Highly selective fluorescent chemosensor for detecting Hg(II) in water based on pyrene functionalized core–shell structured mesoporous silica

Novel pyrene functionalized mesoporous core–shell structured silica (denoted as SiO₂@mSiO₂/Py-Si) was designed and synthesized as a highly selective fluorescent chemosensor for detecting Hg²⁺ in water. The core–shell structured silica was prepared by a simple sol–gel process through coating SiO₂ nanospheres with a layer of ordered mesoporous silica. The surface of outer mesoporous silica shell was then further functionalized by the fluorescent chromophore alkoxysilane modified pyrene (Py-Si). XRD data confirmed that the hexagonal ordered mesoporous structure was preserved after functionalization. The chemosensing material successfully exhibited a remarkable “turn on” response toward Hg²⁺ over miscellaneous metal ions. A good linear response towards Hg²⁺ in the concentration range of 10^?8–10^?4 M was constructed with R²=0.9913. Most importantly, a satisfactory detection limit of 3.4×10^?9 g mL^?1 (down to ppb level) was obtained, which is 100 times lower than our previous report of covalently grafted Py-OH to the bulk mesoporous silica SBA-15. These results indicated that SiO₂@mSiO₂/Py-Si can be used as a highly selective and sensitive fluorescence sensor for Hg²⁺.     

Mesoporous silica-coated superparamagnetic particles prepared by pseudomorphic transformation and their application in purification of plasmid DNA

Abstract  

Mesoporous silica-coated superparamagnetic particles were prepared via pseudomorphic transformation of pre-made amorphous silica-coated Fe₃O₄–polymer composite particles using n-cetyltrimethylammonium bromide (CTAB) and 1,3,5-trimethyl benzene (MES) as template. The mesoporous particles presented almost the same size, shape, and magnetic property as the original amorphous particles but an ordered mesoporous shell with wormhole-like pore structure. The pore size of the shells increased from 2.4 to 3.1 and 4.2 nm as the molar ratio of MES/CTAB increased from 0 to 1.0 and 1.5. DNA extraction experiments showed the mesoporous particles were qualified for purification of plasmid DNA from bacterial lysate.     

Ultrasonic-assisted ultra-rapid synthesis of monodisperse meso-SiO2@Fe3O4 microspheres with enhanced mesoporous structure

A core–shell-type of meso-SiO₂@Fe₃O₄ microsphere was synthesized via an ultrasonic-assisted surfactant-templating process using solvothermal synthesized Fe₃O₄ as core, tetraethoxysilane (TEOS) as silica source, and cetyltrimethyl ammonium bromide (CTAB) as templates. The samples were characterized by FT-IR, XRD, TEM, N₂ adsorption–desorption technology, and vibrating sample magnetometer (VSM). The results show that as-prepared meso-SiO₂@Fe₃O₄(E) and meso-SiO₂@Fe₃O₄(C) microspheres, treated by acetone extraction and high temperature calcination, respectively, still maintain uniform core–shell structure with desirable mesoporous silica shell. Therein, the meso-SiO₂@Fe₃O₄(E) microspheres possess a distinct pore size distribution in 1.8–3.0 nm with large specific surface area (468.6 m²/g) and pore volume (0.35 cm³/g). Noteworthily, the coating period of this ultrasonic-assisted method (40 min) is much shorter than that of the conventional method (12–24 h). The morphology of microspheres and the mesoporous structure of silica shell are significantly influenced by initial concentration of CTAB (C_CTAB), ultrasonic irradiation power (P) and ultrasonic irradiation time (t). The acceleration roles of ultrasonic irradiation take effect during the whole coating process of mesoporous silica shell, including hydrolysis-condensation process of TEOS, co-assembly of hydrolyzed precursors and CTAB, and deposition of silica oligomers. In addition, the use of ultrasonic irradiation is favorable for improving the homogeneity of silica shell and the monodispersity of meso-SiO₂@Fe₃O₄ microspheres.     

Synthesis of multi-wall carbon nanotubes by the pyrolysis of ethanol on Fe/MCM-41 mesoporous molecular sieves

Ordered hexagonal arrangement MCM-41 mesoporous molecular sieves were synthesized by the traditional hydrothermal method, and Fe-loaded MCM-41 mesoporous molecular sieves (Fe/MCM-41) were prepared by the wet impregnation method. Their mesoporous structures were testified by X-ray diffraction (XRD) and the N₂ physical adsorption technique. Carbon nanotubes (CNTs) were synthesized by the chemical vapor deposition (CVD) method via the pyrolysis of ethanol at atmospheric pressure using Fe/MCM-41 as a catalytic template. The effect of different reaction temperatures ranging from 600 to 800 ^°C on the formation of CNTs was investigated. The resulting carbon materials were characterized by various physicochemical techniques such as transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and Raman spectroscopy. The results show that multi-wall carbon nanotubes (MWCNTs) with an internal diameter of ca. 7.7 nm and an external diameter of ca. 16.9 nm were successfully obtained by the pyrolysis of ethanol at 800 ^°C utilizing Fe/MCM-41 as a catalytic template.     

Facile preparation of mesoporous titanium nitride microspheres as novel adsorbent for trace Cd2+ removal from aqueous solution

A simple and facile route is developed for the preparation of mesoporous titanium nitride (TiN) microspheres with a large surface area and a highly porous structure. This method involves the preparation of an amorphous precursor via a solvothermal reaction and subsequent short-time nitridation process to mesoporous TiN. X-ray diffraction and X-ray photoelectron spectroscopy analyses confirm the composition of the resultant sample. The mesoporous structure of the as-prepared TiN sample has been studied by nitrogen adsorption/desorption measurement. The surface area obtained by the Brunauer–Emmett–Teller method is 50.6 m² g⁻¹ and the pore sizes are in the range of 2.0–4.0 nm. In addition, the obtained sample is evaluated as a new sorbent for Cd²⁺ removal. Experimental parameters such as solution pH, contact time and concentration of adsorbate are optimized. The maximum adsorption capacity for Cd²⁺ removal is found to be 12.40 mg g⁻¹ and it is a potentially attractive adsorbent for Cd²⁺ removal from aqueous solution.     

One-pot synthesis of hybrid nanospheres with multistructure for selective adsorption of Hg<Superscript>2+</Superscript>

Novel complex nanospheres with core/shell structure for selective adsorption of Hg²⁺ have been prepared by a simple one-pot method. Scanning electron microscopy (SEM) and transmission electron microscope (TEM) images showed the nanospheres had perpendicularly thiol-functionalized mesoporous SiO₂ hybrid shell and Fe₃O₄@SiO₂ core (Fe₃O₄@nSiO₂@mSiO₂–SH). XRD patterns of as-synthesized nanospheres confirmed the observation of the SEM and TEM. The size of the nanospheres is about 100 nm. Based on the analysis of N₂ sorption–desorption isotherm, the surface area and pore volume of the adsorbent are 861 m²/g and 0.48 cm³/g, respectively. The saturation magnetization value for Fe₃O₄@nSiO₂@mSiO₂–SH is as high as 6.87 emu g⁻¹. The nanospheres showed more accessible active sites and high dispersibility in water, exhibited excellent performance for selective Hg²⁺ adsorption, had a stable structure, and could be recycled easily with magnet.     

Core-shell structured mesoporous silica nanoparticles equipped with pyrene-based chemosensor: Synthesis, characterization, and sensing activity towards Hg(II)

In this paper, we construct core-shell structured mesoporous silica nanoparticles with spherical SiO₂ as the core and mesoporous silica as the shell, offering both large surface-area-to-volume-ratio and short channels. With this core-shell structured mesoporous silica nanoparticles as supporting medium, a chemosensor of pyrene, owing advantages of large Stokes shift, high quantum yield and excellent photostability, is grafted into the channels of the nanoparticles, aiming at a Hg(II) detector with quick response and high selectivity. The sensing performance of the resulting composite material is investigated in detail. Data suggest that the composite material is thermally stable enough for actual applications and highly selective towards Hg(II), and a linear response with detection limit of 10⁻⁸ mol/L is finally realized, which means that it is a promising biochemo-sensing material for Hg(II) detection.     

Effect of the Si/Ce molar ratio on the textural properties of rare earth element cerium incorporated mesoporous molecular sieves obtained room temperature

Rare earth Ce-incorporated MCM-41 mesoporous molecular sieves (CeMCM-41) were synthesized via a direct and nonhydrothermal method at room temperature from sodium silicate and ammonium cerium (IV) nitrate as raw materials. Cetyltrimethyl ammonium bromide (CTAB) was used as a template. The resultant samples were characterized by means of powder X-ray diffraction (XRD), transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FT-IR), diffuse reflectance ultraviolet–visible spectroscopy (UV–vis) and N₂ physical adsorption, respectively. The effect of the Si/Ce molar ratio on the crystalline structure and textural properties of CeMCM-41 was also investigated. The experimental results show that ordered CeMCM-41 mesoporous molecular sieves were successfully synthesized at room temperature and the resultant mesoporous materials have specific surface areas in the range of 594–1369 m²/g and average pore sizes in the range of ca. 2.5–2.8 nm. It has been found that the structural properties are strongly related to the amounts of cerium incorporation. When the cerium content increased in the samples, the intensity of the peak (1 0 0) was gradually reduced, and the surface area and structural regularity were diminished.     

Structural and electrochemical characterization of mesoporous thin films of Nb2xV2 − 2xO5 upon lithium intercalation

Nb_2xV_2 ? 2xO₅ (0 ≤ x ≤ 1) powders were prepared by a synthetic route based on the inorganic polymerization of alkoxy-choride precursors and characterized by a combination of X-ray diffraction, ⁵¹V and ⁹³Nb NMR and Raman spectroscopy. Amorphous mesoporous thin films of similar compositions were successfully prepared by a modified Evaporation Induced Self Assembly method using polystyrene-b-polyethyleneoxide diblock copolymer as structuring agent. The electrochemical properties of the mesoporous films upon lithium insertion–deinsertion are investigated by cyclic voltammetry. This study highlights the advantages of such nanoarchitecture in terms of increased capacity to insert lithium.     

Synthesis and microwave absorbing properties of FeNi alloy incorporated ordered mesoporous carbon–silica nanocomposite

Ordered mesoporous carbon–silica/FeNi nanocomposite were prepared by a sol–gel method and following sintering process. The electromagnetic parameters were measured in the 0.5–18 GHz range. Compared with ordered mesoporous carbon–silica composite, the permittivity of ordered mesoporous carbon–silica/FeNi nanocomposite decreases, while the permeability almost remains unchanged. The optimal reflection loss of ordered mesoporous carbon–silica/FeNi nanocomposite can reach ?45.6 dB at 11.1 GHz for a layer thickness of 3.0 mm. The enhanced microwave absorption of the mesoporous carbon–silica/FeNi nanocomposite is due to better balance between the complex permittivity and permeability, geometrical effect, as well as multiple reflections by the ordered mesoporous structure.     

Adsorptive removal and kinetics of methylene blue from aqueous solution using NiO/MCM-41 composite

Highly ordered mesoporous material MCM-41 was synthesized from tetraethylorthosilicate (TEOS) as Si source and cetyltrimethylammonium bromide (CTAB) as template. Well-dispersed NiO nanoparticles were introduced into the highly ordered mesoporous MCM-41 by chemical precipitation method to prepare the highly ordered mesoporous NiO/MCM-41 composite. X-ray diffraction (XRD) analysis, transmission electron microscopy (TEM) and high-resolution TEM (HRTEM), and nitrogen adsorption–desorption measurement were used to examine the morphology and the microstructure of the obtained composite. The morphological study clearly revealed that the synthesized NiO/MCM-41 composite has a highly ordered mesoporous structure with a specific surface area of 435.9 m² g⁻¹. A possible formation mechanism is preliminary proposed for the formation of the nanostructure. The adsorption performance of NiO/MCM-41 composite as an adsorbent was further demonstrated in the removal azo dyes of methyl orange (MO), Congo red (CR), methylene blue (MB) and rhodaming B (RB) under visible light irradiation and dark, respectively. The kinetics and mechanism of removal methylene blue were studied. The results show that NiO/MCM-41 composite has a good removal capacity for organic pollutant MB from the wastewater under the room temperature. Compared with MCM-41 and NiO nanoparticles, 54.2% and 100% higher removal rate were obtained by the NiO/MCM-41 composite.     

Sonochemical reactions with mesoporous alumina

Herein, we report the sonochemical reactions with MSU-X mesoporous alumina (m-Al₂O₃) in aqueous solutions. Sonication (f = 20 kHz, I = 30 W cm^?2, W_aq = 0.67 W mL^?1, T = 36–38 °C, Ar) causes significant acceleration of m-Al₂O₃ dissolution in the pH range of 4–11. Moreover, power ultrasound has a dramatic effect on the textural properties and phase composition of m-Al₂O₃. Short-time sonication at pH = 4 leads to the formation of nanorods and nanofibers of boehmite, AlO(OH). Prolonged ultrasonic treatment causes high aspect morphology transformation to aggregated nanosheets in weakly acid solutions or plated nanocrystals in alkaline solutions. Sonochemical products in alkaline medium are composed principally from boehmite and small amounts of bayerite, Al(OH)₃. Silent hydrolysis of m-Al₂O₃ yields boehmite at pH = 4 and bayerite at pH = 11. The effect of ultrasound on the textural properties of mesoporous alumina as well as on the transformation of nanosized bayerite to boehmite can be consistently attributed to the transient strong heating of the liquid shell surrounding the cavitation bubble which caused the chemical processes similar to those occurred during hydrothermal treatment.     

Fabrication and application of highly ordered mesoporous Co3O4, NiO, and their metals

Highly ordered mesoporous Co₃O₄, NiO, and their metals were synthesized by nanocasting method using there corresponding mesoporous SBA-15 silica as a template. The obtained porous metal oxides have high surface areas, large pore volume, and a narrow pore size distribution. The N₂-adsorption data for mesoporous metal oxides have provided the BET area of 257.7 m² g⁻¹ and the total pore volume of 0.46 cm³ g⁻¹. The mesoporous metals were employed as a catalyst in the synthesis of (S)-3-pyrrolidinol from chiral (S)-4-chloro-3-hydroxybutyronitrile, and a high yield to (S)-3-pyrrolidinol-salt was obtained on the mesoporous Co metal catalyst.     

Synthesis and characterization of mesoporous ZnS with narrow size distribution of small pores

Pure, nanocrystalline cubic ZnS forming a stable mesoporous structure was synthesized at room temperature by a non-toxic surfactant-assisted liquid–liquid reaction, in the 9.5–10.5 pH range of values. The appearance of an X-ray diffraction (XRD) peak in the region of very small angles (∼ 2°) reveals the presence of a porous material with a narrow pore size distribution, but with an irregular arrangement of the pores, a so-called worm hole or sponge-like material. The analysis of the wide angle XRD diffractograms shows the building blocks to be ZnS nanocrystals with cubic structure and average diameter of 2 nm. Transmission electron microscopy (TEM) investigations confirm the XRD results; ZnS crystallites of 2.5 nm with cubic (blende) structure are the building blocks of the pore walls with pore sizes from 1.9 to 2.5 nm, and a broader size distribution for samples with smaller pores. Textural measurements (N₂ adsorption–desorption isotherms) confirm the presence of mesoporous ZnS with a narrow range of small pore sizes. The relatively lower surface area of around 100 m²/g is attributed to some remaining organic molecules, which are filling the smallest pores. Their presence, confirmed by IR spectroscopy, seems to be responsible for the high stability of the resulting mesoporous ZnS as well. PACS  61.46.Df; 68.37.Lp; 78.67.-n; 81.05.Ea; 81.07.Bc     

Hydrothermal synthesis of mesoporous Co3O4 nanobelts by means of a compound precursor

In the present work, high surface area mesoporous cobalt oxide (Co₃O₄) nanobelts have been synthesized by thermal treatment of cobalt hydroxide carbonate (CHC) precursors. CHC nanobelts were prepared by a facile hydrothermal method. Control experiments with variations in reaction time, solvent and different cobalt source revealed that temperature and sulfates are key factors in determining the formation of CHC nanobelts. Scanning electron microscopy and transmission electron microscopy images showed that the Co₃O₄ nanobelts consisted of mesoporous nanobelts with the average width of 40 nm. Brunauer–Emmett–Teller (BET) gas adsorption measurement further indicated that the products presented a rather large surface area (172.09 m² g^?1).     

Carbon and transition metal containing titanium phosphates as electrodes for lithium ion batteries

We prepared transition metal containing titanium phosphates obtained from mesoporous titanium phosphate treated with cobalt and copper acetates and subsequently heated at 573 K under either air or nitrogen atmospheres. The first treatment with acetates incorporates the metal and acetate ions in the system. Moreover, it partially extracts the director agent. Total extraction of the surfactant can be reached in the copper samples after heating twice. However, the surfactant is not removed from the cobalt samples under the thermal conditions therein used. The composition of the heated materials is close to NASICON structures with a formula close to M_1.5Ti_1.5(PO₄)₃ (M = Co,Cu). A certain content in elemental carbon is observed in the samples obtained under nitrogen atmosphere, which are also more conductive than those prepared under air. The first discharge of lithium cells based in these mesoporous materials show electrochemical activity of Ti⁴⁺/Ti³⁺, Co²⁺/Co⁰ and Cu²⁺/Cu⁰ couples in the OCV–1.0 V region. Below this voltage, the discharge profiles are typical of phosphate systems where Li₃PO₄ is a product of the electrochemical reaction with lithium and, moreover, electrolyte solvent is reduced. Electrolyte is more degraded when the samples contain carbon. Capacities as high as 1600 mA h g^− 1 can be obtained at deep discharge. However, there is an irreversible capacity loss in the four systems due to the occurrence of insulating products as Li₃PO₄ and a solid electrolyte interface.     

Facile preparation and characterization of hollow poly(St-co-MMA-co-BA-co-MAA) core–double shell latex nanoparticles for electrophoretic displays

Novel core–double shell particles with poly(methyl methacrylate-co-butyl acrylate) (PMMA-co-BA) as the cores, poly(methyl methacrylate-co-butyl acrylate-co-methacrylic acid) (PMMA-co-BA-co-MAA) as the inner shells, poly(styrene-co-methyl methacrylate) (PS-co-MMA) as the outer shells were prepared by soap-free emulsion polymerization. The acid–alkali osmotic swelling processes were made before the outer shells wrapped for bigger aperture. The optimal experiment conditions were summarized. The morphology and size of the hollow latex particles were observed by transmission electron microscopy. The results showed that the uniform sizes of the hollow latex particles were about 230 nm. The electrophoretic mobility of them in tetrachloroethylene was 0.91 × 10⁻¹⁰ m² V⁻¹ s⁻¹, and the Zeta-potential was 5.87 mV. The results showed that the hollow polymer particles can used as background particles.     

Synthesis and characterization of Co (Ni or Cu)-MCM-41 mesoporous molecular sieves with different amount of metal obtained by using microwave irradiation method

Co (Ni or Cu)-MCM-41 mesoporous molecular sieves with different amount of metal were synthesized by using cetyltrimethyl ammonium bromide as a template and by a novel microwave irradiation method. These samples were characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR) and N₂ physical adsorption. The experimental results show that Co (Ni or Cu)-MCM-41 mesoporous molecular sieves were successfully synthesized. When the as-synthesized samples were calcined at 550 °C for 10 h, the template was effectively removed. Under microwave irradiation condition, Co-MCM-41 mesoporous molecular sieves have specific surface areas in a range of 745.7-1188.8 m²/g and average pore sizes in a range of 2.46-2.75 nm; Ni-MCM-41 mesoporous molecular sieves have specific surface areas in a range of 625.8-1161.3 m²/g and average pore sizes of ca. 2.7 nm; Cu-MCM-41 mesoporous molecular sieves have specific surface areas in a range of 601.6-1142.9 m²/g and average pore sizes in a range of 2.46-2.76 nm. On the other hand, with increasing the introduced metal amount, the specific surface area and pore volume of the synthesized Co (Ni or Cu)-MCM-41 mesoporous molecular sieves became small, and the mesoporous ordering of the samples became poor. Under the comparable synthesis conditions, the synthesized Co-MCM-41 mesoporous molecular sieve has a bigger specific surface area and a more uniform pore distribution as compared with the synthesized Ni-MCM-41and Cu-MCM-41 mesoporous molecular sieves.     

Chemical effects on the L-shell X-ray fluorescence parameters of Ta and W compounds

The L shell X-ray production cross-sections, the intensity ratios_, and the average fluorescence yields of pure Ta, W and their compounds have been analysed. The targets were irradiated with γ-photons at 59.5 keV from a ²⁴¹Am annular source and detected using an Ultra-LEGe detector with resolution of 150 eV at 5.9 keV. The experimental results were compared with the other theoretical and experimental results. The obtained results were interpreted according to the chemical effect and influence of removing electrons from the shells above the L shell.     

Development of high protonic conductors based on amorphous mesoporous alumina

The proton conductivity of amorphous mesoporous alumina synthesized with various pore sizes was examined. A systematic dependence of conductivity upon pore size was observed, with increased conductivity as the pore size increased. The highest conductivity, 0.004 S·cm^− 1, was obtained at 303 K and 90% relative humidity (RH). The RH dependence of the water content was determined. Proton mobility was investigated by ¹H-NMR. At 30% RH, the width of the ¹H-NMR line decreased with increasing pore size, suggesting an increase in proton mobility. At 90% RH, the increase of the ¹H-NMR sharp peak is accordant with the increase in conductivity as the pore size increased.