Electrospinning is a method to produce fine, biopolymer mesh with a three-dimensional architecture that mimics native extra-cellular matrix. Due to the small fiber diameter created in this process, conventional electrospun scaffolds have pore sizes smaller than the diameter of most cells. These scaffolds have limited application in tissue engineering due to poor cell penetration. We developed a hybrid electrospinning/particulate leaching technique to create scaffolds with increased porosity and improved cellular ingrowth. Poly(glycolic acid) (PGA) and a sucrose-ethanol suspension were electrospun in equal, alternating sequences at intervals of one, two, and ten minutes each. The scaffolds revealed fiber mesh with micropores of 10 m and uniformly distributed sucrose particles. Particulate leaching of sucrose from the one- or two-minute scaffolds revealed honeycomb structures with interconnected macropores between 50 and 250 m. Sucrose leaching from the ten-minute scaffolds resulted in laminated structures with isolated macropores between 200 and 350 m. Macropore size was directly proportional to the duration of the sucrose spinning interval. After 24 hours of cell culture, conventionally spun scaffolds demonstrated no cellular penetration. Conversely, the PGA/sucrose scaffolds demonstrated deep cellular penetration. This hybrid technique represents a novel method of generating electrospun scaffolds with interconnected pores suitable for cellular ingrowth.
Binding energies of different nitrile solvents and their utilization for CuCN formation were investigated through quantum chemical calculations. A pulsed laser ablation in liquid (PLAL) method for CuCN synthesis was developed herein. Initially, the interaction between the pulsed laser and the Cu-target generated Cu-ions and electrons at the point of contact. The laser beam also exhibited sufficient energy to dissociate the bonds of the respective solvents. In the case of acetonitrile, the oxidized Cu-ions bonded with CN− to produce CuCN with a cube-like surface structure. Other nitrile solvents generated spherically-shaped Cu@graphitic carbon (Cu@GC) nanoparticles. Thus, the production of CuCN was favorable only in acetonitrile due to the availability of the cyano group immediately after the fragmentation of acetonitrile (CH3+ and CN−) under PLAL. Conversely, propionitrile and butyronitrile released large amounts of hydrocarbons, which deposited on Cu NPs surface to form GC layers. Following the encapsulation of Cu NPs with carbon shells, further interaction with the cyano group was not possible. Subsequently, theoretical study on the binding energies of nitrile solvents was confirmed by highly correlated basic sets of B3LYP and MP2 which results were consistent with the experimental outcomes. The findings obtained herein could be utilized for the development of novel metal–polymer materials.
Spectroscopic techniques exist that may discern between enantiomers and assess chiral purity. A nonspectroscopic approach that may be directly observed could provide numerous benefits. Using chiral alanine-appended benzene-tricarboxamide gelators, we reveal a methanol gel system that is capable of providing visual discrimination between enantiomers of various diamines. Specifically, gelation is induced by supramolecular nanofiber assembly resulting from interaction between a chiral gelator and a diamine of opposing chirality (i.e., a heterochiral system). Upon further implementing the chiral gelator in electrospun fibers as solid state films, we revealed enantioselective surface wetting properties that allowed for determining chirality through contact angle measurements. While these two approaches of observable gelation and surface wetting offer nonspectroscopic approaches, we also find that the supramolecular nanofiber assembly was able to enhance the induced circular dichroism signal resulting from addition of chiral diamines, allowing precise quantification of their enantiomeric purity.
An Al metal plate was ablated by a pulsed Nd-YAG laser to produce nano-structured Al and gamma-Al(2)O(3) in deionized water without any surfactants or catalysts. In this study, direct evidence for the production of Al(3+) ions from the plasma plume is presented for the first time by characterizing the absorption and emission spectra of their [Al(salophen)](+) complex. Very interestingly, a remarkable increase in the fluorescence intensity was observed when the Al(3+) ions, produced via the pulsed laser ablation, complexed with the salophen ligand. This fluorescence 'turn-on' behaviour of [Al(salophen)](+) was investigated by DFT/TD-DFT calculations. Based on these results, mechanisms for the production of aluminium and alumina nanoparticles in the pulsed laser ablation in liquid (PLAL) process are proposed.
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