Silica Nanoclusters Research Articles

Bulk scale synthesis of high-performance carbon nanomaterial from biogas plant residual waste: Tuned porosity and composition for advanced supercapacitor applications

Carbon based nanomaterials with tuned porosity and compositions are of great interest in terms of energy storing materials. Nevertheless, it is still a challenge to produce such nanostructures on a large scale in cost-effective manner. In this work, we demonstrate that carbon nanomaterial (CNM) can be prepared using biogas plant residual waste (BPRW) as the precursor on a bulk scale under the specific two step pyrolysis technique. The optimized process along with the catalyst used is crucial as the simple pyrolysis of precursor can only produce traditional activated carbon with significantly lower specific capacitance values. The spherical structure of silica nanoclusters and graphitic skeleton of synthesized CNM confirmed with the help of FE-SEM, AFM and HR-TEM along with Raman and XRD while EDX, XPS, and FT-IR studies confirm the presence of various functional groups along with their respective percentage composition. These CNMs show mesoporous structure of the nanomaterial. Among three different aqueous electrolytes, the maximum specific capacitance of 371.88 Fg−1 at 0.5 Ag−1 current density in 1 M H2SO4 indicates its suitability for the practical supercapacitor applications. The fabricated symmetric supercapacitor device using CNMs as the electrode material and 1 M H2SO4 as the electrolyte shows very good specific capacitance value with the high energy density of 34.4 Whkg−1 corresponding to 360 Wkg−1 power density along with the good cyclic stability over 10,000 cycles of charge–discharge. This innovative technique paves the way towards upcycling any lignin containing waste material into carbon-based nanomaterial on a bulk scale by an effective method, which can be further used as high-performance electrode material for energy storage applications like in supercapacitors and batteries.

Electrosprayable Levan-Coated Nanoclusters and Ultrasound-Responsive Drug Delivery for Cancer Therapy.

In this study, we synthesized levan shell hydrophobic silica nanoclusters encapsulating doxorubicin (L-HSi-Dox) and evaluated their potential as ultrasound-responsive drug delivery systems for cancer treatment. L-HSi-Dox nanoclusters were successfully fabricated by integrating a hydrophobic silica nanoparticle-doxorubicin complex as the core and an amphiphilic levan carbohydrate polymer as the shell by using an electrospray technique. Characterization analyses confirmed the stability, size, and composition of the nanoclusters. In particular, the nanoclusters exhibited a controlled release of Dox under aqueous conditions, demonstrating their potential as efficient drug carriers. The levanic groups of the nanoclusters enhanced the targeted delivery of Dox to specific cancer cells. Furthermore, the synergism between the nanoclusters and ultrasound effectively reduced cell viability and induced cell death, particularly in the GLUT5-overexpressing MDA-MB-231 cells. In a tumor xenograft mouse model, treatment with the nanoclusters and ultrasound significantly reduced the tumor volume and weight without affecting the body weight. Collectively, these results highlight the potential of the L-HSi-Dox nanoclusters and ultrasound as promising drug delivery systems with an enhanced therapeutic efficacy for biomedical applications.

One-Pot Synthesis of Ultra-Small Pt Nanoparticles-Loaded Nitrogen-Doped Mesoporous Carbon Nanotube for Efficient Catalytic Reaction.

In this study, Pt nanoparticles-loaded nitrogen-doped mesoporous carbon nanotube (Pt/NMCT) was successfully synthesized through a polydopamine-mediated "one-pot" co-deposition strategy. The Pt source was introduced during the co-deposition of polydopamine and silica on the surface of SiO2 nanowire (SiO2 NW), and Pt atoms were fixed in the skeleton by the chelation of polydopamine. Thus, in the subsequent calcination process in nitrogen atmosphere, the growth and agglomeration of Pt nanoparticles were effectively restricted, achieving the in situ loading of uniformly dispersed, ultra-small (~2 nm) Pt nanoparticles. The method is mild, convenient, and does not require additional surfactants, reducing agents, or stabilizers. At the same time, the use of the dual silica templates (SiO2 NW and the co-deposited silica nanoclusters) brought about a hierarchical pore structure with a high specific surface area (620 m2 g-1) and a large pore volume (1.46 cm3 g-1). The loading process of Pt was studied by analyzing the electron microscope and X-ray photoelectron spectroscopy of the intermediate products. The catalytic performance of Pt/NMCT was investigated in the reduction of 4-nitrophenol. The Pt/NMCT with a hierarchical pore structure had an apparent reaction rate constant of 0.184 min-1, significantly higher than that of the sample, without the removal of the silica templates to generate the hierarchical porosity (0.017 min-1). This work provides an outstanding contribution to the design of supported noble metal catalysts and also highlights the importance of the hierarchical pore structure for catalytic activity.

Electronic and Structural Properties of Core-Shell Amino-Silica Nanoparticles: DFT And SCC-DFTB Calculation

Introduction: Silica nanoparticles (SNP) are extremely promising tools in nanotechnology and nano medicine. In most of applications such as capture and release of bacteriophage viruses the nano-structures of silica are coated by bio-compatible groups such as amine compounds. The presence of amino groups on the surface of the biosensors enables the installation of analyte receptors and antifouling agents such as oligo (ethylene oxide). Therefore, in this study, the electronic and structural properties of Core-Shell amino- Silica Nanoparticles are investigated.Material and Methods: In this investigation, we aim at obtaining the optimized structures and evaluate the geometries of the ground state for (SiO2) n (n=16, 20) nanoclusters. The electronic properties computed by density functional theory with GGA approximation and SCC-DFTB with hybrid Slater-Koster files are investigated and the effect of functionalization on such properties is discussed.Results: Solvolysis of studied structures is examined and it is shown that the highest occupied and lowest unoccupied molecular orbital states shift to obviously higher energy levels, which lead to more stable hydrogenated nanoclusters. The stability of nanoclusters rises by functionalization with amino and methylamine groups. Charge analysis of functionalized systems indicates the reactivity of nanoclusters. The results obtained in this paper are useful for chemical and biochemical applications of silica nanostructures.Conclusion: Results show that the length of amine hydrocarbon chain can control the electronic and magnetic properties of studied silica nanocluster (SNP) with different number of SiO2 unit. Pure ultra-small nanocluster shows the impressive spin splitting around the Fermi level, which is due to the spin splitting of outer silicon atoms. This feature of silica nanoclusters may be notable for applications in electronics.

Colloidal bag of marbles: The structure and properties of lipid-coated silica nanoclusters

Silica particles find applications in drug delivery and bio-sensing, where their large specific surface area can accumulate or release biologically active substances. Such applications would benefit from the ability to control diffusion access to the surfaces of a larger number of silica particles simultaneously. In the present work, we show that a phospholipid bilayer can contain clusters of silica nanoparticles ranging in number from a few to several tens, forming structures resembling a colloidal version of a bag of marbles. The lipidic membrane serves as a diffusion gate that prevents premature leakage of encapsulated substances from the nanoparticles to the bulk during storage, but allows diffusion when the phase transition temperature is exceeded. Using 30 nm SiO2 nanoparticles with or without surface amino groups, combined with lipid membranes containing DPPC, DPPG and cholesterol at molar ratios ranging from 25:60:15–85:0:15, we show that the electrostatic interactions between the nanoparticle surface and the lipid bilayer are crucial for the existence and stability of lipid-coated nanoclusters. We demonstrate the gating mechanism by measuring temperature-dependent diffusion of a model substance 5-(6)-carboxyfluorescein from the clusters. A shift in the phase transition temperature of approx. 20 K has been observed in the lipid-coated silica nanoclusters compared to plain liposomes of identical lipid bilayer composition.

Synthesis of Novel Dental Nanocomposite Resins by Incorporating Polymerizable, Quaternary Ammonium Silane-Modified Silica Nanoparticles.

Diverse approaches dealing with the reinforcement of dental composite resins with quaternary ammonium compounds (QAC) have been previously reported. This work aims to investigate the physicochemical and mechanical performance of dental resins containing silica nanofillers with novel QAC. Different types of quaternary ammonium silane compounds (QASiC) were initially synthesized and characterized with proton nuclear magnetic resonance (1H-NMR) and Fourier transform infrared (FTIR) spectroscopy. Silica nanoparticles were surface modified with the above QASiC and the structure of silanized products (S.QASiC) was confirmed by means of FTIR and thermogravimetric analysis. The obtained S.QASiC were then incorporated into methacrylate based dental resins. Scanning electron microscopy images revealed a satisfactory dispersion of silica nanoclusters for most of the synthesized nanocomposites. Curing kinetics disclosed a rise in both the autoacceleration effect and degree of conversion mainly induced by shorter QASiC molecules. Polymerization shrinkage was found to be influenced by the particular type of S.QASiC. The flexural modulus and strength of composites were increased by 74% and 19%, while their compressive strength enhancement reached up to 19% by adding 22 wt% S.QASiC nanoparticles. These findings might contribute to the proper design of multifunctional dental materials able to meet the contemporary challenges in clinical practice.

Gold nanoclusters modified mesoporous silica coated gold nanorods: Enhanced photothermal properties and fluorescence imaging

Photothermal therapy (PTT) is a non-invasive therapy that is widely used in cancer treatment. Gold nanorods (AuNRs) are particularly suitable as a photothermal reagent due to their unique localized surface plasmon resonance (LSPR) properties. However, bare gold nanorods are not stable enough during radiation to collect enough energy to kill tumor cells. In addition, they showed some biologically toxic originated from the poor colloidal stability and surfactants cetyltrimethyl ammonium bromide (CTAB), making it difficult to apply them directly to clinical research. To solve these problems, a novel nanocomposite was structured by coating silica shell and gold nanocluster on the outer layer of the gold nanorod (AuNRs@SiO2@AuNCs). Compared with the bare gold nanorod, the nanocomposite with the core-shell structure showed superior photothermal effect. The photothermal conversion temperature reached 63 °C under a lower irradiation power. The photothermal conversion efficiency was enhanced to 77.6%. Its photothermal performance remained constant after five cycles of near-infrared laser irradiation, indicating excellent photothermal stability. In vitro cell imaging experiments show that AuNRs@SiO2@ AuNCs can effectively enter tumor cells. By 3-(4,5-Dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) analysis, cancer cells can be effectively killed when exposed to a near-infrared laser. During the synthesis process, the silica and gold nanoclusters replaced the toxic CTAB molecular layer on the surface of AuNRs. Therefore, AuNRs@SiO2@AuNCs has good biocompatibility and fluorescence characteristics. These results suggest that such AuNRs@SiO2@AuNCs nanocomposite shows great potential in imaging guided photothermal therapy for cancer.

Micro-Ribbons and Micro-Wires Silica Synthesis Using Bottom-Top Technique

Silica is one of the most important materials used in many industries. The basic factor on which the selection process depends is the structural form, which is dependent on the various physical and chemical properties. One of the common methods in preparing pure silica is that it needs more than one stage to ensure the preparation process completion. The goal of this research is studying the nucleation technique (Bottom-top) for micro-wires and micro-ribbons silica synthesis. The silica nanoand microstructures are prepared using a duality (one step); a combination of alkali chemical etching process {potassium hydroxide (3 wt %) and n-propanol (30 Vol %)} and the ultra-sonication technique. In addition, the used materials in the preparation process are environmentally friendly materials that produce no harmful residues. The powder product is characterized using XRD, FTIR, Raman spectrum and SEM for determining the shape of architectures. The most significant factor of the nucleation mechanism is the sonication time of silica powder production during the dual technique. The product stages are as follows; silica nanoparticles (21-38 nm), nanoclusters silica (46 – 67 nm), micro-wires silica (1.17 – 6.29 μm), and micro-ribbons silica (19.4 – 54.1 μm). It's allowing for use in environmental applications (multiple wastewater purification, multiple uses in air filters, as well as many industrial applications).

Effects of hydroxyl content in pure silica optical fiber exposed to kGy electron beams

We present a study on the effect of high dose (kGy) electron beams on pure silica core fibers through examining the following phenomena within the fibers: radioluminescence (RL), radiation induced attenuation (RIA), and recovery. The objective is to identify the relevant characteristics of these fibers having favourable radiation response, that can be utilized in the development of dose measurement systems for high dose (kGy) environments. Two types of 20 m long pure silica optical fiber samples have been used, differing in their concentrations of hydroxyl (OH) content. Segments of 3.5 m length from each fiber were wound into coils of radius ~25 cm and exposed to consecutive irradiation doses, in the order of tens of kGy (10 kGy through 70 kGy in individual exposures), leading to a cumulative dose of some 300 kGy. The low-OH fiber showed saturation of response at the shorter wavelengths of the RL spectrum for doses of 30 kGy and above, resulting from presence of Oxygen Defect Centers (ODC). At the longer wavelengths the RL response of the low-OH optical fibers is observed to increase with dose, attributed to various bonding structural defects of silica nanoclusters. The saturation effect at shorter wavelengths is less prominent in the high-OH samples, where a monotonic increase is observed up to ~60 kGy indicating the formation of radiation induced ODC beyond this point. For cumulative dose of ~70 kGy, the highest RIA losses were registered at 550 nm (12.74 dB/m) for low-OH sample, and at 460 nm (4.75 dB/m) for high-OH sample. The high-OH sample showed much faster recovery post-irradiation, making it more suitable for repeated usage. Both the RL and RIA phenomena observed herein show the feasibility of pure silica optical fibers for dose measurement in high dose (kGy) environments up to individual dose of ~70 kGy.

Silica nanocluster binding rate coefficients from molecular dynamics trajectory calculations

Oxide nanoparticle growth from vapor phase precursors occurs in high temperature aerosol reactors first via the formation of nanoclusters, which are nanometer-scale condensed-phase species composed of 101-102 atoms. The binding rate for nanoclusters, defined as the rate at which two nanoclusters collide with and stick to one another, is hence of interest in predicting nanoparticle size distribution functions in an aerosol. We have utilized molecular dynamics (MD) trajectory calculations to determine the homogeneous (equal-sized) and heterogeneous (disparate-sized) binding rate coefficients of SiO2 (silica) nanoclusters composed of 18, 144, and 333 atoms. MD trajectory calculations incorporated all-atom models of nanoclusters using a combined Born–Huggins–Mayer-Lennard-Jones potential model, which accounts for both short range interactions and electrostatic interactions. MD calculations were utilized to determine the binding probability as a function of both initial relative velocity and impact parameter; integration of the binding probability across impact parameter and relative velocity space yields the binding rate coefficient. MD trajectory calculations reveal that the most common type of encounters between nanoclusters leading to binding are grazing collisions, i.e. instances where collision would not occur without induced dipole potential influences. The resulting binding rate coefficients are found to be extremely weakly dependent on system temperature, which is in contrast to the use of rate coefficient models which are the product of a hard-sphere collision rate coefficient and a constant enhancement factor (leading to a rate coefficient proportional to the square root of temperature). Enhancement factors defined from MD trajectory calculations fall in the range of 3–9 as system temperature decreases from 1500 K to 300 K. Such large values suggest that potential interactions need to be considered when modeling oxide nanocluster growth in the gas phase.

Development of mechanical properties in dental resin composite: Effect of filler size and filler aggregation state

The aim of this work was to study the effect of filler size and filler aggregation state on the mechanical properties of dental resin composites evaluated at filler loadings between 20 wt% and up to 76.5 wt%. Non-aggregated silica nanoparticles (SiNPMPS) (80 nm), doughnut-shaped silica nanoclusters obtained by spray drying (SDSiNPMPS) (3.5 μm) and amorphous barium-alumina borosilicate microparticles (BaAlBoSiMPS) (1.0 μm), functionalized by 3-methacryloxypropyl trimethoxysilane (MPS), were the fillers incorporated into resin matrix dental composites composed of triethylene glycoldimethacrylate (TEGDMA), urethane dimethylacrylate (UDMA), bisphenol A polyethylene glycol diether dimethacrylate (Bis EMA), and bisphenol A glycidyl methacrylate (BisGMA) (0.3:0.7:1:1 weight ratio, respectively). The mechanical properties developed in the resin composites were correlated with the formation of percolated-like particle networks, as observed by scanning electron microscopy (SEM), and volume fraction percolation thresholds (ϕc) calculated from a percolation model. Resin composites with non-aggregated SiNPMPS showed an apparent percolation threshold ϕc = 0.15 (i.e. 27 wt%); above this filler concentration and up to a volume fraction of particles (ϕP) of 0.24 (i.e. 40 wt%) there was an increase in the flexural modulus and the compressive strength of the resin composite. However, a further increase in filler concentration diminished all its mechanical properties due to a decrease in the particle-matrix adhesion strength, demonstrated by the increase in surface roughness and fracture steps as observed by SEM images. On the other hand, a resin composite filled with doughnut-shaped silica nanoclusters (SDSiNPMPS) showed an apparent percolation threshold ϕc = 0.41 (i.e. 60 wt%); increasing filler loading over this concentration generated an improvement in its mechanical properties, except the flexural strength also due to a decrease in the particle-matrix adhesion strength. The resin composites obtained with amorphous individual BaAlBoSiMPS microparticles (1.0 μm) and BaAlBoSiMPS microparticle aggregates (ca. 40.0 μm) showed an apparent percolation threshold ϕc = 0.41 (i.e. 64 wt%) that promoted an improvement in all their mechanical properties. SEM image of BaAlBoSiMPS resin composite at high filler loading (≥ 60 wt%) showed a decrease in fracture steps and no presence of voids, indicating a better adhesion between amorphous BaAlBoSiMPS particles and the polymeric matrix, which explains the improvement of mechanical properties. Resin composites filled exclusively with silica doughnut-shape nanoclusters or amorphous BaAlBoSiMPS microparticles could develop mechanical properties similar to or even better than those obtained by mixing nanofillers with spherical nanoclusters, which are commonly used in commercial resin composites.

Molecular-level insights into furfural hydrogenation intermediates over single-atomic Cu catalysts on magnesia and silica nanoclusters

ABSTRACTThis paper addresses the geometrical, charge, topological, and thermochemical data for the adsorption of the relevant furan species during hydrogenation of furfural to furfuryl alcohol over Cu/SiO2 and Cu/MgO catalysts. The calculations indicated that the binding of Cu to magnesia was stronger than that on silica. The results also indicated that the formation of an alkoxide intermediate is more favoured than that of a hydroxyalkyl species. The binding energetic data were in general agreement with the geometrical parameters, electron densities, and molecular orbital energy levels. The QTAIM data revealed the closed-shell interactions between Cu and O atoms on both of the catalysts. Finally, the analysis of the partial charges on the atoms revealed that the Cu atom acquires a positive charge upon interaction with the carbonyl group owing to a π-back-donation from Cu to the C = O bond.

Effects of Silica Nanoparticles and Silica-Zirconia Nanoclusters on Tribological Properties of Dental Resin Composites

Roughness and hardness are among the most important variables in the wear (resistance) performance of dental resin composites. In this study, silica nanoparticles and nanoclusters of silica and silica-zirconia nanoparticles were evaluated for use as reinforcement agents in dental resin composites. Nanoclusters with spherical morphology were obtained from aqueous dispersions of nanoparticles by spray drying. Roughness was measured through atomic force microscopy (AFM) while nanohardness was evaluated by nanoindentation. The roughness values obtained with silica nanoparticles were lower (22.6 ± 6.6 nm) than those obtained with silica and silica-zirconia nanoclusters (138.1 ± 36.6 nm, 116.2 ± 32.2 nm, resp.), while the hardness values of all composites were similar (nanoparticles = 0.24 ± 0.01 GPa, silica nanoclusters = 0.25 ± 0.04 GPa, and silica-zirconia nanoclusters = 0.22 ± 0.02 GPa). Based on this study, it can be established that particle size is a determining factor in the roughness of the final material, while the key variable for nanohardness was the concentration of the reinforcement materials.

Computing Free Energies of Hydroxylated Silica Nanoclusters: Forcefield versus Density Functional Calculations

We assess the feasibility of efficiently calculating accurate thermodynamic properties of (SiO2)n·(H2O)m nanoclusters, using classical interatomic forcefields (FFs). Specifically, we use a recently parameterized FF for hydroxylated bulk silica systems (FFSiOH) to calculate zero-point energies and thermal contributions to vibrational internal energy and entropy, in order to estimate the free energy correction to the internal electronic energy of these nanoclusters. The performance of FFSiOH is then benchmarked against the results of corresponding calculations using density functional theory (DFT) calculations employing the B3LYP functional. Results are reported first for a set of (SiO2)n·(H2O)m clusters with n = 4, 8 and 16, each possessing three different degrees of hydroxylation (R = m/n): 0.0, 0.25 and 0.5. Secondly, we consider five distinct hydroxylated nanocluster isomers with the same (SiO2)16·(H2O)4 composition. Finally, the free energies for the progressive hydroxylation of three nanoclusters with R = 0–0.5 are also calculated. Our results demonstrate that, in all cases, the use of FFSiOH can provide estimates of thermodynamic properties with an accuracy close to that of DFT calculations, and at a fraction of the computational cost.

Global optimisation of hydroxylated silica clusters: A cascade Monte Carlo Basin Hopping approach

We report on a global optimisation study of hydroxylated silica nanoclusters (SiO2)M·(H2O)N with sizes M=6, 8, 10 12, and for each size with a variable number of dissociatively chemisorbed water molecules (N=1, 2, 3…). Due to the high structural complexity of these systems and the associated ruggedness of the underlying potential energy landscape, we employ a “cascade” global optimisation approach. Specifically, we use Monte Carlo Basin Hopping (MCBH) where for each step we employ two energy minimisations with: (i) a lightly parameterised but computationally efficient interatomic potential (IP) which does not distinguish between H-bonded conformational isomers, and then (ii) a more sophisticated IP which accounts for polarisation and H-bonding. Final energies from the MCBH search are then refined with optimisations using density functional theory. The reliability of our approach is first established via comparison with previously reported results for the (SiO2)8·(H2O)N case, and then applied to the M=6, 10 and 12 systems. For all systems studied our results follow the trend in hydroxylation energy versus N, whereby the energy gain with hydroxylation is found to level off at a point where the average tetrahedral distortion of the SiO4 centres is minimised. This optimal hydroxylation point is further found to follow an inverse power law with increasing cluster size (M) with an exponent close to −2/3, further confirming work in previous studies for other cluster sizes.

Influence of Calcium on the Initial Stages of the Sol-Gel Synthesis of Bioactive Glasses.

Understanding how calcium interacts with silica sources and influences their polycondensation in aqueous solutions is of central importance for the development of more effective biomaterials by sol-gel approaches. For this purpose, the atomic-scale evolutions of a calcium-containing precursor solution corresponding to a typical sol-gel bioactive glass and of a corresponding Ca-free solution were compared using reactive molecular dynamics simulations. The simulations highlight a significantly faster rate of condensation when calcium is present in the initial solution, resulting in the formation of large and ramified silica clusters within 5 ns, which are absent in the Ca-free system. This different behavior has been analyzed and interpreted in terms of the Ca-induced nanosegregation in calcium-rich and silica-rich regions, which promotes the condensation reactions within the latter. By identifying a possible mechanism behind the limited incorporation of calcium in the silica nanoclusters formed in the early stages of the sol-gel process, these results could guide further studies aimed at identifying favorable experimental conditions to enhance initial calcium incorporation and thus produce sol-gel biomaterials with improved properties.

Silica subnanometer-sized nodes, nanoclusters and aggregates in Cyanate Ester Resin-based networks: Structure and properties of hybrid subnano- and nanocomposites

A series of the densely cross-linked Cyanate Ester Resins (CER)-based composites with 0.01–10wt.% silica, introduced via sol-gel process, were synthesized using dicyanate ester of bisphenol E (DCBE), tetraethoxysilane (TEOS) and γ-aminopropyltrimethoxysilane (APTMS). Their structure, molecular dynamics and properties are investigated by HAADF STEM, EDXS, DMA, DSC, and FTIR and Far-IR spectroscopies. The extremely high “constrained dynamics” effect and the most enhanced thermal, relaxation and elastic properties are revealed for the composites with ultralow silica contents, e.g., up to 0.1wt.%, in the absence of silica nano- or microclusters: increasing Tg by 50°C and dynamic modulus by 60% at 20°C and as much as forty times at 260°C are observed. EDXS analysis including getting the histograms of Si content shows that chemically embedded silica units are distributed quasi-regularly in nanovolumes of amorphous CER matrix in this case. The results obtained lead to conclusion that at ultralow silica contents only subnanometer-sized silica nodes may be generated within the CER network, i.e., the hybrid polymer subnanocomposites are formed. Formation of silica nanoclusters and, especially, their aggregates of hundreds nanometers in size at silica contents of 2–10wt.% results in their negative impact on the matrix properties.

Core-shell nanoparticles coated with molecularly imprinted polymers: a review

Core-shell surface molecular imprinting technology represents a rather new trend in analytical sciences. In this kind of material, the imprinting sites are located on the surface of the cores or shells of nanoparticles (NPs). This material can improve the capability of recognizing target molecules (analytes), reduce nonspecific adsorption, increase the relative adsorption capacity and selectivity, and accelerate the rate of mass transfer. This review (with 158 references) focuses on recent trends in core-shell MIPs. Following an introduction into the field, a first main section covers common core-materials including silica, magnetic NPs, quantum dots (including semiconductor quantum dots and carbon dots), gold and silver nanoclusters, and up-conversion materials. A further section covers the materials and reagents required for preparing MIPs (with subsections on templates, functional monomers, cross-linkers, initiators, and effects of solvent). A next main section covers synthetic approaches such as precipitation polymerization, emulsion polymerization, and grafting approach. A final section gives examples for applications of core-shell MIPs in analytical assays and in sensing.

Formation of functionalized nanoclusters by solvent evaporation and their effect on the physicochemical properties of dental composite resins

ObjectiveThe aim of this work was to study the effect of silica nanoclusters (SiNC), obtained by a solvent evaporation method and functionalized by 3-methacryloxypropyltrimethoxysilane (MPS) and MPS+octyltrimethoxysilane (OTMS) (50/50wt/wt), on the rheological, mechanical and sorption properties of urethane dimethylacrylate (UDMA)/triethylenglycol dimethacrylate (TEGDMA) (80/20wt/wt) resins blend. MethodsSilica nanoparticles (SiNP) were silanized with MPS or MPS+OTMS (50/50wt/wt) and incorporated in an UDMA-isopropanol mix to produce functionalized silica nanoclusters after evaporating the isopropanol. The effect of functionalized SiNC on resins rheological properties was determined by large and small deformation tests. Mechanical, thermal, sorption and solubility properties were evaluated for composite materials. ResultsThe UDMA/TEGDMA (80/20wt/wt) resins blend with added SiNC (ca. 350nm) and functionalized with MPS showed a Newtonian flow behavior associated to their spheroidal shape, whereas the resins blend with nanoclusters silanized with MPS+OTMS (50/50wt/wt) (ca. 400nm) showed a shear-thinning behavior due to nanoclusters irregular shape. Composite materials prepared with bare silica nanoclusters showed lower compressive strength than functionalized silica nanoclusters. MPS functionalized nanoclusters showed better mechanical properties but higher water sorption than functionalized nanoclusters with both silane coupling agents, MPS and OTMS. SignificanceThe solvent evaporation method applied to functionalized nanoparticles showed to be an alternative way to the sinterization method for producing nanoclusters, which improved some dental composite mechanical properties and reduced water sorption. The shape of functionalized silica nanoclusters showed to have influence on the rheological properties of SiNC resin suspensions and the mechanical and sorption properties of light cured composites.

Hydrated silica exterior produced by biomimetic silicification confers viral vaccine heat-resistance.

Heat-lability is a key roadblock that strangles the widespread applications of many biological products. In nature, archaeal and extremophilic organisms utilize amorphous silica as a protective biomineral and exhibit considerable thermal tolerance. Here we present a bioinspired approach to generate thermostable virus by introducing an artificial hydrated silica exterior on individual virion. Similar to thermophiles, silicified viruses can survive longer at high temperature than their wild-type relatives. Virus inactivation assays showed that silica hydration exterior of the modified virus effectively prolonged infectivity of viruses by ∼ 10-fold at room temperature, achieving a similar result as that obtained by storing native ones at 4 °C. Mechanistic studies indicate that amorphous silica nanoclusters stabilize the inner virion structure by forming a layer that restricts molecular mobility, acting as physiochemical nanoanchors. Notably, we further evaluate the potential application of this biomimetic strategy in stabilizing clinically approved vaccine, and the silicified polio vaccine that can retain 90% potency after the storage at room temperature for 35 days was generated by this biosilicification approach and validated with in vivo experiments. This approach not only biomimetically connects inorganic material and living virus but also provides an innovative resolution to improve the thermal stability of biological agents using nanomaterials.