Tailoring surface engineering with expanded precursor libraries via rapid mussel-inspired chemistry.

Mussel-inspired coating is a substrate-independent surface modification technology. However, its application is limited by time-consuming, tailoring specific functions require tedious secondary reaction. To overcome those drawbacks, a strategy for the rapid fabrication of diverse coatings by expanding the library of precursors using oxidation coupled with polyamine was proposed. Based on DFT simulations of the reaction pathways, a method was developed to achieve rapid deposition of coatings by coupling oxidation and polyamines, which simultaneously accelerated the oxidation of precursors and polymer chain growth. The feasibility and generalizability of the strategy was validated by the rapid coating of 10 catechol derivatives and polyamines on various substrates. The surface properties of the substrates such as functional group densities, Zeta potential and contact angles can be easily tuned. The tailored surface engineering application of the strategy was demonstrated by the heavy metal adsorbents and superwetting materials prepared through the delicate combination of different building blocks. Our strategy was flexible in terms of diverse surface engineering design which greatly enriched the connotation of mussel-inspired technique.

Flexible Supercapacitor with Wide Electrochemical Stable Window Based on Hydrogel Electrolyte.

Hydrogel electrolyte can endow supercapacitors with excellent flexibility, which has developed rapidly in recent years. However, the water-rich structures of hydrogel electrolyte are easy to freeze at subfreezing and dry at high temperatures, which will affect its energy storage characteristics. The low energy density of micro supercapacitors also hinders their development. Herein, a strategy is proposed to reduce the free water activity in the hydrogel to improve the operating voltage and the energy density of the device, which is achieved through the synergistic effect of the hydrogel skeleton, N, N'-dimethylformamide (DMF), NaClO4 and water. High concentrations of DMF and NaClO4 are introduced into sodium alginate/polyacrylamide (SA/PAAM) hydrogel through solvent exchange to obtain SA/PAAM/DMF/NaClO4 hydrogel electrolyte, which exhibited a high ionic conductivity of 82.1 mS cm-1, a high breaking strength of 563.2 kPa, and a wide voltage stability window of 3.5 V. The supercapacitor devices are assembled by the process of direct adhesion of the hydrogel electrolyte and  laser induced graphene (LIG). The micro-supercapacitor exhibited an operating voltage of 2.0 V, with a specific capacitance of 2.41 mF cm-2 and a high energy density of 1.34 µWh cm-2, and it also exhibit a high cycle stability, good flexibility, and integration performance.

Integration of adsorption, reduction, and filtration in PANI/PVDF nanofiber composite membrane for removal of Cr(VI).

Here, polyaniline/polyvinylidene fluoride (PANI/PVDF) nanofiber composite membrane was fabricated using electrostatic spinning technology to remove hexavalent chromium Cr(VI). The employment of PANI not only extremely enhanced the hydrophilic property of the nanofiber membrane, but also facilitated the transfer of Cr2O72- from water to the membrane. The PANI/PVDF membrane had an extremely excellent performance in getting rid of Cr(VI) and a quite large flux (250 L/m2 h). The maximum adsorption quantity of the membrane could reach 334.5 mg/g in which adsorption played 52.12% part and reduction played 47.87% part. The removal rate could reach nearly 100% immediately in the permeate solution under filtration while it needed 240 min to reach 100% only by static adsorption. Therefore, the interception of the membrane and the adsorption reduction of PANI had synergistic effect on removal of Cr(VI). Furthermore, the removal rate of Cr(VI) could still reach 95.97% after reused 8 times. The membrane showed a very good reusability and application prospect.

Superhydrophilic and oleophobic sponges prepared based on Mussel-Inspired chemistry for efficient oil-water separation.

Superhydrophilic/oleophobic materials are considered to be the best materials for achieving oil-water separation, but their preparation is difficult and the existing methods are not universal. In this paper, a two-step modification strategy was used to prepare superhydrophilic/oleophobic sponges by adjusting the polar and nonpolar components of the materials using mussel-inspired chemistry. While remaining superhydrophilic, the modified sponge surface has a maximum contact angle of 135° with different oils in air. The modified sponge exhibited superoleophobicity in water, and the contact angle of oil could reach more than 150°. In addition, the modified sponges were also reusable, chemically stable, and mechanically durable. Its oil-water separation flux was up to 24900 Lm-2 h-1 bar-1 , and the separation efficiency was above 97 %. We believe that this method will provide an environmentally friendly and efficient way to prepare the superhydrophilic/oleophobic materials.

Polypropylene fiber grafted calcium alginate with mesoporous silica for adsorption of Bisphenol A and Pb2.

Polypropylene grafted calcium alginate with mesoporous silica (PP-g-CaAlg@SiO2) for adsorbing Bisphenol A (BPA) and Pb2+ was prepared by calcium chloride (CaCl2) crosslinking and hydrochloric acid solution treatment. The PP-g-CaAlg@SiO2 was characterized by SEM, TEM, BET, XRD, FTIR and TG. PP-g-CaAlg@SiO2 exhibited excellent adsorption capacity for BPA and Pb2+, because the formation of reticulated nanorod structure increased its specific surface area. Subsequently, the adsorption behaviours of BPA and Pb2+, including adsorption isotherms and adsorption kinetics, were investigated. Afterward, isothermal titration calorimetry (ITC) and molecular dynamics (MD) simulation were performed to explore the adsorption mechanism. The results indicated that hydrogen bonding played the leading role in the adsorption of BPA, while the bonding of Pb2+ to carboxyl group binding sites was the focus of Pb2+ adsorption. In addition, the adsorption capacity of PP-g-CaAlg@SiO2 was stable over 10 cycles.

Tailored Sky-Parking Architectures of 3D Graphene Oxide Towards Highly-Efficient Water Purification.

The widespread use of chemicals has brought serious water pollution threatening human health and environment, which requires green, fast, and low-cost purification urgently. Here, we build up a novel material family of sky-parking-like 3D structured graphene oxides (SP-GOs) with adjustable interlayer-space of 0.8-1.7 nm via the insertion of different sized diamine compounds as support pillars between GO layers. The assembled 3D SP-GOs exhibit superior adsorption capacity and short removal time for various aromatic organic compounds in water, achieving record-breaking maximum adsorption capacity of 535.79 mg g-1 toward the most common water-pollutant bisphenol A (BPA) at ambient conditions as well as significantly improved removal of other organic pollutants including sulfapyridine, carbamazepine, ketoprofen and 2-naphthol. The construction of SP-GO provides a simple approach for evolving the GO material from 2D to 3D and a new avenue for the decontamination of pollutants in environmental remediation.

A novel hollow microsphere composite MnOx/PAA: effective catalyst for ozone decomposition at high humidity.

Ozone air pollution poses a serious threat to human health and ecological environment. Manganese oxide (MnOx) is a popular material for ozone decomposition with excellent catalytic performance. However, the catalytic activity may be reduced under high-humidity conditions because of oxygen vacancy of MnOx from the water evaporation. In this paper, a new type of MnOx/poly(acrylic acid-co-divinylbenzene) (PAA) catalyst with MnOx supported on hollow PAA was successfully prepared, which greatly improved the ozone decomposition efficiency under high humidity. It was shown that when the acrylic acid (AA) content was more than 50%, the PAA polymer layer was hydrophilic and the ozone decomposition efficiency would keep high activity for both the low- and high-humidity conditions. The best performance of ozone decomposition was identified for the methanol reduction and AA content of 60%, in which the efficiencies reached 94.5% and 85% at 50% and 90% humidity levels, respectively. It is the synergetic effect of the hydrophilic PAA support and hollow structure that retains and improves the decomposition activity, which can absorb the water vapor molecules and increase the ozone retention time. Therefore, the hollow microsphere catalyst prepared in this paper has great potential in solving the problem of ozone air pollution.

Near infrared spectroscopy combined with chemometrics for quantitative analysis of corn oil in edible blend oil.

In this study, near infrared (NIR) spectroscopy combined with chemometrics was used for the quantitative analysis of corn oil in binary to hexanary edible blend oil. Sesame oil, soybean oil, rice oil, sunflower oil and peanut oil were mixed with corn oil subsequently to form binary, ternary, quaternary, quinary and hexanary blend oil datasets. NIR spectra for the five order blend oil datasets were measured in a transmittance mode in the range of 12000-4000 cm-1. Partial least square (PLS) was used to build models for the five datasets. Six spectral preprocessing methods and their combinations were investigated to improve the prediction performance. Furthermore, the optimal preprocessing-PLS models were further optimized by uninformative variable elimination (UVE), Monte Carlo uninformative variable elimination (MCUVE) and randomization test (RT) variable selection methods. The optimal models acquire root mean square error of prediction (RMSEP) of 1.7299, 2.2089, 2.3742, 2.5608 and 2.6858 for binary, ternary, quaternary, quinary and hexanary blend oil datasets, respectively. The determination coefficients of prediction set (R2P) and residual predictive deviations (RPDs) for the five datasets are all above 0.93 and 3. Results show that the prediction accuracy is gradually decreased with the increasing of mixture order of blend oil. However, with proper spectral preprocessing and variable selection, the optimal models present good prediction accuracy even for the higher order blend oil. It demonstrates that NIR technology is feasible for determining the pure oil contents in binary to hexanary blend oil.

Temperature-controlled ultra-high hydrogen evolution photocatalytic activity of cadmium sulfide without cocatalysts.

Photocatalytic water spitting is one way of hydrogen production from energy conservation and emission reduction. However, the activities of most photocatalytic materials need to be enhanced by cocatalysts. In this study, we explored to control the photocatalytic hydrogen evolution (PHE) ability of cadmium sulfide (CdS) without any cocatalysts by temperature and largely improve its photocatalytic ability. It was experimentally found the activity of CdS without cocatalysts under heating conditions (<100 °C) was much higher than that at room temperature, and increased first and then decreased, with a maximum at 50 °C (169716 umol/h, 68.2 % , λ = 450 nm). Therefore, it is convenient to control the hydrogen production activity of CdS by temperature. The large increment of photocatalytic activity was realized because the temperature complemented the shortcomings of semiconductors in light absorption, and together with light radiation, increased the electron migration rate and density, quantity of surface adsorbed H3O+ and number of active sites, prolonged the living of electrons, and reduced the overpotential of water splitting and the reverse reactions. Heating brings the above advantages, but also exacerbates the recombination of electron-hole pairs. Therefore, the activity shows an extreme value along with the temperature rise. This work experimentally proves temperature control is one of the most efficient and simple ways to largely enhance the PHE ability.

A novel remediation method of cadmium (Cd) contaminated soil: Dynamic equilibrium of Cd2+ rapid release from soil to water and selective adsorption by PP-g-AA fibers-ball at low concentration.

The acid-extractable fraction Cd(II) in soil accumulates easily in organisms, migrates and transforms in the ecological environment, which has posed potential health risks to human. This study found that the acid-extractable fraction Cd(II) in soil could be released rapidly into water at very low Cd2+ concentration. Carboxylated polypropylene (PP-g-AA) fibers-ball with high selectivity as adsorbent was used in the Cd(II) contaminated soil-water system. It could remove promptly trace Cd2+ from water even in the presence of interfering metal ions. Moreover, Cd(II) desorbed from soil to water could be continuously adsorbed by PP-g-AA fibers-ball, which kept the Cd2+ concentration always at a low level. This forms a dynamic equilibrium of rapid release- selective adsorption toward the acid-extractable fraction Cd(II) in the soil-water system. Here, the migratory pathway for the acid-extractable fraction Cd(II) to be released from contaminated soil to water and adsorbed simultaneously on the surface of PP-g-AA fibers-ball was established. This work offers a novel protocol that can remove more than 90% of the acid-extractable fraction Cd(II) from contaminated soil within 12 h, thereby contributes better to mitigate the risk of Cd(II) from soil to the food chain without changing the physical and chemical properties of soil.

Caffeic acid polymer rapidly modified sponge with excellent anti-oil-adhesion property and efficient separation of oil-in-water emulsions.

The efficient treatment of high stability emulsion with small diameter and the prevention of oil contamination of materials are serious issues in the process of emulsion separation. In order to address those issues, we reported a fast and versatile hydrophilic surface coating technology that uses oxidants and diamines to synergistically promote the polymerization of caffeic acid (CA). It was found that amino groups can not only accelerate the polymerization of CA, but also promote the deposition of polymers on the sponge surface. Using silica nanoparticles to improve the roughness, superhydrophilic melamine sponge could be prepared, which exhibited excellent superhydrophlic-underwater superolephobic and anti-oil-adhesion properties. DFT simulation was employed to explore the potential mechanism of the anti-oil adhesion ability. In addition, combined with the mechanical compression strategy, the sponge exhibited a high efficiency of 99.10% with a permeation flux of 19080 ±â€¯700 Lm-2 h-1 in emulsion separation just under the action of gravity. Moreover, based on the interaction between the surfactant and the surface of the material, the separation mechanism was discussed. Overall, this work provided an advanced method for the preparation of superhydrophilic sponge with anti-oil-fouling performance, which showed great potential in dealing with practically challenging emulsified wastewater.

Synthesis of a new ion-imprinted polymer for selective Cr(VI) adsorption from aqueous solutions effectively and rapidly.

Removing hexavalent chromium (Cr(VI)) from aqueous solution is strategically important. A novel and selective adsorbent was synthesized using a high electron beam irradiation pre-grafting and post-surface ion imprinting method using Cr(VI) and polypropylene (PP) fibers as the template and substrates, respectively. The results obtained using Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), and thermogravimetric analysis (TG) indicated that the prepared sorbent was successfully synthesized. At the same time, the adsorption performances were studied through batch experiments. The results exhibited rapid adsorption kinetics, a wide working pH range, and excellent selectivity and regeneration. The equilibrium adsorption was achieved within 30 min, the maximum sorption capacity of Cr(VI)-IIPs was 156.5 mg g-1 and partition coefficients (PC) was 0.591 mg g-1 uM-1 at 400 mg L-1 initial concentration and 298 K. The relative selectivity coefficients of the ion-imprinted polymer (IIP) for Cr2O72-/HPO42- and Cr2O72-/NO3- were 36.7 and 39.9, respectively. In addition, the prepared sorbent has a negligible loss in adsorption capacity after five cycles. IIP has good application prospects in the selective removal of Cr(VI) ions.

Functional group-rich hyperbranched magnetic material for simultaneous efficient removal of heavy metal ions from aqueous solution.

In order to achieve the purpose of simultaneous removal of coexisting heavy metal ions, in this work, functionalized magnetic mesoprous nanomaterials (Fe3O4-HBPA-ASA) with high density and multiple adsorption sites were designed and prepared. The obtained Fe3O4-HBPA-ASA was characterized by SEM, FTIR, VSM, TGA and zeta potential. Cu(II), Pb(II) and Cd(II) were chosen as the model heavy metal ions, the adsorption experiments showed that Fe3O4-HBPA-ASA showed hightheoretical adsorption capacitiesin individual system, and the maximum adsorption capacity was 136.66 mg/g, 88.36 mg/g and 165.46 mg/g, respectively. In the binary and ternary systems, the competitive adsorption leads to a decrease in the adsorption capacity of Cu(II), Pb(II) and Cd(II). However, in the ternary system with a concentration lower than 15 mg/L, the simultaneous removal rate was still higher than 90%. The adsorption isotherms and kineticswere well fitted by Langmuir and pseudo-second-order models, respectively. The XPS and density functional theory (DFT) analysis have confirmed that the adsorption of metal ions was related to various types of functional groups on the surface of Fe3O4-HBPA-ASA, while the adsorption mechanisms of Cu(II), Cd(II) and Pb(II) were different.

Enhanced fluorescence probes based on Schiff base for recognizing Cu2+ and effect of different substituents on spectra.

Three enhanced fluorescence probes based on Rhodamine B-Schiff base structure were synthesized for detecting Cu2+. The corresponding detection limits were found to be 0.25 µM, 0.15 µM and 0.18 µM. Binding ratio and binding sites were determined by Job's and nuclear magnetic titration experiments. The binding constants obtained by the Benesi-Hildebrand equation to be 341.0 M-0.5,1.8 × 104 M-1, and 265.4 M-0.5, respectively. As isomers, the different effects of probes on Cu2+ detection were researched. By adjusting the position and the size of the substituent group, the effects of binding sites and steric hindrance on the complexation ratio, response time and detection limit were discussed. Optimal spatial combination structure with Cu2+ was obtained through energy calculation. Detection mechanism of Rhodamine B ring opening based on the complex of the Schiff base with Cu2+ was confirmed. E. coli staining and detection of real water samples had expanded their applications.

Adsorption and Electrochemical Detection of Bovine Serum Albumin Imprinted Calcium Alginate Hydrogel Membrane.

In this paper, bovine serum albumin (BSA)-imprinted calcium alginate (CaAlg) hydrogel membrane was prepared using BSA as a template, sodium alginate (NaAlg) as a functional monomer, and CaCl2 as a cross-linker. The thickness of the CaAlg membrane was controlled by a glass rod enlaced with brass wires (the diameter was 0.1, 0.2, 0.3, 0.4, and 0.5 mm). The swelling properties of the CaAlg membranes prepared with different contents of NaAlg were researched. Circular dichroism indicated that the conformation of BSA did not change during the preparing and eluting process. The thinner the CaAlg hydrogel membrane was, the larger the adsorption capacity and the higher the imprinting efficiency of the CaAlg. The maximum adsorption capacity of molecularly imprinted polymer (MIP) and non-imprinted CaAlg hydrogel membrane (NIP) was 38.6 mg·g-1 and 9.2 mg·g-1, respectively, with an imprinting efficiency of 4.2. The MIP was loaded on the electrode to monitor the selective adsorption of BSA by voltammetry curve.

[Reduction Cooperated Fenton Oxidation of Zero-valent Iron (ZVI) Immobilized in Alginate Microsphere for Degradation of Acid Red B].

The zero-valent iron (ZVI) immobilized in an alginate microsphere was prepared by using sodium alginate as a support material. The characteristics of the Fe0/alginate microsphere was characterized by FT-IR, SEM, BET, and XPS. The SEM and BET analyses showed that the Fe0/alginate microsphere had a multilevel porous structure and could adsorb ARB. Combined with Fe0 reduction and Fe3+/Fe2+ catalytic oxidation, the mineralization of ARB could be effectively realized. The ARB in the solution was discolored rapidly by the reduction of Fe0/alginate microsphere and then oxidized efficiently by the subsequent Fenton reaction. The discoloration rate of ARB in the reduction stage was 96.8%, with an Fe0/alginate microsphere dosage of 0.24g·L-1 and pH of 2.96 after reaction time of 180 min. ARB was reduced to organics of lower molecular weight due to the degradation of azo groups by Fe0. In the subsequent Fenton oxidation stage, the mineralization degree of ARB increased to 64.7% after the addition of 10.75 mmol·L-1 H2O2. The influence of the Fe0/alginate microsphere dosage, pH, reusability of the Fe0/alginate microsphere, and the stability of iron ions in the alginate microsphere were investigated. Due to the coordination of Fe3+/Fe2+ ions with -COO--in the alginate, the iron ion in the solution was 3.9% of the total iron content in the microsphere. Iron ions could be well immobilized in calcium alginate microspheres, so the iron hydroxides were generated in lower amounts. The Fenton reaction can be conducted in a wide range of pH. The Fe2+/Fe3+immobilized in the alginate microsphere demonstrated good catalytic performance after it was reused four times. Therefore, the synergy of reduction and Fenton oxidation by the Fe0/alginate microsphere was a better strategy for dye degradation.

Dual-channel fluorescence detection of mercuric (II) and glutathione by down- and up-conversion fluorescence carbon dots.

The fluorescent carbon dots (CDs) with high fluorescent quantum yield (φf = 62%) and down- and up-conversion fluorescence properties were synthesized by one-pot hydrothermal treatment of citric acid and tris(hydroxymethyl)methyl aminomethane. The CDs displayed the capability to absorb excitation wavelength at 660 nm and 330 nm with fluorescence emission wavelength at 398 nm and 399 nm, respectively. The CDs showed high selectivity towards Hg2+ against various metal ions. Around 70% fluorescence was quenched by 40 µM Hg2+ through dynamic and static quenching mechanisms. Because of stronger affinity between the thiol and Hg2+, over 90% fluorescence was recovered by adding 40 µM glutathione to CDs-Hg2+ system. The calibration curves exhibited wide linear region for Hg2+ (0-4 µM) and glutathione (0-30 µM). The limits of detection with down- and up-conversion for Hg2+ were calculated to be 0.23 µM and 0.25 µM, and for glutathione were 0.28 µM and 0.29 µM, respectively. Inspired by the sensing results, logic gates with Hg2+ and glutathione as inputs were also established. Most importantly, this method was applied to detect Hg2+ and glutathione in tap water and lake water, and the recovery values were obtained to be 96.2%-110.4% and 93.4%-96.9%.

A dual spectroscopic fluorescence probe based on carbon dots for detection of 2,4,6-trinitrophenol/Fe (III) ion by fluorescence and frequency doubling scattering spectra and its analytical applications.

A convenient, highly sensitive and reliable assay for 2,4,6­trinitrophenol (TNP) and Fe (III) ion (Fe3+) in the dual spectroscopic manner is developed based on novel carbon dots (CDs). The CDs with highly blue emitting fluorescent were easily prepared via the one-step potassium hydroxide-assisted reflux method from dextrin. The as-synthesized CDs exhibited the high crystalline quality, the excellent fluorescence characteristics with a high quantum yield of ~13.1%, and the narrow size distribution with an average diameter of 6.3±0.5nm. Fluorescence and frequency doubling scattering (FDS) spectra of CDs show the unique changes in the presence of TNP/Fe3+ by different mechanism. The fluorescence of CDs decreased apparently in the presence of TNP via electron-transfer. Thus, after the experimental conditions were optimized, the linear range for detection TNP is 0-50µM, the detection limit was 19.1nM. With the addition of Fe3+, the FDS of CDs appeared to be highly sensitive with a quick response to Fe3+ as a result of the change concentration of the scattering particle. The emission peak for FDS at 450nm was enhanced under the excitation wavelength at 900nm. The fluorescence response changes linearly with Fe3+ concentration in the range of 8-40µM, the detection limits were determined to be 44.1nM. The applications of CDs were extended for the detection of TNP, Fe3+ in real water samples with a high recovery. The results reported here may become the potential tools for the fast response of TNP and Fe3+ in the analysis of environmental pollutants.

Preparation of Protein Molecular-Imprinted Polysiloxane Membrane Using Calcium Alginate Film as Matrix and Its Application for Cell Culture.

Bovine serum albumin (BSA) molecular-imprinted polysiloxane (MIP) membrane was prepared by sol-gel technology, using silanes as the functional monomers, BSA as the template and CaAlg hydrogel film as the matrix. The stress-strain curves of wet CaAlg membrane and molecular-imprinted polysiloxane membrane were investigated. We evaluate the adsorption and recognition properties of MIP membrane. Results showed that the adsorption capacity of BSA-imprinted polysiloxane for BSA reached 28.83 mg/g, which was 2.18 times the non-imprinted polysiloxane (NIP) membrane. The adsorption rate was higher than that of the protein-imprinted hydrogel. BSA-imprinted polysiloxane membrane could identify the protein template from competitive proteins such as bovine hemoglobin, ovalbumin and bovine γ-globulin. In order to obtain the biomaterial that can promote cell adhesion and proliferation, fibronectin (FN)-imprinted polysiloxane (FN-MIP) membrane was obtained by using fibronectin as the template, silanes as functional monomers, and CaAlg hydrogel membrane as the substrate or matrix. The FN-MIP adsorbed more FN than NIP. The FN-imprinted polysiloxane membrane was applied to culture mouse fibroblast cells (L929) and the results proved that the FN-MIP had a better effect on cell adhesion than NIP.