Efficient degradation of lignin by chlorine dioxide and preparation of high purity pulp fiber.

High-purity pulp fibers can be obtained by using chlorine dioxide to oxidize lignin. However, organic halogen compounds (AOX) are generated from chlorination side reactions during the lignin oxidation process. In this study, phenolic lignin model compounds with different substituents were selected. The effects of substituent position on the production of free radicals and oxidative ring opening in benzene rings were analyzed. It was found that the structural transformation of lignin and the reaction consumption of ClO2 were significantly changed under high concentration of ClO2. The molar consumption ratio of compound to ClO2 was increased from 1:2 to 1:3. Quinone, an intermediate product that promotes the formation of phenoxy radicals, was found to be stabilized in the reaction. This is attributed to that the benzene ring of lignin is activated through long-range electrostatic interactions. The formation of free radicals and the oxidative ring-opening reaction of benzene rings were facilitated. The efficient oxidation of lignin by ClO2 was fulfilled. Chlorination reactions of lignin were suppressed at elevated oxidation efficiency. The pollution load of wastewater was significantly reduced. AOX generation was reduced by 69.27 %. This provides a new method for efficient oxidative degradation of lignin and preparation of high purity pulp fiber.

Effect of Substituents on Molecular Reactivity during Lignin Oxidation by Chlorine Dioxide: A Density Functional Theory Study.

Lignin is a polymer with a complex structure. It is widely present in lignocellulosic biomass, and it has a variety of functional group substituents and linkage forms. Especially during the oxidation reaction, the positioning effect of the different substituents of the benzene ring leads to differences in lignin reactivity. The position of the benzene ring branched chain with respect to methoxy is important. The study of the effect of benzene substituents on the oxidation reaction's activity is still an unfinished task. In this study, density functional theory (DFT) and the m062x/6-311+g (d) basis set were used. Differences in the processes of phenolic oxygen intermediates formed by phenolic lignin structures (with different substituents) with chlorine dioxide during the chlorine dioxide reaction were investigated. Six phenolic lignin model species with different structures were selected. Bond energies, electrostatic potentials, atomic charges, Fukui functions and double descriptors of lignin model substances and reaction energy barriers are compared. The effects of benzene ring branched chains and methoxy on the mechanism of chlorine dioxide oxidation of lignin were revealed systematically. The results showed that the substituents with shorter branched chains and strong electron-absorbing ability were more stable. Lignin is not easily susceptible to the effects of chlorine dioxide. The substituents with longer branched chains have a significant effect on the flow of electron clouds. The results demonstrate that chlorine dioxide can affect the electron arrangement around the molecule, which directly affects the electrophilic activity of the molecule. The electron-absorbing effect of methoxy leads to a low dissociation energy of the phenolic hydroxyl group. Electrophilic reagents are more likely to attack this reaction site. In addition, the stabilizing effect of methoxy on the molecular structure of lignin was also found.

Novel dual-action vanillic acid pretreatment for efficient hemicellulose separation with simultaneous inhibition of lignin condensation.

Aromatic acids play a selective role in the separation of hemicellulose. Phenolic acids have demonstrated an inhibitory effect on lignin condensation. In the current study, vanillic acid (VA), which combines the characteristics of aromatic and phenolic acids, is used to separate eucalyptus. The efficient and selective separation of hemicellulose is achieved simultaneously at 170 °C, 8.0% VA concentration, and 80 min. The separation yield of xylose increased from 78.80% to 88.59% compared to acetic acid (AA) pretreatment. The separation yield of lignin decreased from 19.32% to 11.19%. In particular, the ß-O-4 content of lignin increased by 5.78% after pretreatment. The results indicate that VA, as a "carbon positive ion scavenger", it preferentially reacts with the carbon-positive ion intermediate of lignin. Surprisingly, the inhibition of lignin condensation is achieved. This study provides a new starting point for the development of an efficient and sustainable commercial technology by organic acid pretreatment.

Simultaneous achievement of efficient hemicellulose separation and inhibition of lignin repolymerization using pyruvic acid treatment.

The efficiency of organic acid treatment in the conversion of lignocellulosic biomass fractions has been widely recognized. In this study, a novel green pyruvic acid (PA) treatment is proposed. The higher separation efficiency of eucalyptus hemicellulose was obtained at 4.0% PA and 150 °C. The hemicellulose separation yield was increased from 71.71 to 88.09% compared to glycolic acid (GA) treatment. In addition, the treatment time was significantly reduced from 180 to 40 min. The proportion of cellulose in the solid increased after PA treatment. However, the accompanying separation of lignin was not effectively controlled. Fortunately, a six-membered ring structure was formed on the diol structure of the lignin ß-O-4 side chain. Fewer lignin-condensed structures were observed. High-value lignin rich in phenol hydroxyl groups were obtained. It provides a green path for the simultaneous achievement of efficient hemicellulose separation and inhibition of lignin repolymerization using organic acid treatment.

Rapid and mild fractionation of hemicellulose through recyclable mandelic acid pretreatment.

The development of organic acid pretreatments from biological sources is essential to facilitate the progress of green and sustainable chemistry. In this study, the effectiveness of mandelic acid pretreatment (MAP) was analyzed for eucalyptus hemicellulose separation. 83.66% of xylose was separated under optimal conditions (temperature: 150 °C; concentration: 6.0 wt%; time: 80 min). The hemicellulose separation selectivity is higher than acetic acid pretreatment (AAP). The stable and effective separation efficiency (56.55%) is observed even after six reuses of the hydrolysate. Higher thermal stability, larger crystallinity index and optimized surface element distribution in the samples were demonstrated by MAP. Lignin condensation is effectively inhibited through MAP, as determined from the structural of different lignin. In particular, the demethoxylation of lignin by MA was found. These results open up a new way to construct a novel organic acid pretreatment for separating hemicellulose with high efficiency.

Pretreatment of poplar with eco-friendly levulinic acid to achieve efficient utilization of biomass.

Organic acid pretreatment is an effective method for green separation of lignocellulosic biomass. However, repolymerization of lignin seriously affects the dissolution of hemicellulose and the conversion of cellulose during organic acid pretreatment. Therefore, a new organic acid pretreatment, levulinic acid (Lev) pretreatment, was studied for the deconstruction of lignocellulosic biomass without adding additional additives. The preferred separation of hemicellulose was realized at Lev concentration 7.0%, temperature 170 °C, and time 100 min. The separation of hemicellulose increased from 58.38% to 82.05% compared with acetic acid pretreatment. It was found that the repolymerization of lignin was effectively inhibited in the efficient separation of hemicellulose. This was attributed to the fact that γ-valerolactone (GVL) is a good green scavenger of lignin fragments. The lignin fragments in the hydrolysate were effectively dissolved. The results provided theoretical support for creating green and efficient organic acid pretreatment and effectively inhibiting lignin repolymerization.

Ribosomal protein L22-like1 promotes prostate cancer progression by activating PI3K/Akt/mTOR signalling pathway.

Prostate cancer (PCa) is one of the most common malignancies in men. Ribosomal protein L22-like1 (RPL22L1), a component of the ribosomal 60 S subunit, is associated with cancer progression, but the role and potential mechanism of RPL22L1 in PCa remain unclear. The aim of this study was to investigate the role of RPL22L1 in PCa progression and the mechanisms involved. Bioinformatics and immunohistochemistry analysis showed that the expression of RPL22L1 was significantly higher in PCa tissues than in normal prostate tissues. The cell function analysis revealed that RPL22L1 significantly promoted the proliferation, migration and invasion of PCa cells. The data of xenograft tumour assay suggested that the low expression of RPL22L1 inhibited the growth and invasion of PCa cells in vivo. Mechanistically, the results of Western blot proved that RPL22L1 activated PI3K/Akt/mTOR pathway in PCa cells. Additionally, LY294002, an inhibitor of PI3K/Akt pathway, was used to block this pathway. The results showed that LY294002 remarkably abrogated the oncogenic effect of RPL22L1 on PCa cell proliferation and invasion. Taken together, our study demonstrated that RPL22L1 is a key gene in PCa progression and promotes PCa cell proliferation and invasion via PI3K/Akt/mTOR pathway, thus potentially providing a new target for PCa therapy.

Microcystin­leucine arginine promotes colorectal cancer cell proliferation by activating the PI3K/Akt/Wnt/ß­catenin pathway.

Microcystin­leucine arginine (MC­LR) is an environmental toxin produced by cyanobacteria and is considered to be a potent carcinogen. However, to the best of our knowledge, the effect of MC­LR on colorectal cancer (CRC) cell proliferation has never been studied. The aim of the present study was to investigate the effect of MC­LR on CRC cell proliferation and the underlying mechanisms. Firstly, a Cell Counting Kit­8 (CCK­8) assay was conducted to determine cell viability at different concentrations, and 50 nM MC­LR was chosen for further study. Subsequently, a longer CCK­8 assay and a cell colony formation assay showed that MC­LR promoted SW620 and HT29 cell proliferation. Furthermore, western blotting analysis showed that MC­LR significantly upregulated protein expression of PI3K, p­Akt (Ser473), p­GSK3ß (Ser9), ß­catenin, c­myc and cyclin D1, suggesting that MC­LR activated the PI3K/Akt and Wnt/ß­catenin pathways in SW620 and HT29 cells. Finally, the pathway inhibitors LY294002 and ICG001 were used to validate the role of the PI3K/Akt and Wnt/ß­catenin pathways in MC­LR­accelerated cell proliferation. The results revealed that MC­LR activated Wnt/ß­catenin through the PI3K/Akt pathway to promote cell proliferation. Taken together, these data showed that MC­LR promoted CRC cell proliferation by activating the PI3K/Akt/Wnt/ß­catenin pathway. The present study provided a novel insight into the toxicological mechanism of MC­LR.

Effects of the Preferential Oxidation of Phenolic Lignin Using Chlorine Dioxide on Pulp Bleaching Efficiency.

Chlorine dioxide is widely used for pulp bleaching because of its high delignification selectivity. However, efficient and clean chlorine dioxide bleaching is limited by the complexity of the lignin structure. Herein, the oxidation reactions of phenolic (vanillyl alcohol) and non-phenolic (veratryl alcohol) lignin model species were modulated using chlorine dioxide. The effects of chlorine dioxide concentration, reaction temperature, and reaction time on the consumption rate of the model species were also investigated. The optimal consumption rate for the phenolic species was obtained at a chlorine dioxide concentration of 30 mmol·L-1, a reaction temperature of 40 °C, and a reaction time of 10 min, resulting in the consumption of 96.3% of vanillyl alcohol. Its consumption remained essentially unchanged compared with that of traditional chlorine dioxide oxidation. However, the consumption rate of veratryl alcohol was significantly reduced from 78.0% to 17.3%. Additionally, the production of chlorobenzene via the chlorine dioxide oxidation of veratryl alcohol was inhibited. The structural changes in lignin before and after different treatments were analyzed. The overall structure of lignin remained stable during the optimization of the chlorine dioxide oxidation treatment. The signal intensities of several phenolic units were reduced. The effects of the selective oxidation of lignin by chlorine dioxide on the pulp properties were analyzed. Pulp viscosity significantly increased owing to the preferential oxidation of phenolic lignin by chlorine dioxide. The pollution load of bleached effluent was considerably reduced at similar pulp brightness levels. This study provides a new approach to chlorine dioxide bleaching. An efficient and clean bleaching process of the pulp was developed.

Application and prospect of organic acid pretreatment in lignocellulosic biomass separation: A review.

As a clean and efficient method of lignocellulosic biomass separation, organic acid pretreatment has attracted extensive research. Hemicellulose or lignin is selectively isolated and the cellulose structure is preserved. Effective fractionation of lignocellulosic biomass is achieved. The separation characteristics of hemicellulose or lignin by different organic acids were summarized. The organic acids of hemicellulose were separated into hydrogen ionized, autocatalytic and α-hydroxy acids according to the separation mechanism. The separation of lignin depends on the dissolution mechanism and spatial effect of organic acids. In addition, the challenges and prospects of organic acid pretreatment were analyzed. The separation of hemicellulose and enzymatic hydrolysis of cellulose were significantly affected by the polycondensation of lignin, which is effectively inhibited by the addition of green additives such as ketones or alcohols. Lignin separation was improved by developing a deep eutectic solvent treatment based on organic acid pretreatment. This work provides support for efficient cleaning of carbohydrate polymers and lignin to promote global carbon neutrality.

Efficient removal of residual lignin from eucalyptus pulp via high-concentration chlorine dioxide treatment and its effect on the properties of residual solids.

In fact, effectively removing lignin from pulp fibers facilitates the conversion and utilization of cellulose. In this study, the residual lignin in eucalyptus pulp was separated using a high concentration of chlorine dioxide. The effects of chlorine dioxide dosage, temperature, and time on lignin removal were investigated. The optimal conditions are chlorine dioxide dosage 5.0%, reaction temperature 40 °C, and reaction time 30 min. The lignin removal yield is 88.21%. The removal yields of cellulose and hemicellulose are 2.28 and 17.00%, respectively. The treated eucalyptus pulp has higher fiber crystallinity and thermal stability. The carbon content on the fiber surface is significantly reduced. The results show that lignin is removed by efficient oxidation, and the degradation of carbohydrates is inhibited using high concentrations of chlorine dioxide at low temperatures and short reaction times. This provides theoretical support for high value conversion of cellulose.

Microcystin-LR induced microfilament rearrangement and cell invasion by activating ERK/VASP/ezrin pathway in DU145 cells.

Microcystin-LR (MC-LR) is an environmental toxin that is synthesized by cyanobacteria and considered a potential human carcinogen. However, the role of MC-LR in prostate cancer progression has not been elucidated. The purpose of this study was to investigate the effect of MC-LR on prostate cancer cell invasion and its underlying mechanisms. Transwell assay was performed, and the result showed that MC-LR increased DU145 cell invasion in a concentration-dependent manner. The result of Western blot showed that MC-LR promoted ERK phosphorylation, while enhancing VASP and ezrin phosphorylation. Moreover, PD0325901 was used to verify the role of the ERK/VASP/ezrin axis in MC-LR-promoted cell invasion. The results revealed that MC-LR promoted microfilament rearrangement and cell invasion by activating the ERK/VASP/ezrin pathway in DU145 cells. Finally, in vivo assay was performed, and the result suggested that MC-LR promoted p-ERK, p-VASP and p-ezrin expression and local invasion in nude mice model. Taken together, our data proved that MC-LR induced microfilament rearrangement and cell invasion by activating the ERK/VASP/ezrin pathway in DU145 cells.

Efficient separation of bagasse lignin by freeze-thaw-assisted p-toluenesulfonic acid pretreatment.

Lignin separation is an important procedure that benefits multiple industries and in particular biomass transformation efforts. In this study, bagasse lignin was separated by freeze-thaw-assisted p-toluenesulfonic acid (p-TsOH) pretreatment. The optimal conditions were freezing temperature -60 °C, freezing time 8.0 h, thawing temperature 15 °C, p-TsOH concentration 60%, pretreatment temperature 70 °C, and time 20 min. Lower acid concentrations and temperatures were used compared with traditional p-TsOH pretreatment. The efficiency and selectivity of lignin separation were improved. It was attributed to freeze-thawing, which provided a more efficient physical channel for the effective penetration of p-TsOH. The separation, extraction and purity of lignin were improved to 89.76%, 78.22% and 77.89%, respectively. High separation, high extraction, high purity and large molecular weight lignin samples were obtained. In addition, the recovery and reuse of p-TsOH was enhanced. This provided a new method for the efficient and clean separation of lignin.

Sustainable Chitosan-Dialdehyde Cellulose Nanocrystal Film.

In this study, we incorporated 2,3-dialdehyde nanocrystalline cellulose (DANC) into chitosan as a reinforcing agent and manufactured biodegradable films with enhanced gas barrier properties. DANC generated via periodate oxidation of cellulose nanocrystal (CNC) was blended at various concentrations with chitosan, and bionanocomposite films were prepared via casting and characterized systematically. The results showed that DANC developed Schiff based bond with chitosan that improved its properties significantly. The addition of DANC dramatically improved the gas barrier performance of the composite film, with water vapor permeability (WVP) value decreasing from 62.94 g·mm·m-2·atm-1·day-1 to 27.97 g·mm·m-2·atm-1·day-1 and oxygen permeability (OP) value decreasing from 0.14 cm3·mm·m-2·day-1·atm-1 to 0.026 cm3·mm·m-2·day-1·atm-1. Meanwhile, the maximum decomposition temperature (Tdmax) of the film increased from 286 °C to 354 °C, and the tensile strength of the film was increased from 23.60 MPa to 41.12 MPa when incorporating 25 wt.% of DANC. In addition, the chitosan/DANC (75/25, wt/wt) films exhibited superior thermal stability, gas barrier, and mechanical strength compared to the chitosan/CNC (75/25, wt/wt) film. These results confirm that the DANC and chitosan induced films with improved gas barrier, mechanical, and thermal properties for possible use in film packaging.

Robust stimulated Raman shortcut-to-adiabatic passage with invariant-based optimal control.

The stimulated Raman adiabatic passage shows an efficient technique that accurately transfers population between two discrete quantum states with the same parity in three-level quantum systems based on adiabatic evolution. This technique has widely theoretical and experimental applications in many fields of physics, chemistry, and beyond. Here, we present a general approach to robust stimulated Raman shortcut-to-adiabatic passage with invariant-based optimal control. By controlling the dynamical process, we inversely design a family of Hamiltonians with non-divergent Rabi frequencies that can realize fast and accurate population transfer from the first to the third level, while the systematic errors are largely suppressed in general. Furthermore, a detailed trade-off relation between the population of the intermediate state and the amplitudes of Rabi frequencies in the transfer process is illustrated. These results provide an optimal route toward manipulating the evolution of three-level quantum systems in future quantum information processing.

Reaction Mechanism of Phenolic Lignin and High Concentration Chlorine Dioxide and Its Application.

In fact, the chemical reaction rate of traditional chlorine dioxide bleaching of pulp is too fast to observe the intermediate process. The mechanism behind the reaction of 4-hydroxy-3-methoxyacetophenone (APO), a phenolic lignin model compound, with high concentrations of chlorine dioxide was investigated. Individual solutions of each compound and a mixture of the two were analyzed by UV-vis spectrophotometry, and an absorbance band at 260 nm was observed for the stable benzoquinone intermediates at room temperature. Free chlorine dioxide displayed an absorbance at 360 nm and changes in this absorbance were studied with different APO concentrations. A fixed molar ratio of 1:3 was obtained between APO and chlorine dioxide consumption. The intermediate absorbance demonstrated a linear relationship with the APO concentration. The reaction path between APO and chlorine dioxide at high concentrations was speculated, and it was observed that the activity of C1, C2, C3, C5, and C6 on the APO benzene ring was enhanced when high concentrations of chlorine dioxide were present. From these results, a new method for efficient and clean chlorine dioxide bleaching can be developed.

Plug-and-Play Approach to Nonadiabatic Geometric Quantum Gates.

Nonadiabatic holonomic quantum computation (NHQC) has been developed to shorten the construction times of geometric quantum gates. However, previous NHQC gates require the driving Hamiltonian to satisfy a set of rather restrictive conditions, reducing the robustness of the resulting geometric gates against control errors. Here we show that nonadiabatic geometric gates can be constructed in an extensible way, called NHQC+, for maintaining both flexibility and robustness against certain types of noises. Consequently, this approach makes it possible to incorporate most of the existing optimal control methods, such as dynamical decoupling, composite pulses, and a shortcut to adiabaticity, into the construction of single-looped geometric gates. Furthermore, this extensible approach of geometric quantum computation can be applied to various physical platforms such as superconducting qubits and nitrogen-vacancy centers. Specifically, we performed numerical simulation to show how the noise robustness in recent experimental implementations [Phys. Rev. Lett. 119, 140503 (2017)PRLTAO0031-900710.1103/PhysRevLett.119.140503; Nat. Photonics 11, 309 (2017)NPAHBY1749-488510.1038/nphoton.2017.40] can be significantly improved by our NHQC+.approach. These results cover a large class of new techniques combing the noise robustness of both geometric phase and optimal control theory.

Experimental Realization of Nonadiabatic Shortcut to Non-Abelian Geometric Gates.

When a quantum system is driven slowly through a parametric cycle in a degenerate Hilbert space, the state would acquire a non-Abelian geometric phase, which is stable and forms the foundation for holonomic quantum computation (HQC). However, in the adiabatic limit, the environmental decoherence becomes a significant source of errors. Recently, various nonadiabatic holonomic quantum computation (NHQC) schemes have been proposed, but all at the price of increased sensitivity to control errors. Alternatively, there exist theoretical proposals for speeding up HQC by the technique of "shortcut to adiabaticity" (STA), but no experimental demonstration has been reported so far, as these proposals involve a complicated control of four energy levels simultaneously. Here, we propose and experimentally demonstrate that HQC via shortcut to adiabaticity can be constructed with only three energy levels, using a superconducting qubit in a scalable architecture. With this scheme, all holonomic single-qubit operations can be realized nonadiabatically through a single cycle of state evolution. As a result, we are able to experimentally benchmark the stability of STA+HQC against NHQC in the same platform. The flexibility and simplicity of our scheme makes it also implementable on other systems, such as nitrogen-vacancy center, quantum dots, and nuclear magnetic resonance. Finally, our scheme can be extended to construct two-qubit holonomic entangling gates, leading to a universal set of STAHQC gates.

Adsorptive removal of adsorbable organic halogens by activated carbon.

Current research mainly focuses on the reduction of adsorbable organic halogen (AOX) sources, while studies on AOX monitoring and management in the environment are scarce. Organic pollutants in water are mainly fixed by sediments. Thus, in this paper, activated carbon was used to simulate the adsorption of AOX by sediments. AOX volatilization and degradation were also studied to exclude their effect on adsorption. Micromolecule chlorides were more easily volatilized and degraded than chlorobenzene and chlorophenol. The adsorption of activated carbon to AOX in bleaching wastewater was also studied and the optimum conditions for AOX removal were elucidated (particle size, 62 µm; time, 120 min; pH, 2.5; temperature, 40°C; and activated carbon dosage, 1.75 g l-1). AOX adsorption by activated carbon is a chemical process. Hence, the chemical compositions of the bleaching effluent with and without adsorption were analysed by GC-MS. The results revealed that activated carbon exhibits a good AOX removal effect, thereby providing a theoretical basis for monitoring the AOX distribution in the environment.