Facile Suzuki coupling over ortho-metalated palladium(II) complex anchored on 2D-hexagonal mesoporous organosilica

Phenyl functionalized 2D-hexagonal mesoporous silica material has been synthesized by cationic/non-ionic mixed surfactant templating route. The phenyl group of this mesoporous material is further functionalized via nitration and then reduction of that nitro group to amino functionality, followed by Schiff base condensation and heterogenization of a palladium(II) complex, yielded an ortho-metalated palladium(II) complex anchored in a ordered mesoporous silica matrix. This supported metal complex acts as an efficient catalyst in the Suzuki cross-coupling reaction and shows high selectivity for the bi-aryl products.     

A Facile Strategy for In Situ Core-Template-Functionalizing Siliceous Hollow Nanospheres for Guest Species Entrapment

The shell wall-functionalized siliceous hollow nanospheres (SHNs) with functional molecules represent an important class of nanocarriers for a rich range of potential applications. Herein, a self-templated approach has been developed for the synthesis of in situ functionalized SHNs, in which the biocompatible long-chain polycarboxylates (i.e., polyacrylate, polyaspartate, gelatin) provide the framework for silica precursor deposition by simply controlling chain conformation with divalent metal ions (i.e., Ca²⁺, Sr²⁺), without the intervention of any external templates. Metal ions play crucial roles in the formation of organic vesicle templates by modulating the long chains of polymers and preventing them from separation by washing process. We also show that, by in situ functionalizing the shell wall of SHNs, it is capable of entrapping nearly an eightfold quantity of vitamin Bc in comparison to the bare bulk silica nanospheres. These results confirm the feasibility of guest species entrapment in the functionalized shell wall, and SHNs are effective carriers of guest (bio-)molecules potentially for a variety of biomedical applications. By rationally choosing the functional (self-templating) molecules, this concept may represent a general strategy for the production of functionalized silica hollow structures.     

Preparation of doubly responsive polymer functionalized silica hybrid nanoparticles via a one‐pot thiol‐isocyanate click reaction at room temperature

Well‐defined poly(N‐isopropylacrylamide) and poly(2‐(diethylamino) ethyl methacrylate) were synthesized first by a reversible addition‐fragmentation chain transfer process. These polymers were then reduced to generate an end thiol group to react with isocyanate groups on the surface of silica nanoparticles, which were pretreated with toluene‐2,4‐diisocyanate, by a one‐pot “click” reaction to prepare temperature and pH responsive polymer functionalized hybrid silica nanoparticles. The polymer functionalized silica hybrid nanoparticles were characterized by a range of techniques such as Fourier transform infrared spectroscopy and dynamic light scattering. The doubly responsive polymer functionalized silica hybrid nanoparticles show both temperature and pH responsive behavior and their solution properties were dependent on the ratio of the two polymers on the surface of silica. Covalent functionalization of the silica nanoparticle with well‐defined temperature and pH responsive polymers was accomplished via a one‐pot thiol‐isocyanate click reaction. This reaction was found to be extremely efficient in producing doubly responsive polymer functionalized silica hybrid nanoparticle, even at relatively low reaction temperature and short reaction time. Thermogravimetric analysis indicated that the same ratio of poly(N‐isopropylacrylamide) and poly(2‐(diethylamino)ethyl methacrylate) functionalized silica hybrid nanoparticle consisted of 42.46 wt% polymer. POLYM. COMPOS., 38:1454–1461, 2017. © 2015 Society of Plastics Engineers     

Functionalized Hybrid Nanoparticles and their Interaction with Spin-Labeled Cyclodextrin

Hybrid nanoparticles of the gold@silica and magnetite@silica type were obtained by embedding gold nanoparticles (protected by captopril, average size 2.3 nm) or magnetite nanoparticles (protected by alanine, average size 10 nm) into larger silica nanoparticles (50–100 nm) using the Stober method. A silica precursor, i.e., a mixture of tetramethoxysilane and 3-aminopropyl-trimethoxysilane (in a 10/1 ratio), was used in order to facilitate the links between inner nanoparticles and the silica layer. These nanoparticles containing free amino-groups were easily functionalized with adamantane, naphtyl and nitrobenzofurazan moieties using appropriate reagents (adamantane-1-carbonylchloride, 1-naphtylisocyanate, and 7-chlor-4-nitrobenzofurazan). The hybrid nanoparticles were characterized by different means (IR and TEM) and their interaction with spin-labeled β-cyclodextrin was also studied (by EPR spectroscopy). EPR spectra show that cyclodextrins are attached to the nanoparticles surface. The hybrid nanoparticles functionalized with nitrobenzofurazan moieties have the largest interaction with the cyclodextrin cavity.     

Crack growth of natural rubber filled with functionalized silica particles

In the present work, functionalized liquid isoprene rubber (FLIR) was used to improve the filler dispersion and filler–rubber interaction in the silica filled natural rubber system. By the infrared spectra and scanning electron microscopy, it was proved that the FLIR was successfully grafted on the silica and the functionalized silica was dispersed in the NR matrix homogeneously. Based on the real‐time crack tip morphology monitoring method, the influence of FLIR on the crack growth behavior of NR filled with silica was analyzed. By the adding of FLIR, the crack resistance of the natural rubber embedded with functionalized silica is remarkably increased. When the weight ratio of FLIR to silica is 3:10, the NR composite has the best crack resistance. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42972.     

Synthesis of urea-pyridyl ligand functionalized mesoporous silica hybrid material for hydrophobic and hydrophilic drug delivery application

In this work, we propose the synthesis of urea-pyridyl (UPy) ligand functionalized mesoporous silica hybrid material as novel and effective drug delivery system for loading/release of both hydrophobic and hydrophilic drugs. For the synthesis of UPy ligand functionalized mesoporous silica hybrid material, the combination of sol–gel co-condensation technique and post silica surface modification method were adapted. The prepared UPy ligand functionalized mesoporous silica hybrid (UPy-MSH) material was characterized by X-ray diffraction, Fourier-transform infrared, N₂ adsorption–desorption analysis. The material morphology and mesopore channels were observed by scanning and transmission electron microscopic analyses. The content of modified organic ligand functionalities present in the UPy-MSH material surface was determined by thermogravimetric analysis. The hydrophilic anticancer drug, 5-Fluorouracil and the hydrophobic anti-inflammatory drug, Ibuprofen was used as a model drugs to determine the loading and pH-responsive release efficiency of the synthesized UPy-MSH material under different pH (pH 7.4 and 5.0) conditions, respectively. In addition, the biocompatibility of the UPy-MSH material was evaluated on MDA-MB-231 cells. The experimental results depicted that the synthesized UPy-MSH material is biocompatible and has high drug loading capacity, selective and controlled release of specific drug with respect to the pH condition.     

Multi-photon imaging of amine-functionalized silica nanoparticles

A convenient and simple strategy for preparing water soluble, photoluminescent functionalized silica nanoparticles (M-dots) in the absence of fluorophores or metal doping is demonstrated. These M-dots can be used for bioimaging using one and two-photon microscopy. Because of their high photostability, low toxicity and high biocompatibility compared with Lumidot? CdSe/ZnS quantum dots, functionalized silica particles are superior alternatives for current bioimaging platforms. Moreover, the presence of a free amine group at the surface of the M-dots allows biomolecule conjugation (e.g. with antibodies, proteins) in a single step for converting these photoluminescent SiO(2) nanoparticles into multifunctional efficient vehicles for theragnostics.     

Effect of functionalization on dispersion of POSS‐silicone rubber nanocomposites

The nanocomposite of PDMS using functionalized fumed silica and nonreactive POSS as fillers were prepared by blend method in a planetary mixer. Fumed silica was functionalized by aliphatic and aromatic groups to study the filler–filler interactions with the aliphatic and aromatic POSS fillers and consequently their influence on the properties in the PDMS matrix. Transmission electron microscope (TEM) showed a good dispersion in the systems having the silica and POSS fillers with similar modifications. However, aliphatic and aromatic filler combinations showed more aggregated structures. Moreover, aliphatic POSS despite of good dispersion at higher loadings, act as lubricant, which is attributed to the disturbance in the PDMS‐ silica filler interaction and also the filler–filler interaction within fumed silica. There is a decrease in complex viscosity with the functionalization of fumed silica and with the aromatic/aliphatic POSS fillers. The thermal stability of aromatic functionalized fillers improves owing to the thermally stable phenyl groups. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

pH响应性PAA/毒死蜱/氨基化介孔硅缓释体系的制备与性能

以共缩聚法合成氨基化介孔硅,采用浸渍法制备毒死蜱/氨基化介孔硅,并以带负电荷的聚丙烯酸（PAA）为功能分子,通过静电吸附作用制备了具有pH响应的PAA/毒死蜱/氨基化介孔硅缓释体系。利用XRD、N₂吸附-脱附、TEM、SEM、TG、Zeta电位和FTIR对PAA/毒死蜱/氨基化介孔硅的结构进行了表征,并探究了其在不同pH和温度下的释药行为。结果表明,PAA通过静电作用包覆于毒死蜱/氨基化介孔硅的表面。缓释体系的药物释放主要受到PAA的阻碍作用,PAA修饰载药氨基化介孔硅显示出明显的pH响应性,当pH≤7时,其药物释放速率随pH减小而增大,而在偏碱性条件下的释药速率稍大于中性环境。同时,载药体系的释药速率还受到温度的影响。其释药行为可用Korsmeryer-Pappas动力学模型来描述。     

Synthesis and characterization of poly(methyl methacrylate)‐grafted silica microparticles

A procedure to synthesize poly(methyl methacrylate)‐grafted silica microparticles was developed by using radical photopolymerization of methyl methacrylate (MMA) initiated from N,N‐diethyldithiocarbamate (DEDT) groups previously bound to the silica surface (grafting “from”). The functionalization of silica microparticles with DEDT groups was performed in two steps: introduction of chlorinated functions onto the surface of silica particles, and then nucleophilic substitution of chlorines by DEDT functions via a S_N2 mechanism. The study was performed with a Kieselgel® S silica which was initially chlorinated in surface, either by direct chlorination of silanols with thionyl chloride, or by using a condensation reaction between silanols and a chlorofunctional trialkoxysilane reagent, 4‐(chloromethyl)phenyltrimethoxysilane and chloromethyltriethoxysilane, respectively. Three types of DEDT‐functionalized silica microparticles were prepared with a good control of the reactions, and then characterized by solid‐state ¹³C and ²⁹Si CP/MAS NMR. Their ability to initiate MMA photopolymerization was studied. The kinetics of MMA photopolymerization was followed by HPLC and ¹H‐NMR. Whatever the silica used the grafting progresses very slowly. On the other hand, the conversion of MMA in PMMA grafts is depending on the structure of the DEDT‐functionalized Kieselgel® S used. Poly(methyl methacrylate)‐grafted silica microparticles bearing high length grafts ( about 100) were synthesized. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Viscoelastic properties and morphological characterization of silica/polystyrene nanocomposites synthesized by nitroxide-mediated polymerization

Polystyrene (PS) chains with molecular weights comprised between 15,000 and 60,000 g/mol and narrow polydispersities were successfully grown from the surface of silica nanoparticles by nitroxide-mediated polymerization (NMP). Small angle X-ray scattering was used to characterize the structure of the interface layer formed around the silica particles, and at a larger scale, dynamic light scattering was used to determine the hydrodynamic diameter of the functionalized silica suspension. In a second part, blends of PS-grafted silica particles and pure polystyrene were prepared to evaluate the influence of the length of the grafted PS segments on the viscoelastic behavior of the so-produced nanocomposites in the linear viscoelasticity domain.Combination of all these techniques shows that the morphology of the nanocomposite materials is controlled by grafting. The steric hindrance generated by the grafted polymer chains enables partial destruction of the agglomerates that compose the original silica particles when the latter are dispersed either in a solvent or in a polymeric matrix.     

More than 100,000 Turnovers with Immobilized Ir‐Diphosphine Catalysts in an Enantioselective Imine Hydrogenation

A modular concept to prepare immobilized enantioselective catalysts is described, consisting of a functionalized xyliphos ligand covalently attached to a support via a linker. Immobilized xyliphos bound to silica and to polystyrene as well as soluble dimeric xyliphos and an extractable analogue were prepared and tested in the Ir‐catalyzed hydrogenation of a hindered N‐arylimine used for the production of (S)‐metolachlor. The best heterogeneous catalyst 9b exhibited TON's >100,000 and TOF's up to 20,000 h⁻¹, the best values so far for immobilized catalysts. The immobilized catalysts gave similar enantioselectivities but lower activities and higher deactivation rates than the homogeneous analogues. These negative effects were tentatively explained by the higher local catalyst concentration on the support surface leading to an increased tendency to deactivation by irreversible dimer formation. Separation of these catalysts by filtration and extraction is easy and efficient.     

Graft-polymerization of phosphine functionalized monomers onto silica particles

Summary Triphenylphosphine (PPh₃), a well-known reagent and catalyst, was successfully grafted onto silica particles in a functionalized polymer form using 4-(diphenylphosphinyl)styrene as a monomer. 4-(Diisopropylphosphinyl)styrene and 4-(ditertbutylphosphinyl)styrene were also grafted onto silica in the form of a functionalized polymer and oligomer, respectively. Two methods were used: A) Copolymerization of phosphine-functionalized monomers with a vinyl compound previously attached to silica; and B) Polymerization of phosphine-functionalized monomers using a radical initiator previously attached to silica. The resulting materials were characterized by FTIR, DTA-TGA, specific surface area (S_BET) and XPS. The best results in grafting percent and molecular weight of the grafts were obtained by method B. Received: 7 February 2002 /Revised: 10 July 2002/ Accepted: 10 July 2002     

Silica nanoparticles functionalized via click chemistry and ATRP for enrichment of Pb(II) ion

ABSTRACT: Silica nanoparticles have been functionalized by click chemistry and atom transfer radical polymerization (ATRP) simultaneously. First, the silanized silica nanoparticles were modified with bromine end group, and then the azide group was grafted onto the surface via covalent coupling. 3-Bromopropyl propiolate was synthesized, and then the synthesized materials were used to react with azide-modified silica nanoparticles via copper-mediated click chemistry and bromine surface-initiated ATRP. Transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and thermogravimetric analysis were performed to characterize the functionalized silica nanoparticles. We investigated the enrichment efficiency of bare silica and poly(ethylene glycol) methacrylate (PEGMA)-functionalized silica nanoparticles in Pb(II) aqueous solution. The results demonstrated that PEGMA-functionalized silica nanoparticles can enrich Pb(II) more quickly than pristine silica nanoparticles within 1 h.     

Production of filled hydrogels by mechanochemically induced polymerization

Silica nanoparticles functionalized with polyvinylpyrrolidone (PVP) were obtained by the grinding/mechanical activation of quartz or nonfunctionalized silica nanoparticles in a stirred media mill in the presence of 1‐vinyl‐2‐pyrrolidone, as proven by Fourier transform infrared spectroscopy. The polymer layer thickness formed on the silica nanoparticles after 8 h of mechanical activation in the absence of polymerization initiators amounted to about 10 nm, as derived from shear rheology. The silica nanoparticles functionalized with the hydrophilic PVP by mechanochemical polymerization reaction were used as fillers for hydrogels based on poly(hydroxyethyl methacrylate) (polyHEMA). The water absorption, release properties, and mechanical properties of the polyHEMA–silica composites were measured as functions of the filler content and particle size of the filler. PolyHEMA samples containing 20 wt % of the functionalized silica particles exhibited a higher maximum water absorption than the unfilled polymer; this showed that the hydrophilic interface between the filler and the matrix improved the water absorption. The release of methylene blue from the polyHEMA–silica composites was governed by diffusion and was almost unaffected by the silica particles. The values for the storage modulus and loss modulus of the polyHEMA–silica composites increased with growing filler content. For constant filler content, the storage modulus increased with decreasing particle diameter of the filler; this showed that the reinforcing effect increased with the interface between the filler particles and the matrix polymer. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Preyssler-Structured Tungstophosphoric Acid Catalyst on Functionalized Silica for Esterification of n-Butanol with Acetic Acid

The Preyssler-structured tungstophosphoric acid catalyst supported on functionalized silica (Preyssler/F-silica) was prepared by means of grafting technique with amine group as coupling media, and its catalytic behavior was investigated in the esterification of n-butanol with acetic acid. The catalyst was characterized by infra-red spectroscopy, UV–Vis spectroscopy, Hammett indicator and N₂ adsorption techniques. Catalysts prepared directly by impregnating Preyssler acid on silica (Preyssler/silica) were also studied for comparison. The Preyssler/F-silica catalyst with the 14.3% loading of Preyssler acid exhibits a considerable conversion of n-butanol of 46.7% with 100% selectivity for n-butyl acetate in the esterification of n-butanol with acetic acid, which is comparative to the 15%Preyssler/silica catalyst. Moreover, a six-cycle reaction test reveals a good reusability for Preyssler/F-silica due to the water-resistance property of the Preyssler structure on the surface of the functionalized silica, and Preyssler/silica looses its high activity immediately at the second reaction cycle. The active sites on functionalized silica can retain the Preyssler structure before and after reaction. At 120 °C of reaction temperature, 140 min of reaction time, 1:1 molar ratio of acetic acid with n-butanol, and 0.005 g/mL of the catalyst content in reaction media are the suitable reaction conditions over the Preyssler/F-silica catalyst.     

Poly(ethyleneimine) infused and functionalized Torlon-silica hollow fiber sorbents for post-combustion CO2 capture

Organic–inorganic hybrid materials functionalized with amine-containing reagents are emerging as an important class of materials for capturing carbon dioxide from flue gas. Polymeric silica hollow fiber sorbents are fabricated through the proven dry-jet/wet-quench spinning process. In our study, a new technique for functionalizing polymeric silica hollow fiber sorbents with poly(ethyleneimine), followed by a post-spinning infusion step was studied. This two step process introduces a sufficient amount of poly(ethyleneimine) to the polymeric silica hybrid material support to improve the CO₂ sorption capacity due to the added amine groups. The poly(ethyleneimine) infused and functionalized hollow fiber sorbents are also characterized by a thermal gravimetric analyzer (TGA) to assess their CO₂ sorption capacities.     

Enantioselective Addition of Diphenylphosphine to 3‐Methyl‐4‐nitro‐5‐alkenylisoxazoles

An enantioselective Michael addition reaction of diphenylphosphine to substituted alkenylisoxazoles has been developed. The reaction proceeds efficiently under mild conditions with high yields (up to 99%) and moderate to excellent enantioselectivities (up to 92%) thus providing a hitherto unavailable direct access to a library of chiral tertiary phosphine‐functionalized isoxazoles.     

高效液相色谱手性冠醚固定相的制备研究

冠醚是具有空腔且非常好的识别能力的大环聚醚化合物。系统地研究了将R-(3,3′-二溴基-1,1′-二萘基)-20-冠-6涂覆在粗制硅胶、精制硅胶、大孔硅胶、苯环修饰粗制硅胶、苯环修饰精制硅胶、苯环修饰大孔硅胶、十八烷基修饰粗制硅胶、十八烷基修饰精制硅胶、十八烷基修饰大孔硅胶、氨丙基修饰粗制硅胶表面制备10种不同支撑体的手性固定相用于苯甘氨酸和对羟基苯甘氨酸的拆分研究。研究表明大孔硅胶以及氨丙基修饰硅胶直接涂覆冠醚的柱皆不能拆分这两种氨基酸,另外硅胶表面是否修饰、以及修饰的基团对手性柱的分离能力具有影响,不同来源的硅胶也强烈地影响着手性柱的拆分效率。     

Microgel/SiO2 hybrid colloids prepared using a water soluble silica precursor

In the present work we demonstrate that functional polymer microgels may act as smart self-catalyzing system inducing controlled formation of silica nanoparticles inside the polymer network and formation of hybrid colloids. We synthesized a water soluble silica precursor PEG-PEOS via post-modification of hyperbranched poly(ethoxysiloxane) (PEOS) with poly(ethylene glycol) monomethyl ether. We used poly(N-vinylcaprolactam)-based microgel functionalized with imidazole and β-diketone groups as a matrix for biomimetic deposition of silica. Composite microgel particles containing silica nanoparticles (up to 20 wt.-%) have been prepared by simultaneous PEG-PEOS conversion and silica deposition in the microgels. TEM studies indicate the infiltration of silica nanoparticles (～10 nm) inside the corona region of the microgels due to the strong acid–base interaction between the acidic silica and basic imidazole groups. The resulting composite particles were found to be colloidally stable and no aggregation was observed even after months of storage. The incorporation of silica nanoparticles increased the rigidity of the microgel particles and reduced their thermal sensitivity.