Shape design of cerium oxide nanoparticles for enhancement of enzyme mimetic activity in therapeutic applications

Cerium oxide nanoparticles (CONPs), widely used in catalytic applications owing to their robust redox reaction, are now being considered in therapeutic applications based on their enzyme mimetic properties such as catalase and super oxide dismutase (SOD) mimetic activities. In therapeutic applications, the emerging demand for CONPs with low cytotoxicity, high cost efficiency, and high enzyme mimetic capability necessitates the exploration of alternative synthesis and effective material design. This study presents a room temperature aqueous synthesis for low-cost production of shape-selective CONPs without potentially harmful organic substances, and additionally, investigates cell viability and catalase and SOD mimetic activities. This synthesis, at room temperature, produced CONPs with particular planes: {111}/{100} nanopolyhedra, {100} nano/submicron cubes, and {111}/{100} nanorods that grew in [110] longitudinal direction. Enzymatic activity assays indicated that nanopolyhedra with a high concentration of Ce⁴⁺ ions promoted catalase mimetic activity, while nanocubes and nanorods with high Ce³⁺ ion concentrations enhanced SOD mimetic activity. This is the first study indicating that shape and facet configuration design of CONPs, coupled with the retention of dominant, specific Ce valence states, potentiates enzyme mimetic activities. These findings may be utilized for CONP design aimed at enhancing enzyme mimetic activities in therapeutic applications.

Open image in new window

     

Interest of molecular functionalization for electrochemical storage

Despite great interests in electrochemical energy storage systems for numerous applications, considerable challenges remain to be overcome. Among the various approaches to improving the stability, safety, performance, and cost of these systems, molecular functionalization has recently been proved an attractive method that allows the tuning of material surface reactivity while retaining the properties of the bulk material. For this purpose, the reduction of aryldiazonium salt, which is a versatile method, is considered suitable; it forms robust covalent bonds with the material surface, however, with the formation of multilayer structures and sp³ defects (for carbon substrate) that can be detrimental to the electronic conductivity. Alternatively, non-covalent molecular functionalization based on π–π interactions using aromatic ring units has been proposed. In this review, the various advances in molecular functionalization concerning the current limitations in lithium-ion batteries and electrochemical capacitors are discussed. According to the targeted applications and required properties, both covalent and non-covalent functionalization methods have proved to be very efficient and versatile. Fundamental aspects to achieve a better understanding of the functionalization reactions as well as molecular layer properties and their effects on the electrochemical performance are also discussed. Finally, perspectives are proposed for future implementation of molecular functionalization in the field of electrochemical storage.

Open image in new window

     

A series of nanoparticles with phase-separated structures by 1,1-diphenylethene controlled one-step soap-free emulsion copolymerization and their application in drug release

A facile one-step approach to synthesize various phase-separated porous, raspberry-like, flower-like, core–shell and anomalous nanoparticles and nanocapsules via 1,1-diphenylethene (DPE) controlled soap-free emulsion copolymerization of styrene (S) with glycidyl methacrylate (GMA), or acrylic acid (AA) is reported. By regulating the mass ratio of S/GMA, transparent polymer solution, porous and anomalous P(S-GMA) particles could be produced. The P(S-GMA) particles turn from flower-like to raspberry-like and then to anomalous structures with smooth surface as the increase of divinylbenzene (DVB) crosslinker. Transparent polymer solution, nanocapsules and core–shell P(S-AA) particles could be obtained by altering the mole ratio of S/AA; anomalous and raspberry-like P(S-AA) particles are produced by adding DVB. The unpolymerized S resulted from the low monomer conversion in the presence of DPE aggregates to form nano-sized droplets, and migrates towards the external surfaces of the GMA-enriched P(S-GMA) particles and the internal bulk of the AA-enriched P(S-AA) particles. The nano-sized droplets function as in situ porogen, porous P(S-GMA) particles and P(S-AA) nanocapsules are produced when the porogen is removed. This novel, facile, one-step method with excellent controllability and reproducibility will inspire new strategies for creating hierarchical phase-separated polymeric particles with various structures by simply altering the species and ratio of comonomers. The drug loading and release experiments on the porous particles and nanocapsules demonstrate that the release of doxorubicin hydrochloride is very slow in weakly basic environment and quick in weakly acidic environment, which enables the porous particles and nanocapsules with promising potential in drug delivery applications.

Open image in new window

     

Determination of the acidic properties of carboxylated carbocatalysts in an acid-catalyzed ring-opening reaction using kinetic profiling

The acid-catalyzed ring-opening reaction of styrene oxide was used as a probe reaction for evaluating the acidic properties of carboxylated carbocatalysts. Significant discrepancies in the initial reaction rates were normalized using the total number of carboxyl groups, and demonstrated that the average catalytic activities of the carboxyl moieties on the carbocatalysts differed. Comparisons between the apparent activation energy E _a and the pre-exponential factor A, derived from Arrhenius analysis, demonstrated that A varied more significantly, and therefore had a more significant effect on the reaction rates than E _a. The variation in the calculated pKa values of the carboxyl groups was attributed to the electronic effects of the nitro groups. This hypothesis was supported by the temperature programmed desorption profiles of nitrogen monoxide ions.

Open image in new window

     

Wissen auf losen Blättern im Kontext starrer Theorien

At the end of the nineteenth century, after twelve years of intensive research, the ophthalmologist Theodor Leber (1840–1917) established the chemotaxis of leukocytes as part of inflammation research. Although at the time his theory was smoothly enlisted into immunological research, up until now his name has been connected to chemotaxis only in the English-language literature. Leber was able to use his experimental system to develop a theory of the chemical attraction of the leukocytes during inflammation processes by the beginning of the 1880s, but his unconventional methodology—introducing chemically neutral contaminants in order to trigger inflammation in the eyes of rabbits—contradicted the basic bacteriological Denkstil (style of thought) of inflammation research at the time. Leber held fast to his research practice, which consisted of closely interlocking experimental and theoretical work. Only when an opening appeared in the bacteriological Denkstil was Leber able to transform his experimental observations, written on loose sheets of paper, into convincing evidence for his theory of inflammation. This micro-historical reconstruction of Leber’s experimental and written work, based on his original lab protocols, opens up the research practice of a scientist who was not recognized by the established microbiological inflammation research of the time. Moreover, persistent factors in the generation of knowledge are revealed by connecting this micro-historical reconstruction with a macro-history analysis. Indeed Leber developed his specific paper technology in order to mobilise and stabilise the scientific findings gained through experiment because of the persistence of the bacteriological Denkstil.     

Mechanical and Thermophysical Properties of Cerium Monopnictides

The ultrasonic attenuation due to phonon–phonon interaction, thermoelastic relaxation and dislocation damping mechanisms has been investigated in cerium monopnictides CeX (X: N, P, As, Sb and Bi) for longitudinal and shear waves along \({\langle }100{\rangle }\), \({\langle }110{\rangle }\) and \({\langle }111{\rangle }\) directions. The second- and third-order elastic constants of CeX have also been computed in the temperature range 0 K to 500 K using Coulomb and Born–Mayer potential upto second nearest neighbours. The computed values of these elastic constants have been applied to find out Young’s moduli, bulk moduli, Breazeale’s non-linearity parameters, Zener anisotropy, ultrasonic velocity, ultrasonic Grüneisen parameter, thermal relaxation time, acoustic coupling constants and ultrasonic attenuation. The fracture/toughness ratio is less than 1.75, which shows that the chosen materials are brittle in nature as found for other monopnictides. The drag coefficient acting on the motion of screw and edge dislocations due to shear and compressional phonon viscosities of the lattice have also been evaluated for both the longitudinal and shear waves. The thermoelastic loss and dislocation damping loss are negligible in comparison to loss due to Akhieser damping (phonon–phonon interaction). The obtained results for CeX are in qualitative agreement with other semi-metallic monopnictides.     

Synthesis and characterization of <Emphasis Type="Italic">Eichhornia</Emphasis>-mediated copper oxide nanoparticles and assessing their antifungal activity against plant pathogens

In this paper, we report the biosynthesis and characterization of copper oxide nanoparticles from an aquatic noxious weed, Eichhornia crassipes by green chemistry approach. The aim of this work is to synthesize copper oxide nanoparticles by simple, cost-effective and ecofriendly method as an alternative to other available techniques. The synthesized copper oxide nanoparticles were characterized by UV–visible spectroscopy, Fourier transform infrared spectroscopy (FTIR), Field emission scanning electron microscopy (FESEM) and Energy dispersive X-ray spectroscopy (EDX) analyses. The synthesized particles were highly stable, spherical in shape with an average diameter of 28 ± 4 nm. The synthesized nanoparticles were then explored to antifungal activity against plant pathogens. Highest zone of inhibition were observed in 100 μg ml ^{? 1} of Eichhornia-mediated copper oxide nanoparticle against Fusarium culmorum and Aspergillus niger. This Eichhornia-mediated copper oxide nanoparticles were proved to be good antifungal agents against plant fungal pathogens.     

Synthesis,characterisation and non-isothermal degradation kinetics of novel poly(mono ethylene glycol dimethacrylate-co-4-aminobenzoate)

Synthesis of a novel co-polymer made by the addition polymerisation between MEGDMA and 4-AB by aza-Michael addition (AMA) polymerisation method is a fascinating field of research. The present investigation yielded a hazardous metal catalyst-free and toxic solvent-free methodology. The AMA polymerisation was carried out at five different [ M ₁/M ₂] values under N₂ atmosphere at 100^°C for 2 h. Thus, obtained co-polymer was characterized by Fourier transform infrared spectroscopy, UV–visible reflectance spectroscopy, X-ray diffraction, differential scanning calorimetry, thermogravimetric analysis and scanning electron microscopy (SEM). The SEM image confirmed the formation of polymer nanoparticles. The non-isothermal degradation kinetics was followed with four different models, such as Flynn-Wall-Ozawa, Auggis-Bennet, Kissinger and Friedman method. Among the models used, the Kissinger method yielded the lowest degradation kinetics. The degradation kinetics of the co-polymer was followed with the help of model-free methods. Moreover, it was critically compared with the literature.     

Tensile Properties and Failure Mechanism of a New 3D Nonorthogonal Woven Composite Material

Tensile properties and failure mechanism of a newly developed three-dimensional (3D) woven composite material named 3D nonorthogonal woven composite are investigated in this paper. The microstructure of the composite is studied and the tensile properties are obtained by quasi-static tensile tests. The failure mechanism of specimen is discussed based on observation of the fracture surfaces via electron microscope. It is found that the specimens always split along the oblique yarns and produce typical v-shaped fracture surfaces. The representative volume cell (RVC) is established based on the microstructure. A finite element analysis is conducted with periodical boundary conditions. The finite element simulation results agree well with the experimental data. By analyzing deformation and stress distribution under different loading conditions, it is demonstrated that finite element model based on RVC is valid in predicting tensile properties of 3D nonorthogonal woven composites. Stress distribution shows that the oblique yarns and warp yarns oriented along the x direction carry primary load under x tension and that warp yarns bear primary load under y tension.     

Fatigue Life Prediction of Carbon Fiber-Reinforced Ceramic-Matrix Composites at Room and Elevated Temperatures. Part I: Experimental Analysis

This paper presents an experimental analysis on the fatigue behavior in C/SiC ceramic-matrix composites (CMCs) with different fiber preforms, i.e., unidirectional, cross-ply and 2.5D woven, at room and elevated temperatures in air atmosphere. The experimental fatigue life S???N curves of C/SiC composites corresponding to different stress levels and test conditions have been obtained. The damage evolution processes under fatigue loading have been analyzed using fatigue hysteresis modulus and fatigue hysteresis loss energy. By comparing the experimental fatigue hysteresis loss energy with theoretical computational values, the interface shear stress corresponding to different peak stress, fiber preforms and test conditions have been estimated. It was found that the degradation of interface shear stress and fibres strength caused by oxidation markedly decreases the fatigue life of C/SiC composites at elevated temperature.