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A hydrophobic heptapeptide, with sequence AFILPTG, as part of a phage capsid protein binds effectively to silica particles carrying negative charge. Here, we explore the silica binding activity of the sequence as a short polypeptide with polar N and C terminals. To describe the structural changes that occur on binding, we fit experimental infrared, Raman and circular dichroism data for a number of structures simulated in the full configuration space of the hepta-peptide using replica exchange molecular dynamics. Quantum chemistry was used to compute normal modes of infrared and Raman spectra and establish a relationship to structures from MD data. To interpret the circular dichroism data, instead of empirical factoring of optical activity into helical/sheet/random components, we exploit natural transition orbital theory and specify the contributions of backbone amide units, side chain functional groups, water, sodium ions and silica to the observed transitions. Computed optical responses suggest a less folded backbone and importance of the N-terminal when close to silica. We further discuss the thermodynamics of the interplay of charged and hydrophobic moieties of the polypeptide on association with the silica surface. The outcomes of this study may assist in the engineering of novel artificial bio-silica heterostructures.

Herein, we demonstrate a novel UV-induced decomposable nanocapsule of natural polysaccharide (HA-azo/PDADMAC). The nanocapsules are fabricated based on layer-by-layer co-assembly of anionic azobenzene functionalized hyaluronic acid (HA-azo) and cationic poly diallyl dimethylammonium chloride (PDADMAC). When the nanocapsules are exposed to 365 nm light, ultraviolet photons can trigger the photo-isomerization of azobenzene groups in the framework. The nanocapsules could decompose from large-sized nanocapsules to small fragments. Due to their optimized original size (~180 nm), the nanocapsules can effectively avoid biological barriers, provide a long blood circulation and achieve high tumor accumulation. It can fast eliminate nanocapsules from tumor and release the loaded drugs for chemotherapy after UV-induced dissociation. Besides, HA is an endogenous polysaccharide that shows intrinsic targetability to CD44 receptors on surface of cancer cells. The intracellular experiment shows that the HA-azo/PDADMAC nanocapsules with CD44 targeting ability and UV-controlled intracellular drug release are promising for cancer chemotherapy., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

X-ray irradiation of high Z elements causes photoelectric effects that include the release of Auger electrons that can induce localized DNA breaks. We have previously established a tumor spheroid-based assay that used gadolinium containing mesoporous silica nanoparticles and synchrotron-generated monochromatic X-rays. In this work, we focused on iodine and synthesized iodine-containing porous organosilica (IPO) nanoparticles. IPO were loaded onto tumor spheroids and the spheroids were irradiated with 33.2 keV monochromatic X-ray. After incubation in CO 2 incubator, destruction of tumor spheroids was observed which was accompanied by apoptosis induction, as determined by the TUNEL assay. By employing the γH2AX assay, we detected double strand DNA cleavages immediately after the irradiation. These results suggest that IPO first generate double strand DNA breaks upon X-ray irradiation followed by apoptosis induction of cancer cells. Use of three different monochromatic X-rays having energy levels of 33.0, 33.2 and 33.4 keV as well as X-rays with 0.1 keV energy intervals showed that the optimum effect of all three events (spheroid destruction, apoptosis induction and generation of double strand DNA breaks) occurred with a 33.2 keV monochromatic X-ray. These results uncover the preferential effect of K-edge energy X-ray for tumor spheroid destruction mediated by iodine containing nanoparticles., (© 2021. The Author(s).)

In this work, we have developed a chemical procedure enabling the preparation of highly ordered and vertically aligned mesoporous silica films containing selected contents of silver ions bonded inside the mesopore channels via anchoring propyl-carboxyl units. The procedure involves the electrochemically assisted self-assembly co-condensation of tetraethoxysilane and (3-cyanopropyl)triethoxysilane in the presence of cetyltrimethylammonium bromide as a surfactant, the subsequent hydrolysis of cyano groups into carboxylate ones, followed by their complexation with silver ions. The output materials have been electrochemically characterized with regard to the synthesis effectiveness in order to confirm and quantify the presence of the silver ions in the material. The mesostructure has been observed by transmission electron microscopy. We have pointed out that it is possible to finely tune the functionalization level by controlling the co-condensation procedure, notably the concentration of (3-cyanopropyl)triethoxysilane in the synthesis medium.

Food additive amorphous silicon dioxide (SiO 2 ) particles are manufactured by two different methods-precipitated and fumed procedures-which can induce different physicochemical properties and biological fates. In this study, precipitated and fumed SiO 2 particles were characterized in terms of constituent particle size, hydrodynamic diameter, zeta potential, surface area, and solubility. Their fates in intestinal cells, intestinal barriers, and tissues after oral administration in rats were determined by optimizing Triton X-114-based cloud point extraction (CPE). The results demonstrate that the constituent particle sizes of precipitated and fumed SiO 2 particles were similar, but their aggregate states differed from biofluid types, which also affect dissolution properties. Significantly higher cellular uptake, intestinal transport amount, and tissue accumulation of precipitated SiO 2 than of fumed SiO 2 was found. The intracellular fates of both types of particles in intestinal cells were primarily particle forms, but slowly decomposed into ions during intestinal transport and after distribution in the liver, and completely dissolved in the bloodstream and kidneys. These findings will provide crucial information for understanding and predicting the potential toxicity of food additive SiO 2 after oral intake.

This work studied the influence of the pore size and morphology of the mesoporous silica as support for formate dehydrogenase (FDH), the first enzyme of a multi-enzymatic cascade system to produce methanol, which catalyzes the reduction of carbon dioxide to formic acid. Specifically, a set of mesoporous silicas was modified with glyoxyl groups to immobilize covalently the FDH obtained from Candida boidinii. Three types of mesoporous silicas with different textural properties were synthesized and used as supports: i) SBA-15 (D P  = 4 nm); ii) MCF with 0.5 wt% mesitylene/pluronic ratio (D P  = 20 nm) and iii) MCF with 0.75 wt% mesitylene/pluronic ratio (D P  = 25 nm). As a whole, the immobilized FDH on MCF 0.75 exhibited higher thermal stability than the free enzyme, with 75% of residual activity after 24 h at 50 °C. FDH/MCF 0.5 exhibited the best immobilization yields: 69.4% of the enzyme supplied was covalently bound to the support. Interestingly, the specific activity increased as a function of the pore size of support and then the FDH/MCF 0.75 exhibited the highest specific activity (namely, 1.05 IU/g MCF0.75 ) with an immobilization yield of 52.1%. Furthermore, it was noted that the immobilization yield and the specific activity of the FDH/MCF 0.75 varied as a function of the supported enzyme: as the enzyme loading increased the immobilization yield decreased while the specific activity increased. Finally, the reuse test has been carried out, and a residual activity greater than 70% was found after 5 cycles of reaction., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021. Published by Elsevier B.V.)

In this paper, the structural and optical properties of ZnO-SiO 2 -based ceramics fabricated from oil palm empty fruit bunch (OPEFB) were investigated. The OPEFB waste was burned at 600, 700 and 800 °C to form palm ash and was then treated with sulfuric acid to extract silica from the ash. X-ray fluorescence (XRF) and X-ray diffraction (XRD) analyses confirmed the existence of SiO 2 in the sample. Field emission scanning electron microscopy (FESEM) showed that the particles displayed an irregular shape and became finer after leaching. Then, the solid-state method was used to produce the ZnO-SiO 2 composite and the samples were sintered at 600, 800, 1000, 1200 and 1400 °C. The XRD peaks of the Zn 2 SiO 4 showed high intensity, which indicated high crystallinity of the composite. FESEM images proved that the grain boundaries were larger as the temperature increased. Upon obtaining the absorbance spectrum from ultraviolet-visible (UV-Vis) spectroscopy, the energy band gaps obtained were 3.192, 3.202 and 3.214 eV at room temperature, 600 and 800 °C, respectively, and decreased to 3.127, 2.854 and 2.609 eV at 1000, 1200 and 1400 °C, respectively. OPEFB shows high potential as a silica source in producing promising optical materials.

Purpose: Mesoporous silica (MSNs) have attracted considerable attention for its application in the field of drug delivery and biomedicine due to its high surface area, large pore volume, and low toxicity. Recently, numerous studies revealed that gut microbiota is of critical relevance to host health. However, the toxicological studies of MSNs were mainly based on the degradation, biodistribution, and excretion in mammalian after oral administration for now. Here in this study, we explored the impacts of oral administration of three kinds of MSNs on gut microbiota in rats to assess its potential toxicity., Methods: Forty rats were divided into four groups: control group; Mobil Composition of Matter No. 41 type mesoporous silica (MCM-41) group; Santa Barbara Amorphous-15 type mesoporous silica (SBA-15) group, and biodegradable dendritic center-radial mesoporous silica nanoparticle (DMSN) group. Fecal samples were collected 3 days and 7 days after the intake of MSNs and analyzed with high throughput sequencing. Gastric tissues in rats were obtained after dissection for the histological study., Results: Three different MSNs (MCM-41, SBA-15, and DMSN) were successfully prepared in this study. The pore size of three MSNs was calculated similarly as (3.54 ± 0.15) nm, (3.48 ± 0.21) nm, and (3.45 ± 0.17) nm according to the BET & BJH model, respectively, while the particle size of MCM-41, SBA-15 and DMSN was around 209.2 nm, 1349.56 nm, and 244.4 nm, respectively. In the gene analysis of 16S rRNA, no significant changes in the diversity and richness were found between groups, while Verrucomicrobia decreased and Candidatus Saccharibacteria increased in MCM-41 treated groups. Meanwhile, no inflammatory and erosion symptoms were observed in the morphological analysis of the colons, except the MCM-41 treated group., Conclusion: Three different MSNs, MCM-41, SBA-15, and DMSN were successfully prepared, and this study firstly suggested the impact of MSNs on the gut microbiota, and further revealing the potential pro-inflammatory effects of oral administration of MCM-41 was possibly through the changing of gut microbiota., Competing Interests: The authors report no conflicts of interest in this work., (© 2021 Yu et al.)

Objective: In this study, amine-functionalized magnetite Kit-6 silica nanocomposite (Fe3O4@SiO2@Kit-6-NH2) was synthesized as an adsorbent for removing Carmoisine food dye from aqueous solutions., Methods: The nanocomposite was chemically synthesized and was characterized by X-ray diffraction analysis (XRD), vibrating sample magnetometery (VSM), energy-dispersive X-ray spectroscopy (EDX), scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR). Taguchi orthogonal array experimental design method was used to optimize the experimental conditions, including adsorbent amount, pH of the solution, amount of salt, the volume of sample and contact time. Pseudo first-order, pseudo second-order, intra-particle diffusion and Elovich kinetic models were investigated to study the kinetic parameters of the sorption process., Results: The kinetic data corresponded to the pseudo second-order kinetic model with R2 = 0.9999. Also, adsorption data were analyzed using Langmuir, Freundlich and Temkin isotherm models. The results indicated that the data were well fitted to the Freundlich isotherm model (R2 = 0.9984, n=1.0786). The reusability tests showed that the proposed nanocomposite could be used for more than 8 cycles with removal efficiency higher than 90%., Conclusion: The applicability study of the proposed nanocomposite proved its ability for efficient removal of Carmoisine dye from real aqueous samples., (Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.net.)

Background: Prostate cancer (PCa) has the second-highest morbidity and mortality rates in men. Possessing facile surface chemistry and unique optical properties make silica nanoparticles(SiO 2 -NPs) promising cancer therapy materials., Objective: This study aimed to investigate the effects of SiO 2 -NPs and their derivatives, including SiNP-NH2, SiNP-Cl, and SiNP-SH against PCa and clarify their molecular mechanism on cell death, gene, and protein expressions., Methods: Following the synthesis and derivation of SiO 2 -NPs, their characterization was carried out using TEM, DLS, BET, and FT-IR. Cytotoxic properties of the compounds were investigated against different human cancerous cells; including HUH-7, A549, DLD-1, HeLa, NCI-H295R, and PC-3, as well as human healthy epithelium cell line PNT1A., Results: SiNP-NH2, SiNP-Cl, and SiNP-SH dose-dependently inhibited the proliferation of PC-3 cells with an IC 50 value as 55.46 μg/mL, 55.09 μg/mL and 72.89 μg/mL, respectively. SiNP-SH significantly(p<0.0001) inhibited metastasis and invasion of PC-3 cells(20.4% and 46.7%, respectively), and significantly(p<0.0001) increased early apoptosis(32.3%) when compared with non-treated cells. Protein and mRNA expressions of BcL-2, Bax, caspase-3, caspase-9, caspase-12, p53, Smad-4, Kras, and Nf-ĸB were also altered following the treatment of SiO 2 -NPs and its derivatives., Conclusion: Our results demonstrated that -SH functioned SiO2-NPs can prevent the proliferation of human PCa by increasing apoptosis by up-regulating gene and protein expression of p53(TP53) as well as caspase-3, caspase-9, and caspase-12 in the apoptotic pathway. Besides, the increased level of Smad-4 has also implicated the decreased cell proliferation. Hence, low sized SiNP-SH nanoparticles might be a suitable candidate for the treatment of human PCa., (Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.net.)

Mesoporous silica with uniform 2-D hexagonal pores has been newly employed as facile reservoir to impove the dissolution rate of water insoluble drugs. However, rapid drug release from mesoporous silica is usually accompanied by the generation of supersaturated solution, which leads to the drug precipitation and compromised absorption. To address this issue, a supersaturated ternary hybrid system was constructed in this study by utilizing inorganic mesoporous silica and organic precipitation inhibitor. Vinylprrolidone-vinylacetate copolymer (PVP VA64) with similar solubility parameter to model drug fenofibrate (FNB) was expected to well inhibit the precipitation. Mesoporous silica Santa Barbara amorphous-15 (SBA-15) was synthesized in acidic media and hybrid matrix was produced by hot melt extrusion technique. The results of in vitro supersaturation dissolution test obviously revealed that the presence of PVP VA64 could effectively sustain a higher apparent concentration. PVP VA64 was suggested to simultaneously reduce the rate of nucleation and crystal growth and subsequently maintain a metastable supersaturated state. The absorption of FNB delivered by the organic-inorganic hybrid matrix was remarkably enhanced in beagle dogs, and its AUC value was 1.92-fold higher than that of FNB loaded mesoporous silica without PVP VA 64. In conclusion, the supersaturated organic-inorganic hybrid matrix can serve as a modular strategy to enhance the oral availability of water insoluble drugs.

Magnetic mesoporous silica material was tested as adsorbent for removal of two usual colored compounds present in industrial wastewater. The magnetic mesoporous silica was synthesized by modified sol-gel method and characterized from the morpho-textural, structural and magnetic point of view. The specific surface area and the total pore volume indicate a good adsorption capacity of the material, and the obtained saturation magnetization strength value denotes a good magnetic separation from solution. The adsorption capacity of magnetic mesoporous silica increases with the increase of the initial dye concentration, and the removal efficiency of the dyes was dependent on the pH of the solution and decreased with increasing temperature. The pseudo-second-order kinetic model described best the adsorption mechanism, and the maximum adsorption capacities were determined from the Sips isotherm model, being 88.29 mg/g for Congo Red and 208.31 mg/g for Methylene Blue. A complete thermodynamic evaluation was performed, by determining the free energy, enthalpy and entropy, and the result showed a spontaneous and exothermic adsorption process. The recovery and reutilization of the adsorbent were estimated in five cycles of adsorption-desorption, and the results indicated a good stability and reusability of magnetic mesoporous silica. The new magnetic mesoporous silica can be easily separated from solution, via an external magnetic field, and may be effectively applied as adsorbent for elimination of dyes from colored polluted waters., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Poly (lactic-co-glycolic acid) (PLGA) in situ-forming implants are well-established drug delivery systems for controlled drug release over weeks up to months. To prevent initial burst release, which is still a major issue associated with PLGA-based implants, drugs attached to particulate carriers have been encapsulated. Unfortunately, former studies only investigated the resulting release of the soluble drugs and hence missed the potential offered by particulate drug release. In this study, we developed a system capable of releasing functional drug-carrying particles over a prolonged time. First, we evaluated the feasibility of our approach by encapsulating silica particles of different sizes (500 nm and 1 μm) and surface properties (OH or NH 2 groups) into in situ-forming PLGA implants. In this way, we achieved sustained release of particles over periods ranging from 30 to 70 days. OH-carrying particles were released much more quickly when compared to NH 2 -modified particles. We demonstrated that the underlying release mechanisms involve size-dependent diffusion and polymer-particle interactions. Second, particles that carried covalently-attached ovalbumin (OVA) on their surfaces were incorporated into the implant. We demonstrated that OVA was released in association with the particles as functional entities over a period of 30 days. The released particle-drug conjugates maintained their colloidal stability and were efficiently taken up by antigen presenting cells. This system consisting of particles incorporated into PLGA-based in situ-forming implants offers the dual advantage of sustained and particulate release of drugs as a functional unit and has potential for future use in many applications, particularly in single-dose vaccines., (Copyright © 2020 Elsevier B.V. All rights reserved.)

The synthesis of Mobil Composition of Matter 41 (MCM-41) mesoporous silica nanoparticles (MSNs) of controlled sizes and porous structure has been performed at laboratory and pilot plant scales. Firstly, the effects of the main operating conditions (TEOS -Tetraethyl ortosilicate- addition rate, nanoparticle maturation time, temperature, and CTAB -Cetrimonium bromide- concentration) on the synthesis at laboratory scale (1 L round-bottom flask) were studied via a Taguchi experimental design. Subsequently, a profound one-by-one study of operating conditions was permitted to upscale the process without significant particle enlargement and pore deformation. To achieve this, the temperature was set to 60 °C and the CTAB to TEOS molar ratio to 8. The final runs were performed at pilot plant scale (5 L cylindrical reactor with temperature and stirring speed control) to analyze stirring speed, type of impeller, TEOS addition rate, and nanoparticle maturation time effects, confirming results at laboratory scale. Despite slight variations on the morphology of the nanoparticles, this methodology provided MSNs with adequate sizes and porosities for biomedical applications, regardless of the reactor/scale. The process was shown to be robust and reproducible using mild synthesis conditions (2 mL⋅min -1 TEOS addition rate, 400 rpm stirred by a Rushton turbine, 60 min maturation time, 60 °C, 2 g⋅L -1 CTAB, molar ratio TEOS/CTAB = 8), providing ca . 13 g of prismatic short mesoporous 100-200 nm nanorods with non-connected 3 nm parallel mesopores.

Ordered mesoporous materials have attracted considerable attention due to their potential applications in catalysis, adsorption, and separation technologies, as well as biomedical applications. In the present manuscript, we aim at a rational design to obtain the desired surface functionality (Ti and/or hydrophobic groups) while obtaining short channels (short diffusion paths) and large pore size (>10 nm). Santa Barbara Amorphous material SBA-15 and periodic mesoporous organosilica PMO materials are synthesized using Pluronic PE 10400 (P104) surfactant under mild acidic conditions to obtain hexagonal platelet-like particles with very short mesochannels (300-450 nm). The use of expanders, such as 1, 3, 5-trimethylbenzene (TMB) and 1, 3, 5-triisopropylbenzene (TIPB) were tested in order to increase the pore size. TMB yielded in the formation of vesicles in all the syntheses attempted, whereas P104 combined with TIPB resulted both in expanded (E) E-SBA-15 and E-PMO with 12.3 nm pore size short channel particles in both cases. Furthermore, the synthesis method was expanded to the incorporation of small amount of Ti via co-condensation method using titanocene as titanium source. As a result, Ti-E-SBA-15 was obtained with 15.5 nm pore size and isolated Ti-sites maintaining platelet hexagonal morphology. Ti-PMO was obtained with 7.8 nm and short channels, although the pore size under the tried synthesis conditions could not be expanded further without losing the structural ordering.

A method is described for the functionalization of magnetic carbon nanotubes to recognize aristolochic acid Ⅰ and Ⅱ. 3-Glycidyloxypropyltrimethoxysilane was used as a coupling agent to immobilize adenine on a solid support. The morphology and structure of adenine-coated magnetic carbon nanotubes was investigated using transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD) and a vibrating sample magnetometer (VSM). The adsorption performance of the adenine-coated magnetic carbon nanotubes was evaluated via adsorption isotherms, the kinetics and selectivity tests. The adsorption capacity of the adenine-functionalized sorbent for aristolochic acid Ⅰ was determined to be 24.5 μg mg -1 . By combining magnetic solid phase extraction with HPLC detection, a method was developed to enrich and detect aristolochic acids used in traditional Chinese medicine. A satisfactory recovery (92.7 - 97.5% for aristolochic acid Ⅰ and 92.6 - 99.4% for aristolochic acid Ⅱ) and an acceptable relative standard deviation (<4.0%) were obtained., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020. Published by Elsevier B.V.)

Targeted alpha therapy, where highly cytotoxic doses are delivered to tumor cells while sparing surrounding healthy tissue, has emerged as a promising treatment against cancer. Radionuclide conjugation with targeting vectors and dose confinement, however, are still limiting factors for the widespread application of this therapy. In the current study, we developed multifunctional silica nanoconstructs for targeted alpha therapy that show targeting capabilities against breast cancer cells, cytotoxic responses at therapeutic dosages, and enhanced clearance. The silica nanoparticles were conjugated to transferrin, which promoted particle accumulation in cancerous cells, and 3,4,3-LI(1,2-HOPO), a chelator with high selectivity and binding affinity for f-block elements. High cytotoxic effects were observed when the nanoparticles were loaded with 225 Ac, a clinically relevant radioisotope. Lastly, in vivo studies in mice showed that the administration of radionuclides with nanoparticles enhanced their excretion and minimized their deposition in bones. These results highlight the potential of multifunctional silica nanoparticles as delivery systems for targeted alpha therapy and offer insight into design rules for the development of new nanotherapeutic agents.

Semiconducting nanoparticles with luminescent properties are used as detection probes and drug carriers in in-vitro and in-vivo analysis. ZnO nanoparticles, due to its biocompatibility and low cost, have shown potential application in bioimaging and drug delivery. Thus, ZnO/SiO 2 core/shell nanoparticle was synthesised by wet chemical method for fluorescent probing and drug delivery application. The synthesised core/shell nanomaterial was characterized using XRD, FTIR, UV-VIS spectroscopy, Raman spectroscopy, TEM and PL analysis. The silicon shell enhances the photoluminescence and aqueous stability of the pure ZnO nanoparticles. The porous surface of the shell acts as a carrier for sustained release of curcumin. The synthesized core/shell particle shows high cell viability, hemocompatibility and promising florescent property. Graphical Abstract.

The potential to impart surfaces with specific lignin-like properties (i.e. resistance to microbes) remains relatively unexplored due to the lack of well-defined lignin-derived small molecules and corresponding surface functionalization strategies. Here, allyl-modified guaiacyl β-O-4 eugenol (G-eug) lignin-derived dimer is synthesized and attached to mesoporous silica nanoparticles (MSNPs) via click chemistry. The ability of G-eug lignin-dimer functionalized particles to interact with and disrupt synthetic lipid bilayers is compared to that of eugenol, a known natural antimicrobial. Spherical MSNPs (∼150 nm diameter with 4.5 nm pores) were synthesized using surfactant templating. Post-synthesis thiol (SH) attachment was performed using (3-mercaptopropyl) trimethoxysilane and quantified by Ellman's test. The resultant SH-MSNPs were conjugated with the G-eug dimers or eugenol by a thiol-ene reaction under ultraviolet light in the presence of a photo initiator. From thermogravimetric analysis (TGA), attachment densities of approximately 0.22 mmol eugenol/g particle and 0.13 mmol G-eug dimer/g particle were achieved. The interaction of the functionalized MSNPs with a phospholipid bilayers of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (representing model cell membranes) supported on gold surface was measured using Quartz Crystal Microbalance with Dissipation monitoring (QCM-D). Eugenol-grafted MSNPs in PBS (up to 1 mg/mL) associated with the bilayer and increased the mass adsorbed on the QCM-D sensor. In contrast, MSNPs functionalized with G-eug dimer show qualitatively different behavior, with more uptake and evidence of bilayer disruption at and above a particle concentration of 0.5 mg/mL. These results suggest that bio-inspired materials with conjugated lignin-derived small molecules can serve as a platform for novel antimicrobial coatings and therapeutic carriers., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Intrinsically disordered proteins (IDPs) can display a broad spectrum of binding modes and highly variable binding affinities when interacting with both biological and nonbiological materials. A quantitative model of such behavior is important for the better understanding of the function of IDPs when encountering inorganic nanomaterials with the potential to control their behavior in vivo and in vitro . Depending on their amino acid composition and chain length, binding properties can vary strongly between different IDPs. Moreover, due to differences in the physical chemical properties of clusters of amino acid residues along the IDP primary sequence, individual residues can adopt a wide range of bound state populations. Quantitative experimental binding affinities with synthetic silica nanoparticles (SNPs) at residue-level resolution, which were obtained for a set of IDPs by solution NMR relaxation experiments, are explained here by a first-principle analytical statistical mechanical model termed SILC. SILC quantitatively predicts residue-specific binding affinities to nanoparticles and it expresses binding cooperativity as the cumulative result of pairwise residue effects. The model, which was parametrized for anionic SNPs and applied to experimental data of four IDP systems with distinctive binding behavior, successfully predicts differences in overall binding affinities, fine details of IDP-SNP affinity profiles, and site-directed mutagenesis effects with a spatial resolution at the individual residue level. The SILC model provides an analytical description of such types of fuzzy IDP-SNP complexes and may help advance understanding nanotoxicity and in vivo targeting of IDPs by specifically designed nanomaterials.

Fully porous silica microspheres (FPSM) with high specific surface area and hierarchical pore as matrix for HPLC were prepared. First, the porous silica nanospheres with controllable particle size and pore diameter were successfully synthesized using a dual-templating approach, the pore size of nanospheres can be increased to 18.4 nm by changing the molar ratios of octyltrimethylammonium bromide (TOMAB) and cetyltrimethyl ammonium bromide (CTAB), which is suitable for separation and analysis of biomolecules without pore enlargement. Then, the micron FPSM with hierarchical pore were synthesized by polymerization-induced colloid aggregation (PICA) using the porous nanospheres as a silicon source, which has a large mesoporous structure (35.2 nm) and high specific surface area (560 m 2  g -1 ). Subsequently, the FPSM modified with octadecyltrichlorosilane were studied as stationary phase for separation of cytochrome C, lysozyme, ribonuclease A, and ovalbumin, bovine serum albumin, and the baseline separation of five proteins was achieved within 1 min. The prepared column was also applied to the fast separation of digests of ovalbumin, and more chromatographic peaks were obtained compared to a commercial column under the same gradient elution conditions. In addition, the static-binding capacity of the functionalized FPSM for bovine serum albumin (BSA) was measured to be 276 mg g -1 , which was nearly twice the static adsorption given in literature. Therefore, these FPSM with high specific surface area and hierarchical pore structure are expected to have great potential for the separation of complex biological samples using HPLC. Graphical abstract A synthetic strategy was provided towards FPSM with hierarchical pores and high specific surface area using porous nanospheres as silicon source. The outstanding performance of the FPSM is that it has a high specific surface area while maintaining a large mesoporous size, which overcomes the disadvantage of sacrificing the specific surface area when increasing the pore size of porous silica microspheres prepared by using the traditional PICA method.

An energy-efficient and environment-friendly approach to prepare porous monodispersed micro-sized silica particles with methyltrimethoxysilane (MTMS) as the precursor is described. The particles were synthesized by a two-step hydrolysis/condensation procedure, with post-synthetic aging and calcination for methyl group removal. They show uniform spherical morphology, narrow particle size distribution (D 90 / 10 , 1.2-1.6), tailored particle size (3, 5, 7 μm) and mesopore structure (10, 13 nm), which can be directly used as packing materials for HPLC without size classification. C 18 , sulfonate, and C 18 /sulfonate mixed-mode stationary phases were produced by a green vapor deposition method based on the synthesized silica particles. The newly synthesized C 18 phase exhibits mechanical stability, kinetic behavior and separation performance expected from the commercial C 18 column. The C 18 /sulfonate phase exhibits prominent mixed-mode retention behavior which can be applied to the simultaneous separation of multiple substances in the compound drugs., Competing Interests: Declaration of Competing Interest None., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Novel green nanocomposite from mesoporous MCM-41 and Co 3 O 4 was synthesized from rice husk based silica gel and using the green extract of Peach leaves as reducing reagent. The composite was labeled as RH-MCM-41/Co 3 O 4 and characterized by different techniques as green photocatalyst in the degradation of Acephate pesticide under visible light illumination. The composite showed well developed spherical MCM-41 particles decorated by nano Co 3 O 4 nanoparticles with stunning surface area and low bandgap energy (1.51 eV). The composite displayed superior photocatalytic activities in the oxidation of Acephate which reflected in a complete degradation of different concentrations of it after 40 min (50 mg/L), 60 min (100 mg/L), 100 min (150 mg/L) and 140 min (200 mg/L) using 0.25 g of the composite. The complete removal of the present TOC for treatment of 100 mg/L acephate was achieved using 0.25 g after 70 min reflecting the formation of intermediate compounds during the oxidation steps. The reported intermediate compounds are CH 3 C(O)NH 2 , CH 3 O(CH 3 S)P(O)NH 2 , (CH 3 O) 2 P(O)SCH 3 , CH 3 OP(O)(OH) 2 , CH 3 SS(O) 2 CH 3 , and (COOH) 2 . All the formed intermediate compounds were degraded under the visible light photocatalytic activity of RH-MCM-41/Co 3 O 4 into NO 3 - , SO 4 2- , PO 4 3- , and CO 2 as final products., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Hypothesis: Flocculation performance using polyelectrolytes is influenced by critical design parameters including molecular weight, amount and sign of the ionic charge, and polymer architecture. It is expected that systematic variation of these characteristics will impact not only flocculation efficiency (FE) achieved but that charge density and architecture, specifically, can alter the flocculation mechanism. Therefore, it should be possible to tune these design parameters for a desired flocculation application., Experiments: Cationic-neutral and polyampholytic copolymers, exhibiting a range of molecular weights (10 3 -10 6 g/mol), varying charge levels (0-100% cationic, neutral and anionic), and random or block copolymer architecture, were applied to dilute suspensions of silica microparticles (control) and Chlorella vulgaris. FE and zeta potential values were determined over a range of flocculant doses to evaluate effectiveness and mechanism achieved., Findings: These different classes of copolymers provide specific benefits for flocculation, with many achieving >95% flocculation. Block copolymer flocculants exhibit a proposed, dominant bridging mechanism, therefore reducing flocculant dosage required for effective flocculation when compared to analogous random copolymer flocculants. Polyampholytic copolymers applied to C. vulgaris generally exhibited a bridging mechanism and increased FE compared to equivalent cationic-neutral copolymers, indicating a benefit of the anionic component on a more, complex, diversely charged suspension., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Inc. All rights reserved.)

Introduction: Over the past several years, nano-based therapeutics were an effective cancer drug candidate in order to overcome the persistence of deadliest diseases and prevalence of multiple drug resistance (MDR)., Methods: The main objective of our program was to design organosilane-modified Fe 3 O 4 /SiO 2 /APTS(~NH 2 ) core magnetic nanocomposites with functionalized copper-Schiff base complex through the use of (3-aminopropyl)triethoxysilane linker as chemotherapeutics to cancer cells. The nanoparticles were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray powder diffraction (XRD), field emission scanning electron microscopy (FE-SEM), TEM, and vibrating sample magnetometer (VSM) techniques. All analyses corroborated the successful synthesis of the nanoparticles. In the second step, all compounds of magnetic nanoparticles were validated as antitumor drugs through the conventional MTT assay against K562 (myelogenous leukemia cancer) and apoptosis study by Annexin V/PI and AO/EB. The molecular dynamic simulations of nanoparticles were further carried out; afterwards, the optimization was performed using MM+, semi-empirical (AM1) and Ab Initio (STO-3G), ForciteGemo Opt, Forcite Dynamics, Forcite Energy and CASTEP in Materials studio 2017., Results: The results showed that the anti-cancer activity was barely reduced after modifying the surface of the Fe 3 O 4 /SiO 2 /APTS nanoparticles with 2-hydroxy-3-methoxybenzaldehyde as Schiff base and then Cu(II) complex. The apoptosis study by Annexin V/PI and AO/EB stained cell nuclei was performed that apoptosis percentage of the nanoparticles increased upon increasing the thickness of Fe 3 O 4 shell on the magnetite core. The docking studies of the synthesized compounds were conducted towards the DNA and Topoisomerase II via AutoDock 1.5.6 (The Scripps Research Institute, La Jolla, CA, USA)., Conclusion: Results of biology activities and computational modeling demonstrate that nanoparticles were targeted drug delivery system in cancer treatment., Competing Interests: The authors report no conflicts of interest in this work., (© 2020 Eshaghi Malekshah et al.)

Microporous organic network (MON) is a promise class of functional materials in solid phase extraction (SPE). However, the previous MON-based SPE works are all focused on off-line mode. The inherent drawbacks of off-line SPE such as complicated operation steps and poor repeatability still hinder the potential applications of MON. In addition, direct use of traditional synthesized nano-sized MON in on-line SPE is impractical. To solve these issues, here we show the synthesis of silica amino-functionalized MON (SiO 2 @MON-NH 2 ) microsphere as an advanced adsorbent for on-line SPE of trace phenols prior to the high performance liquid chromatography (HPLC) analysis. The SiO 2 microsphere is served as the core to support the in-situ engineering of MON-NH 2 to reduce the back pressure during on-line SPE. Integrating amino groups (hydrogen binding sites) with aromatic MON's networks (hydrophobic and π-π interaction sites) on SiO 2 @MON-NH 2 provides supersensitive performance for phenols. The SiO 2 @MON-NH 2 microsphere for on-line SPE coupled with HPLC for the analysis of five phenols offers low limit of detections (S/N = 3, 0.009-0.030 μg L -1 ), wide linear range (0.025-100 μg L -1 ), large enrichment factors (5036-5689) and good intra-day and inter-day precisions (RSDs, 0.7-1.6 and 1.0-2.7%, respectively). The proposed method is also successfully applied to analyze trace phenols in tap, lake and river water samples with good recoveries. The newly-synthesized MON composites own great potential in on-line SPE for further determination of diverse trace contaminants., Competing Interests: Declaration of Competing Interest There are no conflicts to declare., (Copyright © 2019. Published by Elsevier B.V.)

Tea tree oil (TTO) is an efficient natural antibacterial agent. However, the bacteriostatic effect of TTO does not prevail for a long period because of the volatile nature of the oil. Therefore, a novel sustained-release formulation of TTO should be developed for improving the applicability of TTO. Herein, the mesoporous silica was selected for constructing a carrier for TTO. Mesoporous silica is non-toxic, easy to modify and exhibited an adjustable pore size. First, the mesoporous silica was modified by an aminated silane coupling agent (NH 2 -MCM-41). Then, the polyacrylic acid (PAA) was bonded by electrostatic bonds (PAA-NH 2 -MCM-41), which imparted the sustained-release effect in the TTO, supported in the mesoporous silica channel (TTO/PAA-NH 2 -MCM-41). The prepared bacteriostatic agent can achieve long-term sustained-release properties. At room temperature (26 ℃), the release rate of TTO after 11 h release reached 50 %. However, the release rate of TTO from TTO/PAA-NH 2 -MCM-8 reached only 42 % after 24 h. Furthermore, the sustained release behavior of TTO/PAA-NH 2 -MCM-41 was consistent with the Korsmeyer-Peppas kinetic model. Compared to TTO, TTO/PAA-NH 2 -MCM-41 exhibited a stable and sustained bacteriostatic effect even after 50 days in a natural environment. The minimum inhibitory concentration (MIC) value of the TTO/PAA-NH 2 -MCM-41 against Escherichia coli (E. coli) was 0.37∼0.44 mg/mL. TTO altered the cell morphology of E. coli and broke the integrity of the cell membrane, leading to cell death., Competing Interests: Declaration of Competing Interest The authors declare no conflict of interest., (Copyright © 2020 Elsevier B.V. All rights reserved.)

We report novel materials for calcium phosphate mineralization processes. These materials were synthesized via a three-step procedure starting from chitosan. In a first step, N-guanidinium-chitosan acetate was prepared via a direct guanylation reaction with cyanamide. This intermediate was then used as a cationic polymer substrate for attracting two functional anionic silica precursors, which subsequently allowed accessing new ionic hybrid materials via sol-gel chemistry. These N-guanidinium-chitosan acetate/silica hybrid materials, containing either sulfonate or carboxylate groups, were characterized using solid state 13 C NMR, 29 Si NMR and FT-IR spectroscopy. Finally, these two ionic hybrids were used as templates for in-vitro biomimetic calcium phosphate mineralization using simulated body fluid solution. We could show that the two ionic hybrids act as versatile templates for biomineralization, inducing the formation of hydroxyapatite, as proved from XRD, SEM, EDX, TEM and TGA. The current results suggest that the new ionic hybrids may be promising candidates for bone tissue engineering applications., Competing Interests: Declaration of competing interest The authors declare that they have no conflict of interests., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Multifunctional mesoporous silica nanoparticles (MSNs) can confer dynamically varied release kinetics depending on the intermolecular interactions between model drugs and functional decorations on the MSNs. Herein, brush-like fluorescent conjugates were grafted on the pore walls of pristine MSNs for high drug loading and to impart fluorescence properties. The fluorescent MSNs (FMSNs) were further coated with polydopamine (PDA) and graphene oxide (GO) double layer, designated FMSNs@PDA and FMSNs@PDA@GO, respectively. The FMSNs@PDA@GO exhibited highly consistent drug release over one week (∼7 days) because of the consolidated PDA/GO double layer at neutral pH (7.4). However, the release rate of FMSN-Ibu@PDA@GO was increased at acidic pH (5.5) because the PDA/GO double layer was partially disrupted due to weakened π-π stacking and electrostatic interactions. The release kinetics of the FMSNs-based NPs (FMSNs, FMSNs@PDA, and FMSNs@PDA@GO) were systematically investigated using negatively charged hydrophobic ibuprofen and neutral hydrophilic acetaminophen at pH 7.4. In the FMSN-drug system, the release rate of acetaminophen was higher than that of ibuprofen because of the higher solubility of acetaminophen in aqueous solution. In addition, ibuprofen has a bulky molecular structure compared to acetaminophen, leading to its slower transmission through the porous channels of FMSNs. In the FMSNs-drug@PDA system, acetaminophen exhibited a slower release rate than ibuprofen, owing to the π-π stacking interactions in the transmission of neutral acetaminophen by the PDA coating layer. On the other hand, the FMSNs-drug@PDA@GO exhibited a slower ibuprofen release rate than acetaminophen, owing to the electrostatic repulsion effect of the negative GO layer. Our drug delivery system was demonstrated as an advanced delivery platform, in which the transmission rate is controlled by intermolecular interactions between the diffusing drugs and functional decorations on the nanocarrier.

Silica-based nanocomposite syntheses employ many harmful substances, which, in turn, demand the development of new synthetic environmental-friendly routes that meet the principles of green chemistry. In this work, we present a novel magnetic adsorbent, Fe 2 O 3 @SiO 2 nanocomposite (Fe@SiNp), successfully obtained without surfactant, employing an electrochemical method. We characterized the nanocomposite and then applied it to remove aniline from the water medium. Characterization was carried out by vibrating-sample magnetometry (VSM), X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FT-IR). The parameters to the adsorptive removal of aniline were successfully optimized, which made possible to remove 71.04 ± 0.06% (126.6 ± 2.0 mg/g) from a 100 mg/L aniline solution at pH 6 and 323 K, by employing around 50 mg of Fe@SiNp, at a contact time of 40 min. The adsorption of aniline by Fe@SiNp is a spontaneous and exothermic process according to the pseudo-second-order kinetic model (r 2  = 1 at 20 mg/L aniline concentration) and the Freundlich isotherm model (r 2  = 0.9986).

We synthesized nanostructured mesoporous silica (MS)/hydroxyapatite (HA) hybrid particles in the presence of amphiphilic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO 20 PPO 70 PEO 20 ) triblock copolymer (P123). The particles exhibited slit-shaped mesostructures and underwent hybridization reaction between the MS and HA phases containing P123. Furthermore, the aggregated form of the particles exhibited dispersion stability in water in the monodispersed state (average particle size: 145 nm and coefficient of variation: 4.3% in the case of the maximum added amount of P123). Then, the structures of the hydration layer and the adsorbed protein on the particles were investigated to understand the effect of the hydration layer structures on the protein secondary structures. The ratio of the bonding water (intermediate and nonfreezing water) to free water increased upon hybridization, and it decreased with increasing P123 concentration. Upon hybridization, the component ratio of the asymmetric O-H stretching vibration between free water molecules decreased, and that of the symmetric O-H stretching vibration of intermediate water molecules increased. With increasing P123 concentration, the asymmetric O-H stretching vibration between free water molecules increased and the symmetric O-H stretching vibration of intermediate water molecules decreased. It was found that the protein native state component ratios of α-helix and β-sheet increased with increasing symmetric O-H stretching vibration between intermediate water molecules, and they decreased with decreasing asymmetric O-H stretching vibration between free water molecules. Moreover, the cytotoxicity against osteoblasts (MC3T3-E1) was evaluated and the hybrid particles exhibited a high cell density, indicating their bioactivity. On the hybrid particles interacting with P123, the cells were three-dimensionally assembled and uniaxially grown with the culture. Therefore, this is the first successful report of the synthesis of nanostructured MS/HA hybrid particles interacting with P123, and the controlled hydration layer structures on the particle surfaces were found to contribute to the protein secondary structures, promoting cytocompatibility.

An aminophenylboronic acid (APBA)-functionalized thorny-trap-shaped monolayer microarray as a 3D fractal structures' substrate was fabricated to capture and release circulating tumor cells (CTCs) efficiently. The microarray can not only trap cells inside by microbowls but also enhance the interaction between cell and substrate by providing more binding sites and facilitating the spread of cell filopodias via the growth of nanorods. Modification of APBA enhanced the interaction further by binding with sialic acid of CTCs surface. The special topological structure achieved a high capture efficiency of 79.5%. The captured cancer cells were released without introducing any affinity molecules by a ligand exchange reaction with up to 70% efficiency and good proliferation. This substrate can isolate 33 tumor cells from a mimic blood sample even at a low spiked number of 50 cancer cells. This study provides valuable guidance for isolation and release of CTCs and is significant for the further study of tumors.

Hollow mesoporous silica microsphere (HMSM) particles are one of the most promising vehicles for efficient drug delivery owing to their large hollow interior cavity for drug loading and the permeable mesoporous shell for controlled drug release. Here, we report an easily controllable aerosol-based approach to produce HMSM particles by continuous spray-drying of colloidal silica nanoparticles and Eudragit/Triton X100 composite (EUT) nanospheres as templates, followed by template removal. Importantly, the internal structure of the hollow cavity and the external morphology and the porosity of the mesoporous shell can be tuned to a certain extent by adjusting the experimental conditions (i.e., silica to EUT mass ratio and particle size of silica nanoparticles) to optimize the drug loading capacity and the controlled-release properties. Then, the application of aerosol-synthesized HMSM particles in controlled drug delivery was investigated by loading amoxicillin as an antibiotic compound with high entrapment efficiency (up to 46%). Furthermore, to improve the biocompatibility of the amoxicillin-loaded HMSM particles, their surfaces were functionalized with poly(allylamine hydrochloride) and alginate as biocompatible polymers via the layer-by-layer assembly. The resulting particles were evaluated toward Escherichia coli (Gram-negative) bacteria and indicated the bacterial inhibition up to 90% in less than 2 h. Finally, we explored the versatility of HMSMs as drug carriers for pancreatic cancer treatment. Because the pH value of the extracellular medium in pancreatic tumors is lower than that of the healthy tissue, chitosan as a pH-sensitive gatekeeper was grafted to the HMSM surface and then loaded with a pro-apoptotic NCL antagonist agent (N6L) as an anticancer drug. The obtained particles exhibited pH-responsive drug releases and excellent anticancer activities with inhibition of cancer cell growth up to 60%.

Au (III) ion-imprinted mesoporous silica particles (Au-Si-Py) was manufactured by the condensation reaction of (3-Aminopropyl)triethoxysilane (AT)and 2-pyridinecarboxaldehyde (Py). The obtained AT-Py Schiff base ligand was then coordinate with the template gold ions and the polymerizable gold-complex was allowed to gel in presence of tetraethoxysilane (TEOS) and then the coordinated gold ions were leached out of the obtained silica matrix using acidified thiourea solution. During the synthetic steps, the obtained materials were investigated utilizing advanced instrumental and spectral methods. Moreover, the morphological structure of both Au (III) ions imprinted Au-Si-Py and non-imprinted NI-Si-Py silica particles were visualized using scanning electron microscope (SEM). Various adsorption experiments had been carried out using both Au-Si-Py and NI-Si-Py to examine their potential for selective extraction of gold ions under different conditions., (© 2019 John Wiley& Sons, Ltd.)

Glycosylation on the cell surface contains abundant biological information, and detecting the glycan on cell surfaces can offer critical insight into biology and diseases. Here, a signal amplification strategy for the sensitive detection of glycan expression on the cell surface was proposed. In this approach, glycans on the cell surface were detected with poly(glycidyl methacrylate)-grafted silica nanosphere labeled with quantum dots (QDs) and biotin through the specific affinity reaction of avidin-biotin on the cancer cells. Glycans on the cell surface were first labeled via selective oxidization of sialyl groups into aldehydes by periodate. Aniline-catalyzed hydrazone ligation with biotin hydrazide was then used for the specific recognition to avidin. The nanoprobe was fabricated with "living" SiO 2 nanoparticles with alkyl bromide groups on their surfaces. They were then subsequently grafted with poly(glycidyl methacrylate) (PGMA) brushes via the successive surface-initiated atom transfer radical polymerization. The CdTe QDs and biotin were immobilized through a ring-open reaction with epoxy groups in the PGMA brushes to obtain QDs/biotin-polymer brush-functionalized silica nanosphere (SiO 2 -PGMA-QDs/biotin). Enhanced sensitivity could be achieved by an increase in CdTe QDs loading per assay event, because of the large number of surface functional epoxy groups offered by the PGMA. As a result, fluorescence signal increased versus the unamplified method. This method successfully demonstrates a simple, specific, and potent method to detect glycans on the cell surface., (Copyright © 2019 Elsevier B.V. All rights reserved.)

A facile method was developed for synthesis of boronic acid-functionalized silica nanocomposites (SiO 2 -BA) by 'thiol-ene' click reaction, where silica nanoparticles were synthesized by using tetraethoxysilane (TEOS) and γ-mercaptopropyl trimethoxysilane (γ-MPTS) as precursors. The morphology and structure properties of the resultant SiO 2 -BA were characterized by transmission electronic microscopy (TEM), Fourier transform infrared spectroscopy (FT-IR), and Brunner-Emmet-Teller measurements (BET). The adsorption behavior of the SiO 2 -BA for glycoproteins was evaluated. Under the optimized conditions, the SiO 2 -BA exhibited higher adsorption capacity towards glycoproteins (ovalbumin, OVA, 7.64 μmol/g) than non-glycoproteins (bovine serum albumin, BSA, 0.83 μmol/g). In addition, the practicality of the SiO 2 -BA was further assessed by selective enrichment of glycoproteins from egg white samples., (© 2019 Wiley-VHCA AG, Zurich, Switzerland.)

Background: Thiazolidinoneones are important pharmaceutical compounds because of their biological activities. Several methods for the synthesis of 4-thiazolidinones are widely reported in the literature. The main synthetic routes to synthesize 1,3-thiazolidin-4-ones involve three components reaction between amine, a carbonyl compound and thioglycolic acid., Objective: s-Proline covalented silicapropyl modified magnetic nanoparticles (Fe3O4@SiO2-Pr @s-proline) were prepared. The antibacterial activity of synthesized nanoparticles against four bacterias was investigated that showed that 30 Mg/L of synthesized nanoparticles is a suitable concentration for bacterial inhibitory. Finally, the catalytic application of the synthesized s-Proline covalented silicapropyl modified magnetic nanoparticles for the synthesis of thiazolidinones and pyrazolyl thiazolidinones under stirring in aqueous media was evaluated. All of the synthesized organic compounds were characterized by mp, FT IR, 1H NMR, 13C NMR and elemental analysis., Materials and Methods: A combination of aldehyde (1.0 mmol), thioglycolic acid (1.0 mmol), various amines (1mmol) and 0.05 g Fe3O4@SiO2propyl@L-proline, were reacted at room temperature under stirring in 10 mL water. After completion of the reaction, as indicated by TLC (4:1 hexane: ethylacetate), the reaction mixture was filtered in the presence of an effective magnetic bar to separate the nanocatalyst. The nanocatalyst was washed with a mixture of hot EtOH: H2O two times. The crude products were collected and recrystallized from ethanol, if necessary., Results and Discussion: We present a novel avenue for the synthesis of thiazolidinones in the presence of Fe3O4@SiO2-Pr @s-proline under solvent-free conditions., Conclusion: In conclusion, we have synthesized Fe3O4@SiO2-Pr@s-proline nanoparticles. Their biological activity against 4 bacterias was investigated. It released that 30Mg/L is the suitable concentration of synthesized nanoparticle for bacterial inhibitory. The catalytic efficiency of the catalyst was checked in the multicomponent reaction of various aldehyde, thioglycolic acid and various amines under stirring. This nanoparticle is a new organic-inorganic hybrid nanoparticle. The operational simplicity, the excellent yields of products, ease of separation and recyclability of the magnetic catalyst, waste reduction and high selectivity are the main advantages of this catalytic method. Furthermore, this new avenue is inexpensive and environmentally benign., (Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.net.)

Multidrug resistance is recognized as one of the main reasons leading to the failure of chemotherapy. Studies have shown that glutathione S-transferase inhibitors could be regarded as multidrug resistance reversal agents. Herein, a method of applying enzyme immobilization, molecular docking, and high-performance liquid chromatography coupled with quadrupole time-of-flight mass spectrometry was employed to screen glutathione S-transferase inhibitors from natural products. Magnetic mesoporous silica microspheres were synthesized and modified with a poly(dopamine) layer, which has a large quantity of amino, enabling further non-covalent binding with glutathione S-transferase. Moreover, the immobilization conditions, namely, potential of hydrogen, catalase concentration, reaction temperature and reaction time, were optimized. In total, six potential compounds were isolated and identified from Perilla frutescens (L.) Britt leaves and green tea and molecular docking was applied to identify the binding site. Rosmarinic acid, (-)-epigallocatechin-3-O-gallate and (-)-epicatechin-3-gallate showed higher binding affinity than the compounds, and their half maximal inhibitory concentration values were further determined. The results suggested that this proposed method was effective and convenient for identifying glutathione S-transferase inhibitors from natural products., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A phase with both hydrophobic and hydrophilic functionalities has been synthesized by modification of ground silica monolith particles with C18 and 1-[3-(trimethoxysilyl)propyl] urea ligands. A series of phases was prepared by changing the ratio of the two ligands to determine the optimal ratio in view of separation efficiency. The resultant optimized stationary phase was packed in narrow-bore glass-lined stainless-steel columns (1 × 300 mm and 2.1 × 100 mm) and used for the separation of synthetic peptides and proteins. The average numbers of theoretical plates (N) of 52 100/column (174 000/m, 5.75 µm plate height) and 35 500/column (118 000/m, 8.47 µm plate height) were achieved with the 300 mm column at a flow rate of 25 µL/min (0.86 mm/s) in 60:40 v/v acetonitrile/30 mM aqueous ammonium formate for the mixture of peptides (Thr-Tyr-Ser, Val-Ala-Pro-Gly, angiotensin I, isotocin, and bradykinin) and for the mixture of proteins (myoglobin, human serum albumin, and insulin), respectively. Fast analysis of the peptides and proteins was also carried out at a flow rate of 0.9 mL/min (6.88 mm/s) with the 100 mm column and all the analytes were eluted within 2 min with good separation efficiency., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Physicochemical properties of nanomaterials play important roles in determining their toxicological profiles during nano-biointeraction. Among them, surface modification is one of the most effective manners to tune the cytotoxicity induced by nanomaterials. However, currently, there is no consistency in surface modification including moiety types and quantities considering the conflicting toxicological profiles of particles across different studies. In this study, in order to systematically investigate how the moiety density affects cytotoxicity of NPs, we chose three different types of functional groups, that is, -NH 2 , -COOH, and -PEG, and further controlled their densities on modified Stöber silica nanoparticles (NPs). We demonstrated that densities of functional groups could significantly affect the cytotoxicities of Stöber silica NPs. Regardless of the types of functional groups, high grafting densities could ameliorate the cytotoxicities induced by Stöber silica NPs in macrophages, for example, J774A.1 and N9 cells. When equal amounts of functional groups were present, the cell viability increased in the order of -COOH < -NH 2 < -PEG. Furthermore, it was shown that surface modification could significantly affect the quantities of the surface silanol, which is the determining factor that affects their cytotoxicity. These results show that it is critical to control the surface moiety both quantitatively and qualitatively, which can tune the interaction outcomes at the nano-bio interface. The results found in this article provide useful guidance to adjust nanomaterial cytotoxicity for safer biomedical applications.

This study introduced multistage pH-responsive nanohybrids (MSN-hyd-MOP) based on mesoporous silica nanoparticles (MSNs) modified with polymers with charge-reversal property via an acid-labile hydrazone linker, which were applied as a drug delivery system loaded anticancer drugs. In this study, MSN-hyd-MOP nanohybrids were completely investigated for their synthesis, pH response, drug release behavior, cytotoxicity capability and endocytic behavior. Responding to the acidic extracellular microenvironment of solid tumor (pH 6.5), MSN-hyd-MOP nanohybrids exhibited surface charge-reversal characteristic from negative (-10.2 mV, pH 7.4) to positive (16.6 mV, pH 6.5). The model drug doxorubicin (Dox) was efficiently loaded within the channels of MSN-hyd-MOP (encapsulation efficiency about 87%). The increased acidity in endo-/lysosome promote Dox-loaded MSN-hyd-MOP (MSN-hyd-MOP@Dox) release Dox quickly. In vitro study revealed the drug delivery system had good biocompatibility and could deliver the payload to tumor cells. Overall, the described nanohybrids can be used as a potential anticancer drug delivery system., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Synthesis of monodisperse carboxylic acid-functionalized magnetic mesoporous silica nanoparticles is performed by either two-step sol-gel process or post-grafting using citric acid modified isocyanate silane coupling agent (MMSN-NCO-CA) or succinic anhydride modified magnetic mesoporous silica (MMSN-NH-SA). Morphology, structure and magnetic properties of bare and mesoporous silica coated Fe 3 O 4 core were studied using various techniques such as FTIR, VSM, TEM, FESEM, XRD and N 2 adsorption-desorption isotherms (BET). Cisplatin (cis-Pt) adsorption isotherms and its release profile in various media were investigated by ICP-OES. MMSN-NCO-CA with mean particle size 107 nm had lower surface area (87.5 m 2 /g) and larger pore size (6.9 nm) in comparison with MMSN-NH-SA (respective values of 151.2 m 2 /g and 3.5 nm). cis-Pt loading into particles followed a saturable adsorption with respect to the drug to particle mass ratios. More sustained release of cis-Pt was observed for MMSN-NCO-CA, though both nanoparticles exhibited a pH- and saline concentration-dependent drug release. In addition, general and cis-Pt specific cytotoxicity were examined by MTT assay in MDA-MB-231 breast cancer cell line, and to further detect apoptosis, acridine orange/ethidium bromide dual cell staining was investigated by fluorescence microscopy. In-vitro anti-tumor efficiency of cis-Pt loaded MMSN-NCO-CA and MMSN-NH-SA were similarly enhanced in comparison to free cis-Pt; however, more specific apoptotic death occurred for cis-Pt loaded MMSN-NCO-CA. Therefore, the as-synthesized citric acid functionalized core-shell magnetic mesoporous hybrid nanoparticles could be used as a promising drug carriers for cancer therapy in-vivo., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The quantitative uptake of Silica nanoparticles (SiNPs), although representing an essential prerequisite for their theranostic use, is difficult to address and it is still not utterly investigated. In this study, we tested the uptake and toxicity of two different types of luminescent core-shell silica-PEG (polyethylene glycol) nanoparticles SiNP and their carboxylate analogues on human adenocarcinoma cell line LoVo. We assessed the intracellular spatial distribution and concentration of Si element in the cell by a state-of-the-art approach merging synchrotron-based X-ray techniques (XRFM) with scanning transmission X-Ray microscopy (STXM). The concentration maps of Si obtained reflect the distribution of the SiNPs. In addition, we calculated the number of SiNPs per volume unit in each single cell, quantitating the exact amount of conveyed particles. The absence of effects on proliferation and cell death was confirmed by viability assays, morphological analysis and cytofluorimetric evaluation of ROS content. The three-dimensional analysis of intracellular uptake of both types of nanoparticles (with different surface charge) was performed by confocal fluorescence microscopy, which showed a main localization in the cytosolic region with no sign of nuclear uptake., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Nanostructured Ag@SiO 2 -Penicillin was synthesized from high-purity Ag 0 NPs with a mean particle size of about 10 nm produced by electromagnetic levitation gas condensation (ELGC) method. The silver and penicillin contents of the synthesized nano-antibiotic were about 34 wt% and 2.5 wt% respectively, as determined by ICP-OES and TGA analyses. The antibacterial properties and synergistic effects of nanostructured Ag@SiO 2 and Ag@SiO 2 -Penicillin on killing the Methicillin-susceptible S. aureus (MSSA) and Methicillin-resistant S. aureus (MRSA) bacteria were also examined. The nanoparticles were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Ag@SiO 2 -Penicillin NPs showed an outstanding antibacterial activity compared to Penicillin and Ag@SiO 2 NPs. The Fractional inhibitory concentration (FIC) indexes were 0.54 and 0.52 against MSSA and MRSA bacteria respectively, illustrating the synergistic effects of Ag@SiO 2 -Penicillin NPs. In addition, Ag@SiO 2 -Penicillin NPs showed promising dose-dependent cytotoxicity effects indicating the protective effects emanating from anti-inflammatory properties of penicillin., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Based on the mesoporous silica nanoparticles (MSN), a novel, simple and label-free aptamer biosensor was designed for the detection of aflatoxin B 1 (AFB 1 ). Here, the aptamers were used as molecular recognition probes and "gated molecules" while Rh6G was loaded into the interior of the particles as the signal probe. In the absence of AFB 1 , the "gate" was closed to prevent the leakage of the signal probe because of the immobilization of aptamers on the surface of MSN-NH 2 . With the presence of AFB 1 , the "gate" could be opened to release the signal probe for the specifical binding of aptamers to AFB 1 . Our results showed that the fluorescence intensity was positively correlated with the concentration of AFB 1 (0.5-50 ng mL -1 ), with the detection limit as low as 0.13 ng mL -1 . What's more, this design provides a new approach for rapid, sensitive and selective detection based on aptamers and it could be applied to numerous other analytes if appropriate aptamers are available., (Copyright © 2019 Elsevier B.V. All rights reserved.)

In this work, different paper surface modification strategies were compared to obtain an amine functionalized SBA-15 (N-SBA-15) composite for paper-based device development. The synthesized N-SBA-15 was characterized by N 2 adsorption-desorption isotherm, and infrared spectroscopy (FTIR), and it was incorporated to different polymer matrices (κ-carrageenan (CA), polyvinyl alcohol (PVA) and polyethylenimine (PEI)) for the development of the composite modified paper-based device. The retention, interactions, and morphology of the obtained composites were investigated by absorbance measurement, FTIR and scanning electron microscopy (SEM), respectively. To demonstrate the applicability of the modified paper-based device, ascorbic acid (AA) quantification was carried out. Horseradish peroxidase (HRP) was immobilized onto the modified paper surface. HRP in the presence of H 2 O 2 catalyzes the oxidation of 10-acetyl-3,7-dyhidroxyphenoxazine (ADHP) to highly fluorescent resorufin, which was measured by LIF detector. Thus, when AA was added to the solution, it decreases the relative fluorescence signal proportionally to the AA concentration. The linear range from 50 nmol L -1 to 1500 nmol L -1 and a detection limit of 15 nmol L -1 were obtained for AA quantitation. The obtained results allowed us to conclude that N-SBA-15/PEI composite could be considered an excellent choice for the paper-based device modification procedure due to its inherent simplicity, low cost, and sensitivity., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The long-term fate of biomedically relevant nanoparticles (NPs) at the single cell level after uptake is not fully understood yet. We report that lysosomal exocytosis of NPs is not a mechanism to reduce the particle load. Biopersistent NPs such as nonporous silica and gold remain in cells for a prolonged time. The only reduction of the intracellular NP number is observed via cell division, e.g. , mitosis. Additionally, NP distribution after cell division is observed to be asymmetrical, likely due to the inhomogeneous location and distribution of the NP-loaded intracellular vesicles in the mother cells. These findings are important for biomedical and hazard studies as the NP load per cell can vary significantly. Furthermore, we highlight the possibility of biopersistent NP accumulation over time within the mononuclear phagocyte system.

MnFe 2 O 4 NPs are successfully decorated on the surface of SiO 2 sheets to form the SiO 2 -MnFe 2 O 4 composite via one-pot hydrothermal synthesis method. The phase identification, morphology, crystal structure, distribution of elements, and microwave absorbing properties in S-band (1.55~3.4 GHz) of the as-prepared composite were investigated by XRD, SEM, TEM, and Vector Network Analyzer (VNA) respectively. Compared with the pure MnFe 2 O 4 NPs, the as-prepared SiO 2 -MnFe 2 O 4 composite exhibits enhanced microwave absorption performance in this frequency band due to the strong eddy current loss, better impedance matching, excellent attenuation characteristic, and multiple Debye relaxation processes. The maximum reflection loss of -14.87 dB at 2.25 GHz with a broader -10 dB bandwidth over the frequency range of 1.67~2.9 GHz (1.23 GHz) can be obtained at the thickness of 4 mm. Most importantly, the preparation method used here is relatively simple, hence such composite can be served as a potential candidate for effective microwave absorption in S-band., Competing Interests: The authors declare no conflict of interest.

Silica-supported metallic species have emerged as valuable green-chemistry catalysts because their high efficiency enables a wide range of applications, even at industrial scales. As a consequence, the preparation of these systems needs to be finely controlled in order to achieve the desired activity. The present work presents a detailed investigation of an ultrasound-promoted synthetic protocol for the grafting of β-cyclodextrin (β-CD) onto silica. Truly, ultrasound irradiation has emerged as a fast technique for promoting efficient derivatization of a silica surface with organic moieties at low temperature. Three different β-CD silica-grafted derivatives have been obtained, and the ability of β-CD to direct and bind Cu when CD is bonded to silica has been studied. A detailed characterization has been performed using TGA, phenolphthalein titration, FT-IR, diffuse reflectance (DR), DR UV-Vis, as well as the inductively-coupled plasma (ICP) of the β-CD silica-grafted systems and the relative Cu-supported catalysts. Spectroscopic characterization monitored the different steps of the reaction, highlighting qualitative differences in the properties of amino-derivatized precursors and final products. In order to ensure that the Cu-β-CD silica catalyst is efficient and robust, its applicability in Cu(II)-catalyzed alkyne azide reactions in the absence of a reducing agent has been explored. The presence of β-CD and an amino spacer has been shown to be crucial for the reactivity of Cu(II), when supported.