RESUMEN
5-Aminolevulinic acid (5-ALA) is a prodrug of porphyrin IX (PpIX). Disadvantages of 5-ALA include poor stability, rapid elimination, poor bioavailability, and weak cell penetration, which greatly reduce the clinical effect of 5-ALA based photodynamic therapy (PDT). Presently, a novel targeting nanosystem was constructed using gold nanoparticles (AuNPs) as carriers loaded with a CSNIDARAC (CC9)-targeting peptide and 5-ALA via Au-sulphur and ionic bonds, respectively, and then wrapped in polylactic glycolic acid (PLGA) NPs via self-assembly to improve the antitumor effects and reduce the side effect. The successful preparation of ALA/CC9@ AuNPs-PLGA NPs was verified using ultraviolet-visible, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The analyses revealed good sphericity with a particle size of approximately140 nm, Zeta potential of 10.11 mV, and slow-controlled release characteristic in a weak acid environment. Confocal microscopy revealed targeting of NCL-H460 cells by NPs by actively internalising CC9 and avoiding the phagocytic action of RAW264.7 cells, and live fluorescence imaging revealed targeting of tumours in tumour-bearing mice. Compared to free 5-ALA, the nanosystem displayed amplified anticancer activity by increasing production of PpIX and reactive oxygen species to induce mitochondrial pathway apoptosis. Antitumor efficacy was consistently observed in three-dimensionally cultured cells as the loss of integrity of tumour balls. More potent anti-tumour efficacy was demonstrated in xenograft tumour models by decreased growth rate and increased tumour apoptosis. Histological analysis showed that this system was not toxic, with lowered liver toxicity of 5-ALA. Thus, ALA/CC9@AuNPs-PLGA NPs deliver 5-ALA via a carrier cascade, with excellent effects on tumour accumulation and PDT through passive enhanced permeability and retention action and active targeting. This innovative strategy for cancer therapy requires more clinical trials before being implemented.
RESUMEN
Introduction: Therapies targeting histone deacetylase (HDAC) have gained wider attention in the treatment of various clinical conditions. However, the use of HDAC inhibitors in pre-clinical trials in the case of Parkinson's disease (PD) is very limited. In the present study, the HDAC inhibitor, entinostat, was tested in animals induced with Parkinson's disease experimentally. Material and methods: Wistar male rats (150 ±10 g) were administered with rotenone (2 mg/kg/day, s.c.) for 21 days to induce PD, while entinostat (20 mg/kg) was given intraperitoneally. Then, the neurological functions, PD markers, and HDACs were analysed in the control and experimental animals. Results: The results demonstrated that rats that received entinostat displayed progressive motor, behavioural, and neurological function with attenuated α-synuclein and improved tyrosine-hydroxylase compared to control cells. Moreover, the induction of PD in rats demonstrated reduced levels of H2S, dopamine, 3, and 4-dihydroxyphenylacetic acid (DOPAC), and increased monoamine oxidase activity in PD rats. However, the rats that received entinostat demonstrated progressive levels of dopa and DOPAC, with attenuated levels of HDAC-2, -4, and -6 mRNA in the PD rats compared to controls. On the other hand, elevated (p < 0.01) levels of PD marker genes such as GDF3 and NMDA2b were reduced, with a significant increase in neuroprotective genes such as VDAC3 and CBX5 in entinostat-supplemented rats. Conclusions: The study results suggest that inhibition of HDAC systematically improves the neurological functions, and hence treatments, emphasizing that HDACI, as the speculated mechanism, will be a promising mode of treatment in PD.
RESUMEN
OBJECTIVE: Investigation of the effects of 5-5- (4-N, N-diacetoxylphenyl)-10,15,20- tetraphenylporphyrin (DTPP)-mediated photodynamic therapy (PDT) on oxidative stress and mitochondrial apoptosis in LA795 lung cancer cells. METHODS: Proteomics was used to identify differentially expressed proteins after PDT treatment. The apoptosis rate was determined by flow cytometry. Morphologic observation of apoptosis, reactive oxygen species (ROS) levels, antioxidant indices, nitric oxide (NO) content, mitochondrial membrane potential (MMP), and Caspase- 9 and Caspase-3 were determined by assays; apoptosis-related protein levels of Cytochrome (Cyto) c, Bcl- 2, Bax were determined by Western blot. RESULTS: Typical apoptosis morphology of LA795 cells was observed after PDT. The cells were mainly in the apoptosis death pathway with high cell apoptosis rates. The proteomics study observed the apoptosis-associated proteins, oxidative stress proteins, antioxidant proteins, the cytoskeletal protein and mitochondrial dysfunction in LA 795 cells. Additional results indicated that PDT could increase levels of ROS, NO; decrease glutathione (GSH) content and MMP; upregulated Bax, Cyto c, and Caspase-3 protein expression, inhibited Bcl-2 protein expression, and further induced cell apoptosis. The effect of DTPP-PDT on lung cancer was: first, mitochondrial Cyto c is released into the cytoplasm, then Caspase- 9 / Caspase-3 was activated, Bcl-2 decreased/Bax increased, initiating cell apoptosis. CONCLUSION: DTPP-PDT could induce oxidative stress and apoptosis via mitochondrial pathways in LA795 cells.
Asunto(s)
Neoplasias Pulmonares , Compuestos Organofosforados , Fotoquimioterapia , Humanos , Fármacos Fotosensibilizantes/farmacología , Fármacos Fotosensibilizantes/uso terapéutico , Caspasa 3/metabolismo , Fotoquimioterapia/métodos , Proteína X Asociada a bcl-2/metabolismo , Especies Reactivas de Oxígeno , Antioxidantes/metabolismo , Antioxidantes/farmacología , Antioxidantes/uso terapéutico , Apoptosis , Proteínas Proto-Oncogénicas c-bcl-2/metabolismo , Estrés Oxidativo , Neoplasias Pulmonares/tratamiento farmacológicoRESUMEN
BACKGROUND: Many studies have assessed the relationship between gene polymorphisms in multidrug resistance protein 3 (MDR3) and the risk of intrahepatic cholestasis of pregnancy (ICP); however, there are many conflicting narratives. OBJECTIVES: This meta-analysis was conducted to assess the association between MDR3 gene polymorphisms and ICP. MATERIAL AND METHODS: A multi-database search was conducted using Web of Science, Embase, PubMed, and Chinese Biomedical Literature (CBM) databases. Eleven eligible studies focusing on 4 single nucleotide polymorphisms (SNPs) in the MDR3 gene were selected for analysis. A fixedor random-effects model was utilized for allelic, dominant, recessive, and superdominant genes. RESULTS: The pooled results indicated a statistically significant association between MDR3 polymorphism rs2109505 and an increased risk of ICP in both the general population and the Caucasian population. No statistically significant associations were found between MDR3 polymorphism rs2109505 and ICP in Italian or Asian populations for the 4 genetic models. The MDR3 polymorphism rs1202283 was associated with susceptibility to ICP in both the general and Italian populations. CONCLUSION: The MDR3 rs2109505 and rs1202283 polymorphisms are associated with ICP susceptibility: however, they displayed no correlation with an increased risk of ICP.
Asunto(s)
Transportadoras de Casetes de Unión a ATP , Polimorfismo de Nucleótido Simple , Embarazo , Femenino , Humanos , Transportadoras de Casetes de Unión a ATP/genética , Subfamilia B de Transportador de Casetes de Unión a ATP/genética , Predisposición Genética a la EnfermedadRESUMEN
Although accumulated evidence supports the notion that calpain contributes to eye disease, the mechanisms by which calpain promotes RPE injury are not defined. The present study is aimed at investigating whether the effect of NaIO3-exos (exosomes derived from RPE cells under NaIO3 stimulation) on the dysfunction of the autophagy-lysosomal pathway (ALP) and apoptosis is based on its regulation of calpain activation in ARPE-19 cells and rats. The results showed that calpain-2 activation, ALP dysfunction, and apoptosis were induced by NaIO3-exos in ARPE-19 cells. NaIO3-exo significantly increased autophagic substrates by activating lysosomal dysfunction. ALP dysfunction and apoptosis in vitro could be eliminated by knocking down calpain-2 (si-C2) or the inhibitor calpain-2-IN-1. Further studies indicated that NaIO3-exo enhanced calpain-2 expression, ALP dysfunction, apoptosis, and retinal damage in rats. In summary, these results demonstrate for the first time that calpain-2 is one of the key players in the NaIO3-exo-mediated ALP dysfunction, apoptosis, and retinal damage and identify calpain-2 as a promising target for therapies aimed at age-related macular degeneration (AMD).
Asunto(s)
Apoptosis , Autofagia , Calpaína , Exosomas , Animales , Ratas , Calpaína/metabolismo , Lisosomas , Epitelio Pigmentado de la Retina/metabolismoRESUMEN
Osthol (osthole), known as a neuroprotective drug, has shown potent anticancer activity. However, the potential clinical application of osthol is limited due to its low water solubility and low bioavailability. Polybutyl cyanoacrylate (PBCA) has been widely used to improve the solubility of drugs with poor water solubility. In this study, an orthogonal experimental design (OED) was applied to design the preparation process of PBCA nanoparticles (NPs). Then, nanoparticles were prepared and evaluated in terms of physicochemical properties, in vitro release, and cellular uptake, etc. Further, the anti-cancer activity of osthol-PBCA NPs was demonstrated in SH-SY5Y cells. The pharmacokinetics and area under the curve (AUC) were investigated. The obtained osthol-NPs presented a spherical shape with a particle size of 110 ± 6.7 nm, a polydispersity index (PDI) of 0.126, and a zeta potential of −13 ± 0.32 mV. Compared with the free osthol, the drugs in osthol-NPs presented better stability and sustained release pattern activity. In vitro analysis using SH-SY5Y neuroblastoma cells showed that osthol-loaded nanoparticles displayed a significantly enhanced intracellular absorption process (three times) and cytotoxicity compared with free osthol (p < 0.05, increased 10−20%). The in vivo pharmacokinetic study revealed that the AUC of osthol-NPs was 3.3-fold higher than that of free osthol. In conclusion, osthol-PBCA NPs can enhance the bioactivity of osthol, being proposed as a novel, promising vehicle for drug delivery.
Asunto(s)
Enbucrilato , Nanopartículas , Neuroblastoma , Fármacos Neuroprotectores , Humanos , Enbucrilato/química , Portadores de Fármacos/química , Preparaciones de Acción Retardada , Neuroblastoma/tratamiento farmacológico , Nanopartículas/química , Tamaño de la Partícula , AguaRESUMEN
Genetic variation in UDP-glucuronosyltransferase 1A1 gene (UGT1A1) is a lithogenic risk factor for gallstone formation. This study aimed to assess genotype and allele frequencies of common UGT1A1 variants in patients with gallstone and hepatitis B virus (HBV)-related hepatic failure. This study enrolled 113 healthy individuals (CTRL), 54 patients with HBV infection (HBV), 134 patients with gallstone-free hepatic failure and HBV infection, and 34 patients with gallstone-related hepatic failure and HBV infection (GRHF). Peripheral venous blood samples were collected for genomic DNA isolation. Polymerase chain reaction amplification was carried out for UGT1A1, followed by direct sequencing. Analysis for genotype and allele frequencies of UGT1A1 variants (UGT1A1*6, UGT1A1*27, UGT1A1*28, and UGT1A1*60) was performed. The allele distributions of the four groups did not deviate from Hardy-Weinberg equilibrium. Allele (A) and genotype (CA) frequency distributions of UGT1A1*27 were significantly different between GRHF and CTRL, or between GRHF and HBV. GRHF and CTRL exhibited significant differences in allele (A) and genotype (CA) frequency distributions of UGT1A1*28. Linkage disequilibrium analysis suggested that haplotype G-G-[TA]7-T may be associated with gallstone in HBV-related hepatic failure. Our data reveal that UGT1A1*27 and UGT1A1*28 variants are significantly observed in patients with GRHF compared to healthy individuals.
RESUMEN
BACKGROUND: To investigate the susceptibility of SH-SY5Y cells to DTPP-based photodynamic therapy (PDT) and the antagonistic effects of chrysophanol (Chr) on PDT. METHODS: PDT photocytotoxicity to cells was quantified and determined by exposing increasing concentrations of DTPP between 2.5 to 20 µg/mL to radiation with energy densities of 1.2-9.6 J/cm2 at 630-nm wavelength. Sodium azide (SA, NaN3) and d-mannitol (DM) were employed to study the reaction type of PDT. The photodynamic stress after PDT was assessed by superoxide dismutase (SOD), malondialdehyde (MDA), and total antioxidative capacity (T-AOC) assays. The apoptosis pathway of SH-SY5Y cells after PDT was studied by the determination of JC-1 and caspase-9/Caspase-3 concentrations. MTT and double fluorescence staining assays were applied to study the effect of Chr on cell survival and apoptosis rate in PDT, respectively. PI was used to detect the effect of Chr on cell membrane integrity after DTPP-PDT treatment. RESULTS: The dose-dependent killing effect of high DTPP concentrations and irradiation doses were identified. Cell apoptosis is mediated by a mitochondrial pathway with a total apoptosis rate of 33.8% at 10 µg/mL of DTPP after irradiation with 2.4 J/cm2. Oxidative stress was produced by ROS in PDT and non-reversible cell oxidative damage appeared due to the cells' modulation of the oxidative stress balance during the PDT response. Chr had a- effect on ROS capture and an inhibitory effect on the PDT-induced destruction of cell membranes. CONCLUSIONS: SH-SY5Y cells were susceptible to DTPP-PDT, resulting in a mitochondrial apoptosis pathway. There is an antagonistic effect of Chr on PDT in SH-SY5Y neuroblastoma cells.
Asunto(s)
Neuroblastoma , Fotoquimioterapia , Humanos , Fotoquimioterapia/métodos , Línea Celular Tumoral , Apoptosis , Estrés Oxidativo , Supervivencia Celular , Especies Reactivas de Oxígeno/metabolismoRESUMEN
Self-assembled monolayers (SAMs) of thiolates on metal surfaces are of key importance for engineering surfaces with tunable properties. However, it remains challenging to understand binary thiolate SAMs on metals at the nanoscale under ambient conditions. Here, we employ tip-enhanced Raman spectroscopy (TERS) and density functional theory (DFT) calculations to investigate the local information of binary SAMs on Au(111) coadsorbed from an equimolar mixture of p-cyanobenzenethiol (pCTP) and p-aminothiophenol (pATP), including chemical composition, coadsorption behavior, phase segregation, plasmon-induced photocatalysis, and solvation effects. We found that upon competitive adsorption of pCTP and pATP on Au(111) from a methanolic solution, the coadsorption initially occurs randomly and homogeneously; eventually, pATP is replaced by pCTP through the gradual growth of pCTP nanodomains. TERS imaging also allows for visualization of the plasmon-induced coupling of pATP to p,p'-dimercaptoazobenzene (DMAB) and the solvation-induced phase segregation of the binary SAMs into nanodomains, with a spatial resolution of â¼9 nm under ambient conditions. According to DFT calculations, these aromatic thiolates differing only in their functional groups, -CN versus -NH2, show different adsorption energies on Au(111) in vacuum and methanol, and thus, the solvation effect on the adsorption energy of these thiolates in methanol can determine the dispersion state and replacement order of the binary thiolates on Au(111).
Asunto(s)
Diagnóstico por Imagen , Espectrometría Raman , Adsorción , Espectrometría Raman/métodosRESUMEN
Fecundity in livestock is an economically important complex quantitative trait that is influenced by both genetics and the environment. However, the underlying genetic mechanism of reproductive performance in goats has not been well investigated. To investigate the genomic basis of fecundity in goats, genomic sequencing data of the Jining grey goat (a high prolificacy breed in China) were collected, as well as data for other commonly available goat breeds, and a mass of genomic variants were generated after variation calling. We screened the Jining grey goat (20 individuals) using a selective sweep with the Asian wild goat population (5 individuals), and potential candidate genes were proposed, such as STIM1, ESR1, LRRC14B and SLC9A3. Among, STIM1 is a most promising one associated with high reproductive capacity. When compared to Chinese domestic goats with low fecundity (17 individuals), the genes including MLLT10, SPIRE2, TCF25, ZNF276 and FANCA were screened, and the SPIRE2 gene was thought to be associated with fecundity traits. Meanwhile, the functional enrichment of these candidate genes revealed that they were involved in biological processes of mammary gland morphogenesis, uterus development, gastrulation, mesoderm morphogenesis and formation, and blood vessel development, which might undergo natural or artificial selection during reproductive trait formation in goats. Thus, our findings could enrich the genetic basis of reproductive trait selection during goat domestication, which may serve to improve goat breeding practices.
Asunto(s)
Fertilidad/genética , Genoma , Cabras/genética , Animales , Animales Domésticos/genética , Animales Salvajes/genética , Ontología de Genes , Estudios de Asociación Genética , Genética de Población , Cabras/crecimiento & desarrollo , Polimorfismo de Nucleótido Simple/genética , Reproducción/genéticaRESUMEN
BACKGROUND: Acute fatty liver of pregnancy (AFLP) is an acute, rare and potentially lethal disease typically occurring in the third trimester of pregnancy. So far, there is no effective means of prevention. Therefore, in this study, we retrospectively analyzed the clinical features of AFLP patients for a better understanding. Meanwhile, for the first time, the genetic background associated with the onset of AFLP was discussed by high-throughput sequencing, hoping to provide evidence for genetic counseling and prenatal diagnosis of AFLP. METHODS: Thirteen AFLP patients admitted to our hospital and other hospital from March 2012 to February 2020 were selected. Clinical data about general condition, laboratory test, liver biopsy and the prognosis of mother and fetus were collected for retrospective analysis. In addition, the peripheral blood of five patients with AFLP and one newborn infant of his mother with AFLP was sequenced with whole-exome sequencing and gene mutation was analyzed by bioinformatics methods. RESULTS: The initial symptoms of AFLP varied differently, with jaundice (9/13, 69%), fatigue (8/13, 62%) and nausea and vomiting (6/13, 46%) being the most common. Moreover, the main maternal complications were coagulopathy (13/13, 100%), followed by acute renal dysfunction (10/13, 77%). Raised serum bilirubin, transaminases and uric acid were found in all patients (100%), hypoglycemia was found in six patients (46%) and fatty liver on ultrasound was seen in five patients (5/12, 42%). One (7%) maternal death occurred and all neonates survived delivery. In addition, to our surprise, whole-exome sequencing showed that no gene mutation in related enzymes involved in fatty acid metabolism was noted in the pregnant women and children receiving genetic testing. CONCLUSIONS: Early visit, early detection, early termination of pregnancy and multidisciplinary comprehensive treatment are the key factors to improve the prognosis of AFLP patients and their newborn infants. Furthermore, although limited size of study, to our knowledge, this report is the first to present the lack of common mutation involved in fatty acid oxidation in Chinese patients with AFLP via whole-exome sequencing. Thus, further studies are needed with larger and more varied samples to validate the conclusion.
Asunto(s)
Secuenciación del Exoma , Hígado Graso/genética , Hígado Graso/patología , Pruebas Genéticas , Complicaciones del Embarazo/genética , Complicaciones del Embarazo/patología , Adulto , China/epidemiología , Hígado Graso/diagnóstico , Hígado Graso/terapia , Femenino , Secuenciación de Nucleótidos de Alto Rendimiento/métodos , Humanos , Recién Nacido , Resultados Negativos , Embarazo , Complicaciones del Embarazo/diagnóstico , Complicaciones del Embarazo/terapia , Estudios Retrospectivos , Análisis de Secuencia de ADN/métodosRESUMEN
Metal-organic coordination structures at interfaces play an essential role in many biological and chemical systems. Understanding the molecular specificity, orientation, and spatial distribution of the coordination complexes at the nanometer scale is of great importance for effective molecular engineering of nanostructures and fabrication of functional devices with controllable properties. However, fundamental properties of such coordination systems are still rarely studied directly. In this work, we present a spectroscopic approach on the basis of tip-enhanced Raman spectroscopy (TERS) to investigate cobalt(II) tetraphenyl-porphyrine coordination species on the scale of a single molecule under ambient conditions. Coordination species anchored on gold surfaces modified with pyridine thiol self-assembled monolayers can be spectroscopically distinguished and mapped with ca. 2 nm resolution. In addition, in combination with density functional theory simulations, the adsorption configuration and molecular orientation of the coordination complexes are also revealed using TERS imaging.
RESUMEN
Photoswitches can be employed for various purposes, with the half-life being a crucial parameter to optimize for the desired application. The switching of a photochromic hydrazone functionalized with a C6 alkyl thiolate spacer (C6 HAT) was characterized on a number of metal surfaces. C6 HAT exhibits a half-life of 789 years in solution. Tip-enhanced Raman spectroscopy (TERS) was used to study the photoisomerization of the C6 HAT self-assembled monolayers (SAMs) on Au, Ag, and Cu surfaces. The unique spectroscopic signature of the E isomer at 1580 and 1730 cm-1 in TER spectra allowed for its discrimination from the Z isomer. It was found that C6 HAT switches on Au and Cu surfaces when irradiated with 415 nm; however, it cannot isomerize on Ag surfaces, unless higher energy light is used. Based on this finding, and supported by density functional theory calculations, we propose a substrate-mediated photoisomerization mechanism to explain the behavior of C6 HAT on these different metal surfaces. This insight into the hydrazone's switching mechanism on metal surfaces will contribute to the further exploitation of this new family photochromic compounds on metal surfaces. Finally, although we found that the thermal isomerization rate of C6 HAT drastically increases on metal surfaces, the thermal half-life is still 6.9 days on gold, which is longer than that of the majority of azobenzene-based systems.
RESUMEN
BACKGROUND: To evaluate the efficacy and safety of telbivudine in chronic hepatitis B women during the second and third trimesters of pregnancy. METHODS: The week 12-34 of pregnant women were screened in this prospective non-intervention study, with HBV DNA > 106 IU/mL and alanine aminotransferase > 50 IU/L. The patients were received telbivudine treatment as a treatment group or without antiviral treatment as a control group. All infants were received recombinant hepatitis B vaccine 10 µg within 12 h of birth, at week 4 and week 24, immunoglobulin G within 12 h of birth and were detected HBV markers at the range from 7 to 12 months after delivery. RESULTS: A total of 241 patients were finally enrolled, 139 patients in telbivudine group and 102 patients in control group. HBsAg negative rate of infants was 99.3% (135/136) in telbivudine group and was 91.9% (91/99) in control group after 7 months (P = 0.005), respectively. The incidence of undetectable HBV DNA levels (47.5%) was significantly lower in telbivudine-treated mothers than that in the controls (0%), and 75.5% patients alanine aminotransferase returned to normal in telbivudine group, and 51% in control group at delivery (P < 0.001), respectively. CONCLUSIONS: Telbivudine can safely reduce mother-to-child transmission in chronic hepatitis B women after 12 weeks of gestation.
Asunto(s)
Antivirales/uso terapéutico , Vacunas contra Hepatitis B/inmunología , Hepatitis B Crónica/tratamiento farmacológico , Transmisión Vertical de Enfermedad Infecciosa/prevención & control , Telbivudina/uso terapéutico , Adulto , Alanina Transaminasa/sangre , Estudios de Casos y Controles , ADN Viral/sangre , Femenino , Edad Gestacional , Antígenos de Superficie de la Hepatitis B/sangre , Virus de la Hepatitis B/genética , Virus de la Hepatitis B/aislamiento & purificación , Humanos , Inmunoglobulina G/sangre , Lactante , Recién Nacido , Embarazo , Estudios Prospectivos , Adulto JovenRESUMEN
A two-dimensional (2D) covalent monolayer based on [4 + 4] cycloaddition reactions between adjacent anthracene units was synthesized at an air/water interface. For structural analysis, tip-enhanced Raman spectroscopy (TERS) provides direct evidence for the covalent bonds formed between monomer molecules. For the first time, progress of the photopolymerization reaction was monitored by irradiation (λ = 385 nm) of the monomer monolayer for different times, based on averaged TER spectra extracted from maps. In addition, a 2D polymerization on a Au (111) substrate was realized, which opens up new possibilities for such chemical transformations. This work uses TERS as a minimally invasive tool to investigate how the reaction conditions affect polymerization conversion. We show that the high sensitivity and the high spatial resolution of TERS can be used to estimate the crystallinity of 2D covalent monolayers, which is a key question in polymer synthesis.
RESUMEN
In this work we prepare Langmuir-Blodgett monolayers with a trifunctional amphiphilic anthraphane monomer. Upon spreading at the air/water interface, the monomers self-assemble into 1 nm-thin monolayer islands, which are highly fluorescent and can be visualized by the naked eye upon excitation. In situ fluorescence spectroscopy indicates that in the monolayers, all the anthracene units of the monomers are stacked face-to-face forming excimer pairs, whereas at the edges of the monolayers, free anthracenes are present acting as edge groups. Irradiation of the monolayer triggers [4 + 4]-cycloadditions among the excimer pairs, effectively resulting in a two-dimensional (2D) polymerization. The polymerization reaction also completely quenches the fluorescence, allowing to draw patterns on the monomer monolayers. More interestingly, after transferring the monomer monolayer on a solid substrate, by employing masks or the laser of a confocal scanning microscope, it is possible to arbitrarily select the parts of the monolayer that one wants to polymerize. The unpolymerized regions can then be washed away from the substrate, leaving 2D macromolecular monolayer objects of the desired shape. This photolithographic process employs 2D polymerizations and affords 1 nm-thin coatings.
RESUMEN
An understanding of the photoisomerization mechanism of molecules bound to a metal surface at the molecular scale is required for designing photoswitches at surfaces. It has remained a challenge to correlate the surface structure and isomerization of photoswitches at ambient conditions. Herein, the photoisomerization of a self-assembled monolayer of azobenzene-thiol molecules on a Au surface was investigated using scanning tunneling microscopy and tip-enhanced Raman spectroscopy. The unique signature of the cis isomer at 1525â cm-1 observed in tip-enhanced Raman spectra was clearly distinct from the trans isomer. Furthermore, tip-enhanced Raman images of azobenzene thiols after ultraviolet and blue light irradiation are shown with nanoscale spatial resolution, demonstrating a reversible conformational change. Interestingly, the cis isomers of azobenzene-thiol molecules were preferentially observed at Au grain edges, which is confirmed by density functional theory.
RESUMEN
The race for performance of integrated circuits is nowadays facing a downscale limitation. To overpass this nanoscale limit, modern transistors with complex geometries have flourished, allowing higher performance and energy efficiency. Accompanying this breakthrough, challenges toward high-performance devices have emerged on each significant step, such as the inhomogeneous coverage issue and thermal-induced short circuit issue of metal silicide formation. In this respect, we developed a two-step organometallic approach for nickel silicide formation under near-ambient temperature. Transmission electron and atomic force microscopy show the formation of a homogeneous and conformal layer of NiSix on pristine silicon surface. Post-treatment decreases the carbon content to a level similar to what is found for the original wafer (â¼6%). X-ray photoelectron spectroscopy also reveals an increasing ratio of Si content in the layer after annealing, which is shown to be NiSi2 according to X-ray absorption spectroscopy investigation on a Si nanoparticle model. I-V characteristic fitting reveals that this NiSi2 layer exhibits a competitive Schottky barrier height of 0.41 eV and series resistance of 8.5 Ω, thus opening an alternative low-temperature route for metal silicide formation on advanced devices.
RESUMEN
Organophosphate esters, widely used as flame retardants and plasticizers, are regarded as a class of emerging pollutants. In this work, a novel approach was developed for the fabrication of a solid-phase microextraction fiber by using hybrid silica-based materials with immobilized ionic liquids with sol-gel technology, and the prepared solid-phase microextraction fiber was then coupled with gas chromatography and flame photometric detection for the analysis of six organophosphate esters. The high loading of 1-hexadecyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide was confined within the hybrid network. The developed solid-phase microextraction fiber possesses a coating thickness of â¼35 µm with good thermal stability and long lifetime. The parameters affecting the extraction efficiency such as extraction time, temperature, pH, and ionic strength of the sample solution were optimized. Under the optimized conditions, the limits of detection were in the range of 0.04-0.95 µg L-1 , and the precision of the method assessed with repeatability and reproducibility of (RSD%) Ë13 and Ë29%, respectively. The proposed method was successfully applied to determine the six organophosphate esters in three real water samples, with recoveries in the range of 64.8-125.4% at two different spiking concentration levels. As a result, the proposed method demonstrated its potential for application in trace determination of organophosphate esters in actual water samples.