Engineered and Durable Antimicrobial Polymer via Controllable Immobilization of Ionic Liquids onto the Poly(lactic acid) Chains.

Nowadays, the development of effective modification methods for PLA has gained significant interest because of the wide application of antimicrobial PLA materials in the medical progress. Herein, the ionic liquid (IL) 1-vinyl-3-butylimidazolium bis(trifluoromethylsulfonyl)imide, has been grafted onto the PLA chains successfully in the PLA/IL blending films via electron beam (EB) radiation for the miscibility between PLA and IL. It was found that the existence of IL in the PLA matrix can significantly improve the chemical stability under EB radiation. The Mn of PLA-g-IL copolymer did not change obviously but was just decreased from 6.80 × 104 g/mol to 5.20 × 104 g/mol after radiation with 10 kGy. The obtained PLA-g-IL copolymers showed excellent filament forming property during electrospinning process. The spindle structure on the nanofibers can be completely eliminated after feeding only 0.5 wt % ILs for the improvement of ionic conductivity. Specially, the prepared PLA-g-IL nonwovens exhibited outstanding and durable antimicrobial activity for the enrichment of immobilized ILs on the nanofiber surface. This work provides a feasible strategy to realize the modification of functional ILs onto PLA chains with low EB radiation doses, which may have huge potential application in the medical and packaging industry.

Catalytic self-transfer hydrogenolysis of lignin with endogenous hydrogen: road to the carbon-neutral future.

Due to the depletion of fossil sources, it is imperative to develop a sustainable and carbon-neutral biorefinery for supporting the fuel and chemical supply in modern society. Lignin, the only renewable aromatic source, is still an underutilized component in lignocellulose. Very recently, it has been found that hydrogenolysis is a promising technology for lignin valorization. However, high-pressure H2 is necessary during lignin hydrogenolysis, resulting in safety problems. Furthermore, H2 is mainly produced from steam reforming of fossil sources in industry, which makes the conversion of renewable lignin unsustainable and costly. Plentiful aliphatic hydroxyl and methoxy groups exist in native lignin and offer a renewable alternative to H2, and can be hydrogen sources for the depolymerization and upgradation of lignin via the intramolecular catalytic transfer hydrogenation. The hydrogen source in situ generated from lignin is a type of green hydrogen, decreasing the carbon footprint. The purpose of this review is to provide a summary and perspective of lignin valorization via self-transfer hydrogenolysis, mainly focusing on a comprehensive understanding of the mechanism of catalytic self-transfer hydrogenolysis at the molecular level and developing highly effective catalytic systems. Moreover, some opportunities and challenges within this attractive field are given to discuss future research directions.

Conversion of control and genetically-modified poplar into multi-scale products using integrated pretreatments.

In this work, a green and robust pretreatment which integrated acetic acid-catalyzed hydrothermal and wet mechanical pretreatment, was developed to efficiently produce high yield (up to 40.12%) of xylooligosaccharides and digestible substrates from Caffeoyl Shikimate Esterase down-regulated and control poplar wood. Subsequently, superhigh yield (more than 95%) of glucose and residual lignin were obtained after a moderate enzymatic hydrolysis. The residual lignin fraction exhibited a well-preserved ß-O-4 linkages (42.06/100Ar) and high S/G ratio (6.42). Subsequently, lignin-derived porous carbon was successfully synthesized, and it exhibited a high specific capacitance of 273.8 F g-1 at 1.0 A g-1 and long cycling stability (remained 98.5% after 10,000 cycles at 5.0 A g-1) compared to control poplar wood, demonstrating that special advantage of this genetically-modified poplar in this integrated process. This work developed an energy-saving and eco-friendly pretreatment technology as a waste-free route for converting different lignocellulosic biomass to multiple products.

Biological and mechanical response of laser shock peening orthopaedic titanium alloy (Ti-6Al-7Nb).

This paper focuses on the evaluation of mechanical and biological properties of laser shock peening (LSP) orthopaedic grade Ti-6Al-7Nb alloy. LSP surface treatment was conducted at laser energy of 3 to 7 J with overlaps of 33%-67%, and with a 3 mm laser spot size. Cell viability on laser shock peened surface was evaluated through in-vitro MTT assay, using osteoblast-like MG63 cells for the first-time. Residual stresses, microhardness, microstructure, sliding wear and wetting properties were investigated. Compressive residual stresses were found at various depths due to controlling the LSP parameters, compared to the as-received surface. The laser shock peened surfaces were hardened from 365HV0.05 to 405HV0.05, while the as-received surface was 320HV0.05. The average sub-grain size was refined from 14% to 36% after LSP. The wear resistance was also controllable by altering LSP parameters. The MTT results show that the cell viability on the laser shock peened surfaces was comparatively lower than that of the untreated surface after 24 h. However, after 72 h, the cell viability on modified surfaces were significantly improved. This work indicated that laser shock peened surfaces have a strong potential to decrease the pain from orthopaedic implant failures and promote the cytocompatibility between the bone and implant.

Unveiling the Migration and Transformation Mechanism of Lignin in Eucalyptus During Deep Eutectic Solvent Pretreatment.

Deep eutectic solvents (DESs) have unique advantages in biomass conversion. However, the migration and transformation mechanism of lignin in the cell wall during the DES pretreatment is still elusive. In this work, Eucalyptus blocks were pretreated in choline chloride/lactic acid DES to reveal the lignin migration. Meanwhile, the remaining lignin in the pretreated residue, the regenerated DES lignin, and the solubilized degraded lignin in the recovered DES were investigated to decipher the lignin transformation. Results showed that the DES pretreatment resulted in the penetration of DES from the cell lumen to the cell wall, and lignin in the secondary wall was more easily dissolved than that in the cell corner middle lamella. The syringyl unit of lignin was better stabilized in the DES than the guaiacyl unit of lignin. The condensed lignin fraction mainly remained in the pretreated residue, while the solubilized degraded lignin fraction was monomeric aromatic ketone compounds. This study elucidates the fate of lignin during the DES pretreatment, which could also promote the development of a modern lignocellulosic pretreatment technique.

Recent advances in lignocellulose prior-fractionation for biomaterials, biochemicals, and bioenergy.

Due to over-consumption of fossil resources and environmental problems, lignocellulosic biomass as the most abundant and renewable materials is considered as the best candidate to produce biomaterials, biochemicals, and bioenergy, which is of strategic significance and meets the theme of Green Chemistry. Highly efficient and green fractionation of lignocellulose components significantly boosts the high-value utilization of lignocellulose and the biorefinery development. However, heterogeneity of lignocellulosic structure severely limited the lignocellulose fractionation. This paper offers the summary and perspective of the extensive investigation that aims to give insight into the lignocellulose prior-fractionation. Based on the role and structure of lignocellulose component in the plant cell wall, lignocellulose prior-fractionation can be divided into cellulose-first strategy, hemicelluloses-first strategy, and lignin-first strategy, which realizes the selective dissociation and transformation of a component in lignocellulose. Ultimately, the challenges and opportunities of lignocellulose prior-fractionation are proposed on account of the existing problems in the biorefining valorization.

Enhanced cellular osteogenic differentiation on CoFe2O4/P(VDF-TrFE) nanocomposite coatings under static magnetic field.

Cellular responses can be regulated and manipulated through combining stimuli-responsive biomaterial with external stimulus. In this present, the magneto-responsive CoFe2O4/P(VDF-TrFE) nanocomposite coatings were designed to understand cell behaviors of preosteoblasts, as well as get insight into the underlying mechanism of osteogenic differentiation under static magnetic field (SMF). CoFe2O4/P(VDF-TrFE) nanocomposite coatings with differential magnetic property (low, medium and high magnetization) were prepared by incorporation of different mass fraction of CoFe2O4 nanoparticles (6%, 13 %, 20 %) into P(VDF-TrFE) matrix. Cell experiments indicated that all nanocomposite coatings with the assistance of SMF could promote the cell attachment, proliferation and osteogenic differentiation of MC3T3-E1 cells. Among different nanocomposite coatings, low magnetization coating (6%) showed a higher ALP activity and gene expression of Runx2, Col-I, OCN. Molecular biology assays demonstrated that the combination of nanocomposite coatings and SMF could significantly up-regulate the expression level of α2ß1 integrin and p-ERK. Whereas, the addition of inhibitor U0126 down-regulated sharply the expression level of p-ERK, which indicated that cellular osteogenic differentiation of MC3T3-E1 cells was governed through α2ß1 integrin-mediated MEK/ERK signaling pathways during CoFe2O4/P(VDF-TrFE) nanocomposite coatings were combined with SMF. This work provided a promising strategy to enhance cellular osteogenic differentiation through a remote-control manner, which exhibited great potential in the application of bone tissue repair and regeneration.

Novel recyclable deep eutectic solvent boost biomass pretreatment for enzymatic hydrolysis.

Deep eutectic solvent (DES) with protonic acid shows the great potential for biomass valorization. However, the acid corrosion and recycling are still severe challenges in biorefinery. Herein, a novel DES by coordinating FeCl3 in choline chloride/glycerol DES was designed for effective and recyclable pretreatment. As compared to DESs with FeCl2, ZnCl2, AlCl3 and CuCl2, DES with FeCl3 approvingly retained most of cellulose in pretreated Hybrid Pennisetum (95.2%). Meanwhile, the cellulose saccharification significantly increased to 99.5%, which was six-fold higher than that of raw biomass. The excellent pretreatment performance was mainly attributed to the high removal of lignin (78.88 wt%) and hemicelluloses (93.63 wt%) under the synergistic effect of Lewis acid and proper hydrogen-bond interaction of DES with FeCl3. Furthermore, almost all cellulose still can be converted into glucose after five recycling process. Overall, the process demonstrated designed pretreatment was great potential for the low-cost biorefinery and boost the biofuel development.

Lignocellulose fractionation into furfural and glucose by AlCl3-catalyzed DES/MIBK biphasic pretreatment.

Herein, an efficient DES/MIBK biphasic pretreatment system for preparation of furfural and fermentable glucose from lignocellulose was developed with AlCl3 as catalysis. The low-cost and renewable DES (Choline chloride-Oxalic acid) served not only as a Brønsted acid catalyst, but also as a pretreatment solvent in present work, and MIBK as an extracting reagent which can increase the yield of furfural in DES phase. The effects of this biphasic pretreatment on the furfural yield and saccharification of the lignocellulose before and after pretreatment were explored using HPLC, HAPEC, FT-IR, XRD and SEM. Under the best pretreatment condition (at 140 °C for 90 min), furfural could be obtained in 70.3% yield and 80.8% of the pretreated lignocellulose was saccharified, which was 8.4 times higher than that of the raw lignocellulose without pretreatment. In a word, this pretreatment system can be considered as a potential technique for efficient valorization of lignocellulose for production of furfural and fermentable glucose.

Evaluation of organosolv pretreatment on the structural characteristics of lignin polymers and follow-up enzymatic hydrolysis of the substrates from Eucalyptus wood.

In the present study, Eucalyptus was subjected to organosolv pretreatment processes with aqueous 2-propanol at 200-220°C to obtain lignin with benign characters for its valorization and digestible substrates for bioethanol production. Results showed that different delignification ratios (64.00%-81.26%) and molecular weights (Mw=610-2680g/mol) of lignin fractions were dissociated from various pretreatment conditions, and the glucose yields of all the pretreated substrates significantly increased to 54.65-88.59% as compared to that of raw material (9.20%). Additionally, the amounts of ß-O-4, ß-ß, and ß-5 substructures were regularly decreased with the increased temperature and time. By contrast, the structural characteristics of the lignin fractions obtained with 70% 2-PrOH/water were less-altered than those with 50% 2-PrOH/water pretreatment. Remarkably, lignin with the lowest molecular weight (Mw=610g/mol) and less-altered chemical structure was achieved at 200°C for 120min, which is beneficial to subsequent catalytic degradation of lignin.

Effects of aluminum chloride-catalyzed hydrothermal pretreatment on the structural characteristics of lignin and enzymatic hydrolysis.

In this study, Eucalyptus camaldulensis was pretreated with 0.02 M aluminum chloride (AlCl3) at 140-180 °C to obtain digestible substrates for glucose and lignin. The effects of AlCl3-catalyzed hydrothermal pretreatment on the degradation of carbohydrates, structural changes of lignin, crystallinity, morphologic changes, and cellulose conversion of the pretreated biomass have been investigated by HAPEC, HPLC, FT-IR, XRD, CP/MAS NMR, SEM, and 2D-HSQC NMR. Results showed that the pretreatment significantly removed hemicelluloses and cleaved ß-O-4 linkages of lignin at high temperatures. Under an optimum condition (at 170 °C for 1 h), almost all of hemicelluloses were removed and most of ß-O-4 linkages in lignin were cleaved, and 77.8% cellulose conversion of the pretreated biomass was achieved, which was 7.3-fold higher than that of the original biomass. In short, this process was regarded as a promising approach to achieve an efficient conversion of lignocellulosic biomass to fermentable glucose and residual lignin.

[Real-time irrigation forecast of cotton mulched with plastic film under drip irrigation based on meteorological date].

It is important to improve the real-time irrigation forecasting precision by predicting real-time water consumption of cotton mulched with plastic film under drip irrigation based on meteorological data and cotton growth status. The model parameters for calculating ET0 based on Hargreaves formula were determined using historical meteorological data from 1953 to 2008 in Shihezi reclamation area. According to the field experimental data of growing season in 2009-2010, the model of computing crop coefficient Kc was established based on accumulated temperature. On the basis of crop water requirement (ET0) and Kc, a real-time irrigation forecast model was finally constructed, and it was verified by the field experimental data in 2011. The results showed that the forecast model had high forecasting precision, and the average absolute values of relative error between the predicted value and measured value were about 3.7%, 2.4% and 1.6% during seedling, squaring and blossom-boll forming stages, respectively. The forecast model could be used to modify the predicted values in time according to the real-time meteorological data and to guide the water management in local film-mulched cotton field under drip irrigation.