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1.
We propose a new pathway for the adsorption of benzyl alcohol on the surface of TiO2 and the formation of interfacial surface complex (ISC). The reaction free energies and reaction kinetics were thoroughly investigated by density functional calculations. The TiO2 surfaces were modeled by clusters consisting of 4 Ti atoms and 18 O atoms passivated by H, OH group and H2O molecules. Compared with solid-state calculations utilizing the periodicity of the materials, such cluster modeling allows inclusion of the high-order correlation effects that seem to be essential for the adsorption of organic molecules onto solid surfaces. The effects of both acidity and solvation are included in our calculations, which demonstrate that the new pathway is competitive with a previous pathway. The electronic structure calculations based on the relaxed ISC structures reveal that the chemisorption of benzyl alcohol on the TiO2 surface greatly alters the nature of the frontier molecular orbitals. The resulted reduced energy gap in ISC matches the energy of visible light, showing how the adsorption of benzyl alcohol sensitizes the TiO2 surface.
Graphical Abstract The chemisorption of benzyl alcohol on TiO2 surface greatly alters the nature of the frontier molecular orbitals and the formed interfacial surface complex can be sensitized by visible light
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2.
Cu (II) and Ag(I) together with TiO2 powder were deposited on conducting support substrates to enhance the photocatalytic ability. The catalytic efficiency was tested by monitoring the photocatalytic degradation and detriment of methylene blue (MB) and bovine serum albumin (BSA). The conformational change of BSA induced by catalysts was also observed by circular dichroism spectroscopy.The antibacterial activities were studied by Escherichia coli. Both MB and BSA could be degraded more efficiently than pure TiO2. After treatment with catalyst, the morphology of cells became twisted and rougher. Regular wrinkles were damaged and groove-like rift appeared on the surface. The fluorescence polarization has shown a significant decrease in membrane fluidity and the increase of permeability of cell membrane. Changes of the spectral profile of E. coli were observed, which suggested the damages of surface groups on the cell membrane.  相似文献   

3.
TiO2 films may be used to alter the wettability and hemocompatibility of cellulose materials. In this study, pure and stoichiometric TiO2 films were grown using atomic layer deposition on both silicon and cellulose substrates. The films were grown with uniform thicknesses and with a growth rate in agreement with literature results. The TiO2 films were shown to profoundly alter the water contact angle values of cellulose in a manner dependent upon processing characteristics. Higher amounts of protein adsorption indicated by blurry areas on images generated by scanning electron microscopy were noted on TiO2-coated cellulose acetate than on uncoated cellulose acetate. These results suggest that atomic layer deposition is an appropriate method for improving the biological properties of hemostatic agents and other blood-contacting biomaterials.  相似文献   

4.
The moisture content of coal affects the adsorption capacity of CO2 on the coal surface. Since the hydrogen bonds are formed between H2O and oxygen functional group, the H2O cluster more easily adsorbs on the coal micropore than CO2 molecule. The coal micropores are occupied by H2O molecules that cannot provide extra space for CO2 adsorption, which may leads to the reduction of CO2 adsorption capacity. However, without considering factors of micropore and oxygen functional groups, the co-adsorption mechanisms of CO2 and adsorbed H2O molecule are not clear. Density functional theory (DFT) calculations were performed to elucidate the effect of adsorbed H2O to CO2 adsorption. This study reports some typical coal-H2O···CO2 complexes, along with a detailed analysis of the geometry, energy, electrostatic potential (ESP), atoms in molecules (AIM), reduced density gradient (RDG), and energy decomposition analysis (EDA). The results show that H2O molecule can more stably adsorb on the aromatic ring surface than CO2 molecule, and the absolute values of local ESP maximum and minimum of H2O cluster are greater than CO2. AIM analysis shows a detailed interaction path and strength between atoms in CO2 and H2O, and RDG analysis shows that the interactions among CO2, H2O, and coal model belong to weak van der Waals force. EDA indicates that electrostatic and long-range dispersion terms play a primary role in the co-adsorption of CO2 and H2O. According to the DFT calculated results without considering micropore structure and functional group, it is shown that the adsorbed H2O can promote CO2 adsorption on the coal surface. These results demonstrate that the micropore factor plays a dominant role in affecting CO2 adsorption capacity, the attractive interaction of adsorbed H2O to CO2 makes little contribution.  相似文献   

5.
Titanium dioxide (TiO2) has been extensively studied and demonstrated to be suitable to enhance the efficiency of solar cell. In this work, TiO2 is doped with silver nanoparticles (AgNP’s) on glass and the Si substrate by using Pulsed Laser Deposition (PLD) technique. UV–vis spectroscopy, X-ray diffraction (XRD), X-ray fluorescence (XRF), Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Atomic Force Microscope (AFM), electrical conductivity (σ dc), Hall coefficient (RH), current–voltage (I–V), and capacity–voltage (C–V) characterizations have been used to examine the optical, the morphological, and the electrical properties of the films. It has been found that 5 wt.% (Ag) doped TiO2 thin film has the most effect on efficiency of TiO2:Ag /Si solar cell. The (I–V) characteristics showed that the (TiO2) thin film enhances the efficiency of the (p–n) junction solar cell from 1.26 % pure TiO2 to 7.19 % with doping of noble metal (Ag) representing improvement in the efficiency of solar cell leading to estimate empirical equations between efficiency, extinction coefficient, and energy band gap which have a total fit with the experimental data.  相似文献   

6.
The structure and bioactivity of Ginkgo biloba leaves polyprenol (GBP) are similar to that of dolichol which widely exists in human and mammalian organs. GBP possesses potential pharmacological activities against cancer. This study involved oil-in-water type nanoemulsion (NE) loading GBP was prepared by dissolving polyprenol in nanoemulsion of sodium tripolyphosphate (TPP)/TiO2 solution, Triton X-100, and 1-octanol by inversed-phase emulsification (EIP) and ultrasonic emulsification (UE) method. Folic acid (FA)-coupled chitosan (CS) nanoparticles (NPs), GBP-FA-CS-NPs and GBP-TiO2-FA-CS-NPs, were fabricated by ionic cross-linking of positively charged FA-CS conjugates and negatively charged nanoemulsion with TPP/TiO2. And characterizations of them were investigated by TEM, SEM, FTIR, particle size, and zeta potential. The cytotoxic and genotoxic effects of GBP-TiO2-FA-CS-NP treatment were higher than GBP-NE, GBP-FA-CS-NPs, TiO2-NE, GBP-TiO2-NE, TiO2-FA-CS-NPs, and GBP-TiO2-FA-CS-NP treatment at the same tested concentrations in HepG2 cells. GBP-TiO2-FA-CS-NPs at low TiO2 concentration (from 1 to 2.5 μg/ml) showed good inhibition capacity on HepG2 cells and low cytotoxic and genotoxic effects on HL-7702 cells. The possible mechanism of cytotoxicity on GBP-TiO2-FA-CS-NPs against HepG2 cells is by preventing excessive intracellular Ca2+ into extracellular spaces via inhibiting Ca2+-ATPase and Ca2+/Mg2+-ATPase.  相似文献   

7.
The improvement of spinach growth is proved to relate to N2 fixation by nano-anatase TiO2 in this study. The results show that all spinach leaves kept green by nano-anatase TiO2 treatment and all old leaves of control turned yellow white under culture with N-deficient solution. And the fresh weight, dry weight, and contents of total nitrogen, , chlorophyll, and protein of spinach by nano-anatase TiO2 treatment presented obvious enhancement compared with control. Whereas the improvements of yield of spinach were not as good as nano-anatase TiO2 treatment under N-deficient condition, confirming that nano-anatase TiO2 on exposure to sunlight could chemisorb N2 directly or reduce N2 to NH3 in the spinach leaves, transforming into organic nitrogen and improving the growth of spinach. Bulk TiO2 effect, however, was not as significant as nano-anatase TiO2. A possible metabolism of the function of nano-anatase TiO2 reducing N2 to NH3 was discussed.  相似文献   

8.
The adsorption processes of elemental lead on carbonaceous surfaces which adsorbed CO/CO2/NO flue gases were investigated to understand the effects of CO/CO2/NO on elemental lead adsorption on carbonaceous surfaces with density functional theory. All calculations including optimizations, energies, and frequencies were conducted at B3PW91 density functional theory level, utilizing SDD basis set for lead and 6-31G(d) Pople basis set for other atoms. The results indicate that CO, CO2, and NO can promote the adsorption of elemental lead on the carbonaceous surface, but probably compete for adsorption sites with elemental lead. The promotion effects on adsorption can be attributed to active sites on the carbonaceous surface rather than flue gas adsorption on the carbonaceous surface. In addition, the adsorption order of three kinds of flue gas on the carbonaceous surface is CO2?>?NO?>?CO?>?Pb on average. Furthermore, the enhancement order of three kinds of flue gas on the elemental lead adsorption on carbonaceous surfaces is CO-CS?>?CO2-CS?>?NO-CS?>?CS in general. In particular, atomic charge and adsorption energy have good linear relationship in the process of elemental lead adsorption.
Graphical Abstract Competitive adsorption between flue gas and elemental lead on carbonaceous surfaces.
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9.
A novel adsorbent, biodegradable collagen/cellulose hydrogel beads (CCHBs), was prepared by reconstitution from a 1-butyl, 3-methylimidazolium chloride ([C4mim]Cl) solution. The adsorption properties of the CCHBs for Cu(II) ion removal from aqueous solutions were investigated and compared with those of cellulose hydrogel beads (CHBs). The CCHBs have a three-dimensional macroporous structure whose amino groups are believed to be the main active binding sites of Cu(II) ions. The equilibrium adsorption capacity (qe) of the CCHBs is greatly influenced by the collagen/cellulose mass ratio, and steeply increases until the collagen/cellulose mass ratio exceeds 2/1. The maximum adsorption is obtained at pH 6. The qe of Cu(II) ions increases with increased initial concentration of the solution. Based on Langmuir isotherms, the maximum adsorption capacity (qm) of CCHB3 (collagen/cellulose mass ratio of 3/1) is 1.06 mmol/g. The CCHBs maintain good adsorption properties after the fourth cycle of adsorption–desorption.  相似文献   

10.
Three‐dimensional mesoporous TiO2‐Sn/C core‐shell nanowire arrays are prepared on Ti foil as anodes for lithium‐ion batteries. Sn formed by a reduction of SnO2 is encapsulated into TiO2 nanowires and the carbon layer is coated onto it. For additive‐free, self‐supported anodes in Li‐ion batteries, this unique core‐shell composite structure can effectively buffer the volume change, suppress cracking, and improve the conductivity of the electrode during the discharge‐charge process, thus resulting in superior rate capability and excellent long‐term cycling stability. Specifically, the TiO2‐Sn/C nanowire arrays display rechargeable discharge capacities of 769, 663, 365, 193, and 90 mA h g?1 at 0.1C, 0.5C, 2C 10C, and 30C, respectively (1C = 335 mA g?1). Furthermore, the TiO2‐Sn/C nanowire arrays exhibit a capacity retention rate of 84.8% with a discharge capacity of over 160 mA h g?1, even after 100 cycles at a high current rate of 10C.  相似文献   

11.
The composite TiO2/Mo-TiO2 were prepared by a modified sol-gel method. The prepared catalysts were characterized by X-ray diffraction, BET analysis, SEM, X-ray photoelectron spectroscopy, and UV–vis diffused reflectance spectroscopy techniques. The structural characterization results demonstrated that Mo was successfully doped into the TiO2 lattice and caused slight changes in the physiochemical properties. The UV–vis DRS showed a red shift of the adsorption edge to the visible region. The photocatalytic decomposition efficiencies of the catalysts were examined with toluene as a typical VOC in a continuous flow reactor. The photocatalytic activity of the n-n heterogeneous TiO2/Mo-TiO2 was greater than that of pure TiO2 and Mo-TiO2, and the catalyst containing a Mo/Ti mole ratio of 2.5% exhibited optimum photocatalytic properties. In general, a relative humidity of 35%, a higher oxygen content, a lower initial toluene concentration, and a higher UV intensity were beneficial for toluene decomposition.  相似文献   

12.
The fundamental mechanisms of biomineralization and their translation into innovative synthetic approaches have yielded promising perspectives for the fabrication of biomimetic and bioinspired organic–inorganic hybrid materials. In siliceous sponges, the enzyme silicatein catalyzes the polycondensation of molecular precursors to nano-structured SiO2 that is deposited on self-assembled filaments consisting of the two silicatein isoforms (silicatein-α and -β) and the scaffold protein silintaphin-1. Due to its broad substrate specificity silicatein is also able to convert in vitro various other precursors to non-biogenic materials (e.g., hydrolysis of titanium bis(ammonium lactato)-dihydroxide [TiBALDH] and subsequent polycondensation to titania [TiO2]). In the present approach, silicatein was bioengineered to carry a protein tag (Arg-tag) that confers binding affinity to TiO2. Then, by combining Arg-tagged silicatein-α with silicatein-β and silintaphin-1, self-assembled branched hybrid protein microfilaments were fabricated. Upon subsequent incubation with TiBALDH the filaments were decorated with TiO2 and assayed for photocatalytic activity through photodegradation of the dye methylene blue. This is the first approach that considers concomitant application of two silicatein isoforms for the synthesis of bioinspired organic–inorganic hybrid materials. It is also the first time that the biocatalytic activity of the enzymes has been combined with both the structure-providing properties of silintaphin-1 and a TiO2 affinity protein tag to fabricate self-assembled branched protein filaments as template for a silicatein-synthesized TiO2 photocatalyst. The TiO2-decorated filaments might be explored as a practical alternative to approaches where biotemplates have to be laboriously isolated from their original biological source prior to TiO2 immobilization.  相似文献   

13.
The impacts of different concentrations of bulk and nanosized TiO2 on seed germination and seedling growth of wheat were studied in a randomized completely design with four replications in the College of Agriculture, Ferdowsi University of Mashhad, Iran, in 2011. The experimental treatments included five concentrations of bulk (1, 2, 10, 100, and 500 ppm), five concentrations of nanosized TiO2 (1, 2, 10, 100, and 500 ppm), and control (without any TiO2). Results indicated that among the wheat germination indices, only mean germination time was affected by treatments. The lowest and the highest mean germination time (0.89 vs. 1.35 days) were obtained in 10 ppm concentration of nanosized TiO2 and control treatments, respectively. In addition, shoot length, seedling length, and root dry matters were affected by bulk and nanosized TiO2 concentrations, significantly. Shoot and seedling lengths at 2 and 10 ppm concentrations of nanosized TiO2 were higher than those of the untreated control and bulk TiO2 at 2 and 10 ppm concentrations. Employing nanosized TiO2 in suitable concentration could promote the seed germination of wheat in comparison to bulk TiO2 but in high concentrations had inhibitory or any effect on wheat.  相似文献   

14.
In order to study the mechanisms underlying the effects of TiO2 nanoparticles on lactate dehydrogenase (LDH, EC1.1.1.27), Institute of Cancer Research region mice were injected with nanoparticulate anatase TiO2 (5 nm) of various doses into the abdominal cavity daily for 14 days. We then examined LDH activity in vivo and in vitro and direct evident for interaction between nanoparticulate anatase TiO2 and LDH using spectral methods. The results showed that nanoparticulate anatase TiO2 could significantly activate LDH in vivo and in vitro; the kinetics constant (Km) and Vmax were 0.006 μM and 1,149 unit mg−1 protein min−1, respectively, at a low concentration of nanoparticulate anatase TiO2, and 3.45 and 0.031 μM and 221 unit mg−1 protein min−1, respectively, at a high concentration of nanoparticulate anatase TiO2. By fluorescence spectral assays, the nanoparticulate anatase TiO2 was determined to be directly bound to LDH, and the binding constants of the binding site were 1.77 × 108 L mol−1 and 2.15 × 107 L mol−1, respectively, and the binding distance between nanoparticulate anatase TiO2 and the Trp residue of LDH was 4.18 nm, and nanoparticulate anatase TiO2 induced the protein unfolding. It was concluded that the binding of nanoparticulate anatase TiO2 altered LDH structure and function.  相似文献   

15.
Microalgal biomass has been a focus in the sustainable energy field, especially biodiesel production. The purpose of this study was to assess the feasibility of treating microalgal biomass and cellulose by anaerobic digestion for H2 production. A microbial consortium, TC60, known to degrade cellulose and other plant polymers, was enriched on a mixture of cellulose and green microalgal biomass of Dunaliella tertiolecta, a marine species, or Chlorella vulgaris, a freshwater species. After five enrichment steps at 60°C, hydrogen yields increased at least 10% under all conditions. Anaerobic digestion of D. tertiolecta and cellulose by TC60 produced 7.7 mmol H2/g volatile solids (VS) which were higher than the levels (2.9–4.2 mmol/g VS) obtained with cellulose and C. vulgaris biomass. Both microalgal slurries contained satellite prokaryotes. The C. vulgaris slurry, without TC60 inoculation, generated H2 levels on par with that of TC60 on cellulose alone. The biomass-fed anaerobic digestion resulted in large shifts in short chain fatty acid concentrations and increased ammonium levels. Growth and H2 production increased when TC60 was grown on a combination of D. tertiolecta and cellulose due to nutrients released from algal cells via lysis. The results indicated that satellite heterotrophs from C. vulgaris produced H2 but the Chlorella biomass was not substantially degraded by TC60. To date, this is the first study to examine H2 production by anaerobic digestion of microalgal biomass. The results indicate that H2 production is feasible but higher yields could be achieved by optimization of the bioprocess conditions including biomass pretreatment.  相似文献   

16.
The adsorption properties of common gas molecules (NO, NH3, and SO2) on the surface of 3N-graphene and Al/3N graphene fragments are investigated using density functional theory. The adsorption energies have been calculated for the most stable configurations of the molecules on the surface of 3N-graphene and Al/3N graphene fragments. The adsorption energies of Al/3N graphene-gas systems are ?220.5 kJ mol?1 for Al/3NG-NO, ?111.9 kJ mol?1 for Al/3NG-NH3, and ?347.7 kJ mol?1 for Al/3NG-SO2, respectively. Compared with the 3N-graphene fragment, the Al/3N graphene fragment has significant adsorption energy. Furthermore, the molecular orbital, density of states, and electron densities distribution were used to explore the interaction between these molecules and the surface. We found that orbital hybridization exists between these molecules and the Al/3N graphene surface, which indicates that doping Al significantly increases the interaction between the gas molecules and Al/3N graphene. In addition, compared with Li, Al can more powerfully enhance adsorption of the 3N-graphene fragment. The results indicate that Al/3N graphene can be viewed as a new nanomaterial adsorbent for NO, NH3, and SO2.  相似文献   

17.
Adsorption plays an important role in the removal of pollutants such as fluoride from aqueous solutions. With the rapid development of environmental technology, TiO2 particle has become promising material to adsorb fluoride ion because of its low cost, non-toxic, good chemical stability, and good sorption ability. This work used sol-gel and hydrothermal synthesis methods to prepare TiO2 particles and load them onto SiO2 particles. The physicochemical properties such as heat stability, particle size, and surface area of the resulting TiO2 adsorbents were characterized with various analytical methods. In addition, their adsorption abilities to fluoride were determined under various conditions including different initial fluoride concentration, pH and coexisting ions. The maximum adsorption capacity of the TiO2 adsorbents can reach up to 94.3 mg/g. The adsorption isotherms of fluoride onto the TiO2 adsorbents can be closely described by the Langmuir model, suggesting the monolayer adsorption process.  相似文献   

18.
Recent studies demonstrated that titanium dioxide nanoparticles (TiO2 NPs) could significantly promote photosynthesis and plant growth, but its mechanism is still unclear. In this article, we studied the mechanism of light absorption and transfer of chloroplasts of Arabidopsis thaliana caused by TiO2 NPs treated. The results showed that TiO2 NPs could induce significant increases of light-harvesting complex II (LHCII) b gene expression and LHCII II content on the thylakoid membrane in A. thaliana, and the increases in LHCII were higher than the non-nano TiO2 (bulk-TiO2) treatment. Meanwhile, spectroscopy assays indicated that TiO2 NPs obviously increased the absorption peak intensity of the chloroplast in red and blue region, the fluorescence quantum yield near 680 nm, the excitation peak intensity near 440 and 480 nm and/or near 650 and 680 nm of the chloroplast. TiO2 NPs treatment could reduce F 480/F 440 ratio and increase F 650/F 680 ratio and accelerate the rate of whole chain electron transport and oxygen evolution of the chloroplast. However, the photosynthesis improvement of the non-nanoTiO2 treatment was far less effective than TiO2 NPs treatment. Taken together, TiO2 NPs could promote the light absorption of chloroplast, regulate the distribution of light energy from PS I to PS II by increasing LHCII and accelerate the transformation from light energy to electronic energy, water photolysis, and oxygen evolution.  相似文献   

19.
We have investigated the possibility that photoexcited titanium dioxide (TiO2) could inhibit the growth of malignant cells. We studied the anti-glioma effects of nano-TiO2 excited with ultraviolet A (UVA) irradiation both in vitro and in vivo. Transmission electron microscopy demonstrated that glioma cells take up TiO2 by phagocytosis, and vital staining revealed that TiO2 alone has no effect on glioma cell proliferation. However, if TiO2 was combined with UVA irradiation the proliferation rate was decreased significantly compared to controls (P < 0.05). RT–PCR suggested that TiO2 induction of glioma cell apoptosis is associated with changes in the expression of genes encoding Bcl-2 family members. We then investigated the in vivo antitumor effects of combined TiO2 plus UVA treatment of established glioma tumors. TiO2 plus UVA led to pronounced areas of necrosis, elevated indices of apoptosis, delayed tumor growth, and increased survival compared with the TiO2-alone control group (P < 0.001). Log-rank survival analysis showed that median survival duration was prolonged (P < 0.001). These findings suggest that nano-TiO2 based photodynamic therapy has potential in the treatment of glioma.  相似文献   

20.
Despite great efforts in tissue engineering of the ureter, urinary bladder, and urethra, further research is needed in order to improve the patient’s quality of life and minimize the economic burden of different lower urinary tract disorders. The nanostructured titanium dioxide (TiO2) scaffolds have a wide range of clinical applications and are already widely used in orthopedic or dental medicine. The current study was conducted to synthesize TiO2 nanotubes by the anodization method and TiO2 nanowires and nanospheres by the chemical vapor deposition method. These scaffolds were characterized with scanning electron microscopy (SEM) and X-ray diffraction (XRD) methods. In order to test the urologic applicability of generated TiO2 scaffolds, we seeded the normal porcine urothelial (NPU) cells on TiO2 nanotubes, TiO2 nanowires, TiO2 nanospheres, and on the standard porous membrane. The viability and growth of the cells were monitored everyday, and after 3 weeks of culturing, the analysis with scanning electron microscope (SEM) was performed. Our results showed that the NPU cells were attached on all scaffolds; they were viable and formed a multilayered epithelium, i.e., urothelium. The apical plasma membrane of the majority of superficial NPU cells, grown on all three different TiO2 scaffolds and on the porous membrane, exhibited microvilli; thus, indicating that they were at a similar differentiation stage. The maximal caliper diameter measurements of superficial NPU cells revealed significant alterations, with the largest cells being observed on nanowires and the smallest ones on the porous membrane. Our findings indicate that different nanostructured TiO2 scaffolds, especially nanowires, have a great potential for tissue engineering and should be further investigated for various urologic applications.  相似文献   

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