An Update on Molecularly Imprinted Polymer Design through a Computational Approach to Produce Molecular Recognition Material with Enhanced Analytical Performance

Molecularly imprinted polymer (MIP) computational design is expected to become a routine technique prior to synthesis to produce polymers with high affinity and selectivity towards target molecules. Furthermore, using these simulations reduces the cost of optimizing polymerization composition. There are several computational methods used in MIP fabrication and each requires a comprehensive study in order to select a process with results that are most similar to properties exhibited by polymers synthesized through laboratory experiments. Until now, no review has linked computational strategies with experimental results, which are needed to determine the method that is most appropriate for use in designing MIP with high molecular recognition. This review will present an update of the computational approaches started from 2016 until now on quantum mechanics, molecular mechanics and molecular dynamics that have been widely used. It will also discuss the linear correlation between computational results and the polymer performance tests through laboratory experiments to examine to what extent these methods can be relied upon to obtain polymers with high molecular recognition. Based on the literature search, density functional theory (DFT) with various hybrid functions and basis sets is most often used as a theoretical method to provide a shorter MIP manufacturing process as well as good analytical performance as recognition material.     

A microfluidic device using a green organic light emitting diode as an integrated excitation source

A simply fabricated microfluidic device using a green organic light emitting diode (OLED) and thin film interference filter as integrated excitation source is presented and applied to fluorescence detection of proteins. A layer-by-layer compact system consisting of glass/PDMS microchip, pinhole, excitation filter and OLED is designed and equipped with a coaxial optical fiber and for fluorescence detection a 300 microm thick excitation filter is employed for eliminating nearly 80% of the unwanted light emitted by OLEDs which has overlaped with the fluorescence spectrum of the dyes. The distance between OLED illuminant and microchannels is limited to approximately 1 mm for sensitive detection. The achieved fluorescence signal of 300 microM Rhodamine 6G is about 13 times as high as that without the excitation filter and 3.5 times the result of a perpendicular detection structure. This system has been used for fluorescence detection of Rhodamine 6G, Alexa 532 and BSA conjugates in 4% linear polyacrymide (LPA) buffer (in 1 x TBE, pH 8.3) and 1.4 fmol and 35 fmol mass detection limits at 0.7 nl injection volume for Alexa and Rhodamine dye have been obtained, respectively.     

Ferromagnetism and structural deformation in monolayer alpha lead oxide induced by N and F doping: New insights from first principles

We study the structural, electronic, and magnetic properties of monolayer α-PbO_0.875A_0.125 (A = N, F), which are calculated using first principles. As a result, N doping induces local ferromagnetism centered at the N²⁻ site, originating from the spin-down N 2p valence states. On the other hand, F doping induces nonmagnetism and induces ab-plane deformation, where F⁻ receives one electron to its nearest-neighboring Pb^1.75+ ions. N doping redshifts the bandgap of the undoped system and transforms it to be indirect, while F doping blueshifts the bandgap through the Burstein-Moss effect. The hybridization of Pb 6p and O 2p orbitals is stronger near the A site than that of the crystal structure edge. Our result shows new insights, predicting possible experimental results for future functional device applications.     

Strong and Superhydrophobic Wood with Aligned Cellulose Nanofibers as a Waterproof Structural Material†

Lightweight structural materials are important for the energy efficiency of applications, particularly those in the building sector. Here, inspired by nature, we developed a strong, superhydrophobic, yet lightweight material by simple in situ growth of nano‐SiO₂ and subsequent densification of the wood substrate. In situ generation of SiO₂ nanoparticles both inside the wood channels and on the wood surfaces gives the material superhydrophobicity, with static and dynamic contact angles of 159.4^o and 3^o, respectively. Densification of the wood to remove most of the spaces among the lumen and cell walls results in a laminated, dense structure, with aligned cellulose nanofibers, which in turn contributes to a high mechanical strength up to 384.2 MPa (7‐times higher than natural wood). Such treatment enables the strong and superhydrophobic wood (SH‐Wood) to be stable and have excellent water, acid, and alkaline resistance. The high mechanical strength of SH‐Wood combined with its excellent structural stability in harsh environments, as well its low density, positions the strong and superhydrophobic wood as a promising candidate for strong, lightweight, and durable structural materials that could potentially replace steel.     

Rapid crack growth in a thermoelastic solid under mixed-mode thermomechanical loading

A two-dimensional steady-sate analysis of semi-infinite brittlecrack growth at a constant subcritical rate in an unboundedfully-coupled thermoelastic solid under mixed-mode thermomechanicalloading is made. The loading consists of normal and shear tractionsand heat fluxes applied as point sources (line loads in theout-of-plane direction). A related problem is solved exactly in an integral transformspace, and robust asymptotic forms used to reduce the originalproblem to a set of integral equations. The equations are partiallycoupled and exhibit operators of both Cauchy and Abel types,yet can be solved analytically. The temperature change field at a distance from the moving crackedge is then constructed, and its dominant term is found tobe controlled by the imposed heat fluxes. The role of this termis, indeed, enhanced if the heat fluxes serve to render thecrack as a net heat source/sink for the solid, as opposed tobeing a transmitter of heat across its plane. More generally,the influence of the thermoelastic coupling on this field, aswell as other functions, is found to increase with crack speed.     

Quantitative analysis of boldine alkaloid in natural extracts by cyclic voltammetry at a liquid-liquid interface and validation of the method by comparison with high performance liquid chromatography

The quantitative determination of boldine alkaloid in boldo leaf extracts by employing cyclic voltammetry, at a liquid/liquid interface as well as the validation of this methodology against the reference method, high performance liquid chromatography (HPLC), are reported in the present paper. The voltammetric analysis was performed successfully and economically using two kinds of liquid/liquid interfaces: water/1,2-dicholoroethane and water/PVC (polyvinyl chloride)-gelled 1,2-dichloroethane. Linear calibration curves in the concentration range of 1.04 × 10⁻⁵ mol L⁻¹ to 5.19 × 10⁻⁴ mol L⁻¹ were obtained with a detection limit equal to (6.1 ± 0.7) × 10⁻⁵ mol L⁻¹ and the quantitative determination of this alkaloid, in complex matrixes such as boldo leaf extracts, by the electrochemical technique proposed was found to be equal to the values obtained using the standard HPLC method. The validation analysis of this methodology against HPLC demonstrated that accuracy, linearity, limit of detection (LOD), limit of quantification (LOQ), specificity and precision are acceptable. The electroanalytical technique proposed is economical and selective, involves simple equipment and can be applied for the quantitative determination of boldine alkaloid in complex matrixes such as leaf extracts without special drug separation. Moreover, cyclic voltammetry (CV) experiments applied at the liquid/liquid interface under different experimental conditions allowed us to study the transfer mechanism of boldine, and determine a value of pK_a^w = 6.90 for protonated boldine, from the variation of voltammetric peak current with pH.     

Hole‐Boosted Cu(Cr,M)O2 Nanocrystals for All‐Inorganic CsPbBr3 Perovskite Solar Cells

The all‐inorganic CsPbBr₃ perovskite solar cell (PSC) is a promising solution to balance the high efficiency and poor stability of state‐of‐the‐art organic–inorganic PSCs. Setting inorganic hole‐transporting layers at the perovskite/electrode interface decreases charge carrier recombination without sacrificing superiority in air. Now, M‐substituted, p‐type inorganic Cu(Cr,M)O₂ (M=Ba²⁺, Ca²⁺, or Ni²⁺) nanocrystals with enhanced hole‐transporting characteristics by increasing interstitial oxygen effectively extract holes from perovskite. The all‐inorganic CsPbBr₃ PSC with a device structure of FTO/c‐TiO₂/m‐TiO₂/CsPbBr₃/Cu(Cr,M)O₂/carbon achieves an efficiency up to 10.18 % and it increases to 10.79 % by doping Sm³⁺ ions into perovskite halide, which is much higher than 7.39 % for the hole‐free device. The unencapsulated Cu(Cr,Ba)O₂‐based PSC presents a remarkable stability in air in either 80 % humidity over 60 days or 80 °C conditions over 40 days or light illumination for 7 days.     

Alkyl‐Chain‐Regulated Charge Transfer in Fluorescent Inorganic CsPbBr3 Perovskite Solar Cells

Improved charge extraction and wide spectral absorption promote power conversion efficiency of perovskite solar cells (PSCs). The state‐of‐the‐art carbon‐based CsPbBr₃ PSCs have an inferior power output capacity because of the large optical band gap of the perovskite film and the high energy barrier at perovskite/carbon interface. Herein, we use alkyl‐chain regulated quantum dots as hole‐conductors to reduce charge recombination. By precisely controlling alkyl‐chain length of ligands, a balance between the surface dipole induced charge coulomb repulsive force and quantum tunneling distance is achieved to maximize charge extraction. A fluorescent carbon electrode is used as a cathode to harvest the unabsorbed incident light and to emit fluorescent light at 516 nm for re‐absorption by the perovskite film. The optimized PSC free of encapsulation achieves a maximum power conversion efficiency up to 10.85 % with nearly unchanged photovoltaic performances under 80 %RH, 80 °C, or light irradiation in air.     

Properties of Ozone-Oxidized Tapioca Starch and Its Use in Coating of Fried Peanuts

Oxidation of tapioca via ozone oxidation was carried out under different conditions in comparison with H₂O₂. The impact of ozonation on physicochemical properties of tapioca was studied and fried peanuts coated with different tapioca were characterized. Different ozone oxidation times (10, 20, and 30 min) and various pH values (5, 7, and 9) were used for tapioca modification. Tapioca oxidized by ozone for 20 min at pH 7 had higher swelling power (SP), water holding capacity (WHC), oil holding capacity (OHC), and viscosity than the native counterpart (P < 0.05). This coincided with the higher carbonyl and carboxyl contents (P < 0.05). The highest frying expansion (FE) with the lowest hardness was attained for fried peanut coated with tapioca oxidized under the aforementioned condition. Therefore, oxidation of tapioca using ozone under optimal conditions could be a potential means to improve frying expansion as well as the crispiness of the fried coated peanuts.