Structure and functionalization of mesoporous bioceramics for bone tissue regeneration and local drug delivery

This review article describes the importance of structure and functionalization in the performance of mesoporous silica bioceramics for bone tissue regeneration and local drug delivery purposes. Herein, we summarize the pivotal features of mesoporous bioactive glasses, also known as 'templated glasses' (TGs), which present chemical compositions similar to those of conventional bioactive sol-gel glasses and the added value of an ordered mesopore arrangement. An in-depth study concerning the possibility of tailoring the structural and textural characteristics of TGs at the nanometric scale and their influence on bioactive behaviour is discussed. The highly ordered mesoporous arrangement of cavities allows these materials to confine drugs to be subsequently released, acting as drug delivery devices. The functionalization of mesoporous silica walls has been revealed as the cornerstone in the performance of these materials as controlled release systems. The synergy between the improved bioactive behaviour and local sustained drug release capability of mesostructured materials makes them suitable to manufacture three-dimensional macroporous scaffolds for bone tissue engineering. Finally, this review tackles the possibility of covalently grafting different osteoinductive agents to the scaffold surface that act as attracting signals for bone cells to promote the bone regeneration process.     

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

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.     

蒸发诱导自组装仿生合成高有序度三维六方介孔氧化硅薄膜

借鉴自然界生物矿化的形成机理,利用蒸发诱导自组装(EISA)的方法,以十六烷基三甲基溴化铵(CTAB)为结构导向剂,正硅酸乙酯(TEOS)为硅源,通过浸渍提拉在普通玻璃片上制备出高有序度、三维六方结构的介孔氧化硅薄膜,通过XRD、TEM、低温N2吸附/脱附等方法对薄膜进行了表征,并初步讨论了形成三维六方结构的机理.     

Automated Multi- and Block-Copolymer Writing in Mesoporous Films Using Visible-Light PET-RAFT and a Microscope (Small 16/2023)

For high throughput applications, e.g., in the context of sensing especially when being combined with machine learning, large sample numbers in acceptable production time are required. This needs automated synthesis and material functionalization concepts ideally combined with high precision. To automate sensing relevant mesopore polymer functionalization while being highly precise in polymer placement, polymer amount control, and polymer sequence design, a process for polymer writing in mesoporous silica films with pore diameter in the range of 13 nm is developed. Mesoporous films are functionalized with different polymers in adjustable polymer amount including block-copolymer functionalization in an automated process using a visible-light induced, controlled photo electron/energy transfer-reversible addition-fragmentation chain-transfer (PET-RAFT) polymerization. While transferring this PET-RAFT to a commercially available microscope, direct, automated laser writing of three different polymers, as well as polymer re-initiation is demonstrated. Using a laser diameter of ≈72 µm, significantly smaller polymer spots of ≈7 µm in diameter are realized. Micrometerscale resolved polymer images including block-copolymers are written into mesoporous layers covering millimeter scale areas requiring a writing time in the range of one second per polymer spot.     

纯钛表面立方介孔SiO2薄膜诱导沉积碳磷灰石层

采用浸渍-提拉法在预处理纯钛表面制备立方介孔SiO₂薄膜, 通过评价体外诱导类骨碳磷灰石层形成能力研究其生物活性。利用小角X射线衍射、傅立叶变换红外光谱、N₂吸附、电镜和能谱等测试技术对模板剂去除前后、模拟体液浸泡前后介孔薄膜结构、组成与形貌进行了研究; 利用固体表面Zeta电位仪研究薄膜表面荷电性质。结果表明, 介孔薄膜具有三维立方介孔结构, 在模拟体液(1.5SBF)中浸泡14 d即能诱导碳磷灰石层在其表面沉积, 显示出良好的生物活性。介孔薄膜独特的孔道结构以及孔表面Si-OH在体液中呈负电性对其生物活性起关键作用。     

A combined top-down and bottom-up approach to fabricate silica films with bimodal porosity

We report a method to fabricate silica films with bimodal porosity based on the surfactant-directed self-assembly process followed by post-treatment with reactive ion etching (RIE). By RIE of a surfactant-templated mesoporous silica film with a 3D hexagonal structure, vertically-etched pores with the size of several tens of nanometers and the depth of ca. 60 nm are generated, while the original caged mesopores (ca. 5 nm in size) are still retained in the unetched parts of the film. Pre-treatment of the mesoporous silica film by wet-etching to expose the pores on the surface, followed by sputter deposition of a Pt layer for partial masking, is crucial for the anisotropic etching of the film. Such a combined top-down and bottom up approach offers an opportunity to fabricate silica films with hierarchical pore architectures.     

Synthesis of monodisperse fluorinated silica nanoparticles and their superhydrophobic thin films

Monodispersive silica nanoparticles have been synthesized via the Sto?ber process and further functionalized by adding fluorinated groups using fluoroalkylsilane in an ethanolic solution. In this process, six different sizes of fluorinated silica nanoparticles of varying diameter from 40 to 300 nm are prepared and used to deposit thin films on aluminum alloy surfaces using spin coating processes. The functionalization of silica nanoparticles by fluorinated group has been confirmed by the presence C-F bonds along with Si-O-Si bonds in the thin films as analyzed by Fourier transform infrared spectroscopy (FTIR). The surface roughnesses as well as the water contact angles of the fluorinated silica nanoparticle containing thin films are found to be increased with the increase of the diameter of the synthesized fluorinated silica nanoparticles. The thin films prepared using the fluorinated silica nanoparticles having a critical size of 119 ± 12 nm provide a surface roughness of ～0.697 μm rendering the surfaces superhydrophobic with a water contact angle of 151 ± 4°. The roughness as well as the water contact angle increases on the superhydrophobic thin films with further increase in the size of the fluorinated silica nanoparticles in the films.     

Effect of tin addition on mesoporous silica thin film and its application for surface photovoltage NO2 gas sensor

Self-ordered and structure-controlled transparent films of tin-modified mesoporous silica (Sn/Si ratio of 0.5-3%) were first prepared using a molecule surfactant template method employing spin coating. A surface photovoltage (SPV) NO(2) gas sensor was then fabricated using these self-ordered tin-modified mesoporous silica thin films based on a metal-insulator-semiconductor structure. Highly sensitive tin-modified mesoporous silica was obtained that could detect NO(2) gas concentrations of as low as 300 ppb at room temperature. The detection mechanism for NO(2) is believed to involve both the surface area, which contributes to the change in dielectric constant, and the amount of tin incorporated, which contributes to the change in charge. It was found that, in this SPV sensor, the optimal Sn/Si ratio of 0.5% delivered record-high sensing performance.     

Silica films with a single-crystalline mesoporous structure

Films of mesoporous materials attract broad interest because of their wide applicability in the fields of optics and electronics. Although many of these films have a regular local porous structure, the structural regularity has not been used practically yet because of difficulties in its control on macroscopic scales. Here, we demonstrate the preparation of mesoporous silica films whose porous structure can be described as a single crystal, that is, a long-range order of cage-like pores is maintained over centimetre scales. These films have a three-dimensional hexagonal (space group P6(3)/mmc) porous structure, and the in-plane arrangement of the pores is strictly controlled by a polymeric substrate surface that has been treated by rubbing. This new class of single-crystalline films with mesoscopic periodic structure is a significant breakthrough in bottom-up nanotechnology, and could lead to novel devices, for example, optics in a soft X-ray region, and quantum electronics.     

Ordered mesoporous silicon through magnesium reduction of polymer templated silica thin films

This paper describes the process of making ordered mesoporous silicon (Si) thin films. The process begins with mesoporous silica (SiO 2) thin films that are produced via evaporation induced self-assembly (EISA) using sol-gel silica precursors with a diblock copolymer template. This results in a film with a cubic lattice of 15 nm diameter pores and 10 nm thick walls. The silicon is produced through reduction of the silica thin films in a magnesium (Mg) vapor at 675 degrees C. Magnesium reduction preserves the ordered pore-solid architecture but replaces the dense silica walls with 10-17 nm silicon crystallites. The resulting porous silicon films are characterized by a combination of low and high angle X-ray diffraction, combined with direct SEM imaging. The result is a straightforward route to the production of ordered nanoporous silicon.     

Functionalized mesoporous silica for microgravimetric sensing of trace chemical vapors

Featuring a huge surface-to-volume ratio, synthesized SBA-15 mesoporous silica is functionalized by inner-channel-wall modification of sensing groups for highly specific chemical-vapor detection at trace level. With the developed sensing material loaded on resonant microcantilevers, the specifically adsorbed chemical-vapor molecules act as an added mass to shift the cantilever resonant frequency for gravimetric sensing signal readout. Two kinds of sensing materials for trinitrotoluene (TNT) and ammonia/amine are respectively prepared by inner-wall layer-by-layer grafting functionalization. By using hexafluoro-2-propanol-functionalized mesoporous silica (HFMS), experimental results show highly specific and rapid detection of TNT vapor, with a ppt-level detection limit; functionalized with a carboxyl (COOH) group, the mesoporous silica is loaded onto the cantilever resonating sensor that experimentally exhibits an ultrafine detection limit of tens of ppb to ammonia/amine gases.     

Preparation of polyelectrolyte-functionalized mesoporous silicas for the selective adsorption of anionic dye in an aqueous solution

Polyelectrolytes (PDDA, poly (diallydimethylammonium chloride)) functionalized mesoporous silica adsorbent (PDDA/MS) was prepared and characterized by N₂ adsorption, transmission electron microscopy (TEM) and zeta potential. The PDDA/MS showed ordered pore structure and the surface charge was successfully converted from negative to positive by PDDA functionalization. The adsorption capability of the prepared adsorbents was evaluated using nine different dye solutions with positive, neutral and negative charges. For the comparison purpose, commercial silica (CS, Davisil) and granular activated carbon (GAC), which are conventionally used as adsorbents, were also treated by PDDA impregnation. The batch adsorption experiments showed that the PDDA/MS exhibited the highest selective adsorption capacity of negative acid dye dissolved in an aqueous solution. Taken together, the results of this work indicate that polyelectrolyte functionalization of the inorganic surface could be a simple and suitable method for the surface modified adsorbent and the PDDA/MS suggested in this study could be used for the effective removal of acid dye from aqueous solutions.     

Tunable adsorption behavior of silica materials in the removal of dense non-aqueous phase liquids

Mesoporous silica material has dual characteristics including adsorption of organic contaminants and transport through the sediments, making it an ideal material as a platform for zerovalent iron particles in the in situ remediation of dense non-aqueous phase liquids such as trichloroethylene. In this paper, tunable adsorption behavior of silica materials was quantitatively investigated by batches of equilibrium experiments. Significant enhancement in adsorption capacity was observed on mesoporous organo-silica particles as a consequence of the functionalization of particle surface from hydrophilicity to hydrophobicity. The fact that there is a wide difference in adsorption capacities between the non-functionalized mesoporous silica (MCM-41) and the alkyl-functionalized mesoporous silica prompted a study to control adsorption levels by simply adjusting the amount of methyl triethoxysilane (MTES) precursor in a mixture of MTES and tetramethoxysilane. In comparison with the most commonly used adsorbent activated carbon, the higher yield of adsorbent of 83 ± 2.6% was observed for mesoporous methyl silica particles. Particle characterizations were performed by means of X-ray powder diffraction, transmission electron microscopy, scanning electron microscopy, Brunauer–Emmett–Teller, thermogravimetric analysis and Fourier transform infrared measurements.     

One-step synthesis of mesoporous silica–graphene composites by simultaneous hydrothermal coupling and reduction of graphene oxide

Silica–graphene oxide composites were synthesized by hydrothermal method with simultaneous functionalization and reduction of graphene oxide (GO) in the presence of mesoporous silica. Two types of silica were used in the study, mesoporous synthetic silica (MSU-F) synthesized by sol-gel method and mesoporous mineral silica (meso-celite) from pseudomorphic synthesis. The infrared spectra of the composites showed the disappearance of the carboxyl peak at 1735 cm^-1 which could be due to the reduction of the –COOH group. The enhancement of the band at 1385 cm^–1 is attributed to the vibration of the Si–O–C=O moiety formed by reaction of the –COOH group of GO and the silanol (Si–OH) of silica. The Raman spectra of the composites show a diminished intensity ratio of D to G band indicating that GO was reduced to graphene sheets. The TEM images demonstrate the coupling of silica to GO surface revealing dense loading of silica on GO in planar structure.     

Design of single-site Ti embedded highly hydrophilic silica thin films with macro-mesoporous structures

Single-site Ti-containing macroporous silica thin films with mesoporous frameworks were successfully prepared on quartz substrate with high transparency by using poly(methyl methacrylate) (PMMA) microspheres and organic surfactant as template of porous structures. The presence of mesoporous structure and the differences of macroporous structure of film surface were investigated by XRD and FE-SEM measurements. The local structure of Ti moieties embedded within silica matrixes were also confirmed by UV-vis investigations. It was found that the macroporous structure and the embedded single-site Ti moieties within mesoporous frameworks were quite effective for improvement of surface hydrophilicity, i.e., the water droplet was entirely spread on the film surface even before and after irradiation of UV light.     

Disordered mesoporous silica low-k thin films prepared by vapor deposition into a triblock copolymer template film

Mesoporous silica films have been prepared by a vapor phase method using tetraethoxysilane (TEOS) in a batch reactor and in a continuous flow reactor. The TEOS molecules penetrated into a triblock copolymer films and then a triblock copolymer/silica composite structure was formed. A two dimensional grazing-incidence small angle X-ray scattering pattern and field emission scanning electron microscopy images of the films indicated that the films possess ordered and disordered regions. The tortuous pore channels in the wormhole-like disordered structure run parallel to the film surface. The mesostructured triblock copolymer/silica composite films were treated with a trimethylethoxysilane (TMES) vapor before and after calcination. The vapor infiltration treatments effectively improved mechanical strength and hydrothermal stability of the films. The dielectric constant of the TMES-treated mesoporous silica films was reduced into the 1.5–1.7 range.     

2-Mercaptothiazoline modified mesoporous silica for mercury removal from aqueous media

Mesoporous silicas (SBA-15 and MCM-41) have been functionalized by two different methods. Using the heterogeneous route the silylating agent, 3-chloropropyltriethoxysilane, was initially immobilized onto the mesoporous silica surface to give the chlorinated mesoporous silica Cl-SBA-15 or Cl-MCM-41. In a second step a multifunctionalized N, S donor compound (2-mercaptothiazoline, MTZ) was incorporated to obtain the functionalized silicas denoted as MTZ-SBA-15-Het or MTZ-MCM-41-Het. Using the homogeneous route, the functionalization was achieved via the one step reaction of the mesoporous silica with an organic ligand containing the chelating functions, to give the modified mesoporous silicas denoted as MTZ-SBA-15-Hom or MTZ-MCM-41-Hom. The functionalized mesoporous silicas were employed as adsorbents for the regeneration of aqueous solutions contaminated with Hg (II) at room temperature. SBA-15 and MCM-41 functionalized with MTZ by the homogeneous method present good mercury adsorption values (1.10 and 0.7mmolHg (II)/g of silica, respectively). This fact suggests a better applicability of such mesoporous silica supports to extract Hg (II) from aqueous solutions. In addition, it was observed the existence of a correlation between mercury adsorption with pore size and volume since, SBA-15 with lower areas and higher pore sizes functionalized with sterically demanding ligands, show better adsorption capacities than functionalized MCM-41.     

Reflectance of surfactant-templated mesoporous silica thin films: Simulations versus experiments

In this study, cubic and hexagonal mesoporous amorphous silica thin films were synthesized using evaporation-induced self-assembly process followed by calcination leaving highly ordered spherical or cylindrical pores in a silica matrix. The films featured pores with diameter between 4 and 11 nm, lattice parameter from 7.8 to 24 nm, and porosity between 22% and 45%. All films were dehydrated prior to reflectance measurements except for one film which was fully hydrated. The present study compares the spectral reflectance measured experimentally between 400 and 900 nm with that computed numerically by solving three-dimensional Maxwell's equations in mesoporous silica thin films with the same morphology as those synthesized. The matrix was assumed to have the same optical properties as bulk fused silica. The pore optical properties were either those of air or liquid water whether the film was dehydrated or hydrated, respectively. Excellent agreement was found between experimental and numerical reflectance for both cubic and hexagonal mesoporous silica films. This study experimentally validates our simulation tool and offers the prospect of ab-initio design of nanocomposite materials with arbitrary optical properties without using effective medium approximation or mixing rules.     

Designed Patterning of Mesoporous Metal Films Based on Electrochemical Micelle Assembly Combined with Lithographical Techniques

Mesoporous noble metals and their patterning techniques for obtaining unique patterned structures are highly attractive for electrocatalysis, photocatalysis, and optoelectronics device applications owing to their expedient properties such as high level of exposed active locations, cascade electrocatalytic sites, and large surface area. However, patterning techniques for mesoporous substrates are still limited to metal oxide and silica films, although there is growing demand for developing techniques related to patterning mesoporous metals. In this study, the first demonstration of mesoporous metal films on patterned gold (Au) substrates, prefabricated using photolithographic techniques, is reported. First, different growth rates of mesoporous Au metal films on patterned Au substrates are demonstrated by varying deposition times and voltages. In addition, mesoporous Au films are also fabricated on various patterns of Au substrates including stripe and mesh lines. An alternative fabrication method using a photoresist insulating mask also yields growth of mesoporous Au within the patterning. Moreover, patterned mesoporous films of palladium (Pd) and palladium–copper alloy (PdCu) are demonstrated on the same types of substrates to show versatility of this method. Patterned mesoporous Au films (PMGFs) show higher electrochemically active surface area (ECSA) and higher sensitivity toward glucose oxidation than nonpatterned mesoporous Au films (NMGF).     

埃洛石原料无模板法制备高比表面积介孔氧化硅及其在亚甲基蓝吸附中的应用

采用无模板法, 以天然的矿物原料制备介孔材料是一种经济有效的制备方法。本研究利用“煅烧-沸石化-酸处理”工艺制备高比表面积的介孔氧化硅颗粒。研究发现,通过长时间的碱处理将煅烧埃洛石转化为沸石,随后通过酸处理,可制备出比表面积高达767 m²/g的介孔氧化硅材料。该工艺机理为: 850℃煅烧使埃洛石转变为无定型态的Si-O-Al网络结构,煅烧埃洛石在长时间的水热碱处理过程中转化为结晶态的LTA沸石硅铝酸钠,在随后的强酸性环境下,沸石的Al-O和Na-O成分被完全溶解,而残余的Si-O纳米碎片在酸环境中相互聚合,生成无定形态的介孔氧化硅颗粒。本实验制备的介孔氧化硅比表面积高达767 m²/g,最可几孔径为5 nm,其亚甲基蓝平衡吸附量可达741 mg/g,表明其在污染物吸附中具有良好的应用潜力。