Enzymolysis kinetics of corn straw by impeded Michaelis model and Box-Behnken design.

Enzymatic hydrolysis is an essential step in the lignocellulosic biorefining process. In this paper, Box-Behnken was used to optimize the enzymatic hydrolysis process of corn stalk, and the promotion effect of three typical surfactants on the enzymatic hydrolysis process was investigated. The experimental results showed that the total reducing sugar yield reached 67.6% under the best-predicted conditions. When the concentration of Tween 80 is 0.1%, it could be increased to 80.2%. In addition, the Impeded Michaels Model (IMM) is introduced in this study to describe the enzymatic hydrolysis process of corn stalks. Finally, the initial contact coefficient between the enzyme and cellulose (Kobs,0) and the gradual loss coefficient of enzyme activity (ki) caused by reaction obstruction were obtained by fitting data, which successfully verified the rationality of the model.

Photoreactive Mercury-Containing Metallosupramolecular Nanoparticles with Tailorable Properties That Promote Enhanced Cellular Uptake for Effective Cancer Chemotherapy.

A new potential route to enhance the efficiency of supramolecular polymers for cancer chemotherapy was successfully demonstrated by employing a photosensitive metallosupramolecular polymer (Hg-BU-PPG) containing an oligomeric poly(propylene glycol) backbone and highly sensitive pH-responsive uracil-mercury-uracil (U-Hg-U) bridges. This route holds great promise as a multifunctional bioactive nano-object for development of more efficient and safer cancer chemotherapy. Owing to the formation of uracil photodimers induced by ultraviolet irradiation, Hg-BU-PPG can form a photo-cross-linked structure and spontaneously forms spherical nanoparticles in aqueous solution. The irradiated nanoparticles possess many unique characteristics, such as unique fluorescence behavior, highly sensitive pH-responsiveness, and intriguing phase transition behavior in aqueous solution as well as high structural stability and antihemolytic activity in biological media. More importantly, a series of cellular studies clearly confirmed that the U-Hg-U photo-cross-links in the irradiated nanoparticles substantially enhance their selective cellular uptake by cancer cells via macropinocytosis and the mercury-loaded nanoparticles subsequently induce higher levels of cytotoxicity in cancer cells (compared to non-irradiated nanoparticles), without harming normal cells. These results are mainly attributed to cancer cell microenvironment-triggered release of mercury ions from disassembled nanoparticles, which rapidly induce massive levels of apoptosis in cancer cells. Overall, the pH-sensitive U-Hg-U photo-cross-links within this newly discovered supramolecular system are an indispensable factor that offers a potential path to remarkably enhance the selective therapeutic effects of functional nanoparticles toward cancer cells.

Hydrogen Bond Strength-Mediated Self-Assembly of Supramolecular Nanogels for Selective and Effective Cancer Treatment.

This study provides a significant contribution to the development of multiple hydrogen-bonded supramolecular nanocarrier systems by demonstrating that controlling the hydrogen bond strength within supramolecular polymers represents a crucial factor to tailor the drug delivery performance and enhance the effectiveness of cancer therapy. Herein, we successfully developed two kinds of poly(ethylene glycol)-based telechelic polymers Cy-PEG and UrCy-PEG having self-constituted double and quadruple hydrogen-bonding cytosine (Cy) and ureido-cytosine (UrCy) end-capped groups, respectively, which directly assemble into spherical nanogels with a number of interesting physical characteristics in aqueous solutions. The UrCy-PEG nanogels containing quadruple hydrogen-bonded UrCy dimers exhibited excellent long-term structural stability in a serum-containing biological medium, whereas the double hydrogen-bonded Cy moieties could not maintain the structural integrity of the Cy-PEG nanogels. More importantly, after the drug encapsulation process, a series of in vitro experiments clearly confirmed that drug-loaded UrCy-PEG nanogels induced selective apoptotic cell death in cancer cells without causing significant cytotoxicity to healthy cells, while drug-loaded Cy-PEG nanogels exerted nonselective cytotoxicity toward both cancer and normal cells, indicating that increasing the strength of hydrogen bonds in nanogels plays a key role in enhancing the selective cellular uptake and cytotoxicity of drugs and the subsequent induction of apoptosis in cancer cells.

CO2-Responsive Water-Soluble Conjugated Polymers for In Vitro and In Vivo Biological Imaging.

Water-soluble conjugated polymers (WCPs) composed of a hydrophobic polythiophene main chain with hydrophilic tertiary amine side-chains can directly self-assemble into sphere-like nano-objects in an aqueous solution due to phase separation between the hydrophilic and hydrophobic segments of the polymeric structure. Due to the presence of gas-responsive tertiary amine moieties in the spherical structure, the resulting polymers rapidly and reversibly tune their structural features, surface charge, and fluorescence performance in response to alternating carbon dioxide (CO2) and nitrogen (N2) bubbling, which leads to significantly enhanced fluorescence and surface charge switching properties and a stable cycle of on and off switching response. In vitro studies confirmed that the CO2-treated polymers exhibited extremely low cytotoxicity and enhanced cellular uptake ability in normal and tumor cells, and thus possess significantly improved fluorescence stability, distribution, and endocytic uptake efficiency within cellular organisms compared to the pristine polymer. More importantly, in vivo assays demonstrated that the CO2-treated polymers displayed excellent biocompatibility and high fluorescence enhancement in living zebrafish, whereas the fluorescence intensity and stability of zebrafish incubated with the pristine polymer decreased linearly over time. Thus, these CO2 and N2-responsive WCPs could potentially be applied as multifunctional fluorescent probes for in vivo biological imaging.

Self-Assembled pH-Responsive Polymeric Micelles for Highly Efficient, Noncytotoxic Delivery of Doxorubicin Chemotherapy To Inhibit Macrophage Activation: In Vitro Investigation.

Self-assembled pH-responsive polymeric micelles, a combination of hydrophilic poly(ethylene glycol) segments and hydrogen bonding interactions within a biocompatible polyurethane substrate, can spontaneously self-assemble into highly controlled, nanosized micelles in aqueous solution. These newly developed micelles exhibit excellent pH-responsive behavior and biocompatibility, highly controlled drug (doxorubicin; DOX) release behavior, and high drug encapsulation stability in different aqueous environments, making the micelles highly attractive potential candidates for safer, more effective drug delivery in applications such as cancer chemotherapy. In addition, in vitro cell studies revealed the drug-loaded micelles possessed excellent drug entrapment stability and low cytotoxicity toward macrophages under normal physiological conditions (pH 7.4, 37 °C). When the pH of the culture media was reduced to 6.0 to mimic the acidic tumor microenvironment, the drug-loaded micelles triggered rapid release of DOX within the cells, which induced potent antiproliferative and cytotoxic effects in vitro. Importantly, fluorescent imaging and flow cytometric analyses confirmed the DOX-loaded micelles were efficiently delivered into the cytoplasm of the cells via endocytosis and then subsequently gradually translocated into the nucleus. Therefore, these multifunctional micelles could serve as delivery vehicles for precise, effective, controlled drug release to prevent accumulation and activation of tumor-promoting tumor-associated macrophages in cancer tissues. Thus, this unique system may offer a potential route toward the practical realization of next-generation pH-responsive therapeutic delivery systems.

Supramolecular Polymer Network-Mediated Self-Assembly of Semicrystalline Polymers with Excellent Crystalline Performance.

A novel application of supramolecular interactions within semicrystalline polymers, capable of self-assembling into supramolecular polymer networks via self-complementary multiple hydrogen-bonded complexes, is demonstrated for efficient construction of highly controlled self-organizing hierarchical structures to offer a direct, efficient nucleation pathway resulting in superior crystallization performance. Herein, a novel functionalized poly(ε-caprolactone) containing self-complementary sextuple hydrogen-bonded uracil-diamidopyridine (U-DPy) moieties is successfully developed and demonstrated excellent thermal and viscoelastic properties as well as high dynamic structural stability in the bulk state due to physical cross-linking created by reversible sextuple hydrogen bonding between U-DPy units. Due to the ability to vary the extent of the reversible network by tuning the U-DPy content, this newly developed material can be readily adjusted to obtain the desired crystalline products with specific characteristics. Importantly, incorporating only 0.1% U-DPy resulted in a polymer with a high crystallization rate constant, short crystallization half-time, and much more rapid crystallization kinetics than pristine PCL, indicating a low content of U-DPy moieties provides highly efficient nucleation sites that manipulate the nucleation and growth processes of polymer crystals to promote crystallization and chain alignment in bulk. This new system is suggested as a potential new route to substantially improve the performance of polymer crystallization.

Enzymes and enzymatic mechanisms in enzymatic degradation of lignocellulosic biomass: A mini-review.

Enzymatic hydrolysis is the key step limiting the efficiency of the biorefinery of lignocellulosic biomass. Enzymes involved in enzymatic hydrolysis and their interactions with biomass should be comprehended to form the basis for looking for strategies to improve process efficiency. This article updates the contemporary research on the properties of key enzymes in the lignocellulose biorefinery and their interactions with biomass, adsorption, and hydrolysis. The advanced analytical techniques to track the interactions for exploiting mechanisms are discussed. The challenges and prospects for future research are outlined.

Lignin to value-added products: Research updates and prospects.

Due to the urgent need for renewable and clean energy, the efficient use of lignin is of wide interest. A comprehensive understanding of the mechanisms of lignin depolymerization and the generation of high-value products will contribute to the global control of the formation of efficient lignin utilization. This review explores the lignin value-adding process and discusses the link between lignin functional groups and value-added products. Mechanisms and characteristics of lignin depolymerization methods are presented, and challenges and prospects for future research are highlighted.

Modified alginate materials for wastewater treatment: Application prospects.

Sodium alginate is a natural macromolecule widely used because of its abundance, low cost of acquisition, and rich hydroxyl and carboxyl groups in the matrix. The physical modification of sodium alginate can be made by blending it with polymer materials. The so-yielded alginate complex is commonly unstable in an aqueous environment due to alginate backbones' high hydrophilicity. The chemical modification can remove its hydrophilic groups and introduce special functional groups or polymers onto the alginate backbones to provide excess reaction sites for specific reactions and effective complexation sites for accommodating antibiotics, dyes, heavy metal ions, and radioactive elements. Sodium alginate has been used in water treatment engineering under revised modification protocols. This article also reviews the latest modification protocols for sodium alginate and outlines the novel application of the modified materials. The limitations of modified sodium alginate materials are described, and research prospects are put forward.

Manganese ferrite modified agricultural waste-derived biochars for copper ions adsorption.

Biochar is an eco-friendly, low-cost, and carbon-rich material. This study synthesized the biochars from three agricultural wastes, pinecone, white popinac, and sugarcane bagasse, and then modified them by manganese ferrite (MnFe2O4) co-precipitation. These biochars were applied as adsorbents for the removal of Cu(II) ions from water. All three different MnFe2O4-biochars have similar adsorption performances: rapid adsorption kinetics with equilibrium being reached within 5 hr of contact and significantly enhanced adsorption capacities of Cu(II) ions from water. The principal adsorption mechanisms were identified as complexation reactions, contributed by the carboxyl and hydroxyl groups by pristine biochars and by the Mn-O and Fe-O groups for all three MnFe2O4-biochars. The MnFe2O4-biochars can be reused for three cycles, with the maximum adsorption capacities of Cu(II) of the regenerated biochars declining with the loss of precipitated MnFe2O4.

Contemporary proteomic research on lignocellulosic enzymes and enzymolysis: A review.

This review overviewed the current researches on the isolation of novel strains, the development of novel identification protocols, the key enzymes and their synergistic interactions with other functional enzyme systems, and the strategies for enhancing enzymolysis efficiencies. The main obstacle for realizing biorefinery of lignocellulosic biomass to biofuels or biochemicals is the high cost of enzymolysis stage. Therefore, research prospects to reduce the costs for lignocellulose hydrolysis were outlined.

Inhibitor formation and detoxification during lignocellulose biorefinery: A review.

For lignocellulose biorefinery, pretreatment is needed to maximize the cellulose accessibility, frequently generating excess inhibitory substances to decline the efficiency of the subsequent fermentation processes. This mini-review updates the current research efforts to detoxify the adverse impacts of generated inhibitors on the performance of biomass biorefinery. The lignocellulose pretreatment processes are first reviewed. The generation of inhibitors, furans, furfural, phenols, formic acid, and acetic acid, from the lignocellulose, with their action mechanisms, are listed. Then the detoxification processes are reviewed, from which the biological detoxification processes are noted as promising and worth further study. The challenges and prospects for applying biological detoxification in lignocellulose biorefinery are outlined. Integrated studies considering the entire biorefinery should be performed on a case-by-case basis.

Shape stable poly(vinyl alcohol) hydrogels with immobilized metal hexacyanoferrates for cesium removal from waters.

The metal hexacyanoferrates with transition metal ions to replace ferric ions in the face center cubic structure of Prussian blue (PB) crystals are candidate adsorbents for radioactive cesium ions in waters. This study for the first time synthesized the shape stable poly(vinyl alcohol) (PVA) hydrogels with immobilized metal hexacynoferrate (PB analogue) that can be stored at dry and can efficiently adsorb cesium ions from waters after rewetting. A total of eight PB analogue particles in two families M3[Fe(III)(CN)6]2 (MFe(III)) or M4[Fe(II)(CN)6]2 (MFe(II)) with M=Zn, Ni, Cu, or Co were synthesized and were immobilized in the PVA hydrogels following boric acid and sulfate crosslinking. The produced PVA-PB analogue hydrogels are all stable in shape after dry and rewet, and the rewet hydrogels can adsorb cesium ions from waters at much higher rates. As predicted by the diffusion-reaction model, the apparent reaction constants for cesium ion adsorption are 4.2×10-4 1/s, 3.4×10-4 1/s, 3.9×10-4 1/s, 4.1×10-4 1/s, 4.1×10-4 1/s, 3.8×10-4 1/s, 1.1×10-3 1/s, and 9.6×10-4 1/s, for ZnFe(III), ZnFe(II), NiFe(III), NiFe(II), CuFe(III), CuFe(II), CoFe(III), and CoFe(II), respectively. The corresponding maximum adsorption capacities based on Langmuir isotherm model at 25 °C are 232.6 mg/g, 389.0 mg/g, 193.9 mg/g, 256.8 mg/g, 388.2 mg/g, 395.1 mg/g, 297.3 mg/g, and 391.2 mg/g, respectively. The use of PVA-CoFe(III) is the candidate for enhanced Cs removal from waters comparing the use of other PB analogues as adsorbent.

Advances in pretreatment of lignocellulosic biomass for bioenergy production: Challenges and perspectives.

As a clean and renewable energy, bioenergy is one of the most promising alternatives to fossil fuels. Lignocellulose possesses great potential for bioenergy production, but the recalcitrant and heterogeneous structure limits its application. Pretreatment technology offers an effective solution to fractionate the main components of the lignocellulose and uncover the available cellulose. The obtained feedstock can be applied to bioconversion into energy, e.g., bioethanol, biogas, biohydrogen, etc. Here, the current state of lignocellulose pretreatment technologies was comprehensively reviewed, the advances in bioenergy production from pretreated lignocellulose was described, with particular attention to key challenges involved. Several new strategies for overcoming pretreatment barriers to realize highly efficient lignocellulose bioconversion were highlighted. The insights given in this review will facilitate further development on lignocellulosic bioenergy production, towards addressing the global energy crisis and climate change related to the use of fossil fuels.

Recent advances of lignin valorization techniques toward sustainable aromatics and potential benchmarks to fossil refinery products.

Aromatic compounds are important fuels and key chemical precursors for organic synthesis, however the current aromatics market are mainly relying on fossil resources which will eventually contribute to carbon emissions. Lignin has been recognized as a drop-in substitution to conventional aromatics, with its values gradually realized after tremendous research efforts in the recent five years. To facilitate the development of a possible lignin economics, this study overviewed the recent advances of various biorefinery techniques and the remaining challenging for lignin valorization. Starting with recent discovery of unexplored lignin structures, the potential functions of lignin related chemical structures were emphasized. The important breakthrough of lignin-first pretreatment, catalytic lignin depolymerization, and the high value products with possible benchmark with modern aromatics were reviewed with possible future targets. Possible retrofit of conventional petroleum refinery for lignin products were also introduced and hopefully paving a way to progressively migrate the industry towards carbon neutrality.

Fouling with aerobic granule membrane bioreactor.

Aerobic granulation (AG) and membrane bioreactor (MBR) are two promising, novel environmental biotechnological processes that draw interest of researchers working in the area of biological wastewater treatment. Membrane fouling in the combined aerobic granular membrane bioreactor (AGMBR) process and the conventional MBR process was investigated in this work. The irreversible fouling on hollow-fibre membranes in both reactors were observed with the multiple staining and confocal laser scanning microscope technique. Following physical and chemical washing, the external fouling layers were mostly removed. However, the biofilms built up in the interior surface of membrane remained and contributed to the irreversible fouling resistance. AGMBR retained most cells with granules, thereby reducing their penetration through membrane and thus the chance to form internal fouling layer. The internal biofilm layer was principally composed of live cells embedded in a matrix of proteins and polysaccharides, with that on AGMBR denser and thicker than that on MBR. Prevention of development of internal biofilm is essential to reduce irreversible fouling of AGMBR and MBR membranes.

Lignocellulosic biomass pretreatment by deep eutectic solvents on lignin extraction and saccharification enhancement: A review.

Biomass recalcitrance hinders efficient utilization of lignocellulosic biomass, making pretreatment process a crucial step for successful biorefinery process. Pretreatment processes have been developed for processing biomass, while technical obstacles including intensive energy requirement, high operational cost, equipment corrosions resulted from currently applied techniques promote the development of new pretreatment process for biomass. The deep eutectic solvent (DES) has been recognized as a promising solvent for biomass pretreatment, although the DES application toward biomass is still in its nascent stage. This review summarized the current researches using DES for biomass pretreatment, focusing particularly on lignin extraction and saccharification enhancement of lignocellulosic biomass. The mechanisms for biomass fractionation using DES as agents are introduced. Prospect and challenge were outlined.

Strains of internal biofilm in aerobic granular membrane bioreactors.

This study isolated strains in suspended liquor, the surface fouling layer, and biofilm inside hollow-fiber membranes of a membrane bioreactor (MBR); analyzed their distributions, sizes, surface charges, and growth behaviors; and determined the quantities of extracellular polymeric substances (EPS) secreted by these strains under different organic loadings. Three strains, which may penetrate the microfiltration membranes, were close relatives of the Ralstonia mannitolilytica strain SDV (GenBank Accession No. GU451066), Arthrobacter sp. BJQ-2 (GenBank Accession No. GU451067), and Actinobacterium DS3 (GenBank Accession No. GU451068). Among these three strains, only Arthrobacter sp. developed an internal biofilm. The relatively short length of Arthrobacter sp. minimizes resistance to cells moving through the membrane matrix, thereby enhancing its ability to build a biofilm in the interior surface of membranes.

Enhanced hydrolysis and acidification of cellulose at high loading for methane production via anaerobic digestion supplemented with high mobility nanobubble water.

In this study, CH4 production from anaerobic digestion (AD) of refractory cellulose was investigated at a high loading of 3.5 (VScellulose/VSinoculum) under nanobubble water (NBW) addition. A longer proton spin-spin relaxation time (2611-2906 ms) of NBW during 35 days' storage reflected its high mobility and diffusion of water molecules. Higher volatile fatty acids were yielded at the hydrolysis-acidification stage under NBW addition. Methanogenesis tests showed that Air-NBW and CO2-NBW supplementation accelerated the utilization of crystalline cellulose, achieving methane yields of 264 and 246 mL CH4/g-VSreduced, increasing by 18% and 10% compared to deionized water addition (the control), respectively. In addition, under NBW addition the cellulose crystallinity reduction was enhanced by 14-20% with microbial community being enriched with hydrolytic and methanogenic bacteria. Results from this work suggest that NBW environment with no chemical addition and relatively low energy consumption is advantageous for enhanced AD process of cellulosic biomass.

Forward osmosis membrane processes for wastewater bioremediation: Research needs.

Increasing research and development works have been made to develop forward osmosis (FO) processes as a cost-effective substitute for energy intensive water vacuum suction facility in submerged membrane bioreactor (MBR) applications. Perceived to be a spontaneous water driven process without external applied pressures, the FO has been applied in lab and pilot scales for wastewater bioremediation. This paper reviewed the state-of-the-art developments on the FO unit, the process, and ways of enhancing process performance, particularly on the aspects of flux enhancement, flow resistance reduction, and draw solute with low reverse salt diffusion, which are relevant to enhanced osmotic MBR performance. The perspective to realize the use of FO processes in revision of currently existing energy intensive osmotic MBR processes is discussed with research needs being highlighted.