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1.
Sci Rep ; 14(1): 475, 2024 01 04.
Artículo en Inglés | MEDLINE | ID: mdl-38177655

RESUMEN

In recent years, biometrics has been the most popular style of personal identification. The finger vein is an intrinsic and stable trait, and with the ability to detect liveness, it receives academic and industry attention. However, convolution neural networks (CNNs) based finger vein recognition generally can only cover a small input region by using small kernels. Hence, the performance is poor, facing low-quality finger vein images. It is a challenge to effectively use the critical feature of multi-scale for finger veins. In this article, we extract multi-scale features via pyramid convolution. We propose scale attention, namely, the scale-aware attention (SA) module, which enables dynamic adjustment of the weight of each scale to information aggregation. Utilize the complementation of different scale detail features to enhance the discriminativeness of extracted features, thus improving the finger vein recognition performance. In order to verify the present method's efficiency, we carried out experiments on two public data sets and one internal data, and the wide range of experimental results proves the proposed method's effectiveness.


Asunto(s)
Concienciación , Industrias , Biometría , Extremidades , Atención
2.
Brain Topogr ; 36(3): 283-293, 2023 05.
Artículo en Inglés | MEDLINE | ID: mdl-36856917

RESUMEN

To explore alterations of resting-state functional connectivity (rsFC) in sensorimotor cortex following strokes with left or right hemiplegia considering the lateralization and neuroplasticity. Seventy-three resting-state functional near-infrared spectroscopy (fNIRS) files were selected, including 26 from left hemiplegia (LH), 21 from right hemiplegia (RH) and 26 from normal controls (NC) group. Whole-brain analyses matching the Pearson correlation were used for rsFC calculations. For right-handed normal controls, rsFC of motor components (M1 and M2) in the left hemisphere displayed a prominent intensity in comparison with the right hemisphere (p < 0.05), while for stroke groups, this asymmetry has disappeared. Additionally, RH rather than LH showed stronger rsFC between left S1 and left M1 in contrast to normal controls (p < 0.05), which correlated inversely with motor function (r = - 0.53, p < 0.05). Regarding M1, rsFC within ipsi-lesioned M1 has a negative correlation with motor function of the affected limb (r = - 0.60 for the RH group and - 0.43 for the LH group, p < 0.05). The rsFC within contra-lesioned M1 that innervates the normal side was weakened compared with that of normal controls (p < 0.05). Stronger rsFC of motor components in left hemisphere was confirmed by rs-fNIRS as the "secret of dominance" for the first time, while post-stroke hemiplegia broke this cortical asymmetry. Meanwhile, a statistically strengthened rsFC between left S1 and M1 only in right-hemiplegia group may act as a compensation for the impairment of the dominant side. This research has implications for brain-computer interfaces synchronizing sensory feedback with motor performance and transcranial magnetic regulation for cortical excitability to induce cortical plasticity.


Asunto(s)
Corteza Sensoriomotora , Accidente Cerebrovascular , Humanos , Lateralidad Funcional/fisiología , Hemiplejía/diagnóstico por imagen , Imagen por Resonancia Magnética/métodos , Accidente Cerebrovascular/diagnóstico por imagen , Corteza Sensoriomotora/diagnóstico por imagen , Plasticidad Neuronal/fisiología
3.
Adv Colloid Interface Sci ; 314: 102866, 2023 Apr.
Artículo en Inglés | MEDLINE | ID: mdl-36898186

RESUMEN

Peptide amphiphiles (PAs) are peptide-based molecules that contain a peptide sequence as a head group covalently conjugated to a hydrophobic segment, such as lipid tails. They can self-assemble into well-ordered supramolecular nanostructures such as micelles, vesicles, twisted ribbons and nanofibers. In addition, the diversity of natural amino acids gives the possibility to produce PAs with different sequences. These properties along with their biocompatibility, biodegradability and a high resemblance to native extracellular matrix (ECM) have resulted in PAs being considered as ideal scaffold materials for tissue engineering (TE) applications. This review introduces the 20 natural canonical amino acids as building blocks followed by highlighting the three categories of PAs: amphiphilic peptides, lipidated peptide amphiphiles and supramolecular peptide amphiphile conjugates, as well as their design rules that dictate the peptide self-assembly process. Furthermore, 3D bio-fabrication strategies of PAs hydrogels are discussed and the recent advances of PA-based scaffolds in TE with the emphasis on bone, cartilage and neural tissue regeneration both in vitro and in vivo are considered. Finally, future prospects and challenges are discussed.


Asunto(s)
Nanofibras , Nanoestructuras , Ingeniería de Tejidos , Péptidos/química , Nanoestructuras/química , Nanofibras/química , Hidrogeles
4.
Foods ; 11(21)2022 Nov 06.
Artículo en Inglés | MEDLINE | ID: mdl-36360145

RESUMEN

Litopenaeus vannamei is one of the most popular shrimp species in the world and has been reported in studies on its dryness and flavor. However, the aroma characteristics of shrimps dried with different drying methods are compared in a unified way, and there are few reports on the difference in aroma of different shrimps dried. In order to clarify the difference in aroma characteristics of shrimp dried produced by different drying methods. In this study, blanched shrimp (BS) was used as a control to analyze the aroma characteristics of shrimp dried by five different procedures (SD-BFDP) samples, namely vacuum freeze-dried shrimp (VFDS), vacuum dried-shrimp (VDS), heat pump-dried shrimp (HPDS), hot air dried-shrimp (HADS) and microwave vacuum-dried shrimp (MVDS). An electronic nose (E-nose) was used to obtain the aroma fingerprint of SD-BFDP samples. Headspace solid-phase microextraction gas chromatography-mass spectrometry (HS-SPME-GC-MS) was used for qualitative and quantitative analysis of volatile compounds in SD-BFDP samples. Partial least squares regression (PLSR) was used to analyze potential correlations between sensory attributes and aroma-active compounds (AACs). Partial least squares-discrimination analysis (PLS-DA) was used to screen for signature aroma compounds. The results of the E-nose showed that there were differences in the aroma fingerprints of the SD-BFDP samples, and the E-nose could distinguish the five kinds of SD-BFDP. The qualitative and quantitative results of GC-MS showed that the types and contents of the main volatile components of SD-BFDP samples were different. 15 AACs were screened from SD-BFDP based on odor activity value (OAV). The PLSR results showed good correlations between certain sensory attributes and the majority of AACs. PLS-DA results displayed that aroma attributes of SD-BFDP samples could be distinguished by six signature aroma compounds, including trimethylamine, 2,5-dimethylpyrazine, 2-ethyl-5-methylpyrazine, nonanal, 3-ethyl-2,5-dimethylpyrazine, and octanal. These research results reveal that shrimps dried in different procedures have unique aroma characteristics, which could provide a theoretical basis for the rapid identification of aroma attributes of dried shrimps in the future. From a flavor perspective, MVD is the best drying method.

5.
Int J Pharm ; 620: 121762, 2022 May 25.
Artículo en Inglés | MEDLINE | ID: mdl-35472511

RESUMEN

Nanoparticles (NPs) have great potential as efficient drug delivery systems (DDSs) that have been widely used in cancer therapy and vaccines especially in the past decade. The rise in demand from the pharmaceutical industry drives the growth of the global NPs market. However, complex production processes have hindered the market growth. Therefore, the development of advanced preparation techniques such as microfluidics is required to improve productivity and controllability. In this study, we present a novel microfluidic design (swirl mixer) that helps accelerating the translation of many DDSs from laboratory to clinical application. The new swirl mixer provides high production rate, reproducibility, and precise control of particle size with low polydispersity index (PDI). To assess the performance of the swirl mixer, two different types of nanoformulations were used: silk nanoparticles (SNPs) and lipid nanoparticles (LNPs). The microfluidic device produced NPs efficiently with high productivity and allowed for tuning the mean size and size distribution by changing multiple processing parameters.


Asunto(s)
Microfluídica , Nanopartículas , Liposomas , Microfluídica/métodos , Tamaño de la Partícula , Reproducibilidad de los Resultados
6.
Phys Med Biol ; 66(17)2021 08 26.
Artículo en Inglés | MEDLINE | ID: mdl-34375955

RESUMEN

The segmentation results of retinal vessels have a significant impact on the automatic diagnosis of retinal diabetes, hypertension, cardiovascular and cerebrovascular diseases and other ophthalmic diseases. In order to improve the performance of blood vessels segmentation, a pyramid scene parseing U-Net segmentation algorithm based on attention mechanism was proposed. The modified PSP-Net pyramid pooling module is introduced on the basis of U-Net network, which aggregates the context information of different regions so as to improve the ability of obtaining global information. At the same time, attention mechanism was introduced in the skip connection part of U-Net network, which makes the integration of low-level features and high-level semantic features more efficient and reduces the loss of feature information through nonlinear connection mode. The sensitivity, specificity, accuracy and AUC of DRIVE and CHASE_DB1 data sets are 0.7814, 0.9810, 0.9556, 0.9780; 0.8195, 0.9727, 0.9590, 0.9784. Experimental results show that the PSP-UNet segmentation algorithm based on the attention mechanism enhances the detection ability of blood vessel pixels, suppresses the interference of irrelevant information and improves the network segmentation performance, which is superior to U-Net algorithm and some mainstream retinal vascular segmentation algorithms at present.


Asunto(s)
Vasos Retinianos , Algoritmos , Procesamiento de Imagen Asistido por Computador , Redes Neurales de la Computación , Vasos Retinianos/diagnóstico por imagen
7.
J Colloid Interface Sci ; 603: 380-390, 2021 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-34186409

RESUMEN

Guiding neuronal cell growth is desirable for neural tissue engineering but is very challenging. In this work, a self-assembling ultra-short surfactant-like peptide I3K which possesses positively charged lysine head groups, and hydrophobic isoleucine tails, was chosen to investigate its potential for guiding neuronal cell growth. The peptides were able to self-assemble into nanofibrous structures and interact strongly with silk fibroin (SF) scaffolds, providing a niche for neural cell attachment and proliferation. SF is an excellent biomaterial for tissue engineering. However neuronal cells, such as rat PC12 cells, showed poor attachment on pure regenerated SF (RSF) scaffold surfaces. Patterning of I3K peptide nanofibers on RSF surfaces significantly improved cellular attachment, cellular density, as well as morphology of PC12 cells. The live / dead assay confirmed that RSF and I3K have negligible cytotoxicity against PC12 cells. Atomic force microscopy (AFM) was used to image the topography and neurite formation of PC12 cells, where results revealed that self-assembled I3K nanofibers can support the formation of PC12 cell neurites. Immunolabelling also demonstrated that coating of I3K nanofibers onto the RSF surfaces not only increased the percentage of cells bearing neurites but also increased the average maximum neurite length. Therefore, the peptide I3K could be used as an alternative to poly-l-lysine for cell culture and tissue engineering applications. As micro-patterning of neural cells to guide neurite growth is important for developing nerve tissue engineering scaffolds, inkjet printing was used to pattern self-assembled I3K peptide nanofibers on RSF surfaces for directional control of PC12 cell growth. The results demonstrated that inkjet-printed peptide micro-patterns can effectively guide the cell alignment and organization on RSF scaffold surfaces, providing great potential for nerve regeneration applications.


Asunto(s)
Fibroínas , Nanofibras , Animales , Proliferación Celular , Péptidos , Ratas , Seda , Ingeniería de Tejidos , Andamios del Tejido
8.
Med Phys ; 48(7): 3827-3841, 2021 Jul.
Artículo en Inglés | MEDLINE | ID: mdl-34028030

RESUMEN

PURPOSE: The segmentation results of retinal blood vessels have a significant impact on the automatic diagnosis of various ophthalmic diseases. In order to further improve the segmentation accuracy of retinal vessels, we propose an improved algorithm based on multiscale vessel detection, which extracts features through densely connected networks and reuses features. METHODS: A parallel fusion and serial embedding multiscale feature dense connection U-Net structure are designed. In the parallel fusion method, features of the input images are extracted for Inception multiscale convolution and dense block convolution, respectively, and then the features are fused and input into the subsequent network. In serial embedding mode, the Inception multiscale convolution structure is embedded in the dense connection network module, and then the dense connection structure is used to replace the classical convolution block in the U-Net network encoder part, so as to achieve multiscale feature extraction and efficient utilization of complex structure vessels and thereby improve the network segmentation performance. RESULTS: The experimental analysis on the standard DRIVE and CHASE_DB1 databases shows that the sensitivity, specificity, accuracy, and AUC of the parallel fusion and serial embedding methods reach 0.7854, 0.9813, 0.9563, 0.9794; 0.7876, 0.9811, 0.9565, 0.9793 and 0.8110, 0.9737, 0.9547, 0.9667; 0.8113, 0.9717, 0.9574, 0.9750, respectively. CONCLUSIONS: The experimental results show that multiscale feature detection and feature dense connection can effectively enhance the network model's ability to detect blood vessels and improve the network segmentation performance, which is superior to U-Net algorithm and some mainstream retinal blood vessel segmentation algorithms at present.


Asunto(s)
Procesamiento de Imagen Asistido por Computador , Redes Neurales de la Computación , Algoritmos , Bases de Datos Factuales , Vasos Retinianos/diagnóstico por imagen
9.
ACS Nano ; 15(4): 7114-7130, 2021 Apr 27.
Artículo en Inglés | MEDLINE | ID: mdl-33764730

RESUMEN

Lithium-sulfur (Li-S) batteries are severely hindered by the low sulfur utilization and short cycling life, especially at high rates. One of the effective solutions to address these problems is to improve the sulfiphilicity of lithium polysulfides (LiPSs) and the lithiophilicity of the lithium anode. However, it is a great challenge to simultaneously optimize both aspects. Herein, by incorporating the merits of strong absorbability and high conductivity of SnS with good catalytic capability of ZnS, a ZnS-SnS heterojunction coated with a polydopamine-derived N-doped carbon shell (denoted as ZnS-SnS@NC) with uniform cubic morphology was obtained and compared with the ZnS-SnS2@NC heterostructure and its single-component counterparts (SnS@NC and SnS2@NC). Theoretical calculations, ex situ XANES, and in situ Raman spectrum were utilized to elucidate rapid anchoring-diffusion-transformation of LiPSs, inhibition of the shuttling effect, and improvement of the sulfur electrochemistry of bimetal ZnS-SnS heterostructure at the molecular level. When applied as a modification layer coated on the separator, the ZnS-SnS@NC-based cell with optimized lithiophilicity and sulfiphilicity enables desirable sulfur electrochemistry, including high reversibility of 1149 mAh g-1 for 300 cycles at 0.2 C, high rate performance of 661 mAh g-1 at 10 C, and long cycle life with a low fading rate of 0.0126% each cycle after 2000 cycles at 4 C. Furthermore, a favorable areal capacity of 8.27 mAh cm-2 is maintained under high sulfur mass loading of 10.3 mg cm-2. This work furnishes a feasible scheme to the rational design of bimetal sulfides heterostructures and boosts the development of other electrochemical applications.

10.
J Colloid Interface Sci ; 594: 513-521, 2021 Jul 15.
Artículo en Inglés | MEDLINE | ID: mdl-33774407

RESUMEN

HYPOTHESIS: One of the main challenges in cancer therapy is the poor water solubility of many anticancer drugs which results in low bioavailability at the tumour sites and reduced efficacy. The currently available polymer-based anticancer drug delivery systems often suffer from low encapsulation efficiency, uncontrolled release, and lack of long-term stability. Herein, we report the development of novel stiffness-tuneable core-shell nanocarriers composed of naturally derived polymers silk fibroin (SF) and sodium alginate (SA) inside a liposomal shell for enhanced cellular uptake and controlled release of hydrophobic anticancer agent ASC-J9 (Dimethylcurcumin). It is anticipated that the stiffness of the nanocarriers has a significant effect on their cellular uptake and anticancer efficacy. EXPERIMENTS: The nanocarriers were prepared by thin film hydration method followed by extrusion and cross-linking of SA to obtain a uniform size and shape, avoiding harsh processing conditions. The structural transformation of SF in the nanocarriers induced by SA crosslinking was determined using Fourier transform infrared (FTIR) spectroscopy. The size, zeta potential, morphology and stiffness of the nanocarriers were measured using dynamic light scattering (DLS), transmission electron microscopy (TEM) and atomic force microscopy (AFM). Drug loading and release were measured using UV-Vis spectrophotometry. The cellular uptake and anticancer efficacy of the nanocarriers were studied in HCT 116 human colorectal adenocarcinoma cells and 3D tumour spheroids using high content microscopy. FINDINGS: The synthesized nanocarriers had high encapsulation efficiency (62-78%) and were physically stable for up to 5 months at 4 ˚C. The release profile of the drug from the nanocarriers was directed by their stiffness and was easily tuneable by changing the ratio of SF to SA in the core. Furthermore, the designed nanocarriers improved the cellular uptake and anticancer activity of ASC-J9, and enhanced its tumour penetration in HCT 116 3D colorectal cancer spheroids. These findings suggest that the designed core-shell nanocarriers can be used as a highly efficient drug delivery system for cancer therapy.


Asunto(s)
Antineoplásicos , Neoplasias Colorrectales , Nanopartículas , Antineoplásicos/farmacología , Neoplasias Colorrectales/tratamiento farmacológico , Portadores de Fármacos , Sistemas de Liberación de Medicamentos , Humanos , Interacciones Hidrofóbicas e Hidrofílicas , Tamaño de la Partícula , Polímeros
11.
Int J Mol Sci ; 22(3)2021 Feb 02.
Artículo en Inglés | MEDLINE | ID: mdl-33540895

RESUMEN

Tissue engineering (TE) is the approach to combine cells with scaffold materials and appropriate growth factors to regenerate or replace damaged or degenerated tissue or organs. The scaffold material as a template for tissue formation plays the most important role in TE. Among scaffold materials, silk fibroin (SF), a natural protein with outstanding mechanical properties, biodegradability, biocompatibility, and bioresorbability has attracted significant attention for TE applications. SF is commonly dissolved into an aqueous solution and can be easily reconstructed into different material formats, including films, mats, hydrogels, and sponges via various fabrication techniques. These include spin coating, electrospinning, freeze drying, physical, and chemical crosslinking techniques. Furthermore, to facilitate fabrication of more complex SF-based scaffolds with high precision techniques including micro-patterning and bio-printing have recently been explored. This review introduces the physicochemical and mechanical properties of SF and looks into a range of SF-based scaffolds that have been recently developed. The typical TE applications of SF-based scaffolds including bone, cartilage, ligament, tendon, skin, wound healing, and tympanic membrane, will be highlighted and discussed, followed by future prospects and challenges needing to be addressed.


Asunto(s)
Materiales Biocompatibles/química , Fibroínas/química , Implantes Absorbibles , Animales , Biopolímeros , Bioimpresión/métodos , Matriz Extracelular/química , Fibroínas/aislamiento & purificación , Humanos , Hidrogeles/química , Insectos/metabolismo , Ensayo de Materiales , Fenómenos Mecánicos , Especificidad de Órganos , Conformación Proteica , Regeneración , Especificidad de la Especie , Arañas/metabolismo , Tapones Quirúrgicos de Gaza , Ingeniería de Tejidos/métodos , Andamios del Tejido/química
12.
Phys Chem Chem Phys ; 22(27): 15573-15581, 2020 Jul 21.
Artículo en Inglés | MEDLINE | ID: mdl-32613219

RESUMEN

Investigations relevant to ionic liquids (ILs) as antibacterial agents have drawn considerable attention. However, the high cost and potential toxicity of ILs have severely limited their extensive applications, which has motivated researchers to design inexpensive and health-benign ILs. In this work, the interactions between the hydrated zwitterionic phospholipid (POPC) bilayer and a series of hypothetical amino cation-based and acetate anion-based ILs with different counterparts were investigated using molecular dynamics (MD) simulations to predict their antibacterial abilities. The cations of the ILs were found to insert into the lipid bilayer spontaneously, especially amino cations. Reorientation of the inserted imidazolium-based cations was observed, while the inserted amino cations showed no obvious reorientation phenomena, probably because of the strong charge interactions between the positive NH3 groups of the amino cation and the negative PO4 groups of the lipid bilayer. Due to their strong affinity with water, acetate-based anions disperse better in water solution, which weakens the insertion of the cations into the lipid bilayer to some extent. The structure and dynamic properties of the lipid bilayer, such as electrostatic potential, local ordering, area per lipid, volume per lipid, bilayer thickness, and lateral diffusion, are significantly influenced by the insertion of the cations, which results in disorder of the lipid bilayer and further disruption of the activity of the cell membrane. The insights into the relationship between the structures of ILs and their antibacterial activity in this work will provide a good reference for the screening and design of less expensive, safer, and greener IL candidates as antibacterial agents.


Asunto(s)
Antibacterianos/química , Líquidos Iónicos/química , Membrana Dobles de Lípidos/química , Simulación de Dinámica Molecular , Fosfatidilcolinas/química , Estructura Molecular
13.
J Am Chem Soc ; 142(12): 5636-5648, 2020 03 25.
Artículo en Inglés | MEDLINE | ID: mdl-32077695

RESUMEN

A significant enhancement in the Menshutkin SN2 reaction between 1-methylimidazole (MeIm) and methyl thiocyanate (MeSCN) is observed when the reaction is confined in the nanoscale silica pores of MCM41 and SBA15. The experiments in the silica pores are conducted without the surrounding bulk reaction mixture. The influences of temperature, pore radius, and surface chemistry on the kinetics of the confined reaction are analyzed with time-dependent infrared spectroscopy, molecular dynamics simulations, and ab initio calculations. The rate constant of the pseudo-first order reaction increases with decreasing pore size, and the activation energy is found to decrease by 5.6 kJ/mol in the smallest pore studied (2.8 nm) relative to the bulk reaction. The rate constant dependence on pore size is accurately described by a two-state model in which molecules within the 4.6 Å interfacial layer experience a 2.4-fold rate constant increase relative to those reacting at the bulk rate further away from the interface. The removal of polar silanol groups from the silica surface via passivation with trimethylsilyl chloride results in bulk-like kinetics despite a reduction in the pore diameter, demonstrating the role of silanols as catalytic sites. Electronic structure calculations of the energy profile on a model silica surface confirm that silanol groups, particularly those of the vicinal type, can reduce the activation energy and reaction endothermicity through the donation of hydrogen bonds to the reactant, transition state, and product complexes.

14.
Tree Physiol ; 39(1): 88-103, 2019 01 01.
Artículo en Inglés | MEDLINE | ID: mdl-29920609

RESUMEN

Tree-ring δ13C and δ18O of dominant Dahurian larch and Mongolia pine in the permafrost region of the northern Great Higgnan Mountains, China were used to elucidate species-specific ecophysiological responses to warming temperatures and increasing CO2 over the past century. Larch and pine stable carbon discrimination (Δ13C) 13C and δ18O in tree rings both showed synchronous changes during the investigated period (1901-2010), but with species-specific isotopic responses to atmospheric enriched CO2 and warming. Tree-ring Δ13C and δ18O were controlled by both maximum temperature and moisture conditions (precipitation, relative humidity and vapor pressure deficit), but with different growth periods (Δ13C in June-July and δ18O in July-August, respectively). In addition, stable isotopes of larch showed relatively greater sensitivity to moisture deficits than pine. Climatic conditions from 1920 to 1960 strongly and coherently regulated tree-ring Δ13C and δ18O through stomatal conductance. However, climatic-sensitivities of tree-ring Δ13C and δ18O recently diverged, implying substantial adjustments of stomatal conductance, photosynthetic rate and altered water sources over recent decades, which reveal the varied impacts of each factor on tree-ring Δ13C and δ18O over time. Based on expected changes in leaf gas-exchange, we isolated the impacts of atmospheric CO2 and climate change on intrinsic water-use efficiency (iWUE) over the past century. Higher intracellular CO2 in pine than larch from 1960 onwards suggests this species may be more resilient to severe droughts in the future. Our data also illustrated no weakening of the iWUE response to increasing CO2 in trees from this permafrost region. The overall pattern of CO2 enrichment and climate impacts on iWUE of pine and larch were similar, but warming increased iWUE of larch to a greater extent than that of pine over recent two decades. Taken together, our findings highlight the importance of considering how leaf gas-exchange responses to atmospheric CO2 concentration influence species-specific responses to climate and the alteration of the hydrological environment in forests growing in regions historically dominated by permafrost that will be changing rapidly in response to future warming and increased CO2.


Asunto(s)
Dióxido de Carbono/metabolismo , Calentamiento Global , Larix/fisiología , Hielos Perennes , Pinus/fisiología , Árboles/fisiología , China , Agua/metabolismo
15.
J Phys Chem B ; 122(4): 1460-1470, 2018 02 01.
Artículo en Inglés | MEDLINE | ID: mdl-29309149

RESUMEN

The all-atom force field for concentrated sulfuric acid (98.30 wt %) was developed in this work based on ab initio calculations. The structural and dynamical properties of sulfuric acid and the mixing behaviors of sulfuric acid with ionic liquids (ILs), i.e., SFIL (1-methyl-3-(propyl-3-sulfonate) imidazolium bisulfate ([PSMim][HSO4])) and non-SFIL (1-methyl-3-propyl imidazolium bisulfate ([PMim][HSO4])), were investigated using a molecular dynamics simulation. For sulfuric acid, most H3O+ ions were found beside HSO4- ions, forming a contact ion pair with the HSO4- ions, and three-dimensional hydrogen-bonding networks existed in the sulfuric acid. Analyses indicate that both ILs could be miscible with sulfuric acid with a strong exothermic character. The new strong interaction site between the sulfonic acid group of SFIL and an H2SO4 molecule through a strong hydrogen-bonding interaction was observed, which was beneficial to the catalytic activity and stability of the sulfuric acid. This observation is in good agreement with the experimental results that indicate SFILs could enhance the reusability of sulfuric acid for the isobutane alkylation about 4-fold compared to that of non-SFILs. Hopefully this work will provide insights into the screening and designing of new isobutane alkylation catalysts based on sulfuric acid and SFILs.

16.
New Phytol ; 216(4): 1104-1118, 2017 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-28834549

RESUMEN

Stable isotopes in tree rings are increasingly used as proxies for climatic and ecophysiological changes. However, uncertainties remain about the strength and consistency of their response to environmental variation at different temporal (i.e. seasonal to inter-decadal) scales. We developed 5 yr of intra-seasonal and 62 yr of early- and late-wood δ13 C and δ18 O series of Smith fir (Abies georgei var. smithii) on the southeastern Tibetan Plateau, and used a process-based forward model to examine the relative importance of environmental and physiological controls on the isotopic data. In this temperate high-altitude region, the response, both δ18 O and δ13 C, is primarily to variations in relative humidity, but by different processes. In δ18 O, the response is via source water δ18 O but also arises from leaf water 18 O enrichment. In δ13 C, the response is via changes in stomatal conductance but is modified by carry-over effects from prior periods. We conclude that tree-ring δ18 O may be a more robust climate proxy than δ13 C, and δ13 C may be more suited to studies of site-related physiological responses to the local environment.


Asunto(s)
Abies/metabolismo , Isótopos de Carbono/metabolismo , Cambio Climático , Isótopos de Oxígeno/metabolismo , Modelos Lineales , Estaciones del Año , Tibet
17.
J Phys Chem A ; 121(10): 2069-2078, 2017 Mar 16.
Artículo en Inglés | MEDLINE | ID: mdl-28248502

RESUMEN

As important products of heavy oil pyrolysis, heavier components such as gasoline and diesel supply the vast majority of energy demand through combustion, and lighter components such as ethylene and propylene are the main sources of industrial chemicals and plastic products. In this work, pyrolysis of hexadecane, as the model compound, was studied by reactive force field (ReaxFF) molecular simulation at high temperatures and high pressures. It was confirmed by unimolecular simulations that there exist eight different initial mechanisms all starting with C-C bond dissociation. The biradical mechanism was verified, through which the pyrolysis process can be accomplished within a shorter time. The enthalpy of reaction was calculated by the QM method, which was well consistent with ReaxFF calculation results. Multimolecular simulations showed that there is a strong dependency relationship between products distribution and temperature, as well as that between reaction rates and temperature. The optimal condition for ethylene formation in our work is 11.6 MPa and 2000 K, whereas it is best for hydrogen formation at conditions of 11.6 MPa and 3500 K. Kinetic analysis was performed with the activation energy of 113.03 kJ/mol and pre-exponential factor of 4.55 × 1012, and it is in good agreement with previous work.

18.
Bioorg Med Chem Lett ; 23(13): 3785-7, 2013 Jul 01.
Artículo en Inglés | MEDLINE | ID: mdl-23707253

RESUMEN

Analogues of pyrrolo-[1,2,5]benzothiadiazepine were prepared and evaluated against Schistosoma japonica. The biological data revealed that most benzothiazepine derivatives show anti-schistosomal activity to some extent, while α-chloronation of the title compound and another bioisosteric derivative pyrrolo-[1,2,5]benzodiazepine displayed the most distinct worm killing activity. This study proved that benzodiazepine may serve as a novel structural skeleton for the development of anti-schistosomal agents.


Asunto(s)
Diseño de Fármacos , Pirroles/farmacología , Schistosoma japonicum/efectos de los fármacos , Tiazepinas/farmacología , Animales , Estructura Molecular , Pirroles/síntesis química , Pirroles/química , Relación Estructura-Actividad , Tiazepinas/síntesis química , Tiazepinas/química
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