A Multiple Remotely Controlled Platform from Recyclable Polyurethane Composite Network with Shape-Memory Effect and Self-Healing Ability.

Stimuli-responsive materials can transform from temporary to permanent shapes by specific external triggers. However, the damage might inevitably occur to them when exposed to complex environments, causing a significant reduction in their lifetime and quality. In this study, recyclable remotely controlled shape-changing polyurethane composite with self-healing compacity is developed from polyethylene glycol, polytetrahydrofuran diol using isophorone diisocyanate as crosslinker. After the incorporation of magnetite nanoparticles (MNPs), remote heating could be generated by near-infrared irradiation and alternating magnetic fields. The results show that MNPs are uniformly distributed in the smart networks, resulting in tunable temperature changes of the polymer composite material under various direct/indirect triggering in bending experiments, presenting different shape recovery rates. Moreover, to enhance the self-healing capability, a disulfide bond is introduced into the polymer networks, and the results show that highly efficient and rapid healing could be achieved from tensile tests, scanning electron microscopy as well as optical microscopy. Additionally, the synergistic effect of transesterification and the dynamic exchange of disulfide bonds brin the networks reproducibility for recycling use. The obtained material is promising to be an alternative material for soft robots and smart sensors.

Shape Memory Polyester Scaffold Promotes Bone Defect Repair through Enhanced Osteogenic Ability and Mechanical Stability.

Bone tissue engineering involving scaffolds is recognized as the ideal approach for bone defect repair. However, scaffold materials exhibit several limitations, such as low bioactivity, less osseointegration, and poor processability, for developing bone tissue engineering. Herein, a bioactive and shape memory bone scaffold was fabricated using the biodegradable polyester copolymer's four-dimensional fused deposition modeling. The poly(ε-caprolactone) segment with a transition temperature near body temperature was selected as the molecular switch to realize the shape memory effect. Another copolymer segment, i.e., poly(propylene fumarate), was introduced for post-cross-linking and improving the regulation effect of the resulting bioadaptable scaffold on osteogenesis. To mimic the porous structures and mechanical properties of the native spongy bone, the pore size of the printed scaffold was set as ∼300 µm, and a comparable compression modulus was achieved after photo-cross-linking. Compared with the pristine poly(ε-caprolactone), the scaffold made from fumarate-functionalized copolymer considerably enhanced the adhesion and osteogenic differentiation of MC3T3-E1 cells in vitro. In vivo experiments indicated that the bioactive shape memory scaffold could quickly adapt to the defect geometry during implantation via shape change, and bone regeneration at the defect site was remarkably promoted, providing a promising strategy to treat bone defects in the clinic, substantial bone defects with irregular geometry.

4D Printing of Biocompatible Scaffolds via In Situ Photo-crosslinking from Shape Memory Copolyesters.

The complexity of surgical treatments for large-area soft tissue injuries makes placing large implants into injury sites challenging. Aliphatic polyesters are often used for scaffold preparation in tissue engineering owing to their excellent biodegradability and biocompatibility. Scaffolds with shape-memory effect (SME) can also avoid large-volume trauma during the implantation. However, the complexity and diversity of diseases require more adaptable and precise processing methods. Four-dimensional (4D) printing, a booming smart material additive manufacturing technology, provides a new opportunity for developing shape memory scaffolds. With the aim of personalized or patient-adaptable soft tissues such as blood vessels, we developed a feasible strategy for fabricating scaffolds with fine architectures using 4D printing crosslinkable shape memory linear copolyesters using fused deposition modeling (FDM). To overcome the weak bonding strength of each printed layer during FDM, a catalyst-free photo-crosslinkable functional group derived from biocompatible cinnamic acid was embedded into the linear copolyesters as in situ crosslinking points during FDM printing. Under ultraviolet-assisted irradiation, the resulting 4D scaffold models demonstrated excellent SME, desirable mechanical performance, and good stability in a water environment owing to the chemical bonding between each layer. Moreover, the excellent biocompatibility of the scaffold was evaluated in vitro and in vivo. The developed composite scaffolds could be used for minimally invasive soft tissue repair.

Chemistry-Informed Neural Networks modelling of lignocellulosic biomass pyrolysis.

Biomass pyrolysis is a complicated reaction process that involves complex components and reaction pathways. Due to measurement limitations, the intermediate components are difficult to be detected, therefore their detailed kinetics are still not well established. To address this issue, novel Chemistry-Informed Neural Networks (CINNs) were developed to derive the lignocellulosic biomass pyrolysis kinetics from the thermogravimetric analysis (TGA) measurements in published literature. The derived pyrolysis kinetics, involving eight species and eleven reactions, could accurately reproduce the pyrolysis process for both the seen and unseen samples with R2>0.95. The comparisons with the CRECK multi-step and Bio-CPD models also demonstrated the advantages of the derived kinetics in predicting both the final volatiles yield and the pyrolysis process for various biomass types. This study explored a new tool for establishing solid fuel conversion kinetics from TGA measurements using chemistry-informed machine learning approaches.

Settleability and dewaterability of sewage sludge with modified diatomite.

In this study, cationic polyacrylamide (CPAM)-modified diatomite and cetyl trimethyl ammonium bromide (CTAB)-modified diatomite were synthesized and used as conditioners for sewage sludge dewatering. The effects of these two types of modified diatomite on the dewaterability and settling performance of the activated sludge were studied. The mechanisms of the two modified diatomite types in the activated sludge system were elucidated. The efficiency of the CPAM-modified diatomite was better than that of the CTAB-modified diatomite in improving the settleability and dewaterability of sludge. The results indicated that specific resistance to filtration (SRF) was decreased from 8.52 × 1012 to 0.92 × 1012 m/Kg, and the water content in the remaining sludge cake after pumping filtration was decreased from 92.2 to 68.1% by adding 0.4% of CPAM-modified diatomite and pH = 3.5, which resulted in excellent sludge settling of activated sludge. Further studies showed that the polymer/surfactant adsorbed in diatomite increased sludge dewaterability and improved the sedimentation rate owing to stripping extracellular polymeric substances (EPS) and damaging the internal structure of the sludge, leading to sludge conduce bound water release. According to scanning electron microscope (SEM) images, the two types of modified diatomite powder maintained the porous structure and showed a more complete and uniform structure compared to natural diatomite.

Synthesis and Characterization of g-C3N4/Ag3PO4/TiO2/PVDF Membrane with Remarkable Self-Cleaning Properties for Rhodamine B Removal.

g-C3N4/Ag3PO4/TiO2 nanocomposite materials were loaded onto a polyvinylidene fluoride (PVDF) membrane using a phase inversion method to obtain a photocatalytic flat membrane for dye removal. The morphology, structure, and photocatalytic activity of the g-C3N4/Ag3PO4/TiO2 nanoparticles and composite membrane were evaluated. The g-C3N4/Ag3PO4/TiO2/PVDF membrane exhibited superior morphology, hydrophilic properties, and antifouling performance compared with the raw PVDF membrane. Four-stage filtration was performed to evaluate the self-cleaning and antifouling capacity of the g-C3N4/Ag3PO4/TiO2/PVDF membrane. Upon irradiating the composite membrane with visible light for 30 min, its irreversible fouling resistance (Rir) was low (9%), and its flux recovery rate (FRR) was high (71.0%) after five filtration cycles. The removal rate of rhodamine B (RhB) from the composite membrane under visible light irradiation reached 98.1% owing to the high photocatalytic activity of the membrane, which was superior to that of raw PVDF membrane (42.5%). A mechanism of photocatalytic composite membranes for RhB degradation was proposed. Therefore, this study is expected to broaden prospects in the field of membrane filtration technology.

Effect of Sulfonation Group on Polyaniline Copolymer Scaffolds for Tissue Engineering with Laminin Treatment under Electrical Stimulation.

Sulfonated copolyanilines (SPANs), SPAN-40 and SPAN-75, were prepared and applied in this tissue engineering study. SPAN scaffolds (SPANs) and control group polyaniline (PANI) were synthesized by performing oxidative polymerization. To further research the effects of neuron regeneration, PC12 cells were cultured on as-prepared PANI and SPANs with laminin (La) treatment under electrical stimulation. The effects on PC12 cell differentiation were investigated by controlling the amount of sulfonated groups (-SO3H) in the SPAN chain, the electrical stimulation voltage, and the presence or absence of La coating. The adhesion and proliferation of cells increased with the degree of sulfonation; La and electrical stimulation further promoted neuronal cell differentiation as increased neurite length was demonstrated in the micrograph analyses. In summary, the sulfonated copolyaniline coated with La had the best effect on neuronal differentiation under electrical stimulation, suggesting its potential as a substrate for nerve tissue engineering.

The effects of polyethersulfone and Nylon 6 micromembrane filters on the pyraclostrobin detection: adsorption performance and mechanism.

Adsorption of test substances on micromembrane filters during sample pretreatment before qualitative and quantitative analysis has greatly affected the accuracy of the measurement. In the present study, it was found that the adsorption rate of pyraclostrobin reached 77.7-100% when water samples of pyraclostrobin (1 mL) were filtered with polyethersulfone (PES) and Nylon 6 filters. Therefore, the adsorption mechanisms were investigated from the kinetics, isotherms, and thermodynamics of the pyraclostrobin adsorption process, combined with attenuated total reflection-Fourier transform infrared (ATR-FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS) analysis. The results showed that PES accorded with second-order adsorption kinetics and Nylon 6 with first-order adsorption kinetics, and the correlation coefficient R2 was 0.98. The adsorption behavior of the two micromembranes followed the linear isothermal model, indicating that the adsorption process was through monolayer adsorption. Thermodynamic study showed that the adsorption of pyracoethyl on PES membrane was spontaneous endothermic, while that on Nylon 6 was spontaneous exothermic. The π-π electron-donor-acceptor (EDA) between pyraclostrobin and PES may promote the adsorption of PES to pyraclostrobin, and hydrogen bonding between pyraclostrobin and Nylon 6 micromembrane may be involved in the adsorption. Our study also proved that the adding 60% methanol and iodine solution (2 mmol/L) was an effective strategy to reduce the adsorption effects and to increase the accuracy of the detection.

Enhanced biomineralization of shape memory composite scaffolds from citrate functionalized amorphous calcium phosphate for bone repair.

Traditional shape memory polymers (SMPs) could avoid large volume trauma during implantation; however, for bone repair, scaffolds with high porosity and biomineralization are essential to promote bone regeneration. A novel porous composite scaffold with high biomineralization activity was developed by sequential gas foaming and a freeze-drying method. The results showed that the cross-linked block structure of the polymer matrix presented excellent shape memory properties, and osteogenesis was promoted by citrate functionalized amorphous calcium phosphate (CCACP). CCACP improved the mechanical strength of the scaffold, and the synergistic effect of CCACP and PEG promotes hydrophilicity and further promoted cell adhesion. Bending experiments indicated that the shape-memory effect of the scaffolds could be varied by varying the CCACP content. In addition, hydroxyapatite deposition was sped up as CCACP accelerated the mineralization of the scaffolds. Moreover, the result of the CCK-8 assessment suggested that composite scaffolds exhibited high biocompatibility, and the cells extended out abundant filopodia to adhere onto the scaffolds. In rat bone defect models, the obtained scaffolds promoted new bone formation compared to the control group. The developed composite scaffolds show potential for minimally invasive bone repair application.

Biomimetic scaffolds with programmable pore structures for minimum invasive bone repair.

Due to the complexity of surgery for large-area bone injuries, implanting a large volume of materials into the injury site remains a big challenge in orthopedics. To solve this difficulty, in this study, a series of biomimetic hydroxyapatite/shape-memory composite scaffolds were designed and synthesized with programmable pore structures, based on poly(ε-caprolactone) (PCL), polytetrahydrofuran (PTMG) and the osteoconductive hydroxyapatite (HA). The obtained scaffolds presented various pore structures, high connectivity, tunable mechanical properties, and excellent shape memory performance. Moreover, the mineralization activity of the developed scaffolds could enhance the formation of hydroxyapatite and they showed good biocompatibility in vitro. The in vivo experiments show that scaffolds could promote the formation of new bone in critical size cranial defects. The programmable porous scaffold biomaterials exhibited potential application promise in bone regeneration.

Estimating biomass major chemical constituents from ultimate analysis using a random forest model.

Chemical constituents are important properties for utilization of biomass, and experimental approaches are always expensive and time-consuming to determinate those properties. Here, a novel random forest (RF) model is developed for accurately predicting biomass major chemical constituents from the much-easier available ultimate analysis, and compared with the previous correlation as well as the experimental data. Two databases are constructed for training and application of the RF model from available literature. The training results show that the determination coefficients (R2) of the RF model predictions are 0.954, 0.933 and 0.968 for cellulose, hemicellulose and lignin, respectively. The application results show that the present RF model can give accurate predictions on chemical constituents for various biomasses with MAPE<20%, and R2 are 0.862, 0.904 and 0.962 for predictions of cellulose, hemicellulose and lignin, respectively. While the previous correlation only works for a narrow range used to develop the correlation, and gives unrealistic negative predictions with MAPE>500% for outside samples.

Biodegradable interpolyelectrolyte complexes based on methoxy poly(ethylene glycol)-b-poly(alpha,L-glutamic acid) and chitosan.

We synthesized methoxy poly(ethylene glycol)-b-poly(alpha,L-glutamic acid) (mPEGGA) diblock copolymer by ring-opening polymerization of N-carboxy anhydride of gamma-benzyl-L-glutamate (NCA) using amino-terminated methoxy polyethylene glycol (mPEG) as macroinitiator. Polyelectrolyte complexation between mPEGGA as neutral-block-polyanion and chitosan (CS) as polycation has been scrutinized in aqueous solution as well as in the solid state. Water-soluble polyelectrolyte complexes (PEC) can be formed only under nonstoichiometric condition while phase separation is observed when approaching 1:1 molar mixing ratio in spite of the existence of hydrophilic mPEG block. This is likely due to mismatch in chain length between polyanion block of the copolymer and the polycation or hydrogen bonding between the components. Hydrodynamic size of primary or soluble PEC is determined to be about 200 nm, which is larger than those reported in some literatures. The increase in polyion chain length of the copolymer leads to the increase in the hydrodynamic size of the water-soluble PEC. Formation of spherical micelles by the mPEGGA/CS complex at nonstoichiometirc condition has been confirmed by the scanning electron microscopy observation and transmission electron microscopy observations. The homopolymer CS experiences attractive interaction with both mPEGA and PGA blocks within the copolymer. Competition of hydrogen bonding and electrostatic force in the system or hydrophilic mPEG segments weakens the electrostatic interaction between the oppositely charged polyions. The existence of hydrogen bonding restrains the mobility of mPEG chains of the copolymer and completely prohibits crystallization of mPEG segments. In vitro culture of human fibroblasts indicates that mPEGGA/CS-based materials have potential in biomedical application, especially in tissue engineering.

Poly(2-acrylamido-2-methylpropane sulfonic acid) grafted magnetic chitosan microspheres: Preparation, characterization and dye adsorption.

A novel chitosan-based magnetic adsorbent [poly(2-acrylamido-2-methylpropane sulfonic acid) grafted magnetic chitosan microspheres, PMCMs] was successfully fabricated via free radical polymerization for effectively removing the cationic dye methylene blue (MB). The effects of initial solution pH (1.0-10.0), temperature (30-50°C), contact time (0-660min) and initial concentration (50-1600mg/L) were studied. The results indicated that the adsorption capacity increased with the increasing of initial solution pH and temperature. The adsorption kinetic and adsorption equilibrium data fitted closely to the pseudo-second-order kinetic model and Langmuir isotherm model respectively, confirming monolayer adsorption. The maximum adsorption capacity of PMCMs for MB at initial solution 9.0 were 1000, 1250 and 1428mg/g at 30, 40 and 50°C, respectively. Furthermore, the magnetic microspheres could be easily separated using a magnet and effectively regenerated after finishing the treatment process. Therefore, PMCMs are promising candidates for the removal of dye from wastewater.

The daily fluorine and arsenic intake for residents with different dietaries and fluorosis risk in coal-burning fluorosis area, Yunnan, Southwest China.

The daily fluorine (F)/arsenic (As) intake (DFI/DAsI) for residents at different ages with different dietaries and dietary changes was investigated to analyze the fluorosis risk in coal-burning fluorosis area in Yunnan, Southwest China. The DFI for residents with a dietary of roasted corn and roasted chili was 5.06, 9.60, and 14.38 mg for age groups 3-7, 8-15, and over 15 years, respectively. Over 90 % of DFI was from roasted foodstuffs. The DFI for residents of the same age group living on rice and roasted chili was 1.94, 3.50, and 4.95 mg, respectively, which were less than that for the former dietary type, and 65 % of DFI was from roasted chili. The main sources for their DFI are roasted foodstuffs. Both were higher than the dietaries with non-roasted foodstuffs and the recommended daily allowances (RDAs) for USA and China at different levels. The DAsI for all residents ranged from 25 to 135 µg, and at this level of DAsI, it would not influence human health. However, As pollution of roasted foodstuffs might have an important influence for the fluorosis. Residents are changing their staple food from roasted corn to rice, and especially, younger people are more focused on quality life. However, even if residents change their staple food, the habit of eating chili will not change, which also may cause them getting fluorosis. Developing economy, changing dietary types, and changing the habit of drying and keeping chili will help to reduce the fluorosis risk in coal-burning fluorosis area of Southwest China.

Effect of Calcium Ions on Dewaterability of Enzymatic-Enhanced Anaerobic Digestion Sludge.

Waste-activated sludge (WAS) solubilized remarkably after enzymatic-enhanced anaerobic digestion, but its dewaterability was deteriorated. In this study, a novel method was performed to improve the dewaterability of enzymatic-enhanced anaerobic digestion sludge by adding CaCl2 (0.01~1.00 g/g total sludge). The capillary suction time (CST), moisture content, and filtrate turbidity were employed to characterize the dewaterability of WAS, and the possible mechanisms involved were clarified. The results showed the dewaterability did not worsen when CaCl2 was added before sludge digestion, and the CST, moisture content, and filtrate turbidity were notably reduced with the increase of CaCl2 dosage. It also shown that calcium ions played an important role in the bioflocculation of digested sludge by neutralizing negative charges on the surface of sludge. In addition, soluble protein initially lowered a little and then observably improved with the addition of CaCl2, while soluble carbohydrate was reduced sharply first and then bounced back afterwards. The interactions between calcium ions and the biopolymer further enhanced the dewatering of sludge through bridging of colloidal particles together.

Post-anoxic denitrification via nitrite driven by PHB in feast-famine sequencing batch reactor.

Recently, it was found that excess phosphorus removal could be induced by aerobic/extended-idle regime. In this study, an anoxic period was introduced after the aeration to realize simultaneous nitrogen and phosphorus removal. The results demonstrated that stable partial nitrification could be achieved by controlling the aeration duration at 2.5h because it could not only obtain a desirable ammonia oxidation to nitrite but also avoid the extensive aeration converting nitrite to nitrate, and moreover, the accumulated poly-3-hydroxybutyrate still remain in a relative sufficient concentration (1.5mmolCg(-1) VSS), which could subsequently served as internal carbon source for post-anoxic denitrification. The nitrite accumulation ratio was observed to have relatively high correlation with biological nutrient removal. Over stages with stable high-level nitrite accumulation, the process achieved desirable and stable nitrogen and phosphorus removal efficiencies averaging 95% and 99% respectively. Fluorescence in situ hybridization analysis showed that the faster growth rate of the ammonia oxidizing bacteria than the nitrite oxidizing bacteria was the main reason for achieving nitrite accumulation. In addition, the secondary phosphorus release was negligible and the process maintained excellent nutrient removal under low influent ammonia nitrogen.

The pollution control of fluorine and arsenic in roasted corn in "coal-burning" fluorosis area Yunnan, China.

Pilot experiments were carried out to reduce the fluorine (F) and arsenic (As) pollution of roasted corn dried by open ovens in "coal-burning" fluorosis area Yunnan, China. The results indicated that the average emission amount of F and As in briquettes in experimental group were 29.20mg/kg and 0.76 mg/kg in Xiaolongdong, and 46.8 mg/kg and 0.54 mg/kg in Mangbu respectively. The results also indicated that the fixing rate of F and As in briquettes in experimental group was more than 4 times and 1.2 times of that in control group respectively. The average concentration of F and As in roasted corn in experimental group were 3.86 mg/kg and 13.23 µg/kg in Xiaolongdong, and 4.77 mg/kg and 122.96 µg/kg in Mangbu respectively, which reduced by more than 65% and 75% respectively compared with that in control group. Adding local natural calcium-based materials in briquettes can reduce the emission of F and As and their pollution on roasted corn largely, and thus will reduce the risk of fluorosis for residents greatly in "coal-burning" fluorosis area of southwestern China.

Coal-burning roasted corn and chili as the cause of dental fluorosis for children in southwestern China.

To find the pathologic cause of the children's dental fluorosis in southwestern China, diet structure before the age of 6 and prevalence rate of dental fluorosis (DF) of 405 children were investigated, and the fluorine and arsenic content of several materials were determined. The prevalence rate of DF of children living on roasted corn before the age of 6 is 100% with nearly 95% having the mild to severe DF; while that of children living on non-roasted corn or rice is less than 5% with all having very mild DF. The average fluorine and arsenic concentration are 20.26 mg/kg and 0.249 mg/kg in roasted corn, which are about 16 times and 35 times more than in non-roasted corn, respectively. The average fluorine concentration is 78 mg/kg in coal, 1116 mg/kg in binder clay and 313 mg/kg in briquette (coal mixed with clay). The average arsenic concentration of coal is 5.83 mg/kg, the binder clay is 20.94 mg/kg, with 8.52 mg/kg in the briquette. Living on roasted corn and chili is the main pathologic cause of endemic fluorosis in southwestern China. The main source of fluorine and arsenic pollution of roasted corn and chill is the briquette of coal and binder clay.

[Influence of extracellular polymeric substance on enzyme hydrolysis of sludge under anaerobic condition].

The effect of extracellular polymeric substance (EPS) on the enzymatic solubilisation of sludge and the changes of chemical components was investigated. Sludge solubilization with and without EPS was studied in the enzymatic system, and in the normal system without enzyme addition, respectively. The result indicated that only EPS could be hydrolyzed when the enzyme addition less than 20 mg/g, while the cell lysis occurred significantly with the doses of enzymes increasing. Treatment with lysozyme for the original sludge was proved to have a higher hydrolysis efficiency, and the SCOD/TCOD rate reached up to 28.14%. And at the enzyme dosage of 60 mg/g, the VSS removal rate increased to 51.66% and the concentration of DNA attained 68.34 mg/g (calculated by VSS) after 48 h reaction, which were 29.01% and 59.63 mg/g higher than the control test, respectively, and were 24.86% and 53.39 mg/g higher than that with EPS removed in advance, respectively. Meanwhile, NH4+ -N, PO4(3-)-P and SCOD showed high dissolution efficiency, and the maximal concentrations achieved to 503 mg/L, 78.9 mg/L and 3171 mg/L, respectively. After removal of extracellular polymers, higher lysis efficiency was also observed by protease and cellulose, by which VSS reduction rate reached to 49.95% and 39.85%, respectively. The concentration of DNA showed a correlation coefficient of more than 0.9 with the concentrations of SCOD, NH4+ -N and PO4(3-)-P. And the highest hydrolysis rate obtained in 6 hours, which was about 3 hours earlier than the control test. Moreover, under those condition, sludge hydrolyzation could be well realized by only small amount of the enzyme addition.

[Enhanced hydrolysis of excess sludge by external enzymes].

The effects of external enzymes to enhance excess sludge hydrolysis were investigated. Protease and alpha-amylase were added singly and in combination, and it was found that external enzymes can enhance sludge hydrolysis. When treated with single enzyme, alpha-amylase had higher efficiency than protease, SCOD/TCOD rose from 16.3% to 22.3% and VSS reduction improved from 39.8% to 54.24% at the optimal dosage of 60 mg/g (calculated by addition of enzyme in TS). Furthermore, mixture enzymes showed better hydrolysis efficiency than single enzyme. The highest VSS reduction was observed at an enzyme mixture ratio of 1:3 with protease and amylase when the hydrolysis temperature was 50 degrees C, and the VSS reduction achieved 68.43%. Correspondingly, the concentration of reducing sugar and NH4+ -N rose from 37.29, 47.60 mg/L to 177.8, 143.43 mg/L, respectively. According to the kinetic and enzymatic analysis of hydrolysis process, sludge hydrolysis within prior 4 h was consistent with first-order reaction dynamic. During the hydrolysis, both protease and amylase activity rose gradually, the highest activity observed were 2.57 U/mL and 4.64 U/mL at 4h after hydrolysis. Thereafter, the enzyme activity decreased.