Selective dissolution of halide perovskites as a step towards recycling solar cells.

PubMed

Kim, Byeong Jo; Kim, Dong Hoe; Kwon, Seung Lee; Park, So Yeon; Li, Zhen; Zhu, Kai; Jung, Hyun Suk

2016-05-23

Most research on perovskite solar cells has focused on improving power-conversion efficiency and stability. However, if one could refurbish perovskite solar cells, their stability might not be a critical issue. From the perspective of cost effectiveness, if failed, perovskite solar cells could be collected and recycled; reuse of their gold electrodes and transparent conducting glasses could reduce the price per watt of perovskite photovoltaic modules. Herein, we present a simple and effective method for removing the perovskite layer and reusing the mesoporous TiO2-coated transparent conducting glass substrate via selective dissolution. We find that the perovskite layer can be easily decomposed in polar aprotic solvents because of the reaction between polar aprotic solvents and Pb(2+) cations. After 10 cycles of recycling, a mesoporous TiO2-coated transparent conducting glass substrate-based perovskite solar cell still shows a constant power-conversion efficiency, thereby demonstrating the possibility of recycling perovskite solar cells.

Fabrication of highly uniform and porous MgF2 anti-reflective coatings by polymer-based sol-gel processing on large-area glass substrates.

PubMed

Raut, Hemant Kumar; Dinachali, Saman Safari; Ansah-Antwi, Kwadwo Konadu; Ganesh, V Anand; Ramakrishna, Seeram

2013-12-20

Despite recent progress in the fabrication of magnesium fluoride (MgF2) anti-reflective coatings (ARCs), simple, effective and scalable sol-gel fabrication of MgF2 ARCs for large-area glass substrates has prospective application in various optoelectronic devices. In this paper, a polymer-based sol-gel route was devised to fabricate highly uniform and porous MgF2 ARCs on large-area glass substrates. A sol-gel precursor made of polyvinyl acetate and magnesium trifluoroacetate assisted in the formation of uniformly mesoporous MgF2 ARCs on glass substrates, leading to the attainment of a refractive index of ~1.23. Systematic optimization of the thickness of the ARC in the sub-wavelength regime led to achieving ~99.4% transmittance in the case of the porous MgF2 ARC glass. Precise control of the thickness of porous MgF2 ARC glass also resulted in a mere ~0.1% reflection, virtually eliminating reflection off the glass surface at the target wavelength. Further manipulation of the thickness of the ARC on either side of the glass substrate led to the fabrication of relatively broadband, porous MgF2 ARC glass.

Enhanced electrochromic and energy storage performance in mesoporous WO3 film and its application in a bi-functional smart window.

PubMed

Wang, Wei-Qi; Wang, Xiu-Li; Xia, Xin-Hui; Yao, Zhu-Jun; Zhong, Yu; Tu, Jiang-Ping

2018-05-03

Construction of multifunctional photoelectrochemical energy devices is of great importance to energy saving. In this study, we have successfully prepared a mesoporous WO3 film on FTO glass via a facile dip-coating sol-gel method; the designed mesoporous WO3 film exhibited advantages including high transparency, good adhesion and high porosity. Also, multifunctional integrated energy storage and optical modulation ability are simultaneously achieved by the mesoporous WO3 film. Impressively, the mesoporous WO3 film exhibits a noticeable electrochromic energy storage performance with a large optical modulation up to 75.6% at 633 nm, accompanied by energy storage with a specific capacity of 75.3 mA h g-1. Furthermore, a full electrochromic energy storage window assembled with the mesoporous WO3 anode and PANI nanoparticle cathode is demonstrated with large optical modulation and good long-term stability. Our research provides a new route to realize the coincident utilization of optical-electrochemical energy.

Uniform Surface Modification of 3D Bioglass®-Based Scaffolds with Mesoporous Silica Particles (MCM-41) for Enhancing Drug Delivery Capability

PubMed Central

Boccardi, Elena; Philippart, Anahí; Juhasz-Bortuzzo, Judith A.; Beltrán, Ana M.; Novajra, Giorgia; Vitale-Brovarone, Chiara; Spiecker, Erdmann; Boccaccini, Aldo R.

2015-01-01

The design and characterization of a new family of multifunctional scaffolds based on bioactive glass (BG) of 45S5 composition for bone tissue engineering and drug delivery applications are presented. These BG-based scaffolds are developed via a replication method of polyurethane packaging foam. In order to increase the therapeutic functionality, the scaffolds were coated with mesoporous silica particles (MCM-41), which act as an in situ drug delivery system. These sub-micron spheres are characterized by large surface area and pore volume with a narrow pore diameter distribution. The solution used for the synthesis of the silica mesoporous particles was designed to obtain a high-ordered mesoporous structure and spherical shape – both are key factors for achieving the desired controlled drug release. The MCM-41 particles were synthesized directly inside the BG-based scaffolds, and the drug-release capability of this combined system was evaluated. Moreover, the effect of MCM-41 particle coating on the bioactivity of the BG-based scaffolds was assessed. The results indicate that it is possible to obtain a multifunctional scaffold system characterized by high and interconnected porosity, high bioactivity, and sustained drug delivery capability. PMID:26594642

Highly ordered, accessible and nanocrystalline mesoporous TiO₂ thin films on transparent conductive substrates.

PubMed

Violi, Ianina L; Perez, M Dolores; Fuertes, M Cecilia; Soler-Illia, Galo J A A

2012-08-01

Highly porous (V(mesopore) = 25-50%) and ordered mesoporous titania thin films (MTTF) were prepared on ITO (indium tin oxide)-covered glass by a fast two-step method. The effects of substrate surface modification and thermal treatment on pore order, accessibility and crystallinity of the MTTF were systematically studied for MTTF deposited onto bare and titania-modified ITO. MTTF exposed briefly to 550 °C resulted in highly ordered films with grid-like structures, enlarged pore size, and increased accessible pore volume when prepared onto the modified ITO substrate. Mesostructure collapse and no significant change in pore volume were observed for MTTF deposited on bare ITO substrates. Highly crystalline anatase was obtained for MTTF prepared on the modified-ITO treated at high temperatures, establishing the relationship between grid-like structures and titania crystallization. Photocatalytic activity was maximized for samples with increased crystallization and high accessible pore volume. In this manner, a simple way of designing materials with optimized characteristics for optoelectronic applications was achieved through the modification of the ITO surface and a controlled thermal treatment.

Rapid fabrication of mesoporous TiO2 thin films by pulsed fibre laser for dye sensitized solar cells

NASA Astrophysics Data System (ADS)

Hadi, Aseel; Alhabradi, Mansour; Chen, Qian; Liu, Hong; Guo, Wei; Curioni, Michele; Cernik, Robert; Liu, Zhu

2018-01-01

In this paper we demonstrate for the first time that a fibre laser with a wavelength of 1070 nm and a pulse width of milliseconds can be applied to generate mesoporous nanocrystalline (nc) TiO2 thin films on ITO coated glass in ambient atmosphere, by complete vaporisation of organic binder and inter-connection of TiO2 nanoparticles, without thermally damaging the ITO layer and the glass substrate. The fabrication of the mesoporous TiO2 thin films was achieved by stationary laser beam irradiation of 1 min. The dye sensitized solar cell (DSSC) with the laser-sintered TiO2 photoanode reached higher power conversion efficiency (PCE) of 3.20% for the TiO2 film thickness of 6 μm compared with 2.99% for the furnace-sintered. Electrochemical impedance spectroscopy studies revealed that the laser sintering under the optimised condition effectively decreased charge transfer resistance and increased electron lifetime of the TiO2 thin films. The use of the fibre laser with over 40% wall-plug efficiency offers an economically-feasible, industrial viable solution to the major challenge of rapid fabrication of large scale, mass production of mesoporous metal oxide thin film based solar energy systems, potentially for perovskite and monolithic tandem solar cells, in the future.

Mesoporous Nitrogen Doped Carbon-Glass Ceramic Cathode for High Performance Lithium-Oxygen Battery

DTIC Science & Technology

2012-06-01

dry room with controlled moisture content. Composite 3 films on nickel foam were used as working cathodes along with lithium metal as anode and the...cathode formulation [6,7,8,9,10], efficient oxygen reduction catalysts [11,12], electrolyte compositions [13,14], effect of moisture [15], etc...specimens. Structure and purity of these materials were performed by powder X-ray diffraction (XRD) on a Rigaku D/MAX-2250 diffractometer fitted with CuKα

Research on the biological activity and doxorubicin release behavior in vitro of mesoporous bioactive SiO2-CaO-P2O5 glass nanospheres

NASA Astrophysics Data System (ADS)

Wang, Xiang; Wang, Gen; Zhang, Ying

2017-10-01

Mesoporous bioactive glass (MBG) nanospheres have been synthesized by a facile method of sacrificing template using cetyl trimethyl ammonium bromide (CTAB) as surfactant. The prepared MBG nanospheres possess high specific surface area (632 m2 g-1) as well as uniform size (∼100 nm). In addition, MBG nanospheres exhibited a quick in vitro bioactive response in simulated body fluids (SBF) and excellent bioactivity of inducing hydroxyapatite (HA) forming on the surface of MBG nanospheres. Furthermore, MBG nanospheres can sustain release of doxorubicin (DOX) with a higher encapsulation efficiency (63.6%) and show distinct degradation in PBS by releasing Si and Ca ions. The encapsulation efficiency and DOX release of MBG nanospheres could be controlled by mesoporous structure and local pH environment. The greater surface area and pore volumes of prepared MBG nanospheres are conducive to bioactive response and drug release in vitro. The amino groups in DOX can be easily protonated at acidic medium to become positively charged NH+3, which allow these drug molecules to be desorbed from the surface of MBG nanospheres via electrostatic effect. Therefore, the synthesized MBG nanospheres have a pH-sensitive drug release capability. In addition, the cytotoxicity of MBG nanospheres was assessed using a cell counting kit-8 (CCK-8), and results showed that the synthesized MBG nanospheres had no significant cytotoxicity to MC3T3 cells. These all indicated that as-prepared MBG nanospheres are promising candidates for bone tissue engineering.

Prototype of low thermal expansion materials: fabrication of mesoporous silica/polymer composites with densely filled polymer inside mesopore space.

PubMed

Kiba, Shosuke; Suzuki, Norihiro; Okawauchi, Yoshinori; Yamauchi, Yusuke

2010-09-03

A prototype of novel low thermal expansion materials using mesoporous silica particles is demonstrated. Mesoporous silica/polymer composites with densely filled polymer inside the mesopore space are fabricated by mechanically mixing both organically modified mesoporous silica and epoxy polymer. The mesopores are easily penetrated by polymers as a result of the capillary force during the mechanical composite processing. Furthermore, we propose a new model of polymer mobility restriction using mesoporous silica with a large pore space. The robust inorganic frameworks covering the polymer effectively restrict the polymer mobility against thermal energy. As a result, the degree of total thermal expansion of the composites is drastically decreased. From the mass-normalized thermal mechanical analysis (TMA) charts of various composites with different amounts of mesoporous silica particles, it is observed that the coefficient of thermal expansion (CTE) values gradually increase with an increase of the polymer amount outside the mesopores. It is proven that the CTE values in the range over the glass-transition temperatures (T(g)) are perfectly proportional to the outside polymer amounts. Importantly, the Y-intercept of the relation equation obtained by a least-square method is the CTE value and is almost zero. This means that thermal expansion does not occur if no polymers are outside the mesopores. Through such a quantative discussion, we clarify that only the outside polymer affects the thermal expansion of the composites, that is, the embedded polymers inside the mesopores do not expand at all during the thermal treatment.

Selective dissolution of halide perovskites as a step towards recycling solar cells

PubMed Central

Kim, Byeong Jo; Kim, Dong Hoe; Kwon, Seung Lee; Park, So Yeon; Li, Zhen; Zhu, Kai; Jung, Hyun Suk

2016-01-01

Most research on perovskite solar cells has focused on improving power-conversion efficiency and stability. However, if one could refurbish perovskite solar cells, their stability might not be a critical issue. From the perspective of cost effectiveness, if failed, perovskite solar cells could be collected and recycled; reuse of their gold electrodes and transparent conducting glasses could reduce the price per watt of perovskite photovoltaic modules. Herein, we present a simple and effective method for removing the perovskite layer and reusing the mesoporous TiO2-coated transparent conducting glass substrate via selective dissolution. We find that the perovskite layer can be easily decomposed in polar aprotic solvents because of the reaction between polar aprotic solvents and Pb2+ cations. After 10 cycles of recycling, a mesoporous TiO2-coated transparent conducting glass substrate-based perovskite solar cell still shows a constant power-conversion efficiency, thereby demonstrating the possibility of recycling perovskite solar cells. PMID:27211006

Selective dissolution of halide perovskites as a step towards recycling solar cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Byeong Jo; Kim, Dong Hoe; Kwon, Seung Lee

Most research on perovskite solar cells has focused on improving power-conversion efficiency and stability. However, if one could refurbish perovskite solar cells, their stability might not be a critical issue. From the perspective of cost effectiveness, if failed, perovskite solar cells could be collected and recycled; reuse of their gold electrodes and transparent conducting glasses could reduce the price per watt of perovskite photovoltaic modules. Here, we present a simple and effective method for removing the perovskite layer and reusing the mesoporous TiO 2-coated transparent conducting glass substrate via selective dissolution. We find that the perovskite layer can be easilymore » decomposed in polar aprotic solvents because of the reaction between polar aprotic solvents and Pb 2+ cations. After 10 cycles of recycling, a mesoporous TiO 2-coated transparent conducting glass substrate-based perovskite solar cell still shows a constant power-conversion efficiency, thereby demonstrating the possibility of recycling perovskite solar cells.« less

Selective dissolution of halide perovskites as a step towards recycling solar cells

DOE PAGES

Kim, Byeong Jo; Kim, Dong Hoe; Kwon, Seung Lee; ...

2016-05-23

Most research on perovskite solar cells has focused on improving power-conversion efficiency and stability. However, if one could refurbish perovskite solar cells, their stability might not be a critical issue. From the perspective of cost effectiveness, if failed, perovskite solar cells could be collected and recycled; reuse of their gold electrodes and transparent conducting glasses could reduce the price per watt of perovskite photovoltaic modules. Here, we present a simple and effective method for removing the perovskite layer and reusing the mesoporous TiO 2-coated transparent conducting glass substrate via selective dissolution. We find that the perovskite layer can be easilymore » decomposed in polar aprotic solvents because of the reaction between polar aprotic solvents and Pb 2+ cations. After 10 cycles of recycling, a mesoporous TiO 2-coated transparent conducting glass substrate-based perovskite solar cell still shows a constant power-conversion efficiency, thereby demonstrating the possibility of recycling perovskite solar cells.« less

Electrophoretic deposition of mesoporous bioactive glass on glass-ceramic foam scaffolds for bone tissue engineering.

PubMed

Fiorilli, Sonia; Baino, Francesco; Cauda, Valentina; Crepaldi, Marco; Vitale-Brovarone, Chiara; Demarchi, Danilo; Onida, Barbara

2015-01-01

In this work, the coating of 3-D foam-like glass-ceramic scaffolds with a bioactive mesoporous glass (MBG) was investigated. The starting scaffolds, based on a non-commercial silicate glass, were fabricated by the polymer sponge replica technique followed by sintering; then, electrophoretic deposition (EPD) was applied to deposit a MBG layer on the scaffold struts. EPD was also compared with other techniques (dipping and direct in situ gelation) and it was shown to lead to the most promising results. The scaffold pore structure was maintained after the MBG coating by EPD, as assessed by SEM and micro-CT. In vitro bioactivity of the scaffolds was assessed by immersion in simulated body fluid and subsequent evaluation of hydroxyapatite (HA) formation. The deposition of a MBG coating can be a smart strategy to impart bioactive properties to the scaffold, allowing the formation of nano-structured HA agglomerates within 48 h from immersion, which does not occur on uncoated scaffold surfaces. The mechanical properties of the scaffold do not vary after the EPD (compressive strength ~19 MPa, fracture energy ~1.2 × 10(6) J m(-3)) and suggest the suitability of the prepared highly bioactive constructs as bone tissue engineering implants for load-bearing applications.

Formation of Uniform Hollow Silica microcapsules

NASA Astrophysics Data System (ADS)

Yan, Huan; Kim, Chanjoong

2012-02-01

Microcapsules are small containers with diameters in the range of 0.1 -- 100 μm. Mesoporous microcapsules with hollow morphologies possess unique properties such as low-density and high encapsulation capacity, while allowing controlled release by permeating substances with a specific size and chemistry. Our process is a one-step fabrication of monodisperse hollow silica capsules with a hierarchical pore structure and high size uniformity using double emulsion templates obtained by the glass-capillary microfluidic technique to encapsulate various active ingredients. These hollow silica microcapsules can be used as biomedical applications such as drug delivery and controlled release.

Formation of Uniform Hollow Silica microcapsules

NASA Astrophysics Data System (ADS)

Yan, Huan; Kim, Chanjoong

2013-03-01

Microcapsules are small containers with diameters in the range of 0.1 - 100 μm. Mesoporous microcapsules with hollow morphologies possess unique properties such as low-density and high encapsulation capacity, while allowing controlled release by permeating substances with a specific size and chemistry. Our process is a one-step fabrication of monodisperse hollow silica capsules with a hierarchical pore structure and high size uniformity using double emulsion templates obtained by the glass-capillary microfluidic technique to encapsulate various active ingredients. These hollow silica microcapsules can be used as biomedical applications such as drug delivery and controlled release.

Synthesis of coesite nanocrystals from ethane bridged periodic mesoporous organosilica at low temperature and extreme pressure.

PubMed

Liang, Zhili; Mohanty, Paritosh; Fei, Yingwei; Landskron, Kai

2010-12-14

Coesite nanocrystals have been synthesized from periodic mesoporous organosilica (PMO) with (CH(2))(2) bridges heated at 300 °C for 150 min and 12 GPa. The crystals are not sintered, single crystalline, and have diameters of ca. 100-300 nm. Below 300 °C, an amorphous non-porous organosilica glass was obtained. Heating above 300 °C at 12 GPa results in the rapid crystal growth and micron size coesite crystals were formed.

Effect of Mesoporous Diatomite Particles on the Kinetics of SR&NI ATRP of Styrene and Butyl Acrylate

NASA Astrophysics Data System (ADS)

Khezri, Khezrollah; Ghasemi, Moosa; Fazli, Yousef

2018-05-01

Mesoporous diatomite particles were employed to prepare different poly(styrene-co-butyl acrylate)/diatomite nanocomposites. Diatomite nanoplatelets were used for in situ copolymerization of styrene and butyl acrylate by SR&NI ATRP to synthesize well-defined poly(styrene-co-butyl acrylate) nanocomposites. Nitrogen adsorption/desorption isotherm is applied to examine surface area and structural characteristics of the diatomite nanoplatelets. Evaluation of pore size distribution and morphological studies were also performed by SEM and TEM. Conversion and molecular weight determinations were carried out using gas and size exclusion chromatography respectively. Addition of 3 wt% pristine mesoporous diatomite nanoplatelets leads to increase of conversion from 73 to 89%. Molecular weight of poly(styrene-co-butyl acrylate) chains increases from 17,115 to 20,343 g·mol-1 by addition of 3 wt% pristine mesoporous diatomite; however, polydispersity index values increases from 1.14 to 1.37. Increasing thermal stability of the nanocomposites is demonstrated by TGA. Differential scanning calorimetry shows an increase in glass transition temperature from 35.26 to 39.61°C by adding 3 wt% of mesoporous diatomite nanoplatelets.

Fabrication of Co3O4 mesoporous thin films by using cobalt/chitosan precursor on fluorine-doped tin oxide glass

NASA Astrophysics Data System (ADS)

Yang, Hui-Chia; Tsai, Jung-Che

2017-06-01

For the development of high-performance and low-cost electrode materials, many alternative materials have been fabricated by various groups. Among these materials, Co3O4 has been demonstrated to be a promising candidate for pseudocapacitors because of its low potential environmental pollution, low cost, and extremely high theoretical specific capacitance. Chitosan, a linear polysaccharide produced by the deacetylation of chitin, is a nontoxic, tissue-compatible polymeric biomaterial. It is usually used to eliminate or filter the heavy metals in wastewater. That is, chitosan can act as a deliverer of metal ions and a nanostructure constructer of metals (or metal oxides). In this study, a facile approach is developed to synthesize mesoporous cobalt oxide thin films on fluorine-doped tin oxide (FTO)-coated glass with environmentally friendly chitosan, which chelates cobalt ions.

Preparation of Mesoporous Ceramics from Polymer Nanotubes

NASA Astrophysics Data System (ADS)

Chen, Dian; Park, Soojin; Chen, Jiun-Tai; Redston, Emily; Russell, Thomas

2009-03-01

Poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) nanotubes were prepared by placing polymer solution into the cylindrical nanopores of an anodic aluminum oxide (AAO) membrane. The PS-b-P4VP nanotubes within the AAO membranes were exposed to tetrahydrofuran vapor to produce uniform spherical micelles along the tube. The tubes were removed from the membranes, then suspended in ethylene glycol, a preferential solvent for P4VP. At 95^ oC, near the glass transition temperature (Tg) of PS, nanotubes with uniform nanopores were obtained by a reconstruction of the nanotubes. As the temperature was increased, mesoporous polymer structures were obtained. Tetraethyl orthosilicate or titanium tetraethoxide, ceramic precursors, were introduced into the 4VP microdomains. After exposure to an oxygen plasma or high temperature, the copolymer was removed and the precursor converted to a mesoporous ceramic. This process offers a simple route for the fabrication of tunable mesoporous ceramic or metallic structures by changing molecular weight of copolymers.

Prevention of bacterial adhesion to zwitterionic biocompatible mesoporous glasses.

PubMed

Sánchez-Salcedo, Sandra; García, Ana; Vallet-Regí, María

2017-07-15

Novel materials, based on Mesoporous Bioactive Glasses (MBGs) in the ternary system SiO 2 -CaO-P 2 O 5 , decorated with (3-aminopropyl)triethoxysilane (APTES) and subsequently with amino acid Lysine (Lys), by post-grafting method on the external surface of the glasses (named MBG-NH 2 and MBG-Lys), are reported. The surface functionalization with organic groups did not damage the mesoporous network and their structural and textural properties were also preserved despite the high solubility of MBG matrices. The incorporation of Lys confers a zwitterionic nature to these MBG materials due to the presence of adjacent amine and carboxylic groups in the external surface. At physiologic pH, this coexistence of basic amine and carboxilic acid groups from anchored Lys provided zero surface charge named zwitterionic effect. This behaviour could give rise to potential applications of antibacterial adhesion. Therefore, in order to assess the influence of zwitterionic nature in in vitro bacterial adhesion, studies were carried out with Staphylococcus aureus. It was demonstrated that the efficient interaction of these zwitterionic pairs onto the MBG surfaces reduced bacterial adhesion up to 99.9% compared to bare MBGs. In order to test the suitability of zwitterionic MBGs materials as bone grafts, their cytocompatibility was investigated in vitro with MC3T3-E1 preosteoblasts. These findings suggested that the proposed surface functionalization strategy provided MBG materials with notable antibacterial adhesion properties, hence making these materials promising candidates for local bone infection therapy. The present research work is focused in finding a preventive treatment of bone infection based on Mesoporous Bioactive Glasses (MBGs) with antibacterial adhesion properties obtained by zwitterionic surface modification. MBGs exhibit unique nanostructural, textural and bioactive characteristics. The novelty and originality of this manuscript is based on the design and optimization of a straightforward functionalization method capable of providing MBGs with zwitterionic surfaces that are able to inhibit bacterial adhesion without affecting their cytocompatibility. This new characteristic enhanced the MBG properties to avoid the bacterial adherence onto the implant surfaces for bone tissue engineering applications. Subsequently, it could help to decrease the infection rates after implantation surgery, which represents one of the most serious complications associated to surgical treatments of bone diseases and fractures. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Local structures of mesoporous bioactive glasses and their surface alterations in vitro: inferences from solid-state nuclear magnetic resonance

PubMed Central

Gunawidjaja, Philips N.; Mathew, Renny; Lo, Andy Y. H.; Izquierdo-Barba, Isabel; García, Ana; Arcos, Daniel; Mattias Edén, María Vallet-Regí

2012-01-01

We review the benefits of using 29Si and 1H magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy for probing the local structures of both bulk and surface portions of mesoporous bioactive glasses (MBGs) of the CaO–SiO2−(P2O5) system. These mesoporous materials exhibit an ordered pore arrangement, and are promising candidates for improved bone and tooth implants. We discuss experimental MAS NMR results from three MBGs displaying different Ca, Si and P contents: the 29Si NMR spectra were recorded either directly by employing radio-frequency pulses to 29Si, or by magnetization transfers from neighbouring protons using cross polarization, thereby providing quantitative information about the silicate speciation present in the pore wall and at the MBG surface, respectively. The surface modifications were monitored for the three MBGs during their immersion in a simulated body fluid (SBF) for intervals between 30 min and one week. The results were formulated as a reaction sequence describing the interconversions between the distinct silicate species. We generally observed a depletion of Ca2+ ions at the MBG surface, and a minor condensation of the silicate-surface network over one week of SBF soaking. PMID:22349247

Bioactive Glass Nanoparticles: From Synthesis to Materials Design for Biomedical Applications

PubMed Central

Vichery, Charlotte; Nedelec, Jean-Marie

2016-01-01

Thanks to their high biocompatibility and bioactivity, bioactive glasses are very promising materials for soft and hard tissue repair and engineering. Because bioactivity and specific surface area intrinsically linked, the last decade has seen a focus on the development of highly porous and/or nano-sized materials. This review emphasizes the synthesis of bioactive glass nanoparticles and materials design strategies. The first part comprehensively covers mainly soft chemistry processes, which aim to obtain dispersible and monodispersed nanoparticles. The second part discusses the use of bioactive glass nanoparticles for medical applications, highlighting the design of materials. Mesoporous nanoparticles for drug delivery, injectable systems and scaffolds consisting of bioactive glass nanoparticles dispersed in a polymer, implant coatings and particle dispersions will be presented. PMID:28773412

Electrochemical Sensing toward Trace As(III) Based on Mesoporous MnFe₂O₄/Au Hybrid Nanospheres Modified Glass Carbon Electrode.

PubMed

Zhou, Shaofeng; Han, Xiaojuan; Fan, Honglei; Liu, Yaqing

2016-06-22

Au nanoparticles decorated mesoporous MnFe₂O₄ nanocrystal clusters (MnFe₂O₄/Au hybrid nanospheres) were used for the electrochemical sensing of As(III) by square wave anodic stripping voltammetry (SWASV). Modified on a cheap glass carbon electrode, these MnFe₂O₄/Au hybrid nanospheres show favorable sensitivity (0.315 μA/ppb) and limit of detection (LOD) (3.37 ppb) toward As(III) under the optimized conditions in 0.1 M NaAc-HAc (pH 5.0) by depositing for 150 s at the deposition potential of -0.9 V. No obvious interference from Cd(II) and Hg(II) was recognized during the detection of As(III). Additionally, the developed electrode displayed good reproducibility, stability, and repeatability, and offered potential practical applicability for electrochemical detection of As(III) in real water samples. The present work provides a potential method for the design of new and cheap sensors in the application of electrochemical determination toward trace As(III) and other toxic metal ions.

Corrosion behavior of mesoporous bioglass-ceramic coated magnesium alloy under applied forces.

PubMed

Zhang, Feiyang; Cai, Shu; Xu, Guohua; Shen, Sibo; Li, Yan; Zhang, Min; Wu, Xiaodong

2016-03-01

In order to research the corrosion behavior of bioglass-ceramic coated magnesium alloys under applied forces, mesoporous 45S5 bioactive glass-ceramic (45S5 MBGC) coatings were successfully prepared on AZ31 substrates using a sol-gel dip-coating technique followed by a heat treatment at the temperature of 400°C. In this work, corrosion behavior of the coated samples under applied forces was characterized by electrochemical tests and immersion tests in simulated body fluid. Results showed that the glass-ceramic coatings lost the protective effects to the magnesium substrate in a short time when the applied compressive stress was greater than 25MPa, and no crystallized apatite was formed on the surface due to the high Mg(2+) releasing and the peeling off of the coatings. Whereas, under low applied forces, apatite deposition and crystallization on the coating surface repaired cracks to some extent, thus improving the corrosion resistance of the coated magnesium during the long-term immersion period. Copyright © 2015 Elsevier Ltd. All rights reserved.

Synthesis of lithium superionic conductor by growth of a nanoglass within mesoporous silica SBA-15 template

NASA Astrophysics Data System (ADS)

Chatterjee, Soumi; Miah, Milon; Saha, Shyamal Kumar; Chakravorty, Dipankar

2018-04-01

Nanodimensional silica based glasses containing alkali ions have recently been grown using suitable templates. These have shown electrical properties drastically different from those of their bulk counterpart. We have synthesized silicophosphate glasses having lithium ions with concentrations of 15-35 mole% Li2O within mesoporous silica SBA-15 (Santa Barbara amorphous-15) comprising of pores of diameter ~5 nm. The nanoglasses are characterized by electrical conductivities 5-6 orders of magnitude higher than those of the corresponding bulk glasses. These properties are attributed to the presence of a larger free volume in the nanoglasses as compared to their bulk states. The nanocomposites with 35 mole% Li2O exhibit an electrical conductivity of ~3 × 10-4 S · cm-1 at around room temperature. The activation energy for Li+ ion migration has been estimated from the conductivity-temperature variation to be 0.078 eV. These nanocomposites are believed to be ideally suited for the fabrication of solid state lithium ion batteries. We have also explored the efficiency of silicophosphate glass powders as possible electrode materials. Glass of composition 70SiO2/30P2O5 was prepared by using Pluronic P-123 tri-block copolymer along with suitable precursor sols. Cyclic voltammetric and galvanostatic charge/discharge measurements were carried out on the samples prepared in combination with suitable conductive fillers using a two-electrode system. These exhibited a high specific capacitance of 356 F g-1 making them ideally suitable as electrode materials for making a lithium ion solid state battery system.

Breakthrough and future: nanoscale controls of compositions, morphologies, and mesochannel orientations toward advanced mesoporous materials.

PubMed

Yamauchi, Yusuke; Suzuki, Norihiro; Radhakrishnan, Logudurai; Wang, Liang

2009-01-01

Currently, ordered mesoporous materials prepared through the self-assembly of surfactants have attracted growing interests owing to their special properties, including uniform mesopores and a high specific surface area. Here we focus on fine controls of compositions, morphologies, mesochannel orientations which are important factors for design of mesoporous materials with new functionalities. This Review describes our recent progress toward advanced mesoporous materials. Mesoporous materials now include a variety of inorganic-based materials, for example, transition-metal oxides, carbons, inorganic-organic hybrid materials, polymers, and even metals. Mesoporous metals with metallic frameworks can be produced by using surfactant-based synthesis with electrochemical methods. Owing to their metallic frameworks, mesoporous metals with high electroconductivity and high surface areas hold promise for a wide range of potential applications, such as electronic devices, magnetic recording media, and metal catalysts. Fabrication of mesoporous materials with controllable morphologies is also one of the main subjects in this rapidly developing research field. Mesoporous materials in the form of films, spheres, fibers, and tubes have been obtained by various synthetic processes such as evaporation-mediated direct templating (EDIT), spray-dried techniques, and collaboration with hard-templates such as porous anodic alumina and polymer membranes. Furthermore, we have developed several approaches for orientation controls of 1D mesochannels. The macroscopic-scale controls of mesochannels are important for innovative applications such as molecular-scale devices and electrodes with enhanced diffusions of guest species. Copyright 2009 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.

Synthesis of non-siliceous mesoporous oxides.

PubMed

Gu, Dong; Schüth, Ferdi

2014-01-07

Mesoporous non-siliceous oxides have attracted great interest due to their unique properties and potential applications. Since the discovery of mesoporous silicates in 1990s, organic-inorganic assembly processes by using surfactants or block copolymers as soft templates have been considered as a feasible path for creating mesopores in metal oxides. However, the harsh sol-gel conditions and low thermal stabilities have limited the expansion of this method to various metal oxide species. Nanocasting, using ordered mesoporous silica or carbon as a hard template, has provided possibilities for preparing novel mesoporous materials with new structures, compositions and high thermal stabilities. This review concerns the synthesis, composition, and parameter control of mesoporous non-siliceous oxides. Four synthesis routes, i.e. soft-templating (surfactants or block copolymers as templates), hard-templating (mesoporous silicas or carbons as sacrificial templates), colloidal crystal templating (3-D ordered colloidal particles as a template), and super lattice routes, are summarized in this review. Mesoporous metal oxides with different compositions have different properties. Non-siliceous mesoporous oxides are comprehensively described, including a discussion of constituting elements, synthesis, and structures. General aspects concerning pore size control, atomic scale crystallinity, and phase control are also reviewed.

Window Glasses: State and Prospects

NASA Astrophysics Data System (ADS)

Maiorov, V. A.

2018-04-01

Analysis and generalization of the results of investigations devoted to the improvement of optical properties have been carried out, and descriptions of a structure and a reaction mechanism of available and promising window glasses with solar radiation are presented. All devices are divided into groups with static constant and dynamic regulated spectral characteristics. The group of static glasses includes heat-protective and spectrally selective glasses with low-emissivity coatings and infrared filters with dispersed plasmonic nanoparticles. Electrochromic glasses, nanostructured dynamic infrared filters, and glasses with separated regulation of the transmission of visible-light and near-infrared radiation are dynamic devices. It is noted that the use of mesoporous films made of plasmonic nanoparticles open up especially wide possibilities. Their application allows one to realize a dynamic separated regulation of the transmission of visible light and nearinfrared radiation in which, under the gradual increase in the electric potential on the glass, mechanisms of plasmon and polaron reduction of solar radiation gradually change the glass' condition from light warm to light cold and then to dark cold consecutively.

Type I Collagen and Strontium-Containing Mesoporous Glass Particles as Hybrid Material for 3D Printing of Bone-Like Materials.

PubMed

Montalbano, Giorgia; Fiorilli, Sonia; Caneschi, Andrea; Vitale-Brovarone, Chiara

2018-04-28

Bone tissue engineering offers an alternative promising solution to treat a large number of bone injuries with special focus on pathological conditions, such as osteoporosis. In this scenario, the bone tissue regeneration may be promoted using bioactive and biomimetic materials able to direct cell response, while the desired scaffold architecture can be tailored by means of 3D printing technologies. In this context, our study aimed to develop a hybrid bioactive material suitable for 3D printing of scaffolds mimicking the natural composition and structure of healthy bone. Type I collagen and strontium-containing mesoporous bioactive glasses were combined to obtain suspensions able to perform a sol-gel transition under physiological conditions. Field emission scanning electron microscopy (FESEM) analyses confirmed the formation of fibrous nanostructures homogeneously embedding inorganic particles, whereas bioactivity studies demonstrated the large calcium phosphate deposition. The high-water content promoted the strontium ion release from the embedded glass particles, potentially enhancing the osteogenic behaviour of the composite. Furthermore, the suspension printability was assessed by means of rheological studies and preliminary extrusion tests, showing shear thinning and fast material recovery upon deposition. In conclusion, the reported results suggest that promising hybrid systems suitable for 3D printing of bioactive scaffolds for bone tissue engineering have been developed.

Gene delivery nanocarriers of bioactive glass with unique potential to load BMP2 plasmid DNA and to internalize into mesenchymal stem cells for osteogenesis and bone regeneration

NASA Astrophysics Data System (ADS)

Kim, Tae-Hyun; Singh, Rajendra K.; Kang, Min Sil; Kim, Joong-Hyun; Kim, Hae-Won

2016-04-01

The recent development of bioactive glasses with nanoscale morphologies has spurred their specific applications in bone regeneration, for example as drug and gene delivery carriers. Bone engineering with stem cells genetically modified with this unique class of nanocarriers thus holds great promise in this avenue. Here we report the potential of the bioactive glass nanoparticle (BGN) system for the gene delivery of mesenchymal stem cells (MSCs) targeting bone. The composition of 15% Ca-added silica, proven to be bone-bioactive, was formulated into surface aminated mesoporous nanospheres with enlarged pore sizes, to effectively load and deliver bone morphogenetic protein-2 (BMP2) plasmid DNA. The enlarged mesopores were highly effective in loading BMP2-pDNA with an efficiency as high as 3.5 wt% (pDNA w.r.t. BGN), a level more than twice than for small-sized mesopores. The BGN nanocarriers released the genetic molecules in a highly sustained manner (for as long as 2 weeks). The BMP2-pDNA/BGN complexes were effectively internalized to rat MSCs with a cell uptake level of ~73%, and the majority of cells were transfected to express the BMP2 protein. Subsequent osteogenesis of the transfected MSCs was demonstrated by the expression of bone-related genes, including bone sialoprotein, osteopontin, and osteocalcin. The MSCs transfected with BMP2-pDNA/BGN were locally delivered inside a collagen gel to the target calvarium defects. The results showed significantly improved bone regeneration, as evidenced by the micro-computed tomographic, histomorphometric and immunohistochemical analyses. This study supports the excellent capacity of the BGN system as a pDNA-delivery nanocarrier in MSCs, and the engineered system, BMP2-pDNA/BGN with MSCs, may be considered a new promising candidate to advance the therapeutic potential of stem cells through genetic modification, targeting bone defects and diseases.The recent development of bioactive glasses with nanoscale morphologies has spurred their specific applications in bone regeneration, for example as drug and gene delivery carriers. Bone engineering with stem cells genetically modified with this unique class of nanocarriers thus holds great promise in this avenue. Here we report the potential of the bioactive glass nanoparticle (BGN) system for the gene delivery of mesenchymal stem cells (MSCs) targeting bone. The composition of 15% Ca-added silica, proven to be bone-bioactive, was formulated into surface aminated mesoporous nanospheres with enlarged pore sizes, to effectively load and deliver bone morphogenetic protein-2 (BMP2) plasmid DNA. The enlarged mesopores were highly effective in loading BMP2-pDNA with an efficiency as high as 3.5 wt% (pDNA w.r.t. BGN), a level more than twice than for small-sized mesopores. The BGN nanocarriers released the genetic molecules in a highly sustained manner (for as long as 2 weeks). The BMP2-pDNA/BGN complexes were effectively internalized to rat MSCs with a cell uptake level of ~73%, and the majority of cells were transfected to express the BMP2 protein. Subsequent osteogenesis of the transfected MSCs was demonstrated by the expression of bone-related genes, including bone sialoprotein, osteopontin, and osteocalcin. The MSCs transfected with BMP2-pDNA/BGN were locally delivered inside a collagen gel to the target calvarium defects. The results showed significantly improved bone regeneration, as evidenced by the micro-computed tomographic, histomorphometric and immunohistochemical analyses. This study supports the excellent capacity of the BGN system as a pDNA-delivery nanocarrier in MSCs, and the engineered system, BMP2-pDNA/BGN with MSCs, may be considered a new promising candidate to advance the therapeutic potential of stem cells through genetic modification, targeting bone defects and diseases. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr07933k

Organic-inorganic hybrid mesoporous silicas: functionalization, pore size, and morphology control.

PubMed

Park, Sung Soo; Ha, Chang-Sik

2006-01-01

Topological design of mesoporous silica materials, pore architecture, pore size, and morphology are currently major issues in areas such as catalytic conversion of bulky molecules, adsorption, host-guest chemistry, etc. In this sense, we discuss the pore size-controlled mesostructure, framework functionalization, and morphology control of organic-inorganic hybrid mesoporous silicas by which we can improve the applicability of mesoporous materials. First, we explain that the sizes of hexagonal- and cubic-type pores in organic-inorganic hybrid mesoporous silicas are well controlled from 24.3 to 98.0 A by the direct micelle-control method using an organosilica precursor and surfactants with different alkyl chain lengths or triblock copolymers as templates and swelling agents incorporated in the formed micelles. Second, we describe that organic-inorganic hybrid mesoporous materials with various functional groups form various external morphologies such as rod, cauliflower, film, rope, spheroid, monolith, and fiber shapes. Third, we discuss that transition metals (Ti and Ru) and rare-earth ions (Eu(3+) and Tb(3+)) are used to modify organic-inorganic hybrid mesoporous silica materials. Such hybrid mesoporous silica materials are expected to be applied as excellent catalysts for organic reactions, photocatalysis, optical devices, etc. c) 2006 The Japan Chemical Journal Forum and Wiley Periodicals, Inc.

A controlled release of ibuprofen by systematically tailoring the morphology of mesoporous silica materials

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qu Fengyu; Chemistry and Pharmaceutical College, Jiamusi University, Jiamusi 154007; Zhu Guangshan

2006-07-15

A series of mesoporous silica materials with similar pore sizes, different morphologies and variable pore geometries were prepared systematically. In order to control drug release, ibuprofen was employed as a model drug and the influence of morphology and pore geometry of mesoporous silica on drug release profiles was extensively studied. The mesoporous silica and drug-loaded samples were characterized by X-ray diffraction, Fourier transform IR spectroscopy, N{sub 2} adsorption and desorption, scanning electron microscopy, and transmission electron microscopy. It was found that the drug-loading amount was directly correlated to the Brunauer-Emmett-Teller surface area, pore geometry, and pore volume; while the drugmore » release profiles could be controlled by tailoring the morphologies of mesoporous silica carriers. - Graphical abstract: The release of ibuprofen is controlled by tailoring the morphologies of mesoporous silica. The mesoporous silica and drug-loaded samples are characterized by powder X-ray diffraction, Fourier transform IR spectroscopy, N{sub 2} adsorption and desorption, scanning electron microscopy, and transmission electron microscopy. The drug-loading amount is directly correlated to the Brunauer-Emmett-Teller surface area, pore geometry, and pore volume; while the drug release profiles can be controlled by tailoring the morphologies of mesoporous silica carriers.« less

Silica-based mesoporous nanoparticles for controlled drug delivery

PubMed Central

Kwon, Sooyeon; Singh, Rajendra K; Perez, Roman A; Abou Neel, Ensanya A

2013-01-01

Drug molecules with lack of specificity and solubility lead patients to take high doses of the drug to achieve sufficient therapeutic effects. This is a leading cause of adverse drug reactions, particularly for drugs with narrow therapeutic window or cytotoxic chemotherapeutics. To address these problems, there are various functional biocompatible drug carriers available in the market, which can deliver therapeutic agents to the target site in a controlled manner. Among the carriers developed thus far, mesoporous materials emerged as a promising candidate that can deliver a variety of drug molecules in a controllable and sustainable manner. In particular, mesoporous silica nanoparticles are widely used as a delivery reagent because silica possesses favourable chemical properties, thermal stability and biocompatibility. Currently, sol-gel-derived mesoporous silica nanoparticles in soft conditions are of main interest due to simplicity in production and modification and the capacity to maintain function of bioactive agents. The unique mesoporous structure of silica facilitates effective loading of drugs and their subsequent controlled release. The properties of mesopores, including pore size and porosity as well as the surface properties, can be altered depending on additives used to fabricate mesoporous silica nanoparticles. Active surface enables functionalisation to modify surface properties and link therapeutic molecules. The tuneable mesopore structure and modifiable surface of mesoporous silica nanoparticle allow incorporation of various classes of drug molecules and controlled delivery to the target sites. This review aims to present the state of knowledge of currently available drug delivery system and identify properties of an ideal drug carrier for specific application, focusing on mesoporous silica nanoparticles. PMID:24020012

Effect of magnesia on the degradability and bioactivity of sol-gel derived SiO2-CaO-MgO-P2O5 system glasses.

PubMed

Ma, J; Chen, C Z; Wang, D G; Jiao, Y; Shi, J Z

2010-11-01

Mesoporous 58SiO(2)-(38-x)CaO-xMgO-4P(2)O(5) glasses (where x=0, 5, 10 and 20 mol%) have been prepared by the sol-gel synthesis route. The effects of the substitution of MgO for CaO on glass degradation and bioactivity were studied in tris-(hydroxymethyl)-aminomethane and hydrochloric acid buffer solution (Tris-HCl) and simulated body fluid (SBF), respectively. It is observed that the synthesized glasses with various MgO contents possess the similar textural properties. The studies of in vitro degradability and bioactivity show that the rate of glass degradation gradually decreases with the increase of MgO and the formation of apatite layer on glass surface is retarded. The influences of the composition upon glass properties are explained in terms of their internal structures. Copyright (c) 2010 Elsevier B.V. All rights reserved.

Adsorption and release of biocides with mesoporous silica nanoparticles

NASA Astrophysics Data System (ADS)

Popat, Amirali; Liu, Jian; Hu, Qiuhong; Kennedy, Michael; Peters, Brenton; Lu, Gao Qing (Max); Qiao, Shi Zhang

2012-01-01

In this proof-of-concept study, an agricultural biocide (imidacloprid) was effectively loaded into the mesoporous silica nanoparticles (MSNs) with different pore sizes, morphologies and mesoporous structures for termite control. This resulted in nanoparticles with a large surface area, tunable pore diameter and small particle size, which are ideal carriers for adsorption and controlled release of imidacloprid. The effect of pore size, surface area and mesoporous structure on uptake and release of imidacloprid was systematically studied. It was found that the adsorption amount and release profile of imidacloprid were dependent on the type of mesoporous structure and surface area of particles. Specifically, MCM-48 type mesoporous silica nanoparticles with a three dimensional (3D) open network structure and high surface area displayed the highest adsorption capacity compared to other types of silica nanoparticles. Release of imidacloprid from these nanoparticles was found to be controlled over 48 hours. Finally, in vivo laboratory testing on termite control proved the efficacy of these nanoparticles as delivery carriers for biopesticides. We believe that the present study will contribute to the design of more effective controlled and targeted delivery for other biomolecules.In this proof-of-concept study, an agricultural biocide (imidacloprid) was effectively loaded into the mesoporous silica nanoparticles (MSNs) with different pore sizes, morphologies and mesoporous structures for termite control. This resulted in nanoparticles with a large surface area, tunable pore diameter and small particle size, which are ideal carriers for adsorption and controlled release of imidacloprid. The effect of pore size, surface area and mesoporous structure on uptake and release of imidacloprid was systematically studied. It was found that the adsorption amount and release profile of imidacloprid were dependent on the type of mesoporous structure and surface area of particles. Specifically, MCM-48 type mesoporous silica nanoparticles with a three dimensional (3D) open network structure and high surface area displayed the highest adsorption capacity compared to other types of silica nanoparticles. Release of imidacloprid from these nanoparticles was found to be controlled over 48 hours. Finally, in vivo laboratory testing on termite control proved the efficacy of these nanoparticles as delivery carriers for biopesticides. We believe that the present study will contribute to the design of more effective controlled and targeted delivery for other biomolecules. Electronic supplementary information (ESI) available. See DOI: 10.1039/c2nr11691j

Mesoporous metal oxides and processes for preparation thereof

DOE Office of Scientific and Technical Information (OSTI.GOV)

Suib, Steven L.; Poyraz, Altug Suleyman

A process for preparing a mesoporous metal oxide, i.e., transition metal oxide. Lanthanide metal oxide, a post-transition metal oxide and metalloid oxide. The process comprises providing an acidic mixture comprising a metal precursor, an interface modifier, a hydrotropic ion precursor, and a surfactant; and heating the acidic mixture at a temperature and for a period of time sufficient to form the mesoporous metal oxide. A mesoporous metal oxide prepared by the above process. A method of controlling nano-sized wall crystallinity and mesoporosity in mesoporous metal oxides. The method comprises providing an acidic mixture comprising a metal precursor, an interface modifier,more » a hydrotropic ion precursor, and a surfactant; and heating the acidic mixture at a temperature and for a period of time sufficient to control nano-sized wall crystallinity and mesoporosity in the mesoporous metal oxides. Mesoporous metal oxides and a method of tuning structural properties of mesoporous metal oxides.« less

Hydrothermally grown α-MnO2 interlocked mesoporous micro-cubes of several nanocrystals as selective and sensitive nitrogen dioxide chemoresistive gas sensors

NASA Astrophysics Data System (ADS)

Shinde, Pritamkumar V.; Xia, Qi Xun; Ghule, Balaji G.; Shinde, Nanasaheb M.; Seonghee, Jeong; Kim, Kwang Ho; Mane, Rajaram S.

2018-06-01

The interesting and multifunctional properties of alpha-manganese dioxide (α-MnO2) are considered to be highly sensitive and selective to nitrogen dioxide (NO2) chemresistive gas sensors. The α-MnO2 mesoporous interlocked micro-cubes composed of several interconnected nanocrystals synthesized by a facile and low-cost hydrothermal method on soda-lime glass substrate are envisaged as selective and sensitive NO2 gas sensors. Phase-purity and surface area with pore-size distribution are initially screened. The three-dimensional α-MnO2 mesoporous-cube-based gas sensors tested for NO2 gas from room-temperature (27 °C) to 250 °C have demonstrated 33% response for 100 ppm NO2 levels at 150 °C. The response and recovery time values of the α-MnO2 sensor are found to be 26 s and recovery 91 s, respectively, with high selectivity, good sensitivity, and considerable chemical and environmental stabilities, confirming the gas sensor applications potentiality of α-MnO2 morphology which is a combination of interlocked mesoporous micro-cubes and well-connected nanocrystals.

Effects of a mesoporous bioactive glass on osteoblasts, osteoclasts and macrophages.

PubMed

Gómez-Cerezo, N; Casarrubios, L; Morales, I; Feito, M J; Vallet-Regí, M; Arcos, D; Portolés, M T

2018-05-29

A mesoporous bioactive glass (MBG) of molar composition 75SiO 2 -20CaO-5P 2 O 5 (MBG-75S) has been synthetized as a potential bioceramic for bone regeneration purposes. X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), nitrogen adsorption studies and transmission electron microscopy (TEM) demonstrated that MBG-75S possess a highly ordered mesoporous structure with high surface area and porosity, which would explain the high ionic exchange rate (mainly calcium and silicon soluble species) with the surrounded media. MBG-75S showed high biocompatibility in contact with Saos-2 osteoblast-like cells. Concentrations up to 1 mg/ml did not lead to significant alterations on either morphology or cell cycle. Regarding the effects on osteoclasts, MBG-75S allowed the differentiation of RAW-264.7 macrophages into osteoclast-like cells but exhibiting a decreased resorptive activity. These results point out that MBG-75S does not inhibit osteoclastogenesis but reduces the osteoclast bone-resorbing capability. Finally, in vitro studies focused on the innate immune response, evidenced that MBG-75S allows the proliferation of macrophages without inducing their polarization towards the M1 pro-inflammatory phenotype. This in vitro behavior is indicative that MBG-75S would just induce the required innate immune response without further inflammatory complications under in vivo conditions. The overall behavior respect to osteoblasts, osteoclasts and macrophages, makes this MBG a very interesting candidate for bone grafting applications in osteoporotic patients. Copyright © 2018. Published by Elsevier Inc.

One-Pot Fabrication of Antireflective/Antibacterial Dual-Function Ag NP-Containing Mesoporous Silica Thin Films.

PubMed

Wang, Kaikai; He, Junhui

2018-04-04

Thin films that integrate antireflective and antibacterial dual functions are not only scientifically interesting but also highly desired in many practical applications. Unfortunately, very few studies have been devoted to the preparation of thin films with both antireflective and antibacterial properties. In this study, mesoporous silica (MSiO 2 ) thin films with uniformly dispersed Ag nanoparticles (Ag NPs) were prepared through a one-pot process, which simultaneously shows high transmittance, excellent antibacterial activity, and mechanical robustness. The optimal thin-film-coated glass substrate demonstrates a maximum transmittance of 98.8% and an average transmittance of 97.1%, respectively, in the spectral range of 400-800 nm. The growth and multiplication of typical bacteria, Escherichia coli ( E. coli), were effectively inhibited on the coated glass. Pencil hardness test, tape adhesion test, and sponge washing test showed favorable mechanical robustness with 5H pencil hardness, 5A grade adhesion, and functional durability of the coating, which promises great potential for applications in various touch screens, windows for hygiene environments, and optical apparatuses for medical uses such as endoscope, and so on.

Freezing and melting of water in a single cylindrical pore: The pore-size dependence of freezing and melting behavior

NASA Astrophysics Data System (ADS)

Morishige, Kunimitsu; Kawano, Keiji

1999-03-01

In order to clarify the origin of the hysteresis between freezing and melting of pore water, we performed x-ray diffraction measurements of water confined inside the cylindrical pores of seven kinds of siliceous MCM-41 (a member of ordered mesoporous materials denoted by Mobil Oil researchers) with different pore radii (1.2-2.9 nm) and the interconnected pores of Vycor glass as a function of temperature. The hysteresis effect depends markedly on the size of the cylindrical pores: the hysteresis is negligibly small in smaller pores and becomes remarkable in larger pores. This strongly suggests that the hysteresis is arisen from size-dependent supercooling of water confined to the mesopores. For the water confined to the mesopores with pore radius of 1.2 nm, a continuous transition between a liquid and a solid precedes the first-order freezing transition of the pore water which would occur by the same mechanism as in bulk water.

A general soft-enveloping strategy in the templating synthesis of mesoporous metal nanostructures.

PubMed

Fang, Jixiang; Zhang, Lingling; Li, Jiang; Lu, Lu; Ma, Chuansheng; Cheng, Shaodong; Li, Zhiyuan; Xiong, Qihua; You, Hongjun

2018-02-06

Metal species have a relatively high mobility inside mesoporous silica; thus, it is difficult to introduce the metal precursors into silica mesopores and suppress the migration of metal species during a reduction process. Therefore, until now, the controlled growth of metal nanocrystals in a confined space, i.e., mesoporous channels, has been very challenging. Here, by using a soft-enveloping reaction at the interfaces of the solid, liquid, and solution phases, we successfully control the growth of metallic nanocrystals inside a mesoporous silica template. Diverse monodispersed nanostructures with well-defined sizes and shapes, including Ag nanowires, 3D mesoporous Au, AuAg alloys, Pt networks, and Au nanoparticle superlattices are successfully obtained. The 3D mesoporous AuAg networks exhibit enhanced catalytic activities in an electrochemical methanol oxidation reaction. The current soft-enveloping synthetic strategy offers a robust approach to synthesize diverse mesoporous metal nanostructures that can be utilized in catalysis, optics, and biomedicine applications.

Highly-Bioreactive Silica-Based Mesoporous Bioactive Glasses Enriched with Gallium(III).

PubMed

Sanchez-Salcedo, Sandra; Malavasi, Gianluca; Salinas, Antonio J; Lusvardi, Gigliola; Rigamonti, Luca; Menabue, Ledi; Vallet-Regi, Maria

2018-03-02

Beneficial effects in bone cell growth and antibacterial action are currently attributed to Ga 3+ ions. Thus, they can be used to upgrade mesoporous bioactive glasses (MBGs), investigated for tissue engineering, whenever they released therapeutic amounts of gallium ions to the surrounding medium. Three gallium-enriched MBGs with composition (in mol %) x SiO₂- y CaO- z P₂O₅-5Ga₂O₃, being x = 70, y = 15, z = 10 for Ga_1 ; x = 80, y = 12, z = 3 for Ga_2 ; and x = 80, y = 15, z = 0 for Ga_3 , were investigated and compared with the gallium-free 80SiO₂-15CaO-5P₂O₅ MBG ( B ). 29 Si and 31 P MAS NMR analyses indicated that Ga 3+ acts as network modifier in the glass regions with higher polymerization degree and as network former in the zones with high concentration of classical modifiers (Ca 2+ ions). Ga_1 and Ga_2 exhibited a quick in vitro bioactive response because they were coated by an apatite-like layer after 1 and 3 days in simulated body fluid. Although we have not conducted biological tests in this paper (cells or bacteria), Ga_1 released high but non-cytotoxic amounts of Ga 3+ ions in Todd Hewitt Broth culture medium that were 140 times higher than the IC90 of Pseudomonas aeruginosa bacteria, demonstrating its potential for tissue engineering applications.

Functionalized bimodal mesoporous silicas as carriers for controlled aspirin delivery

NASA Astrophysics Data System (ADS)

Gao, Lin; Sun, Jihong; Li, Yuzhen

2011-08-01

The bimodal mesoporous silica modified with 3-aminopropyltriethoxysilane was performed as the aspirin carrier. The samples' structure, drug loading and release profiles were characterized with X-ray diffraction, scanning electron microscopy, N 2 adsorption and desorption, Fourier transform infrared spectroscopy, TG analysis, elemental analysis and UV-spectrophotometer. For further exploring the effects of the bimodal mesopores on the drug delivery behavior, the unimodal mesoporous material MCM-41 was also modified as the aspirin carrier. Meantime, Korsmeyer-Peppas equation ft= ktn was employed to analyze the dissolution data in details. It is indicated that the bimodal mesopores are beneficial for unrestricted drug molecules diffusing and therefore lead to a higher loading and faster releasing than that of MCM-41. The results show that the aspirin delivery properties are influenced considerably by the mesoporous matrix, whereas the large pore of bimodal mesoporous silica is the key point for the improved controlled-release properties.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Khezri, Khezrollah, E-mail: kh.khezri@ut.ac.ir; Roghani-Mamaqani, Hossein

Graphical abstract: Effect of mesoporous silica nanoparticles (MCM-41) on the activator generated by electron transfer for atom transfer radical polymerization (AGET ATRP) is investigated. Decrement of conversion and number average molecular weight and also increment of polydispersity index (PDI) values are three main results of addition of MCM-41 nanoparticles. Incorporation of MCM-41 nanoparticles in the polystyrene matrix can clearly increase thermal stability and decrease glass transition temperature of the nanocomposites. - Highlights: • Spherical morphology, hexagonal structure, and high surface area with regular pore diameters of the synthesized MCM-41 nanoparticles are examined. • AGET ATRP of styrene in the presencemore » of MCM-41 nanoparticles is performed. • Effect of MCM-41 nanoparticles addition on the polymerization rate, conversion and molecular weights of the products are discussed. • Improvement in thermal stability of the nanocomposites and decreasing T{sub g} values was also observed by incorporation of MCM-41 nanoparticles. - Abstract: Activator generated by electron transfer for atom transfer radical polymerization was employed to synthesize well-defined mesoporous silica nanoparticles/polystyrene composites. Inherent features of spherical mesoporous silica nanoparticles were evaluated by nitrogen adsorption/desorption isotherm, X-ray diffraction and scanning electron microscopy analysis techniques. Conversion and molecular weight evaluations were carried out using gas and size exclusion chromatography respectively. By the addition of only 3 wt% mesoporous silica nanoparticles, conversion decreases from 81 to 58%. Similarly, number average molecular weight decreases from 17,116 to 12,798 g mol{sup −1}. However, polydispersity index (PDI) values increases from 1.24 to 1.58. A peak around 4.1–4.2 ppm at proton nuclear magnetic resonance spectroscopy results clearly confirms the living nature of the polymerization. Thermogravimetric analysis shows that thermal stability of the nanocomposites increases by adding nanoparticles content. Decrease of glass transition temperature is also demonstrated by the addition of 3 wt% of silica nanoparticles according to the differential scanning calorimetry results.« less

Cellular membrane trafficking of mesoporous silica nanoparticles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fang, I-Ju

This dissertation mainly focuses on the investigation of the cellular membrane trafficking of mesoporous silica nanoparticles. We are interested in the study of endocytosis and exocytosis behaviors of mesoporous silica nanoparticles with desired surface functionality. The relationship between mesoporous silica nanoparticles and membrane trafficking of cells, either cancerous cells or normal cells was examined. Since mesoporous silica nanoparticles were applied in many drug delivery cases, the endocytotic efficiency of mesoporous silica nanoparticles needs to be investigated in more details in order to design the cellular drug delivery system in the controlled way. It is well known that cells can engulfmore » some molecules outside of the cells through a receptor-ligand associated endocytosis. We are interested to determine if those biomolecules binding to cell surface receptors can be utilized on mesoporous silica nanoparticle materials to improve the uptake efficiency or govern the mechanism of endocytosis of mesoporous silica nanoparticles. Arginine-glycine-aspartate (RGD) is a small peptide recognized by cell integrin receptors and it was reported that avidin internalization was highly promoted by tumor lectin. Both RGD and avidin were linked to the surface of mesoporous silica nanoparticle materials to investigate the effect of receptor-associated biomolecule on cellular endocytosis efficiency. The effect of ligand types, ligand conformation and ligand density were discussed in Chapter 2 and 3. Furthermore, the exocytosis of mesoporous silica nanoparticles is very attractive for biological applications. The cellular protein sequestration study of mesoporous silica nanoparticles was examined for further information of the intracellular pathway of endocytosed mesoporous silica nanoparticle materials. The surface functionality of mesoporous silica nanoparticle materials demonstrated selectivity among the materials and cancer and normal cell lines. We aimed to determine the specific organelle that mesoporous silica nanoparticles could approach via the identification of harvested proteins from exocytosis process. Based on the study of endo- and exocytosis behavior of mesoporous silica nanoparticle materials, we can design smarter drug delivery vehicles for cancer therapy that can be effectively controlled. The destination, uptake efficiency and the cellular distribution of mesoporous silica nanoparticle materials can be programmable. As a result, release mechanism and release rate of drug delivery systems can be a well-controlled process. The deep investigation of an endo- and exocytosis study of mesoporous silica nanoparticle materials promotes the development of drug delivery applications.« less

Isolated Mesoporous Microstructures Prepared by Stress Localization-Induced Crack Manipulation.

PubMed

Wooh, Sanghyuk; Lee, Soojin; Lee, Yunchan; Ryu, Ji Ho; Lee, Won Bo; Yoon, Hyunsik; Char, Kookheon

2016-09-22

Cracks observed in brittle materials are mostly regarded as defects or failures. However, they can be a valuable tool when implemented in a controlled way. Here, we introduce a strategy to control the crack propagation of mesoporous micropatterns (prisms and pyramids), which leads to the isolation of well-defined microstructures. Mesoporous micropatterns were fabricated by the soft imprinting technique with wet TiO 2 nanoparticle (NP) pastes, followed by sintering to remove organic components. Since the volume of the paste significantly shrinks during the sintering step, stress is localized at the edge of micropatterns, in good agreement with finite element method simulations, creating well-defined cracks and their propagation. It was demonstrated that the degree of stress localization is determined by the thickness of residual layers, NP size, and heating rate. After controlled crack propagation and delamination of microparticles from the substrates, mesoporous microwires and microparticles were successfully produced and functionalized from the isolated mesoporous prisms and pyramids. The method proposed in this study for controlled crack manipulation and delamination opens a door for straightforward and economical fabrication of well-defined mesoporous microparticles.

Controlled Synthesis of Pt Nanowires with Ordered Large Mesopores for Methanol Oxidation Reaction

NASA Astrophysics Data System (ADS)

Zhang, Chengwei; Xu, Lianbin; Yan, Yushan; Chen, Jianfeng

2016-08-01

Catalysts for methanol oxidation reaction (MOR) are at the heart of key green-energy fuel cell technology. Nanostructured Pt materials are the most popular and effective catalysts for MOR. Controlling the morphology and structure of Pt nanomaterials can provide opportunities to greatly increase their activity and stability. Ordered nanoporous Pt nanowires with controlled large mesopores (15, 30 and 45 nm) are facilely fabricated by chemical reduction deposition from dual templates using porous anodic aluminum oxide (AAO) membranes with silica nanospheres self-assembled in the channels. The prepared mesoporous Pt nanowires are highly active and stable electrocatalysts for MOR. The mesoporous Pt nanowires with 15 nm mesopores exhibit a large electrochemically active surface area (ECSA, 40.5 m2 g-1), a high mass activity (398 mA mg-1) and specific activity (0.98 mA cm-2), and a good If/Ib ratio (1.15), better than the other mesoporous Pt nanowires and the commercial Pt black catalyst.

Multifunctional mesoporous bioactive glasses for effective delivery of therapeutic ions and drug/growth factors.

PubMed

Wu, Chengtie; Chang, Jiang

2014-11-10

Regeneration of large-size bone defects represents a significant challenge clinically, which requires the use of scaffolds with multifunction, such as anti-bacterial activity, and stimulation of osteogenesis and angiogenesis. It is known that functional ions or drug/growth factors play an important role to stimulate tissue regeneration. Mesoporous bioactive glasses (MBG) possess excellent bioactivity and drug-delivery ability as well as effective ionic release in the body fluids microenvironment due to its specific mesoporous structure and large surface area. For these reasons, functional ions (e.g. lithium (Li), strontium (Sr), Copper (Cu) and Boron (B)) and drug/growth factors (e.g. dexamethasone, vascular endothelial growth factor (VEGF) and bone morphogenetic protein (BMP)) have been incorporated into MBG, which shows high loading efficiency and effective release. The release of therapeutic ions and drug/growth factors from MBG offers it multifunctional properties, such as improved osteogenesis, angiogenesis, anti-bacterial/cancer activity. However, there is no a systematic review about delivery of therapeutic ions and drugs/growth factors from MBG for the functional effect on the tissue regeneration despite that significant progress has been achieved in the past five years. Therefore, in this review, we mainly focused on the new advances for the functional effect of delivering therapeutic ions and drugs/growth factors on the ostegeogenesis, angiogenesis and antibacterial activity. It is expected that the review will offer new concept to develop multifunctional biomaterials for bone regeneration by the synergistic effect of therapeutic ions and drug/growth factors. Copyright © 2014 Elsevier B.V. All rights reserved.

Recent progress in mesoporous titania materials: adjusting morphology for innovative applications.

PubMed

Vivero-Escoto, Juan L; Chiang, Ya-Dong; Wu, Kevin; Yamauchi, Yusuke

2012-02-01

This review article summarizes recent developments in mesoporous titania materials, particularly in the fields of morphology control and applications. We first briefly introduce the history of mesoporous titania materials and then review several synthesis approaches. Currently, mesoporous titania nanoparticles (MTNs) have attracted much attention in various fields, such as medicine, catalysis, separation and optics. Compared with bulk mesoporous titania materials, which are above a micrometer in size, nanometer-sized MTNs have additional properties, such as fast mass transport, strong adhesion to substrates and good dispersion in solution. However, it has generally been known that the successful synthesis of MTNs is very difficult owing to the rapid hydrolysis of titanium-containing precursors and the crystallization of titania upon thermal treatment. Finally, we review four emerging fields including photocatalysis, photovoltaic devices, sensing and biomedical applications of mesoporous titania materials. Because of its high surface area, controlled porous structure, suitable morphology and semiconducting behavior, mesoporous titania is expected to be used in innovative applications.

Three dimensional printing of calcium sulfate and mesoporous bioactive glass scaffolds for improving bone regeneration in vitro and in vivo

NASA Astrophysics Data System (ADS)

Qi, Xin; Pei, Peng; Zhu, Min; Du, Xiaoyu; Xin, Chen; Zhao, Shichang; Li, Xiaolin; Zhu, Yufang

2017-02-01

In the clinic, bone defects resulting from infections, trauma, surgical resection and genetic malformations remain a significant challenge. In the field of bone tissue engineering, three-dimensional (3D) scaffolds are promising for the treatment of bone defects. In this study, calcium sulfate hydrate (CSH)/mesoporous bioactive glass (MBG) scaffolds were successfully fabricated using a 3D printing technique, which had a regular and uniform square macroporous structure, high porosity and excellent apatite mineralization ability. Human bone marrow-derived mesenchymal stem cells (hBMSCs) were cultured on scaffolds to evaluate hBMSC attachment, proliferation and osteogenesis-related gene expression. Critical-sized rat calvarial defects were applied to investigate the effect of CSH/MBG scaffolds on bone regeneration in vivo. The in vitro results showed that CSH/MBG scaffolds stimulated the adhesion, proliferation, alkaline phosphatase (ALP) activity and osteogenesis-related gene expression of hBMSCs. In vivo results showed that CSH/MBG scaffolds could significantly enhance new bone formation in calvarial defects compared to CSH scaffolds. Thus 3D printed CSH/MBG scaffolds would be promising candidates for promoting bone regeneration.

Micelle-Template Synthesis of Nitrogen-Doped Mesoporous Graphene as an Efficient Metal-Free Electrocatalyst for Hydrogen Production

NASA Astrophysics Data System (ADS)

Huang, Xiaodan; Zhao, Yufei; Ao, Zhimin; Wang, Guoxiu

2014-12-01

Synthesis of mesoporous graphene materials by soft-template methods remains a great challenge, owing to the poor self-assembly capability of precursors and the severe agglomeration of graphene nanosheets. Herein, a micelle-template strategy to prepare porous graphene materials with controllable mesopores, high specific surface areas and large pore volumes is reported. By fine-tuning the synthesis parameters, the pore sizes of mesoporous graphene can be rationally controlled. Nitrogen heteroatom doping is found to remarkably render electrocatalytic properties towards hydrogen evolution reactions as a highly efficient metal-free catalyst. The synthesis strategy and the demonstration of highly efficient catalytic effect provide benchmarks for preparing well-defined mesoporous graphene materials for energy production applications.

Micelle-template synthesis of nitrogen-doped mesoporous graphene as an efficient metal-free electrocatalyst for hydrogen production.

PubMed

Huang, Xiaodan; Zhao, Yufei; Ao, Zhimin; Wang, Guoxiu

2014-12-19

Synthesis of mesoporous graphene materials by soft-template methods remains a great challenge, owing to the poor self-assembly capability of precursors and the severe agglomeration of graphene nanosheets. Herein, a micelle-template strategy to prepare porous graphene materials with controllable mesopores, high specific surface areas and large pore volumes is reported. By fine-tuning the synthesis parameters, the pore sizes of mesoporous graphene can be rationally controlled. Nitrogen heteroatom doping is found to remarkably render electrocatalytic properties towards hydrogen evolution reactions as a highly efficient metal-free catalyst. The synthesis strategy and the demonstration of highly efficient catalytic effect provide benchmarks for preparing well-defined mesoporous graphene materials for energy production applications.

Micelle-Template Synthesis of Nitrogen-Doped Mesoporous Graphene as an Efficient Metal-Free Electrocatalyst for Hydrogen Production

PubMed Central

Huang, Xiaodan; Zhao, Yufei; Ao, Zhimin; Wang, Guoxiu

2014-01-01

Synthesis of mesoporous graphene materials by soft-template methods remains a great challenge, owing to the poor self-assembly capability of precursors and the severe agglomeration of graphene nanosheets. Herein, a micelle-template strategy to prepare porous graphene materials with controllable mesopores, high specific surface areas and large pore volumes is reported. By fine-tuning the synthesis parameters, the pore sizes of mesoporous graphene can be rationally controlled. Nitrogen heteroatom doping is found to remarkably render electrocatalytic properties towards hydrogen evolution reactions as a highly efficient metal-free catalyst. The synthesis strategy and the demonstration of highly efficient catalytic effect provide benchmarks for preparing well-defined mesoporous graphene materials for energy production applications. PMID:25523276

Highly-Bioreactive Silica-Based Mesoporous Bioactive Glasses Enriched with Gallium(III)

PubMed Central

Malavasi, Gianluca; Lusvardi, Gigliola; Menabue, Ledi

2018-01-01

Beneficial effects in bone cell growth and antibacterial action are currently attributed to Ga3+ ions. Thus, they can be used to upgrade mesoporous bioactive glasses (MBGs), investigated for tissue engineering, whenever they released therapeutic amounts of gallium ions to the surrounding medium. Three gallium-enriched MBGs with composition (in mol %) xSiO2–yCaO–zP2O5–5Ga2O3, being x = 70, y = 15, z = 10 for Ga_1; x = 80, y = 12, z = 3 for Ga_2; and x = 80, y = 15, z = 0 for Ga_3, were investigated and compared with the gallium-free 80SiO2–15CaO–5P2O5 MBG (B). 29Si and 31P MAS NMR analyses indicated that Ga3+ acts as network modifier in the glass regions with higher polymerization degree and as network former in the zones with high concentration of classical modifiers (Ca2+ ions). Ga_1 and Ga_2 exhibited a quick in vitro bioactive response because they were coated by an apatite-like layer after 1 and 3 days in simulated body fluid. Although we have not conducted biological tests in this paper (cells or bacteria), Ga_1 released high but non-cytotoxic amounts of Ga3+ ions in Todd Hewitt Broth culture medium that were 140 times higher than the IC90 of Pseudomonas aeruginosa bacteria, demonstrating its potential for tissue engineering applications. PMID:29498654

Mesoporous aluminosilicate glasses: Potential materials for dye removal from wastewater effluents

NASA Astrophysics Data System (ADS)

Almeida, Flavio P.; Botelho, Moema B. S.; Doerenkamp, Carsten; Kessler, Elizaveta; Ferrari, Cynthia R.; Eckert, Hellmut; de Camargo, Andrea S. S.

2017-09-01

Mesoporous amorphous sodium-aluminosilicate host matrices of composition Si1-xAlxNaxO2, 0.1 ≤ x ≤ 0.33, obtained by sol-gel methodology, have been used as sequestrating agents for the cationic dye Rhodamine 6 G (Rh6G) in solution. Favorable adsorption kinetics and a wide pH working range (4-10) as well as high sorption capacities for Rh6G render these materials potentially useful reagents for effective dye removal from wastewaters. While the experimentally realized sorption capacities fall significantly below the theoretical limits, used materials can be thermally re-cycled by pyrolizing the sequestrated dye molecules. Solid state NMR and BET measurements show that this process occurs under preservation of the materials' structural integrity, allowing it to be re-used multiple times.

Mesoporous TiO2/graphene composite films for the photocatalytic degradation of eco-persistent pollutants

NASA Astrophysics Data System (ADS)

Kusumawati, Yuly; Pauporté, Thierry; Viana, Bruno; Zouzelka, Radek; Remzova, Monika; Rathousky, Jiri

2017-03-01

Graphene/oxide composite structures are attracting increasing attention for many advanced applications. In the present work, mesoporous layers composed of TiO2 nanoparticles and graphene at various concentrations have been coated on conductive glass substrates. They have been tested for the photocatalytic degradation of 4-chlorophenol used as a model compound of an eco-persistent pollutant dilute in water. The formation of intermediate degradation products, namely, hydroquinone and benzoquinone, has been followed. The results show the high photocatalytic activity of the layers and a beneficial effect of graphene for an optimum concentration of 1.2 wt. %. The decrease in the activity observed at higher graphene content is assigned to the light absorption by this component. The key parameters for the enhancement of the photocatalytic performance are discussed.

Targeted thrombolysis by using of magnetic mesoporous silica nanoparticles.

PubMed

Wang, Mingqi; Zhang, Jixi; Yuan, Ziming; Yang, Wenzhi; Wu, Qiang; Gu, Hongchen

2012-08-01

Thrombolytics inevitably led to the risk of hemorrhagic complications due to their non-specific plasminogen activation in treatment of thrombosis. The aim of this study was to determine whether a kind of superparamagnetic mesoporous silica nanoparticle with expanded pore size could achieve effectively targeted thrombolysis. The magnetic mesoporous silica nanoparticles (M-MSNs) with the pore size of 6 nm were prepared by method of the surfactant templating on nano magnetic particles. We investigated the feasibility and efficacy of target thrombolysis with the resultant spheres through fibrin agarose plate assay (FAPA) and a dynamic flow system in vitro. It displayed a 30-fold enhancement of urokinase (UK) loading capacity over the particles without mesoporous layer or the magnetic spheres with mesopores of 3.7 nm. A sustained release behavior was observed due to its larger pore size, higher surface area and narrow mesopore channals contrast to non-mesoporous and small mesopore of 3.7 nm controls. Meanwhile, fibrin agarose plate assay revealed that UK/M-MSNs exhibited a more rapid growth rate of thrombolysis even lasting for 3 days. Additionally, flow model test in vitro suggested this kind of nanoparticle complex enhanced the thrombolysis efficacy by 3.5 fold over the same amount of native UK in 30 min. When compared to non-mesoporous and small mesopore controls, it also represented an extremely higher lysis efficiency (ANOVA, P < 0.01) and a shorter reperfusion time (ANOVA, P < 0.001). Such a magnetic mesoporous silica nanoparticle carrier was expected to be further studied for targeted thrombolytic therapy.

Ordered mesoporous crystalline gamma-Al2O3 with variable architecture and porosity from a single hard template.

PubMed

Wu, Zhangxiong; Li, Qiang; Feng, Dan; Webley, Paul A; Zhao, Dongyuan

2010-09-01

In this paper, an efficient route is developed for controllable synthesis of ordered mesoporous alumina (OMA) materials with variable pore architectures and high mesoporosity, as well as crystalline framework. The route is based on the nanocasting pathway with bimodal mesoporous carbon as the hard template. In contrast to conventional reports, we first realize the possibility of creating two ordered mesopore architectures by using a single carbon hard template obtained from organic-organic self-assembly, which is also the first time such carbon materials are adopted to replicate ordered mesoporous materials. The mesopore architecture and surface property of the carbon template are rationally designed in order to obtain ordered alumina mesostructures. We found that the key factors rely on the unique bimodal mesopore architecture and surface functionalization of the carbon hard template. Namely, the bimodal mesopores (2.3 and 5.9 nm) and the surface functionalities make it possible to selectively load alumina into the small mesopores dominantly and/or with a layer of alumina coated on the inner surface of the large primary mesopores with different thicknesses until full loading is achieved. Thus, OMA materials with variable pore architectures (similar and reverse mesostructures relative to the carbon template) and controllable mesoporosity in a wide range are achieved. Meanwhile, in situ ammonia hydrolysis for conversion of the metal precursor to its hydroxide is helpful for easy crystallization (as low as approximately 500 degrees C). Well-crystallized alumina frameworks composed of gamma-Al(2)O(3) nanocrystals with sizes of 6-7 nm are obtained after burning out the carbon template at 600 degrees C, which is advantageous over soft-templated aluminas. The effects of synthesis factors are demonstrated and discussed relative to control experiments. Furthermore, our method is versatile enough to be used for general synthesis of other important but difficult-to-synthesize mesoporous metal oxides, such as magnesium oxide. We believe that the fundamentals in this research will provide new insights for rational synthesis of ordered mesoporous materials.

Preparation of mesoporous nanofibers by vapor phase synthesis: control of mesopore structures with the aid of co-surfactants.

PubMed

Min, Sa Hoon; Bae, Joonwon; Jang, Jyongsik; Lee, Kyung Jin

2013-06-28

Mesoporous nanofibers (MSNFs) can be fabricated in the pores of anodic aluminum oxide (AAO) membrane using diverse methods. Among them vapor phase synthesis (VPS) provides several advantages over sol-gel or evaporation-induced self-assembly (EISA) based methods. One powerful advantage is that we can employ multiple surfactants as structural directing agents (SDAs) simultaneously. By adopting diverse pairs of SDAs, we can control the mesopore structures, i.e. pore size, surface area, and even the morphology of mesostructures. Here, we used F127 as a main SDA, which is relatively robust (thus, difficult to change the mesopore structures), and added a series of cationic co-surfactants to observe the systematical changes in their mesostructure with respect to the chain length of the co-surfactant.

Preparation of mesoporous nanofibers by vapor phase synthesis: control of mesopore structures with the aid of co-surfactants

NASA Astrophysics Data System (ADS)

Min, Sa Hoon; Bae, Joonwon; Jang, Jyongsik; Lee, Kyung Jin

2013-06-01

Mesoporous nanofibers (MSNFs) can be fabricated in the pores of anodic aluminum oxide (AAO) membrane using diverse methods. Among them vapor phase synthesis (VPS) provides several advantages over sol-gel or evaporation-induced self-assembly (EISA) based methods. One powerful advantage is that we can employ multiple surfactants as structural directing agents (SDAs) simultaneously. By adopting diverse pairs of SDAs, we can control the mesopore structures, i.e. pore size, surface area, and even the morphology of mesostructures. Here, we used F127 as a main SDA, which is relatively robust (thus, difficult to change the mesopore structures), and added a series of cationic co-surfactants to observe the systematical changes in their mesostructure with respect to the chain length of the co-surfactant.

Synthesis of CaO-SiO2-P2O5 mesoporous bioactive glasses with high P2O5 content by evaporation induced self assembly process.

PubMed

Zhao, Shan; Li, Yanbao; Li, Dongxu

2011-02-01

Mesoporous bioactive glasses (MBGs) of the CaO-SiO(2)-P(2)O(5) system containing relatively high P(2)O(5) contents (10-30 mol%) were prepared from a sol-gel. An evaporation-induced self-assembly (EISA) technique was used with poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (EO(20)-PO(70)-EO(20), P123) acting as a template. The structural, morphological and textural properties of MBGs were investigated by small-angle X-ray diffraction (SAXRD), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy and a N(2) sorption/desorption technique. SAXRD and TEM results display the reduced long-range ordering of mesopores with increasing P(2)O(5) content. N(2) sorption/desorption analysis shows that all three samples exhibit a type IV isotherm with type H1 hysteresis loops, characteristic of independent cylindrical slim pore channels and this material has a Barret-Joyner-Halenda (BJH) model pore size of ~4 nm and BET specific surface area ~430 m(2)/g. NMR results indicate a more condensed framework for samples with 30 mol% P(2)O(5) than samples with 10 mol% P(2)O(5). For in vitro bioactivity tests where samples were soaked in simulated body fluid (SBF), samples with 30 mol% P(2)O(5) showed higher crystallinity than those with lower P(2)O(5) contents Silicon concentration increased in SBF solution during the soaking period, which indicates MBGs can be degradable in SBF solution.

Influences of urea–glycerol mixtures as mixed mesopore-controlling agents on tailoring physicochemical properties and photocatalytic H{sub 2} production activity of sol–gel-derived mesoporous-assembled TiO{sub 2} nanocrystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sreethawong, Thammanoon, E-mail: sreethawongt@imre.a-star.edu.sg; Ngamsinlapasathian, Supachai, E-mail: wonone@hotmail.com; Yoshikawa, Susumu

2013-01-15

Graphical abstract: Display Omitted Highlights: ► Mesoporous-assembled TiO{sub 2} nanocrystals were synthesized by modified sol–gel process. ► Urea–glycerol mixtures were applied as mixed mesopore-controlling agents. ► Urea and glycerol contents affected physicochemical properties of synthesized TiO{sub 2}. ► Photocatalytic H{sub 2} production activity also depended on urea and glycerol contents. ► 75 mol% urea and 25 mol% glycerol yielded the most photocatalytically active TiO{sub 2}. -- Abstract: In this work, the mesoporous-assembled TiO{sub 2} nanocrystal photocatalysts were successfully synthesized by a sol–gel process with the aid of urea–glycerol mixtures used as mixed mesopore-controlling agents. The photocatalytic activity of the synthesizedmore » mesoporous-assembled TiO{sub 2} nanocrystal photocatalysts was investigated for hydrogen production from the water splitting reaction using methanol as a hole scavenger under UV light irradiation. The synthesized TiO{sub 2} nanocrystal photocatalysts were systematically characterized by TG–DTA, N{sub 2} adsorption–desorption, SEM, high resolution TEM, and XRD analyses. The characterization results showed that the well-controlled contents of urea and glycerol in a urea–glycerol mixture at 75 mol% urea and 25 mol% glycerol resulted in not only the most highly porous network (i.e. the highest specific surface area and total pore volume, and the smallest mean mesopore diameter), but also the smallest crystallite size of the synthesized TiO{sub 2} nanocrystal photocatalyst. The photocatalytic reaction results, hence, revealed a much superior photocatalytic hydrogen production activity of the mesoporous-assembled TiO{sub 2} nanocrystal synthesized with 75 mol% urea and 25 mol% glycerol to the other synthesized TiO{sub 2} nanocrystals, also being much higher than those of the commercially available P-25 TiO{sub 2} and ST-01 TiO{sub 2} powders.« less

One-step synthesis of bioactive glass by spray pyrolysis

NASA Astrophysics Data System (ADS)

Shih, Shao-Ju; Chou, Yu-Jen; Chien, I.-Chen

2012-12-01

Bioactive glasses (BGs) have recently received more attention from biologists and engineers because of their potential applications in bone implants. The sol-gel process is one of the most popular methods for fabricating BGs, and has been used to produce BGs for years. However, the sol-gel process has the disadvantages of discontinuous processing and a long processing time. This study presented a one-step spray pyrolysis (SP) synthesis method to overcome these disadvantages. This SP method has synthesized spherical bioactive glass (SBG) and mesoporous bioactive glass (MBG) particles using Si-, Ca- and P-based precursors. This study used transmission electron microscopy, selected area electron diffraction and X-ray dispersive spectroscopy to characterize the microstructure, crystallographic structure, and chemical composition for the BG particles. In addition, in vitro bioactive tests showed the formation of hydroxyl apatite layers on SBG and MBG particles after immersion in simulated body fluid for 5 h. Experimental results show the SP formation mechanisms of SBG and MBG particles.

Fabrication of mesoporous cerium dioxide films by cathodic electrodeposition.

PubMed

Kim, Young-Soo; Lee, Jin-Kyu; Ahn, Jae-Hoon; Park, Eun-Kyung; Kim, Gil-Pyo; Baeck, Sung-Hyeon

2007-11-01

Mesoporous cerium dioxide (Ceria, CeO2) thin films have been successfully electrodeposited onto ITO-coated glass substrates from an aqueous solution of cerium nitrate using CTAB (Cetyltrimethylammonium Bromide) as a templating agent. The synthesized films underwent detailed characterizations. The crystallinity of synthesized CeO2 film was confirmed by XRD analysis and HR-TEM analysis, and surface morphology was investigated by SEM analysis. The presence of mesoporosity in fabricated films was confirmed by TEM and small angle X-ray analysis. As-synthesized film was observed from XRD analysis and HR-TEM image to have well-crystallized structure of cubic phase CeO2. Transmission electron microscopy and small angle X-ray analysis revealed the presence of uniform mesoporosity with a well-ordered lamellar phase in the CeO2 films electrodeposited with CTAB templating.

Potassium-doped mesoporous bioactive glass: Synthesis, characterization and evaluation of biomedical properties.

PubMed

Shoaib, Muhammad; Saeed, Aamer; Akhtar, Javeed; Rahman, Muhammad Saif Ur; Ullah, Aman; Jurkschat, Klaus; Naseer, Muhammad Moazzam

2017-06-01

A bifunctional mesoporous bioactive glass (MBG) with composition (49SiO 2 ·20CaO·20Na 2 O·7K 2 O·4P 2 O 5 mol%) was synthesized by a facile sol-gel method, using polyethylene glycol (PEG 6000) as a soft template. The structure, morphology (spherical with approximate size 1μm) and composition of MBG were determined by fourier transform infrared spectroscopy, the scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX), respectively. The surface area (189.53m 2 g -1 with the pore size of 21nm) of MBG was measured by Brunauer-Emmett-Teller (BET) and Barrett-Joyner-Halenda (BJH) analysis. The formation of hydroxyapatite (HAp) layer on the glass surface upon immersion in simulated body fluid (SBF) was monitored through X-ray diffraction (XRD) which indicates enhanced bioactivity as compared to previous studies. The animals study, protein adsorption ability, and cytotoxicity investigations show no tissue damage, good biomedical properties and no encumbrance with cell cycle (even at a concentration of 80μg/mL). Moreover, the cell proliferation analysis reveals the non-toxic property of MBG at a concentration of 20μg/mL. Notably, a cumulative drug (ciprofloxacin, an antibiotic) release of 75% was observed for first 48h and the further release of 90% was observed over a period of two weeks. The synthesized MBG also shows osteoblast activity and bone mineralization as revealed by alkaline phosphatase activity (ALP) and osteocalcin formation. Copyright © 2017 Elsevier B.V. All rights reserved.

Phosphorus Effects of Mesoporous Bioactive Glass on Occlude Exposed Dentin

PubMed Central

Chen, Wen-Cheng; Chen, Cheng-Hwei; Kung, Jung-Chang; Hsiao, Yu-Cheng; Shih, Chi-Jen; Chien, Chi-Sheng

2013-01-01

In recent studies, sealing of exposed dentinal tubules is generally considered as one of the most effective strategies to treat dentin hypersensitivity. Mesoporous bioactive glass (MBG) is a potential material for treating dentin hypersensitivity due to its highly specific areas for dissolution and re-precipitated reaction for reduction in dentin permeability. The groups of commercial products of PerioGlas®, synthetic MBG and MBG without phosphorus (MBGNP) were compared. The MBG and MBGNP powders were prepared by the sol-gel method and mixed with different calculated ratios of phosphoric acid (PA) and then was brushed onto dentin surfaces. We used X-ray diffractometer (XRD), scanning electronic microscope (SEM), and Fourier transform infrared spectroscopy (FTIR) to investigate the physiochemistry and the occlusion ability of dentinal tubules. The results showed that MBG paste mixed with PA solution has a better ability for occluding dentinal tubules than MBGNP; it has a short reaction time and good operability. The major crystallite phase of MBG agents was monocalcium phosphate monohydrate [Ca(H2PO4)2·H2O] in the early stages of the reactions. MBG pastes that were mixed with 30% and 40% PA had the ability to create excellent penetration depth greater than 80 μm. These agents have the potential to treat dentin hypersensitivity. PMID:28788393

Functionalized mesoporous bioactive glass scaffolds for enhanced bone tissue regeneration

PubMed Central

Zhang, Xingdi; Zeng, Deliang; Li, Nan; Wen, Jin; Jiang, Xinquan; Liu, Changsheng; Li, Yongsheng

2016-01-01

Mesoporous bioactive glass (MBG), which possesses excellent bioactivity, biocompatibility and osteoconductivity, has played an important role in bone tissue regeneration. However, it is difficult to prepare MBG scaffolds with high compressive strength for applications in bone regeneration; this difficulty has greatly hindered its development and use. To solve this problem, a simple powder processing technique has been successfully developed to fabricate a novel type of MBG scaffold (MBGS). Furthermore, amino or carboxylic groups could be successfully grafted onto MBGSs (denoted as N-MBGS and C-MBGS, respectively) through a post-grafting process. It was revealed that both MBGS and the functionalized MBGSs could significantly promote the proliferation and osteogenic differentiation of bMSCs. Due to its positively charged surface, N-MBGS presented the highest in vitro osteogenic capability of the three samples. Moreover, in vivo testing results demonstrated that N-MBGS could promote higher levels of bone regeneration compared with MBGS and C-MBGS. In addition to its surface characteristics, it is believed that the decreased degradation rate of N-MBGS plays a vital role in promoting bone regeneration. These findings indicate that MBGSs are promising materials with potential practical applications in bone regeneration, which can be successfully fabricated by combining a powder processing technique and post-grafting process. PMID:26763311

Functionalized mesoporous bioactive glass scaffolds for enhanced bone tissue regeneration.

PubMed

Zhang, Xingdi; Zeng, Deliang; Li, Nan; Wen, Jin; Jiang, Xinquan; Liu, Changsheng; Li, Yongsheng

2016-01-14

Mesoporous bioactive glass (MBG), which possesses excellent bioactivity, biocompatibility and osteoconductivity, has played an important role in bone tissue regeneration. However, it is difficult to prepare MBG scaffolds with high compressive strength for applications in bone regeneration; this difficulty has greatly hindered its development and use. To solve this problem, a simple powder processing technique has been successfully developed to fabricate a novel type of MBG scaffold (MBGS). Furthermore, amino or carboxylic groups could be successfully grafted onto MBGSs (denoted as N-MBGS and C-MBGS, respectively) through a post-grafting process. It was revealed that both MBGS and the functionalized MBGSs could significantly promote the proliferation and osteogenic differentiation of bMSCs. Due to its positively charged surface, N-MBGS presented the highest in vitro osteogenic capability of the three samples. Moreover, in vivo testing results demonstrated that N-MBGS could promote higher levels of bone regeneration compared with MBGS and C-MBGS. In addition to its surface characteristics, it is believed that the decreased degradation rate of N-MBGS plays a vital role in promoting bone regeneration. These findings indicate that MBGSs are promising materials with potential practical applications in bone regeneration, which can be successfully fabricated by combining a powder processing technique and post-grafting process.

Size-Dependent Mechanism of Intracellular Localization and Cytotoxicity of Mono-Disperse Spherical Mesoporous Nano- and Micron-Bioactive Glass Particles

PubMed Central

Li, Yuli; Hu, Qing; Miao, Guohou; Zhang, Qing; Yuan, Bo; Zhu, Ye; Fu, Xiaoling; Chen, Xiaofeng; Mao, Chuanbin

2016-01-01

Mono-disperse spherical mesoporous nano- and micro- bioactive glass particles (NMBGs) can find potential use in bone tissue engineering. However, their size-dependent interaction with osteoblasts has never been studied. Herein, the proliferation, morphology, cytoskeleton organization and apoptosis of MC3T3-E1 osteoblasts are studied in response to the NMBGs with varying sizes (from 61 to 1085 nm) at different concentrations. Generally, smaller NMBGs at a lower dose show weaker cytotoxicity compared to the larger particles and higher doses, arising from a novel size-dependent mechanism of intracellular localization of NMBGs observed by electron and confocal microscopy. Specifically, NMBGs pass through perinuclear membrane of the cells to initiate endocytosis. Once internalized, the sizes of NMBGs are found to play a significant role in determining their intracellular localization. When the NMBGs are smaller than 174 nm, they are transported via the lysosomal pathway and phagocytized in lysosomes, resulting in little cytotoxicity at later time points. On the contrary, larger NMBGs (over 174 nm) escape from the lysosomes after endocytosis, and are localized inside the intra-cytoplasmic vacuoles or randomly in the cytoplasm of cells. Their lysosomal escape may damage the lysosomes, inducing cell apoptosis and thus the greater cytotoxicity. PMID:27305811

Electrochemical synthesis of mesoporous gold films toward mesospace-stimulated optical properties

NASA Astrophysics Data System (ADS)

Li, Cuiling; Dag, Ömer; Dao, Thang Duy; Nagao, Tadaaki; Sakamoto, Yasuhiro; Kimura, Tatsuo; Terasaki, Osamu; Yamauchi, Yusuke

2015-03-01

Mesoporous gold (Au) films with tunable pores are expected to provide fascinating optical properties stimulated by the mesospaces, but they have not been realized yet because of the difficulty of controlling the Au crystal growth. Here, we report a reliable soft-templating method to fabricate mesoporous Au films using stable micelles of diblock copolymers, with electrochemical deposition advantageous for precise control of Au crystal growth. Strong field enhancement takes place around the center of the uniform mesopores as well as on the walls between the pores, leading to the enhanced light scattering as well as surface-enhanced Raman scattering (SERS), which is understandable, for example, from Babinet principles applied for the reverse system of nanoparticle ensembles.

Controlling the Pore Size of Mesoporous Carbon Thin Films through Thermal and Solvent Annealing.

PubMed

Zhou, Zhengping; Liu, Guoliang

2017-04-01

Herein an approach to controlling the pore size of mesoporous carbon thin films from metal-free polyacrylonitrile-containing block copolymers is described. A high-molecular-weight poly(acrylonitrile-block-methyl methacrylate) (PAN-b-PMMA) is synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization. The authors systematically investigate the self-assembly behavior of PAN-b-PMMA thin films during thermal and solvent annealing, as well as the pore size of mesoporous carbon thin films after pyrolysis. The as-spin-coated PAN-b-PMMA is microphase-separated into uniformly spaced globular nanostructures, and these globular nanostructures evolve into various morphologies after thermal or solvent annealing. Surprisingly, through thermal annealing and subsequent pyrolysis of PAN-b-PMMA into mesoporous carbon thin films, the pore size and center-to-center spacing increase significantly with thermal annealing temperature, different from most block copolymers. In addition, the choice of solvent in solvent annealing strongly influences the block copolymer nanostructure and the pore size of mesoporous carbon thin films. The discoveries herein provide a simple strategy to control the pore size of mesoporous carbon thin films by tuning thermal or solvent annealing conditions, instead of synthesizing a series of block copolymers of various molecular weights and compositions. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bioresponsive controlled release from mesoporous silica nanocontainers with glucometer readout.

PubMed

Hou, Li; Zhu, Chunling; Wu, Xiaoping; Chen, Guonan; Tang, Dianping

2014-02-11

A novel sensing platform for monitoring small molecules without the need for sample separation and washing is developed by using a commercialized personal glucose meter based on bioresponsive controlled release of glucose from aptamer-gated mesoporous silica nanocontainers.

Role of the Short Distance Order in Glass Reactivity

PubMed Central

2018-01-01

In 2005, our group described for the first time the structural characterization at the atomic scale of bioactive glasses and the influence of the glasses’ nanostructure in their reactivity in simulated body fluids. In that study, two bioactive sol-gel glasses with composition 80%SiO2–20%CaO and 80%SiO2–17%CaO–3%P2O5 (in mol-%) were characterized by High-Resolution Transmission Electron Microscopy (HRTEM). Such characterization revealed unknown features of the glasses’ structure at the local scale that allowed the understanding of their different in vitro behaviors as a consequence of the presence or absence of P2O5. Since then, the nanostructure of numerous bioactive glasses, including melt-prepared, sol-gel derived, and mesoporous glasses, was investigated by HRTEM, Nuclear Magnetic Resonance (NMR) spectroscopy, Molecular Dynamics (MD) simulations, and other experimental techniques. These studies have shown that although glasses are amorphous solids, a certain type of short distance order, which greatly influences the in vitro and in vivo reactivity, is always present. This paper reviews the most significant advances in the understanding of bioactive glasses that took place in the last years as a result of the growing knowledge of the glasses’ nanostructure. PMID:29534481

Synthesis and characterization of mesoporous and hollow-mesoporous MxFe3-xO4 (M=Mg, Mn, Fe, Co, Ni, Cu, Zn) microspheres for microwave-triggered controllable drug delivery

NASA Astrophysics Data System (ADS)

Chen, Ping; Cui, Bin; Bu, Yumei; Yang, Zhenfeng; Wang, Yaoyu

2017-12-01

Spinel ferrites can be used in magnetic targeting and microwave heating and can therefore be used for targeted and controllable drug delivery. We used the cetyltrimethylammonium bromide-assisted solvothermal method to synthesize a series of spinel ferrites (MxFe3-xO4, M=Mg, Mn, Fe, Co, Ni, Cu, Zn) with a mesoporous or hollow-mesoporous structure suitable for direct drug loading and the particle diameters ranging from 200 to 350 nm. We investigated the effects of M2+ cation on the morphology and properties of these products by analyzing their transmission electron microscopy images, mesoporous properties, magnetic properties, and microwave responses. We chose hollow-mesoporous MxFe3-xO4 (M=Fe, Co, Zn) nanoparticles, which had better overall properties, for the drug VP16 (etoposide) loading and microwave-controlled release. The CoxFe3-xO4 and Fe3O4 particles trapped 61.5 and 64.8%, respectively, of the VP16, which were higher than that (60.4%) of ZnxFe3-xO4. Controllable drug release by these simple magnetic nanocarriers can be achieved by microwave irradiation, and VP16-loaded CoxFe3-xO4 released the most VP16 molecules (more than 50% after 1 h and 69.1% after 6 h) under microwave irradiation. Our results confirm the favorable drug loading and microwave-controlled delivery by these ferrites, and lay a theoretical foundation to promote clinical application of the targeted controllable drug delivery system. [Figure not available: see fulltext.

Mesoporous inorganic nanoscale particles for drug adsorption and controlled release.

PubMed

Cavallaro, Giuseppe; Lazzara, Giuseppe; Fakhrullin, Rawil

2018-03-01

The review provides an overview of the mesoporous inorganic particles employed as drug delivery systems for controlled and sustained release of drugs. We have classified promising nanomaterials for drug delivery on the basis of their natural or synthetic origin. Nanoclays are available in different morphologies (nanotubes, nanoplates and nanofibers) and they are typically available at low cost from natural resources. The surface chemistry of nanoclays is versatile for targeted modifications to control loading and release properties. Synthetic nanomaterials (imogolite, laponite and mesoporous silica) present the advantages of well-established purity and availability with size features that are finely controlled. Both nanoclays and inorganic synthetic nanoparticles can be functionalized forming organic/inorganic architectures with stimuli-responsive features.

Facile and green synthesis of mesoporous Co3O4 nanocubes and their applications for supercapacitors

NASA Astrophysics Data System (ADS)

Liu, Xiangmei; Long, Qing; Jiang, Chunhui; Zhan, Beibei; Li, Chen; Liu, Shujuan; Zhao, Qiang; Huang, Wei; Dong, Xiaochen

2013-06-01

Nanostructured Co3O4 materials attracted significant attention due to their exceptional electrochemical (pseudo-capacitive) properties. However, rigorous preparation conditions are needed to control the size (especially nanosize), morphology and size distribution of the products obtained by conventional methods. Herein, we describe a novel one step shape-controlled synthesis of uniform Co3O4 nanocubes with a size of 50 nm with the existence of mesoporous carbon nanorods (meso-CNRs). In this synthesis process, meso-CNRs not only act as a heat receiver to directly obtain Co3O4 eliminating the high-temperature post-calcination, but also control the morphology of the resulting Co3O4 to form nanocubes with uniform distribution. More strikingly, mesoporous Co3O4 nanocubes are obtained by further thermal treatment. The structure and morphology of the samples were characterized by scanning electron microscopy, transmission electron microscopy and X-ray diffraction. A possible formation mechanism of mesoporous Co3O4 nanocubes is proposed here. Electrochemical tests have revealed that the prepared mesoporous Co3O4 nanocubes demonstrate a remarkable performance in supercapacitor applications due to the porous structure, which endows fast ion and electron transfer.Nanostructured Co3O4 materials attracted significant attention due to their exceptional electrochemical (pseudo-capacitive) properties. However, rigorous preparation conditions are needed to control the size (especially nanosize), morphology and size distribution of the products obtained by conventional methods. Herein, we describe a novel one step shape-controlled synthesis of uniform Co3O4 nanocubes with a size of 50 nm with the existence of mesoporous carbon nanorods (meso-CNRs). In this synthesis process, meso-CNRs not only act as a heat receiver to directly obtain Co3O4 eliminating the high-temperature post-calcination, but also control the morphology of the resulting Co3O4 to form nanocubes with uniform distribution. More strikingly, mesoporous Co3O4 nanocubes are obtained by further thermal treatment. The structure and morphology of the samples were characterized by scanning electron microscopy, transmission electron microscopy and X-ray diffraction. A possible formation mechanism of mesoporous Co3O4 nanocubes is proposed here. Electrochemical tests have revealed that the prepared mesoporous Co3O4 nanocubes demonstrate a remarkable performance in supercapacitor applications due to the porous structure, which endows fast ion and electron transfer. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr00495c

Functionalized bimodal mesoporous silicas as carriers for controlled aspirin delivery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao Lin; Sun Jihong, E-mail: jhsun@bjut.edu.cn; Li Yuzhen

The bimodal mesoporous silica modified with 3-aminopropyltriethoxysilane was performed as the aspirin carrier. The samples' structure, drug loading and release profiles were characterized with X-ray diffraction, scanning electron microscopy, N{sub 2} adsorption and desorption, Fourier transform infrared spectroscopy, TG analysis, elemental analysis and UV-spectrophotometer. For further exploring the effects of the bimodal mesopores on the drug delivery behavior, the unimodal mesoporous material MCM-41 was also modified as the aspirin carrier. Meantime, Korsmeyer-Peppas equation f{sub t}=kt{sup n} was employed to analyze the dissolution data in details. It is indicated that the bimodal mesopores are beneficial for unrestricted drug molecules diffusing andmore » therefore lead to a higher loading and faster releasing than that of MCM-41. The results show that the aspirin delivery properties are influenced considerably by the mesoporous matrix, whereas the large pore of bimodal mesoporous silica is the key point for the improved controlled-release properties. - Graphical abstract: Loading (A) and release profiles (B) of aspirin in N-BMMs and N-MCM-41 indicated that BMMs have more drug loading capacity and faster release rate than that MCM-41. Highlights: > Bimodal mesoporous silicas (BMMs) and MCM-41 modified with amino group via post-treatment procedure. > Loading and release profiles of aspirin in modified BMMs and MCM-41. > Modified BMMs have more drug loading capacity and faster release rate than that modified MCM-41.« less

Possible pore size effects on the state of tris(8-quinolinato)aluminum(III) (Alq3) adsorbed in mesoporous silicas and their temperature dependence.

PubMed

Tagaya, Motohiro; Ogawa, Makoto

2008-12-07

The states of tris(8-quinolinato)aluminum(III) (Alq3) adsorbed in mesoporous silicas with different pore sizes (2.5, 3.1 and 5.0 nm) were investigated. Alq3 was successfully occluded into the mesoporous silicas from solution and the adsorbed amount of Alq3 per BET surface area was effectively controlled by changing the added amount Alq3 to the solution. The state of Alq3 in the mesopore varied depending on the pore size as well as the adsorbed amount of Alq3 as revealed by variation of the photoluminescence spectra. The luminescence of the adsorbed Alq3 was found to be temperature-dependent, indicating the mobility of the adsorbed Alq3 to temperature variations. The temperature-dependence also depended on the pore size. The guest-guest interactions between Alq3 molecules as well as the host-guest interactions between Alq3 and the mesopore were controlled by the pore size.

Layer-by-Layer Motif Architectures: Programmed Electrochemical Syntheses of Multilayer Mesoporous Metallic Films with Uniformly Sized Pores.

PubMed

Jiang, Bo; Li, Cuiling; Qian, Huayu; Hossain, Md Shahriar A; Malgras, Victor; Yamauchi, Yusuke

2017-06-26

Although multilayer films have been extensively reported, most compositions have been limited to non-catalytically active materials (e.g. polymers, proteins, lipids, or nucleic acids). Herein, we report the preparation of binder-free multilayer metallic mesoporous films with sufficient accessibility for high electrocatalytic activity by using a programmed electrochemical strategy. By precisely tuning the deposition potential and duration, multilayer mesoporous architectures consisting of alternating mesoporous Pd layers and mesoporous PdPt layers with controlled layer thicknesses can be synthesized within a single electrolyte, containing polymeric micelles as soft templates. This novel architecture, combining the advantages of bimetallic alloys, multilayer architectures, and mesoporous structures, exhibits high electrocatalytic activity for both the methanol oxidation reaction (MOR) and the ethanol oxidation reaction (EOR). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Facile and green synthesis of mesoporous Co3O4 nanocubes and their applications for supercapacitors.

PubMed

Liu, Xiangmei; Long, Qing; Jiang, Chunhui; Zhan, Beibei; Li, Chen; Liu, Shujuan; Zhao, Qiang; Huang, Wei; Dong, Xiaochen

2013-07-21

Nanostructured Co3O4 materials attracted significant attention due to their exceptional electrochemical (pseudo-capacitive) properties. However, rigorous preparation conditions are needed to control the size (especially nanosize), morphology and size distribution of the products obtained by conventional methods. Herein, we describe a novel one step shape-controlled synthesis of uniform Co3O4 nanocubes with a size of 50 nm with the existence of mesoporous carbon nanorods (meso-CNRs). In this synthesis process, meso-CNRs not only act as a heat receiver to directly obtain Co3O4 eliminating the high-temperature post-calcination, but also control the morphology of the resulting Co3O4 to form nanocubes with uniform distribution. More strikingly, mesoporous Co3O4 nanocubes are obtained by further thermal treatment. The structure and morphology of the samples were characterized by scanning electron microscopy, transmission electron microscopy and X-ray diffraction. A possible formation mechanism of mesoporous Co3O4 nanocubes is proposed here. Electrochemical tests have revealed that the prepared mesoporous Co3O4 nanocubes demonstrate a remarkable performance in supercapacitor applications due to the porous structure, which endows fast ion and electron transfer.

Role of Confinement on Adsorption and Dynamics of Ethane and an Ethane–CO 2 Mixture in Mesoporous CPG Silica

DOE PAGES

Patankar, Sumant; Gautam, Siddharth; Rother, Gernot; ...

2016-02-10

It was found that ethane is confined to mineral and organic pores in certain shale formations. Effects of confinement on structural and dynamic properties of ethane in mesoporous controlled pore glass (CPG) were studied by gravimetric adsorption and quasi-elastic neutron scattering (QENS) measurements. The obtained isotherms and scattering data complement each other by quantifying the relative strength of the solid–fluid interactions and the transport properties of the fluid under confinement, respectively. We used a magnetic suspension balance to measure the adsorption isotherms at two temperatures and over a range of pressures corresponding to a bulk density range of 0.01–0.35 g/cmmore » 3. Key confinement effects were highlighted through differences between isotherms for the two pore sizes. A comparison was made with previously published isotherms for CO 2 on the same CPG materials. Behavior of ethane in the smaller pore size was probed further using quasi-elastic neutron scattering. By extracting the self-diffusivity and residence time, we were able to study the effect of pressure and transition from gaseous to supercritical densities on the dynamics of confined ethane. Moreover, a temperature variation QENS study was also completed with pure ethane and a CO 2–ethane mixture. Activation energies extracted from the Arrhenius plots show the effects of CO 2 addition on ethane mobility.« less

Electrochemical synthesis of mesoporous Pt-Au binary alloys with tunable compositions for enhancement of electrochemical performance.

PubMed

Yamauchi, Yusuke; Tonegawa, Akihisa; Komatsu, Masaki; Wang, Hongjing; Wang, Liang; Nemoto, Yoshihiro; Suzuki, Norihiro; Kuroda, Kazuyuki

2012-03-21

Mesoporous Pt-Au binary alloys were electrochemically synthesized from lyotropic liquid crystals (LLCs) containing corresponding metal species. Two-dimensional exagonally ordered LLC templates were prepared on conductive substrates from diluted surfactant solutions including water, a nonionic surfactant, ethanol, and metal species by drop-coating. Electrochemical synthesis using such LLC templates enabled the preparation of ordered mesoporous Pt-Au binary alloys without phase segregation. The framework composition in the mesoporous Pt-Au alloy was controlled simply by changing the compositional ratios in the precursor solution. Mesoporous Pt-Au alloys with low Au content exhibited well-ordered 2D hexagonal mesostructures, reflecting those of the original templates. With increasing Au content, however, the mesostructural order gradually decreased, thereby reducing the electrochemically active surface area. Wide-angle X-ray diffraction profiles, X-ray photoelectron spectra, and elemental mapping showed that both Pt and Au were atomically distributed in the frameworks. The electrochemical stability of mesoporous Pt-Au alloys toward methanol oxidation was highly improved relative to that of nonporous Pt and mesoporous Pt films, suggesting that mesoporous Pt-Au alloy films are potentially applicable as electrocatalysts for direct methanol fuel cells. Also, mesoporous Pt-Au alloy electrodes showed a highly sensitive amperometric response for glucose molecules, which will be useful in next-generation enzyme-free glucose sensors.

Rational design of mesoporous metals and related nanomaterials by a soft-template approach.

PubMed

Yamauchi, Yusuke; Kuroda, Kazuyuki

2008-04-07

We review recent developments in the preparation of mesoporous metals and related metal-based nanomaterials. Among the many types of mesoporous materials, mesoporous metals hold promise for a wide range of potential applications, such as in electronic devices, magnetic recording media, and metal catalysts, owing to their metallic frameworks. Mesoporous metals with highly ordered networks and narrow pore-size distributions have traditionally been produced by using mesoporous silica as a hard template. This method involves the formation of an original template followed by deposition of metals within the mesopores and subsequent removal of the template. Another synthetic method is the direct-template approach from lyotropic liquid crystals (LLCs) made of nonionic surfactants at high concentrations. Direct-template synthesis creates a novel avenue for the production of mesoporous metals as well as related metal-based nanomaterials. Many mesoporous metals have been prepared by the chemical or electrochemical reduction of metal salts dissolved in aqueous LLC domains. As a soft template, LLCs are more versatile and therefore more advantageous than hard templates. It is possible to produce various nanostructures (e.g., lamellar, 2D hexagonal (p6mm), and 3D cubic (Ia\\3d)), nanoparticles, and nanotubes simply by controlling the composition of the reaction bath.

Controllable synthesis of hierarchical MgMoO4 nanosheet-arrays and nano-flowers assembled with mesoporous ultrathin nanosheets

NASA Astrophysics Data System (ADS)

Zhang, Lifeng; He, Wenjie; Shen, Kechao; Liu, Yi; Guo, Shouwu

2018-04-01

Self-standing hierarchical mesoporous MgMoO4 nanosheet-arrays and nano-flowers have been built via the self-assembly of ultrathin mesoporous nanosheets. The arrays and flower nanostructures can be facilely controlled by tuning the surfactant dosage. The formation mechanism of such special nanostructures has also been proposed. The flower structure has larger surface area than the arrays, owing to the more mesoporous nature of the former. Additionally, the as-prepared MgMoO4 nanomaterials not doped by any other ion have important optical properties, that enable the generation of strong red light with excitation wavelengths of 369 and 534 nm and emission of bright green light under irradiation by blue light (423 and 451 nm), demonstrating their potential applications in blue phototherapy and fluorescence labeling.

Formation of monodisperse mesoporous silica microparticles via spray-drying.

PubMed

Waldron, Kathryn; Wu, Winston Duo; Wu, Zhangxiong; Liu, Wenjie; Selomulya, Cordelia; Zhao, Dongyuan; Chen, Xiao Dong

2014-03-15

In this work, a protocol to synthesize monodisperse mesoporous silica microparticles via a unique microfluidic jet spray-drying route is reported for the first time. The microparticles demonstrated highly ordered hexagonal mesostructures with surface areas ranging from ~900 up to 1500 m(2)/g and pore volumes from ~0.6 to 0.8 cm(3)/g. The particle size could be easily controlled from ~50 to 100 μm from the same diameter nozzle via changing the initial solute content, or changing the drying temperature. The ratio of the surfactant (CTAB) and silica (TEOS), and the amount of water in the precursor were found to affect the degree of ordering of mesopores by promoting either the self-assembly of the surfactant-silica micelles or the condensation of the silica as two competing processes in evaporation induced self-assembly. The drying rate and the curvature of particles also affected the self-assembly of the mesostructure. The particle mesostructure is not influenced by the inlet drying temperature in the range of 92-160 °C, with even a relatively low temperature of 92 °C producing highly ordered mesoporous microparticles. The spray-drying derived mesoporous silica microparticles, while of larger sizes and more rapidly synthesized, showed a comparable performance with the conventional mesoporous silica MCM-41 in controlled release of a dye, Rhodamine B, indicating that these spray dried microparticles could be used for the immobilisation and controlled release of small molecules. Copyright © 2013 Elsevier Inc. All rights reserved.

Improving the controlled release of water-insoluble emodin from amino-functionalized mesoporous silica

NASA Astrophysics Data System (ADS)

Xu, Yunqiang; Wang, Chunfeng; Zhou, Guowei; Wu, Yue; Chen, Jing

2012-06-01

Several types of amino-functionalized mesoporous silica, including F5-SBA-15, F10-SBA-15, and F15-SBA-15 were prepared through co-condensation of tetraethoxysilane (TEOS) and (3-aminopropyl)triethoxysilane (APTES) in varying molar ratios (5 mol%, 10 mol%, and 15 mol%) via a hydrothermal process. The materials obtained were characterized by means of small-angle X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy, N2 adsorption-desorption, Fourier transformed infrared spectra, and X-ray photoelectron spectroscopy. Increasing APTES molar ratios decreased the degree of orderliness of the functionalized mesoporous silica. Pure and amino-functionalized SBA-15 samples were employed as supports for the controlled release of water-insoluble drug emodin. Loading experiments showed that drug loading capacities mainly depended on the surface areas and pore diameters of the carriers. Controlled release profiles of emodin-loaded samples were studied in phosphate buffered saline (PBS, pH 7.4), and results indicated that the emodin release rate could be controlled by surface amino-functionalized carriers. Emodin loaded on functionalized mesoporous supports exhibited a lower release rate than that of loaded on pure SBA-15, emodin loaded on F10-SBA-15 showed the smallest release amount (71.74 wt%) after stirring in PBS for 60 h. Findings suggest that functionalized mesoporous SBA-15 is a promising carrier for achieving prolonged release time periods.

Ordered mesoporous polymer-silica hybrid nanoparticles as vehicles for the intracellular controlled release of macromolecules.

PubMed

Kim, Tae-Wan; Slowing, Igor I; Chung, Po-Wen; Lin, Victor Shang-Yi

2011-01-25

A two-dimensional hexagonal ordered mesoporous polymer-silica hybrid nanoparticle (PSN) material was synthesized by polymerization of acrylate monomers on the surface of SBA-15 mesoporous silica nanoparticles. The structure of the PSN material was analyzed using a series of different techniques, including transmission electron microscopy, powder X-ray diffraction, and N(2) sorption analysis. These structurally ordered mesoporous polymer-silica hybrid nanoparticles were used for the controlled release of membrane-impermeable macromolecules inside eukaryotic cells. The cellular uptake efficiency and biocompatibility of PSN with human cervical cancer cells (HeLa) were investigated. Our results show that the inhibitory concentration (IC(50)) of PSN is very high (>100 μg/mL per million cells), while the median effective concentration for the uptake (EC(50)) of PSN is low (EC(50) = 4.4 μg/mL), indicating that PSNs are fairly biocompatible and easily up-taken in vitro. A membrane-impermeable macromolecule, 40 kDa FITC-Dextran, was loaded into the mesopores of PSNs at low pH. We demonstrated that the PSN material could indeed serve as a transmembrane carrier for the controlled release of FITC-Dextran at the pH level inside live HeLa cells. We believe that further developments of this PSN material will lead to a new generation of nanodevices for intracellular controlled delivery applications.

Electrochemical characteristics of discrete, uniform, and monodispersed hollow mesoporous carbon spheres in double-layered supercapacitors.

PubMed

Chen, Xuecheng; Kierzek, Krzysztof; Wenelska, Karolina; Cendrowski, Krzystof; Gong, Jiang; Wen, Xin; Tang, Tao; Chu, Paul K; Mijowska, Ewa

2013-11-01

Core-shell-structured mesoporous silica spheres were prepared by using n-octadecyltrimethoxysilane (C18TMS) as the surfactant. Hollow mesoporous carbon spheres with controllable diameters were fabricated from core-shell-structured mesoporous silica sphere templates by chemical vapor deposition (CVD). By controlling the thickness of the silica shell, hollow carbon spheres (HCSs) with different diameters can be obtained. The use of ethylene as the carbon precursor in the CVD process produces the materials in a single step without the need to remove the surfactant. The mechanism of formation and the role played by the surfactant, C18TMS, are investigated. The materials have large potential in double-layer supercapacitors, and their electrochemical properties were determined. HCSs with thicker mesoporous shells possess a larger surface area, which in turn increases their electrochemical capacitance. The samples prepared at a lower temperature also exhibit increased capacitance as a result of the Brunauer-Emmett-Teller (BET) area and larger pore size. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermodynamic sorption analysis and glass transition temperature of faba bean (Vicia faba L.) protein.

PubMed

Alpizar-Reyes, E; Castaño, J; Carrillo-Navas, H; Alvarez-Ramírez, J; Gallardo-Rivera, R; Pérez-Alonso, C; Guadarrama-Lezama, A Y

2018-03-01

Freeze-dried faba bean ( Vicia faba L.) protein adsorption isotherms were determined at 25, 35 and 40 °C and fitted with the Guggenheim-Anderson-de Boer model. The pore radius of protein was in the range of 0.87-6.44 nm, so that they were considered as micropores and mesopores. The minimum integral entropy ranged between 4.33 and 4.44 kg H 2 O/100 kg d.s., was regarded as the point of maximum of stability. The glass transition temperature of the protein equilibrated at the different conditions of storage was determined, showing that the protein remained in glassy state for all cases. The protein showed compact and rigid structures, evidenced by microscopy analysis.

Preparation, structural characterization, and in vitro cell studies of three-dimensional SiO2-CaO binary glass scaffolds built ofultra-small nanofibers.

PubMed

Luo, Honglin; Li, Wei; Ao, Haiyong; Li, Gen; Tu, Junpin; Xiong, Guangyao; Zhu, Yong; Wan, Yizao

2017-07-01

Three-dimensional (3D) nanofibrous scaffolds hold great promises in tissue engineering and regenerative medicine. In this work, for the first time, 3D SiO 2 -CaO binary glass nanofibrous scaffolds have been fabricated via a combined method of template-assisted sol-gel and calcination by using bacterial cellulose as the template. SEM with EDS, TEM, and AFM confirm that the molar ratio of Ca to Si and fiber diameter of the resultant SiO 2 -CaO nanofibers can be controlled by immersion time in the solution of tetraethyl orthosilicate and ethanol. The optimal immersion time was 6h which produced the SiO 2 -CaO binary glass containing 60at.% Si and 40at.% Ca (named 60S40C). The fiber diameter of 60S40C scaffold is as small as 29nm. In addition, the scaffold has highly porous 3D nanostructure with dominant mesopores at 10.6nm and macropores at 20μm as well as a large BET surface area (240.9m 2 g -1 ), which endow the 60S40C scaffold excellent biocompatibility and high ALP activity as revealed by cell studies using osteoblast cells. These results suggest that the 60S40C scaffold has great potential in bone tissue regeneration. Copyright © 2017 Elsevier B.V. All rights reserved.

Kinetically Controlled Synthesis of Pt-Based One-Dimensional Hierarchically Porous Nanostructures with Large Mesopores as Highly Efficient ORR Catalysts.

PubMed

Fu, Shaofang; Zhu, Chengzhou; Song, Junhua; Engelhard, Mark H; Xia, Haibing; Du, Dan; Lin, Yuehe

2016-12-28

Rational design and construction of Pt-based porous nanostructures with large mesopores have triggered significant considerations because of their high surface area and more efficient mass transport. Hydrochloric acid-induced kinetically controlled reduction of metal precursors in the presence of soft template F-127 and hard template tellurium nanowires has been successfully demonstrated to construct one-dimensional hierarchical porous PtCu alloy nanostructures with large mesopores. Moreover, the electrochemical experiments demonstrated that the PtCu hierarchically porous nanostructures synthesized under optimized conditions exhibit enhanced electrocatalytic performance for oxygen reduction reaction in acid media.

Mesoporous carbon nanomaterials in drug delivery and biomedical application.

PubMed

Zhao, Qinfu; Lin, Yuanzhe; Han, Ning; Li, Xian; Geng, Hongjian; Wang, Xiudan; Cui, Yu; Wang, Siling

2017-01-01

Recent development of nano-technology provides highly efficient and versatile treatment methods to achieve better therapeutic efficacy and lower side effects of malignant cancer. The exploration of drug delivery systems (DDSs) based on nano-material shows great promise in translating nano-technology to clinical use to benefit patients. As an emerging inorganic nanomaterial, mesoporous carbon nanomaterials (MCNs) possess both the mesoporous structure and the carbonaceous composition, endowing them with superior nature compared with mesoporous silica nanomaterials and other carbon-based materials, such as carbon nanotube, graphene and fullerene. In this review, we highlighted the cutting-edge progress of carbon nanomaterials as drug delivery systems (DDSs), including immediate/sustained drug delivery systems and controlled/targeted drug delivery systems. In addition, several representative biomedical applications of mesoporous carbon such as (1) photo-chemo synergistic therapy; (2) delivery of therapeutic biomolecule and (3) in vivo bioimaging are discussed and integrated. Finally, potential challenges and outlook for future development of mesoporous carbon in biomedical fields have been discussed in detail.

Versatility of Evaporation-Induced Self-Assembly (EISA) Method for Preparation of Mesoporous TiO2 for Energy and Environmental Applications

PubMed Central

Mahoney, Luther; Koodali, Ranjit T.

2014-01-01

Evaporation-Induced Self-Assembly (EISA) method for the preparation of mesoporous titanium dioxide materials is reviewed. The versatility of EISA method for the rapid and facile synthesis of TiO2 thin films and powders is highlighted. Non-ionic surfactants such as Pluronic P123, F127 and cationic surfactants such as cetyltrimethylammonium bromide have been extensively employed for the preparation of mesoporous TiO2. In particular, EISA method allows for fabrication of highly uniform, robust, crack-free films with controllable thickness. Eleven characterization techniques for elucidating the structure of the EISA prepared mesoporous TiO2 are discussed in this paper. These many characterization methods provide a holistic picture of the structure of mesoporous TiO2. Mesoporous titanium dioxide materials have been employed in several applications that include Dye Sensitized Solar Cells (DSSCs), photocatalytic degradation of organics and splitting of water, and batteries. PMID:28788590

Mesoporous silica film from a solution containing a surfactant and methods of making same

DOEpatents

Liu, Jun [West Richland, WA; Domansky, Karel [Cambridge, MA; Li, Xiaohong [Richland, WA; Fryxell, Glen E [Kennewick, WA; Baskaran, Suresh [Kennewick, WA; Kohler, Nathan J [Richland, WA; Thevuthasan, Suntharampillai [Kennewick, WA; Coyle, Christopher A [Richland, WA; Birnbaum, Jerome C [Richland, WA

2001-12-11

The present invention is a mesoporous silica film having a low dielectric constant and method of making having the steps of combining a surfactant in a silica precursor solution, spin-coating a film from this solution mixture, forming a partially hydroxylated mesoporous film, and dehydroxylating the hydroxylated film to obtain the mesoporous film. It is advantageous that the small polyoxyethylene ether surfactants used in spin-coated films as described in the present invention will result in fine pores smaller on average than about 20 nm. The resulting mesoporous film has a dielectric constant less than 3, which is stable in moist air with a specific humidity. The present invention provides a method for superior control of film thickness and thickness uniformity over a coated wafer, and films with low dielectric constant.

Near-infrared emission from mesoporous crystalline germanium

NASA Astrophysics Data System (ADS)

Boucherif, Abderraouf; Korinek, Andreas; Aimez, Vincent; Arès, Richard

2014-10-01

Mesoporous crystalline germanium was fabricated by bipolar electrochemical etching of Ge wafer in HF-based electrolyte. It yields uniform mesoporous germanium layers composed of high density of crystallites with an average size 5-7 nm. Subsequent extended chemical etching allows tuning of crystallites size while preserving the same chemical composition. This highly controllable nanostructure exhibits photoluminescence emission above the bulk Ge bandgap, in the near-infrared range (1095-1360nm) with strong evidence of quantum confinement within the crystallites.

Mesoporous wormholelike carbon with controllable nanostructure for lithium ion batteries application

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Xiaoqing, E-mail: yxq-886@163.com; Li, Xinxi; Li, Zhenghui

2015-06-15

Highlights: • Wormholelike carbon (WMC) with controllable nanostructure is prepared by sol–gel method. • The reversible capacity of WMC is much higher than that of many other reported nanocarbons. • The effect of pore diameter on Li storage capacity is investigated. - Abstract: A class of mesoporous wormholelike carbon (WMC) with controllable nanostructure was prepared by sol–gel method and then used as the anode material of lithium-ion batteries. Based on the experimental results, it is found that the nanostructure of the as-prepared WMC plays an important role in the electrochemical performances. A suitable mesopore size is necessary for a highmore » performance carbon-based anode material since it can not only guarantee effective mass transport channels but also provide large surface area. As a result, F30 with a mesopore size of 4.4 nm coupled with high surface area of 1077 m{sup 2} g{sup −1} shows a reversible capacity of 630 mAh g{sup −1}, much higher than commercial graphite and many other reported nanocarbons.« less

Controllable synthesis of nitrogen-doped hollow mesoporous carbon spheres using ionic liquids as template for supercapacitors

NASA Astrophysics Data System (ADS)

Chen, Aibing; Li, Yunqian; Liu, Lei; Yu, Yifeng; Xia, Kechan; Wang, Yuying; Li, Shuhui

2017-01-01

We have demonstrated a facile and controllable synthesis of monodispersed nitrogen-doped hollow mesoporous carbon spheres (N-HMCSs) using resorcinol/formaldehyde resin as a carbon precursor, tetraethyl orthosilicate as a structure-assistant agent, ionic liquids (ILs) as soft template, partial carbon sources, and nitrogen sources. The sizes and the architectures including hollow and yolk-shell of resultant carbon spheres can be efficiently controlled through the adjustment of the content of ILs. Alkyl chain length of the ILs also has an important effect on the formation of N-HMCSs. With proper alkyl chain length and content of ILs, the resultant N-HMCSs show monodispersed hollow spheres with high surface areas (up to 1158 m2 g-1), large pore volumes (up to 1.70 cm3 g-1), and uniform mesopore size (5.0 nm). Combining the hollow mesoporous structure, high porosity, large surface area, and nitrogen functionality, the as-synthesized N-HMCSs have good supercapacitor performance with good capacitance (up to 159 F g-1) and favorable capacitance retention (88% capacitive retention after 5000 cycles).

Fabrication of Controllable Pore and Particle Size of Mesoporous Silica Nanoparticles via a Liquid-phase Synthesis Method and Its Absorption Characteristics

NASA Astrophysics Data System (ADS)

Nandiyanto, Asep Bayu Dani; Iskandar, Ferry; Okuyama, Kikuo

2011-12-01

Monodisperse spherical mesoporous silica nanoparticles were successfully synthesized using a liquid-phase synthesis method. The result showed particles with controllable pore size from several to tens nanometers with outer diameter of several tens nanometers. The ability in the control of pore size and outer diameter was altered by adjusting the precursor solution ratios. In addition, we have conducted the adsorption ability of the prepared particles. The result showed that large organic molecules were well-absorbed to the prepared silica porous particles, in which this result was not obtained when using commercial dense silica particle and/or hollow silica particle. With this result, the prepared mesoporous silica particles may be used efficiently in various applications, such as sensors, pharmaceuticals, environmentally sensitive pursuits, etc.

Worm-like mesoporous TiO2 thin films templated using comb copolymer for dye-sensitized solar cells with polymer electrolyte

NASA Astrophysics Data System (ADS)

Lee, Jae Hun; Park, Cheol Hun; Jung, Jung Pyo; Kim, Jong Hak

2015-12-01

A comb copolymer consisting of hydrophobic poly(2-[3-(2H-benzotriazol-2-yl)-4-hydroxyphenyl] ethyl methacrylate) (PBEM) and hydrophilic poly(oxyethylene methacrylate) (POEM) is synthesized via one-pot free radical polymerization. The PBEM-POEM comb copolymer is used as an agent to direct the structure toward one consisting of worm-like mesoporous TiO2 (WM-TiO2) films. The selective, preferential interaction between the titania precursor and the hydrophilic POEM chains is responsible for the formation of a well-organized worm-like mesostructure. The morphology of the WM-TiO2 films is characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). In particular, the effects of film thickness on the optical and electrochemical properties are systematically investigated. The introduction of the WM-TiO2 layer between the nanocrystalline TiO2 (NC-TiO2) layer and fluorine-doped tin oxide (FTO) glass results in increased transmittance of visible light due to an antireflective property, decreased interfacial resistance and suppressed charge recombination at the interfaces of NC-TiO2/FTO glass. As a result, the photovoltaic conversion efficiency of the dye-sensitized solar cell (DSSC) with a polymer electrolyte is improved from 5.3% to 6.6% at an optimum film thickness (310 nm). The obtained efficiency represents a higher efficiency for the N719-based DSSC with a solvent-free, polymer electrolyte.

Multifunctional PEG modified DOX loaded mesoporous silica nanoparticle@CuS nanohybrids as photo-thermal agent and thermal-triggered drug release vehicle for hepatocellular carcinoma treatment

NASA Astrophysics Data System (ADS)

Wu, Lingjie; Wu, Ming; Zeng, Yongyi; Zhang, Da; Zheng, Aixian; Liu, Xiaolong; Liu, Jingfeng

2015-01-01

The combination of a multi-therapeutic mode with a controlled fashion is a key improvement in nanomedicine. Here, we synthesized polyethylene glycol (PEG)-modified doxorubicin (DOX)-loaded mesoporous silica nanoparticle (MSN) @CuS nanohybrids as efficient drug delivery carriers, combined with photothermal therapy and chemotherapy to enhance the therapeutic efficacy on hepatocellular carcinoma (HCC). The physical properties of the nanohybrids were characterized by transmission electron microscopy (TEM), N2 adsorption and desorption experiments and by the Vis-NIR absorption spectra. The results showed that the doxorubicin could be stored in the inner pores of mesoporous silica nanoparticles; the CuS nanoparticles, which are coated on the surface of a mesoporous silica nanoparticle, could serve as efficient photothermal therapy (PTT) agents; the loaded drug release could be easily triggered by NIR irradiation. The combination of the PTT treatment with controlled chemotherapy could further enhance the cancer ablation ability compared to any of the single approaches alone. Hence, the reported PEG-modified DOX-loaded mesoporous silica nanoparticle@CuS nanohybrids might be very promising therapeutic agents for HCC treatment.

Growth of 2D Mesoporous Polyaniline with Controlled Pore Structures on Ultrathin MoS2 Nanosheets by Block Copolymer Self-Assembly in Solution.

PubMed

Tian, Hao; Zhu, Shuyan; Xu, Fugui; Mao, Wenting; Wei, Hao; Mai, Yiyong; Feng, Xinliang

2017-12-20

The development of versatile strategies toward two-dimensional (2D) porous nanocomposites with tunable pore structures draws immense scientific attention in view of their attractive physiochemical properties and a wide range of promising applications. This paper describes a self-assembly approach for the directed growth of mesoporous polyaniline (PANi) with tunable pore structures and sizes on ultrathin freestanding MoS 2 nanosheets in solution, which produces 2D mesoporous PANi/MoS 2 nanocomposites. The strategy employs spherical and cylindrical micelles, which are formed by the controlled solution self-assembly of block copolymers, as the soft templates for the construction of well-defined spherical and cylindrical mesopores in the 2D PANi/MoS 2 nanocomposites, respectively. With potential applications as supercapacitor electrode materials, the resultant 2D composites show excellent capacitive performance with a maximum capacitance of 500 F g -1 at a current density of 0.5 A g -1 , good rate performance, as well as outstanding stability for charge-discharge cycling. Moreover, the 2D mesoporous nanocomposites offer an opportunity for the study on the influence of different pore structures on their capacitive performance, which helps to understand the pore structure-property relationship of 2D porous electrode materials and to achieve their electrochemical performance control.

Recent advances of mesoporous materials in sample preparation.

PubMed

Zhao, Liang; Qin, Hongqiang; Wu, Ren'an; Zou, Hanfa

2012-03-09

Sample preparation has been playing an important role in the analysis of complex samples. Mesoporous materials as the promising adsorbents have gained increasing research interest in sample preparation due to their desirable characteristics of high surface area, large pore volume, tunable mesoporous channels with well defined pore-size distribution, controllable wall composition, as well as modifiable surface properties. The aim of this paper is to review the recent advances of mesoporous materials in sample preparation with emphases on extraction of metal ions, adsorption of organic compounds, size selective enrichment of peptides/proteins, specific capture of post-translational peptides/proteins and enzymatic reactor for protein digestion. Copyright © 2011 Elsevier B.V. All rights reserved.

Controlled release of silyl ether camptothecin from thiol-ene click chemistry-functionalized mesoporous silica nanoparticles.

PubMed

Yan, Yue; Fu, Jie; Wang, Tianfu; Lu, Xiuyang

2017-03-15

As efficient drug carriers, stimuli-responsive mesoporous silica nanoparticles are at the forefront of research on drug delivery systems. An acid-responsive system based on silyl ether has been applied to deliver a hybrid prodrug. Thiol-ene click chemistry has been successfully utilized for tethering this prodrug to mesoporous silica nanoparticles. Here, by altering the steric bulk of the substituent on the silicon atom, the release rate of a model drug, camptothecin, was controlled. The synthesized drug delivery system was investigated by analytical methods to confirm the functionalization and conjugation of the mesoporous silica nanoparticles. Herein, trimethyl silyl ether and triethyl silyl ether were selected to regulate the release rate. Under normal plasma conditions (pH 7.4), both types of camptothecin-loaded mesoporous silica nanoparticles (i.e., MSN-Me-CPT and MSN-Et-CPT) did not release the model drug. However, under in vitro acidic conditions (pH 4.0), based on a comparison of the release rates, camptothecin was released from MSN-Me-CPT more rapidly than from MSN-Et-CPT. To determine the biocompatibility of the modified mesoporous silica nanoparticles and the in vivo camptothecin uptake behavior, MTT assays with cancer cells and confocal microscopy observations were conducted, with positive results. These functionalized nanoparticles could be useful in clinical treatments requiring controlled drug release. As the release rate of drug from drug-carrier plays important role in therapy effects, trimethyl silyl ether (TMS) and triethyl silyl ether (TES) were selected as acid-sensitive silanes to control the release rates of model drugs conjugated from MSNs by thiol-ene click chemistry. The kinetic profiles of TMS and TES materials have been studied. At pH 4.0, the release of camptothecin from MSN-Et-CPT occurred after 2h, whereas MSN-Me-CPT showed immediate drug release. The results showed that silyl ether could be used to control release rates of drugs from MSNs under acid environment, which could be useful in clinical treatments requiring controlled drug release. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Formation pathways of mesoporous silica nanoparticles with dodecagonal tiling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun, Yao; Ma, Kai; Kao, Teresa

Considerable progress in the fabrication of quasicrystals demonstrates that they can be realized in a broad range of materials. However, the development of chemistries enabling direct experimental observation of early quasicrystal growth pathways remains challenging. Here, we report the synthesis of four surfactant-directed mesoporous silica nanoparticle structures, including dodecagonal quasicrystalline nanoparticles, as a function of micelle pore expander concentration or stirring rate. We demonstrate that the early formation stages of dodecagonal quasicrystalline mesoporous silica nanoparticles can be preserved, where precise control of mesoporous silica nanoparticle size down to <30 nm facilitates comparison between mesoporous silica nanoparticles and simulated single-particle growthmore » trajectories beginning with a single tiling unit. Our results reveal details of the building block size distributions during early growth and how they promote quasicrystal formation. This work identifies simple synthetic parameters, such as stirring rate, that may be exploited to design other quasicrystal-forming self-assembly chemistries and processes.« less

Formation pathways of mesoporous silica nanoparticles with dodecagonal tiling

DOE PAGES

Sun, Yao; Ma, Kai; Kao, Teresa; ...

2017-08-15

Considerable progress in the fabrication of quasicrystals demonstrates that they can be realized in a broad range of materials. However, the development of chemistries enabling direct experimental observation of early quasicrystal growth pathways remains challenging. Here, we report the synthesis of four surfactant-directed mesoporous silica nanoparticle structures, including dodecagonal quasicrystalline nanoparticles, as a function of micelle pore expander concentration or stirring rate. We demonstrate that the early formation stages of dodecagonal quasicrystalline mesoporous silica nanoparticles can be preserved, where precise control of mesoporous silica nanoparticle size down to <30 nm facilitates comparison between mesoporous silica nanoparticles and simulated single-particle growthmore » trajectories beginning with a single tiling unit. Our results reveal details of the building block size distributions during early growth and how they promote quasicrystal formation. This work identifies simple synthetic parameters, such as stirring rate, that may be exploited to design other quasicrystal-forming self-assembly chemistries and processes.« less

Shaped platinum nanoparticles directly synthesized inside mesoporous silica supports

NASA Astrophysics Data System (ADS)

Kim, Jiwhan; Bae, Youn-Sang; Lee, Hyunjoo

2014-10-01

It is difficult to deposit shape-controlled nanoparticles into a mesoporous framework while preserving the shape. For shaped platinum nanoparticles, which are typically 5-10 nm in size, capillary inclusion by sonication or the formation of a mesoporous framework around the shaped platinum nanoparticles has been attempted, but the nanoparticles aggregated or their shapes were degraded easily. In this work, we directly nucleated platinum on the surface inside a mesoporous silica support and controlled the overgrowth step, producing cubic shaped nanoparticles. Mercaptopropyltrimethoxysilane was used as an anchoring agent causing nucleation at the silica surface, and it also helped to shape the nanoparticles. Platinum nanocubes, which were synthesized with polymeric capping agents separately, were deposited inside the mesoporous silica by sonication, but most of the nanoparticles were clogged at the entrance to the pores, and the surface of the platinum had very few sites that were catalytically active, as evidenced by the small H2 uptake. Unshaped platinum nanoparticles, which were prepared by conventional wet impregnation, showed a similar amount of H2 uptake as the in situ shaped platinum cubes, but the selectivity for pyrrole hydrogenation was poorer towards the production of pyrrolidine. The mesoporosity and the residual thiol groups on the surface of the in situ shaped Pt nanocubes might cause a high selectivity for pyrrolidine.It is difficult to deposit shape-controlled nanoparticles into a mesoporous framework while preserving the shape. For shaped platinum nanoparticles, which are typically 5-10 nm in size, capillary inclusion by sonication or the formation of a mesoporous framework around the shaped platinum nanoparticles has been attempted, but the nanoparticles aggregated or their shapes were degraded easily. In this work, we directly nucleated platinum on the surface inside a mesoporous silica support and controlled the overgrowth step, producing cubic shaped nanoparticles. Mercaptopropyltrimethoxysilane was used as an anchoring agent causing nucleation at the silica surface, and it also helped to shape the nanoparticles. Platinum nanocubes, which were synthesized with polymeric capping agents separately, were deposited inside the mesoporous silica by sonication, but most of the nanoparticles were clogged at the entrance to the pores, and the surface of the platinum had very few sites that were catalytically active, as evidenced by the small H2 uptake. Unshaped platinum nanoparticles, which were prepared by conventional wet impregnation, showed a similar amount of H2 uptake as the in situ shaped platinum cubes, but the selectivity for pyrrole hydrogenation was poorer towards the production of pyrrolidine. The mesoporosity and the residual thiol groups on the surface of the in situ shaped Pt nanocubes might cause a high selectivity for pyrrolidine. Electronic supplementary information (ESI) available: Fig. S1-S9. See DOI: 10.1039/c4nr03951c

Controllable self-assembly of mesoporous hydroxyapatite.

PubMed

Chen, Jingdi; Wang, Zihao; Wen, Zhenliang; Yang, Shen; Wang, Jianhua; Zhang, Qiqing

2015-03-01

In this paper, mesoporous hydroxyapatite (HAp) of controllable pore size was tailored with the template of a biodegradable mono-alkyl phosphate (MAP) via a simple route by hydrothermal treatment. A serial study of the various experimental parameters on pore size of HAp was investigated. The additive amount of MAP and hydrothermal temperature were important factors for the pore structure and pore size. Powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and nitrogen adsorption-desorption (BET, BJH) were used to characterize the structure and composition of the HAp samples. Both XRD and BJH results indicated that regular mesoporous HAp nanoparticles (with a mean pore size of 3.5nm) were successfully produced. As shown in transmission electron microscopy (TEM), orderly uniform pore structure appeared in the HAp particles. Because of the special structure of the MAP and the interaction between ionized MAP and other ions in solution, the product presents uniform mesoporous structure with well-defined pore size. Copyright © 2015 Elsevier B.V. All rights reserved.

A Review of Recent Developments of Mesoporous Materials.

PubMed

Suib, Steven L

2017-12-01

This personal account concerns novel recent discoveries in the area of mesoporous materials. Most of the papers discussed have been published within the last two to three years. A major emphasis of most of these papers is the synthesis of unique mesoporous materials by a variety of synthetic methods. Many of these articles focus on the control of the pore sizes and shapes of mesoporous materials. Synthetic methods of various types have been used for such control of porosity including soft templating, hard templating, nano-casting, electrochemical methods, surface functionalization, and trapping of species in pores. The types of mesoporous materials range from carbon materials, metal oxides, metal sulfides, metal nitrides, carbonitriles, metal organic frameworks (MOFs), and composite materials. The vast majority of recent publications have centered around biological applications with a majority dealing with drug delivery systems. Several other bio-based articles on mesoporous systems concern biomass conversion and biofuels, magnetic resonance imaging (MRI) studies, ultrasound therapy, enzyme immobilization, antigen targeting, biodegradation of inorganic materials, applications for improved digestion, and antitumor activity. Numerous nonbiological applications of mesoporous materials have been pursued recently. Some specific examples are photocatalysis, photo-electrocatalysis, lithium ion batteries, heterogeneous catalysis, extraction of metals, extraction of lanthanide and actinide species, chiral separations and catalysis, capturing and the mode of binding of carbon dioxide (CO 2 ), optical devices, and magneto-optical devices. Of this latter class of applications, heterogeneous catalysis is predominant. Some of the types of catalytic reactions being pursued include hydrogen generation, selective oxidations, aminolysis, Suzuki coupling and other coupling reactions, oxygen reduction reactions (ORR), oxygen evolution reactions (OER), and bifunctional catalysis. For perspective, there have been over 40,000 articles on mesoporous materials published in the last 4 years and about 1388 reviews. By no means is this personal account thorough or all inclusive. One objective has been to choose a variety of articles of different types to obtain a flavor of the breadth of diversity involved in the area of mesoporous materials. © 2017 The Chemical Society of Japan & Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Controlling drug delivery kinetics from mesoporous titania thin films by pore size and surface energy.

PubMed

Karlsson, Johan; Atefyekta, Saba; Andersson, Martin

2015-01-01

The osseointegration capacity of bone-anchoring implants can be improved by the use of drugs that are administrated by an inbuilt drug delivery system. However, to attain superior control of drug delivery and to have the ability to administer drugs of varying size, including proteins, further material development of drug carriers is needed. Mesoporous materials have shown great potential in drug delivery applications to provide and maintain a drug concentration within the therapeutic window for the desired period of time. Moreover, drug delivery from coatings consisting of mesoporous titania has shown to be promising to improve healing of bone-anchoring implants. Here we report on how the delivery of an osteoporosis drug, alendronate, can be controlled by altering pore size and surface energy of mesoporous titania thin films. The pore size was varied from 3.4 nm to 7.2 nm by the use of different structure-directing templates and addition of a swelling agent. The surface energy was also altered by grafting dimethylsilane to the pore walls. The drug uptake and release profiles were monitored in situ using quartz crystal microbalance with dissipation (QCM-D) and it was shown that both pore size and surface energy had a profound effect on both the adsorption and release kinetics of alendronate. The QCM-D data provided evidence that the drug delivery from mesoporous titania films is controlled by a binding-diffusion mechanism. The yielded knowledge of release kinetics is crucial in order to improve the in vivo tissue response associated to therapeutic treatments.

Hollow-structured mesoporous materials: chemical synthesis, functionalization and applications.

PubMed

Li, Yongsheng; Shi, Jianlin

2014-05-28

Hollow-structured mesoporous materials (HMMs), as a kind of mesoporous material with unique morphology, have been of great interest in the past decade because of the subtle combination of the hollow architecture with the mesoporous nanostructure. Benefitting from the merits of low density, large void space, large specific surface area, and, especially, the good biocompatibility, HMMs present promising application prospects in various fields, such as adsorption and storage, confined catalysis when catalytically active species are incorporated in the core and/or shell, controlled drug release, targeted drug delivery, and simultaneous diagnosis and therapy of cancers when the surface and/or core of the HMMs are functionalized with functional ligands and/or nanoparticles, and so on. In this review, recent progress in the design, synthesis, functionalization, and applications of hollow mesoporous materials are discussed. Two main synthetic strategies, soft-templating and hard-templating routes, are broadly sorted and described in detail. Progress in the main application aspects of HMMs, such as adsorption and storage, catalysis, and biomedicine, are also discussed in detail in this article, in terms of the unique features of the combined large void space in the core and the mesoporous network in the shell. Functionalization of the core and pore/outer surfaces with functional organic groups and/or nanoparticles, and their performance, are summarized in this article. Finally, an outlook of their prospects and challenges in terms of their controlled synthesis and scaled application is presented. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Scalable synthesis of mesoporous titania microspheres via spray-drying method.

PubMed

Pal, Manas; Wan, Li; Zhu, Yongheng; Liu, Yupu; Liu, Yang; Gao, Wenjun; Li, Yuhui; Zheng, Gengfeng; Elzatahry, Ahmed A; Alghamdi, Abdulaziz; Deng, Yonghui; Zhao, Dongyuan

2016-10-01

Mesoporous TiO2 has several potential applications due to its unique electronic and optical properties, although its structures and morphologies are typically difficult to tune because of its uncontrollable and fast sol-gel reaction. In this study we have coupled the template-directed-sol-gel-chemistry with the low-cost, scalable, and environmentally benign aerosol (spray-drying) one-pot preparation technique for the fabrication of hierarchically mesoporous TiO2 microspheres and Fe3O4@mesoporous TiO2-x microspheres in a large scale. Parameters during the pre-hydrolysis and spray-drying treatment were varied to successfully control the bead diameter, morphology, monodispersity, surface area and pore size for improving their effectiveness for better application. Unlike to the previous aerosol synthetic approaches, where mainly quite a high temperature gradient with the strict control of spray-drying precursor concentration is implied, our strategy is lying on comparatively low drying temperature with an additional post-ultrasonication (further hydrolysis and condensation) route of the pre-calcined TiO2 samples. As-synthesized mesoporous microspheres have a size distribution from 500nm to 5μm, specific surface areas ranging from 150 to 162m(2)g(-1) and mean pore sizes of several nanometers (4-6nm). Further Fe3O4@mesoporous TiO2-x microspheres were observed to show remarkable selective phosphopeptide-enrichment activity which might have significant importance in disease diagnosis and other biomedical applications. Copyright © 2016. Published by Elsevier Inc.

Mesoporous bioactive glass nanolayer-functionalized 3D-printed scaffolds for accelerating osteogenesis and angiogenesis

NASA Astrophysics Data System (ADS)

Zhang, Yali; Xia, Lunguo; Zhai, Dong; Shi, Mengchao; Luo, Yongxiang; Feng, Chun; Fang, Bing; Yin, Jingbo; Chang, Jiang; Wu, Chengtie

2015-11-01

The hierarchical microstructure, surface and interface of biomaterials are important factors influencing their bioactivity. Porous bioceramic scaffolds have been widely used for bone tissue engineering by optimizing their chemical composition and large-pore structure. However, the surface and interface of struts in bioceramic scaffolds are often ignored. The aim of this study is to incorporate hierarchical pores and bioactive components into the bioceramic scaffolds by constructing nanopores and bioactive elements on the struts of scaffolds and further improve their bone-forming activity. Mesoporous bioactive glass (MBG) modified β-tricalcium phosphate (MBG-β-TCP) scaffolds with a hierarchical pore structure and a functional strut surface (~100 nm of MBG nanolayer) were successfully prepared via 3D printing and spin coating. The compressive strength and apatite-mineralization ability of MBG-β-TCP scaffolds were significantly enhanced as compared to β-TCP scaffolds without the MBG nanolayer. The attachment, viability, alkaline phosphatase (ALP) activity, osteogenic gene expression (Runx2, BMP2, OPN and Col I) and protein expression (OPN, Col I, VEGF, HIF-1α) of rabbit bone marrow stromal cells (rBMSCs) as well as the attachment, viability and angiogenic gene expression (VEGF and HIF-1α) of human umbilical vein endothelial cells (HUVECs) in MBG-β-TCP scaffolds were significantly upregulated compared with conventional bioactive glass (BG)-modified β-TCP (BG-β-TCP) and pure β-TCP scaffolds. Furthermore, MBG-β-TCP scaffolds significantly enhanced the formation of new bone in vivo as compared to BG-β-TCP and β-TCP scaffolds. The results suggest that application of the MBG nanolayer to modify 3D-printed bioceramic scaffolds offers a new strategy to construct hierarchically porous scaffolds with significantly improved physicochemical and biological properties, such as mechanical properties, osteogenesis, angiogenesis and protein expression for bone tissue engineering applications, in which the incorporation of nanostructures and bioactive components into the scaffold struts synergistically play a key role in the improved bone formation.

Mesoporous nitrogen-doped carbon-glass ceramic cathodes for solid-state lithium-oxygen batteries.

PubMed

Kichambare, Padmakar; Rodrigues, Stanley; Kumar, Jitendra

2012-01-01

The composite of nitrogen-doped carbon (N-C) blend with lithium aluminum germanium phosphate (LAGP) was studied as cathode material in a solid-state lithium-oxygen cell. Composite electrodes exhibit high electrochemical activity toward oxygen reduction. Compared to the cell capacity of N-C blend cathode, N-C/LAGP composite cathode exhibits six times higher discharge cell capacity. A significant enhancement in cell capacity is attributed to higher electrocatalytic activity and fast lithium ion conduction ability of LAGP in the cathode. © 2011 American Chemical Society

Mesoporous TiO2 implants for loading high dosage of antibacterial agent

NASA Astrophysics Data System (ADS)

Park, Se Woong; Lee, Donghyun; Choi, Yong Suk; Jeon, Hoon Bong; Lee, Chang-Hoon; Moon, Ji-Hoi; Kwon, Il Keun

2014-06-01

We have fabricated mesoporous thin films composed of TiO2 nanoparticles on anodized titanium implant surfaces for loading drugs at high doses. Surface anodization followed by treatment with TiO2 paste leads to the formation of mechanically stable mesoporous thin films with controllable thickness. A series of antibacterial agents (silver nanoparticles, cephalothin, minocycline, and amoxicillin) were loaded into the mesoporous thin films and their antibacterial activities were evaluated against five bacterial species including three oral pathogens. Additionally, two agents (silver nanoparticles and minocycline) were loaded together on the thin film and tested for antibacterial effectiveness. The combination of silver nanoparticles and minocycline was found to display a wide range of effectiveness against all tested bacteria.

Mesoporous Aluminosilicates as a Host and Reactor for Preparation of Ordered Metal Nanowires

NASA Astrophysics Data System (ADS)

Eliseev, A. A.; Napolskii, K. S.; Kolesnik, I. V.; Kolenko, Yu. V.; Lukashin, A. V.; Gornert, P.; Tretyakov, Yu. D.

The creation of functional nanomaterials with the controlled properties is emerging as a new area of great technological and scientific interest, in particular, it is a key technology for developing novel high-density data storage devices. Today, no other technology can compete with magnetic carriers in information storage density and access rate. However, usually very small (10-1000 nm3) magnetic nanoparticles shows para- or superparamagnetic properties, with very low blocking temperatures and no coercitivity at normal conditions. One possible solution of this problem is preparation of highly anisotropic nanostructures. From the other hand, the use of purely nanocrystalline systems is limited because of their low stability and tendency to form aggregates. These problems could be solved by encapsulation of nanoparticles to a chemically inert matrix. One of the promising matrices for preparation of highly anisotropic magnetic nanoparticles is mesoporous silica or mesoporous aluminosilicates. Mesoporous silica is an amorphous SiO2 with a highly ordered uniform pore structure (the pore diameter can be controllably varied from 2 to 50 nm). This pore system is a perfect reactor for synthesis of nanocomposites due to the limitation of reaction zone by the pore walls. One could expect that size and shape of nanoparticles incorporated into mesoporous silica to be consistent with the dimensions of the porous framework.

Magnetic mesoporous silica nanoparticles for potential delivery of chemotherapeutic drugs and hyperthermia.

PubMed

Tao, Cuilian; Zhu, Yufang

2014-11-07

Magnetic mesoporous silica (MMS) nanoparticles with controllable magnetization have been synthesized by encapsulating Fe3O4 nanoparticles in a mesoporous silica matrix. The structure, magnetic heating capacity and drug delivery ability of MMS nanoparticles were evaluated. The results showed that MMS nanoparticles had an average particle size of 150 nm and showed low cytotoxicity and efficient cell uptake ability. MMS nanoparticles exhibited a sustained drug release in the medium of pH 5.0, but a very slow release in the medium of pH 7.4. On the other hand, MMS nanoparticles could controllably generate heat to reach the hyperthermia temperature within a short time upon exposure to an alternating magnetic field due to the superparamagnetic behavior and controllable magnetization. Therefore, MMS nanoparticles could provide a promising multifunctional platform for the combination of chemotherapy and hyperthermia for cancer therapy.

Micro-/mesoporous carbons for controlled release of antipyrine and indomethacin

DOE PAGES

Saha, Dipendu; Moken, Tara; Chen, Jihua; ...

2015-02-24

Here, we have demonstrated the potential of meso- and microporous carbons in controlled release applications and targeted oral drug delivery. We have employed two mesoporous and two microporous carbons for the sustained release of one water-soluble drug (antipyrine) and one water-insoluble drug (indomethacin), using these as models to examine the controlled release characteristics. The micro-/mesoporous carbons were characterized as having a BET surface area of 372–2251 m 2 g –1 and pore volume 0.63–1.03 cm 3 g –1. The toxicity studies with E. coli bacterial cells did not reveal significant toxicity, which is in accordance with our previous studies onmore » human cells with similar materials. Mucin adsorption tests with type III pork mucin demonstrated 20–30% mucin adsorption by the carbon samples and higher mucin adsorption could be attributed to higher surface area and more oxygen functionalities. Antipyrine and indomethacin loading was 6–78% in these micro-/mesoporous carbons. The signatures in thermogravimetric studies revealed the presence of drug molecules within the porous moieties of the carbon. The partial shifting of the decomposition peak of the drug adsorbed within the carbon pores was caused by the confinement of drug molecules within the narrow pore space of the carbon. The release profiles of both drugs were examined in simulated gastric fluid (pH = 1.2) and in three other release media with respective pH values of 4.5, 6.8 and 7.4, along with varying residence times to simulate the physiological conditions of the stomach, duodenum, small intestine and colon, respectively. All the release profiles manifested diffusion controlled sustained release that corroborates the effective role of micro-/mesoporous carbons as potential drug carriers.« less

Micro-/mesoporous carbons for controlled release of antipyrine and indomethacin

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saha, Dipendu; Moken, Tara; Chen, Jihua

Here, we have demonstrated the potential of meso- and microporous carbons in controlled release applications and targeted oral drug delivery. We have employed two mesoporous and two microporous carbons for the sustained release of one water-soluble drug (antipyrine) and one water-insoluble drug (indomethacin), using these as models to examine the controlled release characteristics. The micro-/mesoporous carbons were characterized as having a BET surface area of 372–2251 m 2 g –1 and pore volume 0.63–1.03 cm 3 g –1. The toxicity studies with E. coli bacterial cells did not reveal significant toxicity, which is in accordance with our previous studies onmore » human cells with similar materials. Mucin adsorption tests with type III pork mucin demonstrated 20–30% mucin adsorption by the carbon samples and higher mucin adsorption could be attributed to higher surface area and more oxygen functionalities. Antipyrine and indomethacin loading was 6–78% in these micro-/mesoporous carbons. The signatures in thermogravimetric studies revealed the presence of drug molecules within the porous moieties of the carbon. The partial shifting of the decomposition peak of the drug adsorbed within the carbon pores was caused by the confinement of drug molecules within the narrow pore space of the carbon. The release profiles of both drugs were examined in simulated gastric fluid (pH = 1.2) and in three other release media with respective pH values of 4.5, 6.8 and 7.4, along with varying residence times to simulate the physiological conditions of the stomach, duodenum, small intestine and colon, respectively. All the release profiles manifested diffusion controlled sustained release that corroborates the effective role of micro-/mesoporous carbons as potential drug carriers.« less

A Mesopore-Dependent Catalytic Cracking of n-Hexane Over Mesoporous Nanostructured ZSM-5.

PubMed

Qamar, M; Ahmed, M I; Qamaruddin, M; Asif, M; Sanhoob, M; Muraza, O; Khan, M Y

2018-08-01

Herein, pore size, crystalinity, and Si/Al ratio of mesoporous ZSM-5 (MFI) nanocrystals was controlled by synthesis parameters, such as surfactant concentration ([3-(trimethoxysilyl)propyl] hexa-decyl dimethyl ammonium chloride), sodium hydroxide concentrations, synthesis temperature and time. The morphology, surface structure and composition of the MFI particles was systematically investigated. More notably, the mesopore-dependent catalytic activity of ZSM-5 was evaluated by studying the cracking of n-hexane. The findings suggest the porosity has pronounced impact on the catalytic activity, selectivity and stability of ZSM-5 nanocrystals. Critical surface attributes such as nature of acid sites (Brønsted and Lewis), concentration, and strength are obtained by the infrared study of adsorbed probe molecules (pyridine) and the temperature programmed desorption. In spite of being weaker in Si/Al ratio or acidic strength, mesoporous catalysts showed more stable and efficient cracking of n-hexane suggesting that acidity seems not the predominant factor operative in the activity, selectivity and stability.

Controllable synthesis of mesoporous Co{sub 3}O{sub 4} nanoflake array and its application for supercapacitor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xiao, Anguo, E-mail: hixiaoanguo@126.com; Zhou, Shibiao; Zuo, Chenggang

Graphical abstract: Electrodeposited mesoporous Co{sub 3}O{sub 4} nanoflake arrays exhibit porous structure composed of mesoporous nanoflakes and high supercapacitor performance. - Highlights: • Mesoporous Co{sub 3}O{sub 4} nanoflake arrays are prepared via electrodeposition method. • Mesoporous nanowall arrays are favorable for fast ion/electron transfer. • Mesoporous Co{sub 3}O{sub 4} nanoflake arrays show excellent supercapacitor performance. - Abstract: A mesoporous Co{sub 3}O{sub 4} nanoflake array grown on carbon cloth is prepared by a facile electrodeposition method with a following annealing process. The as-prepared Co{sub 3}O{sub 4} nanoflake possesses a continuous mesopores ranging from 2 to 5 nm and grows tightly onmore » the substrate forming a porous net-like structure with macropores of 20–200 nm. The electrochemical performance of the mesoporous Co{sub 3}O{sub 4} nanoflake arrays as pseudocapcitor electrode are investigated by cyclic voltammograms and galvanostatic charge/discharge tests in 2 M KOH. The as-prepared Co{sub 3}O{sub 4} array exhibits a high discharge capacitance and excellent rate capability with 450 F g{sup −1}, 436 F g{sup −1}, 408 F g{sup −1}, 380 F g{sup −1}and 363 F g{sup −1} at 1, 2, 4, 10, and 20 A g{sup −1}, respectively. The specific capacitance of 81% is maintained from 1 A g{sup −1} to 20 A g{sup −1}. The electrode also shows rather good cycling stability and exhibits a specific capacitance of 414 F g{sup −1} after 5000 cycles.« less

Mesoporous Silica Chips for Selective Enrichment and Stabilization of Low Molecular Weight Proteome

PubMed Central

Bouamrani, Ali; Hu, Ye; Tasciotti, Ennio; Li, Li; Chiappini, Ciro; Liu, Xuewu; Ferrari, Mauro

2010-01-01

The advanced properties of mesoporous silica have been demonstrated in applications which include chemical sensing, filtration, catalysis, drug-delivery and selective biomolecular uptake. These properties depend on the architectural, physical and chemical properties of the material, which in turn are determined by the processing parameters in evaporation-induced self-assembly. In this study, we introduce a combinatorial approach for the removal of the high molecular weight proteins and for the specific isolation and enrichment of low molecular weight species. This approach is based on Mesoporous Silica Chips able to fractionate, selectively harvest and protect from enzymatic degradation, peptides and proteins present in complex human biological fluids. We present the characterization of the harvesting properties of a wide range of mesoporous chips using a library of peptides and proteins standard and their selectivity on the recovery of serum peptidome. Using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry, we established the correlation between the harvesting specificity and the physico-chemical properties of mesoporous silica surfaces. The introduction of this mesoporous material with fine controlled properties will provide a powerful platform for proteomics application offering a rapid and efficient methodology for low molecular weight biomarker discovery. PMID:20013801

Mesoporous silica chips for selective enrichment and stabilization of low molecular weight proteome.

PubMed

Bouamrani, Ali; Hu, Ye; Tasciotti, Ennio; Li, Li; Chiappini, Ciro; Liu, Xuewu; Ferrari, Mauro

2010-02-01

The advanced properties of mesoporous silica have been demonstrated in applications, which include chemical sensing, filtration, catalysis, drug delivery and selective biomolecular uptake. These properties depend on the architectural, physical and chemical properties of the material, which in turn are determined by the processing parameters in evaporation-induced self-assembly. In this study, we introduce a combinatorial approach for the removal of the high molecular weight proteins and for the specific isolation and enrichment of low molecular weight species. This approach is based on mesoporous silica chips able to fractionate, selectively harvest and protect from enzymatic degradation, peptides and proteins present in complex human biological fluids. We present the characterization of the harvesting properties of a wide range of mesoporous chips using a library of peptides and proteins standard and their selectivity on the recovery of serum peptidome. Using MALDI-TOF-MS, we established the correlation between the harvesting specificity and the physicochemical properties of mesoporous silica surfaces. The introduction of this mesoporous material with fine controlled properties will provide a powerful platform for proteomics application offering a rapid and efficient methodology for low molecular weight biomarker discovery.

Microfluidic immunosensor based on mesoporous silica platform and CMK-3/poly-acrylamide-co-methacrylate of dihydrolipoic acid modified gold electrode for cancer biomarker detection.

PubMed

Regiart, Matías; Fernández-Baldo, Martin A; Villarroel-Rocha, Jhonny; Messina, Germán A; Bertolino, Franco A; Sapag, Karim; Timperman, Aaron T; Raba, Julio

2017-04-22

We report a hybrid glass-poly (dimethylsiloxane) microfluidic immunosensor for epidermal growth factor receptor (EGFR) determination, based on the covalent immobilization of anti-EGFR antibody (anti-EGFR) on amino-functionalized mesoporous silica (AMS) retained in the central channel of a microfluidic device. The synthetized AMS was characterized by N 2 adsorption-desorption isotherm, scanning electron microscopy (SEM), energy dispersive spectrometry (EDS) and infrared spectroscopy. The cancer biomarker was quantified in human serum samples by a direct sandwich immunoassay measuring through a horseradish peroxidase-conjugated anti-EGFR. The enzymatic product was detected at -100 mV by amperometry on a sputtering gold electrode, modified with an ordered mesoporous carbon (CMK-3) in a matrix of poly-acrylamide-co-methacrylate of dihydrolipoic acid (poly(AC-co-MDHLA)) through in situ copolymerization. CMK-3/poly(AC-co-MDHLA)/gold was characterized by cyclic voltammetry, EDS and SEM. The measured current was directly proportional to the level of EGFR in human serum samples. The linear range was from 0.01 ng mL -1 to 50 ng mL -1 . The detection limit was 3.03 pg mL -1 , and the within- and between-assay coefficients of variation were below 5.20%. The microfluidic immunosensor is a very promising device for the diagnosis of several kinds of epithelial origin carcinomas. Copyright © 2017. Published by Elsevier B.V.

Hierarchical Mesoporous Organosilica-Silica Core-Shell Nanoparticles Capable of Controlled Fungicide Release.

PubMed

Luo, Leilei; Liang, Yucang; Erichsen, Egil Severin; Anwander, Reiner

2018-05-17

A new class of hierarchically structured mesoporous silica core-shell nanoparticles (HSMSCSNs) with a periodic mesoporous organosilica (PMO) core and a mesoporous silica (MS) shell is reported. The applied one-pot, two-step strategy allows rational control over the core/shell chemical composition, topology, and pore/particle size, simply by adjusting the reaction conditions in the presence of cetyltrimethylammonium bromide (CTAB) as structure-directing agent under basic conditions. The spherical, ethylene- or methylene-bridged PMO cores feature hexagonal (p6mm) or cage-like cubic symmetry (Pm3‾ n) depending on the organosilica precursor. The hexagonal MS shell was obtained by n-hexane-induced controlled hydrolysis of TEOS followed by directional co-assembly/condensation of silicate/CTAB composites at the PMO cores. The HSMSCSNs feature a hierarchical pore structure with pore diameters of about 2.7 and 5.6 nm in the core and shell domains, respectively. The core sizes and shell thicknesses are adjustable in the ranges of 90-275 and 15-50 nm, respectively, and the surface areas (max. 1300 m 2  g -1 ) and pore volumes (max. 1.83 cm 3  g -1 ) are among the highest reported for core-shell nanoparticles. The adsorption and controlled release of the fungicide propiconazole by the HSMSCSNs showed a three-stage release profile. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A novel organophosphorus hydrolase-based biosensor using mesoporous carbons and carbon black for the detection of organophosphate nerve agents.

PubMed

Lee, Joon Hwan; Park, Jae Yeon; Min, Kyoungseon; Cha, Hyung Joon; Choi, Suk Soon; Yoo, Young Je

2010-03-15

To detect organophosphate chemicals, which are used both as pesticides and as nerve agents, a novel biosensor based on organophosphorus hydrolase was developed. By using mesoporous carbon (MC) and carbon black (CB) as an anodic layer, the sensitivity of the sensor to p-nitrophenol (PNP), which is the product of the organophosphorus hydrolase reaction, was greatly improved. The MC/CB/glass carbon (GC) layer exhibited an enhanced amperometric response relative to a carbon nanotube (CNT)-modified electrode because it promoted electron transfer of enzymatically generated phenolic compounds (p-nitrophenol). The well-ordered nanopores, many edge-plane-like defective sites (EDSs), and high surface area of the MC resulted in increased sensitivity, and allowed for nanomolar-range detection of the analyte paraoxon. Thus, MCs are suitable for use in real-time biosensors. Under the optimized experimental conditions, the biosensor had a detection limit of 0.12 microM (36 ppb) and a sensitivity of 198 nA/microM for paraoxon. (c) 2009 Elsevier B.V. All rights reserved.

Mesoporous Nickel Oxide (NiO) Nanopetals for Ultrasensitive Glucose Sensing

NASA Astrophysics Data System (ADS)

Mishra, Suryakant; Yogi, Priyanka; Sagdeo, P. R.; Kumar, Rajesh

2018-01-01

Glucose sensing properties of mesoporous well-aligned, dense nickel oxide (NiO) nanostructures (NSs) in nanopetals (NPs) shape grown hydrothermally on the FTO-coated glass substrate has been demonstrated. The structural study based investigations of NiO-NPs has been carried out by X-ray diffraction (XRD), electron and atomic force microscopies, energy dispersive X-ray (EDX), and X-ray photospectroscopy (XPS). Brunauer-Emmett-Teller (BET) measurements, employed for surface analysis, suggest NiO's suitability for surface activity based glucose sensing applications. The glucose sensor, which immobilized glucose on NiO-NPs@FTO electrode, shows detection of wide range of glucose concentrations with good linearity and high sensitivity of 3.9 μA/μM/cm2 at 0.5 V operating potential. Detection limit of as low as 1 μΜ and a fast response time of less than 1 s was observed. The glucose sensor electrode possesses good anti-interference ability, stability, repeatability & reproducibility and shows inert behavior toward ascorbic acid (AA), uric acid (UA) and dopamine acid (DA) making it a perfect non-enzymatic glucose sensor.

Tetracycline-Containing MCM-41 Mesoporous Silica Nanoparticles for the Treatment of Escherichia coli.

PubMed

Koneru, Bhuvaneswari; Shi, Yi; Wang, Yu-Chieh; Chavala, Sai H; Miller, Michael L; Holbert, Brittany; Conson, Maricar; Ni, Aiguo; Di Pasqua, Anthony J

2015-10-30

Tetracycline (TC) is a well-known broad spectrum antibiotic, which is effective against many Gram positive and Gram negative bacteria. Controlled release nanoparticle formulations of TC have been reported, and could be beneficial for application in the treatment of periodontitis and dental bone infections. Furthermore, TC-controlled transcriptional regulation systems (Tet-on and Tet-off) are useful for controlling transgene expression in vitro and in vivo for biomedical research purposes; controlled TC release systems could be useful here, as well. Mesoporous silica nanomaterials (MSNs) are widely studied for drug delivery applications; Mobile crystalline material 41 (MCM-41), a type of MSN, has a mesoporous structure with pores forming channels in a hexagonal fashion. We prepared 41 ± 4 and 406 ± 55 nm MCM-41 mesoporous silica nanoparticles and loaded TC for controlled dug release; TC content in the TC-MCM-41 nanoparticles was 18.7% and 17.7% w/w, respectively. Release of TC from TC-MCM-41 nanoparticles was then measured in phosphate-buffered saline (PBS), pH 7.2, at 37 °C over a period of 5 h. Most antibiotic was released from both over this observation period; however, the majority of TC was released over the first hour. Efficacy of the TC-MCM-41 nanoparticles was then shown to be superior to free TC against Escherichia coli (E. coli) in culture over a 24 h period, while blank nanoparticles had no effect.

Kinetically Controlled Synthesis of Pt-Based One-Dimensional Hierarchically Porous Nanostructures with Large Mesopores as Highly Efficient ORR Catalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fu, Shaofang; Zhu, Chengzhou; Song, Junhua

2016-12-28

Rational design and construction of Pt-based porous nanostructures with large mesopores have triggered significant considerations because of their high surface area and more efficient mass transport. Hydrochloric acid-induced kinetic reduction of metal precursors in the presence of soft template F-127 and hard template tellurium nanowires has been successfully demonstrated to construct one-dimensional hierarchical porous PtCu alloy nanostructures with large mesopores. Moreover, the electrochemical experiments demonstrated that the resultant PtCu hierarchically porous nanostructures with optimized composition exhibit enhanced electrocatalytic performance for oxygen reduction reaction.

Orientation specific deposition of mesoporous particles

NASA Astrophysics Data System (ADS)

Kjellman, Tomas; Bodén, Niklas; Wennerström, Hâkan; Edler, Karen J.; Alfredsson, Viveka

2014-11-01

We present a protocol for a facile orientation specific deposition of plate-like mesoporous SBA-15 silica particles onto a surface (mesopores oriented normal to surface). A drop of an aqueous dispersion of particles is placed on the surface and water vaporizes under controlled relative humidity. Three requirements are essential for uniform coverage: particle dispersion should not contain aggregates, a weak attraction between particles and surface is needed, and evaporation rate should be low. Aggregates are removed by stirring/sonication. Weak attraction is realized by introducing cationic groups to the surface. Insight into the mechanisms of the so-called coffee stain effect is also provided.

Template-Free Mesoporous Electrochromic Films on Flexible Substrates from Tungsten Oxide Nanorods

DOE PAGES

Heo, Sungyeon; Kim, Jongwook; Ong, Gary K.; ...

2017-08-08

Low-temperature processed mesoporous nanocrystal thin films are platforms for fabricating functional composite thin films on flexible substrates. Using a random arrangement of anisotropic nanocrystals can be a facile solution to generate pores without templates. However, the tendency for anisotropic particles to spontaneously assemble into a compact structure must be overcome. Here in this paper, we present a method to achieve random networking of nanorods during solution phase deposition by switching their ligand-stabilized colloidal nature into a charge-stabilized nature by a ligand-stripping chemistry. Ligand-stripped tungsten suboxide (WO 2.72) nanorods result in uniform mesoporous thin films owing to repulsive electrostatic forces preventingmore » nanorods from densely packing. Porosity and pore size distribution of thin films are controlled by changing the aspect ratio of the nanorods. This template-free mesoporous structure, achieved without annealing, provides a framework for introducing guest components, therefore enabling our fabrication of inorganic nanocomposite electrochromic films on flexible substrates. Following infilling of niobium polyoxometalate clusters into pores and successive chemical condensation, a WO x–NbO x composite film is produced that selectively controls visible and near-infrared light transmittance without any annealing required. The composite shows rapid switching kinetics and can be stably cycled between optical states over 2000 times. This simple strategy of using anisotropic nanocrystals gives insight into mesoporous thin film fabrication with broader applications for flexible devices.« less

Template-Free Mesoporous Electrochromic Films on Flexible Substrates from Tungsten Oxide Nanorods

DOE Office of Scientific and Technical Information (OSTI.GOV)

Heo, Sungyeon; Kim, Jongwook; Ong, Gary K.

Low-temperature processed mesoporous nanocrystal thin films are platforms for fabricating functional composite thin films on flexible substrates. Using a random arrangement of anisotropic nanocrystals can be a facile solution to generate pores without templates. However, the tendency for anisotropic particles to spontaneously assemble into a compact structure must be overcome. Here in this paper, we present a method to achieve random networking of nanorods during solution phase deposition by switching their ligand-stabilized colloidal nature into a charge-stabilized nature by a ligand-stripping chemistry. Ligand-stripped tungsten suboxide (WO 2.72) nanorods result in uniform mesoporous thin films owing to repulsive electrostatic forces preventingmore » nanorods from densely packing. Porosity and pore size distribution of thin films are controlled by changing the aspect ratio of the nanorods. This template-free mesoporous structure, achieved without annealing, provides a framework for introducing guest components, therefore enabling our fabrication of inorganic nanocomposite electrochromic films on flexible substrates. Following infilling of niobium polyoxometalate clusters into pores and successive chemical condensation, a WO x–NbO x composite film is produced that selectively controls visible and near-infrared light transmittance without any annealing required. The composite shows rapid switching kinetics and can be stably cycled between optical states over 2000 times. This simple strategy of using anisotropic nanocrystals gives insight into mesoporous thin film fabrication with broader applications for flexible devices.« less

Fabrication of mesoporous silica for ultra-low-k interlayer dielectrics

NASA Astrophysics Data System (ADS)

Fujii, Nobutoshi; Kohmura, Kazuo; Nakayama, Takahiro; Tanaka, Hirofumi; Hata, Nobuhiro; Seino, Yutaka; Kikkawa, Takamaro

2005-11-01

We have developed sol-gel self-assembly techniques to control the pore structure and diameter of ultra-low-k interlayer dielectric (ILD) films. Porous silica films have been fabricated using cationic and nonionic surfactants as templates, resulting in 2D-hexagonal and disordered pore structures, respectively. The disordered mesoporous silica film has a worm-hole like network of pore channels having a uniform diameter. Precursors of the mesoporous silica films were synthesized by use of tetraethyl-orthosilicate (TEOS), inorganic acid, water, ethanol and various surfactants. The surfactants used were cationic alkyltrimethyl-ammonium (ATMA) chloride surfactants for 2D-hexagonal pores and nonionic tri-block copolymer for disordered structures. Dimethyldiethoxysilane (DMDEOS) was added for forming the disordered mesoporous silica. The disordered cylindrical pore structure with a uniform pore size was fabricated by controlling the static electrical interaction between the surfactant and the silica oligomer with methyl group of DMDEOS. Tetramethylcycrotetrasiloxane (TMCTS) vapor treatment was developed, which improved the mechanical strength of mesoporous silica films. The TMCTS polymer covered the pore wall surface and cross-linked to passivate the mechanical defects in the silica wall. Significant enhancement of mechanical strength was demonstrated by TMCTS vapor treatment. The porous silica film modified with a catalyst and a plasma treatment achieved higher mechanical strength and lower dielectric constant than conventional porous silica films because the TMCTS vapor treatment was more effective for mechanical reinforcement and hydrophobicity.

Fabrication of mesoporous polymer monolith: a template-free approach.

PubMed

Okada, Keisuke; Nandi, Mahasweta; Maruyama, Jun; Oka, Tatsuya; Tsujimoto, Takashi; Kondoh, Katsuyoshi; Uyama, Hiroshi

2011-07-14

Mesoporous polyacrylonitrile (PAN) monolith has been fabricated by a template-free approach using the unique affinity of PAN towards a water/dimethyl sulfoxide (DMSO) mixture. A newly developed Thermally Induced Phase Separation Technique (TIPS) has been used to obtain the polymer monoliths and their microstructures have been controlled by optimizing the concentration and cooling temperature.

Micro–mesoporous iron oxides with record efficiency for the decomposition of hydrogen peroxide: morphology driven catalysis for the degradation of organic contaminants

EPA Science Inventory

A template-free solid-state synthesis of a morphologically controlled and highly organized iron(III)oxide micro–mesoporous Fenton catalyst has been engineered through a simple two-step synthetic procedure. The 3D nanoassembly of hematite nanoparticles (5–7 nm) organized into a ro...

Water-assisted crystallization of mesoporous anatase TiO2 nanospheres

NASA Astrophysics Data System (ADS)

Li, Na; Zhang, Qiao; Joo, Ji Bong; Lu, Zhenda; Dahl, Michael; Gan, Yang; Yin, Yadong

2016-04-01

We report a facile water-assisted crystallization process for the conversion of amorphous sol-gel derived TiO2 into mesoporous anatase nanostructures with a high surface area and well-controlled porosity and crystallinity. As an alternative to conventional calcination methods, this approach works under very mild conditions and is therefore much desired for broad biological, environmental and catalytic applications.We report a facile water-assisted crystallization process for the conversion of amorphous sol-gel derived TiO2 into mesoporous anatase nanostructures with a high surface area and well-controlled porosity and crystallinity. As an alternative to conventional calcination methods, this approach works under very mild conditions and is therefore much desired for broad biological, environmental and catalytic applications. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr01892k

Mesoporous silica nanoparticles for stimuli-responsive controlled drug delivery: advances, challenges, and outlook

PubMed Central

Song, Yuanhui; Li, Yihong; Xu, Qien; Liu, Zhe

2017-01-01

With the development of nanotechnology, the application of nanomaterials in the field of drug delivery has attracted much attention in the past decades. Mesoporous silica nanoparticles as promising drug nanocarriers have become a new area of interest in recent years due to their unique properties and capabilities to efficiently entrap cargo molecules. This review describes the latest advances on the application of mesoporous silica nanoparticles in drug delivery. In particular, we focus on the stimuli-responsive controlled release systems that are able to respond to intracellular environmental changes, such as pH, ATP, GSH, enzyme, glucose, and H2O2. Moreover, drug delivery induced by exogenous stimuli including temperature, light, magnetic field, ultrasound, and electricity is also summarized. These advanced technologies demonstrate current challenges, and provide a bright future for precision diagnosis and treatment. PMID:28053526

Mesoporous silica nanoparticles for stimuli-responsive controlled drug delivery: advances, challenges, and outlook.

PubMed

Song, Yuanhui; Li, Yihong; Xu, Qien; Liu, Zhe

With the development of nanotechnology, the application of nanomaterials in the field of drug delivery has attracted much attention in the past decades. Mesoporous silica nanoparticles as promising drug nanocarriers have become a new area of interest in recent years due to their unique properties and capabilities to efficiently entrap cargo molecules. This review describes the latest advances on the application of mesoporous silica nanoparticles in drug delivery. In particular, we focus on the stimuli-responsive controlled release systems that are able to respond to intracellular environmental changes, such as pH, ATP, GSH, enzyme, glucose, and H 2 O 2 . Moreover, drug delivery induced by exogenous stimuli including temperature, light, magnetic field, ultrasound, and electricity is also summarized. These advanced technologies demonstrate current challenges, and provide a bright future for precision diagnosis and treatment.

Mesoporous block-copolymer nanospheres prepared by selective swelling.

PubMed

Mei, Shilin; Jin, Zhaoxia

2013-01-28

Block-copolymer (BCP) nanospheres with hierarchical inner structure are of great interest and importance due to their possible applications in nanotechnology and biomedical engineering. Mesoporous BCP nanospheres with multilayered inner channels are considered as potential drug-delivery systems and templates for multifunctional nanomaterials. Selective swelling is a facile pore-making strategy for BCP materials. Herein, the selective swelling-induced reconstruction of BCP nanospheres is reported. Two poly(styrene-block-2-vinylpyridine) (PS-b-P2VP) samples with different compositions (PS(23600)-b-P2VP(10400) and PS(27700)-b-P2VP(4300)) are used as model systems. The swelling reconstruction of PS-b-P2VP in ethanol, 1-pyrenebutyric acid (PBA)/ethanol, or HCl/ethanol (pH = 2.61) is characterized by scanning electron microscopy and transmission electron microscopy. It is observed that the length of the swellable block in BCP is a critical factor in determining the behavior and nanostructures of mesoporous BCP nanospheres in selective swelling. Moreover, it is demonstrated that the addition of PBA modifies the swelling structure of PS(23600)-b-P2VP(10400) through the interaction between PBA and P2VP blocks, which results in BCP nanospheres with patterned pores of controllable size. The patterned pores can be reversibly closed by annealing the mesoporous BCP nanospheres in different selective solvents. The controllable and reversible open/closed reconstruction of BCP nanospheres can be used to enclose functional nanoparticles or drugs inside the nanospheres. These mesoporous BCP nanospheres are further decorated with gold nanoparticles by UV photoreduction. The enlarged decoration area in mesoporous BCP nanospheres will enhance their activity and sensitivity as a catalyst and electrochemical sensor. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

General and simple approach for control cage and cylindrical mesopores, and thermal/hydrothermal stable frameworks.

PubMed

El-Safty, Sherif A; Mizukami, Fujio; Hanaoka, Takaaki

2005-05-19

Highly ordered cage and cylindrical mesoporeous silica monoliths (HOM) with 2- and 3-dimensional (2D and 3D, respectively) structures, mesopore/micropore volumes, and thick-walled frameworks were successfully fabricated by instant direct templating of lyotropic phases of copolymer (EO(m)-PO(n)-EO(m)) surfactants. Large cage-like pores with uniform constriction sizes up to 10 nm and open cylindrical channel-like mesopores can be easily achieved by this simple and efficient synthesis design. Our results show that the cage-like pores could be fabricated at relatively lower copolymer concentrations used in the lyotropic phase domains at copolymer/TMOS ratios of 35 wt %. These ordered cage pore architectures underwent transition to open-cylindrical pores by increasing the copolymer concentration. High EO/PO block copolymers, in general, were crucially affected on the increase of the interior cavity sizes and on the stability of the cage mesopore characters. However, for F108 (EO(141)PO(44)EO(141)) systems, the fabrication of ordered and stable cage pore monoliths was achieved with significantly higher copolymer concentrations up to 90 wt %. Interestingly, the effective copolymer molecular nature was also observed in the ability to design various ordered mesophase geometries in large domain sizes. Our findings here show evidence that the synthetic strategy provides realistic control over a wide range of mesostructured phase geometries and their extended long-range ordering in the final replicas of the silica monolith frameworks. In addition, the HOM silica monoliths exhibited considerable structural stability against higher thermal temperature (up to 1000 degrees C) and longer hydrothermal treatment times under boiling water and steam. The remarkable structural findings of 3D frameworks, transparent monoliths, and micropores combined with large cage- and cylindrical-like mesopores are expected to find promising uses in materials chemistry.

Potential of hybrid functionalized meso-porous materials for the separation and immobilization of radionuclides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luca, V.

2013-07-01

Functionalized meso-porous materials are a class of hybrid organic-inorganic material in which a meso-porous metal oxide framework is functionalized with multifunctional organic molecules. These molecules may contain one or more anchor groups that form strong bonds to the pore surfaces of the metal oxide framework and free functional groups that can impart and or modify the functionality of the material such as for binding metal ions in solution. Such materials have been extensively studied over the past decade and are of particular interest in absorption applications because of the tremendous versatility in choosing the composition and architecture of the metalmore » oxide framework and the nature of the functional organic molecule as well as the efficient mass transfer that can occur through a well-designed hierarchically porous network. A sorbent for nuclear applications would have to be highly selective for particular radio nuclides, it would need to be hydrolytically and radiolytically stable, and it would have to possess reasonable capacity and fast kinetics. The sorbent would also have to be available in a form suitable for use in a column. Finally, it would also be desirable if once saturated with radio nuclides, the sorbent could be recycled or converted directly into a ceramic or glass waste form suitable for direct repository disposal or even converted directly into a material that could be used as a transmutation target. Such a cradle-to- grave strategy could have many benefits in so far as process efficiency and the generation of secondary wastes are concerned.This paper will provide an overview of work done on all of the above mentioned aspects of the development of functionalized meso-porous adsorbent materials for the selective separation of lanthanides and actinides and discuss the prospects for future implementation of a cradle-to-grave strategy with such materials. (author)« less

The Design, Synthesis, and Study of Solid-State Molecular Rotors: Structure/Function Relationships for Condensed-Phase Anisotropic Dynamics

NASA Astrophysics Data System (ADS)

Vogelsberg, Cortnie Sue

Amphidynamic crystals are an extremely promising platform for the development of artificial molecular machines and stimuli-responsive materials. In analogy to skeletal muscle, their function will rely upon the collective operation of many densely packed molecular machines (i.e. actin-bound myosin) that are self-assembled in a highly organized anisotropic medium. By choosing lattice-forming elements and moving "parts" with specific functionalities, individual molecular machines may be synthesized and self-assembled in order to carry out desirable functions. In recent years, efforts in the design of amphidynamic materials based on molecular gyroscopes and compasses have shown that a certain amount of free volume is essential to facilitate internal rotation and reorientation within a crystal. In order to further establish structure/function relationships to advance the development of increasingly complex molecular machinery, molecular rotors and a molecular "spinning" top were synthesized and incorporated into a variety of solid-state architectures with different degrees of periodicity, dimensionality, and free volume. Specifically, lamellar molecular crystals, hierarchically ordered periodic mesoporous organosilicas, and metal-organic frameworks were targeted for the development of solid-state molecular machines. Using an array of solid-state nuclear magnetic resonance spectroscopy techniques, the dynamic properties of these novel molecular machine assemblies were determined and correlated with their corresponding structural features. It was found that architecture type has a profound influence on functional dynamics. The study of layered molecular crystals, composed of either molecular rotors or "spinning" tops, probed functional dynamics within dense, highly organized environments. From their study, it was discovered that: 1) crystallographically distinct sites may be utilized to differentiate machine function, 2) halogen bonding interactions are sufficiently strong to direct an assembly of molecular machines, 3) the relative flexibility of the crystal environment proximate to a dynamic component may have a significant effect on its function, and, 4) molecular machines, which possess both solid-state photochemical reactivity and dynamics may show complex reaction kinetics if the correlation time of the dynamic process and the lifetime of the excited state occur on the same time scale and the dynamic moiety inherently participates as a reaction intermediate. The study of periodic mesoporous organosilica with hierarchical order probed molecular dynamics within 2D layers of molecular rotors, organized in only one dimension and with ca. 50% exposed to the mesopore free volume. From their study, it was discovered that: 1) molecular rotors, which comprise the layers of the mesopore walls, form a 2D rotational glass, 2) rotator dynamics within the 2D rotational glass undergo a transition to a 2D rotational fluid, and, 3) a 2D rotational glass transition may be exploited to develop hyper-sensitive thermally activated molecular machines. The study of a metal-organic framework assembled from molecular rotors probed dynamics in a periodic three-dimensional free-volume environment, without the presence of close contacts. From the study of this solid-state material, it was determined that: 1) the intrinsic electronic barrier is one of the few factors, which may affect functional dynamics in a true free-volume environment, and, 2) molecular machines with dynamic barriers <

Development of a semigraphitic sulfur-doped ordered mesoporous carbon material for electroanalytical applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maluta, Jaqueline R.; Machado, Sergio A. S.; Chaudhary, Umesh

The modification of traditional electrodes with mesoporous carbons is a promising strategy to produce high performance electrodes for electrochemical sensing. The high surface area of mesoporous carbons provides a large number of electroactive sites for binding analytes. Controlling the pore size and structure of mesoporous carbons and modifying their electronic properties via doping offers additional benefits like maximizing transport and tuning the electrochemical processes associated with analyte detection. This work reports a facile method to produce sulfur-doped ordered mesoporous carbon materials (S-OMC) with uniform pore structure, large pore volume, high surface area and semigraphitic structure. The synthesis used thiophenol asmore » a single source of carbon and sulfur, and iron as a catalyst for low temperature carbonization. The S-OMC material was deposited on a glassy carbon electrode and used as a sensor with high sensitivity (11.7 A L mol-1) and selectivity for chloramphenicol detection in presence of other antibiotics. As a proof-of-concept, the sensor was applied to the direct analysis of the drug in reconstituted powdered milk and in commercial eye drops.« less

Development of a semigraphitic sulfur-doped ordered mesoporous carbon material for electroanalytical applications

DOE PAGES

Maluta, Jaqueline R.; Machado, Sergio A. S.; Chaudhary, Umesh; ...

2017-10-29

The modification of traditional electrodes with mesoporous carbons is a promising strategy to produce high performance electrodes for electrochemical sensing. The high surface area of mesoporous carbons provides a large number of electroactive sites for binding analytes. Controlling the pore size and structure of mesoporous carbons and modifying their electronic properties via doping offers additional benefits like maximizing transport and tuning the electrochemical processes associated with analyte detection. This work reports a facile method to produce sulfur-doped ordered mesoporous carbon materials (S-OMC) with uniform pore structure, large pore volume, high surface area and semigraphitic structure. The synthesis used thiophenol asmore » a single source of carbon and sulfur, and iron as a catalyst for low temperature carbonization. The S-OMC material was deposited on a glassy carbon electrode and used as a sensor with high sensitivity (11.7 A L mol-1) and selectivity for chloramphenicol detection in presence of other antibiotics. As a proof-of-concept, the sensor was applied to the direct analysis of the drug in reconstituted powdered milk and in commercial eye drops.« less

Desilication of ZSM-5 zeolites for mesoporosity development using microwave irradiation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hasan, Zubair; Jun, Jong Won; Kim, Chul-Ung

2015-01-15

Highlights: • Microwaves have beneficial effects on desilication of zeolites. • Produced mesopores with microwaves have narrow pore-size distribution. • Advantages and disadvantages of various desilicating agents were also reported. - Abstract: Mesoporous ZSM-5 zeolite was obtained by desilication in alkaline solutions with microwave (MW) and conventional electric (CE) heating under hydrothermal conditions. Both methods were effective in the production of mesoporous zeolites; however, MW was more efficient than CE as it led to well-defined mesopores with relatively small sizes and a narrow size distribution within a short treatment time. Moreover, the mesoporous ZSM-5 obtained through this method was effectivemore » in producing less bulky products from an acid-catalyzed reaction, specifically the butylation of phenol. Finally, various bases were found to have advantages and disadvantages in desilication. NaOH was the most reactive; however, macroporosity could develop easily under a severe condition. Ammonia water was weakly reactive; however, it could be used to precisely control the pore architecture, and no ion exchange is needed for acid catalysis. Organic amines such as ethylenediamine can also be used in desilication.« less

Synthesis of mesoporous hollow silica nanospheres using polymeric micelles as template and their application as a drug-delivery carrier.

PubMed

Sasidharan, Manickam; Zenibana, Haruna; Nandi, Mahasweta; Bhaumik, Asim; Nakashima, Kenichi

2013-10-07

Mesoporous hollow silica nanospheres with uniform particle sizes of 31-33 nm have been successfully synthesized by cocondensation of tetramethoxysilane (TMOS) and alkyltrimethoxysilanes [RSi(OR)3], where the latter also acts as a porogen. ABC triblock copolymer micelles of poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-PVP-PEO) with a core-shell-corona architecture have been employed as a soft template at pH 4. The cationic shell block with 2-vinyl pyridine groups facilitates the condensation of silica precursors under the sol-gel reaction conditions. Phenyltrimethoxysilane, octyltriethoxysilane, and octadecyltriethoxysilanes were used as porogens for generating mesopores in the shell matrix of hollow silica and the octadecyl precursor produced the largest mesopore among the different porogens, of dimension ca. 4.1 nm. The mesoporous hollow particles were thoroughly characterized by small-angle X-ray diffraction (SXRD), thermal (TG/DTA) and nitrogen sorption analyses, infra-red (FTIR) and nuclear magnetic resonance ((13)C-CP MAS NMR and (29)Si MAS NMR) spectroscopies, and transmission electron microscopy (TEM). The mesoporous hollow silica nanospheres have been investigated for drug-delivery application by an in vitro method using ibuprofen as a model drug. The hollow silica nanospheres exhibited higher storage capacity than the well-known mesoporous silica MCM-41. Propylamine functionalized hollow particles show a more sustained release pattern than their unfunctionalized counterparts, suggesting a huge potential of hollow silica nanospheres in the controlled delivery of small drug molecules.

Recent development, applications, and perspectives of mesoporous silica particles in medicine and biotechnology.

PubMed

Pasqua, Luigi; Cundari, Sante; Ceresa, Cecilia; Cavaletti, Guido

2009-01-01

Mesoporous silica particles (MSP) are a new development in nanotechnology. Covalent modification of the surface of the silica is possible both on the internal pore and on the external particle surface. It allows the design of functional nanostructured materials with properties of organic, biological and inorganic components. Research and development are ongoing on the MSP, which have applications in catalysis, drug delivery and imaging. The most recent and interesting advancements in size, morphology control and surface functionalization of MSP have enhanced the biocompatibility of these materials with high surface areas and pore volumes. In the last 5 years several reports have demonstrated that MSP can be efficiently internalized using in vitro and animal models. The functionalization of MSP with organic moieties or other nanostructures brings controlled release and molecular recognition capabilities to these mesoporous materials for drug/gene delivery and sensing applications, respectively. Herein, we review recent research progress on the design of functional MSP materials with various mechanisms of targeting and controlled release.

Preparation and characterization of glycidyl methacrylate organo bridges grafted mesoporous silica SBA-15 as ibuprofen and mesalamine carrier for controlled release.

PubMed

Rehman, Fozia; Rahim, Abdur; Airoldi, Claudio; Volpe, Pedro L O

2016-02-01

Mesoporous silica SBA-15 was synthesized and functionalized with bridged polysilsesquioxane monomers obtained by the reaction of 3-aminopropyltriethoxy silane with glycidyl methacrylate in 2:1 ratio. The synthesized mesoporous silica materials were characterized by elemental analysis, infrared spectroscopy, nuclear magnetic resonance spectroscopy, nitrogen adsorption, X-ray diffraction, thermogravimetry and scanning electron microscopy. The nuclear magnetic resonance in the solid state is in agreement with the sequence of carbon distributed in the attached organic chains, as expected for organically functionalized mesoporous silica. After functionalization with organic bridges the BET surface area was reduced from 1311.80 to 494.2m(2)g(-1) and pore volume was reduced from 1.98 to 0.89cm(3)g(-1), when compared to original precursor silica. Modification of the silica surface with organic bridges resulted in high loading capacity and controlled release of ibuprofen and mesalamine in biological fluids. The Korsmeyer-Peppas model better fits the release data indicating Fickian diffusion and zero order kinetics for synthesized mesoporous silica. The drug release rate from the modified silica was slow in simulated gastric fluid, (pH1.2) where less than 10% of mesalamine and ibuprofen were released in initial 8h, while comparatively high release rates were observed in simulated intestinal (pH6.8) and simulated body fluids (pH7.2). The preferential release of mesalamine at intestinal pH suggests that the modified silica could be a simple, efficient, inexpensive and convenient carrier for colon targeted drugs, such a mesalamine and also as a controlled drug release system. Copyright © 2015 Elsevier B.V. All rights reserved.

A multifunctional role of trialkylbenzenes for the preparation of aqueous colloidal mesostructured/mesoporous silica nanoparticles with controlled pore size, particle diameter, and morphology

NASA Astrophysics Data System (ADS)

Yamada, Hironori; Ujiie, Hiroto; Urata, Chihiro; Yamamoto, Eisuke; Yamauchi, Yusuke; Kuroda, Kazuyuki

2015-11-01

Both the pore size and particle diameter of aqueous colloidal mesostructured/mesoporous silica nanoparticles (CMSS/CMPS) derived from tetrapropoxysilane were effectively and easily controlled by the addition of trialkylbenzenes (TAB). Aqueous highly dispersed CMPS with large pores were successfully obtained through removal of surfactants and TAB by a dialysis process. The pore size (from 4 nm to 8 nm) and particle diameter (from 50 nm to 380 nm) were more effectively enlarged by the addition of 1,3,5-triisopropylbenzene (TIPB) than 1,3,5-trimethylbenzene (TMB), and the enlargement did not cause the variation of the mesostructure and particle morphology. The larger molecular size and higher hydrophobicity of TIPB than TMB induce the incorporation of TIPB into micelles without the structural change. When TMB was used as TAB, the pore size of CMSS was also enlarged while the mesostructure and particle morphology were varied. Interestingly, when tetramethoxysilane and TIPB were used, CMSS with a very small particle diameter (20 nm) with concave surfaces and large mesopores were obtained, which may strongly be related to the initial nucleation of CMSS. A judicious choice of TAB and Si sources is quite important to control the mesostructure, size of mesopores, particle diameter, and morphology.Both the pore size and particle diameter of aqueous colloidal mesostructured/mesoporous silica nanoparticles (CMSS/CMPS) derived from tetrapropoxysilane were effectively and easily controlled by the addition of trialkylbenzenes (TAB). Aqueous highly dispersed CMPS with large pores were successfully obtained through removal of surfactants and TAB by a dialysis process. The pore size (from 4 nm to 8 nm) and particle diameter (from 50 nm to 380 nm) were more effectively enlarged by the addition of 1,3,5-triisopropylbenzene (TIPB) than 1,3,5-trimethylbenzene (TMB), and the enlargement did not cause the variation of the mesostructure and particle morphology. The larger molecular size and higher hydrophobicity of TIPB than TMB induce the incorporation of TIPB into micelles without the structural change. When TMB was used as TAB, the pore size of CMSS was also enlarged while the mesostructure and particle morphology were varied. Interestingly, when tetramethoxysilane and TIPB were used, CMSS with a very small particle diameter (20 nm) with concave surfaces and large mesopores were obtained, which may strongly be related to the initial nucleation of CMSS. A judicious choice of TAB and Si sources is quite important to control the mesostructure, size of mesopores, particle diameter, and morphology. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr04465k

Synthesis of novel thiol-functionalized mesoporous silica nanorods and their sorbent properties on heavy metals

NASA Astrophysics Data System (ADS)

Chen, Xi; Cai, Qiang; Sun, Lin-Hao; Zhang, Wei; Jiang, Xing-Yu

2012-09-01

Novel thiol-functionalized mesoporous silica nanorods (MSNRs) were synthesized through a base co-condensation method, in which two organoalkoxysilanes, tetraethoxylsilane (TEOS) and bis[3-(triethoxysilyl)propyl]tetrasulfide (TESPT), were used as silica precursors simultaneously. TESPT was firstly used for both morphology control and inner surface functionalization of mesoporous silica hybrid materials. The microstructures as well as porous character of the MSNRs were characterized by means of SEM, XRD, TEM and N2 sorption measurements. Infrared spectrum analysis and heavy metal ions (Ag+ and Cd2+) adsorption measurements were carried out to confirm the functionalized framework of MSNRs.

The enrichment of chlorogenic acid from Eucommia ulmoides leaves extract by mesoporous carbons.

PubMed

Qin, Guotong; Ma, Jing; Wei, Wei; Li, Jaja; Yue, Fangqing

2018-06-15

Herein, we report an efficient separation and enrichment method for chlorogenic acid from crude extracts of Eucommia ulmoides leaves using carbon adsorbents. The effects of the pore structure of the carbon adsorbents on the adsorption capacity were studied. Of the four adsorbents investigated, mesoporous carbon (MC3) showed the highest adsorption capacity (294 mg/g of carbon) for chlorogenic acid due to its high mesopore volume. The static adsorption of CGA on carbon can be accurately described using the Freundlich equation. The kinetics of adsorption follow a pseudo-second-order process. External mass transfer was the controlling step of the adsorption process. Dynamic adsorption on MC3 demonstrated that chlorogenic acid began to break through after 28 bed volumes of extract was loaded. This mesoporous carbon-treatment procedure is safe, economic and has the potential to be scaled up for commercial application. Copyright © 2018 Elsevier B.V. All rights reserved.

Mesoporous Silicate Materials in Sensing

PubMed Central

Melde, Brian J.; Johnson, Brandy J.; Charles, Paul T.

2008-01-01

Mesoporous silicas, especially those exhibiting ordered pore systems and uniform pore diameters, have shown great potential for sensing applications in recent years. Morphological control grants them versatility in the method of deployment whether as bulk powders, monoliths, thin films, or embedded in coatings. High surface areas and pore sizes greater than 2 nm make them effective as adsorbent coatings for humidity sensors. The pore networks also provide the potential for immobilization of enzymes within the materials. Functionalization of materials by silane grafting or through co-condensation of silicate precursors can be used to provide mesoporous materials with a variety of fluorescent probes as well as surface properties that aid in selective detection of specific analytes. This review will illustrate how mesoporous silicas have been applied to sensing changes in relative humidity, changes in pH, metal cations, toxic industrial compounds, volatile organic compounds, small molecules and ions, nitroenergetic compounds, and biologically relevant molecules. PMID:27873810

Facile Control of the Porous Structure of Larch-Derived Mesoporous Carbons via Self-Assembly for Supercapacitors

PubMed Central

Zhao, Xin; Li, Wei; Chen, Honglei; Wang, Shoujuan; Kong, Fangong; Liu, Shouxin

2017-01-01

Mesoporous carbons have been successfully synthesized via self-assembly using larch-based resins as precursors and triblock copolymers as soft templates. The porous structure of mesoporous carbons can be tailored by adjusting the ratio of hydrophilic/hydrophobic (EO/PO) units owing to interfacial curvature. Interestingly, the porous structures show a distinct change from vortex-like to worm-like pores, to stripe-like pores, and to ordered two-dimensional hexagonal pores as the ratio of hydrophilic/hydrophobic units increases, indicating the significant effect of EO/PO ratio on the porous structure. The mesoporous carbons as supercapacitor electrodes exhibit superior electrochemical capacitive performance and a high degree of reversibility after 2000 cycles for supercapacitors due to the well-defined mesoporosity of the carbon materials. Meanwhile, the superior carbon has a high specific capacitance of 107 F·g−1 in 6 M KOH at a current density of 10 A·g−1. PMID:29156641

Facile Control of the Porous Structure of Larch-Derived Mesoporous Carbons via Self-Assembly for Supercapacitors.

PubMed

Zhao, Xin; Li, Wei; Chen, Honglei; Wang, Shoujuan; Kong, Fangong; Liu, Shouxin

2017-11-20

Mesoporous carbons have been successfully synthesized via self-assembly using larch-based resins as precursors and triblock copolymers as soft templates. The porous structure of mesoporous carbons can be tailored by adjusting the ratio of hydrophilic/hydrophobic (EO/PO) units owing to interfacial curvature. Interestingly, the porous structures show a distinct change from vortex-like to worm-like pores, to stripe-like pores, and to ordered two-dimensional hexagonal pores as the ratio of hydrophilic/hydrophobic units increases, indicating the significant effect of EO/PO ratio on the porous structure. The mesoporous carbons as supercapacitor electrodes exhibit superior electrochemical capacitive performance and a high degree of reversibility after 2000 cycles for supercapacitors due to the well-defined mesoporosity of the carbon materials. Meanwhile, the superior carbon has a high specific capacitance of 107 F·g -1 in 6 M KOH at a current density of 10 A·g -1 .

Synthesis and characterization of mesoporous hydrocracking catalysts

NASA Astrophysics Data System (ADS)

Munir, D.; Usman, M. R.

2016-08-01

Mesoporous catalysts have shown great prospective for catalytic reactions due to their high surface area that aids better distribution of impregnated metal. They have been found to contain more adsorption sites and controlled pore diameter. Hydrocracking, in the presence of mesoporous catalyst is considered more efficient and higher conversion of larger molecules is observed as compared to the cracking reactions in smaller microporous cavities of traditional zeolites. In the present study, a number of silica-alumina based mesoporous catalysts are synthesized in the laboratory. The concentration and type of surfactants and quantities of silica and alumina sources are the variables studied in the preparation of catalyst supports. The supports prepared are well characterized using SEM, EDX, and N2-BET techniques. Finally, the catalysts are tested in a high pressure autoclave reactor to study the activity and selectivity of the catalysts for the hydrocracking of a model mixture of plastics comprising of LDPE, HDPE, PP, and PS.

Generalised syntheses of ordered mesoporous oxides: the atrane route

NASA Astrophysics Data System (ADS)

Cabrera, Saúl; El Haskouri, Jamal; Guillem, Carmen; Latorre, Julio; Beltrán-Porter, Aurelio; Beltrán-Porter, Daniel; Marcos, M. Dolores; Amorós *, Pedro

2000-06-01

A new simple and versatile technique to obtain mesoporous oxides is presented. While implying surfactant-assisted formation of mesostructured intermediates, the original chemical contribution of this approach lies in the use of atrane complexes as precursors. Without prejudice to their inherent unstability in aqueous solution, the atranes show a marked inertness towards hydrolysis. Bringing kinetic factors into play, it becomes possible to control the processes involved in the formation of the surfactant-inorganic phase composite micelles, which constitute the elemental building blocks of the mesostructures. Independent of the starting compositional complexity, both the mesostructured intermediates and the final mesoporous materials are chemically homogeneous. The final ordered mesoporous materials are thermally stable and show unimodal porosity, as well as homogeneous microstructure and texture. Examples of materials synthesised on account of the versatility of this new method, including siliceous, non siliceous and mixed oxides, are presented and discussed.

A general route to hollow mesoporous rare-earth silicate nanospheres as a catalyst support.

PubMed

Jin, Renxi; Yang, Yang; Zou, Yongcun; Liu, Xianchun; Xing, Yan

2014-02-17

Hollow mesoporous structures have recently aroused intense research interest owing to their unique structural features. Herein, an effective and precisely controlled synthesis of hollow rare-earth silicate spheres with mesoporous shells is reported for the first time, produced by a simple hydrothermal method, using silica spheres as the silica precursors. The as-prepared hollow rare-earth silicate spheres have large specific surface area, high pore volume, and controllable structure parameters. The results demonstrate that the selection of the chelating reagent plays critical roles in forming the hollow mesoporous structures. In addition, a simple and low-energy-consuming approach to synthesize highly stable and dispersive gold nanoparticle-yttrium silicate (AuNPs/YSiO) hollow nanocomposites has also been developed. The reduction of 4-nitrophenol with AuNPs/YSiO hollow nanocomposites as the catalyst has clearly demonstrated that the hollow rare-earth silicate spheres are good carriers for Au nanoparticles. This strategy can be extended as a general approach to prepare multifunctional yolk-shell structures with diverse compositions and morphologies simply by replacing silica spheres with silica-coated nanocomposites. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Anionic surfactants templating route for synthesizing silica hollow spheres with different shell porosity

NASA Astrophysics Data System (ADS)

Han, Lu; Gao, Chuanbo; Wu, Xiaowei; Chen, Qianru; Shu, Peng; Ding, Zhiguang; Che, Shunai

2011-04-01

Silica hollow spheres with different shell porosity were simply synthesized with micelle and emulsion dual templating route. Various anionic surfactants, such as palmitic acid (C 16AA), N-acyl- L-phenylalanine (C 18Phe), N-palmitoyl- L-alanine (C 16AlaA) and oleic acid (OA) have been used as templates, and 3-aminopropyl-triethoxysilane (APES) and tetraethyl orthosilicate (TEOS) have been used as co-structure directing agent (CSDA) and silica source, respectively. The circle lamellar layer structure and mesopores vertical to the silica hollow spheres surface are believed to originate from the initial formation of amphiphilic carboxylic acid oil drop, which afterwards self-assemble to form the shell of hollow spheres and its mesostructure upon addition of CSDA and silica source. The mesoporous silica hollow spheres with high porosity could be achieved by adding a moderate amount of ethanol in the OA synthesis system, depending on the co-surfactant effect of ethanol that changes the curvature of micelles. The particle diameter and the hollow structure have been controlled by choosing different templates and by manipulating synthesis gel composition. The average particle diameter of the mesoporous silica hollow spheres were controlled in the range of 80-220 nm with constant shell thickness of ˜20 nm and constant mesopore size of ˜4 nm. Besides, the formation of the silica hollow spheres has been investigated in detail with reaction time. These mesoporous silica hollow spheres would have potential applications on catalysis, bimolecular encapsulation, adsorption, drug release, etc.

In vivo experimental study on bone regeneration in critical bone defects using PIB nanogels/boron-containing mesoporous bioactive glass composite scaffold

PubMed Central

Chen, Xiaohui; Zhao, Yanbing; Geng, Shinan; Miron, Richard J; Zhang, Qiao; Wu, Chengtie; Zhang, Yufeng

2015-01-01

Purpose In the present study, the fabrication of novel p(N-isopropylacrylamide-co-butyl methylacrylate) (PIB) nanogels was combined with boron-containing mesoporous bioactive glass (B-MBG) scaffolds in order to improve the mechanical properties of PIB nanogels alone. Scaffolds were tested for mechanical strength and the ability to promote new bone formation in vivo. Patients and methods To evaluate the potential of each scaffold in bone regeneration, ovariectomized rats were chosen as a study model to determine the ability of PIB nanogels to stimulate bone formation in a complicated anatomical bone defect. PIB nanogels and PIB nanogels/B-MBG composites were respectively implanted into ovariectomized rats with critical-sized femur defects following treatment periods of 2, 4, and 8 weeks post-implantation. Results Results from the present study demonstrate that PIB nanogels/B-MBG composites showed greater improvement in mechanical strength when compared to PIB nanogels alone. In vivo, hematoxylin and eosin staining revealed significantly more newly formed bone in defects containing PIB nanogels/B-MBG composite scaffolds when compared to PIB nanogels alone. Tartrate-resistant acid phosphatase-positive staining demonstrated that both scaffolds were degraded over time and bone remodeling occurred in the surrounding bone defect as early as 4 weeks post-implantation. Conclusion The results from the present study indicate that PIB nanogels are a potential bone tissue engineering biomaterial able to treat defects of irregular shapes and deformities as an injectable, thermoresponsive, biocompatible hydrogel which undergoes rapid thermal gelation once body temperature is reached. Furthermore, its combination with B-MBG scaffolds improves the mechanical properties and ability to promote new bone formation when compared to PIB nanogels alone. PMID:25653525

In vivo experimental study on bone regeneration in critical bone defects using PIB nanogels/boron-containing mesoporous bioactive glass composite scaffold.

PubMed

Chen, Xiaohui; Zhao, Yanbing; Geng, Shinan; Miron, Richard J; Zhang, Qiao; Wu, Chengtie; Zhang, Yufeng

2015-01-01

In the present study, the fabrication of novel p(N-isopropylacrylamide-co-butyl methylacrylate) (PIB) nanogels was combined with boron-containing mesoporous bioactive glass (B-MBG) scaffolds in order to improve the mechanical properties of PIB nanogels alone. Scaffolds were tested for mechanical strength and the ability to promote new bone formation in vivo. To evaluate the potential of each scaffold in bone regeneration, ovariectomized rats were chosen as a study model to determine the ability of PIB nanogels to stimulate bone formation in a complicated anatomical bone defect. PIB nanogels and PIB nanogels/B-MBG composites were respectively implanted into ovariectomized rats with critical-sized femur defects following treatment periods of 2, 4, and 8 weeks post-implantation. Results from the present study demonstrate that PIB nanogels/B-MBG composites showed greater improvement in mechanical strength when compared to PIB nanogels alone. In vivo, hematoxylin and eosin staining revealed significantly more newly formed bone in defects containing PIB nanogels/B-MBG composite scaffolds when compared to PIB nanogels alone. Tartrate-resistant acid phosphatase-positive staining demonstrated that both scaffolds were degraded over time and bone remodeling occurred in the surrounding bone defect as early as 4 weeks post-implantation. The results from the present study indicate that PIB nanogels are a potential bone tissue engineering biomaterial able to treat defects of irregular shapes and deformities as an injectable, thermoresponsive, biocompatible hydrogel which undergoes rapid thermal gelation once body temperature is reached. Furthermore, its combination with B-MBG scaffolds improves the mechanical properties and ability to promote new bone formation when compared to PIB nanogels alone.

Collagen hydrogels incorporated with surface-aminated mesoporous nanobioactive glass: Improvement of physicochemical stability and mechanical properties is effective for hard tissue engineering.

PubMed

El-Fiqi, Ahmed; Lee, Jae Ho; Lee, Eun-Jung; Kim, Hae-Won

2013-12-01

Collagen (Col) hydrogels have poor physicochemical and mechanical properties and are susceptible to substantial shrinkage during cell culture, which limits their potential applications in hard tissue engineering. Here, we developed novel nanocomposite hydrogels made of collagen and mesoporous bioactive glass nanoparticles (mBGns) with surface amination, and addressed the effects of mBGn addition (Col:mBG = 2:1, 1:1 and 1:2) and its surface amination on the physicochemical and mechanical properties of the hydrogels. The amination of mBGn was shown to enable chemical bonding with collagen molecules. As a result, the nanocomposite hydrogels exhibited a significantly improved physicochemical and mechanical stability. The hydrolytic and enzymatic degradation of the Col-mBGn hydrogels were slowed down due to the incorporation of mBGn and its surface amination. The mechanical properties of the hydrogels, specifically the resistance to loading as well as the stiffness, significantly increased with the addition of mBGn and its aminated form, as assessed by a dynamic mechanical analysis. Mesenchymal stem cells cultivated within the Col-mBGn hydrogels were highly viable, with enhanced cytoskeletal extensions, due to the addition of surface aminated mBGn. While the Col hydrogel showed extensive shrinkage (down to ∼20% of initial size) during a few days of culture, the shrinkage of the mBGn-added hydrogel was substantially reduced, and the aminated mBGn-added hydrogel had no observable shrinkage over 21 days. Results demonstrated the effective roles of aminated mBGn in significantly improving the physicochemical and mechanical properties of Col hydrogel, which are ultimately favorable for applications in stem cell culture for bone tissue engineering. Copyright © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Control-release microcapsule of famotidine loaded biomimetic synthesized mesoporous silica nanoparticles: Controlled release effect and enhanced stomach adhesion in vitro.

PubMed

Li, Jing; Wang, Hongyu; Yang, Baixue; Xu, Lu; Zheng, Nan; Chen, Hongtao; Li, Sanming

2016-01-01

In the present work, control-release microcapsule of famotidine (FMT) loaded biomimetic synthesized mesoporous silica nanoparticles (B-MSNs) was developed, and controlled release effect and stomach adhesion of this formulation in vitro were mainly investigated. B-MSN was previously synthesized and it was amorphous mesoporous nanoparticles with helical channels. Cytotoxicity of B-MSN was studied using human breast cancer cells (MCF-7) and the result indicated that cytotoxicity of B-MSN can be neglected. After loading FMT into B-MSN, specific surface area, pore volume and pore diameter of B-MSN were obviously reduced. In vitro dissolution test showed that B-MSN had the ability to slow down FMT release for 15 min. In order to prolong controlled release effect and remained the advantage of B-MSN (improve drug stability due to its rigid silica framework), the combined application of control-release microcapsule (using cellulose and hydroxypropyl methylcellulose K15M as excipients) with B-MSN was designed. It was obvious that newly designed formulation significantly controlled FMT release with Fickian diffusion mechanism and showed enhanced stomach adhesion in vitro, which has significant value in widening the application of B-MSN in formulation design. Copyright © 2015 Elsevier B.V. All rights reserved.

Ultrafast Flame Annealing of TiO2 Paste for Fabricating Dye-Sensitized and Perovskite Solar Cells with Enhanced Efficiency.

PubMed

Kim, Jung Kyu; Chai, Sung Uk; Cho, Yoonjun; Cai, Lili; Kim, Sung June; Park, Sangwook; Park, Jong Hyeok; Zheng, Xiaolin

2017-11-01

Mesoporous TiO 2 nanoparticle (NP) films are broadly used as electrodes in photoelectrochemical cells, dye-sensitized solar cells (DSSCs), and perovskite solar cells (PSCs). State-of-the-art mesoporous TiO 2 NP films for these solar cells are fabricated by annealing TiO 2 paste-coated fluorine-doped tin oxide glass in a box furnace at 500 °C for ≈30 min. Here, the use of a nontraditional reactor, i.e., flame, is reported for the high throughput and ultrafast annealing of TiO 2 paste (≈1 min). This flame-annealing method, compared to conventional furnace annealing, exhibits three distinct benefits. First, flame removes polymeric binders in the initial TiO 2 paste more completely because of its high temperature (≈1000 °C). Second, flame induces strong interconnections between TiO 2 nanoparticles without affecting the underlying transparent conducting oxide substrate. Third, the flame-induced carbothermic reduction on the TiO 2 surface facilitates charge injection from the dye/perovskite to TiO 2 . Consequently, when the flame-annealed mesoporous TiO 2 film is used to fabricate DSSCs and PSCs, both exhibit enhanced charge transport and higher power conversion efficiencies than those fabricated using furnace-annealed TiO 2 films. Finally, when the ultrafast flame-annealing method is combined with a fast dye-coating method to fabricate DSSC devices, its total fabrication time is reduced from over 3 h to ≈10 min. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Triconstituent co-assembly to ordered mesostructured polymer-silica and carbon-silica nanocomposites and large-pore mesoporous carbons with high surface areas.

PubMed

Liu, Ruili; Shi, Yifeng; Wan, Ying; Meng, Yan; Zhang, Fuqiang; Gu, Dong; Chen, Zhenxia; Tu, Bo; Zhao, Dongyuan

2006-09-06

Highly ordered mesoporous polymer-silica and carbon-silica nanocomposites with interpenetrating networks have been successfully synthesized by the evaporation-induced triconstituent co-assembly method, wherein soluble resol polymer is used as an organic precursor, prehydrolyzed TEOS is used as an inorganic precursor, and triblock copolymer F127 is used as a template. It is proposed for the first time that ordered mesoporous nanocomposites have "reinforced concrete"-structured frameworks. By adjusting the initial mass ratios of TEOS to resol, we determined the obtained nanocomposites possess continuous composition with the ratios ranging from zero to infinity for the two constituents that are "homogeneously" dispersed inside the pore walls. The presence of silicates in nanocomposites dramatically inhibits framework shrinkage during the calcination, resulting in highly ordered large-pore mesoporous carbon-silica nanocomposites. Combustion in air or etching in HF solution can remove carbon or silica from the carbon-silica nanocomposites and yield ordered mesoporous pure silica or carbon frameworks. The process generates plenty of small pores in carbon or/and silica pore walls. Ordered mesoporous carbons can then be obtained with large pore sizes of approximately 6.7 nm, pore volumes of approximately 2.0 cm(3)/g, and high surface areas of approximately 2470 m(2)/g. The pore structures and textures can be controlled by varying the sizes and polymerization degrees of two constituent precursors. Accordingly, by simply tuning the aging time of TEOS, ordered mesoporous carbons with evident bimodal pores at 2.6 and 5.8 nm can be synthesized.

Facile Synthesis of Uniform Virus-like Mesoporous Silica Nanoparticles for Enhanced Cellular Internalization

PubMed Central

2017-01-01

The low-efficiency cellular uptake property of current nanoparticles greatly restricts their application in the biomedical field. Herein, we demonstrate that novel virus-like mesoporous silica nanoparticles can easily be synthesized, showing greatly superior cellular uptake property. The unique virus-like mesoporous silica nanoparticles with a spiky tubular rough surface have been successfully synthesized via a novel single-micelle epitaxial growth approach in a low-concentration-surfactant oil/water biphase system. The virus-like nanoparticles’ rough surface morphology results mainly from the mesoporous silica nanotubes spontaneously grown via an epitaxial growth process. The obtained nanoparticles show uniform particle size and excellent monodispersity. The structural parameters of the nanoparticles can be well tuned with controllable core diameter (∼60–160 nm), tubular length (∼6–70 nm), and outer diameter (∼6–10 nm). Thanks to the biomimetic morphology, the virus-like nanoparticles show greatly superior cellular uptake property (invading living cells in large quantities within few minutes, <5 min), unique internalization pathways, and extended blood circulation duration (t1/2 = 2.16 h), which is much longer than that of conventional mesoporous silica nanoparticles (0.45 h). Furthermore, our epitaxial growth strategy can be applied to fabricate various virus-like mesoporous core–shell structures, paving the way toward designed synthesis of virus-like nanocomposites for biomedicine applications. PMID:28852697

Hierarchical porous silicon carbide with controlled micropores and mesopores for electric double layer capacitors

NASA Astrophysics Data System (ADS)

Kim, Myeongjin; Oh, Ilgeun; Kim, Jooheon

2015-05-01

Three-dimensional hierarchical micro and mesoporous silicon carbide spheres (MMPSiC) are prepared by the template method and carbonization reaction via the aerosol spray drying method. The mesopores are generated by the self-assembly of the structure-directing agents, whereas the micropores are derived from the partial evaporation of Si atoms during carbonization. To investigate the effect of mesopore size on electrochemical performance, three types of MMPSiC with different mesopore size were fabricated by using three different structure directing agents (cetyltriethylammonium bromide (CTAB), Polyethylene glycol hexadecyl ether (Brij56), and Poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (P123)). The MMPSiC electrode prepared with Brij56 exhibits the highest charge storage capacity with a specific capacitance of 253.7 F g-1 at a scan rate of 5 mV s-1 and 87.9% rate performance from 5 to 500 mV s-1 in 1 M Na2SO4 aqueous electrolyte. The outstanding electrochemical performance might be because of the ideal mesopore size, which effectively reduces the resistant pathways for ion diffusion in the pores and provides a large accessible surface area for ion transport/charge storage. These encouraging results demonstrate that the MMPSiC prepared with Brij56 is a promising candidate for high performance electrode materials for supercapacitors.

Enzyme-Controlled Nanodevice for Acetylcholine-Triggered Cargo Delivery Based on Janus Au-Mesoporous Silica Nanoparticles.

PubMed

Llopis-Lorente, Antoni; Díez, Paula; de la Torre, Cristina; Sánchez, Alfredo; Sancenón, Félix; Aznar, Elena; Marcos, María D; Martínez-Ruíz, Paloma; Martínez-Máñez, Ramón; Villalonga, Reynaldo

2017-03-28

This work reports a new gated nanodevice for acetylcholine-triggered cargo delivery. We prepared and characterized Janus Au-mesoporous silica nanoparticles functionalized with acetylcholinesterase on the Au face and with supramolecular β-cyclodextrin:benzimidazole inclusion complexes as caps on the mesoporous silica face. The nanodevice is able to selectively deliver the cargo in the presence of acetylcholine via enzyme-mediated acetylcholine hydrolysis, locally lowering the pH and opening the supramolecular gate. Given the key role played by ACh and its relation with Parkinson's disease and other nervous system diseases, we believe that these findings could help design new therapeutic strategies. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Controllable growth of polyaniline nanowire arrays on hierarchical macro/mesoporous graphene foams for high-performance flexible supercapacitors

NASA Astrophysics Data System (ADS)

Yu, Pingping; Zhao, Xin; Li, Yingzhi; Zhang, Qinghua

2017-01-01

Free-standing hierarchical macro/mesoporous flexible graphene foam have been constructed by rational intergration ofwell dispersed graphene oxide sheets and amino-modified polystyrene (PS) spheres through a facile ;templating and embossing; technique. The three dimensional (3D) macro/mesoporous flexible graphene foam not only inherits the uniform porous structures of graphene foam, but also contains hierarchical macro/mesopores on the struts by sacrificing PS spheres and the activation of KOH, which could providing rapid pathways for ionic and electronic transport to high specific capacitance. Vertically polyaniline (PANI) nanowire arrays are then uniformly deposited onto the hierarchical macro/mesoporous graphene foam(fRGO-F/PANI) by a simple in situ polymerization, which show a high specific capacitance of 939 F g-1. Thanks to the synergistic function of 3D bicontinuous hierarchical porous structure of graphene foam and effective immobilization of PANI nanowires on the struts, the assembled symmetric supercapctior with fRGO-F/PANI as electrodes exhibits a maximum energy density and power density of 20.9 Wh kg-1 and 103.2 kW kg-1, respectively. Moreover, it also displays an excellent cyclic stability with a 88.7% retention after 5000 cycles.

Direct synthesis of graphitic mesoporous carbon from green phenolic resins exposed to subsequent UV and IR laser irradiations

PubMed Central

Sopronyi, Mihai; Sima, Felix; Vaulot, Cyril; Delmotte, Luc; Bahouka, Armel; Matei Ghimbeu, Camelia

2016-01-01

The design of mesoporous carbon materials with controlled textural and structural features by rapid, cost-effective and eco-friendly means is highly demanded for many fields of applications. We report herein on the fast and tailored synthesis of mesoporous carbon by UV and IR laser assisted irradiations of a solution consisting of green phenolic resins and surfactant agent. By tailoring the UV laser parameters such as energy, pulse repetition rate or exposure time carbon materials with different pore size, architecture and wall thickness were obtained. By increasing irradiation dose, the mesopore size diminishes in the favor of wall thickness while the morphology shifts from worm-like to an ordered hexagonal one. This was related to the intensification of phenolic resin cross-linking which induces the reduction of H-bonding with the template as highlighted by 13C and 1H NMR. In addition, mesoporous carbon with graphitic structure was obtained by IR laser irradiation at room temperature and in very short time periods compared to the classical long thermal treatment at very high temperatures. Therefore, the carbon texture and structure can be tuned only by playing with laser parameters, without extra chemicals, as usually required. PMID:28000781

Synthesis and characterization of amorphous mesoporous silica using TEMPO-functionalized amphiphilic templates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vries, Wilke de; Doerenkamp, Carsten; Zeng, Zhaoyang

Inorganic–organic hybrid materials based on amorphous mesoporous silica containing organized nitroxide radicals within its mesopores have been prepared using the micellar self-assembly of TEOS solutions containing the nitroxide functionalized amphiphile (4-(N,N-dimethyl-N-hexadecylammonium)-2,2,6, 6-tetramethyl-piperidin-N-oxyl-iodide) (CAT-16). This template has been used both in its pure form and in various mixtures with cetyl trimethylammonium bromide (CTAB). The samples have been characterized by chemical analysis, N{sub 2} sorption studies, magnetic susceptibility measurements, and various spectroscopic methods. While electron paramagnetic resonance (EPR) spectra indicate that the strength of the intermolecular spin–spin interactions can be controlled via the CAT-16/CTAB ratio, nuclear magnetic resonance (NMR) data suggest thatmore » these interactions are too weak to facilitate cooperative magnetism. - Graphical abstract: The amphiphilic radical CAT-16 is used as a template for the synthesis of amorphous mesoporous silica. The resulting paramagnetic hybrid materials are characterized by BET, FTIR, NMR, EPR and magnetic susceptibility studies. - Highlights: • Amphiphilic CAT-16 as a template for mesoporous silica. • Comprehensive structural characterization by BET, FTIR; EPR and NMR. • Strength of radical-radical interactions tuable within CAT-16/CTAB mixtures.« less

Surface-functionalized mesoporous carbon materials

DOEpatents

Dai, Sheng; Gorka, Joanna; Mayes, Richard T.

2016-02-02

A functionalized mesoporous carbon composition comprising a mesoporous carbon scaffold having mesopores in which polyvinyl polymer grafts are covalently attached, wherein said mesopores have a size of at least 2 nm and up to 50 nm. Also described is a method for producing the functionalized mesoporous composition, wherein a reaction medium comprising a precursor mesoporous carbon, vinyl monomer, initiator, and solvent is subjected to sonication of sufficient power to result in grafting and polymerization of the vinyl monomer into mesopores of the precursor mesoporous carbon. Also described are methods for using the functionalized mesoporous carbon, particularly in extracting metal ions from metal-containing solutions.

Perovskite solar cells in N-I-P structure with four slot-die-coated layers

PubMed Central

Burkitt, Daniel; Searle, Justin

2018-01-01

The fabrication of perovskite solar cells in an N-I-P structure with compact titanium dioxide blocking, mesoporous titanium dioxide scaffold, single-step perovskite and hole-transport layers deposited using the slot-die coating technique is reported. Devices on fluorine-doped tin oxide-coated glass substrates with evaporated gold top contacts and four slot-die-coated layers are demonstrated, and best cells reach stabilized power conversion efficiencies of 7%. This work demonstrates the suitability of slot-die coating for the production of layers within this perovskite solar cell stack and the potential to transfer to large area and roll-to-roll manufacturing processes. PMID:29892402

Giant dielectric permittivity in interrupted silver nanowires grown within mesoporous silica

NASA Astrophysics Data System (ADS)

Maity, Anupam; Samanta, Subha; Chatterjee, Soumi; Maiti, Ramaprasad; Biswas, Debasish; Saha, Shyamal K.; Chakravorty, Dipankar

2018-06-01

Nanoglasses in the system Ag2O–SiO2 were formed within the pores of mesoporous silica SBA-15 (Santa Barbara Amorphous). Silver nanowires of diameter 5 nm were grown within SBA-15 by the process of electrodeposition. The nanowires were disrupted by applying a suitable voltage pulse. Detailed transmission and scanning electron microscopy studies were carried out. The disrupted silver strands were found to have an average length of 90 nm. The density of interrupted strands was estimated from the electron micrographs and found to have values in the range (10–20)  ×  1010 cm‑2. Dielectric constant and dielectric loss factors of the nanocomposites of disrupted silver strand—containing Ag2O–SiO2 glass and SBA-15 were found to have values in the range 200–300 and 0.014–0.008 respectively at frequencies in the range 10 kHz–2 MHz. These values were found to be in satisfactory agreement with the theoretical model of Rice and Bernasconi emanating from the theory of Gorkhov and Eliashberg. These nanocomposites are expected to be useful in the fabrication of supercapacitors, after developing suitable electrode system for the material.

Synthesis and characterization of hollow mesoporous BaFe{sub 12}O{sub 19} spheres

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Xia; Department of Chemical and Biological Engineering, The University of Alabama, Tuscaloosa, AL 35487; Park, Jihoon

2015-02-15

A facile method is reported to synthesize hollow mesoporous BaFe{sub 12}O{sub 19} spheres using a template-free chemical etching process. Hollow BaFe{sub 12}O{sub 19} spheres were synthesized by conventional spray pyrolysis. The mesoporous structure is achieved by alkaline ethylene glycol etching at 185 °C, with the porosity controlled by the heating time. The hollow porous structure is confirmed by SEM, TEM, and FIB-FESEM characterization. The crystal structure and magnetic properties are not significantly affected after the chemical etching process. The formation mechanism of the porous structure is explained by grain boundary etching. - Graphical abstract: Hollow spherical BaFe{sub 12}O{sub 19} particlesmore » are polycrystalline with both grains and grain boundaries. Grain boundaries have less ordered structure and lower stability. When the particles are exposed to high temperature alkaline ethylene glycol, the grain boundaries are etched, leaving small grooves between grains. These grooves allow ethylene glycol to diffuse inside to further etch the grains. As the grain size decreases, gaps appear on the particle surfaces, and a porous structure is finally formed. - Highlights: • Two-step synthesis method for hollow mesoporous BaFe{sub 12}O{sub 19} spheres is proposed. • Porosity of the product can be regulated by controlling the second step of chemical etching. • The crystal structure and magnetic properties are examined to be little affected during the chemical etching. • The mesoporous structure formation mechanism is explained by grain boundary etching.« less

Novel concept for the preparation of gas selective nanocomposite membranes

NASA Astrophysics Data System (ADS)

Drobek, M.; Ayral, A.; Motuzas, J.; Charmette, C.; Loubat, C.; Louradour, E.; Dhaler, D.; Julbe, A.

2015-07-01

In this work we report on a novel concept for the preparation of gas selective composite membranes by a simple and robust synthesis protocol involving a controlled in-situpolycondensation of functional alkoxysilanes within the pores of a mesoporous ceramic matrix. This innovative approach targets the manufacture of thin nanocomposite membranes, allowing good compromise between permeability, selectivity and thermomechanical strength. Compared to simple infiltration, the synthesis protocol allows a controlled formation of gas separation membranes from size-adjusted functional alkoxysilanes by a chemical reaction within the mesopores of a ceramic support, without any formation of a thick and continuous layer on the support top-surface. Membrane permeability can thus be effectively controlled by the thickness and pore size of the mesoporous layer, and by the oligomers chain length. The as-prepared composite membranes are expected to possess a good mechanical and thermomechanical resistance and exhibit a thermally activated transport of He and H2 up to 150 °C, resulting in enhanced separation factors for specific gas mixtures e.g. FH2/CO ˜ 10; FH2/CO2 ˜ 3; FH2/CH4 ˜ 62.

Sulfur-infiltrated porous carbon microspheres with controllable multi-modal pore size distribution for high energy lithium-sulfur batteries.

PubMed

Zhao, Cunyu; Liu, Lianjun; Zhao, Huilei; Krall, Andy; Wen, Zhenhai; Chen, Junhong; Hurley, Patrick; Jiang, Junwei; Li, Ying

2014-01-21

Sulfur has received increasing attention as a cathode material for lithium-sulfur (Li-S) batteries due to its high theoretical specific capacity. However, the commercialization of Li-S batteries is limited by the challenges of poor electrical conductivity of sulfur, dissolution of the polysulfide intermediates into the electrolyte, and volume expansion of sulfur during cycling. Herein, we report the fabrication of novel-structured porous carbon microspheres with a controllable multi-modal pore size distribution, i.e., a combination of interconnected micropores, mesopores and macropores. Cathodes made of sulfur infiltrated in such a hierarchical carbon framework provide several advantages: (1) a continuous and high surface area carbon network for enhanced electrical conductivity and high sulfur loading; (2) macropores and large mesopores bridged by small mesopores to provide good electrolyte accessibility and fast Li ion transport and to accommodate volume expansion of sulfur; and (3) small mesopores and micropores to improve carbon/sulfur interaction and to help trap polysulfides. An initial discharge capacity at 1278 mA h g(-1) and capacity retention at 70.7% (904 mA h g(-1)) after 100 cycles at a high rate (1 C) were achieved. The material fabrication process is relatively simple and easily scalable.

Synergistic interaction and controllable active sites of nitrogen and sulfur co-doping into mesoporous carbon sphere for high performance oxygen reduction electrocatalysts

NASA Astrophysics Data System (ADS)

Oh, Taeseob; Kim, Myeongjin; Park, Dabin; Kim, Jooheon

2018-05-01

Nitrogen and sulfur co-doped mesoporous carbon sphere (NSMCS) was prepared as a metal-free catalyst by an economical and facile pyrolysis process. The mesoporous carbon spheres were derived from sodium carboxymethyl cellulose as the carbon source and the nitrogen and sulfur dopants were derived from urea and p-benzenedithiol, respectively. The doping level and chemical states of nitrogen and sulfur in the prepared NSMCS can be easily adjusted by controlling the pyrolysis temperature. The NSMCS pyrolyzed at 900 °C (NSMCS-900) exhibited higher oxygen reduction reaction activity than the mesoporous carbon sphere doped solely with nitrogen or sulfur, due to the synergistic effect of co-doping. Among all the NSMCS samples, NSMCS-900 exhibited excellent ORR catalytic activity owing to the presence of a highly active site, consisting of pyridinic N, graphitic N, and thiophene S. Remarkably, the NSMCS-900 catalyst was comparable with commercial Pt/C, in terms of the onset and the half-wave potentials and showed better durability than Pt/C for ORR in an alkaline electrolyte. The approach demonstrated in this work could be used to prepare promising metal-free electrocatalysts for application in energy conversion and storage.

In vitro and in vivo evaluation of ordered mesoporous silica as a novel adsorbent in liquisolid formulation

PubMed Central

Chen, Bao; Wang, Zhouhua; Quan, Guilan; Peng, Xinsheng; Pan, Xin; Wang, Rongchang; Xu, Yuehong; Li, Ge; Wu, Chuanbin

2012-01-01

Background A liquisolid technique has been reported to be a new approach to improve the release of poorly water-soluble drugs for oral administration. However, an apparent limitation of this technique is the formulation of a high dose because a large amount of liquid vehicle is needed, which finally results in a low-dose liquisolid formulation. Silica as an absorbent has been used extensively in liquisolid formulations. Although nanoparticle silica can be prepared and used to improve liquid adsorption capacity, loading a high dose of drug into a liquisolid is still a challenge. With the aim of improving adsorption capacity and accordingly achieving high drug loading, ordered mesoporous silica with a high surface area and narrow pore size distribution was synthesized and used in a liquisolid formulation. Methods Ordered mesoporous silica was synthesized and its particle size and morphology were tailored by controlling the concentration of cetyltrimethyl ammonium bromide. The ordered mesoporous silica synthesized was characterized by transmission electron microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy, small-angle x-ray diffraction, wide angle x-ray diffraction, and nitrogen adsorption-desorption measurements. The liquid adsorption capacity of ordered mesoporous silica was subsequently compared with that of conventional silica materials using PEG400 as the model liquid. Carbamazepine was chosen as a model drug to prepare the liquisolid formulation, with ordered mesoporous silica as the adsorbent material. The preparation was evaluated and compared with commercially available fast-release carbamazepine tablets in vitro and in vivo. Results Characterization of the ordered mesoporous silica synthesized in this study indicated a huge Brunauer–Emmett–Teller surface area (1030 m2/g), an ordered mesoporous structure with a pore size of 2.8 nm, and high adsorption capacity for liquid compared with conventional silica. Compared with fast-release commercial carbamazepine tablets, drug release from the liquisolid capsules was greatly improved, and the bioavailability of the liquisolid preparation was enhanced by 182.7%. Conclusion Ordered mesoporous silica is a potentially attractive adsorbent which may lead to a new approach for development of liquisolid products. PMID:22275835

Encapsulation of ultrafine metal-oxide nanoparticles within mesopores for biomass-derived catalytic applications† †Electronic supplementary information (ESI) available: Experimental section, additional characterization and reaction results. See DOI: 10.1039/c7sc04724j

PubMed Central

Fang, Ruiqi; Tian, Panliang; Yang, Xianfeng

2018-01-01

The development of efficient encapsulation strategies has attracted intense interest for preparing highly active and stable heterogeneous metal catalysts. However, issues related to low loadings, costly precursors and complex synthesis processes restrict their potential applications. Herein, we report a novel and general strategy to encapsulate various ultrafine metal-oxides nanoparticles (NPs) into the mesoporous KIT-6. The synthesis is facile, which only involves self-assembly of a metal–organic framework (MOF) precursor in the silica mesopores and a subsequent calcination process to transform the MOF into metal-oxide NPs. After the controlled calcination, the metal-oxide NPs produced from MOF decomposition are exclusively confined and uniformly distributed in the mesopores of KIT-6 with high metal loadings. Benefitting from the encapsulation effects, as-synthesized Co@KIT-6 materials exhibit superior catalytic activity and recycling stability in biomass-derived HMF oxidation under mild reaction conditions. PMID:29675231

Synthesis and characterization of mesoporous indium tin oxide possessing an electronically conductive framework.

PubMed

Emons, Theo T; Li, Jianquan; Nazar, Linda F

2002-07-24

The new mesoporous transparent conducting oxide based on indium-tin-oxide, meso-ITO, has been synthesized by a modified sol-gel method, using CTAB as the surfactant. Critical was the employment of triethanolamine to control the rate of hydrolysis and inhibit deposition of the bulk oxides. Removal of the surfactant by calcination yielded a relatively well-ordered worm-hole motif arrangement of pores visible in the TEM and stable to 400 degrees C. BET measurements revealed no hysteresis in the absorption-desorption isotherm, consistent with a narrow pore-size distribution (between 20 and 40 A depending on the In:Sn ratio); surface areas ranged between 270 and 310 m2/g. This colorless material is the first mesoporous oxide exhibiting substantial framework conductivity, with a conductivity at 25 degrees C of 1.2 x 10-3 S/cm. This distinguishes it from mesoporous mixed-valence transition-metal oxides that exhibit weak hopping semiconductor behavior and much lower conductivity.

Hyaluronic acid modified mesoporous carbon nanoparticles for targeted drug delivery to CD44-overexpressing cancer cells

NASA Astrophysics Data System (ADS)

Wan, Long; Jiao, Jian; Cui, Yu; Guo, Jingwen; Han, Ning; Di, Donghua; Chang, Di; Wang, Pu; Jiang, Tongying; Wang, Siling

2016-04-01

In this paper, hyaluronic acid (HA) functionalized uniform mesoporous carbon spheres (UMCS) were synthesized for targeted enzyme responsive drug delivery using a facile electrostatic attraction strategy. This HA modification ensured stable drug encapsulation in mesoporous carbon nanoparticles in an extracellular environment while increasing colloidal stability, biocompatibility, cell-targeting ability, and controlled cargo release. The cellular uptake experiments of fluorescently labeled mesoporous carbon nanoparticles, with or without HA functionalization, demonstrated that HA-UMCS are able to specifically target cancer cells overexpressing CD44 receptors. Moreover, the cargo loaded doxorubicin (DOX) and verapamil (VER) exhibited a dual pH and hyaluronidase-1 responsive release in the tumor microenvironment. In addition, VER/DOX/HA-UMCS exhibited a superior therapeutic effect on an in vivo HCT-116 tumor in BALB/c nude mice. In summary, it is expected that HA-UMCS will offer a new method for targeted co-delivery of drugs to tumors overexpressing CD44 receptors.

From microporous regular frameworks to mesoporous materials with ultrahigh surface area: dynamic reorganization of porous polymer networks.

PubMed

Kuhn, Pierre; Forget, Aurélien; Su, Dangsheng; Thomas, Arne; Antonietti, Markus

2008-10-08

High surface area organic materials featuring both micro- and mesopores were synthesized under ionothermal conditions via the formation of polyaryltriazine networks. While the polytrimerization of nitriles in zinc chloride at 400 degrees C produces microporous polymers, higher reaction temperatures induce the formation of additional spherical mesopores with a narrow dispersity. The nitrogen-rich carbonaceous polymer materials thus obtained present surface areas and porosities up to 3300 m(2) g(-1) and 2.4 cm(3) g(-1), respectively. The key point of this synthesis relies on the occurrence of several high temperature polymerization reactions, where irreversible carbonization reactions coupled with the reversible trimerization of nitriles allow the reorganization of the dynamic triazine network. The ZnCl2 molten salt fulfills the requirement of a high temperature solvent, but is also required as catalyst. Thus, this dynamic polymerization system provides not only highly micro- and mesoporous materials, but also allows controlling the pore structure in amorphous organic materials.

1H and 2H NMR studies of benzene confined in porous solids: melting point depression and pore size distribution.

PubMed

Aksnes, D W; Kimtys, L

2004-01-01

The pore size distributions of four controlled pore glasses and three silica gels with nominal diameters in the range 4-24 nm were determined by measuring the 1H and 2H NMR signals from the non-frozen fraction of confined benzene and perdeuterated benzene as a function of temperature, in steps of ca. 0.1-1 K. The liquid and solid components of the adsorbate were distinguished, on the basis of the spin-spin relaxation time T2, by employing a spin-echo sequence. The experimental intensity curves of the liquid component are well represented by a sum of two error functions. The mean melting point depression of benzene and perdeuterated benzene confined in the four controlled pore glasses, with pore radius R, follows the simplified Gibbs-Thompson equation DeltaT=kp/R with a kp value of 44 K nm. As expected, the kp value mainly determines the position of the pore size distribution curve, i.e., the mean pore radius, while the transition width determines the shape of the pore size distribution curve. The excellent agreement between the results from the 1H and 2H measurements shows that the effect of the background absorption from protons in physisorbed water and silanol groups is negligible under the experimental conditions used. The overall pore size distributions determined by NMR are in reasonable agreement with the results specified by the manufacturer, or measured by us using the N2 sorption technique. The NMR method, which is complementary to the conventional gas sorption method, is particularly appropriate for studying pore sizes in the mesoporous range.

Crystalline mesoporous tungsten oxide nanoplate monoliths synthesized by directed soft template method for highly sensitive NO{sub 2} gas sensor applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoa, Nguyen Duc, E-mail: ndhoa@itims.edu.vn; Duy, Nguyen Van; Hieu, Nguyen Van, E-mail: hieu@itims.edu.vn

2013-02-15

Graphical abstract: Display Omitted Highlights: ► Mesoporous WO{sub 3} nanoplate monoliths were obtained by direct templating synthesis. ► Enable effective accession of the analytic molecules for the sensor applications. ► The WO{sub 3} sensor exhibited a high performance to NO{sub 2} gas at low temperature. -- Abstract: Controllable synthesis of nanostructured metal oxide semiconductors with nanocrystalline size, porous structure, and large specific surface area is one of the key issues for effective gas sensor applications. In this study, crystalline mesoporous tungsten oxide nanoplate-like monoliths with high specific surface areas were obtained through instant direct-templating synthesis for highly sensitive nitrogen dioxidemore » (NO{sub 2}) sensor applications. The copolymer soft template was converted into a solid carbon framework by heat treatment in an inert gas prior to calcinations in air to sustain the mesoporous structure of tungsten oxide. The multidirectional mesoporous structures of tungsten oxide with small crystalline size, large specific surface area, and superior physical characteristics enabled the rapid and effective accession of analytic gas molecules. As a result, the sensor response was enhanced and the response and recovery times were reduced, in which the mesoporous tungsten oxide based gas sensor exhibited a superior response of 21,155% to 5 ppm NO{sub 2}. In addition, the developed sensor exhibited selective detection of low NO{sub 2} concentration in ammonia and ethanol at a low temperature of approximately 150 °C.« less

A facile synthesis of mesoporous Pdsbnd ZnO nanocomposites as efficient chemical sensor

NASA Astrophysics Data System (ADS)

Ismail, Adel A.; Harraz, Farid A.; Faisal, M.; El-Toni, Ahmed Mohamed; Al-Hajry, A.; Al-Assiri, M. S.

2016-07-01

Mesoporous ZnO was synthesized through the sol-gel method in the presence of triblock co-polymer Pluronic (F-127) template as the structure directing agent. Palladium nanoparticles were photochemically reduced and deposited onto mesoporous ZnO to obtain 1 wt.% Pd/ZnO nanocomposite. Structural and morphological analysis revealed high homogeneity and monodispersity of Pd nanoclusters with small particle sizes ∼ 2-5 nm onto mesoporous ZnO. The electrochemical detection of ethanol in aqueous solutions was conducted at the newly developed Pd/ZnO modified glassy carbon electrode (GCE) by the current-potential (IV) and cyclic voltammetry (CV) techniques and compared with bare GCE or pure ZnO. The presence of Pd dopant greatly enhances the sensitivity of ZnO, and the obtained mesoporous Pd/ZnO sensor has an excellent performance for precision detection of ethanol in aqueous solution with low concentration. The sensitivity was found to be 33.08 μAcm-2 mM-1 at lower concentration zone (0.05-0.8 mM) and 2.13 μAcm-2 mM-1 at higher concentration zone (0.8-12 mM), with a limit of detection (LOD) 19.2 μM. The kinetics study of ethanol oxidation revealed a characteristic feature for a mixed surface and diffusion-controlled process. These excellent sensing characteristics make the mesoporous Pd/ZnO nanocomposite a good candidate for the production of high-performance electrochemical sensors at low ethanol concentration in aqueous solution.

Amphiphilic Block Copolymers Directed Interface Coassembly to Construct Multifunctional Microspheres with Magnetic Core and Monolayer Mesoporous Aluminosilicate Shell.

PubMed

Zhang, Yu; Yue, Qin; Yu, Lei; Yang, Xuanyu; Hou, Xiu-Feng; Zhao, Dongyuan; Cheng, Xiaowei; Deng, Yonghui

2018-05-11

Core-shell magnetic porous microspheres have wide applications in drug delivery, catalysis and bioseparation, and so on. However, it is great challenge to controllably synthesize magnetic porous microspheres with uniform well-aligned accessible large mesopores (>10 nm) which are highly desired for applications involving immobilization or adsorption of large guest molecules or nanoobjects. In this study, a facile and general amphiphilic block copolymer directed interfacial coassembly strategy is developed to synthesize core-shell magnetic mesoporous microspheres with a monolayer of mesoporous shell of different composition, such as core-shell magnetic mesoporous aluminosilicate (CS-MMAS), silica (CS-MMS), and zirconia-silica (CS-MMZS), open and large pores by employing polystyrene-block-poly (4-vinylpyridine) (PS-b-P4VP) as an interface structure directing agent and aluminum acetylacetonate (Al(acac) 3 ), zirconium acetylacetonate, and tetraethyl orthosilicate as shell precursors. The obtained CS-MMAS microspheres possess magnetic core, perpendicular mesopores (20-32 nm) in the shell, high surface area (244.7 m 2 g -1 ), and abundant acid sites (0.44 mmol g -1 ), and as a result, they exhibit superior performance in removal of organophosphorus pesticides (fenthion) with a fast adsorption dynamics and high adsorption capacity. CS-MMAS microspheres loaded with Au nanoparticles (≈3.5 nm) behavior as a highly active heterogeneous nanocatalyst for N-alkylation reaction for producing N-phenylbenzylamine with a selectivity and yields of over 90% and good magnetic recyclability. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of mesoporous silica nanoparticles and nanorods: Application to doxorubicin delivery

NASA Astrophysics Data System (ADS)

Rahmani, Saher; Durand, Jean-Olivier; Charnay, Clarence; Lichon, Laure; Férid, Mokhtar; Garcia, Marcel; Gary-Bobo, Magali

2017-06-01

The synthesis and application of mesoporous silica nanoparticles (MSN) and mesoporous silica nanorods (MSNR) for drug delivery were described. MSN or MSNR were obtained by adjusting the amount of added cosolvent to the sol-gel solution. Therefore, the addition of ethanol (EtOH) has contributed to the control of the particle shape and to the structure of the mesoporosity. MSN and MSNR particles were then loaded with doxorubicin and incubated with MCF-7 breast cancer cells. MSN and MSNR particles were efficient in killing cancer cells but their behavior in drug delivery was altered on account of the difference in their morphology. MSN showed a burst release of doxorubicin in cells whereas MSNR showed a sustained delivery of the anti-cancer drug.

Sulfur-infiltrated porous carbon microspheres with controllable multi-modal pore size distribution for high energy lithium-sulfur batteries

NASA Astrophysics Data System (ADS)

Zhao, Cunyu; Liu, Lianjun; Zhao, Huilei; Krall, Andy; Wen, Zhenhai; Chen, Junhong; Hurley, Patrick; Jiang, Junwei; Li, Ying

2013-12-01

Sulfur has received increasing attention as a cathode material for lithium-sulfur (Li-S) batteries due to its high theoretical specific capacity. However, the commercialization of Li-S batteries is limited by the challenges of poor electrical conductivity of sulfur, dissolution of the polysulfide intermediates into the electrolyte, and volume expansion of sulfur during cycling. Herein, we report the fabrication of novel-structured porous carbon microspheres with a controllable multi-modal pore size distribution, i.e., a combination of interconnected micropores, mesopores and macropores. Cathodes made of sulfur infiltrated in such a hierarchical carbon framework provide several advantages: (1) a continuous and high surface area carbon network for enhanced electrical conductivity and high sulfur loading; (2) macropores and large mesopores bridged by small mesopores to provide good electrolyte accessibility and fast Li ion transport and to accommodate volume expansion of sulfur; and (3) small mesopores and micropores to improve carbon/sulfur interaction and to help trap polysulfides. An initial discharge capacity at 1278 mA h g-1 and capacity retention at 70.7% (904 mA h g-1) after 100 cycles at a high rate (1 C) were achieved. The material fabrication process is relatively simple and easily scalable.Sulfur has received increasing attention as a cathode material for lithium-sulfur (Li-S) batteries due to its high theoretical specific capacity. However, the commercialization of Li-S batteries is limited by the challenges of poor electrical conductivity of sulfur, dissolution of the polysulfide intermediates into the electrolyte, and volume expansion of sulfur during cycling. Herein, we report the fabrication of novel-structured porous carbon microspheres with a controllable multi-modal pore size distribution, i.e., a combination of interconnected micropores, mesopores and macropores. Cathodes made of sulfur infiltrated in such a hierarchical carbon framework provide several advantages: (1) a continuous and high surface area carbon network for enhanced electrical conductivity and high sulfur loading; (2) macropores and large mesopores bridged by small mesopores to provide good electrolyte accessibility and fast Li ion transport and to accommodate volume expansion of sulfur; and (3) small mesopores and micropores to improve carbon/sulfur interaction and to help trap polysulfides. An initial discharge capacity at 1278 mA h g-1 and capacity retention at 70.7% (904 mA h g-1) after 100 cycles at a high rate (1 C) were achieved. The material fabrication process is relatively simple and easily scalable. Electronic supplementary information (ESI) available: Preparation process scheme; X-ray mapping images and EDX analysis for the surface of PMC/S-40; X-ray mapping images for the cross-section of PMC/S-40; thermogravimetric analysis (TGA) of PMC/S samples; T-plot results for PMC sample; and electrochemical measurements of lithium-sulfur batteries using PMC/S as cathode materials. See DOI: 10.1039/c3nr04532c

Mesoporous systems for poorly soluble drugs.

PubMed

Xu, Wujun; Riikonen, Joakim; Lehto, Vesa-Pekka

2013-08-30

Utilization of inorganic mesoporous materials in formulations of poorly water-soluble drugs to enhance their dissolution and permeation behavior is a rapidly growing area in pharmaceutical materials research. The benefits of mesoporous materials in drug delivery applications stem from their large surface area and pore volume. These properties enable the materials to accommodate large amounts of payload molecules, protect them from premature degradation, and promote controlled and fast release. As carriers with various morphologies and chemical surface properties can be produced, these materials may even promote adsorption from the gastrointestinal tract to the systemic circulation. The main concern regarding their clinical applications is still the safety aspect even though most of them have been reported to be safely excreted, and a rather extensive toxicity screening has already been conducted with the most frequently studied mesoporous materials. In addition, the production of the materials on a large scale and at a reasonable cost may be a challenge when considering the utilization of the materials in industrial processes. However, if mesoporous materials could be employed in the industrial crystallization processes to produce hybrid materials with poorly soluble compounds, and hence to enhance their oral bioavailability, this might open new avenues for the pharmaceutical industry to employ nanotechnology in their processes. Copyright © 2012 Elsevier B.V. All rights reserved.

Functionalization of SBA-15 mesoporous silica by Cu-phosphonate units: Probing of synthesis route

DOE Office of Scientific and Technical Information (OSTI.GOV)

Laskowski, Lukasz, E-mail: lukasz.laskowski@kik.pcz.pl; Czestochowa University of Technology, Institute of Physics, Al. Armii Krajowej 19, 42-201 Czestochowa; Laskowska, Magdalena, E-mail: magdalena.laskowska@onet.pl

2014-12-15

Mesoporous silica SBA-15 containing propyl-copper phosphonate units was investigated. The structure of mesoporous samples was tested by N{sub 2} isothermal sorption (BET and BHJ analysis), TEM microscopy and X-Ray scattering. Quantitative analysis EDX has given information about proportions between component atoms in the sample. Quantitative elemental analysis has been carried out to support EDX. To examine bounding between copper atoms and phosphonic units the Raman spectroscopy was carried out. As a support of Raman scattering, the theoretical calculations were made based on density functional theory, with the B3LYP method. By comparison of the calculated vibrational spectra of the molecule withmore » experimental results, distribution of the active units inside silica matrix has been determined. - Graphical abstract: The present study is devoted to mesoporous silica SBA-15 containing propyl-copper phosphonate units. The species were investigated to confirm of synthesis procedure correctness by the micro-Raman technique combined with DFT numerical simulations. Complementary research was carried out to test the structure of mesoporous samples. - Highlights: • SBA-15 silica functionalized with propyl-copper phosphonate units was synthesized. • Synthesis efficiency probed by Raman study supported with DFT simulations. • Homogenous distribution of active units was proved. • Synthesis route enables precise control of distance between copper ions.« less

Synthesis of pH-sensitive poly(β-amino ester)-coated mesoporous silica nanoparticles for the controlled release of drugs

NASA Astrophysics Data System (ADS)

Talavera-Pech, William A.; Esparza-Ruiz, Adriana; Quintana-Owen, Patricia; Vilchis-Nestor, Alfredo R.; Barrón-Zambrano, Jesus A.; Ávila-Ortega, Alejandro

2018-03-01

This report describes the synthesis of a controlled drug delivery system that was obtained by coating mesoporous silica nanoparticles (MSNs) with poly(β-amino ester) (PbAE), which is a solid and stable material at physiological pH, but is dissolved at acidic pH values, such as those in tumor tissues (from 5.0 to 6.5). To synthesize the system, PbAE chains were grafted onto amino-functionalized MSNs through a reaction between the surface amino groups of MSNs and the ends of acrylate chains of a PbAE. The system was physicochemically characterized by dynamic light scattering (DLS), Fourier transform infrared spectroscopy, transmission electron microscopy, thermogravimetric analysis, X-ray photoelectron spectrometry, and X-ray diffraction analyses. In addition, the in vitro release of doxorubicin (DOX) and doxycycline (DXY) in acidic and physiological media was evaluated. It was observed that the PbAE modification did not affect the mesoporous structure of MSNs. When the amount of 3-aminopropyltriethoxysilane was increased during functionalization, the amount of PbAE binding to MSNs increased as well. With respect to drug release, the sample with the highest amount of PbAE showed better control in the delivery of DXY and DOX in acidic media, because at pH 5.5, the release of both drugs was 40% higher than that at pH 7.4. These results reveal two aspects about the presence of PbAE in MSNs: PbAE does not affect the mesoporous structure of the nanoparticles, and PbAE is the main factor controlling the delivery of drugs in acidic media.

In situ fabrication of hollow hydroxyapatite microspheres by phosphate solution immersion

NASA Astrophysics Data System (ADS)

Wang, Yingchun; Yao, Aihua; Huang, Wenhai; Wang, Deping; zhou, Jun

2011-07-01

Hollow hydroxyapatite (HAP) microspheres with pores on their surfaces were prepared by converting Li 2O-CaO-B 2O 3 (LCB) glass microspheres in phosphate solution. The structure, phase composition, surface morphology, and porosity of the hollow HAP microspheres were characterized by SEM, SEM-EDS, XRD, FTIR, ICP-AES, and N 2 adsorption-desorption techniques. The formation and conversion mechanism of the hollow HAP microspheres during immersion process were discussed. The as-prepared microspheres consisted of calcium deficient carbonated hydroxyapatite, which is biomimetic. FTIR spectra indicated that the resulting apatite were B-type CO 3HAP, in which carbonate ions occupied the phosphate sites. After 600 °C heating treatment, hollow microspheres were completely composed of calcium deficient hydroxyapatite crystals including CO32-. The pore size distribution of the as-prepared hollow HAP microspheres were mainly the mesopores in the range of 2-40 nm with the pore volume 0.5614 cm 3/g, and the mean pore size 10.5 nm, respectively. The results confirmed that LCB glass were transformed to hydroxyapatite without changing the external shape and dimension of the original glass object and the resulting microspheres possessed good hollow structures. Once immersed in phosphate solution, Ca-P-OH hydrates were in situ formed on the surface of the glass and precipitated in the position occupied by Ca 2+, while the pores were formed in the position occupied by Li + and B 3+. These hollow HAP microspheres with such structures may be used as promising drug delivery devices.

Polypyrrole-derived nitrogen and oxygen co-doped mesoporous carbons as efficient metal-free electrocatalyst for hydrazine oxidation.

PubMed

Meng, Yuying; Zou, Xiaoxin; Huang, Xiaoxi; Goswami, Anandarup; Liu, Zhongwu; Asefa, Tewodros

2014-10-08

We demonstrate that polypyrrole-derived nitrogen and oxygen co-doped mesoporous carbons can serve as efficient, metal-free electrocatalysts for hydrazine oxidation reaction, with low overpotential and high current density. The materials' structures and the nature and type of their included dopants, which can be controlled by varying the synthetic conditions, can affect the electrocatalytic properties of the materials. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Morphology-controllable synthesis of cobalt oxalates and their conversion to mesoporous Co3O4 nanostructures for application in supercapacitors.

PubMed

Wang, Dewei; Wang, Qihua; Wang, Tingmei

2011-07-18

In this work, one-dimensional and layered parallel folding of cobalt oxalate nanostructures have been selectively prepared by a one-step, template-free, water-controlled precipitation approach by simply altering the solvents used at ambient temperature and pressure. Encouragingly, the feeding order of solutions played an extraordinary role in the synthesis of nanorods and nanowires. After calcination in air, the as-prepared cobalt oxalate nanostructures were converted to mesoporous Co(3)O(4) nanostructures while their original frame structures were well maintained. The phase composition, morphology, and structure of the as-obtained products were studied in detail. Electrochemical properties of the Co(3)O(4) electrodes were carried out using cyclic voltammetry (CV) and galvanostatic charge-discharge measurements by a three-electrode system. The electrochemical experiments revealed that the layered parallel folding structure of mesoporous Co(3)O(4) exhibited higher capacitance compared to that of the nanorods and nanowires. A maximum specific capacitance of 202.5 F g (-1) has been obtained in 2 M KOH aqueous electrolyte at a current density of 1 A g(-1) with a voltage window from 0 to 0.40 V. Furthermore, the specific capacitance decay after 1000 continuous charge-discharge cycles was negligible, revealing the excellent stability of the electrode. These characteristics indicate that the mesoporous Co(3)O(4) nanostructures are promising electrode materials for supercapacitors.

Motion Control of Urea-Powered Biocompatible Hollow Microcapsules.

PubMed

Ma, Xing; Wang, Xu; Hahn, Kersten; Sánchez, Samuel

2016-03-22

The quest for biocompatible microswimmers powered by compatible fuel and with full motion control over their self-propulsion is a long-standing challenge in the field of active matter and microrobotics. Here, we present an active hybrid microcapsule motor based on Janus hollow mesoporous silica microparticles powered by the biocatalytic decomposition of urea at physiological concentrations. The directional self-propelled motion lasts longer than 10 min with an average velocity of up to 5 body lengths per second. Additionally, we control the velocity of the micromotor by chemically inhibiting and reactivating the enzymatic activity of urease. The incorporation of magnetic material within the Janus structure provides remote magnetic control on the movement direction. Furthermore, the mesoporous/hollow structure can load both small molecules and larger particles up to hundreds of nanometers, making the hybrid micromotor an active and controllable drug delivery microsystem.

Modified release from lipid bilayer coated mesoporous silica nanoparticles using PEO–PPO–PEO triblock copolymers [Modified release from lipid bilayer coated mesoporous silica nanoparticles using PEO PPO PEO triblock copolymers

DOE PAGES

Rahman, Masoud; Yu, Erick; Forman, Evan; ...

2014-08-20

Triblock copolymers comprised of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO, or trade name Pluronic) interact with lipid bilayers to increase their permeability. Here we demonstrate a novel application of Pluronic L61 and L64 as modification agents in tailoring the release rate of a molecular indicator species from 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) bilayer-coated superparamagnetic Fe 3O 4/mesoporous silica coreshell nanoparticles. Lastly, we show there is a direct relationship between Pluronic concentration and the indicator molecule release, suggesting Pluronic may be useful for the controlled release of drugs from lipid bilayer-coated carriers.

Hierarchically Superstructured Metal Sulfides: Facile Perturbation-Assisted Nanofusion Synthesis and Visible Light Photocatalytic Characterizations

DOE PAGES

Yue, Yanfeng; Li, Yunchao; Bridges, Craig A.; ...

2016-11-29

A novel and simple perturbation-assisted nanofusion (PNF) synthetic strategy was developed for the fabrication of stable hierarchically superstructured metal sulfides. This promising approach, based on a kinetically controlled precipitation to simultaneously condense and re-dissolve polymorphic nanocrystallites, provides the resultant samples with a unique mesoporous framework. This PNF approach is environmentally friendly, produces gram-scale products in a matter of hours, and is complimentary to traditional hard or soft templating methods for the construction of mesoporous metal sulfides. PNF derived hierarchical porous CdS exhibited a vastly improved photocatalytic performance over its commercial bulk counterpart under visible light irradiation, demonstrating the advantage ofmore » the porous morphology for photocatalysis resulting from the enlarged surface area and the easy accessibility of the mesopores.« less

High-temperature-stable and regenerable catalysts: platinum nanoparticles in aligned mesoporous silica wells.

PubMed

Xiao, Chaoxian; Maligal-Ganesh, Raghu V; Li, Tao; Qi, Zhiyuan; Guo, Zhiyong; Brashler, Kyle T; Goes, Shannon; Li, Xinle; Goh, Tian Wei; Winans, Randall E; Huang, Wenyu

2013-10-01

We report the synthesis, structural characterization, thermal stability study, and regeneration of nanostructured catalysts made of 2.9 nm Pt nanoparticles sandwiched between a 180 nm SiO2 core and a mesoporous SiO2 shell. The SiO2 shell consists of 2.5 nm channels that are aligned perpendicular to the surface of the SiO2 core. The nanostructure mimics Pt nanoparticles that sit in mesoporous SiO2 wells (Pt@MSWs). By using synchrotron-based small-angle X-ray scattering, we were able to prove the ordered structure of the aligned mesoporous shell. By using high-temperature cyclohexane dehydrogenation as a model reaction, we found that the Pt@MSWs of different well depths showed stable activity at 500 °C after the induction period. Conversely, a control catalyst, SiO2 -sphere-supported Pt nanoparticles without a mesoporous SiO2 shell (Pt/SiO2 ), was deactivated. We deliberately deactivated the Pt@MSWs catalyst with a 50 nm deep well by using carbon deposition induced by a low H2 /cyclohexane ratio. The deactivated Pt@MSWs catalyst was regenerated by calcination at 500 °C with 20 % O2 balanced with He. After the regeneration treatments, the activity of the Pt@MSWs catalyst was fully restored. Our results suggest that the nanostructured catalysts-Pt nanoparticles confined inside mesoporous SiO2 wells-are stable and regenerable for treatments and reactions that require high temperatures. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of polycarbonate-r-polyethylene glycol copolymer for templated synthesis of mesoporous TiO2 films.

PubMed

Patel, Rajkumar; Kim, Jinkyu; Lee, Chang Soo; Kim, Jong Hak

2014-12-01

We synthesized a novel polycarbonate Z-r-polyethylene glycol (PCZ-r-PEG) copolymer by solution polycondensation. Successful synthesis of PCZ-r-PEG copolymer was confirmed by Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance (1H-NMR), gel permeation chromatography (GPC), and transmission electron microscopy (TEM). PCZ-r-PEG copolymer was used as a structure-directing agent for fabrication of mesoporous thin film containing a titanium dioxide (TiO2) layer. To control the porosity of the resultant inorganic layer, the ratio of titanium(IV) isopropoxide (TTIP) to PCZ-r-PEG copolymer was varied. The structure and porosity of the resulting mesoporous films were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) analyses. Mesoporous TiO2 films fabricated on an F-doped tin oxide (FTO) surface were used as photoanodes for quasi-solid-state dye-sensitized solar cells (qssDSSCs). The highest efficiency achieved was 3.3% at 100 mW/cm2 for a film thickness of 750 nm, which is high considering the thickness of TiO2 film, indicating the importance of the structure-directing agent.

Hindered disulfide bonds to regulate release rate of model drug from mesoporous silica.

PubMed

Nadrah, Peter; Maver, Uroš; Jemec, Anita; Tišler, Tatjana; Bele, Marjan; Dražić, Goran; Benčina, Mojca; Pintar, Albin; Planinšek, Odon; Gaberšček, Miran

2013-05-01

With the advancement of drug delivery systems based on mesoporous silica nanoparticles (MSNs), a simple and efficient method regulating the drug release kinetics is needed. We developed redox-responsive release systems with three levels of hindrance around the disulfide bond. A model drug (rhodamine B dye) was loaded into MSNs' mesoporous voids. The pore opening was capped with β-cyclodextrin in order to prevent leakage of drug. Indeed, in absence of a reducing agent the systems exhibited little leakage, while the addition of dithiothreitol cleaved the disulfide bonds and enabled the release of cargo. The release rate and the amount of released dye were tuned by the level of hindrance around disulfide bonds, with the increased hindrance causing a decrease in the release rate as well as in the amount of released drug. Thus, we demonstrated the ability of the present mesoporous systems to intrinsically control the release rate and the amount of the released cargo by only minor structural variations. Furthermore, an in vivo experiment on zebrafish confirmed that the present model delivery system is nonteratogenic.

Mesoporous carbon materials

DOEpatents

Dai, Sheng; Fulvio, Pasquale Fernando; Mayes, Richard T.; Wang, Xiqing; Sun, Xiao-Guang; Guo, Bingkun

2014-09-09

A conductive mesoporous carbon composite comprising conductive carbon nanoparticles contained within a mesoporous carbon matrix, wherein the conductive mesoporous carbon composite possesses at least a portion of mesopores having a pore size of at least 10 nm and up to 50 nm, and wherein the mesopores are either within the mesoporous carbon matrix, or are spacings delineated by surfaces of said conductive carbon nanoparticles when said conductive carbon nanoparticles are fused with each other, or both. Methods for producing the above-described composite, devices incorporating them (e.g., lithium batteries), and methods of using them, are also described.

Dynamics of molecular rotors confined in two dimensions: transition from a 2D rotational glass to a 2D rotational fluid in a periodic mesoporous organosilica.

PubMed

Vogelsberg, Cortnie S; Bracco, Silvia; Beretta, Mario; Comotti, Angiolina; Sozzani, Piero; Garcia-Garibay, Miguel A

2012-02-09

The motional behavior of p-phenylene-d(4) rotators confined within the 2D layers of a hierarchically ordered periodic mesoporous p-divinylbenzenesilica has been elucidated to evaluate the effects of reduced dimensionality on the engineered dynamics of artificial molecular machines. The hybrid mesoporous material, characterized by a honeycomb lattice structure, has arrays of alternating p-divinylbenzene rotors and siloxane layers forming the molecularly ordered walls of the mesoscopic channels. The p-divinylbenzene rotors are strongly anchored between two adjacent siloxane sheets, so that the p-phenylene rotators are unable to experience translational diffusion and are allowed to rotate about only one fixed axis. Variable-temperature (2)H NMR experiments revealed that the p-phenylene rotators undergo an exchange process between sites related by 180° and a non-Arrhenius temperature dependence of the dynamics, with reorientational rates ranging from 10(3) to 10(8) Hz between 215 to 305 K. The regime of motion changes rapidly at about 280 K indicating the occurrence of a dynamical transition. The transition was also recognized by a steep change in the heat capacity at constant pressure. As a result of the robust lamellar architecture comprising the pore walls, the orientational dynamic disorder related to the phase transition is only realized in two dimensions within the layers, that is in the plane perpendicular to the channel axis. Thus, the aligned rotors that form the organic layers exhibit unique anisotropic dynamical properties as a result of the architecture's reduced dimensionality. The dynamical disorder restricted to two dimensions constitutes a highly mobile fluidlike rotational phase at room temperature, which upon cooling undergoes a transition to a more rigid glasslike phase. Activation energies of 5.9 and 9.5 kcal/mol respectively have been measured for the two dynamical regimes of rotation. Collectively, our investigation has led to the discovery of an orientationally disordered 2D rotational glass and its transition from rigid to soft at increasing temperature. The spectral narrowing observed in the (2)H NMR experiments at higher temperatures (310-420 K) is consistent with fast rotational dynamics, which remain anisotropic in nature within the robust lamellar architecture. This study suggests that exploiting reduced dimensionality in the design of solid-state artificial molecular machines and functional materials may yield access to behavior previously unrealized in 3D materials. © 2012 American Chemical Society

A multi-controlled drug delivery system based on magnetic mesoporous Fe3O4 nanopaticles and a phase change material for cancer thermo-chemotherapy

NASA Astrophysics Data System (ADS)

Zhang, Qi; Liu, Jian; Yuan, Kunjie; Zhang, Zhengguo; Zhang, Xiaowen; Fang, Xiaoming

2017-10-01

Herein a novel multi-controlled drug release system for doxorubicin (DOX) was developed, in which monodisperse mesoporous Fe3O4 nanoparticles were combined with a phase change material (PCM) and polyethylene glycol 2000 (PEG2000). It is found that the PCM/PEG/DOX mixture containing 20% PEG could be dissolved into water at 42 °C. The mesoporous Fe3O4 nanoparticles prepared by the solvothermal method had sizes of around 25 nm and exhibited a mesoporous microstructure. A simple solvent evaporation process was employed to load the PCM/PEG/DOX mixture on the mesoporous Fe3O4 nanoparticles completely. In the Fe3O4@PCM/PEG/DOX system, the pores of the Fe3O4 nanoparticles were observed to be filled with the mixture of PCM/PEG/DOX. The Fe3O4@PCM/PEG/DOX system showed a saturation magnetization value of 50.0 emu g-1, lower than 71.1 emu g-1 of the mesoporous Fe3O4 nanoparticles, but it was still high enough for magnetic targeting and hyperthermia application. The evaluation on drug release performance indicated that the Fe3O4@PCM/PEG/DOX system achieved nearly zero release of DOX in vitro in body temperature, while around 80% of DOX could be released within 1.5 h at the therapeutic threshold of 42 °C or under the NIR laser irradiation for about 4 h. And a very rapid release of DOX was achieved by this system when applying an alternating magnetic field. By comparing the systems with and without PEG2000, it is revealed that the presence of PEG2000 makes DOX easy to be released from 1-tetradecanol to water, owing to its functions of increasing the solubility of DOX in 1-tetradecanol as well as decreasing the surface tension between water and 1-tetradecanol. The novel drug release system shows great potential for the development of thermo-chemotherapy of cancer treatment.

Morphology, microstructure, and magnetic properties of ordered large-pore mesoporous cadmium ferrite thin film spin glasses.

PubMed

Reitz, Christian; Suchomski, Christian; Chakravadhanula, Venkata Sai Kiran; Djerdj, Igor; Jagličić, Zvonko; Brezesinski, Torsten

2013-04-01

Herein, we report the synthesis, microstructure, and magnetic properties of cadmium ferrite (CdFe2O4) thin films with both an ordered cubic network of 18 nm diameter pores and single-phase spinel grains averaging 13 nm in diameter. These mesoporous materials were produced through facile polymer templating of hydrated nitrate salt precursors. Both the morphology and the microstructure, including cation site occupancy and electronic bonding configuration, were analyzed in detail by electron microscopy, grazing incidence small-angle X-ray scattering, Raman and X-ray photoelectron spectroscopy, and N2-physisorption. The obtained data demonstrate that the network of pores is retained up to annealing temperatures as high as 650 °C--the onset of crystallization is at ϑ = (590 ± 10) °C. Furthermore, they show that the polymer-templated samples exhibit a "partially" inverted spinel structure with inversion parameter λ = 0.40 ± 0.02. This differs from microcrystalline CdFe2O4 which shows virtually no inversion. Magnetic susceptibility studies reveal ferrimagnetic spin coupling below 147 K and further point to the likelihood of glassy behavior at low temperature (T(f) ≈ 60 K). In addition, analysis of room temperature magnetization data indicates the presence of sub-10 nm diameter superparamagnetic clusters in an otherwise paramagnetic environment.

Mesoporous Cu2O-CeO2 composite nanospheres with enhanced catalytic activity for 4-nitrophenol reduction

NASA Astrophysics Data System (ADS)

Pang, Juanjuan; Li, Wenting; Cao, Zhenhao; Xu, Jingjing; Li, Xue; Zhang, Xiaokai

2018-05-01

In this paper, mesoporous Cu2O-CeO2 nanospheres were fabricated via a facile, low-temperature solution route in the presence of poly(2-vinylpyridine)-b-poly(ethylene Oxide) (P2VP-b-PEO) block copolymers. The prepared mesoporous Cu2O-CeO2 nanospheres were characterized systematically by scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), X-ray photoelectron spectroscopy (XPS) and nitrogen adsorption/desorption. The formation mechanism of mesoporous Cu2O-CeO2 nanospheres was discussed. The results show that the molar ratios of Ce3+/Cu2+ and the reaction time have an important influence on the nanostructure of Cu2O-CeO2 composite spheres. The resultant Cu2O-CeO2 nanospheres exhibit superior catalytic activities in the reduction of 4-nitrophenol to 4-aminophenol by NaBH4. The activity factor (K = k/m) for the Cu2O-CeO2 nanospheres prepared with the molar ratio of Ce3+/Cu2+ of 5/1 is 3006.6 s-1 g-1, which is much higher than reported values. This paper demonstrates a highly controllable approach to the production of mesoporous Cu2O-CeO2 nanospheres, which have potential applications in the areas of catalysis, adsorption, sensors and so on.

Functional mesoporous materials for energy applications: solar cells, fuel cells, and batteries

NASA Astrophysics Data System (ADS)

Ye, Youngjin; Jo, Changshin; Jeong, Inyoung; Lee, Jinwoo

2013-05-01

This feature article presents recent progress made in the synthesis of functional ordered mesoporous materials and their application as high performance electrodes in dye-sensitized solar cells (DSCs) and quantum dot-sensitized solar cells (QDSCs), fuel cells, and Li-ion batteries. Ordered mesoporous materials have been mainly synthesized using two representative synthetic methods: the soft template and hard template methods. To overcome the limitations of these two methods, a new method called CASH was suggested. The CASH method combines the advantages of the soft and hard template methods by employing a diblock copolymer, PI-b-PEO, which contains a hydrophilic block and an sp2-hybridized-carbon-containing hydrophobic block as a structure-directing agent. After discussing general techniques used in the synthesis of mesoporous materials, this article presents recent applications of mesoporous materials as electrodes in DSCs and QDSCs, fuel cells, and Li-ion batteries. The role of material properties and mesostructures in device performance is discussed in each case. The developed soft and hard template methods, along with the CASH method, allow control of the pore size, wall composition, and pore structure, providing insight into material design and optimization for better electrode performances in these types of energy conversion devices. This paper concludes with an outlook on future research directions to enable breakthroughs and overcome current limitations in this field.

Functional mesoporous materials for energy applications: solar cells, fuel cells, and batteries.

PubMed

Ye, Youngjin; Jo, Changshin; Jeong, Inyoung; Lee, Jinwoo

2013-06-07

This feature article presents recent progress made in the synthesis of functional ordered mesoporous materials and their application as high performance electrodes in dye-sensitized solar cells (DSCs) and quantum dot-sensitized solar cells (QDSCs), fuel cells, and Li-ion batteries. Ordered mesoporous materials have been mainly synthesized using two representative synthetic methods: the soft template and hard template methods. To overcome the limitations of these two methods, a new method called CASH was suggested. The CASH method combines the advantages of the soft and hard template methods by employing a diblock copolymer, PI-b-PEO, which contains a hydrophilic block and an sp(2)-hybridized-carbon-containing hydrophobic block as a structure-directing agent. After discussing general techniques used in the synthesis of mesoporous materials, this article presents recent applications of mesoporous materials as electrodes in DSCs and QDSCs, fuel cells, and Li-ion batteries. The role of material properties and mesostructures in device performance is discussed in each case. The developed soft and hard template methods, along with the CASH method, allow control of the pore size, wall composition, and pore structure, providing insight into material design and optimization for better electrode performances in these types of energy conversion devices. This paper concludes with an outlook on future research directions to enable breakthroughs and overcome current limitations in this field.

An NAD(P)H:quinone oxidoreductase 1 (NQO1) enzyme responsive nanocarrier based on mesoporous silica nanoparticles for tumor targeted drug delivery in vitro and in vivo

NASA Astrophysics Data System (ADS)

Gayam, Srivardhan Reddy; Venkatesan, Parthiban; Sung, Yi-Ming; Sung, Shuo-Yuan; Hu, Shang-Hsiu; Hsu, Hsin-Yun; Wu, Shu-Pao

2016-06-01

The synthesis and characterization of an NAD(P)H:quinone oxidoreductase 1 (NQO1) enzyme responsive nanocarrier based on mesoporous silica nanoparticles (MSNPs) for on-command delivery applications has been described in this paper. Gatekeeping of MSNPs is achieved by the integration of mechanically interlocked rotaxane nanovalves on the surface of MSNPs. The rotaxane nanovalve system is composed of a linear stalk anchoring on the surface of MSNPs, an α-cyclodextrin ring that encircles it and locks the payload ``cargo'' molecules in the mesopores, and a benzoquinone stopper incorporated at the end of the stalk. The gate opening and controlled release of the cargo are triggered by cleavage of the benzoquinone stopper using an endogenous NQO1 enzyme. In addition to having efficient drug loading and controlled release mechanisms, this smart biocompatible carrier system showed obvious uptake and consequent release of the drug in tumor cells, could selectively induce the tumor cell death and enhance the capability of inhibition of tumor growth in vivo. The controlled drug delivery system demonstrated its use as a potential theranostic material.The synthesis and characterization of an NAD(P)H:quinone oxidoreductase 1 (NQO1) enzyme responsive nanocarrier based on mesoporous silica nanoparticles (MSNPs) for on-command delivery applications has been described in this paper. Gatekeeping of MSNPs is achieved by the integration of mechanically interlocked rotaxane nanovalves on the surface of MSNPs. The rotaxane nanovalve system is composed of a linear stalk anchoring on the surface of MSNPs, an α-cyclodextrin ring that encircles it and locks the payload ``cargo'' molecules in the mesopores, and a benzoquinone stopper incorporated at the end of the stalk. The gate opening and controlled release of the cargo are triggered by cleavage of the benzoquinone stopper using an endogenous NQO1 enzyme. In addition to having efficient drug loading and controlled release mechanisms, this smart biocompatible carrier system showed obvious uptake and consequent release of the drug in tumor cells, could selectively induce the tumor cell death and enhance the capability of inhibition of tumor growth in vivo. The controlled drug delivery system demonstrated its use as a potential theranostic material. Electronic supplementary information (ESI) available: Synthesis and characterization of the functional molecules and MSNPs is available in the ESI. See DOI: 10.1039/c6nr03525f

Enantioselectively controlled release of chiral drug (metoprolol) using chiral mesoporous silica materials

NASA Astrophysics Data System (ADS)

Guo, Zhen; Du, Yu; Liu, Xianbin; Ng, Siu-Choon; Chen, Yuan; Yang, Yanhui

2010-04-01

Chiral porous materials have attracted burgeoning attention on account of their potential applications in many areas, such as enantioseparation, chiral catalysis, chemical sensors and drug delivery. In this report, chiral mesoporous silica (CMS) materials with various pore sizes and structures were prepared using conventional achiral templates (other than chiral surfactant) and a chiral cobalt complex as co-template. The synthesized CMS materials were characterized by x-ray diffraction, nitrogen physisorption, scanning electron microscope and transmission electron microscope. These CMS materials, as carriers, were demonstrated to be able to control the enantioselective release of a representative chiral drug (metoprolol). The release kinetics, as modeled by the power law equation, suggested that the release profiles of metoprolol were remarkably dependent on the pore diameter and pore structure of CMS materials. More importantly, R- and S-enantiomers of metoprolol exhibited different release kinetics on CMS compared to the corresponding achiral mesoporous silica (ACMS), attributable to the existence of local chirality on the pore wall surface of CMS materials. The chirality of CMS materials on a molecular level was further substantiated by vibrational circular dichroism measurements.

Multifunctional mesoporous silica nanoparticles for combined therapeutic, diagnostic and targeted action in cancer treatment.

PubMed

Rosenholm, Jessica M; Sahlgren, Cecilia; Lindén, Mika

2011-07-01

The main objective in the development of nanomedicine is to obtain delivery platforms for targeted delivery of drugs or imaging agents for improved therapeutic efficacy, reduced side effects and increased diagnostic sensitivity. A (nano)material class that has been recognized for its controllable properties on many levels is ordered mesoporous inorganic materials, typically in the form of amorphous silica (SiO2). Characteristics for this class of materials include mesoscopic order, tunable pore dimensions in the (macro)molecular size range, a high pore volume and surface area, the possibility for selective surface functionality as well as morphology control. The robust but biodegradable ceramic matrix moreover provides shelter for incorporated agents (drugs, proteins, imaging agents, photosensitizers) leaving the outer particle surface free for further modification. The unique features make these materials particularly amenable to modular design, whereby functional moieties and features may be interchanged or combined to produce multifunctional nanodelivery systems combining targeting, diagnostic, and therapeutic actions. This review covers the latest developments related to the use of mesoporous silica nanoparticles (MSNs) as nanocarriers in biomedical applications, with special focus on cancer therapy and diagnostics.

Large-Scale, Three–Dimensional, Free–Standing, and Mesoporous Metal Oxide Networks for High–Performance Photocatalysis

PubMed Central

Bai, Hua; Li, Xinshi; Hu, Chao; Zhang, Xuan; Li, Junfang; Yan, Yan; Xi, Guangcheng

2013-01-01

Mesoporous nanostructures represent a unique class of photocatalysts with many applications, including splitting of water, degradation of organic contaminants, and reduction of carbon dioxide. In this work, we report a general Lewis acid catalytic template route for the high–yield producing single– and multi–component large–scale three–dimensional (3D) mesoporous metal oxide networks. The large-scale 3D mesoporous metal oxide networks possess large macroscopic scale (millimeter–sized) and mesoporous nanostructure with huge pore volume and large surface exposure area. This method also can be used for the synthesis of large–scale 3D macro/mesoporous hierarchical porous materials and noble metal nanoparticles loaded 3D mesoporous networks. Photocatalytic degradation of Azo dyes demonstrated that the large–scale 3D mesoporous metal oxide networks enable high photocatalytic activity. The present synthetic method can serve as the new design concept for functional 3D mesoporous nanomaterials. PMID:23857595

Preparation and improved photocatalytic activity of mesoporous WS{sub 2} using combined hydrothermal-evaporation induced self-assembly method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vattikuti, S.V. Prabhakar, E-mail: vsvprabu@gmail.com; Byon, Chan, E-mail: cbyon@ynu.ac.kr; Reddy, Ch. Venkata

2016-03-15

Highlights: • One-step method for synthesis of mesoporous WS{sub 2} was proposed. • Role of CTAB surfactant on formation of mesoporous WS{sub 2} was elucidated. • Possible growth mechanism of the mesoporous structure is also reported. • 0.1 wt% mesoporous WS{sub 2} catalyst exhibited high photocatalytic activity under UV light. - Abstract: In this paper, we report mesoporous WS{sub 2} nanosheets with a crystalline network that were synthesized using CTAB as a structure-directing agent via self-assembly induced by hydrothermal and thermal evaporation. Powder X-ray diffraction, Raman spectra, and high-resolution X-ray photoelectron spectroscopy results confirmed the formation of WS{sub 2} structures.more » Scanning electron microscopy and transmission electron microscopy were used to observe the as-prepared mesoporous frameworks. The mesoporous WS{sub 2} nanosheets have a surface area of 197 m{sup 2} g{sup −1}. A possible growth mechanism is reported for these mesoporous WS{sub 2} nanosheets. The mesoporous WS{sub 2} nanosheets demonstrate high photocatalytic activity. Among different concentrations, 0.1 wt% mesoporous WS{sub 2} shows superior catalytic activity compared to pristine WS{sub 2} nanosheets.« less

Proton Environments in Biomimetic Calcium Phosphates Formed from Mesoporous Bioactive CaO-SiO2-P2O5 Glasses in Vitro: Insights from Solid-State NMR.

PubMed

Mathew, Renny; Turdean-Ionescu, Claudia; Yu, Yang; Stevensson, Baltzar; Izquierdo-Barba, Isabel; García, Ana; Arcos, Daniel; Vallet-Regí, María; Edén, Mattias

2017-06-22

When exposed to body fluids, mesoporous bioactive glasses (MBGs) of the CaO-SiO 2 -P 2 O 5 system develop a bone-bonding surface layer that initially consists of amorphous calcium phosphate (ACP), which transforms into hydroxy-carbonate apatite (HCA) with a very similar composition as bone/dentin mineral. Information from various 1 H-based solid-state nuclear magnetic resonance (NMR) experiments was combined to elucidate the evolution of the proton speciations both at the MBG surface and within each ACP/HCA constituent of the biomimetic phosphate layer formed when each of three MBGs with distinct Ca, Si, and P contents was immersed in a simulated body fluid (SBF) for variable periods between 15 min and 30 days. Directly excited magic-angle-spinning (MAS) 1 H NMR spectra mainly reflect the MBG component, whose surface is rich in water and silanol (SiOH) moieties. Double-quantum-single-quantum correlation 1 H NMR experimentation at fast MAS revealed their interatomic proximities. The comparatively minor H species of each ACP and HCA component were probed selectively by heteronuclear 1 H- 31 P NMR experimentation. The initially prevailing ACP phase comprises H 2 O and "nonapatitic" HPO 4 2- /PO 4 3- groups, whereas for prolonged MBG soaking over days, a well-progressed ACP → HCA transformation was evidenced by a dominating O 1 H resonance from HCA. We show that 1 H-detected 1 H → 31 P cross-polarization NMR is markedly more sensitive than utilizing powder X-ray diffraction or 31 P NMR for detecting the onset of HCA formation, notably so for P-bearing (M)BGs. In relation to the long-standing controversy as to whether bone mineral comprises ACP and/or forms via an ACP precursor, we discuss a recently accepted structural core-shell picture of both synthetic and biological HCA, highlighting the close relationship between the disordered surface layer and ACP.

Micro-mesoporous carbon spheres derived from carrageenan as electrode material for supercapacitors

NASA Astrophysics Data System (ADS)

Fan, Yang; Yang, Xin; Zhu, Bing; Liu, Pei-Fang; Lu, Hai-Ting

2014-12-01

The polysaccharide carrageenan is used as a natural precursor to prepare micro-mesoporous carbon spheres. The carbon spheres were synthesized by hydrothermal carbonization of carrageenan, and subsequent chemical activation by KOH at different temperatures. The obtained micro-mesoporous carbon spheres have high surface area (up to 2502 m2 g-1) and large pore volume (up to 1.43 cm3 g-1). Moreover, the micro- and mesoporosity can be finely tuned be modifying the activation temperatures in the range of 700-900 °C. The carbon spheres activated at 900 °C present high specific capacitance of 230 F g-1 at a current density of 1 A g-1 and good ion transport kinetics. The good capacitive performance can be ascribed to the high specific surface area, well-controlled micro- and mesoporosity and narrow pore size distribution.

New triethoxysilylated 10-vertex closo-decaborate clusters. Synthesis and controlled immobilization into mesoporous silica.

PubMed

Abi-Ghaida, Fatima; Laila, Zahra; Ibrahim, Ghassan; Naoufal, Daoud; Mehdi, Ahmad

2014-09-14

Novel silylated hydroborate clusters comprising the closo-decaborate cage were prepared and characterized by (1)H, (13)C, (11)B, (29)Si NMR and mass spectroscopy ESI. The synthesis of such silylated clusters was achieved using reactive derivatives of [B10H10](2-), [1-B10H9N2](-) and [2-B10H9CO](-). These silylated decaborate clusters constitute a new class of precursors that can be covalently anchored onto various silica supports without any prior surface modification. As a proof of concept, the synthesized precursors were successfully anchored on mesoporous silica, SBA-15 type, in different percentages, where the mesoporous material retained its structure. All materials modified with closo-decaborate were characterized by (11)B and (29)Si solid state NMR, XRD, TEM and nitrogen sorption.

Synthesis and characterization of mesoporous materials

NASA Astrophysics Data System (ADS)

Cheng, Wei

Mesoporous materials are highly porous solids with pore sizes in the range of 20 to 500 A and a narrow pore size distribution. Creating a mesoporous morphology in transition metal oxides is expected to increase the kinetics of electrochemical photoelectrochemical processes due to the improved accessibility of electrolyte to electrode. The objective of the dissertation research is to prepare functional mesoporous materials based on transition metal oxides and to determine the effects of the mesoporous structure on the resulting charge transfer, electrochromism, and optical properties. In this dissertation, mesoporous tungsten oxide and niobium oxide were synthesized by incorporating tri-block copolymer surfactant templates into the sol-gel synthesis procedure. Both mesoporous materials have surface areas in the range of 130 m2/g with a narrow pore size distribution centered at ˜45A. Their electrochromic properties were characterized and found to be strongly influenced by the mesoporous morphology. Both mesoporous systems exhibit better electrochemical and optical reversibilities than the analogous sol-gel materials (without using surfactant) and the kinetics of bleaching is substantially faster. Coloration efficiencies for the mesoporous tungsten oxide and niobium oxide films are in the range of 16--37 cm 2/C and 12--16 cm2/C, respectively. Dye sensitized solar cells (DSSC) were fabricated using mesoporous niobium oxide as electrodes. Due to the higher surface area, the mesoporous electrodes have greater dye adsorption and electrolyte penetration compared to sol-gel electrodes, which leads to better electron injection, faster dye regeneration and thus, better cell performance. The mesoporous DSSC exhibits photocurrents of 2.9 mA and fill factors of 0.61. Open circuit voltages of the mesoporous DSSC are in the range of 0.6--0.83V.

Free-standing mesoporous carbon thin films with highly ordered pore architectures for nanodevices.

PubMed

Feng, Dan; Lv, Yingying; Wu, Zhangxiong; Dou, Yuqian; Han, Lu; Sun, Zhenkun; Xia, Yongyao; Zheng, Gengfeng; Zhao, Dongyuan

2011-09-28

We report for the first time the synthesis of free-standing mesoporous carbon films with highly ordered pore architecture by a simple coating-etching approach, which have an intact morphology with variable sizes as large as several square centimeters and a controllable thickness of 90 nm to ∼3 μm. The mesoporous carbon films were first synthesized by coating a resol precursors/Pluronic copolymer solution on a preoxidized silicon wafer and forming highly ordered polymeric mesostructures based on organic-organic self-assembly, followed by carbonizing at 600 °C and finally etching of the native oxide layer between the carbon film and the silicon substrate. The mesostructure of this free-standing carbon film is confirmed to be an ordered face-centered orthorhombic Fmmm structure, distorted from the (110) oriented body-centered cubic Im3̅m symmetry. The mesoporosity of the carbon films has been evaluated by nitrogen sorption, which shows a high specific BET surface area of 700 m(2)/g and large uniform mesopores of ∼4.3 nm. Both mesostructures and pore sizes can be tuned by changing the block copolymer templates or the ratio of resol to template. These free-standing mesoporous carbon films with cracking-free uniform morphology can be transferred or bent on different surfaces, especially with the aid of the soft polymer layer transfer technique, thus allowing for a variety of potential applications in electrochemistry and biomolecule separation. As a proof of concept, an electrochemical supercapacitor device directly made by the mesoporous carbon thin films shows a capacitance of 136 F/g at 0.5 A/g. Moreover, a nanofilter based on the carbon films has shown an excellent size-selective filtration of cytochrome c and bovine serum albumin.

Magnesium release from mesoporous carriers on endosseus implants does not influence bone maturation at 6 weeks in rabbit bone.

PubMed

Galli, Silvia; Andersson, Martin; Jinno, Yohei; Karlsson, Johan; He, Wenxiao; Xue, Ying; Mustafa, Kamal; Wennerberg, Ann; Jimbo, Ryo

2017-10-01

The release of magnesium ions (Mg 2+ ) from titanium surfaces has been shown to boost the initial biological response of peri-implant bone and to increase the biomechanical strength of osseointegration. The objective of the present paper was to investigate if the initial improvement in osseointegration would influence the bone remodeling also during the maturation stage of bone healing. Titanium implants were coated with mesoporous titania layers and either loaded with Mg 2+ (test group) or left untreated (control group). The implants were inserted in the tibiae of 10 New Zealand White rabbits. Osseointegration was assessed after 6 weeks by means of biomechanical testing (RTQ), non-decalcified histology and histomorphometry (BIC%, BA%, NBA%). The expression of genes involved in the bone formation and remodeling was quantified using qPCR. Mg 2+ releasing mesoporous titania coatings showed, on average, higher removal torques and histomorphometrical outcomes (RTQ: 17.2 Ncm vs. 15 Ncm; BIC: 38.8% vs. 32.1%; BA%: 71.6% vs. 64%; NBA% 62.5% vs. 54% for the tests vs the controls); however, the differences were not statistically significant. Three osteogenic markers, osteocalcin (OC), collagen 1 alpha 1 (COL1A1), and alkalin phosphatase (ALPL), were respectively 2-fold, 1.53-fold, and 1.13-fold up-regulated in the control group compared to the test. The expression of COL1A1 was particularly high in both groups, while the biomarkers for remodeling and inflammation showed a low expression in both groups. The results suggested that the initial enhancement in osseointegration induced by magnesium release from mesoporous titania coatings has no detrimental effects during bone maturation. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 2118-2125, 2017. © 2016 Wiley Periodicals, Inc.

Drug delivery from hydrophobic-modified mesoporous silicas: Control via modification level and site-selective modification

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tang Qunli, E-mail: tangqunli@hnu.c; State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001; Chen Yuxi

2010-01-15

Dimethylsilyl (DMS) modified mesoporous silicas were successfully prepared via co-condensation and post-grafting modification methods. The post-grafting modification was carried out by the reaction of the as-synthesized MCM-41 material (before CTAB removal) with diethoxydimethylsinale (DEDMS). N{sub 2} adsorption-desorption and {sup 29}Si MAS NMR characterization demonstrated that different amount of DMS groups were successfully incorporated into the co-condensation modified samples, and the functional DMS groups were placed selectively on the pore openings and external pore surfaces in the post-grafting modified samples. Subsequently, the controlled drug delivery properties from the resulting DMS-modified mesoporous silicas were investigated in detail. The drug adsorption experiments showedmore » that the adsorption capacities were mainly depended on the content of silanol group (CSG) in the corresponding carriers. The in vitro tests exhibited that the incorporation of DMS groups greatly retarded the ibuprofen release rate. Moreover, the ibuprofen release profiles could be well modulated by varying DMS modification levels and site-selective distribution of functional groups in mesoporous carriers. - The distribution of DMS groups on the pore surfaces of the mesostructures strongly affects the drug release rate. The P-M41-1 and the P-M41-2 possess the close DMS modification levels as the C-M41-10, but the ibuprofen release rates from the P-M41-1 and P-M41-2 are much slower than that from the C-M41-10.« less

Packaging biological cargoes in mesoporous materials: opportunities for drug delivery.

PubMed

Siefker, Justin; Karande, Pankaj; Coppens, Marc-Olivier

2014-11-01

Confinement of biomolecules in structured nanoporous materials offers several desirable features ranging from chemical and thermal stability, to resistance to degradation from the external environment. A new generation of mesoporous materials presents exciting new possibilities for the formulation and controlled release of biological agents. Such materials address niche applications in enteral and parenteral delivery of biologics, such as peptides, polypeptides, enzymes and proteins for use as therapeutics, imaging agents, biosensors, and adjuvants. Mesoporous silica Santa Barbara Amorphous-15 (SBA-15), with its unique, tunable pore diameter, and easily functionalized surface, provides a representative example of this new generation of materials. Here, we review recent advances in the design and synthesis of nanostructured mesoporous materials, focusing on SBA-15, and highlight opportunities for the delivery of biological agents to various organ and tissue compartments. The SBA-15 platform provides a delivery carrier that is inherently separated from the active biologic due to distinct intra and extra-particle environments. This permits the SBA-15 platform to not require direct modification of the active biological therapeutic. Additionally, this makes the platform universal and allows for its application independent of the desired methods of discovery and development. The SBA-15 platform also directly addresses issues of targeted delivery and controlled release, although future challenges in the implementation of this platform reside in particle design, biocompatibility, and the tunability of the internal and external material properties. Examples illustrating the flexibility in the application of the SBA-15 platform are also discussed.

Building solids inside nano-space: from confined amorphous through confined solvate to confined 'metastable' polymorph.

PubMed

Nartowski, K P; Tedder, J; Braun, D E; Fábián, L; Khimyak, Y Z

2015-10-14

The nanocrystallisation of complex molecules inside mesoporous hosts and control over the resulting structure is a significant challenge. To date the largest organic molecule crystallised inside the nano-pores is a known pharmaceutical intermediate - ROY (259.3 g mol(-1)). In this work we demonstrate smart manipulation of the phase of a larger confined pharmaceutical - indomethacin (IMC, 357.8 g mol(-1)), a substance with known conformational flexibility and complex polymorphic behaviour. We show the detailed structural analysis and the control of solid state transformations of encapsulated molecules inside the pores of mesoscopic cellular foam (MCF, pore size ca. 29 nm) and controlled pore glass (CPG, pore size ca. 55 nm). Starting from confined amorphous IMC we drive crystallisation into a confined methanol solvate, which upon vacuum drying leads to the stabilised rare form V of IMC inside the MCF host. In contrast to the pure form, encapsulated form V does not transform into a more stable polymorph upon heating. The size of the constraining pores and the drug concentration within the pores determine whether the amorphous state of the drug is stabilised or it recrystallises into confined nanocrystals. The work presents, in a critical manner, an application of complementary techniques (DSC, PXRD, solid-state NMR, N2 adsorption) to confirm unambiguously the phase transitions under confinement and offers a comprehensive strategy towards the formation and control of nano-crystalline encapsulated organic solids.

Contribution of mesopores in MgO-templated mesoporous carbons to capacitance in non-aqueous electrolytes

NASA Astrophysics Data System (ADS)

Kado, Yuya; Soneda, Yasushi; Yoshizawa, Noriko

2015-02-01

MgO-templated mesoporous carbons were fabricated by annealing trimagnesium dicitrate nonahydrate at various temperatures from 700 to 1000 °C with subsequent acid leaching of MgO. The obtained carbons contained a large amount of mesopores. Performances of electric double-layer capacitors using these carbons were examined for propylene carbonate electrolyte containing 1 M tetraethylammonium tetrafluoroborate. The mesoporous carbons synthesized at higher temperatures showed better rate capabilities. AC impedance measurements indicated that high-temperature annealing of the carbon precursors and the presence of mesopores were important for high rate performance. In addition, the contribution of mesopores to capacitance was more significant at higher current densities of 30 A g-1.

Hierarchical Metal–Organic Framework Hybrids: Perturbation-Assisted Nanofusion Synthesis

DOE PAGES

Yue, Yanfeng; Fulvio, Pasquale F.; Dai, Sheng

2015-12-04

Metal–organic frameworks (MOFs) represent a new family of microporous materials; however, microporous–mesoporous hierarchical MOF materials have been less investigated because of the lack of simple, reliable methods to introduce mesopores to the crystalline microporous particles. State-of-the-art MOF hierarchical materials have been prepared by ligand extension methods or by using a template, resulting in intrinsic mesopores of longer ligands or replicated pores from template agents, respectively. However, mesoporous MOF materials obtained through ligand extension often collapse in the absence of guest molecules, which dramatically reduces the size of the pore aperture. Although the template-directed strategy allows for the preparation of hierarchicalmore » materials with larger mesopores, the latter requires a template removal step, which may result in the collapse of the implemented mesopores. Recently, a general template-free synthesis of hierarchical microporous crystalline frameworks, such as MOFs and Prussian blue analogues (PBAs), has been reported. Our new method is based on the kinetically controlled precipitation (perturbation), with simultaneous condensation and redissolution of polymorphic nanocrystallites in the mother liquor. This method further eliminates the use of extended organic ligands and the micropores do not collapse upon removal of trapped guest solvent molecules, thus yielding hierarchical MOF materials with intriguing porosity in the gram scale. The hierarchical MOF materials prepared in this way exhibited exceptional properties when tested for the adsorption of large organic dyes over their corresponding microporous frameworks, due to the enhanced pore accessibility and electrolyte diffusion within the mesopores. As for PBAs, the pore size distribution of these materials can be tailored by changing the metals substituting Fe cations in the PB lattice. For these, the textural mesopores increased from approximately 10 nm for Cu analogue (mesoCuHCF), to 16 nm in Co substituted compound (mesoCoHCF), and to as large as 30 nm for the Ni derivative (mesoNiHCF). And while bulk PB and analogues have a higher capacitance than hierarchical analogues for Na-batteries, the increased accessibility to the microporous channels of PBAs allow for faster intercalated ion exchange and diffusion than in bulk PBA crystals. Therefore, hierarchical PBAs are promising candidates for electrodes in future electrochemical energy storage devices with faster charge–discharge rates than batteries, namely pseudocapacitors. Finally, this new synthetic method opens the possibility to prepare hierarchical materials having bimodal distribution of mesopores, and to tailor the structural properties of MOFs for different applications, including contrasting agents for MRI, and drug delivery.« less

Gas-generated thermal oxidation of a coordination cluster for an anion-doped mesoporous metal oxide.

PubMed

Hirai, Kenji; Isobe, Shigehito; Sada, Kazuki

2015-12-18

Central in material design of metal oxides is the increase of surface area and control of intrinsic electronic and optical properties, because of potential applications for energy storage, photocatalysis and photovoltaics. Here, we disclose a facile method, inspired by geochemical process, which gives rise to mesoporous anion-doped metal oxides. As a model system, we demonstrate that simple calcination of a multinuclear coordination cluster results in synchronic chemical reactions: thermal oxidation of Ti8O10(4-aminobenzoate)12 and generation of gases including amino-group fragments. The gas generation during the thermal oxidation of Ti8O10(4-aminobenzoate)12 creates mesoporosity in TiO2. Concurrently, nitrogen atoms contained in the gases are doped into TiO2, thus leading to the formation of mesoporous N-doped TiO2. The mesoporous N-doped TiO2 can be easily synthesized by calcination of the multinuclear coordination cluster, but shows better photocatalytic activity than the one prepared by a conventional sol-gel method. Owing to an intrinsic designability of coordination compounds, this facile synthetic will be applicable to a wide range of metal oxides and anion dopants.

Enabling high-rate electrochemical flow capacitors based on mesoporous carbon microspheres suspension electrodes

NASA Astrophysics Data System (ADS)

Tian, Meng; Sun, Yueqing; Zhang, Chuanfang (John); Wang, Jitong; Qiao, Wenming; Ling, Licheng; Long, Donghui

2017-10-01

Electrochemical flow capacitor (EFC) is a promising technology for grid energy storage, which combines the fast charging/discharging capability of supercapacitors with the scalable energy capacity of flow batteries. In this study, we report a high-power-density EFC using mesoporous carbon microspheres (MCMs) as suspension electrodes. By using a simple yet effective spray-drying technique, monodispersed MCMs with average particle size of 5 μm, high BET surface area of 1150-1267 m2 g-1, large pore volume of 2-4 cm3 g-1 and controllable mesopore size of 7-30 nm have been successfully prepared. The resultant MCMs suspension electrode shows excellent stability and considerable high capacitance of 100 F g-1 and good cycling ability (86% of initial capacitance after 10000 cycles). Specially, the suspension electrode exhibits excellent rate performance with 75% capacitance retention from 2 to 100 mV s-1, significantly higher than that of microporous carbon electrodes (20∼30%), due to the developed mesoporous channels facilitating for rapid ion diffusion. In addition, the electrochemical responses on both negative and positive suspension electrodes are studied, based on which an optimal capacitance matching between them is suggested for large-scale EFC unit.

Mesoporous silica nanoparticles for active corrosion protection.

PubMed

Borisova, Dimitriya; Möhwald, Helmuth; Shchukin, Dmitry G

2011-03-22

This work presents the synthesis of monodisperse, mesoporous silica nanoparticles and their application as nanocontainers loaded with corrosion inhibitor (1H-benzotriazole (BTA)) and embedded in hybrid SiOx/ZrOx sol-gel coating for the corrosion protection of aluminum alloy. The developed porous system of mechanically stable silica nanoparticles exhibits high surface area (∼1000 m2·g(-1)), narrow pore size distribution (d∼3 nm), and large pore volume (∼1 mL·g(-1)). As a result, a sufficiently high uptake and storage of the corrosion inhibitor in the mesoporous nanocontainers was achieved. The successful embedding and homogeneous distribution of the BTA-loaded monodisperse silica nanocontainers in the passive anticorrosive SiOx/ZrOx film improve the wet corrosion resistance of the aluminum alloy AA2024 in 0.1 M sodium chloride solution. The enhanced corrosion protection of this newly developed active system in comparison to the passive sol-gel coating was observed during a simulated corrosion process by the scanning vibrating electrode technique (SVET). These results, as well as the controlled pH-dependent release of BTA from the mesoporous silica nanocontainers without additional polyelectrolyte shell, suggest an inhibitor release triggered by the corrosion process leading to a self-healing effect.

New insights into the photocatalytic activity of 3-D core-shell P25@silica nanocomposites: impact of mesoporous coating.

PubMed

Gong, Yichao; Wang, Dan Ping; Wu, Renbing; Gazi, Sarifuddin; Soo, Han Sen; Sritharan, Thirumany; Chen, Zhong

2017-04-11

In this report, a three-dimensional (3-D) network of core-shell TiO 2 (P25)-mesoporous SiO 2 (P25@mSiO 2 ) nanocomposites was prepared via a controllable surfactant-assisted sol-gel method. The nanocomposites were investigated for photocatalytic reactions of organic dye degradation, water splitting, and CO 2 reduction to understand the roles of the mSiO 2 shell in these photocatalytic reactions. It was found that the mSiO 2 shell accelerates the photodegradation of the organic dye, but dramatically reduces the photocatalytic activity of P25 in water splitting and CO 2 reduction. The roles played by the mSiO 2 shell in the photocatalytic reactions are summarized as: (1) effective prevention of agglomeration of P25 nanoparticles, (2) facilitating the transfer of uncharged photo-generated ˙OH radicals via the abundant -OH groups on the mesoporous surface, (3) provision of increased reaction sites between ˙OH radicals and dye molecules by its mesoporous nanostructure and large surface area, and (4) prevention of diffusion of the photo-generated charge carriers (photoelectrons and photoholes) because of its insulating nature.

Synthesis of mesoporous TiO(2-x)N(x) spheres by template free homogeneous co-precipitation method and their photo-catalytic activity under visible light illumination.

PubMed

Parida, K M; Naik, Brundabana

2009-05-01

The article presents preparation, characterization and catalytic activity evaluation of an efficient nitrogen doped mesoporous titania sphere photo-catalyst for degradation of methylene blue (MB) and methyl orange (MO) under visible light illumination. Nitrogen doped titania was prepared by soft chemical route i.e. template free, slow and controlled homogeneous co-precipitation from titanium oxysulfate sulfuric acid complex hydrate, urea, ethanol and water. The molar composition of TiOSO(4) to urea was varied to prepare different atomic % nitrogen doped titania. Mesoporous anatase TiO(2-x)N(x) spheres with average crystallite size of 10 nm and formation of titanium oxynitride center were confirmed from HRTEM, XRD and XPS study. UV-vis DRS showed a strong absorption in the range of 400-500 nm which supports its use in visible spectrum of light. Nitrogen adsorption-desorption study supports the porous nature of the doped material. All the TiO(2-x)N(x) samples showed higher photo-catalytic activity than Degussa P(25) and undoped mesoporous titania. Sample containing around one atomic % nitrogen showed highest activity among the TiO(2-x)N(x) samples.

In Situ Growth of Mesoporous Silica with Drugs on Titanium Surface and Its Biomedical Applications.

PubMed

Wan, Mimi; Zhang, Jin; Wang, Qi; Zhan, Shuyue; Chen, Xudong; Mao, Chun; Liu, Yuhong; Shen, Jian

2017-06-07

Mesoporous silica has been developed for the modification of titanium surfaces that are used as implant materials. Yet, the traditional modification methods failed to effectively construct mesoporous silica on the titanium surface evenly and firmly, in which the interaction between mesoporous silica and titanium was mainly physical. Here, in situ growth of mesoporous silica on a titanium surface was performed using a simple evaporation-induced self-assembly strategy. Meantime, in situ introduction of drugs (heparin and vancomycin) to mesoporous silica was also adopted to improve the drug-loading amount. Both the above-mentioned processes were completed at the same time. Transmission electron microscopy, N 2 adsorption-desorption isotherms, Fourier transform infrared spectroscopy, scanning electron microscopy, and water contact angle measurements were used to characterize the structure of the mesoporous silica film. Results indicated that the mesoporous silica film that in situ grew on the titanium surface was smooth, thin, transparent, and stable. Cytotoxicity, proliferation performance of osteoblast cells, and in vitro and in vivo studies of the antibacterial activity of the coating were tested. This is the first study to modify the titanium surface by the in situ growth of a mesoporous silica coating with two kinds of drugs. The stability of the mesoporous silica coating can be attributed to the chemical bonding between dopamine and silicon hydroxyl of the mesoporous silica coating, and the smooth surface of mesoporous silica is a result of the method of in situ growth. The large amount of drug-loading also could be ascribed to the in situ introduction of drugs during the synthetic process. The strategy proposed in this work will bring more possibilities for the preparation of advanced functional materials based on the combination of mesoporous structure and metallic materials.

Magnetic mesoporous material for the sequestration of algae

DOEpatents

Trewyn, Brian G.; Kandel, Kapil; Slowing, Igor Ivan; Lee, Show-Ling

2014-09-09

The present invention provides a magnetic mesoporous nanoparticle that includes a mesoporous silicate nanoparticle and iron oxide. The present invention also provides a method of using magnetic mesoporous nanoparticles to sequester microorganisms from a media.

Infrared study of CO{sub 2} sorption over 'molecular basket' sorbent consisting of polyethylenimine-modified mesoporous molecular sieve

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, X.X.; Schwartz, V.; Clark, J.C.

2009-04-15

An infrared study has been conducted on CO{sub 2} sorption into nanoporous CO{sub 2} 'molecular basket' sorbents prepared by loading polyethylenimine (PEI) into mesoporous molecular sieve SBA-15. IR results from DRIFTS showed that a part of loaded PEI is anchored on the surface of SBA-15 through the interaction between amine groups and isolated surface silanol groups. Raising the temperature from 25 to 75{sup o}C increased the molecular flexibility of PEI loaded in the mesopore channels, which may partly contribute to the increase of CO{sub 2} sorption capacity at higher temperatures. CO{sub 2} sorption/desorption behavior studied by in situ transmission FTIRmore » showed that CO{sub 2} is sorbed on amine sites through the formation of alkylammonium carbamates and absorbed into the multiple layers of PEI located in mesopores of SBA-15. A new observation by in situ IR is that two broad IR bands emerged at 2450 and 2160 cm{sup -1} with CO{sub 2} flowing over PEI(50)/SBA-15, which could be attributed to chemically sorbed CO{sub 2} species on PEI molecules inside the mesopores of SBA-15. The intensities of these two bands also increased with increasing CO{sub 2} exposure time and with raising CO{sub 2} sorption temperature. By comparison of the CO{sub 2} sorption rate at 25 and 75{sup o}C in terms of differential IR intensities, it was found that CO{sub 2} sorption over molecular basket sorbent includes two rate regimes which suggest two distinct steps: rapid sorption on exposed outer surface layers of PEI (controlled by sorption affinity or thermodynamics) and the diffusion and sorption inside the bulk of multiple layers of PEI (controlled by diffusion). The sorption of CO{sub 2} is reversible at 75{sup o}C.« less

AND logic-like pH- and light-dual controlled drug delivery by surface modified mesoporous silica nanoparticles.

PubMed

Zhao, Junwei; He, Zhaoshuai; Li, Biao; Cheng, Tanyu; Liu, Guohua

2017-04-01

Recently, the controlled drug delivery system has become a potential platform for biomedical application. Herein, we developed a pH and light-dual controlled cargo release system exhibiting AND logic based on MCM-41 mesoporous silica nanoparticles, which was surface modified using β-cyclodextrin (β-CD) with imine bond and azobenzene derivative. The complex of β-CD and azobenzene derivative effectively blocked the cargo delivery in pH=7.0 phosphate buffered saline (PBS) solution without 365nm UV light irradiation. The cargo was fully released when both factors of acidic environment (pH=5.0 PBS) and 365nm UV light irradiation were satisfied, meanwhile only very little cargo was delivered if one factor was satisfied. The result also demonstrates that the opening/closing of the gate and the release of the cargo in small portions can be controlled. Copyright © 2016 Elsevier B.V. All rights reserved.

Ion-Exchange-Induced Selective Etching for the Synthesis of Amino-Functionalized Hollow Mesoporous Silica for Elevated-High-Temperature Fuel Cells.

PubMed

Zhang, Jin; Liu, Jian; Lu, Shanfu; Zhu, Haijin; Aili, David; De Marco, Roland; Xiang, Yan; Forsyth, Maria; Li, Qingfeng; Jiang, San Ping

2017-09-20

As differentiated from conventional synthetic processes, amino-functionalized hollow mesoporous silica (NH 2 -HMS) has been synthesized using a new and facile strategy of ion-exchange-induced selective etching of amino-functionalized mesoporous silica (NH 2 -meso-silica) by an alkaline solution. Nuclear magnetic resonance (NMR) spectroscopy and in situ time-resolved small-angle X-ray scattering (SAXS) reveal that ion-exchange-induced selective etching arises from the gradient distribution of OH - in the NH 2 -meso-silica nanospheres. Moreover, the ion-exchange-induced selective etching mechanism is verified through a successful synthesis of hollow mesoporous silica. After infiltration with phosphotungstic acid (PWA), PWA-NH 2 -HMS nanoparticles are dispersed in the poly(ether sulfone)-polyvinylpyrrolidone (PES-PVP) matrix, forming a hybrid PWA-NH 2 -HMS/PES-PVP nanocomposite membrane. The resultant nanocomposite membrane with an optimum loading of 10 wt % of PWA-NH 2 -HMS showed an enhanced proton conductivity of 0.175 S cm -1 and peak power density of 420 mW cm -2 at 180 °C under anhydrous conditions. Excellent durability of the hybrid composite membrane fuel cell has been demonstrated at 200 °C. The results of this study demonstrated the potential of the facile synthetic strategy in the fabrication of NH 2 -HMS with controlled mesoporous structure for application in nanocomposite membranes as a technology platform for elevated-temperature proton exchange membrane fuel cells.

Activated Porous Carbon Spheres with Customized Mesopores through Assembly of Diblock Copolymers for Electrochemical Capacitor.

PubMed

Tang, Jing; Wang, Jie; Shrestha, Lok Kumar; Hossain, Md Shahriar A; Alothman, Zeid Abdullah; Yamauchi, Yusuke; Ariga, Katsuhiko

2017-06-07

A series of porous carbon spheres with precisely adjustable mesopores (4-16 nm), high specific surface area (SSA, ∼2000 m 2 g -1 ), and submicrometer particle size (∼300 nm) was synthesized through a facile coassembly of diblock polymer micelles with a nontoxic dopamine source and a common postactivation process. The mesopore size can be controlled by the diblock polymer, polystyrene-block-poly(ethylene oxide) (PS-b-PEO) templates, and has an almost linear dependence on the square root of the degree of polymerization of the PS blocks. These advantageous structural properties make the product a promising electrode material for electrochemical capacitors. The electrochemical capacitive performance was studied carefully by using symmetrical cells in a typical organic electrolyte of 1 M tetraethylammonium tetrafluoroborate/acetonitrile (TEA BF 4 /AN) or in an ionic liquid electrolyte of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF 4 ), displaying a high specific capacitance of 111 and 170 F g -1 at 1 A g -1 , respectively. The impacts of pore size distribution on the capacitance performance were thoroughly investigated. It was revealed that large mesopores and a relatively low ratio of micropores are ideal for realizing high SSA-normalized capacitance. These results provide us with a simple and reliable way to screen future porous carbon materials for electrochemical capacitors and encourage researchers to design porous carbon with high specific surface area, large mesopores, and a moderate proportion of micropores.

Calcium-silicate mesoporous nanoparticles loaded with chlorhexidine for both anti- Enterococcus faecalis and mineralization properties.

PubMed

Fan, Wei; Li, Yanyun; Sun, Qing; Ma, Tengjiao; Fan, Bing

2016-10-21

In infected periapical tissues, Enterococcus faecalis is one of the most common dominant bacteria. Chlorhexidine has been proved to show strong antibacterial ability against E. faecalis but is ineffective in promoting mineralization for tissues around root apex. Mesoporous calcium-silicate nanoparticles are newly synthesized biomaterials with excellent ability to promote mineralization and carry-release bioactive molecules in a controlled manner. In this study, mesoporous calcium-silicate nanoparticles were functionalized with chlorhexidine and their releasing profile, antibacterial ability, effect on cell proliferation and in vitro mineralization property were evaluated. The chlorhexidine was successfully incorporated into mesoporous calcium-silicate nanoparticles by a mixing-coupling method. The new material could release chlorhexidine as well as Ca 2+ and SiO 3 2- in a sustained manner with an alkaline pH value under different conditions. The antimicrobial ability against planktonic E. faecalis was dramatically improved after chlorhexidine incorporation. The nanoparticles with chlorhexidine showed no negative effect on cell proliferation with low concentrations. On dentin slices, the new synthesized material demonstrated a similar inhibitory effect on E. faecalis as the chlorhexidine. After being immersed in SBF for 9 days, numerous apatite crystals could be observed on surfaces of the material tablets. Mesoporous calcium-silicate nanoparticles loaded with chlorhexidine exhibited release of ions and chlorhexidine, low cytotoxicity, excellent antibacterial ability and in vitro mineralization. This material could be developed into a new effective intra-canal medication in dentistry or a new bone defect filling material for infected bone defects.

Tailored Mesoporous Silicas: From Confinement Effects to Catalysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Buchanan III, A C; Kidder, Michelle

2010-01-01

Ordered mesoporous silicas continue to find widespread use as supports for diverse applications such as catalysis, separations, and sensors. They provide a versatile platform for these studies because of their high surface area and the ability to control pore size, topology, and surface properties over wide ranges. Furthermore, there is a diverse array of synthetic methodologies for tailoring the pore surface with organic, organometallic, and inorganic functional groups. In this paper, we will discuss two examples of tailored mesoporous silicas and the resultant impact on chemical reactivity. First, we explore the impact of pore confinement on the thermochemical reactivity ofmore » phenethyl phenyl ether (PhCH2CH2OPh, PPE), which is a model of the dominant {beta}-aryl ether linkage present in lignin derived from woody biomass. The influence of PPE surface immobilization, grafting density, silica pore diameter, and presence of a second surface-grafted inert 'spacer' molecule on the product selectivity has been examined. We will show that the product selectivity can be substantially altered compared with the inherent gas-phase selectivity. Second, we have recently initiated an investigation of mesoporous silica supported, heterobimetallic oxide materials for photocatalytic conversion of carbon dioxide. Through surface organometallic chemistry, isolated M-O-M species can be generated on mesoporous silicas that, upon irradiation, form metal to metal charge transfer bands capable of converting CO{sub 2} into CO. Initial results from studies of Ti(IV)-O-Sn(II) on SBA-15 will be presented.« less

General Method for the Synthesis of Hollow Mesoporous Carbon Spheres with Tunable Textural Properties.

PubMed

Mezzavilla, Stefano; Baldizzone, Claudio; Mayrhofer, Karl J J; Schüth, Ferdi

2015-06-17

A versatile synthetic procedure to prepare hollow mesoporous carbon spheres (HMCS) is presented here. This approach is based on the deposition of a homogeneous hybrid polymer/silica composite shell on the outer surface of silica spheres through the surfactant-assisted simultaneous polycondensation of silica and polymer precursors in a colloidal suspension. Such composite materials can be further processed to give hollow mesoporous carbon spheres. The flexibility of this method allows for independent control of the morphological (i.e., core diameter and shell thickness) and textural features of the carbon spheres. In particular, it is demonstrated that the size of the pores within the mesoporous shell can be precisely tailored over an extended range (2-20 nm) by simply adjusting the reaction conditions. In a similar fashion, also the specific carbon surface area as well as the total shell porosity can be tuned. Most importantly, the textural features can be adjusted without affecting the dimension or the morphology of the spheres. The possibility to directly modify the shell textural properties by varying the synthetic parameters in a scalable process represents a distinct asset over the multistep hard-templating (nanocasting) routes. As an exemplary application, Pt nanoparticles were encapsulated in the mesoporous shell of HMCS. The resulting Pt@HMCS catalyst showed an enhanced stability during the oxygen reduction reaction, one of the most important reactions in electrocatalysis. This new synthetic procedure could allow the expansion, perhaps even beyond the lab-scale, of advanced carbon nanostructured supports for applications in catalysis.

Interactions of Plutonium and Lanthanides with Ordered Mesoporous Materials

NASA Astrophysics Data System (ADS)

Parsons-Moss, Tashi

Ordered mesoporous materials are porous solids with a regular, patterned structure composed of pores between 2 and 50 nm wide. Such materials have attracted much attention in the past twenty years because the chemistry of their synthesis allows control of their unique physicochemical properties, which can be tuned for a variety of applications. Generally, ordered mesoporous materials have very high specific surface areas and pore volumes, and offer unique structures that are neither crystalline nor amorphous. The large tunable interface provided by ordered mesoporous solids may be advantageous in applications involving sequestration, separation, or detection of actinides and lanthanides in solution. However, the fundamental chemical interactions of actinides and lanthanides must be understood before applications can be implemented. This dissertation focuses primarily on the fundamental interactions of plutonium with organically modified mesoporous silica, as well as several different porous carbon materials, both untreated and chemically oxidized. A method for functionalizing mesoporous silica by self assembly and molecular grafting of functional organosilane ligands was optimized for the 2D-hexagonal ordered mesoporous silica known as SBA-15 (Santa Barbara amorphous silica). Four different organically-modified silica materials were synthesized and characterized with several techniques. To confirm that covalent bonds were formed between the silane anchor of the ligand and the silica substrate, functionalized silica samples were analyzed with 29Si nuclear magnetic resonance spectroscopy. Infrared spectroscopy was used in combination with 13C and 31P nuclear magnetic resonance spectroscopy to verify the molecular structures of the ligands after they were synthesized and grafted to the silica. The densities of the functional silane ligands on the silica surface were estimated using thermogravimetric analysis. Batch sorption experiments were conducted with solutions of Pu(IV), Pu(VI), Eu(III), Ce(III), and Zr(IV). The acetamide phosphonate functionalized silica called Ac-Phos-SBA-15 required more extensive synthesis than the other three functionalized silica materials. Development of functionalized mesoporous silica extractants for actinides is contingent on their synthesis and hydrolytic stability, and these two aspects of the Ac-Phos-SBA-15 material are discussed. This material showed the highest binding affinity for all of the target ions, and the sorption and desorption of Pu(VI) to Ac-Phos-SBA-15 was extensively investigated. Ordered mesoporous carbons are attractive as sorbents because of their extremely high surface areas and large pore volumes, and could be suitable substrates for the development of actinide sensors based on their electrochemical properties. Three different mesoporous carbon materials were synthesized by collaborators to test their application as radionuclide sorbent materials. The first is called CMK (carbons mesostructured by Korea Advanced Institute of Science and Technology), and was synthesized using a hard silica template with 3D-bicontinuous ordered mesostructure. Highly ordered body-centered cubic mesoporous carbon was synthesized by self-assembly of a phenol resin around a soft polymer template, and this material is known as FDU-16 (Fudan University). Etching of the silica portion of mesoporous carbon-silica composites created the 2D-hexagonal mesoporous carbon called C-CS (carbon from carbon-silica nanocomposites) with a bimodal pore size distribution. The as-synthesized nanocast mesoporous carbon in this work is called UN CMK, and the same material after oxidation treatment with nitric acid is called OX CMK. A portion of both FDU-16-type and C-CS-type ordered mesoporous carbons were oxidized with acidic ammonium persulfate, which created the oxidized carbon materials called FDU-16-COOH and C-CS-COOH, respectively. The mesoporous carbons were characterized by scanning electron microscopy to view their particle sizes and morphologies. Their porosities and structures on the meso-scale were analyzed using transmission electron microscopy, nitrogen adsorption isotherms, and small-angle X-ray scattering. The identity and density of functional groups on the different carbon surfaces were investigated using infrared spectroscopy, elemental analysis, thermogravimetric analysis, and determination of the point-of-zero-charge with the powder addition technique. The porous carbon materials studied present a wide range of particle morphologies, mesostructures, surface areas, pore volumes, and surface chemistries. (Abstract shortened by UMI.)

An inorganic capping strategy for the seeded growth of versatile bimetallic nanostructures

DOE PAGES

Pei, Yuchen; Maligal-Ganesh, Raghu V.; Xiao, Chaoxian; ...

2015-09-11

Metal nanostructures have attracted great attention in various fields due to their tunable properties through precisely tailored sizes, compositions and structures. Using mesoporous silica (mSiO 2) as the inorganic capping agent and encapsulated Pt nanoparticles as the seeds, we developed a robust seeded growth method to prepare uniform bimetallic nanoparticles encapsulated in mesoporous silica shells (PtM@mSiO 2, M = Pd, Rh, Ni and Cu). Unexpectedly, we found that the inorganic silica shell is able to accommodate an eight-fold volume increase in the metallic core by reducing its thickness. The bimetallic nanoparticles encapsulated in mesoporous silica shells showed enhanced catalytic propertiesmore » and thermal stabilities compared with those prepared with organic capping agents. As a result, this inorganic capping strategy could find a broad application in the synthesis of versatile bimetallic nanostructures with exceptional structural control and enhanced catalytic properties.« less

Synthesis of nitrogen- and sulfur-codoped 3D cubic-ordered mesoporous carbon with superior performance in supercapacitors.

PubMed

Zhang, Deyi; Zheng, Liweng; Ma, Ying; Lei, Longyan; Li, Qinglin; Li, Yan; Luo, Heming; Feng, Huixia; Hao, Yuan

2014-02-26

In this contribution, nitrogen- and sulfur-codoped 3D cubic-ordered mesoporous carbon (KNOMC) materials with controlled dopant content (10.0-4.6 atom % for nitrogen and 0.94-0.75 atom % for sulfur) are presented, using KIT-6 as the template and pyrrole as the precursor, and its supercapacitive behavior is also investigated. The presented materials exhibit excellent supercapacitive performance by combining electrical double-layer capacitance and pseudocapacitance as well as the enhanced wettability and improved conductivity generated from the incorporation of nitrogen and sulfur into the framework of carbon materials. The specific capacitance of the presented materials reaches 320 F g(-1) at a current density of 1 A g(-1), which is significantly larger than that of the pristine-ordered mesoporous carbon reported in the literature and can even compete with some metal oxides and conducting polymers.

Preparation and Characterization of Mesoporous Nickel derived from Liquid crystalline Template and Evaluation of its Electro catalytic activity towards Methanol Oxidation

NASA Astrophysics Data System (ADS)

Mohanapriya, S.; Renuka devi, R.; Raj, V.

2018-02-01

Mesoporous Nickel has been prepared by electrodeposition using non-ionic surfactant based liquid crystalline template under optimized processing conditions. Physico-chemical properties of mesoporous nickel is systematically characterized through XRD, SEM and AFM analyses. Comparison of electrocatalytic activity of mesoporous nickel with smooth nickel was interrogated using cyclic voltammetry (CV), chronoamperometry (CA) and electrochemical impedance spectroscopy (EIS) analyses. Distinctly enhanced electrocatalytic activity with improved surface poisoning resistance related to mesoporous nickel electrode towards methanol oxidation stems from unique mesoporous morphology. This mesoporous morphology with high surface to volume ratio is highly beneficial to promote active catalytic centers to offer readily accessible Pt catalytic sites for MOR, through facilitating mass and electron transports.

Facile synthesis of mesoporous lithium titanate spheres for high rate lithium-ion batteries

NASA Astrophysics Data System (ADS)

Lin, Yu-Sheng; Duh, Jenq-Gong

Lithium titanate is synthesized from titanium isopropoxide and lithium acetate solution under hydrothermal environment and calcinations. Introducing acidized carbon black during synthesis can produce mesoporous Li 4Ti 5O 12. The crystalline structure and morphological observation of the as-synthesized mesoporous Li 4Ti 5O 12 are characterized by X-ray diffraction (XRD) and scanning electron microscopy, respectively. The mesoporous structure can be directly observed through BEI images of the cross-section sample. Besides, N 2 adsorption/desorption isotherm also displays a hysteresis loop, implying the beneficial evidence of mesoporous structure. The pore size distribution of mesoporous lithium titanate evaluated by BJH model is narrow, and the average size of voids is around 4 nm. It is demonstrated that the electrochemical performance is significantly improved by the mesoporous structure. The mesoporous lithium titanate exhibits a stable capacity of 140 mAhg -1 at 0.5 C. Besides, the reversible capacity at 30 C remains over half of that at 0.5 C. The superior C-rate performance is associated with the mesoporous structure, facilitating lithium transportation ability during cycling.

Versatile NiO/mesoporous carbon nanodisks: controlled synthesis from hexagon shaped heterobimetallic metal-organic frameworks.

PubMed

Zeng, Dehong; Yang, Ying; Yang, Feng; Guo, Fangmin; Yang, Senjie; Liu, Baijun; Hao, Shijie; Ren, Yang

2017-08-24

Hexagonal NiO/mesoporous carbon nanodisks (NiO/MCN) are facilely and controllably synthesized via constructing nickel-zinc trimesic acid heterobimetallic metal-organic framework (HMOF) disks before pyrolysis at 910 °C. Tailoring the Ni/(Zn + Ni) feed ratio and the reaction time during the HMOF synthesis creates a well-defined hexagonal carbon nanodisk with properly populated NiO nanocrystals while maintaining high porosity and conductivity. Such an elaborately fabricated NiO/MCN is highly stable, and exhibits the largest specific capacitance of 261 F g -1 and the highest specific activity factor of 1.93 s -1 g -1 of any composite nanodisk during the capacitive test and 4-nitrophenol reduction, respectively.

Template method synthesis of mesoporous carbon spheres and its applications as supercapacitors.

PubMed

Wilgosz, Karolina; Chen, Xuecheng; Kierzek, Krzysztof; Machnikowski, Jacek; Kalenczuk, Ryszard J; Mijowska, Ewa

2012-05-29

Mesoporous carbon spheres (MCS) have been fabricated from structured mesoporous silica sphere using chemical vapor deposition (CVD) with ethylene as a carbon feedstock. The mesoporous carbon spheres have a high specific surface area of 666.8 m2/g and good electrochemical properties. The mechanism of formation mesoporous carbon spheres (carbon spheres) is investigated. The important thing is a surfactant hexadecyl trimethyl ammonium bromide (CTAB), which accelerates the process of carbon deposition. An additional advantage of this surfactant is an increase the yield of product. These mesoporous carbon spheres, which have good electrochemical properties is suitable for supercapacitors.

Template method synthesis of mesoporous carbon spheres and its applications as supercapacitors

NASA Astrophysics Data System (ADS)

Wilgosz, Karolina; Chen, Xuecheng; Kierzek, Krzysztof; Machnikowski, Jacek; Kalenczuk, Ryszard J.; Mijowska, Ewa

2012-05-01

Mesoporous carbon spheres (MCS) have been fabricated from structured mesoporous silica sphere using chemical vapor deposition (CVD) with ethylene as a carbon feedstock. The mesoporous carbon spheres have a high specific surface area of 666.8 m2/g and good electrochemical properties. The mechanism of formation mesoporous carbon spheres (carbon spheres) is investigated. The important thing is a surfactant hexadecyl trimethyl ammonium bromide (CTAB), which accelerates the process of carbon deposition. An additional advantage of this surfactant is an increase the yield of product. These mesoporous carbon spheres, which have good electrochemical properties is suitable for supercapacitors.

"Bricks and mortar" self-assembly approach to graphitic mesoporous carbon nanocomposites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fulvio, P. F.; Mayes, R.; Wang, X. Q.

2011-04-20

Mesoporous carbon materials do not have sufficient ordering at the atomic scale to exhibit good electronic conductivity. To date, mesoporous carbons having uniform mesopores and high surface areas have been prepared from partially-graphitizable precursors in the presence of templates. High temperature thermal treatments above 2000 °C, which are usually required to increase conductivity, result in a partial or total collapse of the mesoporous structures and reduced surface areas induced by growth of graphitic domains, limiting their applications in electric double layer capacitors and lithium-ion batteries. In this work, we successfully implemented a “brick-and-mortar” approach to obtain ordered graphitic mesoporous carbonmore » nanocomposites with tunable mesopore sizes below 850 °C without using graphitization catalysts or high temperature thermal treatments. Phenolic resin-based mesoporous carbons act as mortar to highly conductive carbon blacks and carbon onions (bricks). The capacitance and resistivity of final materials can be tailored by changing the mortar to brick ratios.« less

Brick-and-Mortar Self-Assembly Approach to Graphitic Mesoporous Carbon Nanocomposites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dai, Sheng; Fulvio, Pasquale F; Mayes, Richard T

2011-01-01

Mesoporous carbon materials do not have sufficient ordering at the atomic scale to exhibit good electronic conductivity. To date, mesoporous carbons having uniform mesopores and high surface areas have been prepared from partially-graphitizable precursors in the presence of templates. High temperature thermal treatments above 2000 C, which are usually required to increase conductivity, result in a partial or total collapse of the mesoporous structures and reduced surface areas induced by growth of graphitic domains, limiting their applications in electric double layer capacitors and lithium-ion batteries. In this work, we successfully implemented a 'brick-and-mortar' approach to obtain ordered graphitic mesoporous carbonmore » nanocomposites with tunable mesopore sizes below 850 C without using graphitization catalysts or high temperature thermal treatments. Phenolic resin-based mesoporous carbons act as mortar to highly conductive carbon blacks and carbon onions (bricks). The capacitance and resistivity of final materials can be tailored by changing the mortar to brick ratios.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Larsen, Michael B.; Van Horn, J. David; Wu, Fei

The synthesis of microporous polymers generally requires postpolymerization modification via hyper-cross-linking to trap the polymeric network in a state with high void volume. An alternative approach utilizes rigid, sterically demanding monomers to inhibit efficient packing, thus leading to a high degree of free volume between polymer side groups and main chains. Herein we combine polymers of intrinsic microporosity with polymerization-induced microphase separation (PIMS), a versatile methodology for the synthesis of nanostructured materials that can be rendered mesoporous. Copolymerization of various styrenic monomers with divinylbenzene in the presence of a poly(lactide) terminated with a chain-transfer agent (PLA-CTA) results in kinetic trappingmore » of a microphase-separated state. Subsequent etching of PLA provides a bicontinuous mesoporous network. Using equilibrium and kinetic nitrogen sorption experiments as well as positron annihilation lifetime spectroscopy (PALS), we demonstrate that variations in the steric characteristics of the styrenic monomer impart the network with microporosity, resulting in hierarchically (meso and micro) porous materials. Additionally, structure–property relationships of the styrenic monomer with total surface area and pore volume indicate that the glass transition temperature (Tg) of the corresponding styrenic homopolymers provides a reasonable measure of the steric interactions and resultant microporosity in these systems. Finally, PALS provides insight into micro- and mesoscopic void volume differences between porous monoliths containing either tert-butyl or TMS-modified styrenic monomers compared to the parent, unmodified styrene.« less

Efficient Capture of Perrhenate and Pertechnetate by a Mesoporous Zr Metal–Organic Framework and Examination of Anion Binding Motifs

DOE PAGES

Drout, Riki J.; Otake, Kenichi; Howarth, Ashlee J.; ...

2018-01-10

At the Hanford Site in southeastern Washington state, the U.S. Department of Energy intends to treat 56 million gallons of legacy nuclear waste by encasing it in borosilicate glass via vitrification. This process ineffectively captures radioactive pertechnetate (TcO 4–) because of the ion’s volatility, thereby requiring a different remediation method for this long-lived (t 1/2 = 2.1 × 10 5 years), environmentally mobile species. Currently available sorbents lack the desired combination of high uptake capacity, fast kinetics, and selectivity. Here, we evaluate the ability of the chemically and thermally robust Zr 6-based metal–organic framework (MOF), NU-1000, to capture perrhenate (ReOmore » 4–), a pertechnetate simulant, and pertechnetate. Our material exhibits an excellent perrhenate uptake capacity of 210 mg/g, reaches saturation within 5 min, and maintains perrhenate uptake in the presence of competing anions. Additionally, experiments with pertechnetate confirm perrhenate is a suitable surrogate. Single-crystal X-ray diffraction indicates both chelating and nonchelating perrhenate binding motifs are present in both the small pore and the mesopore of NU-1000. Postadsorption diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) further elucidates the uptake mechanism and powder X-ray diffraction (PXRD) and Brunauer–Emmett–Teller (BET) surface area analysis confirm the retention of crystallinity and porosity of NU-1000 throughout adsorption.« less

Mesoporous polyaniline nanofiber decorated graphene micro-flowers for enzyme-less cholesterol biosensors

NASA Astrophysics Data System (ADS)

Lakshmi, G. B. V. S.; Sharma, Anshu; Solanki, Pratima R.; Avasthi, D. K.

2016-08-01

In the present work, we have studied a nanocomposite of polyaniline nanofiber-graphene microflowers (PANInf-GMF), prepared by an in situ rapid mixing polymerization method. The structural and morphological studies of the nanocomposite (PANInf-GMF) were carried out by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared (FTIR) and Raman spectroscopy. The mesoporous, nanofibrous and microflower structures were observed by scanning electron microscopy. The functional groups and synergetic effects were observed by FTIR and micro-Raman measurements. The water wettability was carried out by a contact angle measurement technique and found to be super hydrophilic in nature towards water. This nanocomposite was deposited onto indium-tin-oxide coated glass substrate by a drop casting method and used for the detection of cholesterol using an electrochemical technique. The differential pulse voltammetry studies show the appreciable increase in the current with the addition of 1.93 to 464.04 mg dl-1 cholesterol concentration. It is also found that the electrodes were highly selective towards cholesterol when compared to other biological interfering analytes, such as glucose, urea, citric acid, cysteine and ascorbic acid. The sensitivity of the sensor is estimated as 0.101 μA mg-1 dl cm-2 and the lower detection limit as 1.93 mg dl-1. This work will throw light on the preparation of non-enzymatic biosensors based on PANInf-carbon nanostructure composites.

Template method synthesis of mesoporous carbon spheres and its applications as supercapacitors

PubMed Central

2012-01-01

Mesoporous carbon spheres (MCS) have been fabricated from structured mesoporous silica sphere using chemical vapor deposition (CVD) with ethylene as a carbon feedstock. The mesoporous carbon spheres have a high specific surface area of 666.8 m2/g and good electrochemical properties. The mechanism of formation mesoporous carbon spheres (carbon spheres) is investigated. The important thing is a surfactant hexadecyl trimethyl ammonium bromide (CTAB), which accelerates the process of carbon deposition. An additional advantage of this surfactant is an increase the yield of product. These mesoporous carbon spheres, which have good electrochemical properties is suitable for supercapacitors. PMID:22643113

Facile synthesis of mesoporous silica sublayer with hierarchical pore structure on ceramic membrane using anionic polyelectrolyte.

PubMed

Kang, Taewook; Oh, Seogil; Kim, Honggon; Yi, Jongheop

2005-06-21

A facile method for introducing mesoporous silica sublayer onto the surface of a ceramic membrane for use in liquid-phase separation is described. To reduce the electrostatic repulsion between the mesoporous silica sol and the ceramic membrane in highly acidic conditions (pH < 2), thus facilitating the approach of hydrolyzed silica sol to the surface of the membrane, poly(sodium 4-styrenesulfonate) (Na+PSS-, denoted as PSS-) was used as an ionic linker. The use of PSS- led to a significant reduction in positive charge on the ceramic membrane, as confirmed by experimental titration data. Consistent with the titration results, the amount of mesoporous silica particles on the surface of the ceramic membrane was low, in the absence of PSS- treatment, whereas mesoporous silica sublayer with hierarchical pore structure was produced, when 1 wt % PSS- was used. The results show that mesoporous silica grows in the confined surface, eventually forming a multistacked surface architecture. The mesoporous silica sublayer contained uniform, ordered (P6 mm) mesopores of ca. 7.5 nm from mesoporous silica as well as macropores ( approximately mum) from interparticle voids, as evidenced by transmission electron microscopy and scanning electron microscopy analyses. The morphologies of the supported mesoporous silica could be manipulated, thus permitting the generation of uniform needlelike forms or uniform spheroid particles by varying the concentration of PSS-.

Functionalized mesoporous silica materials for molsidomine adsorption: Thermodynamic study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alyoshina, Nonna A.; Parfenyuk, Elena V., E-mail: evp@iscras.ru

2013-09-15

A series of unmodified and organically modified mesoporous silica materials was prepared. The unmodified mesoporous silica was synthesized via sol–gel synthesis in the presence of D-glucose as pore-forming agent. The functionalized by phenyl, aminopropyl and mercaptopropyl groups silica materials were prepared via grafting. The fabricated adsorbent materials were characterized by Fourier transform infrared spectroscopy (FTIR) analysis, N{sub 2} adsorption/desorption and elemental analysis methods. Then their adsorption properties for mesoionic dug molsidomine were investigated at 290–313 K and physiological pH value. Thermodynamic parameters of molsidomine adsorption on the synthesized materials have been calculated. The obtained results showed that the adsorption processmore » of molsidomine on the phenyl modified silica is the most quantitatively and energetically favorable. The unmodified and mercaptopropyl modified silica materials exhibit significantly higher adsorption capacities and energies for molsidomine than the aminopropyl modified sample. The effects are discussed from the viewpoint of nature of specific interactions responsible for the adsorption. - Graphical abstract: Comparative analysis of the thermodynamic characteristics of molsidomine adsorption showed that the adsorption process on mesoporous silica materials is controlled by chemical nature of surface functional groups. Molsidomine adsorption on the phenyl modified silica is the most quantitatively and energetically favorable. Taking into account ambiguous nature of mesoionic compounds, it was found that molsidomine is rather aromatic than dipolar. Display Omitted - Highlights: • Unmodified and organically modified mesoporous silica materials were prepared. • Molsidomine adsorption on the silica materials was studied. • Phenyl modified silica shows the highest adsorption capacity and favorable energy. • Molsidomine exhibits the lowest affinity to aminopropyl modified silica.« less

Mesoporous metal oxide microsphere electrode compositions and their methods of making

DOE Office of Scientific and Technical Information (OSTI.GOV)

Parans Paranthaman, Mariappan; Bi, Zhonghe; Bridges, Craig A.

Compositions and methods of making are provided for treated mesoporous metal oxide microspheres electrodes. The compositions include microspheres with an average diameter between about 200 nanometers and about 10 micrometers and mesopores on the surface and interior of the microspheres. The methods of making include forming a mesoporous metal oxide microsphere composition and treating the mesoporous metal oxide microspheres by at least annealing in a reducing atmosphere, doping with an aliovalent element, and coating with a coating composition.

Sol Gel-Derived SBA-16 Mesoporous Material

PubMed Central

Rivera-Muñoz, Eric M.; Huirache-Acuña, Rafael

2010-01-01

The aim of this article is to review current knowledge related to the synthesis and characterization of sol gel-derived SBA-16 mesoporous silicas, as well as a review of the state of the art in this issue, to take stock of knowledge about current and future applications. The ease of the method of preparation, the orderly structure, size and shape of their pores and control, all these achievable through simple changes in the method of synthesis, makes SBA-16 a very versatile material, potentially applicable in many areas of science and molecular engineering of materials. PMID:20957080

Preparation and drug release behavior of temperature-responsive mesoporous carbons

NASA Astrophysics Data System (ADS)

Wang, Xiufang; Liu, Ping; Tian, Yong

2011-06-01

A temperature-responsive composite based on poly (N-isopropylacrylamide) (PNIPAAm) and ordered mesoporous carbons (OMCs) has been successfully prepared by a simple wetness impregnation technique. The structures and properties of the composite were characterized by infrared spectroscopy (IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), N 2 sorption, thermogravimetric analysis (TG) and differential scanning calorimetry (DSC). The results showed that the inclusion of PNIPAAm had not greatly changed the basic ordered pore structure of the OMCs. Ibuprofen (IBU) was selected as model drug, and in vitro test of IBU release exhibited a temperature-responsive controlled release delivery.

TiO2-coated mesoporous carbon: conventional vs. microwave-annealing process.

PubMed

Coromelci-Pastravanu, Cristina; Ignat, Maria; Popovici, Evelini; Harabagiu, Valeria

2014-08-15

The study of coating mesoporous carbon materials with titanium oxide nanoparticles is now becoming a promising and challenging area of research. To optimize the use of carbon materials in various applications, it is necessary to attach functional groups or other nanostructures to their surface. The combination of the distinctive properties of mesoporous carbon materials and titanium oxide is expected to be applied in field emission displays, nanoelectronic devices, novel catalysts, and polymer or ceramic reinforcement. But, their synthesis is still largely based on conventional techniques, such as wet impregnation followed by chemical reduction of the metal nanoparticle precursors, which takes time and money. The thermal heating based techniques are time consuming and often lack control of particle size and morphology. Hence, since there is a growing interest in microwave technology, an alternative way of power input into chemical reactions through dielectric heating is the use of microwaves. This work is focused on the advantages of microwave-assisted synthesis of TiO2-coated mesoporous carbon over conventional thermal heating method. The reviewed studies showed that the microwave-assisted synthesis of such composites allows processes to be completed within a shorter reaction time allowing the nanoparticles formation with superior properties than that obtained by conventional method. Copyright © 2014 Elsevier B.V. All rights reserved.

Effect of mesoporous structure on the Seebeck coefficient and electrical properties of SrTi0.8Nb0.2O3

NASA Astrophysics Data System (ADS)

Park, Chang-Sun; Hong, Min-Hee; Cho, Hyung Hee; Park, Hyung-Ho

2017-07-01

The porosity of mesoporous SrTi0.8Nb0.2O3 (STNO) was controlled by changing the surfactant concentration to investigate the porosity effect on the thermoelectric properties. Mesoporous structure typically induces a large decrease in the carrier mobility and a small increase in the carrier concentration owing to carrier scattering and oxygen vacancies. These changes in the carrier mobility and concentration induce a change in the thermoelectric properties by enhancing the Seebeck coefficient owing to an increase in the electrical resistivity and carrier filtering effect. Brij-S10 surfactant induces a carrier filtering effect in STNO, and so the Seebeck coefficient could be enhanced even with increasing carrier concentration. Because the Seebeck coefficient affects the power factor more strongly than the electrical resistivity does, incorporation of Brij-S10 surfactant into STNO films increases the power factor. The maximum value of the power factor, approximately 2.2 × 10-4 W/mK2 at 200 °C, was obtained at a Brij-S10 molar ratio of 0.075. From this result, we can expect the application of STNO as a thermoelectric material with an enhanced power factor through successful adoption of mesoporous structure.

In-depth porosity control of mesoporous silicon layers by an anodization current adjustment

NASA Astrophysics Data System (ADS)

Lascaud, J.; Defforge, T.; Certon, D.; Valente, D.; Gautier, G.

2017-12-01

The formation of thick mesoporous silicon layers in P+-type substrates leads to an increase in the porosity from the surface to the interface with silicon. The adjustment of the current density during the electrochemical etching of porous silicon is an intuitive way to control the layer in-depth porosity. The duration and the current density during the anodization were varied to empirically model porosity variations with layer thickness and build a database. Current density profiles were extracted from the model in order to etch layer with in-depth control porosity. As a proof of principle, an 80 μm-thick porous silicon multilayer was synthetized with decreasing porosities from 55% to 35%. The results show that the assessment of the in-depth porosity could be significantly enhanced by taking into account the pure chemical etching of the layer in the hydrofluoric acid-based electrolyte.

Mesoporous Aluminosilicate Catalysts for the Selective Isomerization of n-Hexane: The Roles of Surface Acidity and Platinum Metal.

PubMed

Musselwhite, Nathan; Na, Kyungsu; Sabyrov, Kairat; Alayoglu, Selim; Somorjai, Gabor A

2015-08-19

Several types of mesoporous aluminosilicates were synthesized and evaluated in the catalytic isomerization of n-hexane, both with and without Pt nanoparticles loaded into the mesopores. The materials investigated included mesoporous MFI and BEA type zeolites, MCF-17 mesoporous silica, and an aluminum modified MCF-17. The acidity of the materials was investigated through pyridine adsorption and Fourier Transform-Infrared Spectroscopy (FT-IR). It was found that the strong Brönsted acid sites in the micropores of the zeolite catalysts facilitated the cracking of hexane. However, the medium strength acid sites on the Al modified MCF-17 mesoporous silica greatly enhanced the isomerization reaction. Through the loading of different amounts of Pt into the mesopores of the Al modified MCF-17, the relationship between the metal nanoparticles and acidic sites on the support was revealed.

On the Formation of Nanobubbles in Vycor Porous Glass during the Desorption of Halogenated Hydrocarbons

NASA Astrophysics Data System (ADS)

Mitropoulos, A. C.; Stefanopoulos, K. L.; Favvas, E. P.; Vansant, E.; Hankins, N. P.

2015-06-01

Vycor porous glass has long served as a model mesoporous material. During the physical adsorption of halogenated hydrocarbon vapours, such as dibromomethane, the adsorption isotherm exhibits an hysteresis loop; a gradual ascent is observed at higher pressures during adsorption, and a sharp drop is observed at lower pressures during desorption. For fully wetting fluids, an early hypothesis attributed the hysteresis to mechanistic differences between capillary condensation (adsorption) and evaporation (desorption) processes occurring in the wide bodies and narrow necks, respectively, of ‘ink-bottle’ pores. This was later recognized as oversimplified when the role of network percolation was included. For the first time, we present in-situ small angle x-ray scattering measurements on the hysteresis effect which indicate nanobubble formation during desorption, and support an extended picture of network percolation. The desorption pattern can indeed result from network percolation; but this can sometimes be initiated by a local cavitation process without pore blocking, which is preceded by the temporary, heterogeneous formation of nanobubbles involving a change in wetting states. The capacity of the system to sustain such metastable states is governed by the steepness of the desorption boundary.

On the Formation of Nanobubbles in Vycor Porous Glass during the Desorption of Halogenated Hydrocarbons

PubMed Central

Mitropoulos, A. C.; Stefanopoulos, K. L.; Favvas, E. P.; Vansant, E.; Hankins, N. P.

2015-01-01

Vycor porous glass has long served as a model mesoporous material. During the physical adsorption of halogenated hydrocarbon vapours, such as dibromomethane, the adsorption isotherm exhibits an hysteresis loop; a gradual ascent is observed at higher pressures during adsorption, and a sharp drop is observed at lower pressures during desorption. For fully wetting fluids, an early hypothesis attributed the hysteresis to mechanistic differences between capillary condensation (adsorption) and evaporation (desorption) processes occurring in the wide bodies and narrow necks, respectively, of ‘ink-bottle’ pores. This was later recognized as oversimplified when the role of network percolation was included. For the first time, we present in-situ small angle x-ray scattering measurements on the hysteresis effect which indicate nanobubble formation during desorption, and support an extended picture of network percolation. The desorption pattern can indeed result from network percolation; but this can sometimes be initiated by a local cavitation process without pore blocking, which is preceded by the temporary, heterogeneous formation of nanobubbles involving a change in wetting states. The capacity of the system to sustain such metastable states is governed by the steepness of the desorption boundary. PMID:26047466

On the Formation of Nanobubbles in Vycor Porous Glass during the Desorption of Halogenated Hydrocarbons.

PubMed

Mitropoulos, A C; Stefanopoulos, K L; Favvas, E P; Vansant, E; Hankins, N P

2015-06-05

Vycor porous glass has long served as a model mesoporous material. During the physical adsorption of halogenated hydrocarbon vapours, such as dibromomethane, the adsorption isotherm exhibits an hysteresis loop; a gradual ascent is observed at higher pressures during adsorption, and a sharp drop is observed at lower pressures during desorption. For fully wetting fluids, an early hypothesis attributed the hysteresis to mechanistic differences between capillary condensation (adsorption) and evaporation (desorption) processes occurring in the wide bodies and narrow necks, respectively, of 'ink-bottle' pores. This was later recognized as oversimplified when the role of network percolation was included. For the first time, we present in-situ small angle x-ray scattering measurements on the hysteresis effect which indicate nanobubble formation during desorption, and support an extended picture of network percolation. The desorption pattern can indeed result from network percolation; but this can sometimes be initiated by a local cavitation process without pore blocking, which is preceded by the temporary, heterogeneous formation of nanobubbles involving a change in wetting states. The capacity of the system to sustain such metastable states is governed by the steepness of the desorption boundary.

Mesoporous ZnS–NiS Nanocomposites for Nonenzymatic Electrochemical Glucose Sensors

PubMed Central

Wei, Chengzhen; Cheng, Cheng; Zhao, Junhong; Wang, Zhangtao; Wu, Haipeng; Gu, Kaiyue; Du, Weimin; Pang, Huan

2015-01-01

Mesoporous ZnS–NiS composites are prepared via ion- exchange reactions using ZnS as the precursor. The prepared mesoporous ZnS–NiS composite materials have large surface areas (137.9 m2 g−1) compared with the ZnS precursor. More importantly, the application of these mesoporous ZnS–NiS composites as nonenzymatic glucose sensors was successfully explored. Electrochemical sensors based on mesoporous ZnS–NiS composites exhibit a high selectivity and a low detection limit (0.125 μm) toward the oxidation of glucose, which can mainly be attributed to the morphological characteristics of the mesoporous structure with high specific surface area and a rational composition of the two constituents. In addition, the mesoporous ZnS–NiS composites coated on the surface of electrodes can be used to modify the mass transport regime, and this alteration can, in favorable circumstances, facilitate the amperometric discrimination between species. These results suggest that such mesoporous ZnS–NiS composites are promising materials for nonenzymatic glucose sensors. PMID:25861568

Dual-mesoporous ZSM-5 zeolite with highly b-axis-oriented large mesopore channels for the production of benzoin ethyl ether.

PubMed

Zhou, Xiaoxia; Chen, Hangrong; Zhu, Yan; Song, Yudian; Chen, Yu; Wang, Yongxia; Gong, Yun; Zhang, Guobin; Shu, Zhu; Cui, Xiangzhi; Zhao, Jinjin; Shi, Jianlin

2013-07-22

Dual-mesoporous ZSM-5 zeolite with highly b axis oriented large mesopores was synthesized by using nonionic copolymer F127 and cationic surfactant CTAB as co-templates. The product contains two types of mesopores--smaller wormlike ones of 3.3 nm in size and highly oriented larger ones of 30-50 nm in diameter along the b axis--and both of them interpenetrate throughout the zeolite crystals and interconnect with zeolite microporosity. The dual-mesoporous zeolite exhibits excellent catalytic performance in the condensation of benzaldehyde with ethanol and greater than 99 % selectivity for benzoin ethyl ether at room temperature, which can be ascribed to the zeolite lattice structure offering catalytically active sites and the hierarchical and oriented mesoporous structure providing fast access of reactants to these sites in the catalytic reaction. The excellent recyclability and high catalytic stability of the catalyst suggest prospective applications of such unique mesoporous zeolites in the chemical industry. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Highly mesoporous single-crystalline zeolite beta synthesized using a nonsurfactant cationic polymer as a dual-function template.

PubMed

Zhu, Jie; Zhu, Yihan; Zhu, Liangkui; Rigutto, Marcello; van der Made, Alexander; Yang, Chengguang; Pan, Shuxiang; Wang, Liang; Zhu, Longfeng; Jin, Yinying; Sun, Qi; Wu, Qinming; Meng, Xiangju; Zhang, Daliang; Han, Yu; Li, Jixue; Chu, Yueying; Zheng, Anmin; Qiu, Shilun; Zheng, Xiaoming; Xiao, Feng-Shou

2014-02-12

Mesoporous zeolites are useful solid catalysts for conversion of bulky molecules because they offer fast mass transfer along with size and shape selectivity. We report here the successful synthesis of mesoporous aluminosilicate zeolite Beta from a commercial cationic polymer that acts as a dual-function template to generate zeolitic micropores and mesopores simultaneously. This is the first demonstration of a single nonsurfactant polymer acting as such a template. Using high-resolution electron microscopy and tomography, we discovered that the resulting material (Beta-MS) has abundant and highly interconnected mesopores. More importantly, we demonstrated using a three-dimensional electron diffraction technique that each Beta-MS particle is a single crystal, whereas most previously reported mesoporous zeolites are comprised of nanosized zeolitic grains with random orientations. The use of nonsurfactant templates is essential to gaining single-crystalline mesoporous zeolites. The single-crystalline nature endows Beta-MS with better hydrothermal stability compared with surfactant-derived mesoporous zeolite Beta. Beta-MS also exhibited remarkably higher catalytic activity than did conventional zeolite Beta in acid-catalyzed reactions involving large molecules.

Template-assisted electrostatic spray deposition as a new route to mesoporous, macroporous, and hierarchically porous oxide films.

PubMed

Sokolov, S; Paul, B; Ortel, E; Fischer, A; Kraehnert, R

2011-03-01

A novel film coating technique, template-assisted electrostatic spray deposition (TAESD), was developed for the synthesis of porous metal oxide films and tested on TiO(2). Organic templates are codeposited with the titania precursor by electrostatic spray deposition and then removed during calcination. Resultant films are highly porous with pores casted by uniformly sized templates, which introduced a new level of control over the pore morphology for the ESD method. Employing the amphiphilic block copolymer Pluronic P123, PMMA latex spheres, or a combination of the two, mesoporous, macroporous, and hierarchically porous TiO(2) films are obtained. Decoupled from other coating parameters, film thickness can be controlled by deposition time or depositing multiple layers while maintaining the coating's structure and integrity.

In situ monitoring of intracellular controlled drug release from mesoporous silica nanoparticles coated with pH-responsive charge-reversal polymer.

PubMed

Zhang, Peng; Wu, Tong; Kong, Ji-Lie

2014-10-22

Therapeutic platforms such as chemotherapy that respond to physical and biological stimuli are highly desirable for effective cancer therapy. In this study, pH-responsive charge-reversal, polymer-coated mesoporous silica nanoparticles [PAH-cit/APTES-MSNs; PAH-cit refers to poly(allylamine)-citraconic anhydride; APTES refers to (3-aminopropyl)triethoxysilane] were synthesized for application as drug-delivery systems for the treatment of malignant cells. Confocal laser scanning microscopy (CLSM) revealed that the PAH-cit/APTES-MSNs nanocomposite effectively delivered and released doxorubicin hydrochloride to the nucleus of HeLa (human cervical carcinoma) cells. Additionally, the real-time dynamic drug-release process was monitored by CLSM. The current pH-controlled-smart-release platform holds promise in drug-delivery and cancer therapy-related applications.

Inorganic materials for bone repair or replacement applications.

PubMed

Hertz, Audrey; Bruce, Ian J

2007-12-01

In recent years, excipient systems have been used increasingly in biomedicine in reconstructive and replacement surgery, as bone cements, drug-delivery vehicles and contrast agents. Particularly, interest has been growing in the development and application of controlled pore inorganic ceramic materials for use in bone-replacement and bone-repair roles and, in this context, attention has been focused on calcium-phosphate, bioactive glasses and SiO2- and TiO2-based materials. It has been shown that inorganic materials that most closely mimic bone structure and surface chemistry most closely function best in bone replacement/repair and, in particular, if a substance possesses a macroporous structure (pores and interconnections >100 microm diameter), then cell infiltration, bone growth and vascularization can all be promoted. The surface roughness and micro/mesoporosity of a material have also been observed to significantly influence its ability to promote apatite nucleation and cell attachment significantly. Pores (where present) can also be packed with pharmaceuticals and biomolecules (e.g., bone morphogenetic proteins [BMPs], which can stimulate bone formation). Finally, the most bio-efficient - in terms of collagen formation and apatite nucleation - materials are those that are able to provide soluble mineralizing species (Si, Ca, PO(4)) at their implant sites and/or are doped or have been surface-activated with specific functional groups. This article presents the context and latest advances in the field of bone-repair materials, especially with respect to the development of bioactive glasses and micro/mesoporous and macroporous inorganic scaffolds. It deals with the possible methods of preparing porous pure/doped or functionalized silicas or their composites, the studies that have been undertaken to evaluate their abilities to act as bone repair scaffolds and also presents future directions for work in that context.

[Study on absorbing volatile oil with mesoporous carbon].

PubMed

Yan, Hong-mei; Jia, Xiao-bin; Zhang, Zhen-hai; Sun, E; Yang Nan

2014-11-01

Clove oil and turmeric oil were absorbed by mesoporous carbon. The absorption ratio of mesoporous carbon to volatile oil was optimized with the eugenol yield and curcumol yield as criteria Curing powder was characterized by scanning electron microscopy (SEM) and differential scanning calorietry (DSC). The effects of mesoporous carbon on dissolution in vitro and thermal stability of active components were studied. They reached high adsorption rate when the absorption ratio of mesoporous carbon to volatile oil was 1:1. When volatile oil was absorbed, dissolution rate of active components had a little improvement and their thermal stability improved after volatile oil was absorbed by the loss rate decreasing more than 50%. Absorbing herbal volatile oil with mesoporous carbon deserves further studying.

Synthesis and characterization of mesoporous NaY zeolite from natural Blitar’s kaolin

NASA Astrophysics Data System (ADS)

Khalifah, S. N.; aini, Z. N.; Hayati, E. K.; Aini, N.; Prasetyo, A.

2018-03-01

Mesoporous NaY Zeolite has been synthesized from calcined natural Blitar’s kaolin with the addition of NaOH and CTABr surfactant as mesoporous template by hydrothermal method. Natural kaolin was calcinated with different time and temperature to change kaolin to metakaolin. X-ray diffraction data showed that mesoporous NaY zeolite was formed with impurities compound of sodalite, kaolin and quartz phases. The BET analysis resulted that the pore of NaY Zeolite belongs to mesoporous type with pore size 9,421 nm. Characterization from FTIR confirmed about the functional group of zeolites (988, 776, 663, 464 cm-1). Scanning electron microscopy characterization showed that the morphological of mesoporous NaY zeolites have uniform and crystalline particles formed.

Surfactant-assisted Nanocasting Route for Synthesis of Highly Ordered Mesoporous Graphitic Carbon and Its Application in CO2 Adsorption

NASA Astrophysics Data System (ADS)

Wang, Yangang; Bai, Xia; Wang, Fei; Qin, Hengfei; Yin, Chaochuang; Kang, Shifei; Li, Xi; Zuo, Yuanhui; Cui, Lifeng

2016-05-01

Highly ordered mesoporous graphitic carbon was synthesized from a simple surfactant-assisted nanocasting route, in which ordered mesoporous silica SBA-15 maintaining its triblock copolymer surfactant was used as a hard template and natural soybean oil (SBO) as a carbon precursor. The hydrophobic domain of the surfactant assisted SBO in infiltration into the template’s mesoporous channels. After the silica template was carbonized and removed, a higher yield of highly-ordered graphitic mesoporous carbon with rod-like morphology was obtained. Because of the improved structural ordering, the mesoporous carbon after amine modification could adsorb more CO2 compared with the amine-functionalized carbon prepared without the assistance of surfactant.

Self-assembled highly ordered ethane-bridged periodic mesoporous organosilica and its application in HPLC.

PubMed

Huang, Lili; Lu, Juan; Di, Bin; Feng, Fang; Su, Mengxiang; Yan, Fang

2011-09-01

Monodisperse spherical periodic mesoporous organosilicas (PMOs) with ethane integrated in the framework were synthesized and their application as stationary phase for chromatographic separation is demonstrated. The ethane-PMOs were prepared by condensation of 1,2-bis(triethoxysilyl)ethane (BTSE) in basic condition using octadecyltrimethylammonium chloride (C(18)TMACl) as template and ethanol as co-solvent. The morphology and mesoporous structure of ethane-PMOs were controlled under different concentrations of sodium hydroxide (NaOH) and EtOH. The results of scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (XRD), nitrogen sorption measurement, Fourier transform infrared spectroscopy (FT-IR) and elemental analysis showed that ethane-PMOs have spherical morphology, uniform particle distribution, highly ordered pore structure, high surface area and narrow pore-size distribution. The column packed with these materials exhibits good permeability, high chemical stability and good selectivity of mixtures of aromatic hydrocarbons in normal phase high-performance liquid chromatography (HPLC). Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Investigating the Interaction of Water Vapour with Aminopropyl Groups on the Surface of Mesoporous Silica Nanoparticles.

PubMed

Paul, Geo; Musso, Giorgia Elena; Bottinelli, Emanuela; Cossi, Maurizio; Marchese, Leonardo; Berlier, Gloria

2017-04-05

The interaction of water molecules with the surface of hybrid silica-based mesoporous materials is studied by 29 Si, 1 H and 13 C solid-state NMR and IR spectroscopy, with the support of ab initio calculations. The surface of aminopropyl-grafted mesoporous silica nanoparticles is studied in the dehydrated state and upon interaction with controlled doses of water vapour. Former investigations described the interactions between aminopropyl and residual SiOH groups; the present study shows the presence of hydrogen-bonded species (SiOH to NH 2 ) and weakly interacting "free" aminopropyl chains with restricted mobility, together with a small amount of protonated NH 3 + groups. The concentration of the last-named species increased upon interaction with water, and this indicates reversible and fast proton exchange from water molecules to a fraction of the amino groups. Herein, this is discussed and explained for the first time, by a combination of experimental and theoretical approaches. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Titanate-silica mesostructured nanocables: synthesis, structural analysis and biomedical applications

NASA Astrophysics Data System (ADS)

Su, Yonghua; Qiao, Shizhang; Yang, Huagui; Yang, Chen; Jin, Yonggang; Stahr, Frances; Sheng, Jiayu; Cheng, Lina; Ling, Changquan; Qing Lu, Gao

2010-02-01

1D hierarchical composite mesostructures of titanate and silica were synthesized via an interfacial surfactant templating approach. Such mesostructures have complex core-shell architectures consisting of single-crystalline H2Ti3O7 nanobelts inside the ordered mesoporous SiO2 shell, which are nontoxic and highly biocompatible. The overall diameter of as-prepared 1D hierarchical composite mesostructures is only approx. 34.2 nm with a length over 500 nm on average. A model to explain the formation mechanism of these mesostructures has been proposed; the negatively charged surface of H2Ti3O7 nanobelts controls the formation of the octadecyltrimethylammonium bromide (C18TAB) bilayer, which in turn regulates the cooperative self-assembly of silica and C18TAB complex micelles on the interface to produce a mesoporous silica shell. More importantly, the application of synthesized mesostructured nanocables as anticancer drug reservoirs has also been explored, which indicates that the membranes containing these mesoporous nanocables have a great potential to be used as transdermal drug delivery systems.

Cholera toxin subunit B-mediated intracellular trafficking of mesoporous silica nanoparticles toward the endoplasmic reticulum

NASA Astrophysics Data System (ADS)

Walker, William Andrew

In recent decades, pharmaceutical research has led to the development of numerous treatments for human disease. Nanoscale delivery systems have the potential to maximize therapeutic outcomes by enabling target specific delivery of these therapeutics. The intracellular localization of many of these materials however, is poorly controlled, leading to sequestration in degradative cellular pathways and limiting the efficacy of their payloads. Numerous proteins, particularly bacterial toxins, have evolved mechanisms to subvert the degradative mechanisms of the cell. Here, we have investigated a possible strategy for shunting intracellular delivery of encapsulated cargoes from these pathways by modifying mesoporous silica nanoparticles (MSNs) with the well-characterized bacterial toxin Cholera toxin subunit B (CTxB). Using established optical imaging methods we investigated the internalization, trafficking, and subcellular localization of our modified MSNs in an in vitro animal cell model. We then attempted to demonstrate the practical utility of this approach by using CTxB-modified mesoporous silica nanoparticles to deliver propidium iodide, a membrane-impermeant fluorophore.

Mesopores induced zero thermal expansion in single-crystal ferroelectrics.

PubMed

Ren, Zhaohui; Zhao, Ruoyu; Chen, Xing; Li, Ming; Li, Xiang; Tian, He; Zhang, Ze; Han, Gaorong

2018-04-24

For many decades, zero thermal expansion materials have been the focus of numerous investigations because of their intriguing physical properties and potential applications in high-precision instruments. Different strategies, such as composites, solid solution and doping, have been developed as promising approaches to obtain zero thermal expansion materials. However, microstructure controlled zero thermal expansion behavior via interface or surface has not been realized. Here we report the observation of an impressive zero thermal expansion (volumetric thermal expansion coefficient, -1.41 × 10 -6  K -1 , 293-623 K) in single-crystal ferroelectric PbTiO 3 fibers with large-scale faceted and enclosed mesopores. The zero thermal expansion behavior is attributed to a synergetic effect of positive thermal expansion near the mesopores due to the oxygen-based polarization screening and negative thermal expansion from an intrinsic ferroelectricity. Our results show that a fascinating surface construction in negative thermal expansion ferroelectric materials could be a promising strategy to realize zero thermal expansion.

Soft-Templating Synthesis of N-Doped Mesoporous Carbon Nanospheres for Enhanced Oxygen Reduction Reaction.

PubMed

Bayatsarmadi, Bita; Zheng, Yao; Jaroniec, Mietek; Qiao, Shi Zhang

2015-07-01

The development of ordered mesoporous carbon materials with controllable structures and improved physicochemical properties by doping heteroatoms such as nitrogen into the carbon framework has attracted a lot of attention, especially in relation to energy storage and conversion. Herein, a series of nitrogen-doped mesoporous carbon spheres (NMCs) was synthesized via a facile dual soft-templating procedure by tuning the nitrogen content and carbonization temperature. Various physical and (electro)chemical properties of the NMCs have been comprehensively investigated to pave the way for a feasible design of nitrogen-containing porous carbon materials. The optimized sample showed a favorable electrocatalytic activity as evidenced by a high kinetic current and positive onset potential for oxygen reduction reaction (ORR) due to its large surface area, high pore volume, good conductivity, and high nitrogen content, which make it a highly efficient ORR metal-free catalyst in alkaline solutions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tailored porous silicon microparticles: fabrication and properties

PubMed Central

Chiappini, Ciro; Tasciotti, Ennio; Fakhoury, Jean R.; Fine, Daniel; Pullan, Lee; Wang, Young-Chung; Fu, Lianfeng

2010-01-01

The use of mesoporous silicon particles for drug delivery has been widely explored thanks to their biodegradability and biocompatibility. The ability to tailor the physicochemical properties of porous silicon at the micro and nano scale confers versatility to this material. We present a method for the fabrication of highly reproducible, monodisperse mesoporous silicon particles with controlled physical characteristics through electrochemical etch of patterned silicon trenches. We tailored particle size in the micrometer range and pore size in the nanometer range, shape from tubular to discoidal to hemispherical, and porosity from 46% to over 80%. In addition, we correlated the properties of the porous matrix with the loading of model nanoparticles (Q-dots) and observed their three-dimensional arrangement within the matrix by transmission electron microscopy tomography. The methods developed in this study provide effective means to fabricate mesoporous silicon particles according to the principles of rational design for therapeutic vectors and to characterize the distribution of nanoparticles within the porous matrix PMID:20162656

Speciation of copper diffused in a bi-porous molecular sieve

NASA Astrophysics Data System (ADS)

Huang, C.-H.; Paul Wang, H.; Wei, Y.-L.; Chang, J.-E.

2010-07-01

To better understand diffusion of copper in the micro- and mesopores, speciation of copper in a bi-porous molecular sieve (BPMS) possessing inter-connecting 3-D micropores (0.50-0.55 nm) and 2-D mesopores (4.1 nm) has been studied by X-ray absorption near edge structure (XANES) spectroscopy. It is found that about 77% (16% of CuO nanoparticles and 61% of CuO clusters) and 23% (CuO ads) of copper can be diffused into the meso- and micropores, respectively, in the BPMS. At least two diffusion steps in the BPMS may be involved: (i) free diffusion of copper in the mesopores and (ii) diffusion-controlled copper migrating into the micropores of the BPMS. The XANES data also indicate that diffusion rate of copper in the BPMS (4.68×10 -5 g/s) is greater than that in the ZSM-5 (1.11×10 -6 g/s) or MCM-41 (1.17×10 -5 g/s).

Direct synthesis of Al-SBA-15 containing aluminosilicate species plugs in an acid-free medium and structural adjustment by hydrothermal post-treatment

NASA Astrophysics Data System (ADS)

Shi, Lei; Xu, Yan; Zhang, Na; Lin, Sen; Li, Xiangping; Guo, Peng; Li, Xuebing

2013-07-01

A series of Al-SBA-15 with controllable aluminosilicate plug structures inside straight mesopores has been hydrothermally synthesized in a one-step synthesis in an environmentally friendly acid-free medium, using triblock copolymer Pluronic P123 as a structure-directing agent, water as solvent, tetraethyl orthosilicate (TEOS) and aluminum nitrate (Al(NO)3·9H2O) as silica and aluminum sources, respectively. The effects of the P123/Si molar ratio in the initial solution and aging temperature on the structural properties of the resulting materials were investigated by powder X-ray diffraction (XRD), nitrogen adsorption-desorption at 77 K, transmission electron microscopy (TEM), scanning electron microscopy (SEM), thermogravimetric (TG), FT-IR spectra and inductively coupled plasma (ICP) analyses. The nature of the Al species and the acidity of the resultant samples were studied by solid state 27Al MAS NMR and pyridine adsorption measurements. The specific surface area (935-755 m2g-1), pore volume (1.03-0.56 cm3g-1) and especially the concentration and distribution of open type mesopores (0-68% to the total pores) of the synthesized Al-SBA-15 can be controlled by a simple adjustment of the P123/Si molar ratio in the initial solution. Moreover, increasing the aging temperature higher than 363 K can remarkably decrease the formation of plug structures to obtain “open” form mesopores. The observation by TEM of alternate defined gray and white areas inside the mesopores gives the strong evidence of isolated microporous aluminosilicate plugs inside the channels. In addition, a moderate hydrothermal post-treatment can finely modify the mesostructures through the partial or complete dissolution of the aluminosilicate plugs.

Fine-tuning the release of molecular guests from mesoporous silicas by controlling the orientation and mobility of surface phenyl substituents

DOE Office of Scientific and Technical Information (OSTI.GOV)

Manzano, J. Sebastian; Singappuli-Arachchige, Dilini; Parikh, Bosky L.

Phenyl-functionalized mesoporous silica materials were used to explore the effect of non-covalent interactions on the release of Ibuprofen into simulated body fluid. Variations in orientation and conformational mobility of the surface phenyl groups were introduced by selecting different structural precursors: a rigid upright orientation was obtained using phenyl groups directly bound to surface Si atoms (Ph-MSN), mobile groups were produced by using ethylene linkers to connect phenyl groups to the surface (PhEt-MSN), and groups co-planar to the surface were obtained by synthesizing a phenylene-bridged periodic mesoporous organosilica (Ph-PMO). The Ibuprofen release profiles from these materials and non-functionalized mesoporous silica nanoparticlesmore » (MSN) were analyzed using an adsorption-diffusion model. The model provided kinetic and thermodynamic parameters that evidenced fundamental differences in drug-surface interactions between the materials. All phenyl-bearing materials show lower Ibuprofen initial release rates than bare MSN. The conformationally locked Ph-MSN and Ph-PMO have stronger interactions with the drug (negative ΔG of adsorption) than the flexible PhEt-MSN and bare MSN (positive ΔG of adsorption). These differences in strength of adsorption are consistent with differences between interaction geometries obtained from DFT calculations. B3LYP-D3-optimized models show that π-π interactions contribute more to drug adsorption than H-bonding with silanol groups. Here, the results suggest that the type and geometry of interactions control the kinetics and extent of drug release, and should therefore serve as a guide to design new drug delivery systems with precise release behaviors customized to any desired target.« less

Fine-tuning the release of molecular guests from mesoporous silicas by controlling the orientation and mobility of surface phenyl substituents

DOE PAGES

Manzano, J. Sebastian; Singappuli-Arachchige, Dilini; Parikh, Bosky L.; ...

2017-12-05

Phenyl-functionalized mesoporous silica materials were used to explore the effect of non-covalent interactions on the release of Ibuprofen into simulated body fluid. Variations in orientation and conformational mobility of the surface phenyl groups were introduced by selecting different structural precursors: a rigid upright orientation was obtained using phenyl groups directly bound to surface Si atoms (Ph-MSN), mobile groups were produced by using ethylene linkers to connect phenyl groups to the surface (PhEt-MSN), and groups co-planar to the surface were obtained by synthesizing a phenylene-bridged periodic mesoporous organosilica (Ph-PMO). The Ibuprofen release profiles from these materials and non-functionalized mesoporous silica nanoparticlesmore » (MSN) were analyzed using an adsorption-diffusion model. The model provided kinetic and thermodynamic parameters that evidenced fundamental differences in drug-surface interactions between the materials. All phenyl-bearing materials show lower Ibuprofen initial release rates than bare MSN. The conformationally locked Ph-MSN and Ph-PMO have stronger interactions with the drug (negative ΔG of adsorption) than the flexible PhEt-MSN and bare MSN (positive ΔG of adsorption). These differences in strength of adsorption are consistent with differences between interaction geometries obtained from DFT calculations. B3LYP-D3-optimized models show that π-π interactions contribute more to drug adsorption than H-bonding with silanol groups. Here, the results suggest that the type and geometry of interactions control the kinetics and extent of drug release, and should therefore serve as a guide to design new drug delivery systems with precise release behaviors customized to any desired target.« less

Stimulus-response mesoporous silica nanoparticle-based chemiluminescence biosensor for cocaine determination.

PubMed

Chen, Zhonghui; Tan, Yue; Xu, Kefeng; Zhang, Lan; Qiu, Bin; Guo, Longhua; Lin, Zhenyu; Chen, Guonan

2016-01-15

Mesoporous silica nanoparticles (MSN) based controlled release system had been coupled with diverse detection technologies to establish biosensors for different targets. Chemiluminescence (CL) system of luminol/H2O2 owns the characters of simplicity, low cost and high sensitivity, but the targets of which are mostly focused on some oxidants or which can participate in a chemical reaction that yields a product with a role in the CL reaction. In this study, chemiluminescent detection technique had been coupled with mesoporous silica-based controlled released system for the first time to develop a sensitive biosensor for the target which does not cause effect to the CL system itself. Cocaine had been chosen a model target, the MSN support was firstly loaded with glucose, then the positively charged MSN interacted with negatively charged oligonucleotides (the aptamer cocaine) to close the mesopores of MSN. At the present of target, cocaine binds with its aptamer with high affinity; the flexible linear aptamer structured will become stems structured through currently well-defined non-Waston-Crick interactions and causes the releasing of entrapped glucose into the solution. With the assistant of glucose oxidase (GOx), the released glucose can react with the dissolved oxgen to produce gluconic acid and H2O2, the latter can enhance the CL of luminol in the NaOH solution. The enhanced CL intensity has a relationship with the cocaine concentration in the range of 5.0-60μM with the detection limit of 1.43μM. The proposed method had been successfully applied to detect cocaine in serum samples with high selectivity. The same strategy can be applied to develop biosensors for different targets. Copyright © 2015 Elsevier B.V. All rights reserved.

Infrared Study of CO2 Sorption over ?Molecular Basket? Sorbent Consisting of Polyethylenimine-Modified Mesoporous Molecular Sieve

DOE Office of Scientific and Technical Information (OSTI.GOV)

Overbury, Steven; Wang, Xiaoxing; Clark, Jason

2009-01-01

An infrared study has been conducted on CO{sub 2} sorption into nanoporous CO{sub 2} 'molecular basket' sorbents prepared by loading polyethylenimine (PEI) into mesoporous molecular sieve SBA-15. IR results from DRIFTS showed that a part of loaded PEI is anchored on the surface of SBA-15 through the interaction between amine groups and isolated surface silanol groups. Raising the temperature from 25 to 75 C increased the molecular flexibility of PEI loaded in the mesopore channels, which may partly contribute to the increase of CO{sub 2} sorption capacity at higher temperatures. CO{sub 2} sorption/desorption behavior studied by in situ transmission FTIRmore » showed that CO{sub 2} is sorbed on amine sites through the formation of alkylammonium carbamates and absorbed into the multiple layers of PEI located in mesopores of SBA-15. A new observation by in situ IR is that two broad IR bands emerged at 2450 and 2160 cm{sup -1} with CO{sub 2} flowing over PEI(50)/SBA-15, which could be attributed to chemically sorbed CO{sub 2} species on PEI molecules inside the mesopores of SBA-15. The intensities of these two bands also increased with increasing CO{sub 2} exposure time and with raising CO{sub 2} sorption temperature. By comparison of the CO{sub 2} sorption rate at 25 and 75 C in terms of differential IR intensities, it was found that CO{sub 2} sorption over molecular basket sorbent includes two rate regimes which suggest two distinct steps: rapid sorption on exposed outer surface layers of PEI (controlled by sorption affinity or thermodynamics) and the diffusion and sorption inside the bulk of multiple layers of PEI (controlled by diffusion). The sorption of CO{sub 2} is reversible at 75 C. Comparative IR examination of the CO{sub 2} sorption/desorption spectra on dry and prewetted PEI/SBA-15 sorbent revealed that presorbed water does not significantly affect the CO{sub 2}-amine interaction patterns.« less

Enhanced adsorption of Eu(III) on mesoporous Al2O3/expanded graphite composites investigated by macroscopic and microscopic techniques.

PubMed

Sun, Yubing; Chen, Changlun; Tan, Xiaoli; Shao, Dadong; Li, Jiaxing; Zhao, Guixia; Yang, Shubin; Wang, Qi; Wang, Xiangke

2012-11-21

Mesoporous Al(2)O(3) was intercalated into an expanded graphite (EG) interlayer to prepare mesoporous Al(2)O(3)/EG composites. The basal spacing of mesoporous Al(2)O(3)/EG composites was enlarged as compared to raw graphite from the X-ray diffraction analysis. The massive surface functional groups and wedge-shaped pores were observed in terms of potentiometric acid-base titration analysis and scanning electron microscope, respectively. The pH-dependent adsorption of Eu(III) on mesoporous Al(2)O(3)/EG composites was evidently independent of ionic strength. The maximum adsorption capacity of Eu(III) on mesoporous Al(2)O(3)/EG composites at pH 6.0 and T = 293 K was calculated to be 5.14 mg g(-1). Desorption kinetics and cyclic operation results showed that mesoporous Al(2)O(3)/EG composites presented high hydrothermal stability in aqueous solution. The thermodynamic parameters suggested that Eu(III) adsorption on mesoporous Al(2)O(3)/EG composites is an endothermic and a spontaneous process. The decrease of Eu-O bond distance with the increasing pH demonstrated that the adsorption mechanism between Eu(III) and mesoporous Al(2)O(3)/EG composites would shift from outer-sphere surface complexation to inner-sphere surface complexation in terms of extended X-ray absorption fine structure spectroscopy analysis.

Mesoporous materials for antihydrogen production.

PubMed

Consolati, Giovanni; Ferragut, Rafael; Galarneau, Anne; Di Renzo, Francesco; Quasso, Fiorenza

2013-05-07

Antimatter is barely known by the chemist community and this article has the vocation to explain how antimatter, in particular antihydrogen, can be obtained, as well as to show how mesoporous materials could be used as a further improvement for the production of antimatter at very low temperatures (below 1 K). The first experiments with mesoporous materials highlighted in this review show very promising and exciting results. Mesoporous materials such as mesoporous silicon, mesoporous material films, pellets of MCM-41 and silica aerogel show remarkable features for antihydrogen formation. Yet, the characteristics for the best future mesoporous materials (e.g. pore sizes, pore connectivity, shape, surface chemistry) remain to be clearly identified. For now among the best candidates are pellets of MCM-41 and aerogel with pore sizes between 10 and 30 nm, possessing hydrophobic patches on their surface to avoid ice formation at low temperature. From a fundamental standpoint, antimatter experiments could help to shed light on open issues, such as the apparent asymmetry between matter and antimatter in our universe and the gravitational behaviour of antimatter. To this purpose, basic studies on antimatter are necessary and a convenient production of antimatter is required. It is exactly where mesoporous materials could be very useful.

Functional mesoporous silica nanoparticles for bio-imaging applications.

PubMed

Cha, Bong Geun; Kim, Jaeyun

2018-03-22

Biomedical investigations using mesoporous silica nanoparticles (MSNs) have received significant attention because of their unique properties including controllable mesoporous structure, high specific surface area, large pore volume, and tunable particle size. These unique features make MSNs suitable for simultaneous diagnosis and therapy with unique advantages to encapsulate and load a variety of therapeutic agents, deliver these agents to the desired location, and release the drugs in a controlled manner. Among various clinical areas, nanomaterials-based bio-imaging techniques have advanced rapidly with the development of diverse functional nanoparticles. Due to the unique features of MSNs, an imaging agent supported by MSNs can be a promising system for developing targeted bio-imaging contrast agents with high structural stability and enhanced functionality that enable imaging of various modalities. Here, we review the recent achievements on the development of functional MSNs for bio-imaging applications, including optical imaging, magnetic resonance imaging (MRI), positron emission tomography (PET), computed tomography (CT), ultrasound imaging, and multimodal imaging for early diagnosis. With further improvement in noninvasive bio-imaging techniques, the MSN-supported imaging agent systems are expected to contribute to clinical applications in the future. This article is categorized under: Diagnostic Tools > In vivo Nanodiagnostics and Imaging Nanotechnology Approaches to Biology > Nanoscale Systems in Biology. © 2018 Wiley Periodicals, Inc.

Controllable synthesis of mesoporous carbon nanospheres and Fe-N/carbon nanospheres as efficient oxygen reduction electrocatalysts.

PubMed

Wei, Jing; Liang, Yan; Zhang, Xinyi; Simon, George P; Zhao, Dongyuan; Zhang, Jin; Jiang, Sanping; Wang, Huanting

2015-04-14

The synthesis of mesoporous carbon nanospheres (MCNs), especially with diameters below 200 nm remains a great challenge due to weak interactions between the carbon precursors and soft templates, as well as the uncontrollable cross-linking rate of carbon precursors. Herein, we demonstrate a simple acid-assisted, hydrothermal synthesis approach to synthesizing such uniform MCNs with well controlled diameters ranging from 20 to 150 nm under highly acidic conditions (2 M HCl). Both the carbon precursor and the template are partly protonated under such conditions and show additional Coulombic interactions with chloride ions (acts as mediators). This kind of enhanced interaction is similar to that of the "I(+)X(-)S(+)" mechanism in the synthesis of mesoporous metal oxide, which can effectively retard the cross-linking rate of resol molecules and avoid macroscopic phase separation during the hydrothermal synthesis. Due to their uniform spherical morphology, small diameter, and high surface areas, MCNs can be modified with Fe and N species via impregnation of cheap precursors (ferric nitrate and dicyandiamide), which are further converted into nonprecious electrocatalysts for oxygen reduction reactions. The resulting Fe-N/MCNs exhibit high catalytic activities, long-term stability and improved methanol tolerance under alkaline conditions, which can be potentially used in direct methanol fuel cells and metal-air batteries.

Periodically Arranged Arrays of Dendritic Pt Nanospheres Using Cage-Type Mesoporous Silica as a Hard Template.

PubMed

Kani, Kenya; Malgras, Victor; Jiang, Bo; Hossain, Md Shahriar A; Alshehri, Saad M; Ahamad, Tansir; Salunkhe, Rahul R; Huang, Zhenguo; Yamauchi, Yusuke

2018-01-04

Dendritic Pt nanospheres of 20 nm diameter are synthesized by using a highly concentrated surfactant assembly within the large-sized cage-type mesopores of mesoporous silica (LP-FDU-12). After diluting the surfactant solution with ethanol, the lower viscosity leads to an improved penetration inside the mesopores. After Pt deposition followed by template removal, the arrangement of the Pt nanospheres is a replication from that of the mesopores in the original LP-FDU-12 template. Although it is well known that ordered LLCs can form on flat substrates, the confined space inside the mesopores hinders surfactant self-organization. Therefore, the Pt nanospheres possess a dendritic porous structure over the entire area. The distortion observed in some nanospheres is attributed to the close proximity existing between neighboring cage-type mesopores. This new type of nanoporous metal with a hierarchical architecture holds potential to enhance substance diffusivity/accessibility for further improvement of catalytic activity. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thin-Layer Polymer Wrapped Enzymes Encapsulated in Hierarchically Mesoporous Silica with High Activity and Enhanced Stability

NASA Astrophysics Data System (ADS)

Zhang, Fang; Wang, Meitao; Liang, Chao; Jiang, Huangyong; Shen, Jian; Li, Hexing

2014-03-01

A novel soft-hard cooperative approach was developed to synthesize bioactive mesoporous composite by pre-wrapping Penicillin G amidase with poly(acrylaimde) nanogel skin and subsequently incorporating such Penicillin G amidase nanocapsules into hierarchically mesoporous silica. The as-received bioactive mesoporous composite exhibited comparable activity and extraordinarily high stability in comparison with native Penicillin G amidase and could be used repetitively in the water-medium hydrolysis of penicillin G potassium salt. Furthermore, this strategy could be extended to the synthesis of multifunctional bioactive mesoporous composite by simultaneously introducing glucose oxidase nanocapsules and horseradish peroxidase nanocapsules into hierarchically mesoporous silica, which demonstrated a synergic effect in one-pot tandem oxidation reaction. Improvements in the catalytic performances were attributed to the combinational unique structure from soft polymer skin and hard inorganic mesoporous silica shell, which cooperatively helped enzyme molecules to retain their appropriate geometry and simultaneously decreased the enzyme-support negative interaction and mass transfer limitation under heterogeneous conditions.

Mesoporous metal oxide microsphere electrode compositions and their methods of making

DOEpatents

Paranthaman, Mariappan Parans; Liu, Hansan; Brown, Gilbert M.; Sun, Xiao-Guang; Bi, Zhonghe

2016-12-06

Compositions and methods of making are provided for mesoporous metal oxide microspheres electrodes. The mesoporous metal oxide microsphere compositions comprise (a) microspheres with an average diameter between 200 nanometers (nm) and 10 micrometers (.mu.m); (b) mesopores on the surface and interior of the microspheres, wherein the mesopores have an average diameter between 1 nm and 50 nm and the microspheres have a surface area between 50 m.sup.2/g and 500 m.sup.2/g. The methods of making comprise forming composite powders. The methods may also comprise refluxing the composite powders in a basic solution to form an etched powder, washing the etched powder with an acid to form a hydrated metal oxide, and heat-treating the hydrated metal oxide to form mesoporous metal oxide microspheres.

Construction of homogenous/heterogeneous hollow mesoporous silica nanostructures by silica-etching chemistry: principles, synthesis, and applications.

PubMed

Chen, Yu; Chen, Hang-Rong; Shi, Jian-Lin

2014-01-21

Colloidal hollow mesoporous silica nanoparticles (HMSNs) are aspecial type of silica-based nanomaterials with penetrating mesopore channels on their shells. HMSNs exhibit unique structural characteristics useful for diverse applications: Firstly, the hollow interiors can function as reservoirs for enhanced loading of guest molecules, or as nanoreactors for the growth of nanocrystals or for catalysis in confined spaces. Secondly, the mesoporous silica shell enables the free diffusion of guest molecules through the intact shell. Thirdly, the outer silica surface is ready for chemical modifications, typically via its abundant Si-OH bonds. As early as 2003, researchers developed a soft-templating methodto prepare hollow aluminosilicate spheres with penetrating mesopores in a cubic symmetry pattern on the shells. However, adapting this method for applications on the nanoscale, especially for biomedicine, has proved difficult because the soft templating micelles are very sensitive to liquid environments, making it difficult to tune key parameters such as dispersity, morphology and structure. In this Account, we present the most recent developments in the tailored construction of highly dispersive and monosized HMSNs using simple silica-etching chemistry, and we discuss these particles' excellent performance in diverse applications. We first introduce general principles of silica-etching chemistry for controlling the chemical composition and the structural parameters (particle size, pore size, etching modalities, yolk-shell nanostructures, etc.) of HMSNs. Secondly, we include recent progress in constructing heterogeneous, multifunctional, hollow mesoporous silica nanorattles via several methods for diverse applications. These elaborately designed HMSNs could be topologically transformed to prepare hollow mesoporous carbon nanoparticles or functionalized to produce HMSN-based composite nanomaterials. Especially in biomedicine, HMSNs are excellent as carriers to deliver either hydrophilic or hydrophobic anti-cancer drugs, to tumor cells, offering enhanced chemotherapeutic efficacy and diminished toxic side effects. Most recently, research has shown that loading one or more anticancer drugs into HMSNs can inhibit metastasis or reverse multidrug resistance of cancer cells. HMSNs could also deliver hydrophobic perfluorohexane (PFH) molecules to improve high intensity focused ultrasound (HIFU) cancer surgery by changing the tissue acoustic environment; and HMSNs could act as nanoreactors for enhanced catalytic activity and/or durability. The versatility of silica-etching chemistry, a simple but scalable synthetic methodology, offers great potential for the creation of new types of HMSN-based nanostructures in a range of applications.

Design, fabrication, and testing of nanostructured carbons and composites

NASA Astrophysics Data System (ADS)

Wang, Zhiyong

Many applications, such as catalysis, sensing, separation and energy storage and conversion, will benefit from the miniaturization of materials to nanometer length scales. This dissertation details my study of nanocomposites based on three-dimensionally ordered macroporous (3DOM) carbons and zirconia, and three-dimensionally ordered macroporous/mesoporous (3DOM/m) carbons. The macropores of these materials were produced using colloidal crystal templates while the mesopores were generated using surfactant templates. These solids are composed of close-packed and three-dimensionally interconnected spherical macropores surrounded by nanoscale solid or mesoporous wall skeletons. This unique architecture offers large surface areas, pore volumes, and good access into the bulk via a macroporous network. 3DOM carbons have been demonstrated as promising electrode materials for lithium ion batteries and sensors, but their electrochemical performance still needs to be improved. As a model system for the modification of the electrode, 3DOM C/TiO2 was synthesized by fabricating a conformal coating of TiO2 nanoparticles on the macropore walls of 3DOM C. My research further extended the micro-structural design of monolithic carbon from 3DOM to 3DOM/m. 3DOM/m C monoliths with high surface areas, controllable mesopore sizes, and mesopore ordering, were synthesized by three methods. One of the methods is simpler and more environment benign than previously reported methods. The mesopores in 3DOM/m C-based electrode provide room to accommodate secondary phases, such as graphitic carbon, SnO2 and Si which can improve the conductivity or lithium capacity of the electrode. Owing to this advantage, 3DOM/m C/C and 3DOM/m C/SnO2 exhibited significantly improved rate performance, lithium capacity and cycleability, compared with 3DOM C. To meet the demands of nano-sized functional materials in applications such as nano-device fabrication and drug delivery, mesoporous carbon nanoparticles with cubic, spherical and tetrapod shapes were also synthesized. In addition, new methods were developed to assemble nanocomposites of bifunctional catalyst components. These materials were designed for the potential direct conversion of synthesis gas to clean liquid fuels. Coatings of zeolite and cobalt nanoparticles were fabricated on 3DOM promoted zirconia. The 3DOM zirconia-based nanocomposites were characterized by a wide variety of techniques to illustrate their morphologies, internal structures, chemical compositions, porosity, and crystallographic phases.

Photodegradation of Orange II by mesoporous TiO2.

PubMed

Kuang, Liyuan; Zhao, Yaping; Liu, Lu

2011-09-01

Mesoporous TiO(2) microspheres were prepared by a hydrothermal reaction and are characterized in this paper. Decoloration and mineralization during photodegradation of Orange II by mesoporous TiO(2) at different pH values, formation of sulfate, relative luminosity to luminous bacteria and recycling experiments of the catalyst were studied. The FTIR results further suggested that the novel mesoporous TiO(2) can not only decolor and mineralize dyes completely but also can be effectively reused several times. On the basis of the research, mesoporous TiO(2) would be a promising photocatalyst for practical use.

An efficient adsorption of indigo carmine dye from aqueous solution on mesoporous Mg/Fe layered double hydroxide nanoparticles prepared by controlled sol-gel route.

PubMed

Ahmed, M A; Brick, A A; Mohamed, A A

2017-05-01

A new approach for removal of indigo carmine blue (IC) dye which is extensively used in jeans manufacture was successfully performed on novel mesoporous [LDH] nanoparticles prepared by sol-gel route using CTAB as shape and pore directing agent. The physicochemical features were monitored by X-ray diffraction (XRD), Fourier transformer infra-red (FTIR), N 2 adsorption-desorption isotherm, Field emission electron microscope (FESEM) and high resolution transmission electron microscope (HRTEM). The influence of reaction parameters affecting dye adsorption including contact time, initial dye concentration, pH and temperature were investigated. Textural analysis and HRTEM images indicate the existence of mesoporous spherical nanoparticles of size = 26 nm connected to each other's and embedded large numbers of mesopores of average pore radius = 43.5 Å. A successful adsorption of IC on LDH nanoparticles of surface area = 85.6 m 2 /g at various pH with maximum adsorption capacity = 62.8 mg/g at pH = 9.5. Langmuir model is more favorable to describe the adsorption of IC rather than Freundlich model which reflecting the preferential formation of monolayer on the surface of LDH. Both film diffusion and the intraparticle diffusion affect the dye adsorption. The values of enthalpy change (ΔH) for and (ΔS) are + 28.18 and + 0.118 kJ/mol, respectively indicating that the removal process is endothermic. The results indicated that LDH nanoparticles conserved a good activity even after five consecutive cycles of reuse. Our results suggest that mesoporous LDH nanoparticles are considered a potential novel adsorbent for remediation of wastewater containing IC. Copyright © 2017 Elsevier Ltd. All rights reserved.

Fabrication of mesoporous iron (Fe) doped copper sulfide (CuS) nanocomposite in the presence of a cationic surfactant via mild hydrothermal method for supercapacitors

NASA Astrophysics Data System (ADS)

Brown, J. William; Ramesh, P. S.; Geetha, D.

2018-02-01

We report fabrication of mesoporous Fe doped CuS nanocomposites with uniform mesoporous spherical structures via a mild hydrothermal method employing copper nitrate trihydrate (Cu (NO3).3H2O), Thiourea (Tu,Sc(NH2)2 and Iron tri nitrate (Fe(No3)3) as initial materials with cationic surfactant cetyltrimethylamoniame bromide (CTAB) as stabilizer/size controller and Ethylene glycol as solvent at 130 °C temperature. The products were characterized by XRD, SEM/EDX, TEM, FTIR and UV analysis. X-ray diffraction (XRD) spectra confirmed the Fe doped CuS nanocomposites which are crystalline in nature. EDX and XRD pattern confirmed that the product is hexagonal CuS phase. Fe doped spherical structure of CuS with grain size of 21 nm was confirmed by XRD pattern. Fe doping was identified by energy dispersive spectrometry (EDS). The Fourier-transform infrared (FTIR) spectroscopy results revealed the occurrence of active functional groups required for the reduction of copper ions. Studies showed that after a definite time relining on the chosen copper source, the obtained Fe-CuS nanocomposite shows a tendency towards self-assembly and creating mesoporous like nano and submicro structures by TEM/SAED. The achievable mechanism of producing this nanocomposite was primarily discussed. The electrochemical study confirms the pseudocapacitive nature of the CuS and Fe-CuS electrodes. The CuS and Fe-CuS electrode shows a specific capacitance of about 328.26 and 516.39 Fg-1 at a scan rate of 5 mVs-1. As the electrode in a supercapacitor, the mesoporous nanostructured Fe-CuS shows excellent capacitance characteristics.

Proton Environments in Biomimetic Calcium Phosphates Formed from Mesoporous Bioactive CaO–SiO2–P2O5 Glasses in Vitro: Insights from Solid-State NMR

PubMed Central

2017-01-01

When exposed to body fluids, mesoporous bioactive glasses (MBGs) of the CaO–SiO2–P2O5 system develop a bone-bonding surface layer that initially consists of amorphous calcium phosphate (ACP), which transforms into hydroxy-carbonate apatite (HCA) with a very similar composition as bone/dentin mineral. Information from various 1H-based solid-state nuclear magnetic resonance (NMR) experiments was combined to elucidate the evolution of the proton speciations both at the MBG surface and within each ACP/HCA constituent of the biomimetic phosphate layer formed when each of three MBGs with distinct Ca, Si, and P contents was immersed in a simulated body fluid (SBF) for variable periods between 15 min and 30 days. Directly excited magic-angle-spinning (MAS) 1H NMR spectra mainly reflect the MBG component, whose surface is rich in water and silanol (SiOH) moieties. Double-quantum–single-quantum correlation 1H NMR experimentation at fast MAS revealed their interatomic proximities. The comparatively minor H species of each ACP and HCA component were probed selectively by heteronuclear 1H–31P NMR experimentation. The initially prevailing ACP phase comprises H2O and “nonapatitic” HPO42–/PO43– groups, whereas for prolonged MBG soaking over days, a well-progressed ACP → HCA transformation was evidenced by a dominating O1H resonance from HCA. We show that 1H-detected 1H → 31P cross-polarization NMR is markedly more sensitive than utilizing powder X-ray diffraction or 31P NMR for detecting the onset of HCA formation, notably so for P-bearing (M)BGs. In relation to the long-standing controversy as to whether bone mineral comprises ACP and/or forms via an ACP precursor, we discuss a recently accepted structural core–shell picture of both synthetic and biological HCA, highlighting the close relationship between the disordered surface layer and ACP. PMID:28663772

Pendant/bridged/mesoporous silsesquioxane nanoparticles: Versatile and biocompatible platforms for smart delivery of therapeutics

DOE PAGES

Noureddine, Achraf; Brinker, C. Jeffrey

2018-02-02

Silsesquioxane nanoparticles are composed of repetitive organosilica fragments in their frameworks and are now recognized to have outstanding functional fertility. Depending on the organosilane and the synthetic pathways, silsesquioxane NPs can be pendant, bridged, dense or porous. Recently the diverse functionalities of mesoporous silsesquioxane nanoparticles have been exploited for the sake of drug-related biomedicine. Fine-tuning the silsesquioxane nanoparticles characteristics allow not only a superior retention capacity of therapeutics without the need of any further modification, but also a controlled release through various environmentally-stimulated triggers. Furthermore, the main focus of the present review is to highlight the different types of silsesquioxanemore » nanoparticles and their exceptional features focused on controlled delivery of drugs, proteins, antibodies and DNA through pH, redox or light stimuli.« less

Pendant/bridged/mesoporous silsesquioxane nanoparticles: Versatile and biocompatible platforms for smart delivery of therapeutics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Noureddine, Achraf; Brinker, C. Jeffrey

Silsesquioxane nanoparticles are composed of repetitive organosilica fragments in their frameworks and are now recognized to have outstanding functional fertility. Depending on the organosilane and the synthetic pathways, silsesquioxane NPs can be pendant, bridged, dense or porous. Recently the diverse functionalities of mesoporous silsesquioxane nanoparticles have been exploited for the sake of drug-related biomedicine. Fine-tuning the silsesquioxane nanoparticles characteristics allow not only a superior retention capacity of therapeutics without the need of any further modification, but also a controlled release through various environmentally-stimulated triggers. Furthermore, the main focus of the present review is to highlight the different types of silsesquioxanemore » nanoparticles and their exceptional features focused on controlled delivery of drugs, proteins, antibodies and DNA through pH, redox or light stimuli.« less

Control and formation mechanism of extended nanochannel geometry in colloidal mesoporous silica particles.

PubMed

Sokolov, I; Kalaparthi, V; Volkov, D O; Palantavida, S; Mordvinova, N E; Lebedev, O I; Owens, J

2017-01-04

A large class of colloidal multi-micron mesoporous silica particles have well-defined cylindrical nanopores, nanochannels which self-assembled in the templated sol-gel process. These particles are of broad interest in photonics, for timed drug release, enzyme stabilization, separation and filtration technologies, catalysis, etc. Although the pore geometry and mechanism of pore formation of such particles has been widely investigated at the nanoscale, their pore geometry and its formation mechanism at a larger (extended) scale is still under debate. The extended geometry of nanochannels is paramount for all aforementioned applications because it defines accessibility of nanochannels, and subsequently, kinetics of interaction of the nanochannel content with the particle surrounding. Here we present both experimental and theoretical investigation of the extended geometry and its formation mechanism in colloidal multi-micron mesoporous silica particles. We demonstrate that disordered (and consequently, well accessible) nanochannels in the initially formed colloidal particles gradually align and form extended self-sealed channels. This knowledge allows to control the percentage of disordered versus self-sealed nanochannels, which defines accessibility of nanochannels in such particles. We further show that the observed aligning the channels is in agreement with theory; it is thermodynamically favored as it decreases the Gibbs free energy of the particles. Besides the practical use of the obtained results, developing a fundamental understanding of the mechanisms of morphogenesis of complex geometry of nanopores will open doors to efficient and controllable synthesis that will, in turn, further fuel the practical utilization of these particles.

Effect of polyvinylpyrrolidone on mesoporous silica morphology and esterification of lauric acid with 1-butanol catalyzed by immobilized enzyme

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Jinyu; Zhou, Guowei, E-mail: guoweizhou@hotmail.com; Jiang, Bin

2014-05-01

Mesoporous silica materials with a range of morphology evolution, i.e., from curved rod-shaped mesoporous silica to straight rod-shaped mesoporous silica, were successfully prepared using polyvinylpyrrolidone (PVP) and triblock copolymer as dual template. The effects of PVP molecular weight and concentration on mesoporous silica structure parameters were studied. Results showed that surface area and pore volume continuously decreased with increased PVP molecular weight. Mesoporous silica prepared with PVP K30 also possessed larger pore diameter, interplanar spacing (d{sub 100}), and cell parameter (a{sub 0}) than that prepared with PVP K15 and PVP K90. In addition, with increased PVP concentration, d{sub 100} andmore » a{sub 0} continuously decreased. The mechanism of morphology evolution caused by the change in PVP concentration was investigated. The conversion rate of lauric acid with 1-butanol catalyzed by immobilized Porcine pancreatic lipase (PPL) was also evaluated. Results showed that PPL immobilized on amino-functionalized straight rod-shaped mesoporous silica maintained 50% of its esterification conversion rate even after five cycles of use with a maximum conversion rate was about 90.15%. - Graphical abstract: Curved rod-shaped mesoporous silica can be obtained at low and the highest PVP concentration, while straight rod-shaped mesoporous silica can be obtained at higher PVP concentration. - Highlights: • Mesoporous silica with morphology evolution from CRMS to SRMS were prepared. • Effects of PVP molecular weight and concentration on silica morphology were studied. • A possible mechanism for the formation of morphology evolution SiO{sub 2} was proposed. • Esterification of lauric acid with 1-butanol catalyzed by immobilized PPL.« less

Synthesis and electrochemical performance of mesoporous SiO{sub 2}–carbon nanofibers composite as anode materials for lithium secondary batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hyun, Yura; Choi, Jin-Yeong; Park, Heai-Ku

Highlights: • Mesoporous SiO{sub 2}–carbon nanofibers composite synthesized on Ni foam without any binder. • This composite was directly applied as anode material of Li secondary batteries. • Showed the highest initial (2420 mAh/g) and discharging (2092 mAh/g) capacity. • This material achieved a retention rate of 86.4% after 30 cycles. - Abstract: In this study, carbon nanofibers (CNFs) and mesoporous SiO{sub 2}–carbon nanofibers composite were synthesized and applied as the anode materials in lithium secondary batteries. CNFs and mesoporous SiO{sub 2}–CNFs composite were grown via chemical vapor deposition method with iron-copper catalysts. Mesoporous SiO{sub 2} materials were prepared bymore » sol–gel method using tetraethylorthosilicate as the silica source and cetyltrimethylammoniumchloride as the template. Ethylene was used as the carbon source and passes into a quartz reactor of a tube furnace heated to 600 °C, and the temperature was maintained at 600 °C for 10 min to synthesize CNFs and mesoporous SiO{sub 2}–CNFs composite. The electrochemical characteristics of the as-prepared CNFs and mesoporous SiO{sub 2}–CNFs composite as the anode of lithium secondary batteries were investigated using a three-electrode cell. In particular, the mesoporous SiO{sub 2}–CNFs composites synthesized without binder after depositing mesoporous SiO{sub 2} on Ni foam showed the highest charging and discharging capacity and retention rate. The initial capacity (2420 mAh/g) of mesoporous SiO{sub 2}–CNFs composites decreased to 2092 mAh/g after 30 cycles at a retention rate of 86.4%.« less

Exploring the segregating and mineralization-inducing capacities of cationic hydrophilic polymers for preparation of robust, multifunctional mesoporous hybrid microcapsules.

PubMed

Shi, Jiafu; Zhang, Wenyan; Wang, Xiaoli; Jiang, Zhongyi; Zhang, Shaohua; Zhang, Xiaoman; Zhang, Chunhong; Song, Xiaokai; Ai, Qinghong

2013-06-12

A facile approach to preparing mesoporous hybrid microcapsules is developed by exploring the segregating and mineralization-inducing capacities of cationic hydrophilic polymer. The preparation process contains four steps: segregation of cationic hydrophilic polymer during template formation, cross-linking of the segregated polymer, biomimetic mineralization within cross-linked polymer network, and removal of template to simultaneously generate capsule lumen and mesopores on the capsule wall. Poly(allylamine hydrochloride) (PAH) is chosen as the model polymer, its hydrophilicity renders the segregating capacity and spontaneous enrichment in the near-surface region of CaCO3 microspheres; its biopolyamine-mimic structure renders the mineralization-inducing capacity to produce titania from the water-soluble titanium(IV) precursor. Meanwhile, CaCO3 microspheres serve the dual templating functions in the formation of hollow lumen and mesoporous wall. The thickness of capsule wall can be controlled by changing the polymer segregating and cross-linking conditions, while the pore size on the capsule wall can be tuned by changing the template synthesizing conditions. The robust hybrid microcapsules exhibit desirable efficiency in enzymatic catalysis, wastewater treatment and drug delivery. This approach may open facile, generic, and efficient pathway to designing and preparing a variety of hybrid microcapsules with high and tunable permeability, good stability and multiple functionalities for a broad range of applications.

Fabrication of high specificity hollow mesoporous silica nanoparticles assisted by Eudragit for targeted drug delivery.

PubMed

She, Xiaodong; Chen, Lijue; Velleman, Leonora; Li, Chengpeng; Zhu, Haijin; He, Canzhong; Wang, Tao; Shigdar, Sarah; Duan, Wei; Kong, Lingxue

2015-05-01

Hollow mesoporous silica nanoparticles (HMSNs) are one of the most promising carriers for effective drug delivery due to their large surface area, high volume for drug loading and excellent biocompatibility. However, the non-ionic surfactant templated HMSNs often have a broad size distribution and a defective mesoporous structure because of the difficulties involved in controlling the formation and organization of micelles for the growth of silica framework. In this paper, a novel "Eudragit assisted" strategy has been developed to fabricate HMSNs by utilising the Eudragit nanoparticles as cores and to assist in the self-assembly of micelle organisation. Highly dispersed mesoporous silica spheres with intact hollow interiors and through pores on the shell were fabricated. The HMSNs have a high surface area (670 m(2)/g), small diameter (120 nm) and uniform pore size (2.5 nm) that facilitated the effective encapsulation of 5-fluorouracil within HMSNs, achieving a high loading capacity of 194.5 mg(5-FU)/g(HMSNs). The HMSNs were non-cytotoxic to colorectal cancer cells SW480 and can be bioconjugated with Epidermal Growth Factor (EGF) for efficient and specific cell internalization. The high specificity and excellent targeting performance of EGF grafted HMSNs have demonstrated that they can become potential intracellular drug delivery vehicles for colorectal cancers via EGF-EGFR interaction. Copyright © 2014 Elsevier Inc. All rights reserved.

[Adsorption kinetics and mechanism of lead (II) on polyamine-functionalized mesoporous activated carbon].

PubMed

Li, Kun-Quan; Wang, Yan-Jin; Yang, Mei-Rong; Zhu, Zhi-Qiang; Zheng, Zheng

2014-08-01

Bagasse mesoporous carbon was prepared by microwave assisted H3 PO4 activation. Amido and imido groups were modified with ethanediamine on the channels' surface of mesoporous carbon through nitric oxidation and amide reaction. The influence of Pb(II) concentration, adsorption time on Pb(II) adsorption on the ethanediamine-modified mesoporous carbon (AC-EDA) was investigated. The adsorption kinetics and mechanism were also discussed. The results showed that AC-EDA had a great performance for Pb(II) adsorption, and more than 70% of Pb(II) was adsorbed in 5 minutes. The adsorption amount of Pb(II) on the carbon increased with the increase of solution pH in acidic conditions. It was found that AC-EDA had different binding energies on different adsorption sites for Pb(II) separation. The Pb(II) adsorption process on AC-EDA was controlled by intra-particle diffusion in the first 3 min, and then film diffusion played the important pole on the adsorption. The adsorption amount increased with the increase of temperature, indicating the adsorption was an endothermic reaction. The high adsorption energy (> 11 kJ x mol(-1)) implied that the) adsorption was a chemical adsorption. The XPS of AC-EDA before and after Pb(II) adsorption showed that the polyamine group was involved in the adsorption, and should be a main factor of the high efficient adsorption.

A study of some fundamental physicochemical variables on the morphology of mesoporous silica nanoparticles MCM-41 type

NASA Astrophysics Data System (ADS)

Beltrán-Osuna, Ángela A.; Gómez Ribelles, José L.; Perilla, Jairo E.

2017-12-01

All variables affecting the morphology of mesoporous silica nanoparticles (MSN) should be carefully analyzed in order to truly tailored design their mesoporous structure according to their final use. Although complete control on MCM-41 synthesis has been already claimed, reproducibility and repeatability of results remain a big issue due to the lack of information reported in literature. Stirring rate, reaction volume, and system configuration (i.e., opened or closed reactor) are three variables that are usually omitted, making the comparison of product characteristics difficult. Specifically, the rate of solvent evaporation is seldom disclosed, and its influence has not been previously analyzed. These variables were systematically studied in this work, and they were proven to have a fundamental impact on final particle morphology. Hence, a high degree of circularity ( C = 0.97) and monodispersed particle size distributions were only achieved when a stirring speed of 500 rpm and a reaction scale of 500 mL were used in a partially opened system, for a 2 h reaction at 80 °C. Well-shaped spherical mesoporous silica nanoparticles with a diameter of 95 nm, a pore size of 2.8 nm, and a total surface area of 954 m2 g-1 were obtained. Final characteristics made this product suitable to be used in biomedicine and nanopharmaceutics, especially for the design of drug delivery systems.

Multifunctional mesoporous silica catalyst

DOEpatents

Lin, Victor Shang-Yi; Tsai, Chih-Hsiang; Chen, Hung-Ting; Pruski, Marek; Kobayashi, Takeshi

2015-03-31

The present invention provides bifunctional silica mesoporous materials, including mesoporous silica nanoparticles ("MSN"), having pores modified with diarylammonium triflate and perfluoroaryl moieties, that are useful for the acid-catalyzed esterification of organic acids with organic alcohols.

Mesoporous silica formulation strategies for drug dissolution enhancement: a review.

PubMed

McCarthy, Carol A; Ahern, Robert J; Dontireddy, Rakesh; Ryan, Katie B; Crean, Abina M

2016-01-01

Silica materials, in particular mesoporous silicas, have demonstrated excellent properties to enhance the oral bioavailability of poorly water-soluble drugs. Current research in this area is focused on investigating the kinetic profile of drug release from these carriers and manufacturing approaches to scale-up production for commercial manufacture. This review provides an overview of different methods utilized to load drugs onto mesoporous silica carriers. The influence of silica properties and silica pore architecture on drug loading and release are discussed. The kinetics of drug release from mesoporous silica systems is examined and the manufacturability and stability of these formulations are reviewed. Finally, the future prospects of mesoporous silica drug delivery systems are considered. Substantial progress has been made in the characterization and development of mesoporous drug delivery systems for drug dissolution enhancement. However, more research is required to fully understand the drug release kinetic profile from mesoporous silica materials. Incomplete drug release from the carrier and the possibility of drug re-adsorption onto the silica surface need to be investigated. Issues to be addressed include the manufacturability and regulation status of formulation approaches employing mesoporous silica to enhance drug dissolution. While more research is needed to support the move of this technology from the bench to a commercial medicinal product, it is a realistic prospect for the near future.

A rational repeating template method for synthesis of 2D hexagonally ordered mesoporous precious metals.

PubMed

Takai, Azusa; Doi, Yoji; Yamauchi, Yusuke; Kuroda, Kazuyuki

2011-03-01

A repeating template method is presented for the synthesis of mesoporous metals with 2D hexagonal mesostructures. First, a silica replica (i.e., silica nanorods arranged periodically) is prepared by using 2D hexagonally ordered mesoporous carbon as the template. After that, the obtained silica replica is used as the second template for the preparation of mesoporous ruthenium. After the ruthenium species are introduced into the silica replica, the ruthenium species are then reduced by a vapor-infiltration method by using the reducing agent dimethylamine borane. After the ruthenium deposition, the silica is chemically removed. Analysis by transmission and scanning electron microscopies, a nitrogen-adsorption-desorption isotherm, and small-angle X-ray scattering revealed that the mesoporous ruthenium had a 2D hexagonal mesostructure, although the mesostructural ordering is decreased compared to that of the original mesoporous carbon template. This method is widely applicable to other metal systems. By changing the metal species introduced into the silica replica, several mesoporous metals (palladium and platinum) can be synthesized. Ordered mesoporous ruthenium and palladium, which are not easily attainable by the soft-templating methods, can be prepared. This study has overcome the composition variation limitations of the soft-templating method. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface functionalized mesoporous material and method of making same

DOEpatents

Feng, Xiangdong [West Richland, WA; Liu, Jun [West Richland, WA; Fryxell, Glen E [Kennewick, WA

2001-12-04

According to the present invention, an organized assembly of functional molecules with specific interfacial functionality (functional group(s)) is attached to available surfaces including within mesopores of a mesoporous material. The method of the present invention avoids the standard base soak that would digest the walls between the mesopores by boiling the mesoporous material in water for surface preparation then removing all but one or two layers of water molecules on the internal surface of a pore. Suitable functional molecule precursor is then applied to permeate the hydrated pores and the precursor then undergoes condensation to form the functional molecules on the interior surface(s) of the pore(s).

Sample Desorption/Onization From Mesoporous Silica

DOEpatents

Iyer, Srinivas; Dattelbaum, Andrew M.

2005-10-25

Mesoporous silica is shown to be a sample holder for laser desorption/ionization of mass spectrometry. Supported mesoporous silica was prepared by coating an ethanolic silicate solution having a removable surfactant onto a substrate to produce a self-assembled, ordered, nanocomposite silica thin film. The surfactant was chosen to provide a desired pore size between about 1 nanometer diameter and 50 nanometers diameter. Removal of the surfactant resulted in a mesoporous silica thin film on the substrate. Samples having a molecular weight below 1000, such as C.sub.60 and tryptophan, were adsorbed onto and into the mesoporous silica thin film sample holder and analyzed using laser desorption/ionization mass spectrometry.

A review on chemical methodologies for preparation of mesoporous silica and alumina based materials.

PubMed

Naik, Bhanudas; Ghosh, Narendra Nath

2009-01-01

The discovery of novel family of molecular sieves called M41S aroused a worldwide resurgence in the field of porous materials. According to IUPAC definition inorganic solids that contain pores with diameter in the size range of 20-500 A are considered mesoporous materials. Mesoporous silica and alumina based materials find applications in catalysis, adsorption, host- guest encapsulation etc. This article reviews the current state of art and outline the recent patents in mesoporous materials research in three general areas: Synthesis, various mechanisms involved for porous structure formation and applications of silica and alumina based mesoporous materials.

Investigation of the stability of Platinum nanoparticles incorporated in mesoporous silica with different pore sizes.

PubMed

Yano, Kazuhisa; Zhang, Shuyi; Pan, Xiaoqing; Tatsuda, Narihito

2014-05-01

The effect of the pore size of mesoporous silica on the stability of Pt nanoparticles (NPs) has been investigated. TEM observation and XRD measurement were conducted in situ for Pt loaded mesoporous silica with different mesopore sizes. It turns out that smaller pores are more effective to stabilize Pt NPs below 600 °C. However, aggregation of Pt NPs on the surface of particles is not fully suppressed more than 1000 °C in ambient atmosphere even though smaller mesopore size is applied. The type of precursor does not affect the stability of Pt NPs. Copyright © 2014. Published by Elsevier Inc.

N, P-codoped Mesoporous Carbon Supported PtCox Nanoparticles and Their Superior Electrochemical toward Methanol Oxidation

NASA Astrophysics Data System (ADS)

Cui, Hangjun; Li, Yueming; Liu, Shimin

2018-03-01

In this report, a novel strategy by using the N, P co-doped mesoporous carbon structure as catalyst support to enhance the electrochemical catalytic activity of Pt-based catalysts is proposed. The as-synthesized PtCox@N, P-doped mesoporous carbon nanocomposties have been studied as an anode catalyst toward methanol oxidation, exhibiting greatly improved electrochemical activity and stability compared with Pt@mesoporous carbon. The synergistic effects of N, P dual-doping and porous carbon structure help to achieve better electron transport at the electrode surface, which eventually leads to greatly enhanced catalytic activity compared to the pristine Pt/mesoporous carbon.…

The cementogenic differentiation of periodontal ligament cells via the activation of Wnt/β-catenin signalling pathway by Li+ ions released from bioactive scaffolds.

PubMed

Han, Pingping; Wu, Chengtie; Chang, Jiang; Xiao, Yin

2012-09-01

Lithium (Li) has been widely used as a long-term mood stabilizer in the treatment of bipolar and depressive disorders. Li(+) ions are thought to enhance the remyelination of peripheral nerves and also stimulate the proliferation of neural progenitor cells and retinoblastoma cells via activation of the Wnt/β-catenin signalling pathway. Until now there have been no studies reporting the biological effects of released Li(+) in bioactive scaffolds on cemetogenesis in periodontal tissue engineering applications. In this study, we incorporated parts of Li(+) ions into the mesoporous bioactive glass (MBG) scaffolds and showed that this approach yielded scaffolds with a favourable composition, microstructure and mesopore properties for cell attachment, proliferation, and cementogenic differentiation of human periodontal ligament-derived cells (hPDLCs). We went on to investigate the biological effects of Li(+) ions themselves on cell proliferation and cementogenic differentiation. The results showed that 5% Li(+) ions incorporated into MBG scaffolds enhanced the proliferation and cementogenic differentiation of hPDLCs on scaffolds, most likely via activation of Wnt/β-catenin signalling pathway. Further study demonstrated that Li(+) ions by themselves significantly enhanced the proliferation, differentiation and cementogenic gene expression of PDLCs. Our results indicate that incorporation of Li(+) ions into bioactive scaffolds is a viable means of enhancing the Wnt canonical signalling pathway to stimulate cementogenic differentiation of PDLCs. Copyright © 2012 Elsevier Ltd. All rights reserved.

A simple large-scale synthesis of mesoporous In2O3 for gas sensing applications

NASA Astrophysics Data System (ADS)

Zhang, Su; Song, Peng; Yan, Huihui; Yang, Zhongxi; Wang, Qi

2016-08-01

In this paper, large-scale mesoporous In2O3 nanostructures were synthesized by a facile Lewis acid catalytic the furfural alcohol resin (FAR) template route for the high-yield. Their morphology and structure were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), differential thermal and thermogravimetry analysis (DSC-TG) and the Brunauer-Emmett-Teller (BET) approach. The as-obtained mesoporous In2O3 nanostructures possess excellent mesoporous and network structure, which increases the contact area with the gases, it is conducive for adsorption-desorption of gas on the surface of In2O3. The In2O3 particles and pores were both about 15 nm and very uniform. In gas-sensing measurements with target gases, the gas sensor based on mesoporous In2O3 nanostructures showed a good response, short response-recovery time, good selectivity and stability to ethanol. These properties are due to the large specific surface area of mesoporous structure. This synthetic method could use as a new design concept for functional mesoporous nanomaterials and for mass production.

Tailored Design of Bicontinuous Gyroid Mesoporous Carbon and Nitrogen-Doped Carbon from Poly(ethylene oxide-b-caprolactone) Diblock Copolymers.

PubMed

Chu, Wei-Cheng; Bastakoti, Bishnu Prasad; Kaneti, Yusuf Valentino; Li, Jheng-Guang; Alamri, Hatem R; Alothman, Zeid A; Yamauchi, Yusuke; Kuo, Shiao-Wei

2017-10-04

Highly ordered mesoporous resol-type phenolic resin and the corresponding mesoporous carbon materials were synthesized by using poly(ethylene oxide-b-caprolactone) (PEO-b-PCL) diblock copolymer as a soft template. The self-assembled mesoporous phenolic resin was found to form only in a specific resol concentration range of 40-70 wt % due to an intriguing balance of hydrogen-bonding interactions in the resol/PEO-b-PCL mixtures. Furthermore, morphological transitions of the mesostructures from disordered to gyroid to cylindrical and finally to disordered micelle structure were observed with increasing resol concentration. By calcination under nitrogen atmosphere at 800 °C, the bicontinuous mesostructured gyroid phenolic resin could be converted to mesoporous carbon with large pore size without collapse of the original mesostructure. Furthermore, post-treatment of the mesoporous gyroid phenolic resin with melamine gave rise to N-doped mesoporous carbon with unique electronic properties for realizing high CO 2 adsorption capacity (6.72 mmol g -1 at 0 °C). © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Study on the pyrolysis of cellulose for bio-oil with mesoporous molecular sieve catalysts.

PubMed

Yu, Feng-wen; Ji, Deng-xiang; Nie, Yong; Luo, Yao; Huang, Cheng-jie; Ji, Jian-bing

2012-09-01

Mesoporous materials possess a hexagonal array of uniform mesopores, high surface areas, and moderate acidity. They are one of the important catalysts in the field of catalytic pyrolysis. In this paper, mesoporous materials of Al-MCM-41, La-Al-MCM-41, and Ce-Al-MCM-41 were synthesized, characterized, and tested as catalysts in the cellulose catalytic pyrolysis process using a fixed bed pyrolysis reactor. The results showed that mesoporous materials exhibited a strong influence on the pyrolytic behavior of cellulose. The presence of these mesoporous molecular sieve catalysts could vary the yield of products, which was that they could decrease the yield of liquid and char and increase the yield of gas product, and could promote high-carbon chain compounds to break into low-carbon chain compounds. Mesoporous molecular sieve catalysts were benefit to the reaction of dehydrogenation and deoxidation and the breakdown of carbon chain. Further, La-Al-MCM-41 and Ce-Al-MCM-41 catalysts can produce more toluene and 2-methoxy-phenol, as compared to the non-catalytic runs.

Cluster-randomized controlled trial of the effects of free glasses on purchase of children's glasses in China: The PRICE (Potentiating Rural Investment in Children's Eyecare) study.

PubMed

Wang, Xiuqin; Congdon, Nathan; Ma, Yue; Hu, Min; Zhou, Yuan; Liao, Weiqi; Jin, Ling; Xiao, Baixiang; Wu, Xiaoyi; Ni, Ming; Yi, Hongmei; Huang, Yiwen; Varga, Beatrice; Zhang, Hong; Cun, Yongkang; Li, Xianshun; Yang, Luhua; Liang, Chaoguang; Huang, Wan; Rozelle, Scott; Ma, Xiaochen

2017-01-01

Offering free glasses can be important to increase children's wear. We sought to assess whether "Upgrade glasses" could avoid reduced glasses sales when offering free glasses to children in China. In this cluster-randomized, controlled trial, children with uncorrected visual acuity (VA)< = 6/12 in either eye correctable to >6/12 in both eyes at 138 randomly-selected primary schools in 9 counties in Guangdong and Yunnan provinces, China, were randomized by school to one of four groups: glasses prescription only (Control); Free Glasses; Free Glasses + offer of $15 Upgrade Glasses; Free Glasses + offer of $30 Upgrade Glasses. Spectacle purchase (main outcome) was assessed 6 months after randomization. Among 10,234 children screened, 882 (8.62%, mean age 10.6 years, 45.5% boys) were eligible and randomized: 257 (29.1%) at 37 schools to Control; 253 (28.7%) at 32 schools to Free Glasses; 187 (21.2%) at 31 schools to Free Glasses + $15 Upgrade; and 185 (21.0%) at 27 schools to Free Glasses +$30 Upgrade. Baseline ownership among these children needing glasses was 11.8% (104/882), and 867 (98.3%) children completed follow-up. Glasses purchase was significantly less likely when free glasses were given: Control: 59/250 = 23.6%; Free glasses: 32/252 = 12.7%, P = 0.010. Offering Upgrade Glasses eliminated this difference: Free + $15 Upgrade: 39/183 = 21.3%, multiple regression relative risk (RR) 0.90 (0.56-1.43), P = 0.65; Free + $30 Upgrade: 38/182 = 20.9%, RR 0.91 (0.59, 1.42), P = 0.69. Upgrade glasses can prevent reductions in glasses purchase when free spectacles are provided, providing important program income. ClinicalTrials.gov Identifier: NCT02231606. Registered on 31 August 2014.

Photo-Definable Self Assembled Maerials

DOEpatents

DOSHI, DHAVAL; [et al

2004-10-26

The present invention provides a mesoporous material comprising at least one region of mesoporous material patterned at a lithographic scale. The present invention also provides a a method for forming a patterned mesoporous material comprising: coating a sol on a substrate to form a film, the sol comprising: a templating molecule, a photoactivator generator, a material capable of being sol-gel processed, water, and a solvent; and exposing the film to light to form a patterned mesoporous material.

Mesoporous metal oxide microsphere electrode compositions and their methods of making

DOEpatents

Parans Paranthaman, Mariappan; Bi, Zhonghe; Bridges, Craig A; Brown, Gilbert M

2014-12-16

Compositions and methods of making are provided for treated mesoporous metal oxide microspheres electrodes. The compositions comprise (a) microspheres with an average diameter between 200 nanometers (nm) and 10 micrometers (.mu.m); (b) mesopores on the surface and interior of the microspheres, wherein the mesopores have an average diameter between 1 nm and 50 nm and the microspheres have a surface area between 50 m.sup.2/g and 500 m.sup.2/g, and wherein the composition has an electrical conductivity of at least 1.times.10.sup.-7 S/cm at 25.degree. C. and 60 MPa. The methods of making comprise forming a mesoporous metal oxide microsphere composition and treating the mesoporous metal oxide microspheres by at least one method selected from the group consisting of: (i) annealing in a reducing atmosphere, (ii) doping with an aliovalent element, and (iii) coating with a coating composition.

Controlled release of ibuprofen by meso–macroporous silica

DOE Office of Scientific and Technical Information (OSTI.GOV)

Santamaría, E., E-mail: esthersantamaria@ub.edu; Maestro, A.; Porras, M.

2014-02-15

Structured meso–macroporous silica was successfully synthesized from an O/W emulsion using decane as a dispersed phase. Sodium silicate solution, which acts as a silica source and a poly(ethylene oxide)–poly(propylene oxide)–poly(ethylene oxide) (EO{sub 19}PO{sub 39}EO{sub 19}) denoted as P84 was used in order to stabilize the emulsion and as a mesopore template. The materials obtained were characterized through transmission electron microscopy (TEM), scanning electron microscopy (SEM), small-angle X-ray diffraction scattering (SAXS) and nitrogen adsorption–desorption isotherms. Ibuprofen (IBU) was selected as the model drug and loaded into ordered meso–macroporous materials. The effect of the materials’ properties on IBU drug loading and releasemore » was studied. The results showed that the loading of IBU increases as the macropore presence in the material is increased. The IBU adsorption process followed the Langmuir adsorption isotherm. A two-step release process, consisting of an initial fast release and then a slower release was observed. Macropores enhanced the adsorption capacity of the material; this was probably due to the fact that they allowed the drug to access internal pores. When only mesopores were present, ibuprofen was probably adsorbed on the mesopores close to the surface. Moreover, the more macropore present in the material, the slower the release behaviour observed, as the ibuprofen adsorbed in the internal pores had to diffuse along the macropore channels up to the surface of the material. The material obtained from a highly concentrated emulsion was functionalized with amino groups using two methods, the post-grafting mechanism and the co-condensation mechanism. Both routes improve IBU adsorption in the material and show good behaviour as a controlled drug delivery system. - Graphical abstract: Ibuprofen release profiles for the materials obtained from samples P84{sub m}eso (black diamonds), P84{sub 2}0% (white squares), P84{sub 5}0% (black triangles), P84{sub 7}5% (white diamonds), P84{sub 7}5% functionalized by grafting (black squares) and P84{sub 7}5% functionalized by co-condensation method (white triangles). Display Omitted - Highlights: • Ordered meso–macroporous material is used as a controlled delivery system for ibuprofen. • Incorporation of macropores in mesoporous silica improves ibuprofen adsorption. • Meso–macroporous structures provide a lower delivery than mesoporous silica. • APTES functionalization in meso–macroporous materials improves ibuprofen adsorption and delivery behaviour.« less

A novel strategy to design sustained-release poorly water-soluble drug mesoporous silica microparticles based on supercritical fluid technique.

PubMed

Li-Hong, Wang; Xin, Che; Hui, Xu; Li-Li, Zhou; Jing, Han; Mei-Juan, Zou; Jie, Liu; Yi, Liu; Jin-Wen, Liu; Wei, Zhang; Gang, Cheng

2013-09-15

The organic solvent solution immersion method was often used to achieve the loading of the drugs into mesoporous silica, but the drugs that have loaded into the pores of the mesoporous silica would inevitable migrate from the inside to the external surface or near the outside surface during the process of drying. Hence, it often leads to the pores of mesoporous materials not be fully utilized, and results in a low drug loading efficiency and a fast releasing rate. The purpose of this study was to develop a novel drug loading strategy to avoid soluble component migration during the process of drying, then, to prepare poorly water-soluble drug mesoporous silica microparticles with higher drug loading efficiency and longer sustained-release time. Ibuprofen was used as model drug. The microparticles were prepared by a novel method based on mesoporous silica and supercritical fluid (SCF) technique. The drug-loaded mesoporous silica microparticles prepared by SCF technique were analyzed by thermogravimetric analysis (TGA), N2 adsorption/desorption, scanning electron microscopy (SEM), powder X-ray diffraction (XRD) and differential scanning calorimetry (DSC). In vitro releasing study was used to evaluate the sustained-release effect of the drug-loaded microparticles. By virtue of the high diffusibility and the high dissolving capacity of the supercritical carbon dioxide (SCF-CO2), the poorly water-soluble drugs, ibuprofen, entered the pores of the mesoporous silica. The amount and the depth of ibuprofen entered the pores of the mesoporous silica by SCF technique were both larger than those by the solution immersion method. It was found that ibuprofen loaded into the mesoporous silica by SCF technique was amorphous and the largest amount of the ibuprofen loaded into the mesoporous silica by SCF technique could reach 386 mg/g (w/w, ibuprofen/SiO2), it was more than that by the solution immersion method. In vitro releasing study showed that the sustained-release effect of ibuprofen in the samples prepared by SCF technique was 50% in 15 min and 90% in 60 min. It was longer than that prepared by the solution immersion method. Present study showed that sustained-release poorly water-soluble drug mesoporous silica microparticle based on SCF technique has twofold advantages. One is the larger drug loading amount in internal pores of the mesoporous silica, the other is the longer drug releasing time. Copyright © 2013 Elsevier B.V. All rights reserved.

Study of CO2 adsorption capacity of mesoporous carbon and activated carbon modified by triethylenetetramine (TETA)

NASA Astrophysics Data System (ADS)

Sulistianti, I.; Krisnandi, Y. K.; Moenandar, I.

2017-04-01

Mesoporous carbon was synthesized by soft template method using phloroglucinol and formaldehyde as a carbon source; and Pluronic F-127 as a mesoporous template. The synthesized mesoporous carbon and commercial activated carbon were modified with triethylenetetramine (TETA) to increase CO2 adsorption capacity. Based on FTIR characterization, the synthesized mesoporous carbon and the activated carbon without modification process has similarity pattern. After the modification, both of them showed absorption peaks in the area around 1580 to 1650 cm-1 which is known as N-H bending vibration and absorption peaks in the area around 3150 to 3380 cm-1 which is known as N-H stretching vibration. The XRD results showed two peaks at 2θ = 24.21° and 2θ = 43.85°, according to JCPDS index No. 75-1621 those peak are the typical peaks for hexagonal graphite carbon. In BET analysis, the synthesized mesoporous carbon and activated carbon modified TETA have surface area, pore volume and pore diameter lower than without modification process. In carbon dioxide adsorption testing, the synthesized mesoporous carbon showed better performance than the commercial activated carbon for CO2 adsorption both without modification and by modification. The synthesized mesoporous carbon obtained CO2 adsorption of 9.916 mmol/g and the activated carbon of 3.84 mmol/g for on 3.5 hours of adsorption. It is three times better than activated carbon for adsorption of carbon dioxide. The modified mesoporous carbon has the best performance for adsorption of gas CO2 if compared by unmodified.

Insights into the Formation and Properties of Templated Dual Mesoporous Titania with Enhanced Photocatalytic Activity.

PubMed

Naboulsi, Issam; Lebeau, Bénédicte; Michelin, Laure; Carteret, Cédric; Vidal, Loic; Bonne, Magali; Blin, Jean-Luc

2017-01-25

The one pot synthesis of dual mesoporous titania (2.3 and 7.7 nm) has been achieved from a mixture of fluorinated and Pluronic surfactants. The small and large mesopore networks are templated, respectively, by a fluorinated-rich liquid crystal and a Pluronic-rich liquid crystal, which are in equilibrium. After calcination at 350 °C, the amorphous walls are transformed into semicrystalline anatase preserving the mesoporous structure. Results concerning the photodegradation of methyl orange using the calcined photocatalysts highlight that the kinetic rate constant (k) determined for the dual mesoporous titania is 2.6 times higher than the k value obtained for the monomodal ones.

Performance and Mechanism of Uranium Adsorption from Seawater to Poly(dopamine)-Inspired Sorbents.

PubMed

Wu, Fengcheng; Pu, Ning; Ye, Gang; Sun, Taoxiang; Wang, Zhe; Song, Yang; Wang, Wenqing; Huo, Xiaomei; Lu, Yuexiang; Chen, Jing

2017-04-18

Developing facile and robust technologies for effective enrichment of uranium from seawater is of great significance for resource sustainability and environmental safety. By exploiting mussel-inspired polydopamine (PDA) chemistry, diverse types of PDA-functionalized sorbents including magnetic nanoparticle (MNP), ordered mesoporous carbon (OMC), and glass fiber carpet (GFC) were synthesized. The PDA functional layers with abundant catechol and amine/imine groups provided an excellent platform for binding to uranium. Due to the distinctive structure of PDA, the sorbents exhibited multistage kinetics which was simultaneously controlled by chemisorption and intralayer diffusion. Applying the diverse PDA-modified sorbents for enrichment of low concentration (parts per billion) uranium in laboratory-prepared solutions and unpurified seawater was fully evaluated under different scenarios: that is, by batch adsorption for MNP and OMC and by selective filtration for GFC. Moreover, high-resolution X-ray photoelectron spectroscopic and extended X-ray absorption fine structure studies were performed for probing the underlying coordination mechanism between PDA and U(VI). The catechol hydroxyls of PDA were identified as the main bidentate ligands to coordinate U(VI) at the equatorial plane. This study assessed the potential of versatile PDA chemistry for development of efficient uranium sorbents and provided new insights into the interaction mechanism between PDA and uranium.

Utilization of a by-product produced from oxidative desulfurization process over Cs-mesoporous silica catalysts.

PubMed

Kim, Hyeonjoo; Jeong, Kwang-Eun; Jeong, Soon-Yong; Park, Young-Kwon; Kim, Do Heui; Jeon, Jong-Ki

2011-02-01

We investigated the use of Cs-mesoporous silica catalysts to upgrade a by-product of oxidative desulfurization (ODS). Cs-mesoporous silica catalysts were characterized through N2 adsorption, XRD, CO2-temperature-programmed desorption, and XRF. Cs-mesoporous silica prepared by the direct incorporation method showed higher catalytic performance than a Cs/MCM-41 catalyst by impregnation method for the catalytic decomposition of sulfone compounds produced from ODS process.

Mesoporous metal oxide graphene nanocomposite materials

DOEpatents

Liu, Jun; Aksay, Ilhan A.; Kou, Rong; Wang, Donghai

2016-05-24

A nanocomposite material formed of graphene and a mesoporous metal oxide having a demonstrated specific capacity of more than 200 F/g with particular utility when employed in supercapacitor applications. A method for making these nanocomposite materials by first forming a mixture of graphene, a surfactant, and a metal oxide precursor, precipitating the metal oxide precursor with the surfactant from the mixture to form a mesoporous metal oxide. The mesoporous metal oxide is then deposited onto a surface of the graphene.

Synthesis of Ordered Mesoporous Phenanthrenequinone-Carbon via π-π Interaction-Dependent Vapor Pressure for Rechargeable Batteries

PubMed Central

Kwon, Mi-Sook; Choi, Aram; Park, Yuwon; Cheon, Jae Yeong; Kang, Hyojin; Jo, Yong Nam; Kim, Young-Jun; Hong, Sung You; Joo, Sang Hoon; Yang, Changduk; Lee, Kyu Tae

2014-01-01

The π-π interaction-dependent vapour pressure of phenanthrenequinone can be used to synthesize a phenanthrenequinone-confined ordered mesoporous carbon. Intimate contact between the insulating phenanthrenequinone and the conductive carbon framework improves the electrical conductivity. This enables a more complete redox reaction take place. The confinement of the phenanthrenequinone in the mesoporous carbon mitigates the diffusion of the dissolved phenanthrenequinone out of the mesoporous carbon, and improves cycling performance. PMID:25490893

Diffusion of aromatic hydrocarbons in hierarchical mesoporous H-ZSM-5 zeolite

DOE PAGES

Bu, Lintao; Nimlos, Mark R.; Robichaud, David J.; ...

2018-02-08

Hierarchical mesoporous zeolites exhibit higher catalytic activities and longer lifetime compared to the traditional microporous zeolites due to improved diffusivity of substrate molecules and their enhanced access to the zeolite active sites. Understanding diffusion of biomass pyrolysis vapors and their upgraded products in such materials is fundamentally important during catalytic fast pyrolysis (CFP) of lignocellulosic biomass, since diffusion makes major contribution to determine shape selectivity and product distribution. However, diffusivities of biomass relevant species in hierarchical mesoporous zeolites are poorly characterized, primarily due to the limitations of the available experimental technology. In this work, molecular dynamics (MD) simulations are utilizedmore » to investigate the diffusivities of several selected coke precursor molecules, benzene, naphthalene, and anthracene, in hierarchical mesoporous H-ZSM-5 zeolite. The effects of temperature and size of mesopores on the diffusivity of the chosen model compounds are examined. The simulation results demonstrate that diffusion within the microspores as well as on the external surface of mesoporous H-ZSM-5 dominates only at low temperature. At pyrolysis relevant temperatures, mass transfer is essentially conducted via diffusion along the mesopores. Additionally, the results illustrate the heuristic diffusion model, such as the extensively used Knudsen diffusion, overestimates the diffusion of bulky molecules in the mesopores, thus making MD simulation a powerful and compulsory approach to explore diffusion in zeolites.« less

Dual stimuli-responsive nano-vehicles for controlled drug delivery: mesoporous silica nanoparticles end-capped with natural chitosan.

PubMed

Hakeem, Abdul; Duan, Ruixue; Zahid, Fouzia; Dong, Chao; Wang, Boya; Hong, Fan; Ou, Xiaowen; Jia, Yongmei; Lou, Xiaoding; Xia, Fan

2014-11-11

Herein, we report natural chitosan end-capped MCM-41 type MSNPs as novel, dual stimuli, responsive nano-vehicles for controlled anticancer drug delivery. The chitosan nanovalves tightly close the pores of the MSNPs to control premature cargo release under physiological conditions but respond to lysozyme and acidic media to release the trapped cargo.

Control of drug release through the in situ assembly of stimuli-responsive ordered mesoporous silica with magnetic particles.

PubMed

Zhu, Shenmin; Zhou, Zhengyang; Zhang, Di

2007-12-03

A site-selective controlled delivery system for controlled drug release is fabricated through the in situ assembly of stimuli-responsive ordered SBA-15 and magnetic particles. This approach is based on the formation of ordered mesoporous silica with magnetic particles formed from Fe(CO)5 via the surfactant-template sol-gel method and control of transport through polymerization of N-isopropyl acrylamide inside the pores. Hydrophobic Fe(CO)5 acts as a swelling agent as well as being the source of the magnetic particles. The obtained system demonstrates a high pore diameter (7.1 nm) and pore volume (0.41 cm(3) g(-1)), which improves drug storage for relatively large molecules. Controlled drug release through the porous network is demonstrated by measuring the uptake and release of ibuprofen (IBU). The delivery system displays a high IBU storage capacity of 71.5 wt %, which is almost twice as large as the highest value based on SBA-15 ever reported. In vitro testing of IBU loading and release exhibits a pronounced transition at around 32 degrees C, indicating a typical thermosensitive controlled release.

Spatially orthogonal chemical functionalization of a hierarchical pore network for catalytic cascade reactions

NASA Astrophysics Data System (ADS)

Parlett, Christopher M. A.; Isaacs, Mark A.; Beaumont, Simon K.; Bingham, Laura M.; Hondow, Nicole S.; Wilson, Karen; Lee, Adam F.

2016-02-01

The chemical functionality within porous architectures dictates their performance as heterogeneous catalysts; however, synthetic routes to control the spatial distribution of individual functions within porous solids are limited. Here we report the fabrication of spatially orthogonal bifunctional porous catalysts, through the stepwise template removal and chemical functionalization of an interconnected silica framework. Selective removal of polystyrene nanosphere templates from a lyotropic liquid crystal-templated silica sol-gel matrix, followed by extraction of the liquid crystal template, affords a hierarchical macroporous-mesoporous architecture. Decoupling of the individual template extractions allows independent functionalization of macropore and mesopore networks on the basis of chemical and/or size specificity. Spatial compartmentalization of, and directed molecular transport between, chemical functionalities affords control over the reaction sequence in catalytic cascades; herein illustrated by the Pd/Pt-catalysed oxidation of cinnamyl alcohol to cinnamic acid. We anticipate that our methodology will prompt further design of multifunctional materials comprising spatially compartmentalized functions.

Synthesis of mesoporous poly(melamine-formaldehyde) particles by inverse emulsion polymerization.

PubMed

Schwarz, Dana; Weber, Jens

2017-07-15

Mesoporous poly(melamine-formaldehyde) (MF) particles with surface areas of up to 200m 2 g -1 were synthesized by an inverse emulsion polymerization using dodecane and Span80® as continuous phase. The finer details of the shape control (using emulsion techniques) and the porosity control (using silica nanoparticles as hard-template) are discussed. The impact of phase-separation processes on the observable porosity of the 20-200µm sized spherical particles is analysed by gas sorption methods and electron microscopy. The high density of amine and triazine functional groups in the porous MF particles make the material a promising adsorber for heavy metal ions and methylene blue. In a preliminary column experiment, the synthesized material exhibited a total capacity of 2.54mmol/g (≙ 812.4mg/g) for the adsorption of methylene blue. Copyright © 2017 Elsevier Inc. All rights reserved.

Noninvasive remote-controlled release of drug molecules in vitro using magnetic actuation of mechanized nanoparticles.

PubMed

Thomas, Courtney R; Ferris, Daniel P; Lee, Jae-Hyun; Choi, Eunjoo; Cho, Mi Hyeon; Kim, Eun Sook; Stoddart, J Fraser; Shin, Jeon-Soo; Cheon, Jinwoo; Zink, Jeffrey I

2010-08-11

Mesoporous silica nanoparticles are useful nanomaterials that have demonstrated the ability to contain and release cargos with mediation by gatekeepers. Magnetic nanocrystals have the ability to exhibit hyperthermic effects when placed in an oscillating magnetic field. In a system combining these two materials and a thermally sensitive gatekeeper, a unique drug delivery system can be produced. A novel material that incorporates zinc-doped iron oxide nanocrystals within a mesoporous silica framework that has been surface-modified with pseudorotaxanes is described. Upon application of an AC magnetic field, the nanocrystals generate local internal heating, causing the molecular machines to disassemble and allowing the cargos (drugs) to be released. When breast cancer cells (MDA-MB-231) were treated with doxorubicin-loaded particles and exposed to an AC field, cell death occurred. This material promises to be a noninvasive, externally controlled drug delivery system with cancer-killing properties.

Gated Silica Mesoporous Materials in Sensing Applications.

PubMed

Sancenón, Félix; Pascual, Lluís; Oroval, Mar; Aznar, Elena; Martínez-Máñez, Ramón

2015-08-01

Silica mesoporous supports (SMSs) have a large specific surface area and volume and are particularly exciting vehicles for delivery applications. Such container-like structures can be loaded with numerous different chemical substances, such as drugs and reporters. Gated systems also contain addressable functions at openings of voids, and cargo delivery can be controlled on-command using chemical, biochemical or physical stimuli. Many of these gated SMSs have been applied for drug delivery. However, fewer examples of their use in sensing protocols have been reported. The approach of applying SMSs in sensing uses another concept-that of loading pores with a reporter and designing a capping mechanism that is selectively opened in the presence of a target analyte, which results in the delivery of the reporter. According to this concept, we provide herein a complete compilation of published examples of probes based on the use of capped SMSs for sensing. Examples for the detection of anions, cations, small molecules and biomolecules are provided. The diverse range of gated silica mesoporous materials presented here highlights their usefulness in recognition protocols.

Gated Silica Mesoporous Materials in Sensing Applications

PubMed Central

Sancenón, Félix; Pascual, Lluís; Oroval, Mar; Aznar, Elena; Martínez-Máñez, Ramón

2015-01-01

Silica mesoporous supports (SMSs) have a large specific surface area and volume and are particularly exciting vehicles for delivery applications. Such container-like structures can be loaded with numerous different chemical substances, such as drugs and reporters. Gated systems also contain addressable functions at openings of voids, and cargo delivery can be controlled on-command using chemical, biochemical or physical stimuli. Many of these gated SMSs have been applied for drug delivery. However, fewer examples of their use in sensing protocols have been reported. The approach of applying SMSs in sensing uses another concept—that of loading pores with a reporter and designing a capping mechanism that is selectively opened in the presence of a target analyte, which results in the delivery of the reporter. According to this concept, we provide herein a complete compilation of published examples of probes based on the use of capped SMSs for sensing. Examples for the detection of anions, cations, small molecules and biomolecules are provided. The diverse range of gated silica mesoporous materials presented here highlights their usefulness in recognition protocols. PMID:26491626

Mesoporous silicon oxide films and their uses as templates in obtaining nanostructured conductive polymers

NASA Astrophysics Data System (ADS)

Salgado, R.; Arteaga, G. C.; Arias, J. M.

2018-04-01

Obtaining conductive polymers (CPs) for the manufacture of OLEDs, solar cells, electrochromic devices, sensors, etc., has been possible through the use of electrochemical techniques that allow obtaining films of controlled thickness with positive results in different applications. Current trends point towards the manufacture of nanomaterials, and therefore it is necessary to develop methods that allow obtaining CPs with nanostructured morphology. This is possible by using a porous template to allow the growth of the polymeric materials. However, prior and subsequent treatments are required to separate the material from the template so that it can be evaluated in the applications mentioned above. This is why mesoporous silicon oxide films (template) are essential for the synthesis of nanostructured polymers since both the template and the polymer are obtained on the electrode surface, and therefore it is not necessary to separate the material from the template. Thus, the material can be evaluated directly in the applications mentioned above. The dimensions of the resulting nanostructures will depend on the power, time and technique used for electropolymerization as well as the monomer and the surfactant of the mesoporous film.

A Magnetically Separable, Highly Stable Enzyme System Based on Nanocomposites of Enzymes and Magnetic Nanoparticles Shipped in Hierarchically Ordered, Mesocellular, Mesoporous Silica

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Jungbae; Lee, Jinwoo; Na, Hyon Bin

2005-12-01

Enzymes are versatile nanoscale biocatalysts, and find increasing applications in many areas, including organic synthesis[1-3] and bioremediation.[4-5] However, the application of enzymes is often hampered by the short catalytic lifetime of enzymes and by the difficulty in recovery and recycling. To solve these problems, there have been a lot of efforts to develop effective enzyme immobilization techniques. Recent advances in nanotechnology provide more diverse materials and approaches for enzyme immobilization. For example, mesoporous materials offer potential advantages as a host of enzymes due to their well-controlled porosity and large surface area for the immobilization of enzymes.[6,7] On the other hand,more » it has been demonstrated that enzymes attached on magnetic iron oxide nanoparticles can be easily recovered using a magnet and recycled for iterative uses.[8] In this paper, we report the development of magnetically-separable and highly-stable enzyme system by the combined use of two different kinds of nanostructured materials: magnetic nanoparticles and mesoporous silica.« less

A flexible, bolaamphiphilic template for mesoporous silicas.

PubMed

Yuen, Alexander K L; Heinroth, Falk; Ward, Antony J; Masters, Anthony F; Maschmeyer, Thomas

2013-08-28

A novel symmetrical bolaamphiphile, containing two N-methylimidazolium head-groups bridged by a 32-methylene linker, was synthesized and characterized. A variety of mesoporous silicas was prepared using the bolaamphiphile as a "soft template". The effects of absolute surfactant concentration and synthesis conditions upon the morphologies of these silicas were investigated. For a given surfactant concentration, particle morphology; pore size; and pore ordering were modified through control of the template to silica-precursor ratio and synthesis conditions. Observed morphologies included: lenticular core-shell nanoparticles and decorticated globules, truncated hexagonal plates, and sheets. In all cases the mesopores are aligned along the shortest axis of the nanomaterial. Decorticated materials displayed surface areas of up to 1200 m(2) g(-1) and pore diameters (D(BJH)) of 24-28 Å. Small-angle X-ray diffraction and transmission electron microscopy measurements revealed that the majority of the materials has elliptical pores arranged in rectangular lattices (c2mm). Adoption of this symmetry group is a result of the template aggregate deformation from a regular hexagonal phase of cylindrical rods to a ribbon phase under the synthetic conditions.

Fabrication and properties of an immobilized P25TiO{sub 2}-montmorillonite bilayer system for the synergistic photocatalytic–adsorption removal of methylene blue

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ngoh, Y.S.; Nawi, M.A., E-mail: masri@usm.my

2016-04-15

Highlights: • P25TiO{sub 2} and montmorillonite was integrated via an immobilized bilayer approach. • Synergistic dual photocatalytic–adsorptive removal of MB was observed. • Removal rate of MB was 4 times better than P25TiO{sub 2} alone. • Excellent reusability with sustainable rate of removal of MB. • Treated water can be discharged directly without the need of a filtration system. - Abstract: A bilayer immobilized system consisting of a mesoporous montmorillonite (MT) as the sublayer and a porous P25TiO{sub 2} toplayer was successfully fabricated on a glass plate. The MT sublayer was immobilized onto the glass plate by means of amore » glutaraldehyde (GLA) cross-linked poly (vinyl) alcohol (PVA) as the binder (MT-PVAB) while the top layer constituted of nano-sized TiO{sub 2} bound by the ENR-PVC polymer blends (P-25TiO{sub 2}). The incorporation of MT-PVAB to P-25TiO{sub 2} caused a reduction in the band gap energy while PLS emission spectra suggested higher separation rate for the photo-generated electron–hole pairs in the P-25TiO{sub 2}/MT-PVAB/GP. The photocatalytic–adsorption removal experiments showed that the P-25TiO{sub 2}/MT-PVAB/GP enhanced removal rate of MB by an average of 4 times as compared with the immobilized monolayer P-25TiO{sub 2} on a glass plate (P-25TiO{sub 2}/GP).« less

From harmful Microcystis blooms to multi-functional core-double-shell microsphere bio-hydrochar materials.

PubMed

Bi, Lei; Pan, Gang

2017-11-13

Harmful algal blooms (HABs) induced by eutrophication is becoming a serious global environmental problem affecting public health and aquatic ecological sustainability. A novel strategy for the utilization of biomass from HABs was developed by converting the algae cells into hollow mesoporous bio-hydrochar microspheres via hydrothermal carbonization method. The hollow microspheres were used as microreactors and carriers for constructing CaO 2 core-mesoporous shell-CaO 2 shell microspheres (OCRMs). The CaO 2 shells could quickly increase dissolved oxygen to extremely anaerobic water in the initial 40 min until the CaO 2 shells were consumed. The mesoporous shells continued to act as regulators restricting the release of oxygen from CaO 2 cores. The oxygen-release time using OCRMs was 7 times longer than when directly using CaO 2 . More interestingly, OCRMs presented a high phosphate removal efficiency (95.6%) and prevented the pH of the solution from rising to high levels in comparison with directly adding CaO 2 due to the OH - controlled-release effect of OCRMs. The distinct core-double-shell micro/nanostructure endowed the OCRMs with triple functions for oxygen controlled-release, phosphorus removal and less impact on water pH. The study is to explore the possibility to prepare smarter bio-hydrochar materials by utilizing algal blooms.

Stimuli-responsive hybrid nanocarriers developed by controllable integration of hyperbranched PEI with mesoporous silica nanoparticles for sustained intracellular siRNA delivery

PubMed Central

Prabhakar, Neeraj; Zhang, Jixi; Desai, Diti; Casals, Eudald; Gulin-Sarfraz, Tina; Näreoja, Tuomas; Westermarck, Jukka; Rosenholm, Jessica M

2016-01-01

Small interfering RNA (siRNA) is a highly potent drug in gene-based therapy with the challenge being to deliver it in a sustained manner. The combination of mesoporous silica nanoparticles (MSNs) and polycations in the confined pore space allows for incorporation and controlled release of therapeutic siRNA payloads. We hereby constructed MSNs with expanded mesopores and pore-surface-hyperbranched poly(ethyleneimine) (PEI) tethered with redox-cleavable linkers that could carry a high payload of siRNA (120 mg·g−1). The developed nanocarriers were efficiently taken up by cancer cells and were subsequently able to escape to the cytoplasm from the endosomes, most likely owing to the integrated PEI. Triggered by the intracellular redox conditions, the siRNA was sustainably released inside the cells over a period of several days. Functionality of siRNAs was demonstrated by using cell-killing siRNA as cargo. Despite not being the aim of the developed system, in vitro experiments using cell-killing siRNAs showed that the efficacy of siRNA transfection was comparable to the commercial in vitro transfection agent Lipofectamine. Consequently, the developed MSN-based delivery system offers a potential approach to hybrid nanocarriers for more efficient and long-term siRNA delivery and, in a longer perspective, in vivo gene silencing for RNA interference (RNAi) therapy. PMID:27994460

Efficient photodecomposition of herbicide imazapyr over mesoporous Ga2O3-TiO2 nanocomposites.

PubMed

Ismail, Adel A; Abdelfattah, Ibrahim; Faisal, M; Helal, Ahmed

2018-01-15

The unabated release of herbicide imazapyr into the soil and groundwater led to crop destruction and several pollution-related concerns. In this contribution, heterogeneous photocatalytic technique was employed utilizing mesoporous Ga 2 O 3 -TiO 2 nanocomposites for degrading imazapyr herbicide as a model pollutant molecule. Mesoporous Ga 2 O 3 -TiO 2 nanocomposites with varied Ga 2 O 3 contents (0-5wt%) were synthesized through sol-gel process. XRD and Raman spectra exhibited extremely crystalline anatase TiO 2 phase at low Ga 2 O 3 content which gradually reduced with the increase of Ga 2 O 3 content. TEM images display uniform TiO 2 particles (10±2nm) with mesoporous structure. The mesoporous TiO 2 exhibits large surface areas of 167m 2 g -1 , diminished to 108m 2 g -1 upon 5% Ga 2 O 3 incorporation, with tunable mesopore diameter in the range of 3-9nm. The photocatalytic efficiency of synthesized Ga 2 O 3 -TiO 2 nanocomposites was assessed by degrading imazapyr herbicide and comparing with commercial photocatalyst UV-100 and mesoporous Ga 2 O 3 under UV illumination. 0.1% Ga 2 O 3 -TiO 2 nanocomposite is considered the optimum photocatalyst, which degrades 98% of imazapyr herbicide within 180min. Also, the photodegradation rate of imazapyr using 0.1% Ga 2 O 3 -TiO 2 nanocomposite is nearly 10 and 3-fold higher than that of mesoporous Ga 2 O 3 and UV-100, respectively. The high photonic efficiency and long-term stability of the mesoporous Ga 2 O 3 -TiO 2 nanocomposites are ascribed to its stronger oxidative capability in comparison with either mesoporous TiO 2 , Ga 2 O 3 or commercial UV-100. Copyright © 2017 Elsevier B.V. All rights reserved.

Controlling morphology, mesoporosity, crystallinity, and photocatalytic activity of ordered mesoporous TiO2 films prepared at low temperature

NASA Astrophysics Data System (ADS)

Elgh, Björn; Yuan, Ning; Cho, Hae Sung; Magerl, David; Philipp, Martine; Roth, Stephan V.; Yoon, Kyung Byung; Müller-Buschbaum, Peter; Terasaki, Osamu; Palmqvist, Anders E. C.

2014-11-01

Partly ordered mesoporous titania films with anatase crystallites incorporated into the pore walls were prepared at low temperature by spin-coating a microemulsion-based reaction solution. The effect of relative humidity employed during aging of the prepared films was studied using SEM, TEM, and grazing incidence small angle X-ray scattering to evaluate the mesoscopic order, porosity, and crystallinity of the films. The study shows unambiguously that crystal growth occurs mainly during storage of the films and proceeds at room temperature largely depending on relative humidity. Porosity, pore size, mesoscopic order, crystallinity, and photocatalytic activity of the films increased with relative humidity up to an optimum around 75%.

Efficient MgO-based mesoporous CO2 trapper and its performance at high temperature.

PubMed

Han, Kun Kun; Zhou, Yu; Chun, Yuan; Zhu, Jian Hua

2012-02-15

A novel MgO-based porous adsorbent has been synthesized in a facile co-precipitation method for the first time, in order to provide a candidate for trapping CO(2) in flue gas at high temperature. The resulting composite exhibits a mesoporous structure with a wide pore size distribution, due to the even dispersion and distribution of microcrystalline MgO in the framework of alumina to form a concrete-like structure. These sorbents can capture CO(2) at high temperature (150-400°C), possessing high reactivity and stability in cyclic adsorption-desorption processes, providing competitive candidates to control CO(2) emission. Copyright © 2011 Elsevier B.V. All rights reserved.

Nitrogen-enriched carbon with extremely high mesoporosity and tunable mesopore size for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Yang, Xiaoqing; Li, Chengfei; Fu, Ruowen

2016-07-01

As one of the most potential electrode materials for supercapacitors, nitrogen-enriched nanocarbons are still facing challenge of constructing developed mesoporosity for rapid mass transportation and tailoring their pore size for performance optimization and expanding their application scopes. Herein we develop a series of nitrogen-enriched mesoporous carbon (NMC) with extremely high mesoporosity and tunable mesopore size by a two-step method using silica gel as template. In our approach, mesopore size can be easily tailored from 4.7 to 35 nm by increasing the HF/TEOS volume ratio from 1/100 to 1/4. The NMC with mesopores of 6.2 nm presents the largest mesopore volume, surface area and mesopore ratio of 2.56 cm3 g-1, 1003 m2 g-1 and 97.7%, respectively. As a result, the highest specific capacitance of 325 F g-1 can be obtained at the current density of 0.1 A g-1, which can stay over 88% (286 F g-1) as the current density increases by 100 times (10 A g-1). This approach may open the doors for preparation of nitrogen-enriched nanocarbons with desired nanostructure for numerous applications.

Preparation of mesoporous alumina particles by spray pyrolysis and application to double bond migration of 2-butene.

PubMed

Song, Ki Chang; Kim, Joo Hyun; Kim, Jin Han; Jung, Kyeong Youl; Park, Young-Kwon; Jeon, Jong-Ki

2011-07-01

The objective of the present study is to investigate the catalytic performance of mesoporous alumina that were prepared via spray pyrolysis for double bond migration from 2-butene to 1-butene. The mesoporous alumina particles were prepared via spray pyrolysis by changing the types of organic surfactants and Al precursors. The texture and acidic properties of mesoporous alumina were analyzed through N2 adsorption, SEM, ammonia-temperature programmed desorption, and FT-IR of adsorbed pyridine. The morphologies and texture properties of the mesoporous alumina were found to have been strongly influenced by the combination of the Al precursor and the structure-directing agents. The mesoporous alumina samples had two kinds of acidic sites: a Lewis acid site and a H-bonded weak acid site. 1-Butene was produced selectively through double bond migration of 2-butene over all of the mesoporous alumina catalysts. The catalyst prepared by using a chloride compound as an aluminium precursor and CTAC as a structure-directing agent showed the highest activity in the double bond migration of 2-butene, which was attributed to its large surface area and an overall high amount of acid sites.

Dye-sensitized solar cells using laser processing techniques

NASA Astrophysics Data System (ADS)

Kim, Heungsoo; Pique, Alberto; Kushto, Gary P.; Auyeung, Raymond C. Y.; Lee, S. H.; Arnold, Craig B.; Kafafi, Zakia H.

2004-07-01

Laser processing techniques, such as laser direct-write (LDW) and laser sintering, have been used to deposit mesoporous nanocrystalline TiO2 (nc-TiO2) films for use in dye-sensitized solar cells. LDW enables the fabrication of conformal structures containing metals, ceramics, polymers and composites on rigid and flexible substrates without the use of masks or additional patterning techniques. The transferred material maintains a porous, high surface area structure that is ideally suited for dye-sensitized solar cells. In this experiment, a pulsed UV laser (355nm) is used to forward transfer a paste of commercial TiO2 nanopowder (P25) onto transparent conducting electrodes on flexible polyethyleneterephthalate (PET) and rigid glass substrates. For the cells based on flexible PET substrates, the transferred TiO2 layers were sintered using an in-situ laser to improve electron paths without damaging PET substrates. In this paper, we demonstrate the use of laser processing techniques to produce nc-TiO2 films (~10 μm thickness) on glass for use in dye-sensitized solar cells (Voc = 690 mV, Jsc = 8.7 mA/cm2, ff = 0.67, η = 4.0 % at 100 mW/cm2). This work was supported by the Office of Naval Research.

Crystalline mesoporous zirconia catalysts having stable tetragonal pore wall structure

DOEpatents

Sachtler, W.M.H.; Huang, Y.Y.

1998-07-28

Methods are disclosed for the preparation of new sulfated mesoporous zirconia materials/catalysts with crystalline pore walls of predominantly tetragonal crystal structure, characterized by nitrogen physical sorption measurement, X-ray diffraction, transmission electron microscopy and catalytic tests using n-butane isomerization to iso-butane and alkylation of 1-naphthol with 4-tert-butylstyrene as probe reactions. Sulfate deposition is preferred for the transformation of a mesoporous precursor with amorphous pore walls into a material with crystalline pore walls maintaining the mesoporous characteristics. 17 figs.

Crystalline mesoporous zirconia catalysts having stable tetragonal pore wall structure

DOEpatents

Sachtler, Wolfgang M. H.; Huang, Yin-Yan

1998-01-01

Methods for the preparation of new sulfated mesoporous zirconia materials/catalysts with crystalline pore walls of predominantly tetragonal crystal structure, characterized by nitrogen physisorption measurement, X-ray diffraction, transmission electron microscopy and catalytic tests using n-butane isomerization to iso-butane and alkylation of 1-naphthol with 4-tert-butylstyrene as probe reactions. Sulfate deposition is preferred for the transformation of a mesoporous precursor with amorphous pore walls into a material with crystalline pore walls maintaining the mesoporous characteristics.

Surfactant-Templated Mesoporous Metal Oxide Nanowires

DOE PAGES

Luo, Hongmei; Lin, Qianglu; Baber, Stacy; ...

2010-01-01

We demore » monstrate two approaches to prepare mesoporous metal oxide nanowires by surfactant assembly and nanoconfinement via sol-gel or electrochemical deposition. For example, mesoporous Ta 2 O 5 and zeolite nanowires are prepared by block copolymer Pluronic 123-templated sol-gel method, and mesoporous ZnO nanowires are prepared by electrodeposition in presence of anionic surfactant sodium dodecyl sulfate (SDS) surfactant, in porous membranes. The morphologies of porous nanowires are studied by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) analyses.« less

Glass Membrane For Controlled Diffusion Of Gases

DOEpatents

Shelby, James E.; Kenyon, Brian E.

2001-05-15

A glass structure for controlled permeability of gases includes a glass vessel. The glass vessel has walls and a hollow center for receiving a gas. The glass vessel contains a metal oxide dopant formed with at least one metal selected from the group consisting of transition metals and rare earth metals for controlling diffusion of the gas through the walls of the glass vessel. The vessel releases the gas through its walls upon exposure to a radiation source.

Rare earth (Eu{sup 3+}, Tb{sup 3+}) mesoporous hybrids with calix[4]arene derivative covalently linking MCM-41: Physical characterization and photoluminescence property

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li Yajuan; Yan Bing, E-mail: byan@tongji.edu.cn; Wang Li

2011-09-15

MCM-41 mesoporous silica has been functionalized with two kinds of macrocylic calixarene derivatives Calix[4] and Calix[4]Br (Calix[4]=P-tert-butylcalix[4]arene, Calix[4]Br=5.11,17.23-tetra-tert-butyl-25.27-bihydroxy- 26.28-bibromopropoxycalix[4]arene) through condensation approach of tetraethoxysilane (TEOS) in the presence of the cetyltrimethylammonium bromide (CTAB) surfactant as a template. Novel organic-inorganic mesoporous luminescent hybrid containing RE{sup 3+} (Eu{sup 3+}, Tb{sup 3+}) complexes covalently attached to the functionalized ordered mesoporous MCM-41, which are designated as RE-Calix[4]-MCM-41 and RE-Calix[4]Br-MCM-41, respectively, are obtained by sol-gel process. It is found that they all have high surface area, uniform in the mesostructure and good crystallinity. Measurement of the photoluminescence properties show the mesoporous material covalently bonded Tb{supmore » 3+} complexes (Tb-Calix[4]-MCM-41 and Tb-Calix[4]Br-MCM-41) exhibit the stronger characteristic emission of Tb{sup 3+} and longer lifetime than the corresponding Eu-containing materials Eu-Calix[4]-MCM-41 and Eu-Calix[4]Br-MCM-41 due to the triplet state energy of modified organic ligands Calix[4]-Si and Calix[4]Br-Si match with the emissive energy level of Tb{sup 3+} very well. - Graphical abstract: MCM-41 mesoporous silica is functionalized with two kinds of macrocylic calixarene derivatives and luminescent organic-inorganic mesoporous hybrids containing Ln{sup 3+} complexes covalently attached to the functionalized ordered mesoporous MCM-41. Highlights: > Novel linkages of functionalized calixarene derivative. > New rare earth mesoporous hybrids. > Luminescence in visible region.« less

A facile FeBr3 based photoATRP for surface modification of mesoporous silica nanoparticles for controlled delivery cisplatin

NASA Astrophysics Data System (ADS)

Huang, Long; Liu, Meiying; Mao, Liucheng; Huang, Qiang; Huang, Hongye; Zeng, Guangjian; Tian, Jianwen; Wen, Yuanqing; Zhang, Xiaoyong; Wei, Yen

2018-03-01

Mesoporous silica nanoparticles (MSNs) should be one of the most important materials for biomedical application owing to their high specific surface area, regular porous structure, adjustable pore size and chemical inert. However, the biomedical applications of unmodified MSNs are largely impeded for their poor hydrophilicity and lack of functional groups. In this work, a novel photo-initiated atom transfer radical polymerization (ATRP) strategy has been reported for modified mesoporous silica nanoparticles (MSNs) with hydrophilicility copolymers using FeBr3 as the novel photocatalyst and itaconic acid (IA) and 2-methacryloyloxyethyl phosphorylcholine (MPC) as monomers. Because of the hydrophilicity and anticancer agent cis-dichlorodiamineplatinum(II) (CDDP) loading capacity of poly(MPC-co-IA), the controlled drug delivery applications MSNs-NH2-poly(MPC-co-IA) composites toward CDDP were further investigated. A series of characterization results demonstrated that MSNs-NH2-poly(MPC-co-IA) composites can be successfully fabricated through the novel photo-initiated ATRP. MSNs-NH2-poly(MPC-co-IA) composites showed obvious enhancement of water dispersibility, desirable biocompatibility, high drug loading capability, making them great potential for controlled drug delivery of CDDP. Moreover, as compared with the traditional ATRP, that using the transition metal ions and organic ligands as the catalysis systems in elevated temperature, our method provides a more facile, benign and cost-effective route for fabrication of multifunctional MSNs with great potential for biomedical applications. Finally, this FeBr3 based photoATRP strategy should be further extended for the fabrication of many other polymeric composites owing to its good monomer adoptability.

Efficiency enhancement in dye sensitized solar cells using dual function mesoporous silica as scatterer and back recombination inhibitor

NASA Astrophysics Data System (ADS)

Tanvi; Mahajan, Aman; Bedi, R. K.; Kumar, Subodh; Saxena, Vibha; Aswal, D. K.

2016-08-01

In the present work, we report the usage of mesoporous silica for improving light harvesting as well as for suppression of back recombination without affecting the extent of dye loading on TiO2 films. Synthesized mesoporous SiO2 was characterized by X-ray photoelectron spectroscopy, X-ray diffraction, Brunauer Emmett and Teller measurement, Scanning electron microscopy and Transmission electron microscopy. DSSCs were fabricated by incorporating different wt% of mesoporous SiO2 in TiO2 paste. An improvement of 50% was observed for devices fabricated using 0.75 wt% of mesoporous SiO2. The mechanism behind the improvement was investigated using electrochemical impedance spectroscopy and UV-Vis spectroscopy.

Liquid Photonic Crystals for Mesopore Detection.

PubMed

Zhu, Biting; Fu, Qianqian; Chen, Ke; Ge, Jianping

2018-01-02

Nitrogen adsorption-desorption for mesopore characterization requires the using of expensive instrumentation, time-consuming processes, and the consumption of liquid nitrogen. Herein, a new method is developed to measure the pore parameters through mixing a mesoporous substance with a supersaturated SiO 2 colloidal solution at different temperatures, and subsequent rapid measurement of reflection changes of the precipitated liquid photonic crystals. The pore volumes and diameters of mesoporous silica were measured according to the positive correlation between unit mass reflection change (Δλ/m) and pore volume (V), and the negative correlation between average absorption temperature (T) and pore diameter (D). This new approach may provide an alternative method for fast, convenient and economical characterization of mesoporous materials. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Amperometric hydrogen peroxide and glucose biosensor based on NiFe2/ordered mesoporous carbon nanocomposites.

PubMed

Xiang, Dong; Yin, Longwei; Ma, Jingyun; Guo, Enyan; Li, Qun; Li, Zhaoqiang; Liu, Kegao

2015-01-21

Nanocomposites of NiFex embedded in ordered mesoporous carbon (OMC) (x = 0, 1, 2) were prepared by a wet impregnation and hydrogen reduction process and were used to construct electrochemical biosensors for the amperometric detection of hydrogen peroxide (H2O2) or glucose. The NiFe2/OMC nanocomposites were demonstrated to have a large surface area, suitable mesoporous channels, many edge-plane-like defective sites, and a good distribution of alloyed nanoparticles. The NiFe2/OMC and Nafion modified glass carbon electrode (GCE) exhibited excellent electrocatalytic activities toward the reduction of H2O2 as well. By utilizing it as a bioplatform, GOx (glucose oxidase) cross-linked with Nafion was immobilized on the surface of the electrode for the construction of an amperometric glucose biosensor. Our results indicated that the amperometric hydrogen peroxide biosensor (NiFe2/OMC + Nafion + GCE) showed good analytical performances in term of a high sensitivity of 4.29 μA mM(-1) cm(-2), wide linearity from 6.2 to 42,710 μM and a low detection limit of 0.24 μM at a signal-to-noise ratio of 3 (S/N = 3). This biosensor exhibited excellent selectivity, high stability and negligible interference for the detection of H2O2. In addition, the immobilized enzyme on NiFe2/OMC + Nafion + GCE, retaining its bioactivity, exhibited a reversible two-proton and two-electron transfer reaction, a fast heterogeneous electron transfer rate and an effective Michaelis-Menten constant (K) (3.18 mM). The GOx + NiFe2/OMC + Nafion + GCE could be used to detect glucose based on the oxidation of glucose catalyzed by GOx and exhibited a wide detection range of 48.6-12,500 μM with a high sensitivity of 6.9 μA mM(-1) cm(-2) and a low detection limit of 2.7 μM (S/N = 3). The enzymic biosensor maintained a high selectivity and stability features, and shows great promise for application in the detection of glucose.

Synthesis of thick mesoporous gamma-alumina films, loading of Pt nanoparticles, and use of the composite film as a reusable catalyst.

PubMed

Dandapat, Anirban; Jana, Debrina; De, Goutam

2009-04-01

Nanocrystalline mesoporous gamma-Al2O3 film of high thickness has been developed and characterized. The films were prepared on ordinary glass substrates by a single dip-coating method using boehmite (AlOOH) sols derived from aluminum tri-sec-butoxide in presence of cetyltrimethylammonium bromide (CTAB) as structure-directing agent. The dried films were heat-treated at 500 degrees C in air to remove the organics and strengthen the network. The GIXRD of the heat-treated (500 degrees C) film shows a broad peak in the low-angle region supporting the formation of worm-hole-like disordered mesostructures. The high-angle GIXRD, FTIR, and TEM of the films confirm the formation of gamma-Al2O3. N2 adsorption-desorption analyses showed that the heat-treated (500 degrees C) film has a BET surface area of 171 m(2) g(-1) with a pore volume of 0.188 cm(3) g(-1) and mean pore diameter 4.3 nm. Pt nanoparticles (NPs) (approximately 2.7 mol % with respect to the equivalent AlO(1.5)) were generated inside the mesopores of the heat-treated films simply by soaking H2PtCl6 solutions into it, and followed by thermal decomposition at 500 degrees C. The surface area and pore volume of the Pt-incorporated film have been reduced to 101 m(2) g(-1) and 0.119 cm(3) g(-1) respectively, confirming the inclusion of Pt NPs inside the pores. FESEM and TEM studies revealed uniform distribution of Pt NPs (2-8.5 nm; average diameter 4.9 nm) in the films. Catalytic properties of the Pt-incorporated films were investigated in two model (one inorganic and other organic) systems: reduction of hexacyanoferrate(III) ions by thiosulfate to ferrocyanide, and p-nitrophenol to p-aminophenol. In both the cases, the catalyst showed excellent activities, and the reduction reactions followed smoothly, showing isosbestic points in the UV-visible spectra. The catalyst films can be separated easily after the reactions and reused several times.

Palladium-zinc catalysts on mesoporous titania prepared by colloid synthesis. II. Synthesis and characterization of PdZn/TiO2 coating on inner surface of fused silica capillary

NASA Astrophysics Data System (ADS)

Okhlopkova, Lyudmila B.; Kerzhentsev, Michail A.; Tuzikov, Fedor V.; Larichev, Yurii V.; Ismagilov, Zinfer R.

2012-09-01

Nanoparticle-doped mesoporous titania coating was synthesized by incorporation of PdZn nanoparticles into TiO2 sol followed by dip coating of the sol on inner surface of fused silica capillary. Monodispersed PdZn bimetallic colloidal particles with average particle diameters of approximately 2 nm have been prepared by an ethylene glycol reduction of ZnCl2 and Pd(CH3COO)2 in the presence of polyvinylpyrrolidone. The textural properties, surface structure, chemical composition, and morphology of the samples were investigated by means of N2 sorption measurements, TEM, and X-ray diffraction. PdZn/TiO2 coating has been further analyzed by quantitative analysis of the SAXS data in combination with the density contrast method, providing direct structural-dispersion information about the active component and support. Calcination conditions suitable for surfactant removal have been optimized to obtain PdZn/TiO2 coatings with required metal particle size and composition. The high dispersion and chemical composition of the nanoparticles embedded in mesoporous titania coating have been retained with no modification after thermal treatment in vacuum at 300 °C. Results suggest how porous structure of the PdZn coating may be fine-tuned to improve the accessibility of the pores to reactants. The control of the pore size in the range of 4.9-6.8 nm of the mesoporous titania was achieved by adding co-surfactants, such as n-butanol.

Mesoporous TiO2 Bragg Stack Templated by Graft Copolymer for Dye-sensitized Solar Cells

PubMed Central

Park, Jung Tae; Chi, Won Seok; Kim, Sang Jin; Lee, Daeyeon; Kim, Jong Hak

2014-01-01

Organized mesoporous TiO2 Bragg stacks (om-TiO2 BS) consisting of alternating high and low refractive index organized mesoporous TiO2 (om-TiO2) films were prepared to enhance dye loading, light harvesting, electron transport, and electrolyte pore-infiltration in dye-sensitized solar cells (DSSCs). The om-TiO2 films were synthesized via a sol-gel reaction using amphiphilic graft copolymers consisting of poly(vinyl chloride) backbones and poly(oxyethylene methacrylate) side chains, i.e., PVC-g-POEM as templates. To generate high and low index films, the refractive index of om-TiO2 film was tuned by controlling the grafting ratio of PVC-g-POEM via atomic transfer radical polymerization (ATRP). A polymerized ionic liquid (PIL)-based DSSC fabricated with a 1.2-μm-thick om-TiO2 BS-based photoanode exhibited an efficiency of 4.3%, which is much higher than that of conventional DSSCs with a nanocrystalline TiO2 layer (nc-TiO2 layer) (1.7%). A PIL-based DSSC with a heterostructured photoanode consisting of 400-nm-thick organized mesoporous TiO2 interfacial (om-TiO2 IF) layer, 7-μm-thick nc-TiO2, and 1.2-μm-thick om-TiO2 BS as the bottom, middle and top layers, respectively, exhibited an excellent efficiency of 7.5%, which is much higher than that of nanocrystaline TiO2 photoanode (3.5%). PMID:24980936

Soft-Template-Synthesized Mesoporous Carbon for Oral Drug Delivery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Saha, Dipendu; Warren, Kaitlyn E; Naskar, Amit K

Template-synthesized mesoporous carbons were successfully used in in vitro investigations of controlled delivery of three model drugs, captopril, furosemide, and ranitidine hydrochloride. Captopril and furosemide exhibited desorption kinetics over 30 40 h, and ranitidine HCl had a complete release time of 5 10 h. As evident from the slow release kinetics, we contend that our mesoporous carbon is an improved drug-delivery medium compared to state-of-the-art porous silica-based substrates. The mesoporous carbons, synthesized from phloroglucinol and lignin, a synthetic and a sustainable precursor, respectively, exhibit BET surface area of 200 400 m2 g-1 and pore volume of 0.2 0.6 cm3 g-1.more » The phloroglucinol-based carbon has narrower pore widths and higher pore volume than the lignin-derived counterpart and maintains a longer release time. Numerical modeling of the release kinetics data reveals that the diffusivities of all the drugs from lignin-based carbon media are of equivalent magnitude (10-22 to 10-24 m2 s-1). However, a tailored reduction of pore width in the sorbent reduces the diffusivity of smaller drug molecules (captopril) by an order of magnitude. Thus, engineered pore morphology in our synthesized carbon sorbent, along with its potential to tailor the chemistry of its interaction with sorbet, can be exploited for optimal delivery system of a preferred drug within its therapeutic level and below the level of toxicity.« less

High-yield harvest of nanofibers/mesoporous carbon composite by pyrolysis of waste biomass and its application for high durability electrochemical energy storage.

PubMed

Liu, Wu-Jun; Tian, Ke; He, Yan-Rong; Jiang, Hong; Yu, Han-Qing

2014-12-02

Disposal and recycling of the large scale biomass waste is of great concern. Themochemically converting the waste biomass to functional carbon nanomaterials and bio-oil is an environmentally friendly apporach by reducing greenhouse gas emissions and air pollution caused by open burning. In this work, we reported a scalable, "green" method for the synthesis of the nanofibers/mesoporous carbon composites through pyrolysis of the Fe(III)-preloaded biomass, which is controllable by adjustment of temperature and additive of catalyst. It is found that the coupled catalytic action of both Fe and Cl species is able to effectively catalyze the growth of the carbon nanofibers on the mesoporous carbon and form magnetic nanofibers/mesoporous carbon composites (M-NMCCs). The mechanism for the growth of the nanofibers is proposed as an in situ vapor deposition process, and confirmed by the XRD and SEM results. M-NMCCs can be directly used as electrode materials for electrochemical energy storage without further separation, and exhibit favorable energy storage performance with high EDLC capacitance, good retention capability, and excellent stability and durability (more than 98% capacitance retention after 10,000 cycles). Considering that biomass is a naturally abundant and renewable resource (over billions tons biomass produced every year globally) and pyrolysis is a proven technique, M-NMCCs can be easily produced at large scale and become a sustainable and reliable resource for clean energy storage.

Hierarchically ordered mesoporous Co3O4 materials for high performance Li-ion batteries.

PubMed

Sun, Shijiao; Zhao, Xiangyu; Yang, Meng; Wu, Linlin; Wen, Zhaoyin; Shen, Xiaodong

2016-01-19

Highly ordered mesoporous Co3O4 materials have been prepared via a nanocasting route with three-dimensional KIT-6 and two-dimensional SBA-15 ordered mesoporous silicas as templates and Co(NO3)2 · 6H2O as precursor. Through changing the hydrothermal treating temperature of the silica template, ordered mesoporous Co3O4 materials with hierarchical structures have been developed. The larger pores around 10 nm provide an efficient transport for Li ions, while the smaller pores between 3-5 nm offer large electrochemically active areas. Electrochemical impedance analysis proves that the hierarchical structure contributes to a lower charge transfer resistance in the mesoporous Co3O4 electrode than the mono-sized structure. High reversible capacities around 1141 mAh g(-1) of the hierarchically mesoporous Co3O4 materials are obtained, implying their potential applications for high performance Li-ion batteries.

Facile Synthesis of Wormhole-Like Mesoporous Tin Oxide via Evaporation-Induced Self-Assembly and the Enhanced Gas-Sensing Properties

NASA Astrophysics Data System (ADS)

Li, Xiaoyu; Peng, Kang; Dou, Yewei; Chen, Jiasheng; Zhang, Yue; An, Gai

2018-01-01

Wormhole-like mesoporous tin oxide was synthesized via a facile evaporation-induced self-assembly (EISA) method, and the gas-sensing properties were evaluated for different target gases. The effect of calcination temperature on gas-sensing properties of mesoporous tin oxide was investigated. The results demonstrate that the mesoporous tin oxide sensor calcined at 400 °C exhibits remarkable selectivity to ethanol vapors comparison with other target gases and has a good performance in the operating temperature and response/recovery time. This might be attributed to their high specific surface area and porous structure, which can provide more active sites and generate more chemisorbed oxygen spices to promote the diffusion and adsorption of gas molecules on the surface of the gas-sensing material. A possible formation mechanism of the mesoporous tin oxide and the enhanced gas-sensing mechanism are proposed. The mesoporous tin oxide shows prospective detecting application in the gas sensor fields.

Facile hydrothermal synthesis of mesoporous In2O3 nanoparticles with superior formaldehyde-sensing properties

NASA Astrophysics Data System (ADS)

Zhang, Su; Song, Peng; Yang, Zhongxi; Wang, Qi

2018-03-01

Mesoporous In2O3 nanoparticles were successfully synthesized via a facile, template free, and low-cost hydrothermal method. Their morphology and structure were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), differential thermal and thermogravimetry analysis (DSC-TG), and N2 adsorption-desorption analyses. The results reveal that mesoporous In2O3 nanoparticles with a size range of 40-60 nm, possess plenty of pores, and average pore size is about 5 nm. Importantly, the mesoporous structure, large specific surface area, and small size endow the mesoporous In2O3 nanoparticles with highly sensing performance for formaldehyde detection. The response value to 10 ppm HCHO is 20 at an operating temperature of 280 °C, and the response and recovery time are 4 and 8 s, respectively. It is expected that the mesoporous In2O3 nanoparticles with large specific surface area and excellent sensing properties will become a promising functional material in monitoring and detecting formaldehyde.

Mesoporous metallic rhodium nanoparticles

NASA Astrophysics Data System (ADS)

Jiang, Bo; Li, Cuiling; Dag, Ömer; Abe, Hideki; Takei, Toshiaki; Imai, Tsubasa; Hossain, Md. Shahriar A.; Islam, Md. Tofazzal; Wood, Kathleen; Henzie, Joel; Yamauchi, Yusuke

2017-05-01

Mesoporous noble metals are an emerging class of cutting-edge nanostructured catalysts due to their abundant exposed active sites and highly accessible surfaces. Although various noble metal (e.g. Pt, Pd and Au) structures have been synthesized by hard- and soft-templating methods, mesoporous rhodium (Rh) nanoparticles have never been generated via chemical reduction, in part due to the relatively high surface energy of rhodium (Rh) metal. Here we describe a simple, scalable route to generate mesoporous Rh by chemical reduction on polymeric micelle templates [poly(ethylene oxide)-b-poly(methyl methacrylate) (PEO-b-PMMA)]. The mesoporous Rh nanoparticles exhibited a ~2.6 times enhancement for the electrocatalytic oxidation of methanol compared to commercially available Rh catalyst. Surprisingly, the high surface area mesoporous structure of the Rh catalyst was thermally stable up to 400 °C. The combination of high surface area and thermal stability also enables superior catalytic activity for the remediation of nitric oxide (NO) in lean-burn exhaust containing high concentrations of O2.

Cluster-randomized controlled trial of the effects of free glasses on purchase of children's glasses in China: The PRICE (Potentiating Rural Investment in Children's Eyecare) study

PubMed Central

Wang, Xiuqin; Ma, Yue; Hu, Min; Zhou, Yuan; Liao, Weiqi; Jin, Ling; Xiao, Baixiang; Wu, Xiaoyi; Ni, Ming; Yi, Hongmei; Huang, Yiwen; Varga, Beatrice; Zhang, Hong; Cun, Yongkang; Li, Xianshun; Yang, Luhua; Liang, Chaoguang; Huang, Wan; Rozelle, Scott; Ma, Xiaochen

2017-01-01

Background Offering free glasses can be important to increase children’s wear. We sought to assess whether “Upgrade glasses” could avoid reduced glasses sales when offering free glasses to children in China. Methods In this cluster-randomized, controlled trial, children with uncorrected visual acuity (VA)< = 6/12 in either eye correctable to >6/12 in both eyes at 138 randomly-selected primary schools in 9 counties in Guangdong and Yunnan provinces, China, were randomized by school to one of four groups: glasses prescription only (Control); Free Glasses; Free Glasses + offer of $15 Upgrade Glasses; Free Glasses + offer of $30 Upgrade Glasses. Spectacle purchase (main outcome) was assessed 6 months after randomization. Results Among 10,234 children screened, 882 (8.62%, mean age 10.6 years, 45.5% boys) were eligible and randomized: 257 (29.1%) at 37 schools to Control; 253 (28.7%) at 32 schools to Free Glasses; 187 (21.2%) at 31 schools to Free Glasses + $15 Upgrade; and 185 (21.0%) at 27 schools to Free Glasses +$30 Upgrade. Baseline ownership among these children needing glasses was 11.8% (104/882), and 867 (98.3%) children completed follow-up. Glasses purchase was significantly less likely when free glasses were given: Control: 59/250 = 23.6%; Free glasses: 32/252 = 12.7%, P = 0.010. Offering Upgrade Glasses eliminated this difference: Free + $15 Upgrade: 39/183 = 21.3%, multiple regression relative risk (RR) 0.90 (0.56–1.43), P = 0.65; Free + $30 Upgrade: 38/182 = 20.9%, RR 0.91 (0.59, 1.42), P = 0.69. Conclusions Upgrade glasses can prevent reductions in glasses purchase when free spectacles are provided, providing important program income. Trial registration ClinicalTrials.gov Identifier: NCT02231606. Registered on 31 August 2014. PMID:29161286

Magnetic ordered mesoporous Fe3O4/CeO2 composites with synergy of adsorption and Fenton catalysis

NASA Astrophysics Data System (ADS)

Li, Keyan; Zhao, Yongqin; Song, Chunshan; Guo, Xinwen

2017-12-01

Magnetic Fe3O4/CeO2 composites with highly ordered mesoporous structure and large surface area were synthesized by impregnation-calcination method, and the mesoporous CeO2 as support was synthesized via the hard template approach. The composition, morphology and physicochemical properties of the materials were characterized by XRD, SEM, TEM, XPS, Raman spectra and N2 adsorption/desorption analysis. The mesoporous Fe3O4/CeO2 composite played a dual-function role as both adsorbent and Fenton-like catalyst for removal of organic dye. The methylene blue (MB) removal efficiency of mesoporous Fe3O4/CeO2 was much higher than that of irregular porous Fe3O4/CeO2. The superior adsorption ability of mesoporous materials was attributed to the abundant oxygen vacancies on the surface of CeO2, high surface area and ordered mesoporous channels. The good oxidative degradation resulted from high Ce3+ content and the synergistic effect between Fe and Ce. The mesoporous Fe3O4/CeO2 composite presented low metal leaching (iron 0.22 mg L-1 and cerium 0.63 mg L-1), which could be ascribed to the strong metal-support interactions for dispersion and stabilization of Fe species. In addition, the composite can be easily separated from reaction solution with an external magnetic field due to its magnetic property, which is important to its practical applications.

High-pressure synthesis of mesoporous stishovite: potential applications in mineral physics

NASA Astrophysics Data System (ADS)

Stagno, Vincenzo; Mandal, Manik; Landskron, Kai; Fei, Yingwei

2015-06-01

Recently, we have described a successful synthesis route to obtain mesoporous quartz and its high-pressure polymorph coesite by nanocasting at high pressure using periodic mesostructured precursors, such as SBA-16 and FDU-12/carbon composite as starting materials. Periodic mesoporous high-pressure silica polymorphs are of particular interest as they combine transport properties and physical properties such as hardness that potentially enable the industrial use of these materials. In addition, synthesis of mesoporous crystalline silica phases can allow more detailed geology-related studies such as water/mineral interaction, dissolution/crystallization rate and the surface contribution to the associated thermodynamic stability (free energy and enthalpy) of the various polymorphs and their crossover. Here, we present results of synthesis of mesoporous stishovite from cubic large-pore periodic mesoporous silica LP-FDU-12/C composite as precursor with an fcc lattice. We describe the synthesis procedure using multi-anvil apparatus at 9 GPa (about 90,000 atm) and temperature of 500 °C. The synthetic mesoporous stishovite is, then, characterized by wide and small-angle X-ray diffraction, scanning/transmission electron microscopy and gas adsorption. Results show that this new material is characterized by accessible mesopores with wide pore size distribution, surface area of ~45 m2/g and volume of pores of ~0.15 cm3/g. Results from gas adsorption indicate that both porosity and permeability are retained at the high pressures of synthesis but with weak periodic order of the pores.

Environmental and Biomedical Applications of Iron Oxide/Mesoporous Silica Core-Shell Nanocomposites

NASA Astrophysics Data System (ADS)

Egodawatte, Shani Nirasha

Mesoporous silica has shown great potential as an adsorbent for environmental contaminants and as a host for imaging and therapeutic agents. Mesoporous silica materials have a high surface area, tunable pore sizes and well defined surface properties which are governed by the surface hydroxyl groups. Surface modification of the mesoporous silica can tailor the adsorption properties for a specific metal ion or a small drug molecule by providing better sites for chelation or electrostatic interactions. Iron oxide / mesoporous silica core shell materials couple the favorable properties of both the iron oxide and mesoporous silica materials. The core-shell materials have higher adsorption properties compared to the parent material. With magnetic iron oxide nanoparticle cores, an additional magnetic property is introduced that can be used as magnetic recovery or separation. Heavy metals such as Chromium (Cr) and Arsenic (As) discharged from residential and environmental sources pose a serious threat to human health as well as groundwater pollution. In this thesis, iron oxide nanoparticles and nanofibers were coated with mesoporous silica and functionalized with (3-aminopropyl)triethoxysilane (APTES) using the post synthesis grafting method. The parent and the functionalized magnetic silica samples were characterized using powder X-ray diffraction (pXRD), thermal gravimetric analysis (TGA), Fourier Transform Infrared (FTIR) spectroscopy and nitrogen adsorption desorption isotherms for surface area and pore volumes. These materials were evaluated for Cr(III) and As(III)/As(V) adsorption from aqueous solutions in the optimum pH range for the specific metal. The aminopropyl functionalized magnetic mesoporous silica displayed the highest adsorption capacity for Cr(III) and Cu(II) of all the materials evaluated in this study. The high heavy metal adsorption capacity was attributed to a synergistic effect of iron oxide nanoparticles and amine functionalization on mesoporous silica as well as a judicious choice of pH. Modified magnetic mesoporous silica material was also found to have high adsorption capacity for high and low pH aqueous solutions of Uranium (VI). Tuning the loading and release of a small drug molecule (5-FU) onto these iron oxide/ mesoporous silica core-shell materials was also investigated. The polarity of the solvent used to load 5-FU onto the host had an impact not only on the loading but also on the release percentage of 5-FU. The synthesis of a novel core-shell material with a hematite nanofiber core and a SBA type mesoporous silica shell was also explored.

Natural material-decorated mesoporous silica nanoparticle container for multifunctional membrane-controlled targeted drug delivery

PubMed Central

Hu, Yan; Ke, Lei; Chen, Hao; Zhuo, Ma; Yang, Xinzhou; Zhao, Dan; Zeng, Suying; Xiao, Xincai

2017-01-01

To avoid the side effects caused by nonspecific targeting, premature release, weak selectivity, and poor therapeutic efficacy of current nanoparticle-based systems used for drug delivery, we fabricated natural material-decorated nanoparticles as a multifunctional, membrane-controlled targeted drug delivery system. The nanocomposite material coated with a membrane was biocompatible and integrated both specific tumor targeting and responsiveness to stimulation, which improved transmission efficacy and controlled drug release. Mesoporous silica nanoparticles (MSNs), which are known for their biocompatibility and high drug-loading capacity, were selected as a model drug container and carrier. The membrane was established by the polyelectrolyte composite method from chitosan (CS) which was sensitive to the acidic tumor microenvironment, folic acid-modified CS which recognizes the folate receptor expressed on the tumor cell surface, and a CD44 receptor-targeted polysaccharide hyaluronic acid. We characterized the structure of the nanocomposite as well as the drug release behavior under the control of the pH-sensitive membrane switch and evaluated the antitumor efficacy of the system in vitro. Our results provide a basis for the design and fabrication of novel membrane-controlled nanoparticles with improved tumor-targeting therapy. PMID:29200852

Synthesis of ordered mesoporous carbon monoliths with bicontinuous cubic pore structure of Ia3d symmetry.

PubMed

Yang, Haifeng; Shi, Qihui; Liu, Xiaoying; Xie, Songhai; Jiang, Decheng; Zhang, Fuqiang; Yu, Chengzhong; Tu, Bo; Zhao, Dongyuan

2002-12-07

Large-diameter-sized mesoporous carbon monoliths with bicontinuous cubic structure of Ia3d symmetry have been synthesized by using mesoporous silica monoliths as hard templates; such carbon monoliths show potential application of advanced electrodes and electrochemical double layer capacitors.

Phenol-formaldehyde carbon with ordered/disordered bimodal mesoporous structure as high-performance electrode materials for supercapacitors

NASA Astrophysics Data System (ADS)

Cai, Tingwei; Zhou, Min; Han, Guangshuai; Guan, Shiyou

2013-11-01

A novel phenol-formaldehyde carbon with ordered/disordered bimodal mesoporous structure is synthesized by the facile evaporation induced self-assembly strategy under a basic aqueous condition with SiO2 particles as template. The prepared bimodal mesoporous carbons (BMCs) are composed of ordered mesoporous and disordered mesoporous with diameter of about 3.5 nm and 7.0 nm, respectively. They can be employed as supercapacitor electrodes in H2SO4 aqueous electrolyte after the simple acid-treatment. BMC exhibits an exceptional specific capacitance of 344 F g-1 at the current density of 0.1 A g-1, although it has a relatively low surface area of 722 m2 g-1. And the BMC electrode displays an excellent cycling stability over 10,000 cycles.

Conversion of kraft lignin over hierarchical MFI zeolite.

PubMed

Kim, Seong-Soo; Lee, Hyung Won; Ryoo, Ryong; Kim, Wookdong; Park, Sung Hoon; Jeon, Jong-Ki; Park, Young-Kwon

2014-03-01

Catalytic pyrolysis of kraft lignin was carried out using pyrolysis gas chromatography/mass spectrometry. Hierarchical mesoporous MFI was used as the catalyst and another mesoporous material Al-SBA-15 was also used for comparison. The characteristics of mesoporous MFI were analyzed by X-ray diffraction patterns, N2 adsorption-desorption isotherms, and temperature programmed desorption of NH3. Two catalyst/lignin mass ratios were tested: 5/1 and 10/1. Aromatics and alkyl phenolics were the main products of the catalytic pyrolysis of lignin over mesoporous MFI. In particular, the yields of mono-aromatics such as benzene, toluene, ethylbenzene, and xylene were increased substantially by catalytic upgrading. Increase in the catalyst dose enhanced the production of aromatics further, which is attributed to decarboxylation, decarbonlyation, and aromatization reactions occurring over the acid sites of mesoporous MFI.

Pair distribution function (PDF) analysis of mesoporous α-Fe2O3 and Cr2O3.

PubMed

Hill, Adrian H; Allieta, Mattia

2013-06-14

We have measured atomic pair distribution functions of novel mesoporous metal oxides, α-Fe2O3 and Cr2O3. These have an ordered pore mosaic as well as crystalline structure within the pore walls, making them an interesting class of materials to characterise. Comparison of "bulk" and mesoporous data sets has allowed an estimate of long range structural coherence to be derived; ≈125 Å and ≈290 Å for α-Fe2O3 and Cr2O3 respectively. Further "box-car" analysis has shown that above ≈40 Å both mesoporous samples deviate greatly from their bulk counterparts. This is attributed to the pores of the mesoporous structure creating voids in the pair-correlations, disrupting long range order.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bu, Lintao; Nimlos, Mark R.; Robichaud, David J.

Hierarchical mesoporous zeolites exhibit higher catalytic activities and longer lifetime compared to the traditional microporous zeolites due to improved diffusivity of substrate molecules and their enhanced access to the zeolite active sites. Understanding diffusion of biomass pyrolysis vapors and their upgraded products in such materials is fundamentally important during catalytic fast pyrolysis (CFP) of lignocellulosic biomass, since diffusion makes major contribution to determine shape selectivity and product distribution. However, diffusivities of biomass relevant species in hierarchical mesoporous zeolites are poorly characterized, primarily due to the limitations of the available experimental technology. In this work, molecular dynamics (MD) simulations are utilizedmore » to investigate the diffusivities of several selected coke precursor molecules, benzene, naphthalene, and anthracene, in hierarchical mesoporous H-ZSM-5 zeolite. The effects of temperature and size of mesopores on the diffusivity of the chosen model compounds are examined. The simulation results demonstrate that diffusion within the microspores as well as on the external surface of mesoporous H-ZSM-5 dominates only at low temperature. At pyrolysis relevant temperatures, mass transfer is essentially conducted via diffusion along the mesopores. Additionally, the results illustrate the heuristic diffusion model, such as the extensively used Knudsen diffusion, overestimates the diffusion of bulky molecules in the mesopores, thus making MD simulation a powerful and compulsory approach to explore diffusion in zeolites.« less

Rod-shaped silica particles derivatized with elongated silver nanoparticles immobilized within mesopores

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mnasri, Najib; Materials, Environment and Energy Laboratory; Charnay, Clarence

Silver-derivatized silica particles possessing a non-spherical morphology and surface plasmon resonance properties have been achieved. Nanometer-sized silica rods with uniformly sized mesopore channels were prepared first making use of alkyltrimethyl ammonium surfactants as porogens and the 1:0.10 tetraethyl orthosilicate (TEOS) : 3-aminopropyltriethoxysilane (APTES) mixture as a silicon source. Silica rods were subsequently functionalized by introducing elongated silver nanoparticles within the intra-particle mesopores thanks to the AgNO{sub 3} reduction procedure based on the action of hemiaminal groups previously located on the mesopore walls. The textural and structural features of the samples were inferred from the combined characterization studies including SEM andmore » TEM microscopy, nitrogen adsorption-desorption at 77 K, powder XRD in the small- and wide-angle region, as well as UV–visible spectroscopy. {sup 129}Xe NMR spectroscopy appeared particularly useful to obtain a correct information about the porous structure of rod-shaped silica particles and the silver incorporation within their intra-particle mesopores. - Highlights: • Mesoporous monodisperse submicron-sized silica rods were achieved. • Silver nanoparticles were located lengthwise within the intra-particle mesopores. • Textural and plasmonic properties of particles studied by {sup 129}Xe NMR and UV–Vis.« less

Electrochemical characterisation and anodic stripping voltammetry at mesoporous platinum rotating disc electrodes.

PubMed

Lozano-Sanchez, Pablo; Elliott, Joanne M

2008-02-01

Using the technique of liquid crystal templating a rotating disc electrode (RDE) was modified with a high surface area mesoporous platinum film. The surface area of the electrode was characterised by acid voltammetry, and found to be very high (ca. 86 cm(2)). Acid characterisation of the electrode produced distorted voltammograms was interpreted as being due to the extremely large surface area which produced a combination of effects such as localised pH change within the pore environment and also ohmic drop effects. Acid voltammetry in the presence of two different types of surfactant, namely Tween 20 and Triton X-100, suggested antifouling properties associated with the mesoporous deposit. Further analysis of the modified electrode using a redox couple in solution showed typical RDE behaviour although extra capacitive currents were observed due to the large surface area of the electrode. The phenomenon of underpotential deposition was exploited for the purpose of anodic stripping voltammetry and results were compared with data collected for microelectrodes. Underpotential deposition of metal ions at the mesoporous RDE was found to be similar to that at conventional platinum electrodes and mesoporous microelectrodes although the rate of surface coverage was found to be slower at a mesoporous RDE. It was found that a mesoporous RDE forms a suitable system for quantification of silver ions in solution.

Template-directed hydrothermal synthesis of hydroxyapatite as a drug delivery system for the poorly water-soluble drug carvedilol

NASA Astrophysics Data System (ADS)

Zhao, Qinfu; Wang, Tianyi; Wang, Jing; Zheng, Li; Jiang, Tongying; Cheng, Gang; Wang, Siling

2011-09-01

In order to improve the dissolution rate and increase the bioavailability of a poorly water-soluble drug, intended to be administered orally, the biocompatible and bioactive mesoporous hydroxyapatite (HA) was successfully synthesized. In the present study, mesoporous HA nanoparticles were produced using Pluronic block co-polymer F127 and cetyltrimethylammonium bromide (CTAB) as templates by the hydrothermal method. The obtained mesoporous HA was employed as a drug delivery carrier to investigate the drug storage/release properties using carvedilol (CAR) as a model drug. Characterizations of the raw CAR powder, mesoporous HA and CAR-loaded HA were carried out by the scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray powder diffraction (XRPD), differential scanning calorimetry (DSC), Fourier transform infrared (FT-IR) spectroscopy, N2 adsorption/desorption, thermogravimetric analysis (TGA), and UV-VIS spectrophotometry. The results demonstrated that CAR was successfully incorporated into the mesoporous HA host. In vitro drug release studies showed that mesoporous HA had a high drug load efficiency and provided immediate release of CAR compared with micronized raw drug in simulated gastric fluid (pH 1.2) and intestinal fluid (pH 6.8). Consequently, mesoporous HA is a good candidate as a drug carrier for the oral delivery of poorly water-soluble drugs.

Effective Enrichment and Mass Spectrometry Analysis of Phosphopeptides Using Mesoporous Metal Oxide Nanomaterials

PubMed Central

Nelson, Cory A.; Szczech, Jeannine R.; Dooley, Chad J.; Xu, Qingge; Lawrence, Matthew J.; Zhu, Haoyue; Jin, Song; Ge, Ying

2010-01-01

Mass spectrometry (MS)-based phosphoproteomics remains challenging due to the low abundance of phosphoproteins and substoichiometric phosphorylation. This demands better methods to effectively enrich phosphoproteins/peptides prior to MS analysis. We have previously communicated the first use of mesoporous zirconium oxide (ZrO2) nanomaterials for effective phosphopeptide enrichment. Here we present the full report including the synthesis, characterization, and application of mesoporous titanium dioxide (TiO2), ZrO2, and hafnium oxide (HfO2) in phosphopeptide enrichment and MS analysis. Mesoporous ZrO2 and HfO2 are demonstrated to be superior to TiO2 for phosphopeptide enrichment from a complex mixture with high specificity (>99%), which could almost be considered as “a purification”, mainly because of the extremely large active surface area of mesoporous nanomaterials. A single enrichment and Fourier transform MS analysis of phosphopeptides digested from a complex mixture containing 7% of α-casein identified 21 out of 22 phosphorylation sites for α-casein. Moreover, the mesoporous ZrO2 and HfO2 can be reused after a simple solution regeneration procedure with comparable enrichment performance to that of fresh materials. Mesoporous ZrO2 and HfO2 nanomaterials hold great promise for applications in MS-based phosphoproteomics. PMID:20704311

Steam-assisted crystallization of TPA{sup +}-exchanged MCM-41 type mesoporous materials with thick pore walls

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Hong Li; Zhang, Kun; Wang, Yi Meng, E-mail: ymwang@chem.ecnu.edu.cn

2012-07-15

Highlights: ► Mesoporous Ti-containing silica with thicker pore walls was synthesized. ► Ion-exchange and steam-assisted crystallization led to MCM-41/MFI composite. ► The introduction of Ti inhibited the formation of separated MFI particles. ► Lower temperature favored retaining mesoporous characteristics and morphology. -- Abstract: Hierarchical MCM-41/MFI composites were synthesized through ion-exchange of as-made MCM-41 type mesoporous materials with tetrapropylammonium bromide and subsequent steam-assisted recrystallization. The obtained samples were characterized by powder X-ray diffraction (XRD), UV–vis diffuse reflectance spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis, FT-IR, {sup 1}H–{sup 13}C CP/MAS and nitrogen adsorption–desorption. The XRD patterns show thatmore » the MCM-41/MFI composite possesses both ordered MCM-41 phase and zeolite MFI phase. SEM and TEM images indicate that the recrystallized materials retained the mesoporous characteristics and the morphology of as-made mesoporous materials without the formation of bulky zeolite, quite different from the mechanical mixture of MCM-41 and MFI structured zeolite. Among others, lower recrystallization temperature and the introduction of the titanium to the parent materials are beneficial to preserve the mesoporous structure during the recrystallization process.« less

Chemistry of alkali cation exchanged faujasite and mesoporous NaX using alkyl halides and phosphates

NASA Astrophysics Data System (ADS)

Lee, Min-Hong

The purpose of this work was to increase the reactivity of Faujasite X (NaX) zeolite toward the reactive decontamination of materials subject to nucleophilic attack by means of zeolite cation optimization and by means of the synthesis of mesoporous Faujasite X. Primary alkyl halides and trialkyl phosphates have been the test materials on which the cation-optimized and mesoporous zeolites have been tested. In the alkali cation optimization work, reactions of methyl iodide and 1-chloropropane with alkali metal cation exchanged Faujasite zeolite X were investigated at room temperature. The reactivity of the framework and the product formation were shown to depend on zeolite framework counter-cation. A quantitative study of zeolite product formation has been carried out, primarily using solid-state NMR spectroscopy. Large alkali cations showed preference toward substitution chemistry. In contrast, alkyl halide exposed LiX and NaX zeolites underwent both substitution and elimination. Subsequently introduced water molecules led to hydrolysis of framework species that was sensitive to framework counter-cation. The mesoporous NaX zeolites work undertakes to test whether an improvement in surface chemical reactivity can be achieved by introducing mesopores into the already reactive nucleophilic microporous NaX zeolite. Incorporation of the polydiallyl dimethyl ammonium chloride (PDADMAC) template and the formation of mesopores in Faujasite X zeolite (NaX) were successful and well-characterized. The mesopores are proposed to have occurred from incorporation of the cationic PDADMAC polymer into the zeolite by compensating zeolite framework charge. Subsequent sodium cation exchange of calcined mesoporous NaX was shown to restore the chemical reactivity characteristic of as-synthesized NaX. Trialkyl organophosphorous compounds underwent substitution reactions. The reactivity of both microporous and mesoporous Faujasite zeolite X and the product formation was shown to depend on the length of the alkyl chain. Although introduced mesopores alleviated the limited reagent diffusion to reactive sites due to the microporosity of the NaX zeolites, no marked improvement in the product yields was achieved with either the 1-chloroalkanes or the trialkyl phosphates test compounds, regardless of alkyl chain length. The disappointing results have been attributed to lack of substantial net increase in the numbers of zeolite nucleophilic sites accompanying mesopore introduction.

New dye-sensitized solar cells obtained from extracted bracts of Bougainvillea glabra and spectabilis betalain pigments by different purification processes.

PubMed

Hernandez-Martinez, Angel Ramon; Estevez, Miriam; Vargas, Susana; Quintanilla, Fracisco; Rodriguez, Rogelio

2011-01-01

The performance of a new dye-sensitized solar cell (DSSC) based in a natural dye extracted from the Bougainvillea spectabilis' bracts, is reported. The performance of this solar cell was compared with cells prepared using extract of the Bougainvillea glabra and mixture of both extracts; in both cases the pigments were betalains, obtained from Reddish-purple extract. These dyes were purified to different extents and used for the construction of solar cells that were electrically characterized. The materials were characterized using FTIR and UV-Vis. Solar cells were assembled using TiO(2) thin film on indium tin oxide (ITO)-coated glass; a mesoporous film was sensitized with the Bougainvillea extracts. The obtained solar energy conversion efficiency was of 0.48% with a current density J(SC) of 2.29 mA/cm(2) using an irradiation of 100 mW/cm(2) at 25 °C.

Effect of Different CH3NH3PbI3 Morphologies on Photovoltaic Properties of Perovskite Solar Cells

NASA Astrophysics Data System (ADS)

Chen, Lung-Chien; Lee, Kuan-Lin; Wu, Wen-Ti; Hsu, Chien-Feng; Tseng, Zong-Liang; Sun, Xiao Hong; Kao, Yu-Ting

2018-05-01

In this study, the perovskite layers were prepared by two-step wet process with different CH3NH3I (MAI) concentrations. The cell structure was glass/FTO/TiO2-mesoporous/CH3NH3PbI3 (MAPbI3)/spiro-OMeTAD/Ag. The MAPbI3 perovskite films were prepared using high and low MAI concentrations in a two-step process. The perovskite films were optimized at different spin coating speed and different annealing temperatures to enhance the power conversion efficiency (PCE) of perovskite solar cells. The PCE of the resulting device based on the different perovskite morphologies was discussed. The PCE of the best cell was up to 17.42%, open circuit voltage of 0.97 V, short current density of 24.06 mA/cm2, and fill factor of 0.747.

Effect of Different CH3NH3PbI3 Morphologies on Photovoltaic Properties of Perovskite Solar Cells.

PubMed

Chen, Lung-Chien; Lee, Kuan-Lin; Wu, Wen-Ti; Hsu, Chien-Feng; Tseng, Zong-Liang; Sun, Xiao Hong; Kao, Yu-Ting

2018-05-08

In this study, the perovskite layers were prepared by two-step wet process with different CH 3 NH 3 I (MAI) concentrations. The cell structure was glass/FTO/TiO 2 -mesoporous/CH 3 NH 3 PbI 3 (MAPbI 3 )/spiro-OMeTAD/Ag. The MAPbI 3 perovskite films were prepared using high and low MAI concentrations in a two-step process. The perovskite films were optimized at different spin coating speed and different annealing temperatures to enhance the power conversion efficiency (PCE) of perovskite solar cells. The PCE of the resulting device based on the different perovskite morphologies was discussed. The PCE of the best cell was up to 17.42%, open circuit voltage of 0.97 V, short current density of 24.06 mA/cm 2 , and fill factor of 0.747.

Adsorption and desorption performance of benzene over hierarchically structured carbon-silica aerogel composites.

PubMed

Dou, Baojuan; Li, Jinjun; Wang, Yufei; Wang, Hailin; Ma, Chunyan; Hao, Zhengping

2011-11-30

Hierarchically structured carbon-silica aerogel (CSA) composites were synthesized from cheap water glass precursors and granulated activated carbon via a post-synthesis surface modification with trimethylchlorosilane (TMCS) and a low-cost ambient pressure drying procedure. The resultant CSA composites possess micro/mesoporous structure and hydrophobic surface. The adsorption and desorption performance of benzene on carbon-silica aerogel composite (CSA-2) under static and dynamic conditions were investigated, comparing with pure silica aerogel (CSA-0) and microporous activated carbon (AC). It was found that CSA-2 has high affinity towards aromatic molecules and fast adsorption kinetics. Excellent performance of dynamic adsorption and desorption observed on CSA-2 is related to its higher adsorption capacity than CSA-0 and less mass transfer resistance than AC, arising from the well-developed microporosity and open foam mesostructure in the CSA composites. Copyright © 2011 Elsevier B.V. All rights reserved.

The biocompatability of mesoporous inorganic-organic hybrid resin films with ionic and hydrophilic characteristics.

PubMed

Kim, Gahee; Hong, Lan Young; Jung, Jungwoon; Kim, Dong-Pyo; Kim, Heesoo; Kim, Ik Jung; Kim, Jung Ran; Ree, Moonhor

2010-03-01

New mesoporous silicate-titania resin systems hybridized with 4,5-dihydroxy-m-benzenedisulfonic acid and poly(ethylene glycol)-dimethacrylate component were developed. These inorganic-organic hybrid resins were found to reveal highly controlled ionic and hydrophilic surface with excellent durability and adhesion onto various substrates. The resin films revealed high resistance to nonspecific adsorption of fibrinogen and to adherence by several bacterial pathogens such as Escherichia coli, Staphylococcus aureus, Staphylococcus epidermidis and Enterococcus faecalis. Furthermore, excellent biocompatibility of the developed resins was proved by both HEp-2 cell adhesion in vitro and subcutaneous implantation in mice. The inorganic-organic hybrid resins are strongly promising for biomedical applications including biomedical devices and biosensors. Copyright 2009 Elsevier Ltd. All rights reserved.

A Novel Conductive Mesoporous Layer with a Dynamic Two-Step Deposition Strategy Boosts Efficiency of Perovskite Solar Cells to 20.

PubMed

Sun, Haoxuan; Deng, Kaimo; Zhu, Yayun; Liao, Min; Xiong, Jie; Li, Yanrong; Li, Liang

2018-05-22

Lead halide perovskite solar cells (PSCs) with the high power conversion efficiency (PCE) typically use mesoporous metal oxide nanoparticles as the scaffold and electron-transport layers. However, the traditional mesoporous layer suffers from low electron conductivity and severe carrier recombination. Here, antimony-doped tin oxide nanorod arrays are proposed as novel transparent conductive mesoporous layers in PSCs. Such a mesoporous layer improves the electron transport as well as light utilization. To resolve the common problem of uneven growth of perovskite on rough surface, the dynamic two-step spin coating strategy is proposed to prepare highly smooth, dense, and crystallized perovskite films with micrometer-scale grains, largely reducing the carrier recombination ratio. The conductive mesoporous layer and high-quality perovskite film eventually render the PSC with a remarkable PCE of 20.1% with excellent reproducibility. These findings provide a new avenue to further design high-efficiency PSCs from the aspect of carrier transport and recombination. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Catalytic properties of mesoporous Al–La–Mn oxides prepared via spray pyrolysis

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kim, Goun; Jung, Kyeong Youl; Lee, Choul-Ho

Highlights: • Al–La–Mn oxides were prepared using spray pyrolysis. • Al–La–Mn oxides exhibit large and uniform pore sizes. • Mesoporous Al–La–Mn oxides were compared with those prepared by conventional precipitation. • Mesoporous Al–La–Mn oxides show superior activity in decomposition of hydrogen peroxide. - Abstract: Mesoporous Al–La–Mn oxides are prepared via spray pyrolysis and are applied to the catalytic decomposition of hydrogen peroxide. The characteristics of the mesoporous Al–La–Mn oxides are examined using N{sub 2} adsorption, X-ray diffraction, and X-ray fluorescence measurements. The surface area and pore size of the Al–La–Mn oxides prepared via spray pyrolysis are larger than those ofmore » the Al–La–Mn oxides prepared using a precipitation method. The catalytic performance of the materials during the decomposition of hydrogen peroxide is examined in a pulse-injection reactor. It is confirmed that the mesoporous Al–La–Mn oxides prepared via spray pyrolysis exhibit higher catalytic activity and stability in the decomposition of hydrogen peroxide than Al–La–Mn oxides prepared using a conventional precipitation method.« less

Electrorheological behavior of copper phthalocyanine-doped mesoporous TiO2 suspensions.

PubMed

Di, Kai; Zhu, Yihua; Yang, Xiaoling; Li, Chunzhong

2006-02-15

A type of anhydrous electrorheological (ER) material of copper phthalocyanine (CuPC)-doped mesoporous TiO2 was synthesized by in situ micelle-assisted incorporation CuPC during mesoporous TiO2 synthesis. TEM, XRD and the nitrogen adsorption-desorption isotherms demonstrated that the material had mesoporous structure and an anatase framework. The ER behavior of the suspensions of CuPC-doped mesoporous TiO2 in silicone oil with the different volume fractions was investigated under an applied electric field. It is found that the suspensions showed visible electrorheological behavior which were compared with that of pure TiO2. The dopants of CuPC molecules within the mesochannel of TiO2 mesoporous sieve improved the conductivity of the particles and produced a proper conductivity of approximately 10(-7) S m(-1). Dielectric spectra of the ER fluid were measured to examine the peak of epsilon'' should appear in the frequency range of 10(2)-10(5) Hz and have a large Deltaepsilon' in this frequency range. Therefore, the both properties may make a conjunct effect on electrorheological behavior.

Design and functionalization of photocatalytic systems within mesoporous silica.

PubMed

Qian, Xufang; Fuku, Kojirou; Kuwahara, Yasutaka; Kamegawa, Takashi; Mori, Kohsuke; Yamashita, Hiromi

2014-06-01

In the past decades, various photocatalysts such as TiO2, transition-metal-oxide moieties within cavities and frameworks, or metal complexes have attracted considerable attention in light-excited catalytic processes. Owing to high surface areas, transparency to UV and visible light as well as easily modified surfaces, mesoporous silica-based materials have been widely used as excellent hosts for designing efficient photocatalytic systems under the background of environmental remediation and solar-energy utilization. This Minireview mainly focuses on the surface-chemistry engineering of TiO2/mesoporous silica photocatalytic systems and fabrication of binary oxides and nanocatalysts in mesoporous single-site-photocatalyst frameworks. Recently, metallic nanostructures with localized surface plasmon resonance (LSPR) have been widely studied in catalytic applications harvesting light irradiation. Accordingly, silver and gold nanostructures confined in mesoporous silica and their corresponding catalytic activity enhanced by the LSPR effect will be introduced. In addition, the integration of metal complexes within mesoporous silica materials for the construction of functional inorganic-organic supramolecular photocatalysts will be briefly described. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Mesoporous CLEAs-silica composite microparticles with high activity and enhanced stability

PubMed Central

Cui, Jiandong; Jia, Shiru; Liang, Longhao; Zhao, Yamin; Feng, Yuxiao

2015-01-01

A novel enzyme immobilization approach was used to generate mesoporous enzymes-silica composite microparticles by co-entrapping gelatinized starch and cross-linked phenylalanine ammonia lyase (PAL) aggregates (CLEAs) containing gelatinized starch into biomemitic silica and subsequently removing the starch by α-amylase treatment. During the preparation process, the gelatinzed starch served as a pore-forming agent to create pores in CLEAs and biomimetic silica. The resulting mesoporous CLEAs-silica composite microparticles exhibited higher activity and stability than native PAL, conventional CLEAs, and PAL encapsulated in biomimetic silica. Furthermore, the mesoporous CLEAs-silica composite microparticles displayed good reusability due to its suitable size and mechanical properties, and had excellent stability for storage. The superior catalytic performances were attributed to the combinational unique structure from the intra-cross-linking among enzyme aggregates and hard mesoporous silica shell, which not only decreased the enzyme-support negative interaction and mass-transfer limitations, but also improved the mechanical properties and monodispersity. This approach will be highly beneficial for preparing various bioactive mesoporous composites with excellent catalytic performance. PMID:26374188

Mesoporous carbon incorporated metal oxide nanomaterials as supercapacitor electrodes.

PubMed

Jiang, Hao; Ma, Jan; Li, Chunzhong

2012-08-08

Supercapacitors have attracted huge attention in recent years as they have the potential to satisfy the demand of both huge energy and power density in many advanced technologies. However, poor conductivity and cycling stability remains to be the major challenge for its widespread application. Various strategies have been developed for meeting the ever-increasing energy and power demands in supercapacitors. This Research News article aims to review recent progress in the development of mesoporous carbon incorporated metal oxide nanomaterials, especially metal oxide nanoparticles confined in ordered mesoporous carbon and 1D metal oxides coated with a layer of mesoporous carbon for high-performance supercapacitor applications. In addition, a recent trend in supercapacitor development - hierarchical porous graphitic carbons (HPGC) combining macroporous cores, mesoporous walls, and micropores as an excellent support for metal oxides - is also discussed.

Controllable synthesis of mesoporous carbon nanospheres and Fe-N/carbon nanospheres as efficient oxygen reduction electrocatalysts

NASA Astrophysics Data System (ADS)

Wei, Jing; Liang, Yan; Zhang, Xinyi; Simon, George P.; Zhao, Dongyuan; Zhang, Jin; Jiang, Sanping; Wang, Huanting

2015-03-01

The synthesis of mesoporous carbon nanospheres (MCNs), especially with diameters below 200 nm remains a great challenge due to weak interactions between the carbon precursors and soft templates, as well as the uncontrollable cross-linking rate of carbon precursors. Herein, we demonstrate a simple acid-assisted, hydrothermal synthesis approach to synthesizing such uniform MCNs with well controlled diameters ranging from 20 to 150 nm under highly acidic conditions (2 M HCl). Both the carbon precursor and the template are partly protonated under such conditions and show additional Coulombic interactions with chloride ions (acts as mediators). This kind of enhanced interaction is similar to that of the ``I+X-S+'' mechanism in the synthesis of mesoporous metal oxide, which can effectively retard the cross-linking rate of resol molecules and avoid macroscopic phase separation during the hydrothermal synthesis. Due to their uniform spherical morphology, small diameter, and high surface areas, MCNs can be modified with Fe and N species via impregnation of cheap precursors (ferric nitrate and dicyandiamide), which are further converted into nonprecious electrocatalysts for oxygen reduction reactions. The resulting Fe-N/MCNs exhibit high catalytic activities, long-term stability and improved methanol tolerance under alkaline conditions, which can be potentially used in direct methanol fuel cells and metal-air batteries.The synthesis of mesoporous carbon nanospheres (MCNs), especially with diameters below 200 nm remains a great challenge due to weak interactions between the carbon precursors and soft templates, as well as the uncontrollable cross-linking rate of carbon precursors. Herein, we demonstrate a simple acid-assisted, hydrothermal synthesis approach to synthesizing such uniform MCNs with well controlled diameters ranging from 20 to 150 nm under highly acidic conditions (2 M HCl). Both the carbon precursor and the template are partly protonated under such conditions and show additional Coulombic interactions with chloride ions (acts as mediators). This kind of enhanced interaction is similar to that of the ``I+X-S+'' mechanism in the synthesis of mesoporous metal oxide, which can effectively retard the cross-linking rate of resol molecules and avoid macroscopic phase separation during the hydrothermal synthesis. Due to their uniform spherical morphology, small diameter, and high surface areas, MCNs can be modified with Fe and N species via impregnation of cheap precursors (ferric nitrate and dicyandiamide), which are further converted into nonprecious electrocatalysts for oxygen reduction reactions. The resulting Fe-N/MCNs exhibit high catalytic activities, long-term stability and improved methanol tolerance under alkaline conditions, which can be potentially used in direct methanol fuel cells and metal-air batteries. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr00331h

Acid-base equilibria inside amine-functionalized mesoporous silica.

PubMed

Yamaguchi, Akira; Namekawa, Manato; Kamijo, Toshio; Itoh, Tetsuji; Teramae, Norio

2011-04-15

Acid-base equilibria and effective proton concentration inside a silica mesopore modified with a trimethyl ammonium (TMAP) layer were studied by steady-state fluorescence experiments. The mesoporous silica with a dense TMAP layer (1.4 molecules/nm(2)) was prepared by a post grafting of N-trimethoxysilylpropyl-N,N,N-trimethylammonium at surfactant-templated mesoporous silica (diameter of silica framework =3.1 nm). The resulting TMAP-modified mesoporous silica strongly adsorbed of anionic fluorescence indicator dyes (8-hydroxypyrene-1,3,6-trisulfonate (pyranine), 8-aminopyrene-1,3,6-trisulfonate (APTS), 5,10,15,20-tetraphenyl-21H,23H-porphinetetrasulfonic acid disulfuric acid (TPPS), 2-naphthol-3,6-disulfonate (2NT)) and fluorescence excitation spectra of these dyes within TMAP-modified mesoporous silica were measured by varying the solution pH. The fluorescence experiments revealed that the acid-base equilibrium reactions of all pH indicator dyes within the TMAP-modified silica mesopore were quite different from those in bulk water. From the analysis of the acid-base equilibrium of pyranine, the following relationships between solution pH (pH(bulk)) and the effective proton concentration inside the pore (pH(pore)) were obtained: (1) shift of pH(pore) was 1.8 (ΔpH(pore)=1.8) for the pH(bulk) change from 2.1 to 9.1 (ΔpH(bulk)=7.0); (2) pH(pore) was not simply proportional to pH(bulk); (3) the inside of the TMAP-modified silica mesopore was suggested to be in a weak acidic or neutral condition when pH(bulk) was changed from 2.0 to 9.1. Since these relationships between pH(bulk) and pH(pore) could explain the acid-base equilibria of other pH indicator dyes (APTS, TPPS, 2NT), these relationships were inferred to describe the effective proton concentration inside the TMAP-modified silica mesopore. © 2011 American Chemical Society

Solar hydrogen and solar electricity using mesoporous materials

NASA Astrophysics Data System (ADS)

Mahoney, Luther

The development of cost-effective materials for effective utilization of solar energy is a major challenge for solving the energy problems that face the world. This thesis work relates to the development of mesoporous materials for solar energy applications in the areas of photocatalytic water splitting and the generation of electricity. Mesoporous materials were employed throughout the studies because of their favorable physico-chemical properties such as high surface areas and large porosities. The first project was related to the use of a cubic periodic mesoporous material, MCM-48. The studies showed that chromium loading directly affected the phase of mesoporous silica formed. Furthermore, within the cubic MCM-48 structure, the loading of polychromate species determined the concentration of solar hydrogen produced. In an effort to determine the potential of mesoporous materials, titanium dioxide was prepared using the Evaporation-Induced Self-Assembly (EISA) synthetic method. The aging period directly determined the amount of various phases of titanium dioxide. This method was extended for the preparation of cobalt doped titanium dioxide for solar simulated hydrogen evolution. In another study, metal doped systems were synthesized using the EISA procedure and rhodamine B (RhB) dye sensitized and metal doped titania mesoporous materials were evaluated for visible light hydrogen evolution. The final study employed various mesoporous titanium dioxide materials for N719 dye sensitized solar cell (DSSC) materials for photovoltaic applications. The materials were extensively characterized using powder X-ray diffraction (XRD), nitrogen physisorption, diffuse reflectance spectroscopy (DRS), UV-Vis spectroscopy, Fourier-Transform-Infrared Spectroscopy (FT-IR), Raman spectroscopy, chemisorption, photoluminescence (PL), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). In addition, photoelectrochemical measurements were completed using current-voltage (I-V) curves, external quantum efficiency (EQE) curves, electrochemical impedance spectroscopy (EIS), and transient spectroscopy. The thesis work presented provides a better understanding of the role of mesoporous materials for solar hydrogen and solar electricity production.

Structural and diffusion characterizations of steam-stable mesostructured zeolitic UL-ZSM-5 materials.

PubMed

Vinh-Thang, Hoang; Huang, Qinglin; Ungureanu, Adrian; Eić, Mladen; Trong-On, Do; Kaliaguine, Serge

2006-05-09

A series of mesoporous UL-ZSM-5 materials (Si/Al = 50) with different micro- and mesoporosity as well as crystallinity was prepared following the procedure proposed in one of our recent studies (Trong-On, D.; Kaliaguine, S. Angew. Chem. Int. Ed. 2001, 40, 3248-3251. Trong-On, D.; Kaliaguine, S. U.S. Patent 6,669,924, B1, 2003). These materials have zeolitic structure in the form of nanoparticles intergrown in the walls of the amorphous wormhole-like aluminosilicate mesopores of Al-Meso-50, which was used as a precursor in the synthesis. The structure, crystallinity, and textural properties of the synthesized materials, as well as a reference ZSM-5 zeolite sample, were determined by X-ray diffraction (XRD), transmission electron microscopy (TEM)/scanning electron microscoy (SEM) analyses, Fourier transform infrared spectroscopy (FTIR), 27Al magic angle spinning (MAS) nuclear magnetic resonance (NMR), and nitrogen adsorption/desorption techniques. The acid properties were examined by FTIR of adsorbed pyridine. UL-ZSM-5 materials were shown to be highly hydrothermally stable. The diffusion of two C7 hydrocarbons, i.e., n-heptane and toluene, in four UL-ZSM-5 materials with different microporosities, related acidities, and crystallinities were investigated using the zero-length column (ZLC) method. Furthermore, the wormhole-like mesostructured aluminosilicate precursor (Al-Meso-50) and a reference MFI zeolite sample were also investigated using the same technique. A theoretical model considering a combination of mesopore diffusion (with surface slip in the main channels) with an activated, mainly surface diffusion mechanism in the intrawall biporous structure, was proposed and employed to interpret the experimental ZLC results. A classical Knudsen type of diffusion was replaced by an activated surface slip type of diffusion mechanism in the mesopores. The transport of n-heptane in UL-ZSM-5 materials was found to be mainly controlled by mesopore diffusion in the main-channel structure, while that of toluene was dominated by the intrawall diffusion process. Diffusion activation energies of n-heptane are about 2 times higher in comparison to toluene, which has a larger kinetic diameter. The main mesopore channel structure seems to appreciably contribute to the overall mass transport. Furthermore, the effect of hydrothermal treatment (20% steam at 800 degrees C for 24 h) on the diffusion of these two sorbates on UL-ZSM-5 materials was also evaluated.

Development of mesoporous silica-based nanoparticles with controlled release capability for cancer therapy☆

PubMed Central

Mekaru, Harutaka; Lu, Jie; Tamanoi, Fuyuhiko

2015-01-01

Nanoparticles that respond to internal and external stimuli to carry out controlled release of anticancer drugs have been developed. In this review, we focus on the development of mesoporous silica based nanoparticles, as this type of materials provides a relatively stable material that is amenable to various chemical modifications. We first provide an overview of various designs employed to construct MSN-based controlled release systems. These systems respond to internal stimuli such as pH, redox state and the presence of biomolecules as well as to external stimuli such as light and magnetic field. They are at a different stage of development; depending on the system, their operation has been demonstrated in aqueous solution, in cancer cells or in animal models. Efforts to develop MSNs with multi-functionality will be discussed. Safety and biodegradation of MSNs, issues that need to be overcome for clinical development of MSNs, will be discussed. Advances in the synthesis of mechanized theranostic nanoparticles open up the possibility to start envisioning future needs for medical equipment. PMID:26434537

Critical aspects in the production of periodically ordered mesoporous titania thin films.

PubMed

Soler-Illia, Galo J A A; Angelomé, Paula C; Fuertes, M Cecilia; Grosso, David; Boissiere, Cedric

2012-04-21

Periodically ordered mesoporous titania thin films (MTTF) present a high surface area, controlled porosity in the 2-20 nm pore diameter range and an amorphous or crystalline inorganic framework. These materials are nowadays routinely prepared by combining soft chemistry and supramolecular templating. Photocatalytic transparent coatings and titania-based solar cells are the immediate promising applications. However, a wealth of new prospective uses have emerged on the horizon, such as advanced catalysts, perm-selective membranes, optical materials based on plasmonics and photonics, metamaterials, biomaterials or new magnetic nanocomposites. Current and novel applications rely on the ultimate control of the materials features such as pore size and geometry, surface functionality and wall structure. Even if a certain control of these characteristics has been provided by the methods reported so far, the needs for the next generation of MTTF require a deeper insight in the physical and chemical processes taking place in their preparation and processing. This article presents a critical discussion of these aspects. This discussion is essential to evolve from know-how to sound knowledge, aiming at a rational materials design of these fascinating systems.

Tri-metallic PtPdAu mesoporous nanoelectrocatalysts.

PubMed

Li, Chunjie; Wang, Hongjing; Li, Yinghao; Yu, Hongjie; Yin, Shuli; Xue, Hairong; Li, Xiaonian; Xu, You; Wang, Liang

2018-06-22

The design of mesoporous materials with multi-metallic compositions is highly important for various electrocatalytic applications. In this paper, we demonstrate an efficient method to directly fabricate tri-metallic PtPdAu mesoporous nanoparticles (PtPdAu MNs) in a high yield, which is simply performed by heating treatment of the reaction mixture aqueous solution at 40 °C for 4 h. Profiting from its mesoporous structure and multi-metallic components, the as-prepared PtPdAu MNs exhibit enhanced electrocatalytic activities toward both methanol oxidation reaction and oxygen reduction reaction in comparison with bi-metallic PtPd MNs and commercial Pt/C catalyst.

A mini review of designed mesoporous materials for energy-storage applications: from electric double-layer capacitors to hybrid supercapacitors.

PubMed

Lim, Eunho; Jo, Changshin; Lee, Jinwoo

2016-04-21

In recent years, porous materials have attracted significant attention in various research fields because of their structural merits. In particular, well-designed mesoporous structures with two- or three-dimensionally interconnected pores have been recognized as electrode materials of particular interest for achieving high-performance electrochemical capacitors (ECs). In this mini review, recent progress in the design of mesoporous electrode materials for ECs, from electric double-layer capacitors (EDLCs) and pseudocapacitors (PCs) to hybrid supercapacitors (HSCs), and research challenges for the development of new mesoporous electrode materials has been discussed.

A mini review of designed mesoporous materials for energy-storage applications: from electric double-layer capacitors to hybrid supercapacitors

NASA Astrophysics Data System (ADS)

Lim, Eunho; Jo, Changshin; Lee, Jinwoo

2016-04-01

In recent years, porous materials have attracted significant attention in various research fields because of their structural merits. In particular, well-designed mesoporous structures with two- or three-dimensionally interconnected pores have been recognized as electrode materials of particular interest for achieving high-performance electrochemical capacitors (ECs). In this mini review, recent progress in the design of mesoporous electrode materials for ECs, from electric double-layer capacitors (EDLCs) and pseudocapacitors (PCs) to hybrid supercapacitors (HSCs), and research challenges for the development of new mesoporous electrode materials has been discussed.

Tri-metallic PtPdAu mesoporous nanoelectrocatalysts

NASA Astrophysics Data System (ADS)

Li, Chunjie; Wang, Hongjing; Li, Yinghao; Yu, Hongjie; Yin, Shuli; Xue, Hairong; Li, Xiaonian; Xu, You; Wang, Liang

2018-06-01

The design of mesoporous materials with multi-metallic compositions is highly important for various electrocatalytic applications. In this paper, we demonstrate an efficient method to directly fabricate tri-metallic PtPdAu mesoporous nanoparticles (PtPdAu MNs) in a high yield, which is simply performed by heating treatment of the reaction mixture aqueous solution at 40 °C for 4 h. Profiting from its mesoporous structure and multi-metallic components, the as-prepared PtPdAu MNs exhibit enhanced electrocatalytic activities toward both methanol oxidation reaction and oxygen reduction reaction in comparison with bi-metallic PtPd MNs and commercial Pt/C catalyst.

Mesoporous Prussian blue analogues: template-free synthesis and sodium-ion battery applications.

PubMed

Yue, Yanfeng; Binder, Andrew J; Guo, Bingkun; Zhang, Zhiyong; Qiao, Zhen-An; Tian, Chengcheng; Dai, Sheng

2014-03-17

The synthesis of mesoporous Prussian blue analogues through a template-free methodology and the application of these mesoporous materials as high-performance cathode materials in sodium-ion batteries is presented. Crystalline mesostructures were produced through a synergistically coupled nanocrystal formation and aggregation mechanism. As cathodes for sodium-ion batteries, the Prussian blue analogues all show a reversible capacity of 65 mA h g-1 at low current rate and show excellent cycle stability. The reported method stands as an environmentally friendly and low-cost alternative to hard or soft templating for the fabrication of mesoporous materials.

A chemical approach to perovskite solar cells: control of electron-transporting mesoporous TiO2 and utilization of nanocarbon materials.

PubMed

Umeyama, Tomokazu; Imahori, Hiroshi

2017-11-21

Over the past several years, organometal halide perovskite solar cells (PSCs) have attracted considerable interest from the scientific research community because of their potential as promising photovoltaic devices for use in renewable energy production. To date, high power conversion efficiencies (PCEs) of more than 20% have been primarily achieved with mesoscopic-structured PSCs, where a mesoporous TiO 2 (mTiO 2 ) layer is incorporated as an electron-transporting mesoporous scaffold into the perovskite crystal, in addition to a compact TiO 2 (cTiO 2 ) as an electron-transporting layer (ETL). In this Perspective, we first summarize recent research on the preparation strategies of the mTiO 2 layer with a high electron transport capability by facile sol-gel methods instead of the conventional nanoparticle approach. The importance of the control of the pore size and grain boundaries of the mTiO 2 in achieving high PCEs for PSCs is discussed. In addition, an alternative method to improve the electron transport in the mTiO 2 layer via the incorporation of highly conductive nanocarbon materials, such as two-dimensional (2D) graphene and one-dimensional (1D) carbon nanotubes, is also summarized. Finally, we highlight the utilization of zero-dimensional (0D) nanocarbon, i.e., fullerenes, as an n-type semiconducting material in mesostructure-free planar PSCs, which avoids high-temperature sintering during the fabrication of an ETL.

Preparation and controlled drug delivery applications of mesoporous silica polymer nanocomposites through the visible light induced surface-initiated ATRP

NASA Astrophysics Data System (ADS)

Huang, Long; Liu, Meiying; Mao, Liucheng; Xu, Dazhuang; Wan, Qing; Zeng, Guangjian; Shi, Yingge; Wen, Yuanqing; Zhang, Xiaoyong; Wei, Yen

2017-08-01

The mesoporous materials with large pore size, high specific surface area and high thermal stability have been widely utilized in a variety of fields ranging from environmental remediation to separation and biomedicine. However, surface modification of these silica nanomaterials is required to endow novel properties and achieve better performance for most of these applications. In this work, a new method has been established for surface modification of mesoporous silica nanoparticles (MSNs) that relied on the visible light induced atom transfer radical polymerization (ATRP). In the procedure, the copolymers composited with itaconic acid (IA) and poly(ethylene glycol)methyl acrylate (PEGMA) were grafted from MSNs using IA and PEGMA as the monomers and 10-Phenylphenothiazine(PTH) as the organic catalyst. The successful preparation of final polymer nanocomposites (named as MSNs-NH2-poly(IA-co-PEGMA)) were evidenced by a series of characterization techniques. More importantly, the anticancer agent cisplatin can be effectively loaded on MSNs-NH2-poly(IA-co-PEGMA) and controlled release it from the drug-loading composites with pH responsive behavior. As compared with conventional ATRP, the light induced surface-initiated ATRP could also be utilized for preparation of various silica polymer nanocomposites under rather benign conditions (e.g. absent of transition metal ions, low polymerization temperature and short polymerization time). Taken together, we have developed a rather promising strategy method for fabrication of multifunctional MSNs-NH2-poly(IA-co-PEGMA) with great potential for biomedical applications.

Fluorescence imaging of antibiotic clofazimine encapsulated within mesoporous silica particle carriers: relevance to drug delivery and the effect on its release kinetics.

PubMed

Angiolini, Lorenzo; Valetti, Sabrina; Cohen, Boiko; Feiler, Adam; Douhal, Abderrazzak

2018-05-03

We report on the encapsulation of the antibiotic clofazimine (CLZ) within the pores of mesoporous silica particles having hydrophilic (CBET value of 137) and more hydrophobic (CBET value of 94 after calcination at 600 °C) surfaces. We studied the effect of pH on the released amount of CLZ in aqueous solutions and observed a maximum at pH 4.1 in correlation with the solubility of the drug. Less release of the drug was observed from the more hydrophobic particles which was attributed to a difference in the affinity of the drug to the carrier particles. Fluorescence lifetime imaging microscopy, emission spectra, and fluorescence lifetimes of single drug loaded particles provided detailed understanding and new knowledge of the physical form of the encapsulated drug and the distribution within the particles. The distribution of CLZ within the particles was independent of the surface chemistry of the particles. The confirmation of CLZ molecules as monomers or aggregates was revealed by controlled removal of the drug with solvent. Additionally, the observed optical "halo effect" in the fluorescent images was interpreted in terms of specific quenching of high concentration of molecules. The emission lifetime experiments suggest stronger interaction of CLZ with the more hydrophobic particles, which is relevant to its release. The results reported in this work demonstrate that tuning the hydrophilicity/hydrophobicity of mesoporous silica particles can be used as a tool to control the release without impacting their loading ability.

Small-angle X-ray scattering (SAXS) studies of the structure of mesoporous silicas

NASA Astrophysics Data System (ADS)

Zienkiewicz-Strzałka, M.; Skibińska, M.; Pikus, S.

2017-11-01

Mesoporous ordered silica nanostructures show strong interaction with X-ray radiation in the range of small-angles. Small-angle X-ray scattering (SAXS) measurements based on the elastically scattered X-rays are important in analysis of condensed matter. In the case of mesoporous silica materials SAXS technique provides information on the distribution of electron density in the mesoporous material, in particular describing their structure and size of the unit cell as well as type of ordered structure and finally their parameters. The characterization of nanopowder materials, nanocomposites and porous materials by Small-Angle X-ray Scattering seems to be valuable and useful. In presented work, the SAXS investigation of structures from the group of mesoporous ordered silicates was performed. This work has an objective to prepare functional materials modified by noble metal ions and nanoparticles and using the small-angle X-ray scattering to illustrate their properties. We report the new procedure for describing mesoporous materials belonging to SBA-15 and MCM-41 family modified by platinum, palladium and silver nanoparticles, based on detailed analysis of characteristic peaks in the small-angle range of X-ray scattering. This procedure allows to obtained the most useful parameters for mesoporous materials characterization and their successfully compare with experimental measurements reducing the time and material consumption with good precision for particles and pores with a size below 10 nm.

Porous silica nanoparticles as carrier for curcumin delivery

NASA Astrophysics Data System (ADS)

Hartono, Sandy Budi; Hadisoewignyo, Lannie; Irawaty, Wenny; Trisna, Luciana; Wijaya, Robby

2018-04-01

Mesoporous silica nanoparticles (MSN) with large surface areas and pore volumes show great potential as drug and gene carriers. However, there are still some challenging issues hinders their clinical application. Many types of research in the use of mesoporous silica material for drug and gene delivery involving complex and rigorous procedures. A facile and reproducible procedure to prepare combined drug carrier is required. We investigated the effect of physiochemical parameters of mesoporous silica, including structural symmetry (cubic and hexagonal), particles size (micro size: 1-2 µm and nano size: 100 -300 nm), on the solubility and release profile of curcumin. Transmission Electron Microscopy, X-Ray Powder Diffraction, and Nitrogen sorption were used to confirm the synthesis of the mesoporous silica materials. Mesoporous silica materials with different mesostructures and size have been synthesized successfully. Curcumin has anti-oxidant, anti-inflammation and anti-virus properties which are beneficial to fight various diseases such as diabetic, cancer, allergic, arthritis and Alzheimer. Curcumin has low solubility which minimizes its therapeutic effect. The use of nanoporous material to carry and release the loaded molecules is expected to enhance curcumin solubility. Mesoporous silica materials with a cubic mesostructure had a higher release profile and curcumin solubility, while mesoporous silica materials with a particle size in the range of nano meter (100-300) nm also show better release profile and solubility.

Designed synthesis and stacking architecture of solid and mesoporous TiO(2) nanoparticles for enhancing the light-harvesting efficiency of dye-sensitized solar cells.

PubMed

Ahn, Ji Young; Moon, Kook Joo; Kim, Ji Hoon; Lee, Sang Hyun; Kang, Jae Wook; Lee, Hyung Woo; Kim, Soo Hyung

2014-01-22

We fabricated solid and mesoporous TiO2 nanoparticles (NPs) with relatively large primary sizes of approximately 200 nm via inorganic templates for aero-sol-gel and subsequent aqueous-washing processes. The amount of dye molecules adsorbed by the internal pores in the mesoporous TiO2 NPs was increased by creating the nanopores within the solid TiO2 NPs. Simultaneously, the light-scattering effect of the mesoporous TiO2 NPs fabricated by this approach was secured by maintaining their spherical shape and relatively large average size. By precisely accumulating the fabricated solid or mesoporous 200 nm diameter TiO2 NPs on top of a conventional 25 nm diameter TiO2 NP-based underlayer, we could systematically examine the effect of the solid and mesoporous TiO2 NPs on the photovoltaic performance of dye-sensitized solar cells (DSSCs). Consequently, the stacking architecture of the mesoporous TiO2 NP-based overlayer, which functioned as both a light-scattering and dye-supporting medium, on top of a conventional solid TiO2 NP-based underlayer in a DSSC photoelectrode (i.e., double-layer structures) was found to be very promising for significantly improving the photovoltaic properties of conventional solid TiO2 NP single-layer-based DSSCs.

Preparation of Carbon Nanotube/TiO2 Mesoporous Hybrid Photoanode with Iron Pyrite (FeS2) Thin Films Counter Electrodes for Dye-Sensitized Solar Cell

PubMed Central

Kilic, Bayram; Turkdogan, Sunay; Astam, Aykut; Ozer, Oguz Can; Asgin, Mansur; Cebeci, Hulya; Urk, Deniz; Mucur, Selin Pravadili

2016-01-01

Multi-walled carbon nanotube (MWCNT)/TiO2 mesoporous networks can be employed as a new alternative photoanode in dye-sensitized solar cells (DSSCs). By using the MWCNT/TiO2 mesoporous as photoanodes in DSSC, we demonstrate that the MWCNT/TiO2 mesoporous photoanode is promising alternative to standard FTO/TiO2 mesoporous based DSSC due to larger specific surface area and high electrochemical activity. We also show that iron pyrite (FeS2) thin films can be used as an efficient counter electrode (CE), an alternative to the conventional high cost Pt based CE. We are able to synthesis FeS2 nanostructures utilizing a very cheap and easy hydrothermal growth route. MWCNT/TiO2 mesoporous based DSSCs with FeS2 CE achieved a high solar conversion efficiency of 7.27% under 100 mW cm−2 (AM 1.5G 1-Sun) simulated solar irradiance which is considerably (slightly) higher than that of A-CNT/TiO2 mesoporous based DSSCs with Pt CE. Outstanding performance of the FeS2 CE makes it a very promising choice among the various CE materials used in the conventional DSSC and it is expected to be used more often to achieve higher photon-to-electron conversion efficiencies. PMID:27243374

Investigation of heterogeneous asymmetric dihydroxylation over OsO{sub 4}-(QN){sub 2}PHAL catalysts of functionalized bimodal mesoporous silica with ionic liquid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Qiu, Shenjie; Sun, Jihong, E-mail: jhsun@bjut.edu.cn; Li, Yuzhen

2011-08-15

Highlights: {yields} Functionalized bimodal mesoporous silica with MTMSPIm{sup +}Cl{sup -}. {yields} Mesoporous catalyst immobilized with OsO{sub 4}-(QN){sub 2}PHAL. {yields} Catalysts for asymmetric dihydroxylation reaction with high yield and enatioselectivity. {yields} Recyclable catalysts. -- Abstract: A novel synthesis of the functionalized bimodal mesoporous silica with ionic liquid (FBMMs) was performed. After grafting 1-methyl-3-(trimethoxysilyl)propylimidazolium chloride onto the surface of bimodal mesoporous silicas, 1,4-bis(9-O-quininyl)phthalazine ((QN){sub 2}-PHAL) and K{sub 2}Os(OH){sub 4}.2H{sub 2}O were immobilized onto the modified FBMMs by adsorption or ionic exchange methods, and then, the asymmetric dihydroxylation reaction was carried out by using solid catalysts. Techniques such as X-ray diffraction, Fourier Transformmore » Infrared spectroscopy, N{sub 2} adsorption and desorption were employed to characterize their structure and properties. The results showed that the mesoporous ordering degree of bimodal mesoporous silica decreased after functionalization and immobilization of OsO{sub 4}-(QN){sub 2}PHAL. Being very effective in asymmetric dihydroxylation with high yield and enantioselectivity, the prepared heterogeneous solid catalyst could be recycled for five times with little loss of enantioselectivity, with comparison of those results obtained in homophase system. Moreover, the effect of Osmium catalyst on asymmetric dihydroxylation was investigated.« less

Mesoporous silica nanoparticles supported copper(II) and nickel(II) Schiff base complexes: Synthesis, characterization, antibacterial activity and enzyme immobilization

NASA Astrophysics Data System (ADS)

Tahmasbi, Leila; Sedaghat, Tahereh; Motamedi, Hossein; Kooti, Mohammad

2018-02-01

Mesoporous silica nanoparticles (MSNs) were prepared by sol-gel method and functionalized with 3-aminopropyltriethoxysilane. Schiff base grafted mesoporous silica nanoparticle was synthesized by the condensation of 2-hydroxy-3-methoxybenzaldehyde and amine-functionalized MSNs. The latter material was then treated with Cu(II) and Ni(II) salts separately to obtain copper and nickel complexes anchored mesoporous composites. The newly prepared hybrid organic-inorganic nanocomposites have been characterized by several techniques such as FT-IR, LA-XRD, FE-SEM, TEM, EDS, BET and TGA. The results showed all samples have MCM-41 type ordered mesoporous structure and functionalization occurs mainly inside the mesopore channel. The presence of all elements in synthesized nanocomposites and the coordination of Schiff base via imine nitrogen and phenolate oxygen were confirmed. MSNs and all functionalized MSNs have uniform spherical nanoparticles with a mean diameter less than 100 nm. The as-synthesized mesoporous nanocomposites were investigated for antibacterial activity against Gram-positive (B. subtilis and S. aureus) and Gram-negative (E. coli and P. aeruginosa) bacteria, as carrier for gentamicin and also for immobilization of DNase, coagulase and amylase enzymes. MSN-SB-Ni indicated bacteriocidal effect against S.aureus and all compounds were found to be good carrier for gentamicin. Results of enzyme immobilization for DNase and coagulase and α-amylase revealed that supported metal complexes efficiently immobilized enzymes.

Influence of metal electrodes on the response of humidity sensors coated with mesoporous silica

NASA Astrophysics Data System (ADS)

Bearzotti, Andrea

2008-01-01

Interesting effects of different metal electrodes on the behaviour of mesoporous based humidity sensors have been observed and studied by chemical characterization and electric measurements. The devices were prepared on passivated silicon slices utilizing an interdigitated structure as contacts. For comparison, the response of a device implemented on an alumina substrate has been reported. A block copolymer Pluronic F-127 has been used as the organic template and has been partially removed from the films by thermal calcination. A thin film mesoporous membrane has been deposited by dip-coating on the substrates in a sol-gel solution containing non-ionic block copolymers. Silica mesostructured films have been produced using an evaporation induced self-assembling process. The films were calcined at 150 °C to obtain the best performances in terms of stability, hysteresis and reproducibility of the response. The performance of the sensor has been found to be dependent on the film preparation method, the used electrodes and the substrate when exposed to different contents of relative humidity. Electrical characterization was performed under vacuum and dark conditions to investigate the properties of the materials in the absence of interfering chemicals, while the sensory properties were obtained in a controlled environment.

Synthesis of rambutan-like MoS2/mesoporous carbon spheres nanocomposites with excellent performance for supercapacitors

NASA Astrophysics Data System (ADS)

Zhang, Shouchuan; Hu, Ruirui; Dai, Peng; Yu, Xinxin; Ding, Zongling; Wu, Mingzai; Li, Guang; Ma, Yongqing; Tu, Chuanjun

2017-02-01

A novel rambutan-like composite of MoS2/mesoporous carbon spheres were synthesized by a simple two-step hydrothermal and post-annealing approach via using glucose as C source and Na2MoO4·2H2O and thiourea as Mo and S sources. It is found that the morphology and electrochemical properties can be effectively controlled by the change of the weight ratio of coated MoS2 sheets to carbon spheres. When used as electrode material for supercapacitor, the hybrid MoS2/carbon spheres show a high specific capacity of 411 F/g at a current density of 1 A/g and 272 F/g at a high discharge current density of 10 A/g. The annealing treatment at 700 °C transformed the core carbon spheres into mesoporous ones, which served as the conduction network and favor the enhancement of the specific capacitance. In addition, the strain released during the charge/discharge process can be accommodated and the structural integrity can be kept, improving the cycling life. After 1000 cycles, the capacitance retention of the hybrid MoS2/carbon spheres is 93.2%.

Deliberate Design of TiO2 Nanostructures towards Superior Photovoltaic Cells.

PubMed

Sun, Ziqi; Liao, Ting; Sheng, Liyuan; Kou, Liangzhi; Kim, Jung Ho; Dou, Shi Xue

2016-08-01

TiO2 nanostructures are being sought after as flexibly utilizable building blocks for the fabrication of the mesoporous thin-film photoelectrodes that are the heart of the third-generation photovoltaic devices, such as dye-sensitized solar cells (DSSCs), quantum-dot-sensitized solar cells (QDSSCs), and the recently promoted perovskite-type solar cells. Here, we report deliberate tailoring of TiO2 nanostructures for superior photovoltaic cells. Morphology engineering of TiO2 nanostructures is realized by designing synthetic protocols in which the precursor hydrolysis, crystal growth, and oligomer self-organization are precisely controlled. TiO2 nanostructures in forms varying from isolated nanocubes, nanorods, and cross-linked nanorods to complex hierarchical structures and shape-defined mesoporous micro-/nanostructures were successfully synthesized. The photoanodes made from the shape-defined mesoporous TiO2 microspheres and nanospindles presented superior performances, owing to the well-defined overall shapes and the inner ordered nanochannels, which allow not only a high amount of dye uptake, but also improved visible-light absorption. This study provides a new way to seek an optimal synthetic protocol to meet the required functionality of the nanomaterials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effect of synthesis parameters on the geometry and dimensions of mesoporous hydroxyapatite nanoparticles in the presence of 1-dodecanethiol as a pore expander.

PubMed

Bakhtiari, L; Rezaie, H R; Javadpour, J; Erfan, M; Shokrgozar, M A

2015-08-01

Mesoporous hydroxyapatite with different pore diameters and pore volumes were synthesized by the self-assembly method using Cetyltrimethylammonium bromide (CTAB) as the cationic surfactant and 1-dodecanethiol as the pore expander at different micellization pHs, solvent types and surfactant concentrations. Results of field emission scanning electron microscopy (FESEM) showed a decrease in length/diameter ratio of rod-like particles by an increase in micellization pH and also a sphere to rod transition in morphology by an increase in CTAB concentration. Brunauer-Emmett-Teller (BET) surface area and Low angle X-ray diffraction analysis revealed that the optimized mesoporous hydroxyapatite with controlled pore structure can be obtained under basic micellization pH (about 12, pH of complete ionization of 1-dodecanethiol) by using water as the solvent and a high content of cationic surfactant. The results also show that micellization pH has a strong effect on pore structure and changing the pH can shift the mesostructure to a macroporous structure with morphological changes. Copyright © 2015 Elsevier B.V. All rights reserved.

Preparation and CO 2 adsorption properties of soft-templated mesoporous carbons derived from chestnut tannin precursors

DOE PAGES

Nelson, Kimberly M.; Mahurin, Shannon Mark; Mayes, Richard T.; ...

2015-10-09

This paper presents a soft templating approach for mesoporous carbon using the polyphenolic heterogeneous biomass, chestnut tannin, as the carbon precursor. By varying synthesis parameters such as tannin:surfactant ratio, cross-linker, reaction time and acid catalyst, the pore structure could be controllably modulated from lamellar to a more ordered hexagonal array. Carbonization at 600 °C under nitrogen produced a bimodal micro-mesoporous carbonaceous material exhibiting enhanced hydrogen bonding with the soft template, similar to that shown by soft-templating of phenolic-formaldehyde resins, allowing for a tailorable pore size. By utilizing the acidic nature of chestnut tannin (i.e. gallic and ellagic acid), hexagonal-type mesostructuresmore » were formed without the use of an acid catalyst. The porous carbon materials were activated with ammonia to increase the available surface area and incorporate nitrogen-containing functionality which led to a maximum CO 2 adsorption capacity at 1 bar of 3.44 mmol/g and 2.27 mmol/g at 0 °C and 25 °C, respectively. The ammonia-activated carbon exhibited multiple peaks in the adsorption energy distribution which indicates heterogeneity of adsorption sites for CO 2 capture.« less

Controllable Synthesis of Ordered Mesoporous Mo2C@Graphitic Carbon Core-Shell Nanowire Arrays for Efficient Electrocatalytic Hydrogen Evolution.

PubMed

Zhu, Jiahui; Yao, Yan; Chen, Zhi; Zhang, Aijian; Zhou, Mengyuan; Guo, Jun; Wu, Winston Duo; Chen, Xiao Dong; Li, Yanguang; Wu, Zhangxiong

2018-06-06

Mo 2 C is a possible substitute to Pt-group metals for electrocatalytic hydrogen evolution reaction (HER). Both support-free and carbon-supported Mo 2 C nanomaterials with improved HER performance have been developed. Herein, distinct from prior research, novel ordered mesoporous core-shell nanowires with Mo 2 C cores and ultrathin graphitic carbon (GC) shells are rationally synthesized and demonstrated to be excellent for HER. The synthesis is fulfilled via a hard-templating approach combining in situ carburization and localized carbon deposition. Phosphomolybdic acid confined in the SBA-15 template is first converted to MoO 2 , which is then in situ carburized to Mo 2 C nanowires with abundant surface defects. Simultaneously, GC layer (the thickness is down to ∼1.0 nm in most areas) is controlled to be locally deposited on the Mo 2 C surface because of its strong affinity with carbon and catalytic effect on graphitization. Removal of the template results in the Mo 2 C@GC core-shell nanowire arrays with the structural properties well-characterized. They exhibit excellent performance for HER with a low overpotential of 125 mV at 10 mA cm -2 , a small Tafel slope of 66 mV dec -1 , and an excellent stability in acidic electrolytes. The influences of several factors, especially the spatial configuration and relative contents of the GC and Mo 2 C components, on HER performance are elucidated with control experiments. The excellent HER performance of the mesoporous Mo 2 C@GC core-shell nanowire arrays originates from the rough Mo 2 C nanowires with diverse active sites and short charge-transfer paths and the ultrathin GC shells with improved surface area, electronic conductivity, and stabilizing effect on Mo 2 C.

Synthesis and characterization of mesoporous magnetic nanocomposites wrapped with chitosan gatekeepers for pH-sensitive controlled release of doxorubicin.

PubMed

Wu, Juan; Jiang, Wei; Shen, Yewen; Jiang, Wei; Tian, Renbing

2017-01-01

Multifunctional nanocarriers based on the Fe 3 O 4 nanoparticles core and mesoporous silica shell (mSiO 2 ) were synthesized for controlled drug release through magnetic targeting and pH-sensitive performances. The developed Fe 3 O 4 @mSiO 2 nanocarriers exhibited a suitable size (63nm) and good magnetic responsibility, doxorubicin (DOX) could be successfully loaded into the mesoporous of Fe 3 O 4 @mSiO 2 via electrostatic interaction, and the drug loading content and loading efficiency are 29.3% and 93.6%, respectively. The chitosan (CS) was employed to wrap the Fe 3 O 4 @mSiO 2 -DOX as the blocking agent to inhibit premature drug release, and the final CS/Fe 3 O 4 @mSiO 2 -DOX exhibited excellent pH-sensitivity, 86.1% DOX was released within 48h at pH4.0. Furthermore, all the release behaviors fit the Higuchi model very well and a purely diffusion-controlled process played a major role on DOX release from CS/Fe 3 O 4 @mSiO 2 -DOX. In addition, MTT assays in human liver hepatocellular carcinoma cells (HepG2) demonstrated that the CS/Fe 3 O 4 @mSiO 2 -DOX had high anti-tumor activity, while the Fe 3 O 4 @mSiO 2 nanocarriers were practically non-toxic. Thus, our results revealed that the CS/Fe 3 O 4 @mSiO 2 -DOX could play an important role in the development of intracellular delivery nanodevices for cancer therapy. Copyright © 2016 Elsevier B.V. All rights reserved.

Combined Spectroscopic and Calorimetric Studies to Reveal Absorption Mechanisms and Conformational Changes of Protein on Nanoporous Biomaterials

PubMed Central

Ahmadi, Saharnaz; Farokhi, Maryam; Padidar, Parisa; Falahati, Mojtaba

2015-01-01

In this study the effect of surface modification of mesoporous silica nanoparticles (MSNs) on its adsorption capacities and protein stability after immobilization of beta-lactoglobulin B (BLG-B) was investigated. For this purpose, non-functionalized (KIT-6) and aminopropyl-functionalized cubic Ia3d mesoporous silica ([n-PrNH2-KIT-6]) nanoparticles were used as nanoporous supports. Aminopropyl-functionalized mesoporous nanoparticles exhibited more potential candidates for BLG-B adsorption and minimum BLG leaching than non-functionalized nanoparticles. It was observed that the amount of adsorbed BLG is dependent on the initial BLG concentration for both KIT-6 and [n-PrNH2-KIT-6] mesoporous nanoparticles. Also larger amounts of BLG-B on KIT-6 was immobilized upon raising the temperature of the medium from 4 to 55 °C while such increase was undetectable in the case of immobilization of BLG-B on the [n-PrNH2-KIT-6]. At temperatures above 55 °C the amounts of adsorbed BLG on both studied nanomaterials decreased significantly. By Differential scanning calorimetry or DSC analysis the heterogeneity of the protein solution and increase in Tm may indicate that immobilization of BLG-B onto the modified KIT-6 results in higher thermal stability compared to unmodified one. The obtained results provide several crucial factors in determining the mechanism(s) of protein adsorption and stability on the nanostructured solid supports and the development of engineered nano-biomaterials for controlled drug-delivery systems and biomimetic interfaces for the immobilization of living cells. PMID:26230687

Mesoporous orthorhombic Nb2O5 nanofibers as pseudocapacitive electrodes with ultra-stable Li storage characteristics

NASA Astrophysics Data System (ADS)

Cheong, Jun Young; Jung, Ji-Won; Youn, Doo-Young; Kim, Chanhoon; Yu, Sunmoon; Cho, Su-Ho; Yoon, Ki Ro; Kim, Il-Doo

2017-08-01

Ultra-stable pseudocapacitive electrodes for lithium-ion batteries (LIBs) are increasing in demand as highly sustainable energy storage system with excellent charge transport is important. The establishment of facile, controllable, and scalable synthesis of pseudocapacitive electrode materials is an attractive solution to realize such objectives. Here, we have successfully fabricated mesoporous orthorhombic Nb2O5 nanofibers (m-T-Nb2O5 NFs) by simple single-spinneret electrospinning followed by calcination at 600 °C. As-formed m-T-Nb2O5 NFs exhibit high surface area (23.7 m2 g-1) and a number of mesopores in the vacant sites where organic polymer was once decomposed. Such rationally designed m-T-Nb2O5-NFs allow facile Li ion and electron transport, with pseudocapacitive behavior. Arising from the high surface area coupled with mesopores in-between the Nb2O5 nanograins, it exhibits ultra-long cycle retention (a capacity of ∼160 mAh g-1 at 500 mA g-1 after 2000 cycles and ∼88 mAh g-1 at 3000 mA g-1 after 5000 cycles) and higher rate capability (∼70 mAh g-1 at 5000 mA g-1). Such cycle retention characteristics of m-T-Nb2O5-NFs are at least 100-fold slower capacity decay compared with previously reported one-dimensional (1D) Nb2O5 nanostructures and even superior or comparable to recently reported Nb2O5-graphene composite materials.

Highly sensitive biofunctionalized mesoporous electrospun TiO(2) nanofiber based interface for biosensing.

PubMed

Mondal, Kunal; Ali, Md Azahar; Agrawal, Ved V; Malhotra, Bansi D; Sharma, Ashutosh

2014-02-26

The surface modified and aligned mesoporous anatase titania nanofiber mats (TiO2-NF) have been fabricated by electrospinning for esterified cholesterol detection by electrochemical technique. The electrospinning and porosity of mesoporous TiO2-NF were controlled by use of polyvinylpyrrolidone (PVP) as a sacrificial carrier polymer in the titanium isopropoxide precursor. The mesoporous TiO2-NF of diameters ranging from 30 to 60 nm were obtained by calcination at 470 °C and partially aligned on a rotating drum collector. The functional groups such as -COOH, -CHO etc. were introduced on TiO2-NF surface via oxygen plasma treatment making the surface hydrophilic. Cholesterol esterase (ChEt) and cholesterol oxidase (ChOx) were covalently immobilized on the plasma treated surface of NF (cTiO2-NF) via N-ethyl-N0-(3-dimethylaminopropyl carbodiimide) and N-hydroxysuccinimide (EDC-NHS) chemistry. The high mesoporosity (∼61%) of the fibrous film allowed enhanced loading of the enzyme molecules in the TiO2-NF mat. The ChEt-ChOx/cTiO2-NF-based bioelectrode was used to detect esterified cholesterol using electrochemical technique. The high aspect ratio, surface area of aligned TiO2-NF showed excellent voltammetric and catalytic response resulting in improved detection limit (0.49 mM). The results of response studies of this biosensor show excellent sensitivity (181.6 μA/mg dL(-1)/cm(2)) and rapid detection (20 s). This proposed strategy of biomolecule detection is thus a promising platform for the development of miniaturized device for biosensing applications.

Recent Advance on Mesoporous Silica Nanoparticles-Based Controlled Release System: Intelligent Switches Open up New Horizon

PubMed Central

Sun, Ruijuan; Wang, Wenqian; Wen, Yongqiang; Zhang, Xueji

2015-01-01

Mesoporous silica nanoparticle (MSN)-based intelligent transport systems have attracted many researchers’ attention due to the characteristics of uniform pore and particle size distribution, good biocompatibility, high surface area, and versatile functionalization, which have led to their widespread application in diverse areas. In the past two decades, many kinds of smart controlled release systems were prepared with the development of brilliant nano-switches. This article reviews and discusses the advantages of MSN-based controlled release systems. Meanwhile, the switching mechanisms based on different types of stimulus response are systematically analyzed and summarized. Additionally, the application fields of these devices are further discussed. Obviously, the recent evolution of smart nano-switches promoted the upgrading of the controlled release system from the simple “separated” switch to the reversible, multifunctional, complicated logical switches and selective switches. Especially the free-blockage switches, which are based on hydrophobic/hydrophilic conversion, have been proposed and designed in the last two years. The prospects and directions of this research field are also briefly addressed, which could be better used to promote the further development of this field to meet the needs of mankind. PMID:28347110

Synthesis and energy applications of mesoporous titania thin films

NASA Astrophysics Data System (ADS)

Islam, Syed Z.

The optical and electronic properties of TiO2 thin films provide tremendous opportunities in several applications including photocatalysis, photovoltaics and photoconductors for energy production. Despite many attractive features of TiO2, critical challenges include the innate inability of TiO2 to absorb visible light and the fast recombination of photoexcited charge carriers. In this study, mesoporous TiO2 thin films are modified by doping using hydrogen and nitrogen, and sensitization using graphene quantum dot sensitization. For all of these modifiers, well-ordered mesoporous titania films were synthesized by surfactant templated sol-gel process. Two methods: hydrazine and plasma treatments have been developed for nitrogen and hydrogen doping in the mesoporous titania films for band gap reduction, visible light absorption and enhancement of photocatalytic activity. The hydrazine treatment in mesoporous titania thin films suggests that hydrazine induced doping is a promising approach to enable synergistic incorporation of N and Ti3+ into the lattice of surfactant-templated TiO2 films and enhanced visible light photoactivity, but that the benefits are limited by gradual mesostructure deterioration. The plasma treated nitrogen doped mesoporous titania showed about 240 times higher photoactivity compared to undoped film in hydrogen production from photoelectrochemical water splitting under visible light illumination. Plasma treated hydrogen doped mesoporous titania thin films has also been developed for enhancement of visible light absorption. Hydrogen treatment has been shown to turn titania (normally bright white) black, indicating vastly improved visible light absorption. The cause of the color change and its effectiveness for photocatalysis remain open questions. For the first time, we showed that a significant amount of hydrogen is incorporated in hydrogen plasma treated mesoporous titania films by neutron reflectometry measurements. In addition to the intrinsic modification of titania by doping, graphene quantum dot sensitization in mesoporous titania film was also investigated for visible light photocatalysis. Graphene quantum dot sensitization and nitrogen doping of ordered mesoporous titania films showed synergistic effect in water splitting due to high surface area, band gap reduction, enhanced visible light absorption, and efficient charge separation and transport. This study suggests that plasma based doping and graphene quantum dot sensitization are promising strategies to reduce band gap and enhance visible light absorption of high surface area surfactant templated mesoporous titania films, leading to superior visible-light driven photoelectrochemical hydrogen production. The results demonstrate the importance of designing and manipulating the energy band alignment in composite nanomaterials for fundamentally improving visible light absorption, charge separation and transport, and thereby photoelectrochemical properties.

Functionalized mesoporous materials for adsorption and release of different drug molecules: A comparative study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang Gang; Otuonye, Amy N.; Blair, Elizabeth A.

2009-07-15

The adsorption capacity and release properties of mesoporous materials for drug molecules can be improved by functionalizing their surfaces with judiciously chosen organic groups. Functionalized ordered mesoporous materials containing various types of organic groups via a co-condensation synthetic method from 15% organosilane and by post-grafting organosilanes onto a pre-made mesoporous silica were synthesized. Comparative studies of their adsorption and release properties for various model drug molecules were then conducted. Functional groups including 3-aminopropyl, 3-mercaptopropyl, vinyl, and secondary amine groups were used to functionalize the mesoporous materials while rhodamine 6G and ibuprofen were utilized to investigate the materials' relative adsorption andmore » release properties. The self-assembly of the mesoporous materials was carried out in the presence of cetyltrimethylammonium bromide (CTAB) surfactant, which produced MCM-41 type materials with pore diameters of {approx}2.7-3.3 nm and moderate to high surface areas up to {approx}1000 m{sup 2}/g. The different functional groups introduced into the materials dictated their adsorption capacity and release properties. While mercaptopropyl and vinyl functionalized samples showed high adsorption capacity for rhodamine 6G, amine functionalized samples exhibited higher adsorption capacity for ibuprofen. While the diffusional release of ibuprofen was fitted on the Fickian diffusion model, the release of rhodamine 6G followed Super Case-II transport model. - Graphical abstract: The adsorption capacity and release properties of mesoporous materials for various drug molecules are tuned by functionalizing the surfaces of the materials with judiciously chosen organic groups. This work reports comparative studies of the adsorption and release properties of functionalized ordered mesoporous materials containing different hydrophobic and hydrophilic groups that are synthesized via a co-condensation and post-grafting methods for various model drug molecules.« less

Oriented and selective enzyme immobilization on functionalized silica carrier using the cationic binding module Z basic2: design of a heterogeneous D-amino acid oxidase catalyst on porous glass.

PubMed

Bolivar, Juan M; Nidetzky, Bernd

2012-06-01

D-amino acid oxidase from Trigonopsis variabilis (TvDAO) is applied in industry for the synthesis of pharmaceutical intermediates. Because free TvDAO is extremely sensitive to exposure to gas-liquid interfaces, biocatalytic processing is usually performed with enzyme immobilizates that offer enhanced stability under bubble aeration. We herein present an "Immobilization by Design" approach that exploits engineered charge complementarity between enzyme and carrier to optimize key features of the immobilization of TvDAO. A fusion protein between TvDAO and the positively charged module Z(basic2) was generated, and a corresponding oppositely charged carrier was obtained by derivatization of mesoporous glass with 3-(trihydroxysilyl)-1-propane-sulfonic acid. Using 250 mM NaCl for charge screening at pH 7.0, the Z(basic2) fusion of TvDAO was immobilized directly from E. coli cell extract with almost absolute selectivity and full retention of catalytic effectiveness of the isolated enzyme in solution. Attachment of the homodimeric enzyme to the carrier was quasi-permanent in low-salt buffer but fully reversible upon elution with 5 M NaCl. Immobilized TvDAO was not sensitive to bubble aeration and received substantial (≥ tenfold) stabilization of the activity at 45°C as compared to free enzyme, suggesting immobilization via multisubunit oriented interaction of enzyme with the insoluble carrier. The Z(basic2) enzyme immobilizate was demonstrated to serve as re-usable heterogeneous catalyst for D-amino acid oxidation. Z(basic2) -mediated binding on a sulfonic acid group-containing glass carrier constitutes a generally useful strategy of enzyme immobilization that supports transition from case-specific empirical development to rational design. Copyright © 2012 Wiley Periodicals, Inc.

Synthesis and Catalytic Performance of Gold Intercalated in the Walls of Mesoporous Silica.

PubMed

Ji, Yazhou; Caskey, Christopher; Richards, Ryan M

2015-07-09

As a promising catalytically active nano reactor, gold nanoparticles intercalated in mesoporous silica (GMS) were successfully synthesized and properties of the materials were investigated. We used a one pot sol-gel approach to intercalate gold nano particles in the walls of mesoporous silica. To start with the synthesis, P123 was used as template to form micelles. Then TESPTS was used as a surface modification agent to intercalate gold nano particles. Following this process, TEOS was added in as a silica source which underwent a polymerization process in acid environment. After hydrothermal processing and calcination, the final product was acquired. Several techniques were utilized to characterize the porosity, morphology and structure of the gold intercalated mesoporous silica. The results showed a stable structure of mesoporous silica after gold intercalation. Through the oxidation of benzyl alcohol as a benchmark reaction, the GMS materials showed high selectivity and recyclability.

Synthesis and Catalytic Performance of Gold Intercalated in the Walls of Mesoporous Silica

PubMed Central

Ji, Yazhou; Caskey, Christopher; Richards, Ryan M.

2015-01-01

As a promising catalytically active nano reactor, gold nanoparticles intercalated in mesoporous silica (GMS) were successfully synthesized and properties of the materials were investigated. We used a one pot sol-gel approach to intercalate gold nano particles in the walls of mesoporous silica. To start with the synthesis, P123 was used as template to form micelles. Then TESPTS was used as a surface modification agent to intercalate gold nano particles. Following this process, TEOS was added in as a silica source which underwent a polymerization process in acid environment. After hydrothermal processing and calcination, the final product was acquired. Several techniques were utilized to characterize the porosity, morphology and structure of the gold intercalated mesoporous silica. The results showed a stable structure of mesoporous silica after gold intercalation. Through the oxidation of benzyl alcohol as a benchmark reaction, the GMS materials showed high selectivity and recyclability. PMID:26274058

Catalytic removal of sulfur dioxide from dibenzothiophene sulfone over Mg-Al mixed oxides supported on mesoporous silica.

PubMed

You, Nansuk; Kim, Min Ji; Jeong, Kwang-Eun; Jeong, Soon-Yong; Park, Young-Kwon; Jeon, Jong-Ki

2010-05-01

Dibenzothiophene sulfone (DBTS), one of the products of the oxidative desulfurization of heavy oil, can be removed through extraction as well as by an adsorption process. It is necessary to utilize DBTS in conjunction with catalytic cracking. An object of the present study is to provide an Mg-Al-mesoporous silica catalyst for the removal of sulfur dioxide from DBTS. The characteristics of the Mg-Al-mesoporous silica catalyst were investigated through N2 adsorption, XRD, ICP, and XRF. An Mg-Al-mesoporous silica catalyst formulated in a direct incorporation method showed higher catalytic performance compared to pure MgO during the catalytic removal of sulfur dioxide from DBTS. The higher dispersion of Mg as well as the large surface area of the Mg-Al-mesoporous silica catalyst strongly influenced the catalyst basicity in DBTS cracking.

The layer boundary effect on multi-layer mesoporous TiO 2 film based dye sensitized solar cells

DOE PAGES

Xu, Feng; Zhu, Kai; Zhao, Yixin

2016-10-10

Multi-layer mesoporous TiO 2 prepared by screen printing is widely used for fabrication of high-efficiency dye-sensitized solar cells (DSSCs). Here, we compare the three types of ~10 um thick mesoporous TiO 2 films, which were screen printed as 1-, 2- and 4-layers using the same TiO 2 nanocrystal paste. The layer boundary of the multi-layer mesoporous TiO 2 films was observed in the cross-section SEM. The existence of a layer boundary could reduce the photoelectron diffusion length with the increase of layer number. However, the photoelectron diffusion lengths of the Z907 dye sensitized solar cells based on these different layeredmore » mesoporous TiO 2 films are all longer than the film thickness. Consequently, the photovoltaic performance seems to have little dependence on the layer number of the multi-layer TiO 2 based DSSCs.« less

Mesoporous gold sponges: electric charge-assisted seed mediated synthesis and application as surface-enhanced Raman scattering substrates

NASA Astrophysics Data System (ADS)

Yi, Zao; Luo, Jiangshan; Tan, Xiulan; Yi, Yong; Yao, Weitang; Kang, Xiaoli; Ye, Xin; Zhu, Wenkun; Duan, Tao; Yi, Yougen; Tang, Yongjian

2015-11-01

Mesoporous gold sponges were prepared using 4-dimethylaminopyridine (DMAP)-stabilized Au seeds. This is a general process, which involves a simple template-free method, room temperature reduction of HAuCl4·4H2O with hydroxylamine. The formation process of mesoporous gold sponges could be accounted for the electrostatic interaction (the small Au nanoparticles (~3 nm) and the positively charged DMAP-stabilized Au seeds) and Ostwald ripening process. The mesoporous gold sponges had appeared to undergo electrostatic adsorption initially, sequentially linear aggregation, welding and Ostwald ripening, then, they randomly cross link into self-supporting, three-dimensional networks with time. The mesoporous gold sponges exhibit higher surface area than the literature. In addition, application of the spongelike networks as an active material for surface-enhanced Raman scattering has been investigated by employing 4-aminothiophenol (4-ATP) molecules as a probe.

Template-free synthesis of mesoporous nanoring-like Zn-Co mixed oxides with high lithium storage performance

NASA Astrophysics Data System (ADS)

Lu, Lun; Gao, Yan-Li; Yang, Zhi-Zheng; Wang, Cheng; Wang, Jin-Guo; Wang, Hui-Yuan; Jiang, Qi-Chuan

2018-04-01

Mesoporous nanoring-like Zn-Co mixed oxides are synthesized via a simple template-free solvothermal method with a subsequent annealing process. The ring-like nanostructures with hollow interiors are formed under the complexing effects of potassium sodium tartrate. Numerous mesopores are generated after the precursor is annealed at 500 °C. When applied as anode materials, the mesoporous nanoring-like Zn-Co mixed oxides can deliver a high discharge capacity of 1102 mAh g-1 after 200 cycles at 500 mA g-1. Even when the current density is increased to 2 A g-1, the mixed oxides can still retain a reversible capacity of 761 mAh g-1. Such high cycling stability and rate capability are mainly derived from the unique mesoporous ring-like nanostructures and the synergistic effects between Zn and Co based oxides.

The layer boundary effect on multi-layer mesoporous TiO 2 film based dye sensitized solar cells

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Feng; Zhu, Kai; Zhao, Yixin

Multi-layer mesoporous TiO 2 prepared by screen printing is widely used for fabrication of high-efficiency dye-sensitized solar cells (DSSCs). Here, we compare the three types of ~10 um thick mesoporous TiO 2 films, which were screen printed as 1-, 2- and 4-layers using the same TiO 2 nanocrystal paste. The layer boundary of the multi-layer mesoporous TiO 2 films was observed in the cross-section SEM. The existence of a layer boundary could reduce the photoelectron diffusion length with the increase of layer number. However, the photoelectron diffusion lengths of the Z907 dye sensitized solar cells based on these different layeredmore » mesoporous TiO 2 films are all longer than the film thickness. Consequently, the photovoltaic performance seems to have little dependence on the layer number of the multi-layer TiO 2 based DSSCs.« less

Synthesis and characterization of nanoparticulate MnS within the pores of mesoporous silica

NASA Astrophysics Data System (ADS)

Barry, Louse; Copley, Mark; Holmes, Justin D.; Otway, David J.; Kazakova, Olga; Morris, Michael A.

2007-12-01

Mesoporous silica was loaded with nanoparticulate MnS via a simple post-synthesis treatment. The mesoporous material that still contained surfactant was passivated to prevent MnS formation at the surface. The surfactant was extracted and a novel manganese ethylxanthate was used to impregnate the pore network. This precursor thermally decomposes to yield MnS particles that are smaller or equal to the pore size. The particles exhibit all three common polymorphs. The passivation treatment is most effective at lower loadings because at the highest loadings (SiO 2:MnS molar ratio of 6:1) large particles (>50 nm) form at the exterior of the mesoporous particles. The integrity of the mesoporous network is maintained through the preparation and high order is maintained. The MnS particles exhibit unexpected ferromagnetism at low temperatures. Strong luminescence of these samples is observed and this suggests that they may have a range of important application areas.

Mesoporous gold sponges: electric charge-assisted seed mediated synthesis and application as surface-enhanced Raman scattering substrates

PubMed Central

Yi, Zao; Luo, Jiangshan; Tan, Xiulan; Yi, Yong; Yao, Weitang; Kang, Xiaoli; Ye, Xin; Zhu, Wenkun; Duan, Tao; Yi, Yougen; Tang, Yongjian

2015-01-01

Mesoporous gold sponges were prepared using 4-dimethylaminopyridine (DMAP)-stabilized Au seeds. This is a general process, which involves a simple template-free method, room temperature reduction of HAuCl4·4H2O with hydroxylamine. The formation process of mesoporous gold sponges could be accounted for the electrostatic interaction (the small Au nanoparticles (~3 nm) and the positively charged DMAP-stabilized Au seeds) and Ostwald ripening process. The mesoporous gold sponges had appeared to undergo electrostatic adsorption initially, sequentially linear aggregation, welding and Ostwald ripening, then, they randomly cross link into self-supporting, three-dimensional networks with time. The mesoporous gold sponges exhibit higher surface area than the literature. In addition, application of the spongelike networks as an active material for surface-enhanced Raman scattering has been investigated by employing 4-aminothiophenol (4-ATP) molecules as a probe. PMID:26538365

Mesoporous nitrogen-doped carbon microfibers derived from Mg-biquinoline-dicarboxy compound for efficient oxygen electroreduction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kong, Aiguo, E-mail: agkong@chem.ecnu.edu.cn; Fan, Xiaohong; Chen, Aoling

An in-situ MgO-templating synthesis route was introduced to obtain the mesoporous nitrogen-doped carbon microfibers by thermal conversion of new Mg-2,2′-biquinoline 4,4-dicarboxy acid coordination compound (Mg-DCA) microfibers. The investigated crystal structure of Mg-DCA testified that the assembling of Mg{sup 2+} and DCA through Mg-O coordination bond and hydrogen bond contributed to the formation of one-dimensional (1D) crystalline Mg-DCA microfibers. The nitrogen-doped carbons derived from the pyrolysis of Mg-DCA showed the well-defined microfiber morphology with high mesopore-surface area. Such mesoporous microfibers exhibited the efficient catalytic activity for oxygen reduction reaction (ORR) in alkaline solutions with better stability and methanol-tolerance performance. - Graphicalmore » abstract: Mesoporous nitrogen-doped carbon microfibers with efficient oxygen electroreduction activity were prepared by thermal conversion of new Mg-biquinoline-based coordination compound microfibers.« less

Mesoporous Iron Sulfide for Highly Efficient Electrocatalytic Hydrogen Evolution

DOE PAGES

Miao, Ran; Dutta, Biswanath; Sahoo, Sanjubala; ...

2017-09-05

Here, we report a facile synthetic protocol to pre-pare mesoporous FeS 2 without the aid of hard template as an electrocatalyst for the hydrogen evolution reaction (HER). The mesoporous FeS 2 materials with high surface area were successfully prepared by a sol-gel method follow-ing a sulfurization treatment in an H 2S atmosphere. A re-markable HER catalytic performance was achieved with a low overpotential of 96 mV at a current density of 10 mA·cm 2 and a Tafel slope of 78 mV per decade under alka-line conditions (pH 13). These theoretical calculations indicate that the excellent catalytic activity of mesoporous FeSmore » 2 is attributed to the exposed (210) facets. The mesoporous FeS 2 material might be a promising alternative to the Pt-based electrocatalysts for water splitting.« less

Materials with engineered mesoporosity for programmed mass transport

NASA Astrophysics Data System (ADS)

Gough, Dara V.

Transport in nanostructured materials is of great interest for scientists in various fields, including molecular sequestration, catalysis, artificial photosynthesis and energy storage. This thesis will present work on the transport of molecular and ionic species in mesoporous materials (materials with pore sizes between 2 and 50 nm). Initially, discussion will focus on the synthesis of mesoporous ZnS nanorattles and the size selected mass transport of small molecules through the mesopores. Discussion will then shift of exploration of cation exchange and electroless plating of metals to alter the mesoporous hollow sphere (MHS) materials and properties. The focus of discussion will then shift to the transport of ions into and out of a hierarchically structured gold electrode. Finally, a model gamma-bactiophage was developed to study the electromigration of charged molecules into and out of a confined geometry. A catalytically active biomolecular species was encapsulated within the central cavity of ZnS MHS. Both the activity of the encapsulated enzyme and the size-selective transport through the wall of the MHS were verified through the use of a common fluorogen, hydrogen peroxide, and sodium azide. Additionally, the protection of the enzyme was shown through size-selected blocking of a protease. The mesoporous hollow sphere system introduces size-selectivity to catalyzed chemical reactions; future work may include variations in pore sizes, and pore wall chemical functionalization. The pore size in ZnS mesoporous hollow spheres is controlled between 2.5 and 4.1 nm through swelling of the lyotropic liquid crystal template. The incorporation of a swelling agent is shown to linearly vary the hexagonal lyotropic liquid crystalline phase, which templates the mesopores, while allowing the high fidelity synthesis of mesoporous hollow spheres. Fluorescnently labeled ssDNA was utilized as a probe to explore the change in mesopore permeability afforded by the swollen template relative to the unswollen template. Electroless plating and cation exchange were explored as methods to vary the shell material of MHS. Mesoporous Ni MHS were obtained by the reduction of Ni2+ with dimethylamine borane onto a CML latex core. However, the resultant MHS were damaged due to core swelling during etch. To successfully obtain undeformed MHS, a silica core must be utilized; one possible route to explore, in order to reach this goal, is the surface chemistry/ligand effects on Ni2+. Cation exchange was performed in order to obtain CuS MHS; however, it proved an unsuccessful route to PbS, S and HgS. CdS-ZnS, Bi2S3 and Ag2S MHS were obtained only with significant defects. A novel hierarchically structured material, porous opal, was prepared using a colloidal crystal template and the dealloying of silver from gold and possed porosity on length scales range from 10s of nanometers (due to the colloidal crystal template) down to ca. 10 nm (due to dealloying). The transport properties of the material were studied using cyclic voltammetry and electrochemical impedance spectroscopy. The porous opal was found to posses enhanced charge transport properties relative to a unimodal porous gold film and a higher surface area than a gold opal. An equivalent circuit model was presented to explain the enhanced charge transport properties. A biomimetic system for studying the translocation of polymers through a channel and into a spherical cavity was developed based on inspiration from the gamma-bacteriophage. The nanocavity system was synthesized using two template length scales: 250 nm and 1.2 mum. Fabrication challenges that arose when using 1.2 mum colloidal templates were addressed, and the system was optimized for confinement studies of plasmid dsDNA.

Bioinspired Diselenide-Bridged Mesoporous Silica Nanoparticles for Dual-Responsive Protein Delivery.

PubMed

Shao, Dan; Li, Mingqiang; Wang, Zheng; Zheng, Xiao; Lao, Yeh-Hsing; Chang, Zhimin; Zhang, Fan; Lu, Mengmeng; Yue, Juan; Hu, Hanze; Yan, Huize; Chen, Li; Dong, Wen-Fei; Leong, Kam W

2018-05-28

Controlled delivery of protein therapeutics remains a challenge. Here, the inclusion of diselenide-bond-containing organosilica moieties into the framework of silica to fabricate biodegradable mesoporous silica nanoparticles (MSNs) with oxidative and redox dual-responsiveness is reported. These diselenide-bridged MSNs can encapsulate cytotoxic RNase A into the 8-10 nm internal pores via electrostatic interaction and release the payload via a matrix-degradation controlled mechanism upon exposure to oxidative or redox conditions. After surface cloaking with cancer-cell-derived membrane fragments, these bioinspired RNase A-loaded MSNs exhibit homologous targeting and immune-invasion characteristics inherited from the source cancer cells. The efficient in vitro and in vivo anti-cancer performance, which includes increased blood circulation time and enhanced tumor accumulation along with low toxicity, suggests that these cell-membrane-coated, dual-responsive degradable MSNs represent a promising platform for the delivery of bio-macromolecules such as protein and nucleic acid therapeutics. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of providing free glasses on children's educational outcomes in China: cluster randomized controlled trial.

PubMed

Ma, Xiaochen; Zhou, Zhongqiang; Yi, Hongmei; Pang, Xiaopeng; Shi, Yaojiang; Chen, Qianyun; Meltzer, Mirjam E; le Cessie, Saskia; He, Mingguang; Rozelle, Scott; Liu, Yizhi; Congdon, Nathan

2014-09-23

To assess the effect of provision of free glasses on academic performance in rural Chinese children with myopia. Cluster randomized, investigator masked, controlled trial. 252 primary schools in two prefectures in western China, 2012-13. 3177 of 19,934 children in fourth and fifth grades (mean age 10.5 years) with visual acuity <6/12 in either eye without glasses correctable to >6/12 with glasses. 3052 (96.0%) completed the study. Children were randomized by school (84 schools per arm) to one of three interventions at the beginning of the school year: prescription for glasses only (control group), vouchers for free glasses at a local facility, or free glasses provided in class. Spectacle wear at endline examination and end of year score on a specially designed mathematics test, adjusted for baseline score and expressed in standard deviations. Among 3177 eligible children, 1036 (32.6%) were randomized to control, 988 (31.1%) to vouchers, and 1153 (36.3%) to free glasses in class. All eligible children would benefit from glasses, but only 15% wore them at baseline. At closeout glasses wear was 41% (observed) and 68% (self reported) in the free glasses group, and 26% (observed) and 37% (self reported) in the controls. Effect on test score was 0.11 SD (95% confidence interval 0.01 to 0.21) when the free glasses group was compared with the control group. The adjusted effect of providing free glasses (0.10, 0.002 to 0.19) was greater than parental education (0.03, -0.04 to 0.09) or family wealth (0.01, -0.06 to 0.08). This difference between groups was significant, but was smaller than the prespecified 0.20 SD difference that the study was powered to detect. The provision of free glasses to Chinese children with myopia improves children's performance on mathematics testing to a statistically significant degree, despite imperfect compliance, although the observed difference between groups was smaller than the study was originally designed to detect. Myopia is common and rarely corrected in this setting.Trial Registration Current Controlled Trials ISRCTN03252665. © Ma et al 2014.

Rare-earth metal oxide doped transparent mesoporous silica plates under non-aqueous condition as a potential UV sensor.

PubMed

Lee, Sang-Joon; Park, Sung Soo; Lee, Sang Hyun; Hong, Sang-Hyun; Ha, Chang-Sik

2013-11-01

Transparent mesoporous silica plates doped with rare-earth metal oxide were prepared using solvent-evaporation method based on the self-organization between structure-directing agent and silicate in a non-aqueous solvent. A triblock copolymer, Pluronic (F127 or P123), was used as the structure-directing agent, while tetraethyl orthosilicate (TEOS) was used as a silica source. The pore diameter and the surface area of the mesoporous silica plate prepared with the optimized conditions were ca 40 A and 600 m2 g(-1), respectively, for both structure-directing agent. Rare-earth metal oxides (Eu, Tb, Tm oxide) in mesochannel were formed via one-step synthetic route based on the preparation method of a silica plate. Optical properties of rare-earth metal oxide-doped mesoporous silica plates were investigated by UV irradiation and photoluminescence (PL) spectroscopy. Under the exitation wavelength of 254 nm, the doped mesoporous silica plates emitted red, green and blue for Eu, Tb and Tm oxides, respectively. Rare-earth metal oxide-doped mesoporous silica plates showed enhanced PL intensity compared to that of the bulk rare-earth metal oxide.

Mesoporous mixed metal oxides derived from P123-templated Mg-Al layered double hydroxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang Jun, E-mail: zhqw1888@sohu.co; College of Chemical Engineering, Harbin Institute of Technology, Harbin 150001; Key Laboratory of Superlight Materials and Surface Technology, Ministry of Education, 150001

2010-11-15

We report the preparation of mesoporous mixed metal oxides (MMOs) through a soft template method. Different amounts of P123 were used as structure directing agent to synthesize P123-templated Mg-Al layered double hydroxides (LDHs). After calcination of as-synthesized LDHs at 500 {sup o}C, the ordered mesopores were obtained by removal of P123. The mesoporous Mg-Al MMOs fabricated by using 2 wt% P123 exhibited a high specific surface area of 108.1 m{sup 2}/g, and wide distribution of pore size (2-18 nm). An investigation of the 'memory effect' of the mesoporous MMOs revealed that they were successfully reconstructed to ibuprofen intercalated LDHs havingmore » different gallery heights, which indicated different intercalation capacities. Due to their mesoporosity these unique MMOs have particular potential as drug or catalyst carriers. - Graphical abstract: Ordered mesoporous Mg-Al MMOs can be obtained through the calcination of P123-templated Mg-Al-CO{sub 3} LDHs. The pore diameter is 2.2 nm. At the presence of ibuprofen, the Mg-Al MMOs can recover to Mg-Al-IBU LDHs, based on its 'remember effect'. Display Omitted« less

Mesoporous Germanium Anode Materials for Lithium-Ion Battery with Exceptional Cycling Stability in Wide Temperature Range.

PubMed

Choi, Sinho; Cho, Yoon-Gyo; Kim, Jieun; Choi, Nam-Soon; Song, Hyun-Kon; Wang, Guoxiu; Park, Soojin

2017-04-01

Porous structured materials have unique architectures and are promising for lithium-ion batteries to enhance performances. In particular, mesoporous materials have many advantages including a high surface area and large void spaces which can increase reactivity and accessibility of lithium ions. This study reports a synthesis of newly developed mesoporous germanium (Ge) particles prepared by a zincothermic reduction at a mild temperature for high performance lithium-ion batteries which can operate in a wide temperature range. The optimized Ge battery anodes with the mesoporous structure exhibit outstanding electrochemical properties in a wide temperature ranging from -20 to 60 °C. Ge anodes exhibit a stable cycling retention at various temperatures (capacity retention of 99% after 100 cycles at 25 °C, 84% after 300 cycles at 60 °C, and 50% after 50 cycles at -20 °C). Furthermore, full cells consisting of the mesoporous Ge anode and an LiFePO 4 cathode show an excellent cyclability at -20 and 25 °C. Mesoporous Ge materials synthesized by the zincothermic reduction can be potentially applied as high performance anode materials for practical lithium-ion batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Kinetic and catalytic analysis of mesoporous metal oxides on the oxidation of Rhodamine B

NASA Astrophysics Data System (ADS)

Xaba, Morena S.; Noh, Ji-Hyang; Mokgadi, Keabetswe; Meijboom, Reinout

2018-05-01

In this study, we demonstrate the synthesis and catalytic activity of different mesoporous transition metal oxides, silica (SiO2), copper oxide (CuO), chromium oxide (Cr2O3), iron oxide (Fe2O3) cobalt oxide (Co3O4), cerium oxide (CeO2) and nickel oxide (NiO), on the oxidation of a pollutant dye, Rhodamine B (RhB). These metal oxides were synthesized by inverse micelle formation method and characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), adsorption-desorption isotherms (BET) and H2-temperature programmed reduction (TPR). UV-vis spectrophotometry was used to monitor the time-resolved absorbance of RhB at λmax = 554 nm. Mesoporous copper oxide was calcined at different final heating temperatures of 250, 350, 450 and 550 °C, and each mesoporous copper oxide catalyst showed unique physical properties and catalytic behavior. Mesoporous CuO-550 with the smallest characteristic path length δ, proved to be the catalyst of choice for the oxidation of RhB in aqueous media. We observed that the oxidation of RhB in aqueous media is dependent on the crystallite size and characteristic path length of the mesoporous metal oxide. The Langmuir-Hinshelwood model was used to fit the experimental data and to prove that the reaction occurs on the surface of the mesoporous CuO. The thermodynamic parameters, EA, ΔH#, ΔS# and ΔG# were calculated and catalyst recycling and reusability were demonstrated.

Bone tissue engineering using silica-based mesoporous nanobiomaterials:Recent progress.

PubMed

Shadjou, Nasrin; Hasanzadeh, Mohammad

2015-10-01

Bone disorders are of significant concern due to increase in the median age of our population. It is in this context that tissue engineering has been emerging as a valid approach to the current therapies for bone regeneration/substitution. Tissue-engineered bone constructs have the potential to alleviate the demand arising from the shortage of suitable autograft and allograft materials for augmenting bone healing. Silica based mesostructured nanomaterials possessing pore sizes in the range 2-50 nm and surface reactive functionalities have elicited immense interest due to their exciting prospects in bone tissue engineering. In this review we describe application of silica-based mesoporous nanomaterials for bone tissue engineering. We summarize the preparation methods, the effect of mesopore templates and composition on the mesopore-structure characteristics, and different forms of these materials, including particles, fibers, spheres, scaffolds and composites. Also, the effect of structural and textural properties of mesoporous materials on development of new biomaterials for production of bone implants and bone cements was discussed. Also, application of different mesoporous materials on construction of manufacture 3-dimensional scaffolds for bone tissue engineering was discussed. It begins by giving the reader a brief background on tissue engineering, followed by a comprehensive description of all the relevant components of silica-based mesoporous biomaterials on bone tissue engineering, going from materials to scaffolds and from cells to tissue engineering strategies that will lead to "engineered" bone. Copyright © 2015 Elsevier B.V. All rights reserved.

Supported mesoporous carbon ultrafiltration membrane and process for making the same

DOEpatents

Strano, Michael; Foley, Henry C.; Agarwal, Hans

2004-04-13

A novel supported mesoporous carbon ultrafiltration membrane and process for producing the same. The membranes comprise a mesoporous carbon layer that exists both within and external to the porous support. A liquid polymer precursor composition comprising both carbonizing and noncarbonizing templating polymers is deposited on the porous metal support. The coated support is then heated in an inert-gas atmosphere to pyrolyze the polymeric precursor and form a mesoporous carbon layer on and within the support. The pore-size of the membranes is dependent on the molecular weight of the noncarbonizing templating polymer precursor. The mesoporous carbon layer is stable and can withstand high temperatures and exposure to organic chemicals. Additionally, the porous metal support provides excellent strength properties. The composite structure of the membrane provides novel structural properties and allows for increased operating pressures allowing for greater membrane flow rates. The invention also relates to the use of the novel ultrafiltration membrane to separate macromolecules from solution. An example is shown separating bovine serum albumin from water. The membrane functions by separating and by selective adsorption. Because of the membrane's porous metal support, it is well suited to industrial applications. The unique properties of the supported mesoporous carbon membrane also allow the membrane to be used in transient pressure or temperature swing separations processes. Such processes were not previously possible with existing mesoporous membranes. The present invention, however, possesses the requisite physical properties to perform such novel ultrafiltration processes.

Characterizing porosity of selected Early Palaeozoic shales from the Baltic Basin: organic petrology, gas adsorption and WIP and KIP approach.

NASA Astrophysics Data System (ADS)

Słomski, Piotr; Mastalerz, Maria; Szczepański, Jacek; Derkowski, Arkadiusz; Topór, Tomasz

2017-04-01

The porosity in the selected Ordovician and Silurian mudstones from the Baltic Basin collected from three wells (W1, M1, B1 and O3) was examined in a suite of 78 samples representing the Kopalino, Sasino, Prabuty, Pasłęk (including Jantar Member) and Pelplin Formations. Organic petrology, mineral composition along with N2 low-pressure adsorption (NLPA), water and kerosene immersion porosimetry (WIP and KIP, respectively) as well as image analysis techniques were used to determine pore volumes, pore sizes and pore-size distributions and to evaluate factors controlling porosity. The majority of the investigated samples represent argillaceous mudstones. Only a few samples from O3 and W1 are different lithologically and represent siliceous-argillaceous, calcareous, or calcareous-argillicaous mudstones. The samples are characterized by total organic carbon (TOC) content ranging from 0.13 to 7.20 wt. % and vitrinite reflectance (Ro) ranging from 1.02 to 1.22%, indicating late mature rocks within condensate - wet gas window. Total porosity measured using WIP is in the range from 4.6 % to 10 %, while KIP gave values from 1.5 % to 8.9 %. NLPA technique on the 75 µm size fraction revealed that mesopores area is in the range from 10.59 to 34.34 m2/g, while mesopores volume ranges from 0.024 to 0.062 cm3/g. Correlation between mesopores surface area and Ro is weak, but in general the surface area of mesopores is the largest in the least mature samples. Moreover, as indicated by gas adsorption data, both pores greater than 30 nm and smaller than 4 nm are important contributors to the total mesoporess surface area. In general, rather weak correlation between different mudstone constituents (including kerogen types) and porosity measured by means of various techniques (WIP, KIP and NLPA) reveal that there is no single factor controlling porosity in the investigated suite of samples. This conclusion is also confirmed by image analysis performed on large-scale high-resolution BSE images for selected representative samples. However, for mesopores, the dominant contribution comes from organic matter for the Jantar, Prabuty and Sasino Formations, as indicated by NLPA technique. Furthermore, importance of clay minerals for macropore volume is indicated by WIP and KIP technique. Acknowledgments: the study was supported from grant SHALESEQ (No PL12-0109) and SHALEMECH (No BG2/ShaleMech/14) funded by the National Centre for Research and Development.

Thermoswitchable catalysis controlled by reversible dispersion/aggregation change of nanoreactors in the presence of α-CD polymers

NASA Astrophysics Data System (ADS)

Li, Yinfeng; Hu, Jie; Niu, Chengrong; Leng, Jinghang; Li, Songjun

2018-06-01

The present work was aimed at preparing a thermosensitive nanoreactor system which could adjust its dispersion/aggregation status according to external temperature change to achieve the switchable catalysis. The mesoporous silica nanoparticle (MSNP) was selected as the framework material of the nanoreactor, and Ag nanoparticles were encapsulated in the mesoporous silica by an in situ reaction. Dodecyl groups were introduced onto MSNP surface, which could transform reversibly between complexation and disassociation with α-cyclodextrin (CD) cavity upon temperature change. It was found that the nanoreactors aggregated and the catalysis was effectively switched ‘off’ in the presence of CD polymers at low temperature (20 °C). However, when the temperature increased to 50 °C, the nanoreactors redispersed and catalysis successfully switched ‘on’.

Thermoswitchable catalysis controlled by reversible dispersion/aggregation change of nanoreactors in the presence of α-CD polymers.

PubMed

Li, Yinfeng; Hu, Jie; Niu, Chengrong; Leng, Jinghang; Li, Songjun

2018-06-01

The present work was aimed at preparing a thermosensitive nanoreactor system which could adjust its dispersion/aggregation status according to external temperature change to achieve the switchable catalysis. The mesoporous silica nanoparticle (MSNP) was selected as the framework material of the nanoreactor, and Ag nanoparticles were encapsulated in the mesoporous silica by an in situ reaction. Dodecyl groups were introduced onto MSNP surface, which could transform reversibly between complexation and disassociation with α-cyclodextrin (CD) cavity upon temperature change. It was found that the nanoreactors aggregated and the catalysis was effectively switched 'off' in the presence of CD polymers at low temperature (20 °C). However, when the temperature increased to 50 °C, the nanoreactors redispersed and catalysis successfully switched 'on'.

ENVIRONMENTAL TECHNOLOGY VERIFICATION REPORT, KMC CONTROLS, INC. SLE-1001 SIGHT GLASS MONITOR

EPA Science Inventory

The Environmental Technology Verification report discusses the technology and performance of the KMC SLE-1001 Sight Glass Monitor manufactured by KMC Controls, Inc. The sight glass monitor (SGM) fits over the sight glass that may be installed in a refrigeration system for the pur...

BMP2-loaded hollow hydroxyapatite microspheres exhibit enhanced osteoinduction and osteogenicity in large bone defects.

PubMed

Xiong, Long; Zeng, Jianhua; Yao, Aihua; Tu, Qiquan; Li, Jingtang; Yan, Liang; Tang, Zhiming

2015-01-01

The regeneration of large bone defects is an osteoinductive, osteoconductive, and osteogenic process that often requires a bone graft for support. Limitations associated with naturally autogenic or allogenic bone grafts have demonstrated the need for synthetic substitutes. The present study investigates the feasibility of using novel hollow hydroxyapatite microspheres as an osteoconductive matrix and a carrier for controlled local delivery of bone morphogenetic protein 2 (BMP2), a potent osteogenic inducer of bone regeneration. Hollow hydroxyapatite microspheres (100±25 μm) with a core (60±18 μm) and a mesoporous shell (180±42 m(2)/g surface area) were prepared by a glass conversion technique and loaded with recombinant human BMP2 (1 μg/mg). There was a gentle burst release of BMP2 from microspheres into the surrounding phosphate-buffered saline in vitro within the initial 48 hours, and continued at a low rate for over 40 days. In comparison with hollow hydroxyapatite microspheres without BMP2 or soluble BMP2 without a carrier, BMP2-loaded hollow hydroxyapatite microspheres had a significantly enhanced capacity to reconstitute radial bone defects in rabbit, as shown by increased serum alkaline phosphatase; quick and complete new bone formation within 12 weeks; and great biomechanical flexural strength. These results indicate that BMP2-loaded hollow hydroxyapatite microspheres could be a potential new option for bone graft substitutes in bone regeneration.

Electrospun cellulose acetate composites containing supported metal nanoparticles for antifungal membranes.

PubMed

Quirós, Jennifer; Gonzalo, Soledad; Jalvo, Blanca; Boltes, Karina; Perdigón-Melón, José Antonio; Rosal, Roberto

2016-09-01

Electrospun cellulose acetate composites containing silver and copper nanoparticles supported in sepiolite and mesoporous silica were prepared and tested as fungistatic membranes against the fungus Aspergillus niger. The nanoparticles were in the 3-50nm range for sepiolite supported materials and limited by the size of mesopores (5-8nm) in the case of mesoporous silica. Sepiolite and silica were well dispersed within the fibers, with larger aggregates in the micrometer range, and allowed a controlled release of metals to create a fungistatic environment. The effect was assessed using digital image analysis to evaluate fungal growth rate and fluorescence readings using a viability stain. The results showed that silver and copper nanomaterials significantly impaired the growth of fungi when the spores were incubated either in direct contact with particles or included in cellulose acetate composite membranes. The fungistatic effect took place on germinating spores before hyphae growth conidiophore formation. After 24h the cultures were separated from fungistatic materials and showed growth impairment only due to the prior exposure. Growth reduction was important for all the particles and membranes with respect to non-exposed controls. The effect of copper and silver loaded materials was not significantly different from each other with average reductions around 70% for bare particles and 50% for membranes. Copper on sepiolite was particularly efficient with a decrease of metabolic activity of up to 80% with respect to controls. Copper materials induced rapid maturation and conidiation with fungi splitting in sets of subcolonies. Metal-loaded nanomaterials acted as reservoirs for the controlled release of metals. The amount of silver or copper released daily by composite membranes represented roughly 1% of their total load of metals. Supported nanomaterials encapsulated in nanofibers allow formulating active membranes with high antifungal performance at the same time minimizing the risk of nanoparticle release into the environment. Copyright © 2015 Elsevier B.V. All rights reserved.

Writing on the wall with a new synthetic quill

PubMed

MacLachlan; Asefa; Ozin

2000-07-14

A new class of periodic mesoporous organosilicas (PMOs) with organic groups incorporated inside the channel walls of the material is discussed. In particular, the unique properties and chemistry exhibited by periodic mesoporous methylenesilica, an isoelectronic analogue of periodic mesoporous silica, are highlighted. Finally, some of the advances made in our group and others, as well as future directions that we envision in the field are described.

Synthesis, characterization, and performance evaluation of multilayered photoanodes by introducing mesoporous carbon and TiO2 for humic acid adsorption.

PubMed

Hosseini, Soraya; Jahangirian, Hossein; Webster, Thomas J; Soltani, Salman Masoudi; Aroua, Mohamed Kheireddine

2016-01-01

Nanostructured photoanodes were prepared via a novel combination of titanium dioxide (TiO2) nanoparticles and mesoporous carbon (C). Four different photoanodes were synthesized by sol-gel spin coating onto a glassy substrate of fluorine-doped tin oxide. The photocatalytic activities of TiO2, TiO2/C/TiO2, TiO2/C/C/TiO2, and TiO2/C/TiO2/C/TiO2 photoanodes were evaluated by exposing the synthesized photoanodes to UV-visible light. The photocurrent density observed in these photoanodes confirmed that an additional layer of mesoporous carbon could successfully increase the photocurrent density. The highest photocurrent density of ~1.022 mA cm(-2) at 1 V/saturated calomel electrode was achieved with TiO2/C/C/TiO2 under an illumination intensity of 100 mW cm(-2) from a solar simulator. The highest value of surface roughness was measured for a TiO2/C/C/TiO2 combination owing to the presence of two continuous layers of mesoporous carbon. The resulting films had a thickness ranging from 1.605 µm to 5.165 µm after the calcination process. The presence of double-layer mesoporous carbon resulted in a 20% increase in the photocurrent density compared with the TiO2/C/TiO2 combination when only a single mesoporous carbon layer was employed. The improved performance of these photoanodes can be attributed to the enhanced porosity and increased void space due to the presence of mesoporous carbon. For the first time, it has been demonstrated here that the photoelectrochemical performance of TiO2 can be improved by integrating several layers of mesoporous carbon. Comparison of the rate of removal of humic acid by the prepared photoanodes showed that the highest performance from TiO2/C/C/TiO2 was due to the highest photocurrent density generated. Therefore, this study showed that optimizing the sequence of mesoporous carbon layers can be a viable and inexpensive method for enhanced humic acid removal.

Synthesis, characterization, and performance evaluation of multilayered photoanodes by introducing mesoporous carbon and TiO2 for humic acid adsorption

PubMed Central

Hosseini, Soraya; Jahangirian, Hossein; Webster, Thomas J; Soltani, Salman Masoudi; Aroua, Mohamed Kheireddine

2016-01-01

Nanostructured photoanodes were prepared via a novel combination of titanium dioxide (TiO2) nanoparticles and mesoporous carbon (C). Four different photoanodes were synthesized by sol–gel spin coating onto a glassy substrate of fluorine-doped tin oxide. The photocatalytic activities of TiO2, TiO2/C/TiO2, TiO2/C/C/TiO2, and TiO2/C/TiO2/C/TiO2 photoanodes were evaluated by exposing the synthesized photoanodes to UV–visible light. The photocurrent density observed in these photoanodes confirmed that an additional layer of mesoporous carbon could successfully increase the photocurrent density. The highest photocurrent density of ~1.022 mA cm−2 at 1 V/saturated calomel electrode was achieved with TiO2/C/C/TiO2 under an illumination intensity of 100 mW cm−2 from a solar simulator. The highest value of surface roughness was measured for a TiO2/C/C/TiO2 combination owing to the presence of two continuous layers of mesoporous carbon. The resulting films had a thickness ranging from 1.605 µm to 5.165 µm after the calcination process. The presence of double-layer mesoporous carbon resulted in a 20% increase in the photocurrent density compared with the TiO2/C/TiO2 combination when only a single mesoporous carbon layer was employed. The improved performance of these photoanodes can be attributed to the enhanced porosity and increased void space due to the presence of mesoporous carbon. For the first time, it has been demonstrated here that the photoelectrochemical performance of TiO2 can be improved by integrating several layers of mesoporous carbon. Comparison of the rate of removal of humic acid by the prepared photoanodes showed that the highest performance from TiO2/C/C/TiO2 was due to the highest photocurrent density generated. Therefore, this study showed that optimizing the sequence of mesoporous carbon layers can be a viable and inexpensive method for enhanced humic acid removal. PMID:27574426

Fluorescent carbon dot-gated multifunctional mesoporous silica nanocarriers for redox/enzyme dual-responsive targeted and controlled drug delivery and real-time bioimaging.

PubMed

Wang, Ying; Cui, Yu; Zhao, Yating; He, Bing; Shi, Xiaoli; Di, Donghua; Zhang, Qiang; Wang, Siling

2017-08-01

A distinctive and personalized nanocarrier is described here for controlled and targeted antitumor drug delivery and real-time bioimaging by combining a redox/enzyme dual-responsive disulfide-conjugated carbon dot with mesoporous silica nanoparticles (MSN-SS-CD HA ). The carbon dot with controlling and targeting abilities was prepared through a polymerizing reaction by applying citric acid and HA as starting materials (named CD HA ). The as-prepared MSN-SS-CD HA exhibited not only superior photostability and excellent biocompatibility, but also the ability to target A549 cells with overexpression of CD44 receptors. Upon loading the antitumor drug, doxorubicin (DOX), into the mesoporous channels of MSN nanoparticles, CD HA with a diameter size of 3nm completely blocked the pore entrance of DOX-encapsulated MSN nanoparticles with a pore size of about 3nm, thus preventing the premature leakage of DOX and increasing the antitumor activity until being triggered by specific stimuli in the tumor environment. The results of the cell imaging and cytotoxicity studies demonstrated that the redox/enzyme dual-responsive DOX-encapsulated MSN-SS-CD HA nanoparticles can selectively deliver and control the release of DOX into tumor cells. Ex vivo fluorescence images showed a much stronger fluorescence of MSN-SS-CD HA -DOX in the tumor site than in normal tissues, greatly facilitating the accumulation of DOX in the target tissue. However, its counterpart, MSN-SH-DOX exhibited no or much lower tumor cytotoxicity and drug accumulation in tumor tissue. In addition, MSN-SS-CD was also used as a control to investigate the ability of MSN-SS-CD HA to target A549 cells. The results obtained indicated that MSN-SS-CD HA possessed a higher cellular uptake through the CD44 receptor-mediated endocytosis compared with MSN-SS-CD in the A549 cells. Such specific redox/enzyme dual-responsive targeted nanocarriers are a useful strategy achieving selective controlled and targeted delivery of therapeutic reagents with real-time bioimaging, and may also facilitate the development of drug delivery systems for a number of clinical applications. Copyright © 2017 Elsevier B.V. All rights reserved.

Electron anions and the glass transition temperature.

PubMed

Johnson, Lewis E; Sushko, Peter V; Tomota, Yudai; Hosono, Hideo

2016-09-06

Properties of glasses are typically controlled by judicious selection of the glass-forming and glass-modifying constituents. Through an experimental and computational study of the crystalline, molten, and amorphous [Ca12Al14O32](2+) ⋅ (e(-))2, we demonstrate that electron anions in this system behave as glass modifiers that strongly affect solidification dynamics, the glass transition temperature, and spectroscopic properties of the resultant amorphous material. The concentration of such electron anions is a consequential control parameter: It invokes materials evolution pathways and properties not available in conventional glasses, which opens a unique avenue in rational materials design.

Electron anions and the glass transition temperature

DOE PAGES

Johnson, Lewis E.; Sushko, Peter V.; Tomota, Yudai; ...

2016-08-24

Properties of glasses are typically controlled by judicious selection of the glass-forming and glass-modifying constituents. Through an experimental and computational study of the crystalline, molten, and amorphous [Ca 12Al 14O 32] 2+ ∙ (e –) 2, we demonstrate that electron anions in this system behave as glass-modifiers that strongly affect solidification dynamics, the glass transition temperature, and spectroscopic properties of the resultant amorphous material. Concentration of such electron anions is a consequential control parameter: it invokes materials evolution pathways and properties not available in conventional glasses, which opens a new avenue in rational materials design.

Experimental and theoretical investigation of a mesoporous KxWO3 material having superior mechanical strength

NASA Astrophysics Data System (ADS)

Dey, Sonal; Anderson, Sean T.; Mayanovic, Robert A.; Sakidja, Ridwan; Landskron, Kai; Kokoszka, Berenika; Mandal, Manik; Wang, Zhongwu

2016-01-01

Mesoporous materials with tailored properties hold great promise for energy harvesting and industrial applications. We have synthesized a novel tungsten bronze mesoporous material (KxWO3; x ~ 0.07) having inverse FDU-12 type pore symmetry and a crystalline framework. In situ small angle X-ray scattering (SAXS) measurements of the mesoporous K0.07WO3 show persistence of a highly ordered meso-scale pore structure to high pressure conditions (~18.5 GPa) and a material with remarkable mechanical strength despite having ~35% porosity. Pressure dependent in situ SAXS measurements reveal a bulk modulus κ = 44 +/- 4 GPa for the mesoporous KxWO3 which is comparable to the corresponding value for the bulk monoclinic WO3 (γ-WO3). Evidence from middle angle (MAXS) and wide angle X-ray scattering (WAXS), high-resolution transmission electron microscopy (HR-TEM) and Raman spectroscopy shows that the presence of potassium leads to the formation of a K-bearing orthorhombic tungsten bronze (OTB) phase within a monoclinic WO3 host structure. Our ab initio molecular dynamics calculations show that the formation of the OTB phase provides superior strength to the mesoporous K0.07WO3.Mesoporous materials with tailored properties hold great promise for energy harvesting and industrial applications. We have synthesized a novel tungsten bronze mesoporous material (KxWO3; x ~ 0.07) having inverse FDU-12 type pore symmetry and a crystalline framework. In situ small angle X-ray scattering (SAXS) measurements of the mesoporous K0.07WO3 show persistence of a highly ordered meso-scale pore structure to high pressure conditions (~18.5 GPa) and a material with remarkable mechanical strength despite having ~35% porosity. Pressure dependent in situ SAXS measurements reveal a bulk modulus κ = 44 +/- 4 GPa for the mesoporous KxWO3 which is comparable to the corresponding value for the bulk monoclinic WO3 (γ-WO3). Evidence from middle angle (MAXS) and wide angle X-ray scattering (WAXS), high-resolution transmission electron microscopy (HR-TEM) and Raman spectroscopy shows that the presence of potassium leads to the formation of a K-bearing orthorhombic tungsten bronze (OTB) phase within a monoclinic WO3 host structure. Our ab initio molecular dynamics calculations show that the formation of the OTB phase provides superior strength to the mesoporous K0.07WO3. Electronic supplementary information (ESI) available: Experimental details of SEM and TEM measurements, SAXS data analysis, the procedure for Rietveld refinement, peak fitting for the Raman results, the modelling approach, UV-Vis and N2 sorption measurements. See DOI: 10.1039/c5nr07941a

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bolotov, V. V.; Knyazev, E. V.; Ponomareva, I. V.

The oxidation of mesoporous silicon in a double-layer “macroporous silicon–mesoporous silicon” structure is studied. The morphology and dielectric properties of the buried insulating layer are investigated using electron microscopy, ellipsometry, and electrical measurements. Specific defects (so-called spikes) are revealed between the oxidized macropore walls in macroporous silicon and the oxidation crossing fronts in mesoporous silicon. It is found that, at an initial porosity of mesoporous silicon of 60%, three-stage thermal oxidation leads to the formation of buried silicon-dioxide layers with an electric-field breakdown strength of E{sub br} ~ 10{sup 4}–10{sup 5} V/cm. Multilayered “porous silicon-on-insulator” structures are shown to bemore » promising for integrated chemical micro- and nanosensors.« less

A novel low-temperature dendritic cyclotrimerization of 2,6-diacetyl pyridine leading to mesoporous carbon containing pyridine rings

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shin, Yongsoon; Wang, Chong M.; Engelhard, Mark H.

2009-07-01

A simple, direct synthesis of a mesoporous carbon containing pyridine rings is described. This synthesis utilizes the SiCl4 induced cyclotrimerization of 2,6-diacetylpyridine to make a dendritic polymer, built of alternating benzene and pyridine rings. The cyclotrimerization allows for a high degree of crosslinking to take place at low temperatures stabilizing the mesostructure and allowing the carbonization to be carried out at only 600°C, the lowest temperature reported to date for an N-doped mesoporous carbon. The functional mesoporous carbon so formed was found to have a surface area of 1275 m2/g, 35Å pores, and contain 6.8% N.

Mesoporous carbon materials

DOEpatents

Dai, Sheng [Knoxville, TN; Wang, Xiqing [Oak Ridge, TN

2012-02-14

The invention is directed to a method for fabricating a mesoporous carbon material, the method comprising subjecting a precursor composition to a curing step followed by a carbonization step, the precursor composition comprising: (i) a templating component comprised of a block copolymer, (ii) a phenolic compound or material, (iii) a crosslinkable aldehyde component, and (iv) at least 0.5 M concentration of a strong acid having a pKa of or less than -2, wherein said carbonization step comprises heating the precursor composition at a carbonizing temperature for sufficient time to convert the precursor composition to a mesoporous carbon material. The invention is also directed to a mesoporous carbon material having an improved thermal stability, preferably produced according to the above method.

Mesoporous carbon materials

DOEpatents

Dai, Sheng; Wang, Xiqing

2013-08-20

The invention is directed to a method for fabricating a mesoporous carbon material, the method comprising subjecting a precursor composition to a curing step followed by a carbonization step, the precursor composition comprising: (i) a templating component comprised of a block copolymer, (ii) a phenolic compound or material, (iii) a crosslinkable aldehyde component, and (iv) at least 0.5 M concentration of a strong acid having a pKa of or less than -2, wherein said carbonization step comprises heating the precursor composition at a carbonizing temperature for sufficient time to convert the precursor composition to a mesoporous carbon material. The invention is also directed to a mesoporous carbon material having an improved thermal stability, preferably produced according to the above method.

Adsorption studies of heavy metal ions on mesoporous aluminosilicate, novel cation exchanger.

PubMed

Sepehrian, H; Ahmadi, S J; Waqif-Husain, S; Faghihian, H; Alighanbari, H

2010-04-15

Mesoporous aluminosilicates, have been prepared with various mole ratios of Si/Al and Cethyltrimethylammonium bromide (CTAB). They have been characterized by XRD, nitrogen adsorption/desorption measurements, FT-IR and thermogravimetry. Adsorption behavior of heavy metal ions on this adsorbent have been studied and discussed. The results show that incorporation of aluminum ions in the framework of the mesoporous MCM-41 has transformed it into an effective cation exchanger. The K(d) values of several metal ions have been increased. Separation of Sr(II)-Ce(III), Sr(II)-U(VI) and Cd(II)-Ce(III) has been developed on columns of this novel mesoporous cation exchanger. 2009 Elsevier B.V. All rights reserved.

Ordered mesoporous ternary mixed oxide materials as potential adsorbent of biomolecules

NASA Astrophysics Data System (ADS)

Pal, Nabanita; Bhaumik, Asim

2012-05-01

Designing a suitable mesoporous framework material for the selective adsorption or immobilization of biomolecules is a very challenging area of research. Mesoporous ternary Co-Si-Al oxide materials with large mesopore and their nanoscale ordering have been reported. The synthesis of these ternary oxides are accomplished through evaporation induced self-assembly (EISA) method using Pluronic non-ionic surfactant F127 under non-aqueous sol-gel route. N2 sorption study revealed high BET surface areas for these materials. These materials exhibited very efficient and selective adsorption for the essential biomolecules like vitamin C (ascorbic acid), vitamin B6 (pyridoxine) and vitamin B3 (nicotinic acid) from their respective aqueous solutions.

Efficient adsorption concentration and photolysis of acetaldehyde on titania-mesoporous silica composite

NASA Astrophysics Data System (ADS)

Yamaguchi, Satoshi; Matsumoto, Akihiko

2017-07-01

Titania-mesoporous silica composite (TiO2/MCM) was prepared by hydrolysis of titaniumtetraisopropoxide (TTIP) with the presence of mesoporous silica MCM-41. The TiO2/MCM samples consisted of highly dispersed TiO2 on the surface of MCM-41. Dynamic adsorption and photocatalytic decomposition features for acetaldehyde (CH3CHO) were measured by flow method. The amount of CH3CHO decomposition on TiO2/MCM-41 increased with the TiO2 amount, suggesting that a large amount of CH3CHO was adsorbed on mesopores of MCM-41 of the TiO2/MCM and was efficiently decomposed on finely dispersed TiO2 surface by ultraviolet irradiation.

Synthesis of three-dimensionally ordered macro-/mesoporous Pt with high electrocatalytic activity by a dual-templating approach

NASA Astrophysics Data System (ADS)

Zhang, Chengwei; Yang, Hui; Sun, Tingting; Shan, Nannan; Chen, Jianfeng; Xu, Lianbin; Yan, Yushan

2014-01-01

Three dimensionally ordered macro-/mesoporous (3DOM/m) Pt catalysts are fabricated by chemical reduction employing a dual-templating synthesis approach combining both colloidal crystal (opal) templating (hard-templating) and lyotropic liquid crystal templating (soft-templating) techniques. The macropore walls of the prepared 3DOM/m Pt exhibit a uniform mesoporous structure composed of polycrystalline Pt nanoparticles. Both the size of the mesopores and Pt nanocrystallites are in the range of 3-5 nm. The 3DOM/m Pt catalyst shows a larger electrochemically active surface area (ECSA), and higher catalytic activity as well as better poisoning tolerance for methanol oxidation reaction (MOR) than the commercial Pt black catalyst.

Desorption of water from hydrophilic MCM-41 mesopores: positron annihilation, FTIR and MD simulation studies.

PubMed

Maheshwari, Priya; Dutta, D; Muthulakshmi, T; Chakraborty, B; Raje, N; Pujari, P K

2017-02-08

The desorption mechanism of water from the hydrophilic mesopores of MCM-41 was studied using positron annihilation lifetime spectroscopy (PALS) and attenuated total reflection Fourier transform infrared spectroscopy supplemented with molecular dynamics (MD) simulation. PALS results indicated that water molecules do not undergo sequential evaporation in a simple layer-by-layer manner during desorption from MCM-41 mesopores. The results suggested that the water column inside the uniform cylindrical mesopore become stretched during desorption and induces cavitation (as seen in the case of ink-bottle type pores) inside it, keeping a dense water layer at the hydrophilic pore wall, as well as a water plug at both the open ends of the cylindrical pore, until the water was reduced to a certain volume fraction where the pore catastrophically empties. Before being emptied, the water molecules formed clusters inside the mesopores. The formation of molecular clusters below a certain level of hydration was corroborated by the MD simulation study. The results are discussed.

Low-Temperature Fluorination of Soft-Templated Mesoporous Carbons for a High-Power Lithium/Carbon Fluoride Battery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fulvio, Pasquale F.; Brown, Suree S.; Adcock, Jamie

Soft-templated mesoporous carbons and activated mesoporous carbons were fluorinated using elemental fluorine between room temperature and 235 °C. The mesoporous carbons were prepared via self-assembly synthesis of phloroglucinol–formaldehyde as a carbon precursor in the presence of triblock ethylene oxide–propylene oxide–ethylene oxide copolymer BASF Pluronic F127 as the template. The F/C ratios ranged from ~0.15 to 0.75 according to gravimetric, energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy analysis. Materials have mesopore diameters up to 11 nm and specific surface areas as high as 850 m² g⁻¹ after fluorination as calculated from nitrogen adsorption isotherms at -196 °C. Furthermore, the materialsmore » exhibit higher discharge potentials and energy and power densities as well as faster reaction kinetics under high current densities than commercial carbon fluorides with similar fluorine contents when tested as cathodes for Li/CF x batteries.« less

Low-Temperature Fluorination of Soft-Templated Mesoporous Carbons for a High-Power Lithium/Carbon Fluoride Battery

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fulvio, Pasquale F; Dai, Sheng; Guo, Bingkun

Soft-templated mesoporous carbons and activated mesoporous carbons were fluorinated using elemental fluorine between room temperature and 235 C. The mesoporous carbons were prepared via self-assembly synthesis of phloroglucinol formaldehyde as a carbon precursor in the presence of triblock ethylene oxide propylene oxide ethylene oxide copolymer BASF Pluronic F127 as the template. The F/C ratios ranged from 0.15 to 0.75 according to gravimetric, energy dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy analysis. Materials have mesopore diameters up to 11 nm and specific surface areas as high as 850 m2 g 1 after fluorination as calculated from nitrogen adsorption isotherms at 196more » C. Furthermore, the materials exhibit higher discharge potentials and energy and power densities as well as faster reaction kinetics under high current densities than commercial carbon fluorides with similar fluorine contents when tested as cathodes for Li/CFx batteries.« less

Ordered mesoporous silica to enhance the bioavailability of poorly water-soluble drugs: Proof of concept in man.

PubMed

Bukara, Katarina; Schueller, Laurent; Rosier, Jan; Martens, Mark A; Daems, Tinne; Verheyden, Loes; Eelen, Siemon; Van Speybroeck, Michiel; Libanati, Cristian; Martens, Johan A; Van Den Mooter, Guy; Frérart, Françoise; Jolling, Koen; De Gieter, Marjan; Bugarski, Branko; Kiekens, Filip

2016-11-01

Formulating poorly water soluble drugs using ordered mesoporous silica materials is an emerging approach to tackle solubility-related bioavailability problems. The current study was conducted to assess the bioavailability-enhancing potential of ordered mesoporous silica in man. In this open-label, randomized, two-way cross-over study, 12 overnight fasted healthy volunteers received a single dose of fenofibrate formulated with ordered mesoporous silica or a marketed product based on micronized fenofibrate. Plasma concentrations of fenofibric acid, the pharmacologically active metabolite of fenofibrate, were monitored up to 96h post-dose. The rate (C max /dose increased by 77%; t max reduced by 0.75h) and extent of absorption (AUC 0-24h /dose increased by 54%) of fenofibrate were significantly enhanced following administration of the ordered mesoporous silica based formulation. The results of this study serve as a proof of concept in man for this novel formulation approach. Copyright © 2016 Elsevier B.V. All rights reserved.

A mesoporous silica composite scaffold: Cell behaviors, biomineralization and mechanical properties

NASA Astrophysics Data System (ADS)

Xu, Yong; Gao, Dan; Feng, Pei; Gao, Chengde; Peng, Shuping; Ma, HaoTian; Yang, Sheng; Shuai, Cijun

2017-11-01

Mesoporous structure is beneficial to cellular response due to the large specific surface area and high pore volume. In this study, mesoporous silica (SBA15) was incorporated into poly-L-lactic acid (PLLA) to construct composite scaffold by selective laser sintering. The results showed that SBA15 facilitated cells proliferation, which was mainly attributed to its unique intrinsic mesoporous structure and the released bioactive silicon. Moreover, the hydrolyzate of soluble mesoporous silica can adsorb ions to form nucleation sites that promote biomineralization, leading to improve biological activity of the composite scaffold. In addition, the compressive strength, compressive modulus and Vickers hardness of the scaffold were increased by 47.6%, 35.5% and 29.53% respectively with 1.5 wt.% SBA15. It was found that the particle enhancement of uniform distributed SBA15 accounted for the mechanic reinforcement of the composite scaffold. It indicated that the PLLA-SBA15 composite scaffold had potential applications in bone tissue engineering.

Tubular structured hierarchical mesoporous titania material derived from natural cellulosic substances and application as photocatalyst for degradation of methylene blue

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, Haiqing; Liu, Xiaoyan; Huang, Jianguo, E-mail: jghuang@zju.edu.cn

Graphical abstract: Bio-inspired, tubular structured hierarchical mesoporous titania material with high photocatalytic activity under UV light was fabricated employing natural cellulosic substance (cotton) as hard template and cetyltrimethylammonium bromide (CTAB) surfactant as soft template using a one-pot sol-gel method. Highlights: {yields} Tubular structured mesoporous titania material was fabricated by sol-gel method. {yields} The titania material faithfully recorded the hierarchical structure of the template substrate (cotton). {yields} The titania material exhibited high photocatalytic activity in decomposition of methylene blue. -- Abstract: Bio-inspired, tubular structured hierarchical mesoporous titania material was designed and fabricated employing natural cellulosic substance (cotton) as hard template andmore » cetyltrimethylammonium bromide (CTAB) surfactant as soft template by one-pot sol-gel method. The tubular structured hierarchical mesoporous titania material processes large specific surface area (40.23 m{sup 2}/g) and shows high photocatalytic activity in the photodegradation of methylene blue under UV light irradiation.« less

Barium and manganese-doped zinc silicate rods prepared by mesoporous template route and their luminescence property

NASA Astrophysics Data System (ADS)

Dang, Lingyan; Tian, Chen; Zhao, Shifeng; Lu, Qingshan

2018-06-01

Barium and manganese-doped zinc silicates was prepared under hydrothermal treatment by mesoporous template route employing mesoporous silica as an active template. The sample displays a rod-like morphology with a mean diameter of ∼40 nm and a mean length of ∼450 nm, which inherits the characteristics of mesoporous silica. The individual rods show single crystalline and assemble into bundle-like hierarchical structure along the channels of the mesoporous silica. When barium ions together with manganese ions are co-doped in zinc silicate, the green emission corresponding to manganese ions display a significant enhancement, especially for the sample with the barium doping concentration of 0.08, which indicates that an energy transfer from barium to manganese ions takes place. With further increasing barium concentration from 0.08 to 0.10, the recombination between the defects related to barium and the excitation states of the manganese dominates accompanying non-radiative transitions which can reduce the emission efficiency.

Structure of water in mesoporous organosilica by calorimetry and inelastic neutron scattering

NASA Astrophysics Data System (ADS)

Levy, Esthy; Kolesnikov, Alexander I.; Li, Jichen; Mastai, Yitzhak

2009-01-01

In this paper, we describe the preparation of mesoporous organosilica samples with hydrophilic or hydrophobic organic functionality inside the silica channel. We synthesized mesoporous organosilica of identical pore sizes based on two different organic surface functionality namely hydrophobic (based on octyltriethoxysilane OTES) and hydrophilic (3-aminopropyltriethoxysilane ATES) and MCM-41 was used as a reference system. The structure of water/ice in those porous silica samples have been investigated over a range temperatures by differential scanning calorimetry (DSC) and inelastic neutron scattering (INS). INS study revealed that water confined in hydrophobic mesoporous organosilica shows vibrational behavior strongly different than bulk water. It consists of two states: water with strong and weak hydrogen bonds (with ratio 1:2.65, respectively), compared to ice-Ih. The corresponding O-O distances in these water states are 2.67 and 2.87 Ǻ, which strongly differ compared to ice-Ih (2.76 Ǻ). INS spectra for water in hydrophilic mesoporous organosilica ATES show behavior similar to bulk water, but with greater degree of disorder.

Mesoporous Transition Metal Oxides for Supercapacitors.

PubMed

Wang, Yan; Guo, Jin; Wang, Tingfeng; Shao, Junfeng; Wang, Dong; Yang, Ying-Wei

2015-10-14

Recently, transition metal oxides, such as ruthenium oxide (RuO₂), manganese dioxide (MnO₂), nickel oxides (NiO) and cobalt oxide (Co₃O₄), have been widely investigated as electrode materials for pseudo-capacitors. In particular, these metal oxides with mesoporous structures have become very hot nanomaterials in the field of supercapacitors owing to their large specific surface areas and suitable pore size distributions. The high specific capacities of these mesoporous metal oxides are resulted from the effective contacts between electrode materials and electrolytes as well as fast transportation of ions and electrons in the bulk of electrode and at the interface of electrode and electrolyte. During the past decade, many achievements on mesoporous transition metal oxides have been made. In this mini-review, we select several typical nanomaterials, such as RuO₂, MnO₂, NiO, Co₃O₄ and nickel cobaltite (NiCo₂O₄), and briefly summarize the recent research progress of these mesoporous transition metal oxides-based electrodes in the field of supercapacitors.

Hierarchical mesoporous perovskite La0.5Sr0.5CoO2.91 nanowires with ultrahigh capacity for Li-air batteries

PubMed Central

Zhao, Yunlong; Xu, Lin; Mai, Liqiang; Han, Chunhua; An, Qinyou; Xu, Xu; Liu, Xue; Zhang, Qingjie

2012-01-01

Lithium-air batteries have captured worldwide attention due to their highest energy density among the chemical batteries. To provide continuous oxygen channels, here, we synthesized hierarchical mesoporous perovskite La0.5Sr0.5CoO2.91 (LSCO) nanowires. We tested the intrinsic oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activity in both aqueous electrolytes and nonaqueous electrolytes via rotating disk electrode (RDE) measurements and demonstrated that the hierarchical mesoporous LSCO nanowires are high-performance catalysts for the ORR with low peak-up potential and high limiting diffusion current. Furthermore, we fabricated Li-air batteries on the basis of hierarchical mesoporous LSCO nanowires and nonaqueous electrolytes, which exhibited ultrahigh capacity, ca. over 11,000 mAh⋅g –1, one order of magnitude higher than that of LSCO nanoparticles. Besides, the possible reaction mechanism is proposed to explain the catalytic activity of the LSCO mesoporous nanowire. PMID:23150570

The adsorption of gold, palladium and platinum from acidic chloride solutions on mesoporous carbons.

DOE PAGES

Zalupski, Peter R.; McDowell, Rocklan; Dutech, Guy

2014-08-05

Studies on the adsorption characteristics of gold, palladium and platinum on mesoporous carbon (CMK-3) and sulfur-impregnated mesoporous carbon (CMK-3/S) evaluated the benefits/drawbacks of the presence of a layer of elemental sulfur inside mesoporous carbon structures. Adsorption isotherms collected for Au(III), Pd(II) and Pt(IV) on those materials suggest that sulfur does enhance the adsorption of those metal ions in mildly acidic environment (pH 3). The isotherms collected in 1 M HCl show that the benefit of sulfur disappears due to the competing influence of large concentration of hydrogen ions on the ion-exchanging mechanism of metal ions sorption on mesoporous carbon surfaces.more » The collected acid dependencies illustrate similar adsorption characteristics for CMK-3 and CMK-3/S in 1-5 M HCl concentration range. Sorption of metal ions from diluted aqueous acidic mixtures of actual leached electronic waste demonstrated the feasibility of recovery of gold from such liquors.« less