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Gold nanoshells currently attract increasing researchinterestsdue to the important role in many subjects. For practical applications,random arrangement of the nanoparticles is often unfavored so thatthe assembly of gold nanoshells is becoming a central issue. We hereproposed to utilize time-variant magnetic field to direct the assemblyof gold nanoshells. It was discovered that the alternating magneticfield can mediate the vortex-like assembly of gold nanoshells. Themechanism was explored and thought to be relative with the electricfield of induction which caused the thermal gradient on the substrateand the electric force. The vortexlike structure as well as the assemblymechanism will play an important role in research and applicationof gold nanomaterials. [ABSTRACT FROM AUTHOR]

Pyrethroid, a pesticide widely used worldwide, could mimic, block, or synergize the effects of endogenous hormones in humans or mammals after entering into the atmosphere and after being sprayed and applied in large quantities. This research aims to study the mechanism, kinetics, and eco-toxicity evaluation of the ozonolysis of permethrin (PER)-one of the typical pyrethroid (type I) pesticides. Existing experimental studies only predicted that ozonolysis of PER could generate a cycloperoxy analogue of PER (IM13-1-11), and the reaction mechanism has not yet been completed. To make up for the lack of experimental results, the 13 primary reaction pathways of PER and ozone, as well as the subsequent reactions of Criegee intermediates with small molecules such as NO x , CO x , SO 2 , and O 2 , have been studied to propose new reaction paths by quantum chemical calculations in this work. We calculated the total reaction rate constant of PER and ozone at 298 K and 1 atm based on the calculated thermodynamic data and the transition state theory (TST), which was compared with the experimental values to prove the reliability of our results. Based on the quantitative structure and activity relationship, we predicted the acute and chronic toxicity of PER and its products of ozonolysis to three representative organisms-fish, daphnia, and green algae to avoid animal experiments. The results show that ozonolysis products of PER are still extremely harmful to the environment and should be taken seriously, although the products have less toxicity than PER.

Parabens are widely employed in toothpaste, cosmetics, textiles, beverages, and preservatives, causing a serious environmental concern because they are endocrine-disrupting compounds (EDCs). As one of the highly reactive oxidants, ozone has a great effect on EDC removal. To understand the degradation and transformation of parabens in the aquatic environment and their toxicity to aquatic organisms, the degradation reaction of parabens initiated by O 3 was studied meticulously using quantum chemical calculations. The degradation process includes multiple initial reaction channels and consequent degradation pathways of the Criegee intermediates. Through thermodynamic data, the rate constants were computed using the transition state theory (TST). At a temperature of 298 K and a pressure of 1 atm, the calculated rate constants were 3.92 and 3.94 M -1 s -1 for methylparaben (MPB) and ethylparaben (EPB), respectively. The rate constants increased as the temperature increased or as the length of the alkyl chain on the benzene ring increased. Through the ecotoxicity assessment procedure, the ecotoxicity of parabens and the products in the degradation process can be assessed. Most degradation byproducts are either less toxic or nontoxic. Some byproducts are still harmful, such as oxalaldehyde (P2) and ethyl 2,3-dioxopropanoate (P10). Furthermore, the ecological toxicity of parabens increased with augmentation of the alkyl chain on the benzene ring. The effect of the alkyl chain length on the benzene ring in the compound cannot be ignored.

Ozonolysis of unsaturated ketones is a common atmospheric chemical process that plays a significant role in controlling the atmospheric budget of OH and O 3 , organic acids, and secondary organic aerosols (SOA). In this work, the detailed reaction mechanism and rate coefficients for the reactions of O 3 with two unsaturated ketones, 3-methyl-3-buten-2-one (MBO332) and 3-methyl-3-penten-2-one (MPO332), were investigated by using density functional theory (DFT) and Rice-Ramsperger-Kassel-Marcus (RRKM) theory. The results indicate that the major products are butanedione and formaldehyde for MBO332, and butanedione and acetaldehyde for MPO332. Possible reaction mechanism and thermodynamic parameters of some complex stable Criegee intermediates (SCIs) RR'COO were also be investigated in this study. Some organic peroxides can be regarded as the main products for the further reactions of SCIs. The rate constants calculated with O 3 are 2.59 × 10 -16 cm 3 molecule -1 s -1 and 2.28 × 10 -16 cm 3 molecule -1 s -1 for MBO332 and MPO332 at 298 K and 1 atm. The total rate constant is negatively correlated with temperature (200-400 K) and positively correlated with pressure. The atmospheric half-lives of MBO332 and MPO332 based on O 3 are estimated.

One of the key factors in tissue engineering and regenerative medicine is to optimize the interaction between seed cells and scaffolds such that the cells can grow in naturally biomimetic conditions. Their similarity to macromolecules and many unique properties mean that functional nanoparticles have promising potential for the modification and improvement of traditional scaffolds to obtain excellent biocompatibility, tunable stiffness, physical sensing, and stimulus-response capabilities. In the present study, we report magnetic poly(lactic- co-glycolic acid)/polycaprolactone (PLGA/PCL) scaffolds that were fabricated using a combination of the electrospinning technique and layer-by-layer assembly of superparamagnetic iron oxide nanoparticles (IONPs). PLGA/PCL scaffolds assembled with gold nanoparticles were prepared using the same method for comparison. The results showed that the assembled film of nanoparticles on the surface greatly enhanced the hydrophilicity and increased the elastic modulus of the scaffold, which subsequently improved the osteogenesis of the stem cells. Furthermore, the magnetic property of the IONPs proved to be the key factor in enhancing osteogenic differentiation, which explained the superior osteogenic capacity of the magnetic scaffolds compared with that of the gold nanoparticle-assembled scaffold. These results demonstrated the importance of magnetic nanomaterials as a bioactive interface between cells and scaffolds and will promote the design of biomaterials to improve tissue engineering and regenerative medicine efficacy.

In recent years, multicellular spheroid (MCS) culture has been extensively studied both in fundamental research and application fields since it inherits much more characteristics from in vivo solid tumor than conventional two-dimensional (2D) cell culture. However, anticell adhesive MCS culture systems such as hanging drop allow certain cell lines only to form loose, irregular aggregates rather than MCS with physiological barriers and pathophysiological gradients, which failed to mimic in vivo solid tumor in these aspects. To address this issue, we improved our previously established anisotropic magnetic hydrogel platform, enabling it to generate multicellular spheroids with higher efficiency. The qualities of multicellular tumor spheroids (MCTSs) obtained on our platform and from classic 3D culture systems were compared in terms of morphology, biological molecule expression profiles, and drug resistance. In this novel platform, mature MCTSs with necrotic cores could be observed in 1 week. And results of molecular biological assays with real time-PCR and western-blot confirmed that MCTSs obtained from our platform performed higher cell pluripotency than those obtained from the hanging drop system. Moreover, a lower cell apoptosis ratio and better viability of cancer cells were observed on our platform both under culturing and drug treatment. In conclusion, higher quality of MCTSs obtained from this anisotropic magnetic hydrogel than classic hanging drop system validate its potential to be an in vitro platform of inducing tumor MCTS formation and drug efficacy evaluation.

Cell-adhesive properties are of great significance to materials serving as extracellular matrix mimics. Appropriate cell-adhesive property of material interface can balance the cell-matrix interaction and cell-cell interaction and can promote cells to form 3D structures. Herein, a novel magnetic polyacrylamide (PAM) hydrogel fabricated via combining magnetostatic field induced magnetic nanoparticles assembly and hydrogel gelation was applied as a multicellular spheroids culturing platform. When cultured on the cell-adhesive microarray interface of sliced magnetic hydrogel, normal and tumor cells from different cell lines could rapidly form multicellular spheroids spontaneously. Furthermore, cells which could only form loose cell aggregates in a classic 3D cell culture model (such as hanging drop system) were able to be promoted to form multicellular spheroids on this platform. In the light of its simplicity in fabricating as well as its effectiveness in promoting formation of multicellular spheroids which was considered as a prevailing tool in the study of the microenvironmental regulation of tumor cell physiology and therapeutic problems, this composite material holds promise in anticancer drugs or hyperthermia therapy evaluation in vitro in the future.

For mimicking the fibrous extracellular matrix (ECM), a facile method for patterning anticell adhesive substrate was novelly applied on agarose hydrogel. Without using masks or templates for etching, we applied the magnetic field-induced colloidal assembly of magnetic nanoparticles on the flat agarose hydrogel to form cell-adhesive micropatterns. Meanwhile, tuning the hydrogel substrate's modulus to fit real tissue was experimentally demonstrated. Magnetic nanobeads were also assembled on this hydrogel surface and formed more complete and regular patterns. The patterned hydrogel substrate could actually influence behaviors of different cancer cells, including adhesion, growth, and migration.

Recent studies have conclusively shown that the plasmonic performance of Au nanostructures can be enhanced by incorporating Ag. Here, we developed a simple and robust approach for preparing core-shell Au-Ag nanoshuttles (NSs) using single-crystal Au nanorods (NRs) as cores. Upon tailoring the temperature of the reaction system containing alkaline glycine buffer (pH 8.5), exceptionally monodisperse Au-Ag NSs with sharp tips and tunable shell thickness could be routinely achieved in high yield through an epitaxial growth process. In particular, high-resolution transmission electron microscopy and nitric acid corrosive experiments revealed that the shells of these NSs consisted of a homogeneous Au-Ag alloy, rather than pure Ag or Au as previously reported. It was found that glycine played an important role in determining the final metal contents of the shell by regulating the reduction kinetics. In addition, the obatined Au-Ag NSs with sharp tips were shown to have significantly improved refractive index sensitivity and surface-enhanced Raman scattering activity relative to the original Au NRs, making these materials promising for biomedical applications, such as biosensing and biolabeling.

In search of multifunctional cholinesterase inhibitors as potential anti-Alzheimer drug candidates, tacrine-ferulic acid-NO donor trihybrids were synthesized and tested for their cholinesterase inhibitory activities, release of nitric oxide, vasodilator properties, cognition improving potency, and hepatotoxicity. All of the novel target compounds show higher in vitro cholinesterase inhibitory activity than tacrine. Three selected compounds (3a, 3f, and 3k) produce moderate vasorelaxation in vitro, which correlates with the release of nitric oxide. Compared to its non-nitrate dihybrid analogue (3u), the trihybrid 3f exhibits better performance in improving the scopolamine-induced cognition impairment (mice) and, furthermore, less hepatotoxicity than tacrine.