有序介孔SBA-15复合稀土Tb络合物的制备和发光特性

以三嵌段化合物P123为模板剂、正硅酸乙酯(TEOS)为硅源,利用水热法制备出有序介孔二氧化硅SBA-15,随后利用3-氨丙基三乙氧基硅烷(APTES)、乙酰丙酮(ACAC)分步对该有序介孔材料进行改性,再将其置于乙醇溶液中,加入三价稀土Tb的盐溶液进行络合,制备出具有强发光性能的有序介孔纳米复合稀土材料。采用XRD、FTIR和荧光光谱等分析方法对复合材料的结构与性能进行了研究。发现有序介孔材料、第二配体(邻菲口罗啉Phen)对稀土络合物发光强度有重要影响,并对其机理进行了解释。另外,发现其热稳定性也有所提高。     

有序介孔SiO2的制备及其在色谱填料方面的应用

利用水热合成方法,在低浓度盐酸下用三嵌段共聚物EO106PO70EO106（F127）作为模板剂,在100℃,130℃和150℃的条件下,制备了3种笼型介孔二氧化硅.通过粉末N2气吸附-脱附实验表征其孔径（PD）及比表面积（BET）、扫描电镜（SEM）观察其表面形貌、透射电子显微镜（TEM）分析其微观结构;通过表征结果分析,该材料具有笼型介孔结构.同时,将该介孔材料应用在色谱分离方面,对氯苯,苯乙烯,1,2-二苯乙烯,联苯4种物质混合物进行分离,与其他多种二氧化硅材料比较,150℃的条件下合成的KIT-5-150分离效果最好.     

Ordered mesoporous silica materials (SBA-15) with good heat-resistant magnetism

A series of highly ordered mesoporous materials (CF-SBA-15) with heat-resistant magnetism have been successfully prepared from impregnation of cobalt salt, iron salt, and citric acid with as-synthesized SBA-15. XRD and N₂ isotherms indicate that these materials have highly ordered hexagonal mesoporous symmetry and open pore systems. The measurement of magnetic property shows that these materials are ferromagnetic even if calcined at 550 °C for 10 h in air, indicating their good heat-resistant magnetism. These results would be very important for recycle and regeneration of adsorbents and catalysts in practical applications. Moreover, this method may be useful for other mesoporous materials with thermally stable magnetism from a combination of other mesoporous materials such as MCM-41 with magnetic nanoparticles of MnFe₂O₄ and NiFe₂O₄.     

介孔二氧化硅基导电聚合物复合材料热导率的实验研究

本文首先制备并表征了介孔二氧化硅SBA-15、 填充导电聚合物的复合材料PANI/SBA-15和复合材料PPy/SBA-15, 并建立双流计实验台开展了材料压片情况下的热导率研究. 在测量得到复合材料热导率的基础上, 引入当量孔径, 结合测量孔径对 PANI/SBA-15和PPy/SBA-15复合材料热导率随填充量的变化进行了定性分析. 分析表明: PANI/SBA-15和PPy/SBA-15复合材料的热导率比基材SBA-15的热导率大得多; 在相同的测量孔径和当量孔径情况下, PANI/SBA-15复合材料的热导率比PPy/SBA-15复合材料的热导率大; 导电聚合物填充到复合材料孔道内和孔道外都有助于热导率的提高, 填充到孔道内比填充到孔道外对热导率提高的贡献更大.     

Functionalized Ultrabright Fluorescent Mesoporous Silica Nanoparticles

The problem of functionalization of recently reported ultrabright fluorescent mesoporous silica nanoparticles while preserving their fluorescent brightness is solved. This is a serious issue because of the open geometry of mesoporous channels and physical encapsulation of fluorescent dye inside those channels. Amine modification of mesoporous nanoparticles is described to preserve the brightness comparable to that of earlier reported ultrabright silica nanoparticles. Scaling to 40 nm sized particles, amine‐functionalized nanoparticle have fluorescent brightness equivalent to the one of 630 free rhodamine 6G (R6G) dye molecules in water. To demonstrate further most challenging functionalization, which relies on using organic‐solvent‐based chemistry, folic acid conjugation is developed. Two different methods are used to conjugate folites to the amine functionalities. Both methods result in a decrease of fluorescence intensity, which can nonetheless still be called ultrabright. The brightness can drop to either 310 or 80 R6G dye molecules per particle of nominal diameter of 40 nm.     

Adsorption of octadecyltrichlorosilane on mesoporous SBA-15

Adsorption of octadecyltrichlorosilane (OTS) on mesoporous SBA-15 has been studied by using Brunauer-Emmett-Teller (BET) surface area analysis, scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX), Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and thermo-gravimetric analysis (TGA) techniques. BET surface area analysis shows decrease of surface area from 930 to 416 m²/g after OTS adsorption. SEM pictures show close attachment of SBA-15 particles. EDAX measurements show increase of carbon weight percentage and decrease of oxygen and silicon weight percentage. XPS results closely support EDAX analysis. FTIR spectra shows presence of methyl (-CH₃) and methylene (-CH₂) bands and oriented OTS monolayer on SBA-15. Thermo-gravimetric analysis shows that the OTS adsorbed on SBA-15 are stable up to a temperature of 230 °C and that the OTS monolayers decompose between 230 and 400 °C.     

Functionalized SBA-15 materials for bilirubin adsorption

To investigate the driving force for bilirubin adsorption on mesoporous materials, a comparative study was carried out between pure siliceous SBA-15 and three functionalized SBA-15 mesoporous materials: CH₃-SBA-15 (MS), NH₂-SBA-15 (AS), and CH₃/NH₂-SBA-15 (AMS) that were synthesized by one-pot method. The obtained materials exhibited large surface areas (553-810 m²/g) and pore size (6.6-7.1 nm) demonstrated by XRD and N₂-ad/desorption analysis. The SEM images showed that the materials had similar fiberlike morphology. The functionalization extent was calculated according to ²⁹Si MAS NMR spectra and it was close to the designed value (10%). The synthesized mesoporous materials were used as bilirubin adsorbents and showed higher bilirubin adsorption capacities than the commercial active carbon. The adsorption capacities of amine functionalized samples AMS and AS were larger than those of pure siliceous SBA-15 and MS, indicating that electrostatic interaction was the dominant driving force for bilirubin adsorption on mesoporous materials. Increasing the ionic strength of bilirubin solution by adding NaCl would decrease the bilirubin adsorption capacity of mesoporous material, which further demonstrated that the electrostatic interaction was the dominant driving force for bilirubin adsorption. In addition, the hydrophobic interaction provided by methyl groups could promote the bilirubin adsorption.     

Silica Monolith Properties Modified by Reaction Mixture Composition and Calcination Process

Russian Physics Journal - The paper presents the sol-gel synthesis of porous silica monolith in the presence of cetyltrimethylammonium bromide and polyethylene glycol. Parameters of the porous...     

Melting of Naphthalene Confined in Mesoporous Silica MCM-41

The ²H nuclear magnetic resonance (NMR) solid-echo spectra of naphthalene molecules as guests in the mesopores of neat MCM-41 with a pore width of 3.3 nm were measured in the temperature regime from 180 to 250 K. A strong reduction of the melting point of the naphthalene molecules by 152 K is observed. The line shape changes in the melting region were simulated with two different models, namely, the model of a narrow distribution of activation energies, which is typical for a crystal-like phase, and a two-phase model. Both models indicate a relatively narrow distribution of melting points of the naphthalene molecules inside the pores, indicative of a rather well-defined structure of the naphthalene molecules inside the pores. This finding supports the proposal of a plastic crystalline phase previously proposed by other groups.     

Direct synthesis and characterization of phenyl-functionalized SBA-15

Phenyl-functionalized SBA-15 materials (Ph-SBA-15) were directly synthesized by using tri-block copolymer Pluronic P123 as templating agent under acidic conditions. The samples were characterized by Fourier transform infrared (FT-IR) spectra, X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), thermogravimetry analysis (TGA) and N₂ adsorption-desorption. The results show that the phenyl groups are covalently attached to the pore wall of SBA-15 after modification. The functionalized materials still preserve a desirable two-dimensional P6mm hexagonal structure and have large specific surface area and pore volume although the molar ratio of phenyltrimethoxysilane in total silica precursors is as high as 23.0%.     

Effects of Vacuum on Fused Silica UV Damage

Damage points induced by 355 nm laser irradiation increase more quickly on the surface of fused silica in vacuum of about 10^-3 Pa than in atmospheric air at the same fluence. The larger concentration of point defects in vacuum is confirmed by photoluminescence intensity. X-ray photoelectron spectroscopy and infrared absorption indicate the formation of sub-stoichiometric silica on the surface. The degradation mechanism of fused silica in vacuum is discussed.     

Solid-State MAS NMR Studies of Sulfonic Acid-Functionalized SBA-15

Solid-state magic-angle spinning (MAS) nuclear magnetic resonance (NMR) was used to characterize propylsulfonic acid-functionalized SBA-15 materials prepared by the cocondensation method. The propylsulfonic acid-group concentration and distribution was systematically varied from 2.5 to 10%. As a way of coupling two acid sites and controlling the acid site spatial distribution, tethered propylsulfonic acid groups were incorporated into SBA-15. ¹³C, ²⁹Si and ¹H MAS NMR were used to determine the extent of functionalization. Probe molecules, such as triethylphosphine oxide and diphenyldiphosphines were used to evaluate acid site strength and acid site distributions, respectively. Authors' address: Sarah C. Larsen, Department of Chemistry, University of Iowa, Iowa City, IA 52242, USA     

Humidity sensitive properties of K-doped mesoporous silica SBA-15

Humidity sensors based on K-doped mesoporous silica SBA-15 were prepared and characterized by XRD, SEM, TEM and N₂ adsorption-desorption isotherms. The humidity sensing test results show that KCl doping improves the sensing characteristic of humidity sensors. The optimal result is obtained via sample 50 wt% KCl-doped SBA-15, which exhibits an excellent linearity in the whole humidity range of 11%-95%. It also shows satisfactory reversibility and fast responses to the environmental moisture. The investigation of the humidity sensitive characteristics of the K-doped SBA-15 sensor shows that this material could have good prospects of application in humidity sensor.     

Efficient epoxidation over cyanocobalamine containing SBA-15 organic-inorganic nanohybrids

SBA-15 mesoporous silica is synthesized using triblock copolymer P123 surfactant and chemically modified by aminopropyl, thiol, ammonium and sulfonic acid functional groups. Functionalization is performed via post synthesize method using 3-aminopropyltriethoxysilane (APTES) or 3-mercatopropyl trimethoxysilane (MPTMS) precursor. The as synthesized mesoporous systems are applied for immobilization of cyanocobalamine. Functionalization effectively improves sorption properties of the supports, while different functional groups exert different effects. The organic-inorganic mesoporous materials are characterized via X-ray diffraction (XRD), nitrogen adsorption and desorption, transmission electron microscopy (TEM), FT-IR and inductively coupled plasma-optical emission (ICP). The newly synthesized systems exhibit high catalytic activity for heterogeneous epoxidation of cyclooctene in presence of hydrogen peroxide. Reaction conditions are optimized, effect of functional groups on performance of the catalysts is taken into consideration and reusability of the designed heterogeneous systems is studied. Systems with chemically modified supports are shown to be more efficient and stable catalysts however; chemical nature of functional groups plays a crucial role.     

Naproxen drug delivery using periodic mesoporous silica SBA-15

In this paper, we present the release of naproxen from hexagonal periodic mesoporous silica SBA-15, which serves as a drug delivery system. Naproxen, the well-known nonsteroidal anti-inflammatory drug (NSAID), was loaded into the pores of SBA-15 silica modified with aminopropyl groups. The physicochemical properties of the modified sample (A-SBA-15/napro) were compared with the unmodified SBA-15 mesoporous silica loaded with the drug (SBA-15/napro). The kinetic of the naproxen release into the physiological solution was studied. The released amount of naproxen represented 90.7% from the unmodified SBA-15 in 72 h, while from the sample A-SBA-15/napro the released amount represented about 80.9%. The prepared materials were characterized by nitrogen adsorption/desorption, Small angle X-ray scattering (SAXS), Fourier-transform infrared spectroscopy (FT-IR) and the thermoanalytical methods (TG/DTA). Thin layer chromatography (TLC) was used for quantitative determination of the released naproxen.     

Thermal conductivity of a kind of mesoporous silica SBA-15

Mesoporous silica SBA-15 consists of uniform hexagonal, unconnected cylindrical channels with diameters that can be tuned within a range of 1.5 nm-30 nm, and is thought to have a special thermal conductivity. The theoretical investigation of the shell thermal conductivity of the mesoporous silica is performed in the relaxation time approximation in this paper and an available one-dimensional heat transfer model is used to predict the effective thermal conductivity （ETC） of the mesoporous silica. The experimental result of the ETC is also presented for comparison. The shell thermal conductivity of the mesoporous silica decreases with mesochannel radius increasing or wall thickness decreasing, but does not strictly decrease with porosity increasing. The thermal radiation possibly plays a primary role in heat transfer at the large porosity scale. The predicted ETC of SBA-15 with only conduction considered is quite low at the large porosity, even lower than the thermal conductivity of the silica aerogels. To realize it, doping carbon or other matters which can strongly absorb infrared light into SBA-15 is a possible way.     

Highly anisotropic distribution of iron nanoparticles within MCM-41 Mesoporous Silica

Electron microscopy techniques are used to visualize the spatial distribution of iron nanoparticles inside a mesoporous MCM-41 molecular sieve. Direct observation of the iron oxide nanoparticles by STEM-HAADF imaging reveals a highly non-uniform spatial distribution inside the mesopores. These particles are retained in the pores after a reduction treatment unlike the behavior found in other similar systems. It is found that thermal treatments induce changes in its morphology, creating nanowires from particle strings.     

Long-Range Behavior of Dual-Restricted QCD Vacuum

We analyze the geometrical structure of the local non-Abelian gauge theory in terms of the magnetic symmetry, using the resemblance between the non-Abelian gauge formulations and Einstein's theory of gravitation in a higher dimensional unified space. The mathematical foundation of dual QCD in fiber bundle form is then discussed and used for the analysis of the important problem of color confinement in QCD. The associated Lagrangian formulation in magnetic gauge is shown to lead to dual dynamics due to the emergence of the topological charges of magnetic nature. The dynamical breaking of magnetic symmetry is shown to lead to the magnetic condensation of the QCD vacuum. A state of the dual superconductivity in the QCD vacuum is then shown to evolve which ultimately pushes the QCD vacuum to the confining phase. The flux tube structure of the magnetically condensed QCD vacuum is analyzed by computing the asymptotic string solutions of the field equations. The energy content of such confining structures is computed and analyzed in terms of its logarithmic and linear nature.     

高比表面积有序介孔碳的制备及光谱表征

以酚醛树脂低聚物为有机前驱体、正硅酸四乙酯(TEOS)为无机前驱体、嵌段共聚物F127为模板,采用蒸发诱导三组分共组装的方法合成了具有高比表面积的有序介孔碳材料.利用X射线衍射仪(XRD)、透射电子显微镜(TEM)、傅里叶变换红外光谱仪(FTIR)、拉曼光谱仪(Raman)、氮气吸附脱附仪对该材料的组成、结构及形貌等进...     

Multifunctional Iron-Doped Hollow Mesoporous Silica Nanoregulator for Enhanced Tumor Chemodynamic Therapy

Chemodynamic therapy (CDT) is a promising method that uses endogenous hydrogen peroxide (H₂O₂) to produce cytotoxic hydroxyl radicals (•OH) via Fenton reaction to kill tumor cells. However, the insufficient contents of H₂O₂ and the presence of glutathione (GSH) can significantly reduce the therapeutic effect of CDT. Herein, a multifunctional nanoregulator (3-AT&MA@FHM) that combines Fe-doped hollow mesoporous silica nanoparticles (Fe-doped hMSN, or FHM) with 3-amino-1,2,4-triazole (3-AT) and maleimide (MA) are developed to overcome these challenges. After endocytosis by tumor cells, FHM part of the nanoregulator degrades in a mildly acidic intracellular environment and releases Fe³⁺ for CDT. The subsequently released 3-AT serves as a catalase inhibitor to promote the accumulation of H₂O_2, while MA acts as a GSH scavenger to decrease the GSH content in tumor cells. This multifunctional nanoplatform simultaneously regulates the contents of H₂O₂-the substrate for Fenton reaction and GSH-the main antioxidant, resulting in a significantly enhanced CDT effect. Moreover, organoids are used for safety and toxicity evaluation. The results of organoids experiments showed similar trends to those of cellular experiments, but MIO is more resistant to stress than cells. This study is expected to provide a novel idea for the design of highly efficient CDT nanosystems.