[Landscape Pattern Vulnerability and Its Driving Forces in Different Geomorphological Divisions in the Middle Yellow River].

The ecological environment of the middle Yellow River is highly vulnerable. Conducting a scientific assessment of landscape pattern vulnerability holds great significance, as it serves as the basis for the rational construction of the ecological environment in this area. Based on five periods of land use data from the middle Yellow River from 1990 to 2018, the landscape pattern vulnerability index was employed to analyze the spatio-temporal evolution of the landscape pattern vulnerability. Furthermore, the influencing factors for landscape pattern vulnerability in different natural geomorphological divisions were explored using an optimal parameters-based geographical detector model. The results showed that:① From 1990 to 2018, cultivated land (which accounted for 36.96 % to 39.97 % of the area) remained the predominant landscape in the middle Yellow River. Among all landscape types, cultivated land and construction land exhibited the most significant changes. The area of cultivated land decreased by 10 185.00 km2, whereas the area of construction land increased by 7 678.46 km2. ② From 1990 to 2018, the landscape pattern was dominated by low and medium vulnerability and accounted for 70 %-80 % of the total area. The high and higher vulnerability areas were concentrated in the loess hilly and gully region, whereas the lower vulnerability area was concentrated in the valley plain and the earth-rock mountain regions. During this period, landscape pattern vulnerability underwent an incipient decrease, followed by a subsequent increase. From 1990 to 2000 and from 2000 to 2005, the changes in the level of landscape pattern vulnerability were dominated by a "reduction in the degree of vulnerability". However, from 2005 to 2010 and from 2010 to 2018, it was mainly an "increase in the degree of vulnerability". ③ Annual precipitation and NDVI were the main factors influencing the vulnerability of landscape patterns, whereas the influencing factors varied across different natural geomorphological divisions:the loess hilly and gully region and the earth-rock mountain region were dominated by natural factors, with annual precipitation and DEM being the dominant factors, respectively; the loess plateau tableland-gully region, valley plain region, and sandy land and desert region were dominated by human factors, with population density, degree of land use, and distance from roads being the dominant factors, respectively. The interaction results of any two influencing factors were manifested as two-factor enhancement or nonlinear enhancement. Risk detection revealed that high vulnerability areas of landscape patterns in different natural geomorphological divisions were distributed over distinct ranges of their corresponding dominant factors. Therefore, in the practices of ecological management in the middle Yellow River, appropriate management strategies should be implemented based on the vulnerability characteristics of different natural landforms, to further improve the ecological management level of the watershed.

Ontogeny of myeloperoxidase (MPO) positive cells in flounder (Paralichthys olivaceus).

Neutrophils represent an important asset of innate immunity. Neutrophils express myeloperoxidase (MPO) which is a heme-containing peroxidase involved in microbial killing. In this study, by using real-time quantitative PCR and Western blot analysis, the flounder MPO (PoMPO) was observed to be highly expressed in the head kidney, followed by spleen, gill, and intestine during ontogeny - during developmental stages from larvae to adults. Furthermore, PoMPO positive cells were present in major immune organs of flounder at all developmental stages, and the number of neutrophils was generally higher as the fish grew to a juvenile stage. In addition, flow cytometry analysis revealed that the proportion of PoMPO positive cells relative to leukocytes, in the peritoneal cavity, head kidney, and peripheral blood of flounder juvenile stage was 18.3 %, 34.8 %, and 6.0 %, respectively, which is similar to the adult stage in flounder as previously reported. The presence and tissue distribution of PoMPO during ontogeny suggests that PoMPO positive cells are indeed a player of the innate immunity at all developmental stages of flounder.

Review of the Application of Microwave Heating Technology in Asphalt Pavement Self-Healing and De-icing.

In the past decades, a large amount of research was conducted to investigate the application prospect of microwave heating technology in improving the efficiency of asphalt pavement self-healing and de-icing. This paper reviewed the achievements in this area. Firstly, the properties of asphalt concrete after microwave heating were summarized, including microwave sensitivity and heating uniformity. Then, the evaluation indicators and influence factors of the self-healing properties of the asphalt mixtures heated by microwave were reviewed. Finally, the application of microwave heating in asphalt pavement de-icing was explored. In addition, asphalt pavement aging due to microwave heating was also reviewed. It was found that microwave heating technology has good prospects in promoting asphalt pavement self-healing and de-icing. There are also some problems that should be studied in depth, such as the cost-effectiveness of microwave-sensitive additives (MSAs), the performance of the pavement with MSAs, mechanism-based self-healing performance indicators, and the aging of asphalt pavements under cycling microwave heating.

Evaluating soil-water conserving performance of land management strategies for spoil tips on the Chinese Loess Plateau.

Surface runoff decrease (SRD) and sediment concentration change (SCC) are accountable for sediment reduction by anti-erosion strategies. Using a design of horizontal stages, contour trenches, fish-scale pits, as well as their combinations, this study evaluated the two components for sediment reduction after the implementation of various land management strategies on steep spoil tips. The study highlighted the interactions between SRD and SCC in reducing sediment, and characterized the temporal variations of sediment-reducing capacity by SRD and SCC. Results showed that slope erosion was well controlled with control ratios of sediment yield ranging from 0.4 to 0.59, 0.2 to 0.22, for horizontal stage- and contour trench-based strategies, respectively. Sediment-reducing benefit by SRD accounted for 52%-77% of the total sediment reduction and highly determined the performance of SCC. Quadratic relationships between sediment-reducing capacity by SCC and that by SRD were observed. The function of SCC only operated when the sediment-reducing capacity by SRD reached a certain threshold. These thresholds varied greatly in the range of 0.75 kg m-3-0.91 kg m-3 and 0.61 kg m-3-0.66 kg m-3 for horizontal stage- and contour trench-based strategies, respectively. The upper limits for sediment-reducing capacity by SCC varied in the range of 0.32 kg m-3-0.44 kg m-3 and 0.63 kg m-3-0.76 kg m-3 for horizontal stage- and contour trench-based strategies, respectively. An efficiency coefficient of 55% and an M-N ratio of 1:1 indicated that sediment-reducing benefits by SRD and SCC were effectively exerted by combining contour trenches and fish-scale pits. The findings emphasized that the application of land management strategies must be considered based on particular goals to restore spoil tips. In practice, if targeted to enhancing sediment-reducing efficiency, contour trenches and fish-scale pits should be primarily considered. However, if the aim is to decrease water consumed for sediment control, then horizontal stages should be principally considered.

Research on cropping intensity mapping of the Huai River Basin (China) based on multi-source remote sensing data fusion.

As a key input variable to many global climates, land surfaces and crop models, cropping intensity (CI) accurately assesses and predicts crops' output, in view of the global decline in food production in recent years due to declining natural resources, urban expansion and declining quality of arable land. Hence, research on CI mapping can have a contribution to solve this problem. Unfortunately, existing remote sensing data for CI mapping research, including Moderate Resolution Imaging Spectroradiometer (MODIS) and Landsat images, are not adequate for obtaining CI information at higher spatial and temporal resolution. In this regard, we develop an algorithm to extract CI based on per-pixel physiognomy. To be specific, the algorithm is based on the Google Earth Engine (GEE) platform and constructs a high temporal (10 days) spatial (30 m) resolution dataset with the fusion of Landsat 7/8 and Sentinel-2 A/B image data and extracts CI information using a time series of peak discovery method, threshold method and phenological period feature extraction to obtain the 2018 Chinese Huai River Basin (HRB) CI map. Our results suggest that the overall accuracy (OA) of CI extraction in the HRB is 92.72%, with a kappa coefficient of 0.864. The single-season crop, double-season crop and three-season crop account for 41.6%, 57.7% and 0.7% of the total farmland area, respectively. Compared to existing CI identification and extraction methods, this approach achieves higher accuracy in the identification and extraction of CI information over a larger area.

Influences of conservation measures on runoff and sediment yield in different intra-event-based flood regimes in the Chabagou watershed.

The Loess Plateau in China has suffered severe soil erosion. To control soil erosion, extensive conservation measures aimed at redistributing rainfall, hindering flow velocity and intercepting sediment were implemented on the Loess Plateau. To accurately evaluate the combined effect of conservation measures in the Chabagou watershed, this study classified intra-event-based floods into four regimes via cluster and discriminant analyses. Regime A was characterized by short flood duration and low erosive energy, regime B was characterized by short flood duration and high erosive energy, regime C was characterized by long flood duration and low erosive energy, and regime D was characterized by long flood duration and high erosive energy. The results indicated that peak discharge (qp), runoff depth (H), mean discharge (qm), and runoff erosion power (E) decreased by 75.2%, 56.0%, 68.0% and 89.2%, respectively, in response to conservation measures. Moreover, area-specific sediment yield (SSY), average suspended sediment concentration (SCE), and maximum suspended sediment concentration (MSCE) decreased by 69.2%, 33.3% and 11.9%, respectively, due to conservation measures. The nonlinear regression analysis revealed a power function relationship between SSY and E in both the baseline (1961-1969) and measurement period (1971-1990) in all regimes. Conservation measures reduced sediment yield by not only reducing the runoff amount and soil erosion energy but also transforming the flood regime, for example, transforming a high-sediment-yield regime into a low-sediment-yield regime. Moreover, conservation measures altered the SSY-E relationship in regime A, whereas no obvious difference in regime B or C/D was observed between the measurement period and the baseline period. This study provides a better understanding of the mechanism of runoff regulation and the sediment yield reduction under comprehensive conservation measures in a small watershed on the Chinese Loess Plateau.

Preparation of Poly(acrylic acid-acrylamide/starch) Composite and Its Adsorption Properties for Mercury (II).

The poly(acrylic acid-acrylamide/starch) composite was synthesized by solution polymerization, aiming to adsorb mercury (II) in water. The resulted copolymer was characterized by particle size exclusion chromatography (SEC), Fourier transform infrared spectroscopy (FTIR), thermogravimetry (TG), scanning electron microscopy (SEM) and dynamic light scattering particle size analyzer (DLS). It turned out that starch was successfully incorporated with the macromolecular polymer matrix and played a key role for improving the performance of the composites. These characterization results showed that the graft copolymer exhibited narrow molecular weight distribution, rough but uniform morphology, good thermal stability and narrow particle size distribution. The graft copolymer was used to remove Hg(II) ions from aqueous solution. The effects of contact time, pH value, initial mercury (II) concentration and temperature on the adsorption capacity of Hg(II) ions were researched. It was found that after 120 min of interaction, poly(acrylic acid-acrylamide/starch) composite achieved the maximum adsorption capacity of 19.23 mg·g-1 to Hg(II) ions with initial concentration of 15 mg·L-1, pH of 5.5 at 45 °C. Compared with other studies with the same purpose, the composites synthesized in this study present high adsorption properties for Hg(II) ion in dilute solution. The adsorption kinetics of Hg(II) on the poly(acrylic acid-acrylamide/starch) composite fits well with the pseudo second order model.

Porphyrin-Based Covalent Organic Framework Thin Films as Cathodic Materials for "On-Off-On" Photoelectrochemical Sensing of Lead Ions.

Currently, cathodic photoelectrochemical (PEC) sensors, which could effectively reduce background interference, are urgently required for ultrasensitive environmental monitoring. Herein, porphyrin-based covalent organic framework (TAPP-COF) thin films were fabricated via a bottom-up growth approach on the liquid/liquid interface and applied as a photocathode material to "on-off-on" PEC sensing of Pb2+. Benefitting from the unique charge channels of COFs and the good photoelectric properties of porphyrin, the as-prepared TAPP-COF thin films presented an improved photocathodic current, with a strongly enhanced "signal-on" response with low background. Then, CdSe@SiO2 quantum dots (QDs), as a quenching agent, were introduced through a hybridization chain reaction (HCR) to obtain a "signal off" PEC response. Afterward, with the introduction of target Pb2+, CdSe@SiO2 QDs were detached from TAPP-COF thin films, and the PEC response transformed into a signal-on state. Benefiting from the multiple-quenching and steric hindrance effect of CdSe@SiO2 QDs and the photocathodic property of TAPP-COFs, accurate monitoring of Pb2+ in a wide detection range from 0.05 to 1000 nM with a lower detection limit of 0.012 nM was realized based on the proposed on-off-on PEC approach. Notably, the methodology provides an efficient platform for ultrasensitive determination of heavy metal ions, which would play a significant role in environmental monitoring and public safety fields.

Self-Circulation Oxygen-Hydrogen Peroxide-Oxygen System for Ultrasensitive Cathode Photoelectrochemical Bioassay Using a Stacked Sealed Paper Device.

In this work, a self-circulation oxygen-hydrogen peroxide-oxygen (O2-H2O2-O2) system with photogenerated electrons as fuel and highly active hemin monomers as operators was engineered for ultrasensitive cathode photoelectrochemical bioassay of microRNA-141 (miRNA-141) using a stacked sealed paper device. During the circulation, the photogenerated electrons from BiVO4/Cu2O photosensitive structures assembled on a reduced graphene oxide paper electrode first reduced the electron acceptors (dissolved O2) to H2O2, which was then catalytically decomposed by hemin monomers to generate O2 again. The regenerated O2 continued to be reduced, which made O2 and H2O2 stuck in the infinite loop of O2-H2O2-O2 accompanied by the fast consumption of photogenerated electrons, generating an amplified photocurrent signal. When a target existed, a duplex-specific nuclease-induced target recycling reaction with dual trigger DNA probes as the output was performed to initiate the assembly of bridge-like DNA nanostructures, which endowed the self-circulation system with dual destruction functions as follows. (i) Reduced fuel supply: the assembled DNA bridges acting as a negatively charged barrier prevented the photogenerated electrons from participating in the O2 reduction to H2O2. (ii) Incapacitation of operators: DNA bridging induced the dimerization of hemin monomers linked on the DNA hairpins to catalytically inactive hemin dimers, leading to the abortive regeneration of O2. These destruction functions resulted in the circulation interruption and a remarkably decreased photocurrent signal. Thus, the developed cathode photoelectrochemical biosensing platform achieved ultrasensitive miRNA-141 detection with a linear range of 0.25 fM to 1 nM and a detection limit of 83 aM, and it also exhibited high accuracy, selectivity, and practicability.

Silanization of a Metal-Polyphenol Coating onto Diverse Substrates as a Strategy for Controllable Wettability with Enhanced Performance to Resist Acid Corrosion.

Wettability is a crucial characteristic of materials that plays a vital role in surface engineering. Surface modification is the key to changing the wettability of materials, and a simple and universal modification approach is being extensively pursued by researchers. Recently, metal-phenolic networks (MPNs) have been widely studied because they impart versatility and functionality in surface modification. However, an MPN is not stable for long periods, especially under acidic conditions, and is susceptible to pollution by invasive species. Spurred by the versatility of MPNs and various functionalities achieved by silanization, we introduce a general strategy to fabricate functionally stable coatings with controllable surface wettability by combining the two methods. The formation process of MPN and silane-MPN coatings was characterized by spectroscopic ellipsometry (SE), UV-visible-near-infrared (UV-vis-NIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), atomic force microscopy (AFM), water contact angle (WCA), etc. We found that the stability of the MPN was greatly enhanced after silanization, which is attributed to the cross-linking effect that occurs between silane and the MPN, namely, the cross-linking protection produced in this case. Additionally, the wettability of an MPN can be easily changed through our strategy. We trust that our strategy can further extend the applications of MPNs and points toward potential prospects in surface modification.

Medical Applications Based on Supramolecular Self-Assembled Materials From Tannic Acid.

Polyphenol, characterized by various phenolic rings in the chemical structure and an abundance in nature, can be extracted from vegetables, grains, chocolates, fruits, tea, legumes, and seeds, among other sources. Tannic acid (TA), a classical polyphenol with a specific chemical structure, has been widely used in biomedicine because of its outstanding biocompatibility and antibacterial and antioxidant properties. TA has tunable interactions with various materials that are widely distributed in the body, such as proteins, polysaccharides, and glycoproteins, through multimodes including hydrogen bonding, hydrophobic interactions, and charge interactions, assisting TA as important building blocks in the supramolecular self-assembled materials. This review summarizes the recent immense progress in supramolecular self-assembled materials using TA as building blocks to generate different materials such as hydrogels, nanoparticles/microparticles, hollow capsules, and coating films, with enormous potential medical applications including drug delivery, tumor diagnosis and treatment, bone tissue engineering, biofunctional membrane material, and the treatment of certain diseases. Furthermore, we discuss the challenges and developmental prospects of supramolecular self-assembly nanomaterials based on TA.

Density-Adjustable Bio-Based Polysulfide Composite Prepared by Inverse Vulcanization and Bio-Based Fillers.

Excess sulfur has become a global problem in petrochemical industry. Inexpensive and easily available cottonseed oil (CSO) is still underutilized. To resolve these issues, bio-based polysulfide composites were prepared via inverse vulcanization of sulfur and CSO. The density of polysulfide composites was adjusted by fillers. The results showed that Elm and cattail as the fillers had no effects on the thermal properties and chemical structures of polysulfide composites. However, the morphologies of polysulfide composites were significantly influenced by the fillers. Different types and amounts of fillers produced significantly different holes and folds in the composites. The fillers were embedded in polysulfide composites by physical filling. This study provides an alternative and promising approach for preparing affordable density-adjustable bio-based polysulfide composite.

Effective oxidative degradation of coal gasification wastewater by ozonation: A process study.

Coal gasification wastewater (CGW) has attracted considerable industrial attention because of its high toxicity and poor biodegradability. Ozonation is a promising process for CGW treatment. In this study, the effects of ozone concentration, pH, and ozonation time on CGW treatment were investigated. The results confirmed that CGW was degraded effectively and that the chemical oxygen demand (COD) was reduced from 1057 to 362 mgL-1, utilizing 50 mgL-1 ozone for 90 min. Further, the color of CGW changed from brown to clear and colorless, and the pH decreased from 8.5 to 4.7. Importantly, molds were observed in the oxidized CGW after 14 d at room temperature (23 ± 2 °C), indicating that CGW is significantly biodegradable by ozonation. The CGW components were extracted with three different organic solvents (chloroform, n-hexane, and benzene), and their compositions were analyzed by gas chromatography-mass spectrometry (GC-MS) before and after ozonation. The results proved that considerable amounts of highly toxic refractory compounds in CGW, such as phenolic compounds, polynuclear aromatic hydrocarbons (PAHs), and nitrogenous heterocyclic compounds (NHCs), were degraded to compounds that included olefins, carboxylic acids, and cycloalkanes, or minerals, which are relatively environmentally benign. Moreover, the number of substances in CGW decreased significantly from 127 to 74 after ozonation. Summarily, ozonation is a promising approach for the treatment of highly toxic refractory wastewater, such as CGW.

Preparation and Modification of Biomass-Based Functional Rubbers for Removing Mercury(II) from Aqueous Solution.

Biomass-based functional rubber adsorbents were designed and prepared via inverse vulcanization and post-modification. The plant rubber was synthesized with sulfur and renewable cottonseed oil as well as various micromolecular modifiers with nitrogen-containing functional groups. Results showed that types of nitrogen-containing functional groups and dosages of modifiers had a significant impact on the adsorption capacities of the resulting polymers for Hg2+. Notably, when the mass ratio of 2-aminoethyl methacrylate (AEMA) to sulfur was 0.05, the resulting polymer polysulfide-co-cottonseed oil modified by AEMA (SCOA2) showed the highest adsorption capacity (343.3 mg g-1) among all the prepared samples. Furthermore, the Hg2+ removal efficiency of SCOA2 remained over 80% of its original value after five adsorption-desorption cycles. It demonstrated a promising case for utilizing cheap industrial by-products (sulfur) and renewable materials (cottonseed oil). The prepared functional rubber provides alternative approach for mercury removal in waste utilization and sustainable chemistry.

Improved Ozonation Efficiency for Polymerization Mother Liquid from Polyvinyl Chloride Production Using Tandem Reactors.

Polymerization mother liquid (PML) is one of the main sources of wastewater in the chlor-alkali industry. The effective degradation of the PML produced in PVC polymerization using three or five ozone reactors in tandem was designed with a focus on improving the ozonation efficiency. The ozonation efficiency of the tandem reactors for the degradation of PML, along with the effect of ozone concentration, the number of reactors utilized in series, and the reaction time on the chemical oxygen demand (COD) removal were investigated in detail. The results showed that the COD removal increased as the ozone concentration was increased from 10.6 to 60 mg·L-1, achieving 66.4% COD removal at ozone concentration of 80.6 mg·L-1. However, when the ozone concentration was increased from 60 mg·L-1 to 80 mg·L-1, the COD removal only increased very little. The COD decreased with increasing ozone concentration. During the initial degradation period, the degradation rate was the highest at both low and high ozone concentrations. The degradation rate decreased with reaction time. The rate at a low ozone concentration decreased more significantly than at high ozone concentration. Although high ozone concentration is desirable for COD removal and degradation rate, the utilization efficiency of ozone decreased with increasing ozone concentration. The ozone utilization efficiency of the five-reactor device was three times higher than that of three tandem reactors, demonstrating that ozonation utilization efficiency can be improved by increasing the number of tandem reactors. Ozonation in tandem reactors is a promising approach for PML treatment.

Investigating Stability and Tautomerization of Gossypol-A Spectroscopy Study.

The stability of gossypol was investigated by the spectroscopic method. Gossypol was dissolved in three different solvents (CHCl3, DMSO, and CH3OH) under different storage conditions (dark and with nitrogen protection, natural light and with nitrogen protection, ambient air conditions) for different time intervals (0 days, 3 days, 5 days, 7 days, 15 days, 30 days, and 45 days) at room temperature. Then, the stability of gossypol was investigated by ¹H NMR, UV-vis, and HPLC-QTOF-MS spectrometry. Results showed that gossypol existed in aldehyde-aldehyde form in chloroform within five days. Then, both aldehyde-aldehyde and lactol-lactol tautomeric forms existed and maintained a stable solution for 45 days. Gossypol dissolved in methanol mainly existed in aldehyde-aldehyde form. Only a tiny amount of lactol-lactol was found in freshly prepared methanol solution. Gossypol was found to only exist in lactol-lactol form between 30-45 days. Gossypol existed in aldehyde-aldehyde, lactol-lactol, and ketol-ketol forms in dimethyl sulfoxide, and there was a competitive relationship between aldehyde-aldehyde and lactol-lactol form during the 45 days. Among all the solvents and conditions studied, gossypol was found to be highly stable in chloroform. Under the tested conditions, the natural light and atmospheric oxygen had little effect on its stability. Although the spectroscopy data seemed to be changed over time in the three different solvents, it was actually due to the tautomeric transformation rather than molecular decomposition.

Molecularly Imprinted Polymers for Gossypol via Sol⁻Gel, Bulk, and Surface Layer Imprinting-A Comparative Study.

Three gossypol molecularly imprinted polymers (MIPs) were prepared by bulk polymerization (MIP1), surface layer imprinting using silica gel as the support (MIP2), and the sol-gel process (MIP3). The as-prepared MIPs were characterized by SEM and nitrogen adsorption-desorption techniques to study the morphology structure. The adsorption experiments exhibited that MIP1 had adsorption capacity as high as 564 mg·g-1. The MIP2 showed faster adsorption kinetics than MIP1 and MIP3. The adsorption equilibrium could be reached for gossypol in 40 min. A selectivity study showed that the adsorption capacity of MIPs for gossypol was about 1.9 times higher than that of the structurally-similar analogs ellagic acid and 6.6 times higher than that of the quercetin. It was found that the pseudo-second-order kinetic model and the Freundlich isotherm model were more applicable for the adsorption kinetics and adsorption isotherm of gossypol binding onto the MIP1 and MIP2, respectively. Results suggested that among those three, the MIP2 was a desirable sorbent for rapid adsorption and MIP1 was suitable for selective recognition of gossypol.

Preparation and Applications of Salt-Resistant Superabsorbent Poly (Acrylic Acid-Acrylamide/Fly Ash) Composite.

Solution polymerization synthesized alt-resistant superabsorbent poly (acrylic acid-acrylamide/fly ash) composites. The mass ratio of acrylic acid (AA) to acrylamide (AM), the concentration of crosslinker, the neutralization degree (ND) of AA, and the polymerization temperature were investigated by single-factor method. Optimized conditions for the synthesis of poly (acrylic acid-acrylamide/fly ash) (PAA-AM/FA) are, as following: m (AA)/m (AM) is 1.5, the content of crosslinker N, N-methylenebisacrylamide. (MBA) is 0.7%, neutralization degree of AA is 70%, polymerization temperature is 70 °C, and fly ash (FA) content is 50%. The prepared PAA-AM/FA demonstrated superior water absorption performance. The absorption capacities of PAA-AM/FA for pure water and 0.9% NaCl solution were found to be 976 g·g-1 and 81 g·g-1, respectively. Furthermore, PAA-AM/FA was found to have excellent adsorption capacity (148 mg·g-1) for Rhodamine B in water. Fourier Transform-Infrared Spectroscopy (FT-IR), Thermogravimetric Analysis (TGA), and Scanning Electron Microscopy (SEM) characterized the prepared materials. Results showed that fly ash was incorporated into the macromolecular polymer matrix and played a key role in improving the performance of the polymer composites.

Design and synthesis of supramolecular functional monomers bearing urea and norbornene motifs.

Three sets of functional monomers namely urea-based, 2-ureido-4[1H]-primidone (UPy)-based and norbornene based functional monomers were designed and synthesized. These functional monomers (FM) were obtained in decent yields using amine and isocyanate/norbornene as starting materials. Methacrylate and styrene isocyanate with 1,4-diaminobutane/tris(2-aminoethyl)amine were chosen for the synthesis of symmetrical, asymmetrical and three-branched urea-functional monomers, respectively. UPy-based FMs were synthesized with isocyanate and 2-amino-4-hydroxy-6-methylpyrimidine. The synthesis of these monomers feature short reaction times, mild reaction conditions and no need for column chromatographic purification. Furthermore, the norbornene based FM was used for preparing molecularly imprinted polymers (MIPs) by Ring-Opening Metathesis Polymerization (ROMP). Results showed that these synthetic routes represent a convenient and useful approach for synthesis of novel functional monomers.

Influence of Size and Shape of Silica Supports on the Sol⁻Gel Surface Molecularly Imprinted Polymers for Selective Adsorption of Gossypol.

The influence of various silica gel supports with different shapes and sizes on the recognition properties of surface molecular imprinted polymers (MIPs) was investigated. MIPs for selective recognition and adsorption of gossypol were synthesized via the sol⁻gel process with a surface imprinting technique on silica gel substrates. 3-aminopropyltriethoxysilane (APTES) and tetraethoxysilane (TEOS) were chosen as the functional monomer and the cross-linker. The morphology and structure of the gossypol-MIPs were characterized using Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and a standard Brunauer⁻Emett⁻Teller (BET) analysis. Results indicated that the surface imprinted polymer layer facilitated the removal and rebinding of the template, and thus, achieved fast binding kinetics. Compared with the MIPs prepared on irregularly shaped silica with a broad particle size distribution, the MIPs using regularly-shaped silica of uniform size showed higher imprinting factor (IF), and the MIP made with a relatively larger sized (60 μm) spherical silica, demonstrated higher adsorption capacity compared to the MIPs made with smaller sized, spherical silica. The MIP prepared with 60 μm spherically shaped silica, featured a fast adsorption kinetic of 10 min, and a saturated adsorption capacity of 204 mg·g−1. The gossypol-MIP had higher selectivity (IF = 2.20) for gossypol over its structurally-similar analogs ellagic acid (IF = 1.13) and quercetin (IF = 1.20). The adsorption data of the MIP correlated well with the pseudo-second-order kinetic model and the Freundlich isotherm model, which implied that chemical adsorption dominated, and that multilayer adsorption occurred. Furthermore, the MIP exhibited an excellent regeneration performance, and the adsorption capacity of the MIP for gossypol only decreased by 6% after six reused cycles, indicating good application potential for selective adsorption of gossypol.