Tunable Colloidal Properties of Lauramidopropyl Betaine and Li Co-modified Montmorillonite in Ethanol/Water.

Montmorillonite (Mt) is a hydrophilic clay mineral with a generally high cationic exchange capacity and a remarkable swellability in water. Yet the application of Mt in cosmetics, paints, polymer nanocomposites, drug delivery systems, and tissue engineering are limited due to its unfavorable swelling and dispersion in alcohol/water mixtures. Improving the swellability and dispersibility of Mt in mixtures of ethanol and water remains challenging. Here, we showed that the swellability and dispersibility of Mt in ethanol/water could be significantly enhanced when lithium-Mt (Li-Mt) was intercalated by zwitterionic surfactant lauramidopropyl betaine (LPB). The binding mechanism of the LPB intercalate to Li-Mt originated from a combination of van der Waals forces, ion-dipole interaction, and electrostatic attraction. Due to the synergistic effect of Li+ and LPB, the comodified Mt (LPB-Li-Mt) exhibited excellent swellability, dispersibility, and rheological properties. The structure, morphology, zeta potential, dispersibility, and gel-forming performance of LPB-Li-Mt can be modulated by the concentrations of ethanol in ethanol/water mixtures. When the ethanol concentration increased to 75% v/v ethanol solution, the free swelling of LPB-Li-Mt remained above 80%. The results from X-ray diffraction, thermogravimetric analysis, Fourier transform infrared spectroscopy, X-ray photoemission spectrometry, and small-angle X-ray scattering confirmed the full exfoliation of LPB-Li-Mt at 75% (v/v) ethanol solution. The formation of a stable colloidal LPB-Li-Mt dispersion in a mixture of ethanol/water might be derived from the association between water molecules and the Li+, the hydrophobic interaction, and the ion-dipole of ethanol with the LPB molecules. The findings provide a guide for improving dispersion and swelling of Mt and modified ones in water-miscible organic solvents.

Invisible Bactericidal Coatings on Generic Surfaces through a Convenient Hand Spray.

Robust antimicrobial coatings featuring high transparency, strong bactericidal activity, and an easy application procedure on generic surfaces can be widely accepted by the public to prevent pandemics. In this work, we demonstrated the hand-sprayer-based approach to deposit complex oxide coatings composed of Co-Mn-Cu-Zn-Ag on screen protectors of smartphones through acidic redox-assisted deposition (ARD). The as-obtained coatings possess high transparency (99.74% transmittance at 550 nm) and long-lasting durability against swiping (for 135 days of average use) or wet cleaning (for a routine of 3 times/day for 33 days). The spray coating enabling 3.14% Escherichia coli viability can further be reduced to 0.21% through a consistent elemental composition achieved via the immersion method. The high intake of Cu2+ in the coating is majorly responsible for the bactericidal activity, and the presence of Ag+ and Zn2+ is necessary to achieve almost complete eradication. The success of extending the bactericidal coatings on other typical hand-touched surfaces (e.g., stainless steel railings, rubber handrails, and plastic switches) in public areas has been demonstrated.

Enhanced Thermal Conducting Behavior of Pressurized Graphene-Silver Flake Composites.

Modern electronics continue to shrink down the sizes while becoming more and more powerful. To improve heat dissipation of electronics, fillers used in the semiconductor packaging process need to possess both high electrical and thermal conductivity. Graphene is known to improve thermal conductivity but suffers from van der Waals interactions and thus poor processibility. In this study, we wrapped silver microflakes with graphene sheets, which can enable intercoupling of phonon- and electron-based thermal transport, to improve the thermal conductivity. Using just 1.55 wt % graphene for wrapping can achieve a 2.64-times greater thermal diffusivity (equivalent to 254.196 ± 10.123 W/m·K) over pristine silver flakes. Graphene-wrapped silver flakes minimize the increase of electrical resistivity, which is one-order higher (1.4 × 10-3 Ω·cm) than the pristine flakes (5.7 × 10-4 Ω·cm). Trace contents of wrapped graphene (<1.55 wt %) were found to be enough to bridge the void between Ag flakes, and this enhances the thermal conductivity. Graphene loading at 3.76 wt % (beyond the threshold of 1.55 wt %) results in the significant graphene aggregation that decreases thermal diffusivity to as low as 16% of the pristine Ag filler. This work recognizes that suitable amounts of graphene wrapping can enhance heat dissipation, but too much graphene results in unwanted aggregation that hinders thermal conducting performance.

Inclusion of organic species in exfoliated montmorillonite nanolayers towards hierarchical functional inorganic-organic nanostructures.

Montmorillonite (Mt) can readily undergo spontaneous delamination or exfoliation into nanolayers by various physical and chemical processes, which allow various strategies to engineer hierarchical functional inorganic-organic nanostructures. This review aims to discuss the recent progress in the liquid-phase exfoliation of Mt into individual nanolayers and the inclusion chemistry of functional organic species, ions, or molecules into the exfoliated Mt nanolayers to produce hierarchical functional inorganic-organic nanostructures. The exfoliation methods include mechanical force, ultrasonication, and intercalation-assisted exfoliation. Techniques for quickly assessing the quality of the exfoliated Mt nanolayers are still needed. Layer-by-layer (LbL) deposition, template, and evaporation-induced inclusions are examined to fabricate hierarchical Mt-organic species nanocomposites with unique functionalities and properties. The nanocomposites can be produced as multilayered porous films, brick-and-mortar coatings, hydrogels with a house-of-cards structure, core-shell materials, and hollow and mesoporous spherical nanocomposites, which exhibit significant potential for adsorption, catalysis, targeted delivery and controlled drug release, highly sensitive sensors, flame retardant coatings, and thermal energy storage and release (i.e. phase change materials). Finally, the challenges and prospects for the future development of hierarchical nanocomposites of exfoliated Mt nanolayers and organic species, particularly in hierarchical supramolecular nanostructured composites, are highlighted.

Efficient One-Step Conversion of a Low-Grade Vegetable Oil to Biodiesel over a Zinc Carboxylate Metal-Organic Framework.

In this study, a metal-organic framework, namely, Zn3(BTC)2 (BTC = 1,3,5-benzenetricaboxylic acid), was solvothermally synthesized and employed as a catalyst for biodiesel production from degummed vegetable oil via a one-step transesterification and esterification reaction. The resulting Zn3(BTC)2 particles exhibit a well-defined triclinic structure with an average size of about 1.2 µm, high specific surface area of 1176 m2/g, and thermal stability up to 300 °C. The response surface methodology-Box-Behnken design (RSM-BBD) was employed to identify the optimal reaction conditions and to model the biodiesel yield in relation to three important parameters, namely, the methanol/oil molar ratio (4:1-8:1), temperature (45-65 °C), and time (1.5-4.5 h). Under the optimized reaction conditions (i.e., 6:1 methanol/oil molar ratio, 65 °C, 4.5 h), the maximum biodiesel yield reached 89.89% in a 1 wt % catalyst, which agreed very well with the quadratic polynomial model's prediction (89.96%). The intrinsic catalytic activity of Zn3(BTC)2, expressed as the turnover frequency, was found to be superior to that of other MOF catalysts applied in the transesterification and esterification reactions. The reusability study showed that the as-synthesized Zn3(BTC)2 catalyst exhibited good stability upon three consecutive reuses without a noticeable decrease in the methyl ester yield (∼4%) and any appreciable metal leaching (<5%). Furthermore, a preliminary technoeconomic analysis showed that the total direct operating cost for the kilogram-scale production of Zn3(BTC)2 is estimated to be US$50, which may sound economically attractive.

Modulated transdermal delivery of nonsteroidal anti-inflammatory drug by macroporous poly(vinyl alcohol)-graphene oxide nanocomposite films.

In this study, a facile, economically feasible, and scalable approach to fabricate macroporous poly(vinyl alcohol)-GO (PVA-GO) nanocomposite films with varying filler loadings was demonstrated. The nanocomposite films were prepared using a solvent casting process and employed as a diffusion layer for modulating the transdermal delivery of an anti-inflammatory drug (i.e., ketoprofen). The diffusion membrane was assembled in a three-layer structure with PVA/PVA-GO films between ketoprofen-loaded cellulose and cellulose acetate to mimic skin barrier. Through the incorporation of GO sheets into PVA matrix, the mass diffusion and drug release rate of ketoprofen could be modulated to attain a controlled-release system within period in comparison to that of neat PVA film, which showed more rapid release. It was observed that the dispersion level of GO sheets in the polymer matrix played a crucial role to slow the diffusion rate and drug release, where 3 wt% filler loading gave the slowest rate of release. The results from the present study shed light on the mechanism of and may provide guidelines for modulating drug release rates of NSAID in film-based delivery vehicles for transdermal delivery applications.

Single step and mask-free 3D wax printing of microfluidic paper-based analytical devices for glucose and nitrite assays.

Microfluidic paper-based analytical devices (µPADs) have recently emerged as a simple, portable, user-friendly, and affordable alternative to more instrument-intensive analytical approaches for point-of-care testing (POCT), food safety analysis, and environmental monitoring. However, most of the existing methods for the fabrication of µPADs still face a great challenge because of different trade-offs among cost, convenience, and the pattern resolution. In this work, we report a facile one-step approach to prepare a µPAD using an affordable, easy-to-build 3D printer to generate patterns of solid wax on laboratory filter paper. The presented wax printing method did not require the use of predesigned masks and an external heat source to form complete hydrophobic wax barrier through the use of a custom-made extruder. The results revealed a strong linear relationship (R2 = 0.985) between the nominal and the printed widths of the wax barriers. The achievable resolution of the wax barrier printed on filter paper was 468 ±â€¯72 µm, which was lower than previously reported minimum barrier feature sizes achieved by wax printing and other wax patterning techniques, such as stamping and screen-printing. The analytical utility of the fabricated µPADs was evaluated for colorimetric nitrite and glucose detection in artificial solutions. It was found that the fabricated µPADs provided adequate accuracy and reproducibility for quantitative determination of nitrite and glucose within concentration ranges relevant to the disease detection in human saliva and urine. The wax printing approach reported here provides a simple, rapid, and cost-effective fabrication method for paper-based microfluidics and may bring benefits to medical diagnostics in the developing world.

Interfacial Effect of Oxygen-Doped Nanodiamond on CuO and Micropyramidal Silicon Heterostructures for Efficient Nonenzymatic Glucose Sensor.

Herein, the novel strategy of copper oxide (CuO) deposited oxygen-doped nitrogen incorporated nanodiamond (NOND)/Si pyramids (Pyr-Si) heterostructure is studied for high-performance nonenzymatic glucose sensor. The combined properties of surface-modified NOND/Pyr-Si induced by different growth durations (5 to 20 min) of CuO is envisioned to improve glucose sensitivity and stability. For comparison, the same methods and parameters were deposited on the plane silicon wafers. The systematic analysis reveals the best glucose sensing properties of 15 min grown CuO/NOND/Pyr-Si based sensor, with a high sensitivity of 1993 µA mM-1 cm-2, a lower limit of detection of 0.1 µm, and a longer stability of 28 d (∼96%). In addition, the present sensor exhibits good selectivity of glucose among other analytes such as sodium chloride, ascorbic acid, uric acid, and so on. The enhancement in glucose sensing performances of the as-fabricated CuO/NOND/Pyr-Si is ascribed to the interfacial effect of NOND and the synergistic effect of CuO and NOND/Pyr-Si. Moreover, the oxygen dopant in NOND and CuO stimulates the reactive oxygen species while measuring glucose and affords rapid recovery (<2 s). This promotes fast electron kinetics in the electrocatalytic solutions, which enhances the electroactive area and thereby contributes to a high sensitivity. These salient results suggested that the as-fabricated CuO/NOND/Pyr-Si sensor is more suitable for high-performance biosensors and effective energy storage device applications.

Electrospun titania fiber mats spin coated with thin polymer films as nanofibrous scaffolds for enhanced cell proliferation.

The incorporation of inorganic materials into electrospun nanofibres has recently gained considerable attention for the development of extracellular matrix-like scaffolds with improved mechanical properties and enhanced biological functions for tissue engineering applications. In this study, polymer-inorganic composite fibres consisting of poly(2-ethyl-2-oxazoline) (PEOXA) and tetrabutyl titanate as the titanium precursor were successfully fabricated through a combined sol-gel/electrospinning approach. PEOXA/Ti(OR)n composite fibres were obtained with varying amounts of polymer and titanium precursors. Calcinations of the composite fibres were performed at varying temperatures to produce TiO2 fibres (TiO2 -T-60) with anatase, anatase/rutile mixed phase, and rutile crystal structures. Thin polymer films (i.e., poly(2-ethyl-2-oxazoline) (PEOXA), polycaprolactone (PCL), and poly(methyl methacrylate) (PMMA)) were subsequently deposited onto TiO2 -T-60 fibre mats by spin coating to facilitate handling of the electrospun substrates after calcination, which are rather brittle and disintegrate easily, and to probe cell-materials interactions. The cellular behaviour of mouse L929 fibroblasts after culture periods of 1-5 days was compared on the following fibre scaffolds: PEOXA/Ti(OR)n , TiO2 -T-60 (T = 600, 650, and 700 °C), TiO2 -T-60 spin-coated with thin PCL film (PCL/TiO2 -T-60), and pure PCL. The results obtained from in vitro cell culture studies for the lactate dehydrogenase release assay and confocal microscopic visualization pointed out the synergistic interplay between the TiO2 crystal structure and spin-coated PCL film in facilitating cell interactions with the scaffold surface. The L929 cells were observed to adhere and proliferate better on the surface of TiO2 -700-60 having the rutile structure than on the surfaces of TiO2 -600-60 and TiO2 -650-60 fibre scaffolds with anatase and anatase/rutile mixed phase structures, respectively.

Cellulose nanocrystals from passion fruit peels waste as antibiotic drug carrier.

Due to its excellent chemical and physical properties, cellulose nanocrystals (CNC) possess many potential advanced functional applications. In this study, CNC was extracted from natural product by hydrolyzing cellulose segment of passionfruit peels using sulphuric acid solution. The capability of CNC as drug carrier was tested toward tetracycline antibiotic. The drug loading processes were carried out at various pH (3-7) with the optimum uptake of tetracycline achieved at pH 3. The in vitro release of tetracycline drug was carried out in phosphoric buffer medium with two different pH conditions at 37°C. The highest release of tetracycline (82.21%) was achieved at pH 7.2, while the lowest one (25.1%) was achieved at pH 2.1, where the release pattern follow a second order kinetic model. This study highlight the potential application of CNC derived from natural resources as drug carrier without harmful chemical excipients that comply with health safety, biocompatible, biodegradable.

Gold nanoparticles-decorated electrospun poly(N-vinyl-2-pyrrolidone) nanofibers with tunable size and coverage density for nanomolar detection of single and binary component dyes by surface-enhanced raman spectroscopy.

The application of the electrospun nanomaterials to surface-enhanced Raman spectroscopy (SERS) is a rapidly evolving field which holds potential for future developments in the generation of portable plasmonic-based detection platforms. In this study, a simple approach to fabricate electrospun poly(N-vinylpyrrolidone) (PVP) mats decorated with gold nanoparticles (AuNPs) by combining electrospinning and calcination was presented. AuNPs were decorated on the fiber mat surface through electrostatic interactions between positively charged aminosilane groups and negatively charged AuNPs. The size and coverage density of AuNPs on the fiber mats could be tuned by varying the calcination temperature. Calcination of AuNPs-decorated PVP fibers at 500 °C-700 °C resulted in the uniform decoration of high density AuNPs with very narrow gaps on every single fiber, which in turn contribute to strong electromagnetic SERS enhancement. The robust free-standing AuNPs-decorated mat which calcined at 500 °C (500/AuNPs-F) exhibited high SERS activity toward cationic (methylene blue, MB) and anionic (methyl orange, MO) dyes in single and binary systems with a detection range from tens of nM to a few hundred µM. The fabricated SERS substrate demonstrated high reproducibility with the spot-to-spot variation in SERS signal intensities was ±10% and ±12% for single and binary dye systems, respectively. The determination of MB and MO in spiked river water and tap water with 500/AuNPs-F substrate gave satisfactory results in terms of the percent spike recoveries (ranging from 92.6%-96.6%) and reproducibility (%RSD values less than 15 for all samples).

Biocompatibility and drug release behavior of curcumin conjugated gold nanoparticles from aminosilane-functionalized electrospun poly(N-vinyl-2-pyrrolidone) fibers.

Curcumin (CUR) has a wide spectrum of biological and pharmacological activities, yet problems of its bioavailability remained a major challenge in preclinical studies. Thus, the design of the delivery systems with CUR as a model drug featuring dual release process - an initial burst followed by sustained release - to provide the optimal drug pharmacokinetics in the therapeutic region has been actively pursued. In this study, the 3-aminopropyltriethoxysilane (APTES)-functionalized electrospun poly(N-vinyl-2-pyrrolidone) fibers (NH2-PVP) were utilized as a free-standing substrate for the immobilization of CUR-PVP capped gold nanoparticles (CUR-PGNPs) conjugates. The conjugate was synthesized by sonication and the drug entrapment percentage was determined to be 54.2 ±1.8. CUR-PGNPs immobilized on NH2-PVP fibers showed a moderate burst release during the first few hours, followed by a sustained release lasting for 2days. The drug release was found pH-dependent (pH 5.0>6.0>7.4). The two-stage release profiles of CUR-PGNPs@NH2-PVP fibers were fitted well to Korsmeyer-Peppas model, indicating a non-Fickian diffusion mechanism for initial burst release and Fickian diffusion-controlled mechanism for the sustained release. Initial biocompatibility assessments based on lactate dehydrogenase (LDH) assay and morphological examination by SEM with L-929 mouse fibroblasts revealed that CUR-PGNPs@NH2-PVP nanofibrous scaffold was capable of supporting cell growth over a culture period of 3days.

Adsorption and photocatalytic performance of bentonite-titanium dioxide composites for methylene blue and rhodamine B decoloration.

Bentonite - TiO2 composites were prepared by impregnation of TiO2 and bentonite, followed by microwave irradiation processes. The composites were characterized using FTIR, SEM, XRD, and nitrogen sorption methods. Anatase phase of TiO2 in all composites are observed through XRD diffraction peaks and surface morphology of the composites. The adsorption and photocatalytic capabilities of the composites were tested in liquid phase adsorption of methylene blue and Rhodamine B. The adsorption and photocatalytic degradation experiments were conducted in the presence or absence of UV light irradiation. Langmuir and Freundlich models were employed to correlate the experimental adsorption data, and it was found that Langmuir gave better performance in correlating the experimental data. Modification of Langmuir equation to accommodate photocatalytic degradation process was conducted, and the model could represent the experimental results very well.

Bio-oil from cassava peel: a potential renewable energy source.

In this work, liquid biofuel (bio-oil) was produced by pyrolizing cassava peel. The experiments were conducted isothermally in a fixed-bed tubular reactor at temperatures ranging from 400 to 600°C with a heating rate of 20°C/min. The chemical compositions of bio-oil were analyzed by a gas chromatography mass spectrometry (GC-MS) technique. For the optimization of liquid product, temperature was plotted to be the most decisive factor. The maximum yield of bio-oil ca. 51.2% was obtained at 525°C and the biofuel has a gross calorific value of 27.43 MJ/kg. The kinetic-based mechanistic model fitted well with experimental yield of pyrolysis products with the mean squared error (MSE) of 13.37 (R(2)=0.96) for solid (char), 16.24 (R(2)=0.95) for liquid (bio-oil), and 0.49 (R(2)=0.99) for gas.

Modified Ponorogo bentonite for the removal of ampicillin from wastewater.

The adsorption of ampicillin onto natural and organo-bentonite was studied. Organo-bentonite was obtained by modifying the natural bentonite obtained from Ponorogo, Indonesia, using CTAB surfactant by microwave heating. The temperature dependent form of the Langmuir, Freundlich, Sips and Toth equations was employed to correlate equilibrium data. Based on the evaluation of the physical meaning of fitted isotherm parameters of each model, it is clear that Toth equation can represent the equilibrium data better than other models. The adsorption performance of natural and organo-bentonite for the removal of ampicillin from pharmaceutical company wastewater was also studied. In real wastewater, both adsorbents could not completely remove the ampicillin due to the sorption competition with other substances which also present in the wastewater.