Nanostructured Mesoporous Silica Films

Abstract. The lyotropic liquid crystalline phases of surfactants have been used as templates for the synthesis of mesoporous nanostructured materials. To achieve direct templating by liquid crystalline phases, surfactant concentrations in excess of 30 wt. % in water are used. Here we report on the processing of thin films of nanostructured mesoporous silicas by dip coating from mixtures that contain high surfactant concentrations. By altering the surfactant to water ratio we were able to obtain films that had micellar cubic (I1), normal topology hexagonal (HI), or lamellar(L α) organization. Calcination of these films afforded adherent films that in most cases retained the long-ranged architecture of the liquid crystalline phase. 1

Self-assembly of highly symmetrical, ultrasmall inorganic cages directed by surfactant micelles

Nanometre-sized objects with highly symmetrical, cage-like polyhedral shapes, often with icosahedral symmetry, have recently been assembled from DNA(1-3), RNA(4) or proteins(5,6) for applications in biology and medicine. These achievements relied on advances in the development of programmable self-assembling biological materials(7-10), and on rapidly developing techniques for generating three-dimensional (3D) reconstructions from cryo-electron microscopy images of single particles, which provide high-resolution structural characterization of biological complexes(11-13). Such single-particle 3D reconstruction approaches have not yet been successfully applied to the identification of synthetic inorganic nanomaterials with highly symmetrical cage-like shapes. Here, however, using a combination of cryo-electron microscopy and single-particle 3D reconstruction, we suggest the existence of isolated ultrasmall (less than 10 nm) silica cages ('silicages') with dodecahedral structure. We propose that such highly symmetrical, self-assembled cages form through the arrangement of primary silica clusters in aqueous solutions on the surface of oppositely charged surfactant micelles. This discovery paves the way for nanoscale cages made from silica and other inorganic materials to be used as building blocks for a wide range of advanced functional-materials applications

Structure and Luminescence Properties of Eu3+-Doped Cubic Mesoporous Silica Thin Films

Eu3+ ions-doped cubic mesoporous silica thin films with a thickness of about 205 nm were prepared on silicon and glass substrates using triblock copolymer as a structure-directing agent using sol–gel spin-coating and calcination processes. X-ray diffraction and transmission electron microscopy analysis show that the mesoporous silica thin films have a highly ordered body-centered cubic mesoporous structure. High Eu3+ ion loading and high temperature calcination do not destroy the ordered cubic mesoporous structure of the mesoporous silica thin films. Photoluminescence spectra show two characteristic emission peaks corresponding to the transitions of5D0-7F1 and 5D0-7F2 of Eu3+ ions located in low symmetry sites in mesoporous silica thin films. With the Eu/Si molar ratio increasing to 3.41%, the luminescence intensity of the Eu3+ ions-doped mesoporous silica thin films increases linearly with increasing Eu3+ concentration

Blue-phase templated fabrication of three-dimensional nanostructures for photonic applications

A promising approach to the fabrication of materials with nanoscale features is the transfer of liquid-crystalline structure to polymers. However, this has not been achieved in systems with full three-dimensional periodicity. Here we demonstrate the fabrication of self-assembled three-dimensional nanostructures by polymer templating blue phase I, a chiral liquid crystal with cubic symmetry. Blue phase I was photopolymerized and the remaining liquid crystal removed to create a porous free-standing cast, which retains the chiral three-dimensional structure of the blue phase, yet contains no chiral additive molecules. The cast may in turn be used as a hard template for the fabrication of new materials. By refilling the cast with an achiral nematic liquid crystal, we created templated blue phases that have unprecedented thermal stability in the range -125 to 125 °C, and that act as both mirrorless lasers and switchable electro-optic devices. Blue-phase templated materials will facilitate advances in device architectures for photonics applications in particular

A study of some fundamental physicochemical variables on the morphology of mesoporous silica nanoparticles MCM-41 type

[EN] 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 degrees 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 m(2) 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.This study was funded partially by Departamento Administrativo de Ciencia Tecnología e Innovación–COLCIENCIAS (recipient, Angela A. Beltrán-Osuna); Ministerio de Economía y Competitividad, MINECO, research number MAT2016-76039-C4-1-R (Recipient, José L. Gómez-Ribelles); and Universidad Nacional de Colombia, grant number DIB201010021438 (Recipient, Jairo E. Perilla).Beltrán-Osuna, A.; Gómez Ribelles, JL.; Perilla-Perilla, JE. (2017). A study of some fundamental physicochemical variables on the morphology of mesoporous silica nanoparticles MCM-41 type. Journal of Nanoparticle Research. 19(12):1-14. https://doi.org/10.1007/s11051-017-4077-2S1141912Barrabino A (2011) Synthesis of mesoporous silica particles with control of both pore diameter and particle size. Master Thesis, Chalmers University of Technology, SwedenBastos FS, Lima OA, Filho CR, Fernandes LD (2011) Mesoporous molecular sieve MCM-41 synthesis from fluoride media. Brazilian. J Chem Eng 28:649–658Beck JS, Vartuli JC, Roth WJ, Leonowicz ME, Kresge CT, Schmitt KD, Chu CTW, Olson DH, Sheppard EW, McCullen SB, Higgins JB, Schlenker JL (1992) A new family of mesoporous molecular sieves prepared with liquid crystal templates. J Am Chem Soc 114(27):10834–10843. https://doi.org/10.1021/ja00053a020Beltrán-Osuna AA, Perilla JE (2016) Colloidal and spherical mesoporous silica particles: synthesis and new technologies for delivery applications. J Sol-Gel Sci Technol 77(2):480–496. https://doi.org/10.1007/s10971-015-3874-2Bernardos A, Mondragón L, Aznar E et al (2010) Enzyme-responsive intracellular controlled release using nanometric silica mesoporous supports capped with “saccharides”. ACS Nano 4(11):6353–6368. https://doi.org/10.1021/nn101499dBharti C, Nagaich U, Pal AK, Gulati N (2015) Mesoporous silica nanoparticles in target drug delivery system: a review. Int J Pharm Investig 5(3):124–133. https://doi.org/10.4103/2230-973X.160844Brevet D, Hocine O, Delalande A, Raehm L, Charnay C, Midoux P, Durand JO, Pichon C (2014) Improved gene transfer with histidine-functionalized mesoporous silica nanoparticles. Int J Pharm 471(1-2):197–205. https://doi.org/10.1016/j.ijpharm.2014.05.020Cai Q, Luo Z, Pang W et al (2001) Dilute solution routes to various controllable morphologies of MCM-41 silica with a basic medium. Chem Mater 13(2):258–263. https://doi.org/10.1021/cm990661zChakraborty I, Mascharak PK (2016) Mesoporous silica materials and nanoparticles as carriers for controlled and site-specific delivery of gaseous signaling molecules. Microporous Mesoporous Mater 234:409–419. https://doi.org/10.1016/j.micromeso.2016.07.028Chen L, Zhang Z, Yao X, Chen X, Chen X (2015a) Intracellular pH-operated mechanized mesoporous silica nanoparticles as potential drug carries. Microporous Mesoporous Mater 201:169–175. https://doi.org/10.1016/j.micromeso.2014.09.023Chen X, Yao X, Wang C, Chen L, Chen X (2015b) Mesoporous silica nanoparticles capped with fluorescence-conjugated cyclodextrin for pH-activated controlled drug delivery and imaging. Microporous Mesoporous Mater 217:46–53. https://doi.org/10.1016/j.micromeso.2015.06.012Chen Y, Chen H, Shi J (2013) In vivo bio-safety evaluations and diagnostic / therapeutic applications of chemically designed mesoporous silica nanoparticles. Adv Mater 25(23):3144–3176. https://doi.org/10.1002/adma.201205292Chen Y, Shi X, Han B, Qin H, Li Z, Lu Y, Wang J, Kong Y (2012) The complete control for the nanosize of spherical MCM-41. J Nanosci Nanotechnol 12(9):7239–7249. https://doi.org/10.1166/jnn.2012.6459Cheng Y-J, Zeng X, Cheng D-B, Xu XD, Zhang XZ, Zhuo RX, He F (2016) Functional mesoporous silica nanoparticles (MSNs) for highly controllable drug release and synergistic therapy. Colloids Surfaces B Biointerfaces 145:217–225. https://doi.org/10.1016/j.colsurfb.2016.04.051Crommelin DJA, Florence AT (2013) Towards more effective advanced drug delivery systems. Int J Pharm 454(1):496–511. https://doi.org/10.1016/j.ijpharm.2013.02.020Edler KJ (1997) Synthesis and characterisation of the mesoporous molecular sieve, MCM-41. Doctoral dissertation, The Australian National University, AustraliaGuo Z, Liu X-M, Ma L, Li J, Zhang H, Gao YP, Yuan Y (2013) Effects of particle morphology, pore size and surface coating of mesoporous silica on naproxen dissolution rate enhancement. Colloids Surf B Biointerfaces 101:228–235. https://doi.org/10.1016/j.colsurfb.2012.06.026Han N, Wang Y, Bai J, Liu J, Wang Y, Gao Y, Jiang T, Kang W, Wang S (2016) Facile synthesis of the lipid bilayer coated mesoporous silica nanocomposites and their application in drug delivery. Microporous Mesoporous Mater 219:209–218. https://doi.org/10.1016/j.micromeso.2015.08.006Hu X, Wang Y, Peng B (2014) Chitosan-capped mesoporous silica nanoparticles as pH-responsive nanocarriers for controlled drug release. Chem - An Asian J 9(1):319–327. https://doi.org/10.1002/asia.201301105Huh S, Wiench JW, Yoo J et al (2003) Organic functionalization and morphology control of mesoporous silicas via a co-condensation synthesis method. Chem Mater 15(22):4247–4256. https://doi.org/10.1021/cm0210041Ikari K, Suzuki K, Imai H (2006) Structural control of mesoporous silica nanoparticles in a binary surfactant system. Langmuir 22(2):802–806. https://doi.org/10.1021/la0525527Iliade P, Miletto I, Coluccia S, Berlier G (2012) Functionalization of mesoporous MCM-41 with aminopropyl groups by co-condensation and grafting: a physico-chemical characterization. Res Chem Intermed 38(3-5):785–794. https://doi.org/10.1007/s11164-011-0417-5IUPAC (1985) Reporting physisorption data for gas/solid systems. Pure Appl Chem 57:603–619IUPAC (2014) Compendium of chemical terminology-gold book, 2.3.3. International Union of Pure and Applied ChemistryKhezri K, Roghani-Mamaqani H, Sarsabili M, Sobani M, Mirshafiei-Langari SA (2014) Spherical mesoporous silica nanoparticles/tailor-made polystyrene nanocomposites by in situ reverse atom transfer radical polymerization. Polym Sci Ser B 56(6):909–918. https://doi.org/10.1134/S1560090414660026Kresge CT, Leonowicz ME, Roth WJ, Vartuli JC, Beck JS (1992) Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism. Nature 359(6397):710–712. https://doi.org/10.1038/359710a0Lelong G, Bhattacharyya S, Kline S, Cacciaguerra T, Gonzalez MA, Saboungi ML (2008) Effect of surfactant concentration on the morphology and texture of MCM-41 materials. J Phys Chem C 112(29):10674–10680. https://doi.org/10.1021/jp800898nLv X, Zhang L, Xing F, Lin H (2016) Controlled synthesis of monodispersed mesoporous silica nanoparticles: particle size tuning and formation mechanism investigation. Microporous Mesoporous Mater 225:238–244. https://doi.org/10.1016/j.micromeso.2015.12.024Mamaeva V, Sahlgren C, Lindén M (2013) Mesoporous silica nanoparticles in medicine: recent advances. Adv Drug Deliv Rev 65(5):689–702. https://doi.org/10.1016/j.addr.2012.07.018Manzano M, Aina V, Areán CO, Balas F, Cauda V, Colilla M, Delgado MR, Vallet-Regí M (2008) Studies on MCM-41 mesoporous silica for drug delivery: effect of particle morphology and amine functionalization. Chem Eng J 137(1):30–37. https://doi.org/10.1016/j.cej.2007.07.078Merkus HG (2009) Particle size measurements: fundamentals, practice, quality. Springer Science +Businees Media B.V, The NetherlandsMorishige K, Fujii H, Uga M, Kinukawa D (1997) Capillary critical point of argon, nitrogen, oxygen, ethylene, and carbon dioxide in MCM-41. Langmuir 13(13):3494–3498. https://doi.org/10.1021/la970079ude Padua Oliveira DC, de Barros ALB, Belardi RM et al (2016) Mesoporous silica nanoparticles as a potential vaccine adjuvant against Schistosoma mansoni. J Drug Deliv Sci Technol 35:234–240. https://doi.org/10.1016/j.jddst.2016.07.002Phillips E, Penate-Medina O, Zanzonico PB, Carvajal RD, Mohan P, Ye Y, Humm J, Gonen M, Kalaigian H, Schoder H, Strauss HW, Larson SM, Wiesner U, Bradbury MS (2014) Clinical translation of an ultrasmall inorganic optical-PET imaging nanoparticle probe. Sci Transl Med 6(260):260ra149. https://doi.org/10.1126/scitranslmed.3009524Qu F, Zhu G, Lin H, Zhang W, Sun J, Li S, Qiu S (2006) A controlled release of ibuprofen by systematically tailoring the morphology of mesoporous silica materials. J Solid State Chem 179(7):2027–2035. https://doi.org/10.1016/j.jssc.2006.04.002Rafi AA, Mahkam M, Davaran S, Hamishehkar H (2016) A smart pH-responsive nano-carrier as a drug delivery system: a hybrid system comprised of mesoporous nanosilica MCM-41 (as a nano-container) & a pH-sensitive polymer (as smart reversible gatekeepers): preparation, characterization and in vitro releas. Eur J Pharm Sci 93:64–73. https://doi.org/10.1016/j.ejps.2016.08.005Rouquerol J, Rouquerol F, Llewellyn P, et al (2014) Adsorption by powders and porous solids: principles, methodology and applications. Elsevier Ltd.Selvam P, Bhatia SK, Sonwane CG (2001) Recent advances in processing and characterization of periodic mesoporous MCM-41 silicate molecular sieves. Ind Eng Chem Res 40(15):3237–3261. https://doi.org/10.1021/ie0010666Shi YT, Cheng HY, Geng Y, Nan HM, Chen W, Cai Q, Chen BH, Sun XD, Yao YW, Li HD (2010) The size-controllable synthesis of nanometer-sized mesoporous silica in extremely dilute surfactant solution. Mater Chem Phys 120(1):193–198. https://doi.org/10.1016/j.matchemphys.2009.10.045Shibata H, Chiba Y, Kineri T, Matsumoto M, Nishio K (2010) The effect of heat treatment on the interplanar spacing of the mesostructure during the synthesis of mesoporous MCM-41 silica. Colloids Surfaces A Physicochem Eng Asp 358(1-3):1–5. https://doi.org/10.1016/j.colsurfa.2009.12.020Slowing II, Vivero-Escoto JL, Wu C-W, Lin VSY (2008) Mesoporous silica nanoparticles as controlled release drug delivery and gene transfection carriers. Adv Drug Deliv Rev 60(11):1278–1288. https://doi.org/10.1016/j.addr.2008.03.012Sun R, Wang W, Wen Y, Zhang X (2015) Recent advance on mesoporous silica nanoparticles-based controlled release system: intelligent switches open up. Nano 5(4):2019–2053. https://doi.org/10.3390/nano5042019U.S. Department of Health & Human Services (2015) Cancer Nanotechnology PlanUkmar T, Maver U, Planinšek O, Kaučič V, Gaberšček M, Godec A (2011) Understanding controlled drug release from mesoporous silicates: theory and experiment. J Control Release 155(3):409–417. https://doi.org/10.1016/j.jconrel.2011.06.038Vallet-Regi M, Arcos Navarrete D (2016) Nanoceramics in clinical use, 1st edn. The Royal Society of Chemistry, CambridgeVallet-Regi M, Rámila A, Del Real RP, Pérez-Pariente J (2001) A new property of MCM-41: drug delivery system. Chem Mater 13(2):308–311. https://doi.org/10.1021/cm0011559Varga N, Benko M, Sebok D et al (2015) Mesoporous silica core-shell composite functionalized with polyelectrolytes for drug delivery. Microporous Mesoporous Mater 213:134–141. https://doi.org/10.1016/j.micromeso.2015.02.008Wang Y, Zhao Q, Han N, Bai L, Li J, Liu J, Che E, Hu L, Zhang Q, Jiang T, Wang S (2015) Mesoporous silica nanoparticles in drug delivery and biomedical applications. Nanomed Nanotechnol Biol Med 11(2):313–327. https://doi.org/10.1016/j.nano.2014.09.014Wanyika H, Gatebe E, Kioni P et al (2011) Synthesis and characterization of ordered mesoporous silica nanoparticles with tunable physical properties by varying molar composition of reagents. African J Pharm Pharmacol 5(21):2402–2410. https://doi.org/10.5897/AJPP11.592Wu SH, Mou CY, Lin HP (2013) Synthesis of mesoporous silica nanoparticles. Chem Soc Rev 42(9):3862–3875. https://doi.org/10.1039/c3cs35405aXu X, Lü S, Gao C, Wang X, Bai X, Gao N, Liu M (2015a) Facile preparation of pH-sensitive and self-fluorescent mesoporous silica nanoparticles modified with PAMAM dendrimers for label-free imaging and drug delivery. Chem Eng J 266:171–178. https://doi.org/10.1016/j.cej.2014.12.075Xu X, Lü S, Gao C, Wang X, Bai X, Duan H, Gao N, Feng C, Liu M (2015b) Polymeric micelle-coated mesop orous silica nanoparticle for enhanced fluorescent imaging and pH-responsive drug delivery. Chem Eng J 279:851–860. https://doi.org/10.1016/j.cej.2015.05.085Xu X, Lü S, Gao C, Feng C, Wu C, Bai X, Gao N, Wang Z, Liu M (2016) Self-fluorescent and stimuli-responsive mesoporous silica nanoparticles using a double-role curcumin gatekeeper for drug delivery. Chem Eng J 300:185–192. https://doi.org/10.1016/j.cej.2016.04.087Yang Y, Yu C (2015) Advances in silica based nanoparticles for targeted cancer therapy. Nanomedicine nanotechnology. Biol Med 12(2):317–332. https://doi.org/10.1016/j.nano.2015.10.018Zhang H, Tong C, Sha J, Liu B, Lü C (2015) Fluorescent mesoporous silica nanoparticles functionalized graphene oxide: a facile FRET-based ratiometric probe for Hg2+. Sensors Actuators B Chem 206:181–189. https://doi.org/10.1016/j.snb.2014.09.051Zhou C, Yan C, Zhao J, Wang H, Zhou Q, Luo W (2016) Rapid synthesis of morphology-controlled mesoporous silica nanoparticles from silica fume. J Taiwan Inst Chem Eng 62:307–312. https://doi.org/10.1016/j.jtice.2016.01.03