not sensitive to TRAIL. However, non-cytotoxic doses of ipatasertib in conjunction with TRAIL could induce apoptosis in HT-29 cell. Mechanism studies showed that intracellular ROS level was significant increased during ipatasertib treatment. Excessive cellular levels of ROS further induced DNA damage and subsequently activated apoptotic signaling pathways in TRAIL-resistant HT-29 cells. Combined treatment with sub-toxic doses of ipatasertib and TRAIL leads to caspase activation and PARP-1 cleavage in HT-29 cells. Pretreated with NAC, an antioxidant, could inhibit ROS production and PARP-1 cleavage as well as prevent cell apoptotic death induced by combination therapy with TRAIL and ipatasertib. In addition, NAC can block the up-regulation of p53/PUMA induced by combined treatment with ipatasertib and TRAIL. Transfection with p53 or Puma siRNA for 48 h can reverse ipatasertib-mediated TRAIL sensitization. In conclusion, p53 and PUMA may play a pivotal role in sensitizing colon cancer cell to TRAIL-induced apoptosis by sub-toxic doses of ipatasertib treatment.


Asunto(s)
Apoptosis/efectos de los fármacos , Caspasas/metabolismo , Neoplasias del Colon/tratamiento farmacológico , Neoplasias del Colon/patología , Piperazinas/farmacología , Pirimidinas/farmacología , Especies Reactivas de Oxígeno/metabolismo , Receptores del Ligando Inductor de Apoptosis Relacionado con TNF/metabolismo , Supervivencia Celular/efectos de los fármacos , Células Cultivadas , Neoplasias del Colon/metabolismo , Relación Dosis-Respuesta a Droga , Activación Enzimática/efectos de los fármacos , Células HT29 , Humanos
12.
Environ Sci Technol ; 53(7): 3672-3680, 2019 04 02.
Artículo en Inglés | MEDLINE | ID: mdl-30807126

RESUMEN

Dipeptides are widely present in surface water and serve as precursors to form disinfection byproducts (DBPs) during disinfection (e.g., chloramination). Bromide (Br-) and iodide (I-) are common in many source waters, enhancing Br- and I-DBP formation. Recently Cl-, I-, and Cl-I-dipeptides were identified after chloramination of tyrosyl dipeptides in the presence of I- and were detected in authentic disinfected drinking water samples. However, the formation and occurrence of Br- and mixed halogen (Cl, Br, and/or I)-dipeptides in disinfected water have not been studied. Here we investigated the formation of halogenated dipeptides from three aromatic dipeptides, phenylalanylglycine (Phe-Gly), tyrosylalanine (Tyr-Ala), and tyrosylglycine (Tyr-Gly), under chloramination in the presence of Br- and I- at environmentally relevant levels ([Br-] and [I-], 0 and 0 µg L-1, 6 and 30 µg L-1, 30 and 30 µg L-1, 150 and 30 µg L-1, 300 and 30 µg L-1, and 900 and 30 µg L-1, respectively). For the first time, N-Br- and N,N-di-Br- as well as N-Br- N-Cl- and N-Br-3-I-tyrosyl dipeptides were identified using infusion electrospray quadrupole time-of-flight mass spectrometry. Tyrosyl dipeptides produced N-Cl-, 3-I-/3,5-di-I-, and N-Cl-3-I-tyrosyl dipeptides, while Phe-Gly formed only N-Cl-/ N, N-di-Cl-Phe-Gly. To determine halogenated dipeptides in authentic water samples, we developed a new method of solid phase extraction and high-performance liquid chromatography with quadrupole ion trap mass spectrometry using reaction monitoring. 3,5-Di-I-Tyr-Ala and N-Br-Tyr-Ala were detected in treated water but not in the corresponding raw water, warranting further investigation into the occurrence of halogenated peptides in other drinking water systems.


Asunto(s)
Desinfectantes , Agua Potable , Contaminantes Químicos del Agua , Purificación del Agua , Dipéptidos , Desinfección , Halogenación
13.
J Environ Sci (China) ; 85: 82-93, 2019 Nov.
Artículo en Inglés | MEDLINE | ID: mdl-31471034

RESUMEN

Cannabis is increasingly used for both medicinal and recreational purposes with an estimate of over 180 million users annually. Canada has recently legalized cannabis use in October 2018, joining several states in the United States of America (e.g., Colorado, California, and Oregon) and a few other countries. A variety of cannabis products including dry flowers, edibles, and oil products are widely consumed. With high demand for cannabis products worldwide, the quality of cannabis and its related products has become a major concern for consumer safety. Various guidelines have been set by different countries to ensure the quality, safety, and efficacy of cannabis products. In general, these guidelines require control of contaminants including pesticides, toxic elements, mycotoxins, and pathogens, as well as residual solvents in regard to cannabis oil. Accordingly, appropriate analytical methods are required to determine these contaminants in cannabis products for quality control. In this review, we focus on the current analytical challenges and method development for detection of pesticides and toxic elements in cannabis to meet various guidelines.


Asunto(s)
Cannabis/química , Contaminantes Ambientales/análisis , Plaguicidas/análisis , Oligoelementos/análisis , Estados Unidos
14.
Anal Chem ; 89(8): 4655-4662, 2017 04 18.
Artículo en Inglés | MEDLINE | ID: mdl-28316239

RESUMEN

Hierarchically porous materials have become a key feature of biological materials and have been widely applied for adsorption or catalysis. Herein, we presented a new approach to directly prepare a phosphate-functionalized hierarchically porous hybrid monolith (HPHM), which simultaneously contained mesopores and macropores. The design was based on the copolymerization of polyhedral oligomeric vinylsilsesquioxanes (vinylPOSS) and vinylphosphonic acid (VPA) by adding degradable polycaprolactone (PCL) additive. The phosphate groups could be directly introduced into the hybrid monoliths. This approach was simple and time-saving, and overcame the defect of a rigorous, complex process for preparing traditional Ti4+-immobilized metal ion affinity chromatography (IMAC) materials. The specific surface area of an optimal hybrid monolith could reach 502 m2/g obtained by nitrogen adsorption/desorption measurements, which originated from the degradation of PCL. Meanwhile, the characterization of scanning electron microscopy (SEM) and mercury intrusion porosimetry (MIP) also suggested that the macropores existed in the hybrid monoliths. The size of macropores could be controlled by the content of PCL in the polymerization mixture. The prepared Ti4+-IMAC HPHMs exhibited high adsorption capacity (63.6 mg/g for pyridocal 5'-phosphatemonohydrate), and excellent enrichment specificity (tryptic digest of ß-casein/BSA at a molar ratio of 1:1000) and sensitivity (tryptic digest of 5 fmol of ß-casein). Moreover, the Ti4+-IMAC HPHMs provided effective enrichment ability of low-abundance phosphopeptides from human serum and HeLa cell digests.


Asunto(s)
Cromatografía de Afinidad/métodos , Fosfopéptidos/análisis , Titanio/química , Adsorción , Animales , Caseínas/metabolismo , Bovinos , Células HeLa , Humanos , Organofosfonatos/química , Compuestos de Organosilicio/química , Fosfopéptidos/sangre , Fosfopéptidos/aislamiento & purificación , Poliésteres/química , Porosidad , Albúmina Sérica Bovina/metabolismo , Compuestos de Vinilo/química
16.
Int J Gynecol Cancer ; 27(4): 768-775, 2017 05.
Artículo en Inglés | MEDLINE | ID: mdl-28267131

RESUMEN

OBJECTIVE: We present a new technique of 3-dimensional computed tomography-guided interstitial (IS) brachytherapy (BT) for locally advanced cervical cancer, offering a more advantageous clinical treatment approach. MATERIALS/METHODS: Interstitial BT was performed using an applicator combining uterine tandem and metal needles; needles were inserted freehand under real-time 3-dimensional computed tomography guidance. Twenty-eight patients with bulky tumors and/or parametrial extension (tumor size > 5 cm) after external beam radiotherapy received IS BT. Dosimetric outcomes of the IS BT including the total dose (external beam radiotherapy and high dose-rate BT) D90 for the high-risk clinical target volume (HR-CTV) and D2cc for the organs at risk (OARs) were investigated and compared with a former patient group consisting of 30 individuals who received the conventional intracavitary (IC) BT. RESULTS: The mean D90 values for HR-CTV in the IC BT and IS BT groups were 76.9 ± 5.7 and 88.1 ± 3.3 Gy, respectively. Moreover, 85.7% of the patients received D90 for HR-CTV of 87 Gy or greater in the IS BT group, and only 6.7% of the patients received D90 for HR-CTV of 87 Gy or greater in the IC BT group. The D2cc for the bladder, rectum, and sigmoid were 84.7 ± 6.8, 69.2 ± 4.2, and 67.8 ± 4.5 Gy in the IC BT group and 81.8 ± 6.5, 66.8 ± 4.0, and 64.8 ± 4.1 Gy in the IS BT group. The mean number of needles was 6.9 ± 1.4, with a mean depth of 2.9 ± 0.9 mm for each IS BT. Interstitial BT was associated with only minor complications. CONCLUSIONS: The IS BT technique resulted in better dose-volume histogram parameters for large volume tumors (>5 cm) compared with the conventional IC BT and acceptable risk of acute complications in locally advanced cervical cancer and is clinically feasible.


Asunto(s)
Braquiterapia/métodos , Planificación de la Radioterapia Asistida por Computador/métodos , Radioterapia Guiada por Imagen/métodos , Neoplasias del Cuello Uterino/diagnóstico por imagen , Neoplasias del Cuello Uterino/radioterapia , Braquiterapia/instrumentación , Femenino , Humanos , Imagenología Tridimensional/instrumentación , Imagenología Tridimensional/métodos , Persona de Mediana Edad , Planificación de la Radioterapia Asistida por Computador/instrumentación , Radioterapia Guiada por Imagen/instrumentación , Tomografía Computarizada por Rayos X/instrumentación , Tomografía Computarizada por Rayos X/métodos
17.
Anal Chem ; 88(10): 5058-64, 2016 05 17.
Artículo en Inglés | MEDLINE | ID: mdl-27101427

RESUMEN

In this study, we developed a Ti(IV) monolithic spin tip for phosphoproteome analysis of a minute amount of biological sample for the first time. The surface of polypropylene pipet tip was activated by the photoinitiator benzophenone under UV light radiation followed by polymerization of ethylene glycol methacrylate phosphate and bis-acrylamide in the tip to form a porous monolith with reactive phosphate groups. The as-prepared tips grafted with monolithic adsorbent were then chelated with titanium(IV) ion for phosphopeptide enrichment. It was found that the tips enabled fast and efficient capture of phosphopeptides from microscale complex samples. The monolithic tip was demonstrated to have a detection limit as low as 5 fmol ß-casein tryptic digest, along with an exceptionally high specificity to capture phosphopeptides from complex tryptic digest mixed with an unphosphorylated protein and a phosphorylated protein at a molar ratio up to 1000:1. When the tip was applied to enrich phosphopeptides from 5 µg of tryptic digest of complex HeLa cell proteins, 1185 high confidence of phosphorylated sites were successfully identified with the specificity as high as 92.5%. So far, this is the most sensitive phosphoproteomics analysis using a standard liquid chromatography-tandem mass spectrometry (LC-MS/MS) system for proteome-wide phosphorylation analysis in mammalian cells.


Asunto(s)
Cromatografía Liquida/instrumentación , Fosfoproteínas/análisis , Polipropilenos/química , Proteoma/análisis , Espectrometría de Masas en Tándem/instrumentación , Titanio/química , Acrilamidas/química , Adsorción , Benzofenonas/efectos de la radiación , Caseínas/análisis , Cromatografía Liquida/métodos , Células HeLa , Humanos , Límite de Detección , Metacrilatos/química , Fragmentos de Péptidos/análisis , Fosfatos/química , Porosidad , Proteómica , Espectrometría de Masas en Tándem/métodos , Rayos Ultravioleta
18.
J Sep Sci ; 39(6): 1110-7, 2016 Mar.
Artículo en Inglés | MEDLINE | ID: mdl-27027591

RESUMEN

Cyclodextrins and their derivatives are one of the most common and successful chiral selectors. However, there have been few publications about the use of cyclodextrin-modified monoliths. In this study, organic hybrid monoliths were prepared by the immobilization of derivatized ß-cyclodextrin alone or with l-2-allylglycine hydrochloride to the polyhedral oligomeric silsesquioxane methacryl substituted monolith. The main topic of this study is a combined system with dual chiral selectors (l-2-allylglycine hydrochloride and ß-cyclodextrin) as monolithic chiral stationary phase. The effect of l-2-allylglycine hydrochloride concentration on enantioseparation was investigated. The enantioseparation of the four acidic compounds with resolutions up to 2.87 was achieved within 2.5 min on the prepared chiral monolithic column in capillary liquid chromatography. Moreover, the possible mechanism of enantioseparation was discussed.

19.
Anal Chem ; 87(17): 8789-97, 2015 Sep 01.
Artículo en Inglés | MEDLINE | ID: mdl-26223285

RESUMEN

A novel "one-pot" approach was developed for ultrarapid preparation of various hybrid monolithic columns in UV-transparent fused-silica capillaries via photoinitiated thiol-acrylate polymerization of an acrylopropyl polyhedral oligomertic silsesquioxane (acryl-POSS) and a monothiol monomer (1-octadecanethiol or sodium 3-mercapto-1-propanesulfonate) within 5 min, in which the acrylate not only homopolymerizes, but also couples with the thiol. This unique combination of two types of free-radical reaction mechanisms offers a simple way to fabricate various acrylate-based hybrid monoliths. The physical characterization, including scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy, and thermal gravimetric analysis was performed. The results indicated that the monothiol monomers were successfully incorporated into acryl-POSS-based hybrid monoliths. The column efficiencies for alkylbenzenes on the C18-functionalized hybrid monolithic column reached to 60 000-73 500 plates/m at the velocity of 0.33 mm/s in capillary liquid chromatography, which was far higher than that of previously reported POSS-based columns prepared via thermal-initiated free-radical polymerization without adding any thiol monomers. By plotting the plate height (H) of the alkylbenzenes versus the linear velocity (u) of the mobile phase, the results revealed a retention-independent efficient performance of small molecules in the isocratic elution. These results indicated that more homogeneous hybrid monoliths formed via photoinitiated thiol-acrylate polymerization; particularly, the use of the multifunctional cross-linker possibly prevented the generation of gel-like micropores, reducing mass transfer resistance (C-term). Another sulfonate-containing hybrid monolithic column also exhibited hydrophobicity and ion-exchange mechanism, and the dynamic binding capacity was calculated as 71.1 ng/cm (75 µm i.d.).

20.
Anal Chem ; 87(6): 3476-83, 2015 Mar 17.
Artículo en Inglés | MEDLINE | ID: mdl-25679546

RESUMEN

A facile approach was developed for direct preparation of organic monoliths via the alkaline-catalyzed thiol-epoxy click polymerization. Two organic monoliths were prepared by using tetraphenylolethane glycidyl ether as a multiepoxy monomer, and trimethylolpropane tris(3-mercaptopropionate) and pentaerythritol tetrakis(3-mercaptopropionate) as the multithiol monomer, respectively, in the presence of a ternary porogenic system (DMSO/PEG200/H2O). The obtained organic monoliths showed high thermal, mechanical and chemical stabilites. Benefiting from the step-growth polymerization process, two organic monoliths possessed well-defined 3D framework microstructure, and exhibited high permeabilities and column efficiencies in capillary liquid chromatography. A series of neutral, basic and acidic small molecules were used to comprehensively evaluate the separation abilities of these monoliths, and satisfactory chromatographic performance with column efficiencies ranged from 35,500 to 132,200 N/m was achieved, demonstrating good separation abilities of these organic monoliths prepared via thiol-epoxy click polymerization approach. Besides, multiple retention mechanisms, including hydrophobic, hydrophilic and π-π conjugate interactions were observed during the separation of analytes on these monoliths, which would make them promising for more extensive applications in capillary liquid chromatography.

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