Electrospinning of photochromic poly(ethylene terephthalate) nanofibers toward information authentication.

The use of photochromism to enhance the anti-counterfeiting of a wide range of economic goods is an intriguing prospect. Creating a translucent anti-counterfeiting nanocomposite is critical to improving the engineering procedures of the encoding materials. Herein, we use electrospinning to produce anti-counterfeiting nanofibrous films from nanoparticles of rare-earth aluminate (NREA) and recycled poly(ethylene terephthalate) (PET). Different nanofiber films with distinct emission properties were created using different ratios of NREA. The ultraviolet (UV)-induced photochromism of the NREA@PET nanofibers was proved. Immobilizing NREA at the nanoscale ensures better dispersion without agglomeration in the PET nanofibrous matrix, which is essential for the development of transparent NREA@PET films. Diameters of 4-13 nm for NREA were shown using transmission electron microscopy. X-ray fluorescence spectroscopy, energy-dispersive X-ray spectroscopy, Fourier-transform infrared spectroscopy, scanning electron microscopy, elemental mapping, and other techniques were used to investigate the photochromic nanofibers' morphology, elemental contents, optical transmittance, and mechanical performance. It was observed that the nanofiber diameter in NREA@PET was between 150 and 250 nm. Excitation and emission bands of electrospun NREA@PET nanofibrous films were monitored at 365 and 518 nm, respectively. The superhydrophobicity of NREA@PET increased with increasing NREA concentration. The transparent nanofibers exhibited fast and reversible dual-mode fluorescent photochromism to green emission without fatigue when stimulated beneath a UV source. Using the present anti-counterfeiting films can be regarded as a simple technique to develop flexible materials to launch an ideal marketplace with affordable societal and economic advantages.

Preparation of photoluminescent nano-biocomposite nacre from graphene oxide and polylactic acid.

Nano-biocomposites of inorganic and organic components wereprepared to produce long-persistent phosphorescent artificial nacre-like materials. Biodegradable polylactic acid (PLA), graphene oxide (GO), and nanoparticles (13-20 nm) of lanthanide-doped aluminate pigment (NLAP) were used in a simple production procedure of an organic/inorganic hybrid nano-biocomposite. Both polylactic acid and GO nanosheets were chemically modified to form covalent and hydrogen bonding. The high toughness, good tensile strength, and great endurance of those bonds were achieved by their interactions at the interfaces. Long-persistent and reversible photoluminescence was shown by the prepared nacre substrates. Upon excitation at 365 nm, the nacre substrates generated an emission peak at 517 nm. When ultraviolet light was shone on luminescent nacres, they displayed a bright green colour. The high superhydrophobicity of the generated nacres was obtained without altering their mechanical characteristics.

Electrospinning of poly(ethylene oxide)/glass hybrid nanofibres for anticounterfeiting encoding.

The use of photochromism to increase the credibility of consumer goods has shown great promise. To provide mechanically dependable anticounterfeiting nanofibres, it has also been critical to improve the engineering processes of authentication patterns. Mechanically robust and photoluminescent electrospun poly(ethylene oxide)/glass (PGLS) nanofibres (150-350 nm) immobilized with nanoparticles of lanthanide-doped aluminate (NLA; 8-15 nm) were developed using electrospinning technology for anticounterfeiting purposes. The provided nanofibrous membranes changed colour from transparent to green when irradiated with ultraviolet light. By delivering NLA with homogeneous distribution without aggregations, we were able to keep the nanofibrous membrane transparent. When excited at 365 nm, NLA@PGLS nanofibres showed an emission intensity at 517 nm. The hydrophobicity of NLA@PGLS nanofibres improved by raising the pigment concentration as the contact angle was increased from 146.4° to 160.3°. After being triggered by ultraviolet light, NLA@PGLS showed quick and reversible photochromism without fatigue. It was shown that the suggested method can be applied to reliably produce various anticounterfeiting materials.

New Amphiphilic Ionic Liquids for the Demulsification of Water-in-Heavy Crude Oil Emulsion.

This work aimed to use abietic acid (AA), as a widely available natural product, as a precursor for the synthesis of two new amphiphilic ionic liquids (AILs) and apply them as effective demulsifiers for water-in-crude oil (W/O) emulsions. AA was esterified using tetraethylene glycol (TEG) in the presence of p-toluene sulfonic acid (PTSA) as a catalyst obtaining the corresponding ester (AATG). AATG was reacted with 1-vinylimidazole (VIM) throughout the Diels-Alder reaction, forming the corresponding adduct (ATI). Following this, ATI was quaternized using alkyl iodides, ethyl iodide (EI), and hexyl iodide (HI) to obtain the corresponding AILs, ATEI-IL, and ATHI-IL, respectively. The chemical structure, surface activity, thermal stability, and relative solubility number (RSN) were investigated using different techniques. The efficiency of ATEI-IL and ATHI-IL to demulsify W/O emulsions in different crude oil: brine volumetric ratios were evaluated. ATEI-IL and ATHI-IL achieved promising results as demulsifiers. Their demulsification efficiency increased as the brine ratios decreased where their efficiency reached 100% at the crude oil: brine ratio (90:10), even at low concentrations.

Preparation of flame-retardant, hydrophobic, ultraviolet protective, and luminescent transparent wood.

Transparent wood with multifunctional properties has recently attracted more attention as an efficient building product. Here, we describe the development of transparent wood with long-persistent phosphorescence, tough surface, high durability, photostability, and reversibility without fatigue, and with ultraviolet shielding, superhydrophobicity, and flame-retardant activity. This long-persistent phosphorescent, or glow-in-the-dark, smart wood exhibited an ability to continue emitting light for prolonged periods of time. The photoluminescent translucent wooden substrate was prepared by immobilizing lignin-modulated wooden bulk with an admixture of methylmethacrylate (MMA), ammonium polyphosphate (APP), and lanthanide-doped strontium aluminate (LSA; SrAl2 O4 :Eu2+ ,Dy3+ ) phosphor nanoparticles. The photoluminescent transparent wood displayed a colour switch from colourless to bright white beneath ultraviolet (UV) light and greenish-yellow in the dark as reported by Commission Internationale de l'Éclairage laboratory colorimetric space coordinates. The generated phosphorescent wooden substrates demonstrated an absorbance band at 365 nm and an emission band at 516 nm. The phosphorescent transparent wood was improved flame-retardant properties, ultraviolet shielding, and superhydrophobic properties, as well as a reversible long-persistent phosphorescent responsiveness to UV light without fatigue. The current approach demonstrated a potential large-scale production strategy for multifunctional transparent wooden substrates for a range of applications such as smart windows, gentle indoor and outdoor lighting, and safety directional signs in buildings.

Facile production of smart superhydrophobic nanocomposite for wood coating towards long-lasting glow-in-the-dark photoluminescence.

A smart photoluminescent nanocomposite surface coating was prepared for simple industrial production of long-persisting phosphorescence and superhydrophobic wood. The photoluminescent nanocomposite coatings were capable of continuing to emit light in the dark for prolonged time periods that could reach 1.5 h. Lanthanide-doped aluminium strontium oxide (LASO) nanoparticles at different ratios were immobilized in polystyrene (PS) and developed as a nanocomposite coating for wood substrates. To produce transparency in the prepared nanocomposite coating, LASO was efficiently dispersed in the form of nanoscaled particles to ensure homogeneous dispersion without agglomeration in the PS matrix. The coated wood showed an absorption band at 374 nm and two emission bands at 434 nm and 518 nm. The luminescence spectra showed both long-persisting phosphorescence as well as photochromic fluorescence relying on the LASO ratio. The improved superhydrophobicity and resistance to scratching of the coated wood could be attributed to the LASO NPs incorporated in the polystyrene matrix. Compared with the uncoated wood substrate, the coated LASO-PS nanocomposite film also displayed photostability and high durability. The current study demonstrated the potential high-scale manufacturing of smart wood for some applications such as safety directional signs in buildings, household products, and smart windows.

Facile development of photochromic cellulose acetate transparent nanocomposite film immobilized with lanthanide-doped pigment: ultraviolet blocking, superhydrophobic, and antimicrobial activity.

Smart photochromic and fluorescent products can respond to an external stimulus by changing their colour and emission spectra with light. Here, we developed a simple formulation of an organic-inorganic nanocomposite photoluminescent cellulose acetate (CA) film based on immobilization of a lanthanide-doped pigment. Strontium aluminium oxide pigment doped with Eu2+ and Dy3+ (SAOED) exhibits an optimal excitation wavelength at 365 nm. For better fabrication of the multifunctional colourless pigment-cellulose acetate composites (CA-SAOED), the lanthanide-doped colourant must be well-dispersed physically without agglomeration. The fabricated photoluminescence cellulose film exhibited an excitation peak at 436 nm and two fluorescence peaks at 494 and 524 nm. The findings revealed that the originated nanocomposite films demonstrated improved superhydrophobic activity, high ultraviolet light protection and enhanced antibacterial activity without adversely influencing its native physico-mechanical characteristics. The films demonstrated fast and reversible photochromic responsiveness without fatigue during ultraviolet light irradiation.

Chloroquine and hydroxychloroquine inhibitors for COVID-19 sialic acid cellular receptor: Structure, hirshfeld atomic charge analysis and solvent effect.

COVID-19, the pandemic disease recently discovered in Wuhan (China), severely spread and affected both social and economic activity all over the world. Attempts to find an effective vaccine are challenging, time-consuming though interminable. Hence, re-proposing effective drugs is reliable and effective alternative. Taking into account the genome similarity of COVID-19 with SARS-CoV, drugs with safety profiles could be fast solution. Clinical trials encouraged the use of Chloroquine and Hydroxychloroquine for COVID-19 inhibition. One of the possible inhibition pathways is the competitive binding with the angiotension-converting enzyme-2 (ACE-2), in particular with the cellular Sialic acid (Neu5Ac). Here, we investigate the possible binding mechanism of ClQ and ClQOH with sialic acid both in the gas phase and in water using density functional theory (DFT). We investigated the binding of the neutral, monoprotonated and diprotonated ClQs and ClQOHs to sialic acid to simulate the pH effect on the cellular receptor binding. DFT results reveals that monoprotonated ClQ+ and ClQOH+, which account for more than 66% in the solution, possess high reactivity and binding towards sialic acid. The Neu5Ac-ClQ and the analogues Neu5Ac-ClQOH adducts were stabilized in water than in the gas phase. The molecular complexes stabilize by strong hydrogen bonding and π - π stacking forces. In addition, proton-transfer in Neu5Ac-ClQOH+ provides more stabilizing power and cellular recognition binding forces. These results shed light on possible recognition mechanism and help future breakthroughs for COVID-19 inhibitors.

DNA-Based Fabrication for Nanoelectronics.

The bottom-up DNA-templated nanoelectronics exploits the unparalleled self-assembly properties of DNA molecules and their amenability with various types of nanomaterials. In principle, nanoelectronic devices can be bottom-up assembled with near-atomic precision, which compares favorably with well-established top-down fabrication process with nanometer precision. Over the past decade, intensive effort has been made to develop DNA-based nanoassemblies including DNA-metal, DNA-polymer, and DNA-carbon nanotube complexes. This review introduces the history of DNA-based fabrication for nanoelectronics briefly and summarizes the state-of-art advances of DNA-based nanoelectronics. In particular, the most widely applied characterization techniques to explore their unique electronic properties at the nanoscale are described and discussed, including scanning tunneling microscopy, conductive atomic force microscopy, and Kelvin probe force microscopy. We also provide a perspective on potential applications of DNA-based nanoelectronics.

Greener Synthesis of Zinc Oxide Nanoparticles: Characterization and Multifaceted Applications.

Nanoparticles (NPs) have unique properties compared to their bulk counterparts, and they have potentials for various applications in many fields of life science. Green-synthesized NPs have garnered considerable interest due to their inherent features such as rapidity, eco-friendliness and cost-effectiveness. Zinc oxide nanoparticles (ZnO NPs) were synthesized using an aqueous extract of Kalanchoe blossfeldiana as a reducing agent. The resulting nanoparticles were characterized via X-ray diffraction (XRD), dynamic light scattering (DLS), UV-Vis spectroscopy, photoluminescence (PL), transmission electron microscopy (TEM), scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS). The antimicrobial potential of the synthesized ZnO NPs against bacterial and fungal strains was examined by the disk diffusion method, and they showed a promising antibacterial and antifungal potential. The catalytic activity of the synthesized ZnO NPs in reducing methylene blue (MB) and eosin was studied via UV-Vis spectroscopy. The decolorization percentages of the MB and Eosin Y dyes were 84% and 94%, respectively, which indicate an efficient degradation of the ZnO NPs. In addition, the cytotoxic activity of the ZnO NPs on the HeLa cell line was evaluated via in vitro assay. The MTT assay results demonstrate a potent cytotoxic effect of the ZnO NPs against the HeLa cancer cell line.

Programmable Live-Cell CRISPR Imaging with Toehold-Switch-Mediated Strand Displacement.

The widespread application of CRISPR-Cas9 has transformed genome engineering. Nevertheless, the precision to control the targeting activity of Cas9 requires further improvement. We report a toehold-switch-based approach to engineer the conformation of single guide RNA (sgRNA) for programmable activation of Cas9. This activation circuit is responsive to multiple inputs and can regulate the conformation of the sgRNA through toehold-switch-mediated strand displacement. We demonstrate the orthogonal suppression and activation of Cas9 with orthogonal DNA inputs. Combination of toehold switches leads to a variety of intracellular Cas9 activation programs with simultaneous and orthogonal responses, through which multiple genome loci are displayed in different colors in a controllable manner. This approach provides a new route for programing CRISPR in living cells for genome imaging and engineering.

Golden single-atomic-site platinum electrocatalysts.

Bimetallic nanoparticles with tailored structures constitute a desirable model system for catalysts, as crucial factors such as geometric and electronic effects can be readily controlled by tailoring the structure and alloy bonding of the catalytic site. Here we report a facile colloidal method to prepare a series of platinum-gold (PtAu) nanoparticles with tailored surface structures and particle diameters on the order of 7 nm. Samples with low Pt content, particularly Pt4Au96, exhibited unprecedented electrocatalytic activity for the oxidation of formic acid. A high forward current density of 3.77 A mgPt-1 was observed for Pt4Au96, a value two orders of magnitude greater than those observed for core-shell structured Pt78Au22 and a commercial Pt nanocatalyst. Extensive structural characterization and theoretical density functional theory simulations of the best-performing catalysts revealed densely packed single-atom Pt surface sites surrounded by Au atoms, which suggests that their superior catalytic activity and selectivity could be attributed to the unique structural and alloy-bonding properties of these single-atomic-site catalysts.

Glucosamine-6-phosphate synthase inhibiting C3-ß-cholesterol tethered spiro heterocyclic conjugates: Synthesis and their insight of DFT and docking study.

A series of novel covalent cholesterol-spiro pyrrolidine/pyrrolizidine heterocyclic hybrids possessing biologically active oxindole, indanedione, and acenaphthylene-1-one have been synthesized by the reaction of C3-ß-cholesteroalacrylate with heterocyclic di- and tri-ketones. All the sixteen compounds were obtained as a single isomer in good yield through a stereo- and regio- selective 1,3-dipolar cycloaddition methodology. Stereochemistry of the spiranic cycloadducts has been established by spectroscopic analysis and the regioselectivity outcome of the spiro adducts has been accomplished by DFT calculations at B3LYP/6-31G (d,p) level study. In vitro antibacterial activity of the newly synthesized cycloadducts were evaluated against highly pathogenic Gram-positive and Gram-negative bacteria and the most active compounds 5a, 13, and 14 underwent automated in silico molecular docking analysis in order to validate their effective orientation as a inhibitors bound in the active site of glucosamine-6-phosphate synthase (1XFF) enzyme by employing AutoDock Tools.

Convection-Driven Pull-Down Assays in Nanoliter Droplets Using Scaffolded Aptamers.

One of the great challenges in cellular studies is to develop a rapid and biocompatible analytical tool for single-cell analysis. We report a rapid, DNA nanostructure-supported aptamer pull-down (DNaPull) assay under convective flux in a glass capillary for analyzing the contents of droplets with nano- or picoliter volumes. We have demonstrated that the scaffolded aptamer can greatly improve the efficiency of target molecules' pull down. The convective flux allows complete reaction in <5 min, which is an 18-fold improvement compared to purely diffusive flux (traditional model of the stationary case). This established DNaPull assay can serve as a rapid and sensitive analytical platform for analyzing a variety of bioactive molecules, including small molecules [ATP, limit of detecton (LOD) of 1 µM], a drug (cocaine, LOD of 1 µM), and a biomarker (thrombin, LOD of 0.1 nM). Significantly, the designed microfluidic device compartmentalizes live cells into nanoliter-sized droplets to present single-cell samples. As a proof of concept, we demonstrated that cellular molecules (ATP) from a discrete number of HNE1 cells (zero to five cells) lysed inside nanoliter-sized droplets can be analyzed using our DNaPull assay, in which the intracellular ATP level was estimated to be ∼3.4 mM. Given the rapid assay feature and single-cell sample analysis ability, we believe that our analytical platform of convection-driven DNaPull in a glass capillary can provide a new paradigm in biosensor design and will be valuable for single-cell analysis.

Dynamic Modulation of DNA Hybridization Using Allosteric DNA Tetrahedral Nanostructures.

The fixed dynamic range of traditional biosensors limits their utility in several real applications. For example, viral load monitoring requires the dynamic range spans several orders of magnitude; whereas, monitoring of drugs requires extremely narrow dynamic range. To overcome this limitation, here, we devised tunable biosensing interface using allosteric DNA tetrahedral bioprobes to tune the dynamic range of DNA biosensors. Our strategy takes the advantage of the readily and flexible structure design and predictable geometric reconfiguration of DNA nanotechnology. We reconfigured the DNA tetrahedral bioprobes by inserting the effector sequence into the DNA tetrahedron, through which, the binding affinity of DNA tetrahedral bioprobes can be tuned. As a result, the detection limit of DNA biosensors can be programmably regulated. The dynamic range of DNA biosensors can be tuned (narrowed or extended) for up to 100-fold. Using the regulation of binding affinity, we realized the capture and release of biomolecules by tuning the binding behavior of DNA tetrahedral bioprobes.

PolyA-Mediated DNA Assembly on Gold Nanoparticles for Thermodynamically Favorable and Rapid Hybridization Analysis.

Understanding the behavior of biomolecules on nanointerface is critical in bioanalysis, which is great challenge due to the instability and the difficulty to control the orientation and loading density of biomolecules. Here, we investigated the thermodynamics and kinetics of DNA hybridization on gold nanoparticle, with the aim to improve the efficiency and speed of DNA analysis. We achieved precise and quantitative surface control by applying a recently developed poly adenines (polyA)-based assembly strategy on gold nanoparticles (DNA-AuNPs). PolyA served as an effective anchoring block based on the preferential binding with the AuNP surface and the appended recognition block adopted an upright conformation that favors DNA hybridization. The lateral spacing and surface density of DNA on AuNPs can be systematically modulated by adjusting the length of polyA block. We found the stability of duplex on AuNP was enhanced with the increasing length of polyA block. When the length of polyA block reached to 40 bases, the thermodynamic properties were more similar to that of duplex in solution. Fast hybridization rate was observed on the diblock DNA-AuNPs and was increased along with the length of polyA block. We consider the high stability and excellent hybridization performance come from the minimization of the DNA-DNA and DNA-AuNP interactions with the use of polyA block. This study provides better understanding of the behavior of biomolecules on the nanointerface and opens new opportunities to construct high-efficiency and high-speed biosensors for DNA analysis.

Electrochemical detection of PCR amplicons of Escherichia coli genome based on DNA nanostructural probes and polyHRP enzyme.

Fast, portable and sensitive analysis of E. coli is becoming an important challenge in many critical fields (e.g., food safety, environmental monitoring and clinical diagnosis). Thus, electrochemical biosensing of PCR amplicons from the bacterial genome has attracted reasonable research attention. In this work, we utilized a 3D DNA tetrahedral probe to establish a "sandwich-type" electrochemical DNA biosensor for sensitive and specific analysis of a 250 bp unpurified PCR amplicon from the uidA gene of the E. coli genome. Asymmetric PCR was used to produce single-stranded PCR products. Streptavidin-polyHRP80 was employed to improve the signal gain during electrochemical detection. We optimized important experimental conditions for DNA sensing, including the streptavidin-polyHRP, the signal probe and the ion strength. Finally, we achieved a remarkable sensitivity of 10 fM synthetic DNA target, and successfully performed the analysis of PCR amplicons from as low as 0.2 pg µL(-1) of E. coli genome. Compared with traditional single stranded DNA (ssDNA) probe based detection, our present work demonstrated 3 orders of magnitude improvement in sensitivity. In addition, our electrochemical DNA biosensor was 4 orders of magnitude more sensitive than normal electrophoretic analysis of PCR products. Our work made important progress in DNA nanostructured probe-based biosensors toward application in real applications.

A strategy to achieve enhanced electromagnetic interference shielding at low concentration with a new generation of conductive carbon black in a chlorinated polyethylene elastomeric matrix.

The fabrication of scalable and affordable conductive Ketjen carbon black (K-CB)-elastomer composites for adjustable electromagnetic interference (EMI) shielding remains a difficult challenge. Herein, chlorinated polyethylene (CPE)-K-CB composites have been developed by single step solution mixing to achieve high EMI shielding performance associated with absorption dominance potency by conductive dissipation as well as the reflection of electromagnetic waves. The dispersion of K-CB inside the CPE matrix has been corroborated by electron micrographs and atomic force microscopy (AFM). The K-CB filler and CPE polymer interaction has been investigated through the bound rubber content (Bdr) and the dynamic mechanical properties. The relatively low loading of K-CB with respect to other conventional carbon fillers contributes to a promising low percolation threshold (9.6 wt% K-CB) and a reasonably high EMI shielding effectiveness (EMI SE) value of 38.4 dB (at 30 wt% loading) in the X-band region (8.2 to 12.4 GHz). Classical percolation theory reveals that the electrical conduction behavior through the composite system is quasi-two dimensional in nature. Our belief lies in the promotion of scalable production of flexible and cost-effective K-CB-CPE composites of superior EMI SE to avoid electromagnetic radiation pollution.

Synthesis, Antiphospholipase A2, Antiprotease, Antibacterial Evaluation and Molecular Docking Analysis of Certain Novel Hydrazones.

Some novel hydrazone derivatives 6a-o were synthesized from the key intermediate 4-Chloro-N-(2-hydrazinocarbonyl-phenyl)-benzamide 5 and characterized using IR, ¹H-NMR, 13C-NMR, mass spectroscopy and elemental analysis. The inhibitory potential against two secretory phospholipase A2 (sPLA2), three protease enzymes and eleven bacterial strains were evaluated. The results revealed that all compounds showed preferential inhibition towards hGIIA isoform of sPLA2 rather than DrG-IB with compounds 6l and 6e being the most active. The tested compounds exhibited excellent antiprotease activity against proteinase K and protease from Bacillus sp. with compound 6l being the most active against both enzymes. Furthermore, the maximum zones of inhibition against bacterial growth were exhibited by compounds; 6a, 6m, and 6o against P. aeruginosa; 6a, 6b, 6d, 6f, 6l, 6m, 6n, and 6o against Serratia; 6k against S. mutans; and compounds 6a, 6d, 6e, 6m, and 6n against E. feacalis. The docking simulations of hydrazones 6a-o with GIIA sPLA2, proteinase K and hydrazones 6a-e with glutamine-fructose-6-phosphate transaminase were performed to obtain information regarding the mechanism of action.

Dual soft-template system based on colloidal chemistry for the synthesis of hollow mesoporous silica nanoparticles.

A new dual soft-template system comprising the asymmetric triblock copolymer poly(styrene-b-2-vinyl pyridine-b-ethylene oxide) (PS-b-P2VP-b-PEO) and the cationic surfactant cetyltrimethylammonium bromide (CTAB) is used to synthesize hollow mesoporous silica (HMS) nanoparticles with a center void of around 17 nm. The stable PS-b-P2VP-b-PEO polymeric micelle serves as a template to form the hollow interior, while the CTAB surfactant serves as a template to form mesopores in the shells. The P2VP blocks on the polymeric micelles can interact with positively charged CTA(+) ions via negatively charged hydrolyzed silica species. Thus, dual soft-templates clearly have different roles for the preparation of the HMS nanoparticles. Interestingly, the thicknesses of the mesoporous shell are tunable by varying the amounts of TEOS and CTAB. This study provides new insight on the preparation of mesoporous materials based on colloidal chemistry.