Residue-Free and Recyclable Starch-Based Flocculants for Dye Wastewater Flocculation.

Flocculants are crucial agents in wastewater treatment because they can remove oppositely charged impurities effectively and swiftly. However, flocculation also inevitably causes secondary contamination due to the residual properties, nonreusability, and nondegradability of traditional flocculant molecules. Herein, an ecofriendly starch-based flocculant, i.e., 2,4-bis(dimethylamino)-[1,3,5]-triazine-6-starch, was synthesized via a preactivation-etherification strategy. The large molecular weight property of the flocculant produced by this method enhances the intermolecular hydrophobic association, achieving complete phase separation of all flocculant molecules from water and residue-free flocculation for the first time. Importantly, a large molecular weight tertiary amine starch-based flocculant (LMTS) exhibits a remarkable flocculation capacity of over 1800 mg·g-1 for dye wastewater, which is significantly higher than that of traditional polyacrylamide and polyaluminum chloride flocculants. Furthermore, the LMTS flocculant could be recycled by pH adjustment, and its structural stability ensured sustained reusability. This high-performance residue-free biomass-based flocculant offers a green advance for wastewater treatment.

Catalyst-free readily dual-recyclable acetal-based covalent adaptable cellulose networks.

Despite covalent adaptable networks (CANs) imparting the favorable features of crosslinked polymers, as well as the functionality of reprocessing, reshaping and welding, due to exchange reaction enabled topology changes; it is still a huge challenge to design catalyst-free, fast reprocessing, controlled degradation and polymer recyclable biomass base CANs. Herein, for the first time, acetal-based covalent adaptable cellulose networks (ACCs) were utilized to synthesize readily reconstructable cellulose-based thermosets with mechanical tunability. ACCs were synthesized via catalyst-free "click" addition of cellulose and divinyl ether without releasing small molecule byproducts. Different crosslinking densities and crosslinkers were used to explore the structure-property relationship, the mechanical and thermal properties of the ACCs were strongly influenced by these factors. ACCs can obtain enhanced tensile strength or elongation at break by changing the structure of the crosslinker. Furthermore, the reworking, welding and shape memory properties of these ACCs, based on the dynamic exchange reaction of acetal bonds, were investigated. In addition, these ACCs can be degraded under acidic conditions, and closed-loop utilization of polymer was possible. Thus, ACCs can be mechanically and chemically double-cycled, which will contribute to solving the white pollution problem and resource waste as a new class of sustainable plastics.

Fully bio-based hydroxy ester vitrimer synthesized by crosslinking epoxidized soybean oil with doubly esterified starch.

Catalyst-free fully bio-based hydroxyester (BHE) vitrimers were synthesized by crosslinking and plasticizing epoxidized soybean oil with synthesized acetylated starch succinate monoesters to investigate the effects of different starch structures on the properties of the BHE vitrimers. The BHE vitrimers possessed a lower glass transition temperature as well as better solvent resistance and reprocessing performance compared to traditional starch-based materials. Owing to dynamically covalent bonds, the migration and exudation of plasticizers were avoided. A maximum strain of 230 % was achieved to prevent the retrogradation and brittleness of starch-based materials. Furthermore, the mechanical properties remained unchanged after three reprocessing cycles. Consequently, the obtained BHE vitrimers are eco-friendly and sustainable.

Dispersion and weak retardation performance of sulfate-based starch maleic acid monoesters in cement.

To reduce the influence of a sulfate-based starch water-reducing agent on the setting time of cement, a novel starch-based water-reducing agent, namely sulfate-based starch maleic acid monoester (SAMAS), was designed to adjust its hydrophilicity by maleic acid monoester. Gel permeation chromatography, Fourier transform infrared spectroscopy, and 1H NMR nuclear magnetic resonance spectroscopy were used to characterize the prepared SAMAS, while Zeta potential, UV-Vis absorption, X-ray photoelectron spectroscopy, X-ray diffraction, cement paste fluidity, and setting time measurements were conducted to investigate its dispersion performance, retardation performance, adsorption behavior, and mechanism of action. SAMAS exhibited good dispersion performance and did not significantly prolong the setting time of the cement. In addition, the dispersion performance of SAMAS was found to depend mainly on steric hindrance, and its weak retardation performance originated from the hydrophilic regulation of the maleic acid monoester groups, which ensures the normal progress of the cement hydration reaction by hindering the formation of a hydration film.

Twin-screw extrusion molding of a cellulose-based vitrimer containing a crosslinkable macromolecular plasticizer.

Cellulose-based vitrimers were prepared using a crosslinkable macromolecular plasticizer and acetylated carboxymethyl cellulose via twin-screw extrusion. The cellulose-based material was toughened by the entanglement between the macromolecular plasticizer segments, and the exudation of the plasticizer was avoided by crosslinking. The prepared materials exhibited excellent hydrophobicity and shape memory properties. The plasticizer was evidently effective, and the reprocessing was completed at 130 °C within 15 min. The materials could be reprocessed at a lower temperature over a short period of time without any obvious degradation. After reprocessing three times, the material performance did not decrease significantly, thus showing good potential for regeneration and recycling.

pH-sensitive, tail-modified, ester-linked ionizable cationic lipids for gene delivery.

Ionizable cationic lipids have great potential for gene delivery, yet the effect of the molecular structure of such lipids on gene delivery efficiency is an ongoing research challenge. To better understand corresponding structure-function activity relationships, we synthesized four ester-linked, pH-responsive, ionizable cationic lipids. The screened DEDM4 lipid, containing 2-ethylenedimethylamine in the headgroup and a branched-chain tail, exhibited a high delivery efficacy of plasmid DNA and siRNA in A549 cells, which was comparable with that of the commercial reagent lipofectamine 3000 (lipo3000). Moreover, because of its pKa value of 6.35 and pH-sensitivity under acidic conditions, DEDM4 could carry sufficient positive charge in the acidic environment of endosomes and interact with the endosome lumen, leading to destruction of the endomembrane and subsequent release of siRNA into the cytoplasm with endosomal escape. Furthermore, we used DEDM4 to deliver IGF-1R siRNA to induce cancer cell apoptosis, thereby leading to great tumor inhibition. More importantly, it also showed very low toxicity in vivo. These structure-activity data for DEDM4 demonstrate potential clinical applications of DEDM4-mediated gene delivery for cancer.

Cationic Nanoparticulate System for Codelivery of MicroRNA-424 and Podophyllotoxin as a Multimodal Anticancer Therapy.

Because of the complexity of cancer ecosystems, the efficacy of single-agent chemotherapy is limited. Herein, we report the use of cationic nanoparticles (designated PPCNs) generated from a chemically modified form of the chemotherapeutic agent podophyllotoxin (PPT) to deliver both microRNA-424 (miR-424) and PPT to tumor cells, thus combining chemotherapy and gene therapy. We evaluated the optimal loading ratio of miR-424─which targets programmed cell death ligand 1 (PD-L1) mRNA and reduces PD-L1 production, thus promoting the attack of tumor cells by T cells─for effective delivery of miR-424 and PPCNs into nonsmall-cell lung cancer cells (H460). Because miR-424 can reverse chemotherapy resistance, treatment of the tumor cells with the combination of miR-424 and PPT enhanced their sensitivity to PPT. Because miR-424 and the PPCNs regulated PD-L1 production in different ways, the miR-424@PPCN complexes were significantly more efficacious than either miR-424 or PPCNs alone. We also demonstrated that treatment of tumor-bearing mice with these complexes significantly inhibited tumor growth and extended survival. Moreover, additional in vitro experiments revealed that the complexes could remodel the tumor immune microenvironment, relieve immunosuppression, and achieve immune normalization. This novel system for delivering a combination of PPT and miR-424 shows great potential for the multimodal treatment of lung cancer.

Bioinspired Polypeptide Photonic Films with Tunable Structural Color.

We report a new synthetic strategy of combining N-carboxyanhydride (NCA) chemistry and photonic crystals for the fabrication of polypeptide structural color films. Driven by surface-initiated ring-opening polymerization, the di-NCA derivative of l-cystine (Cys) is introduced to replicate the functionalized colloidal crystal templates and construct freestanding P(Cys) films with tunable structural color. Furthermore, the feasibility of preparing patterned polypeptide photonic films is demonstrated via template microfabrication. Because of the incorporation of l-glutamate (Glu) components, the P(Cys-co-Glu) co-polypeptide films are endowed with a visual color responsiveness toward pH changes. Additionally, the polypeptide photonic films show on-demand degradability. Given the large family of amino acid building blocks, this powerful and versatile approach paves the way for chemical derivatization of multifunctional peptide-based optical platforms.

Self-Assembly of Podophyllotoxin-Loaded Lipid Bilayer Nanoparticles for Highly Effective Chemotherapy and Immunotherapy via Downregulation of Programmed Cell Death Ligand 1 Production.

Low drug delivery efficiency elevates the cost of medication, lowers the therapeutic efficacy, and appears as a leading reason for unmet needs in anticancer therapies. Herein, we report the development of self-assembled podophyllotoxin-loaded lipid bilayer nanoparticles that inhibit the production of programmed cell death ligand 1 in lung cancer cells and promote tumor-specific immune responses, thus offering a strategy for regulating the immunosuppressive microenvironment of tumors. In addition, encapsulation of podophyllotoxin in the nanoparticles reduced its systemic toxicity, enhanced its penetration into tumors, and increased its antitumor efficacy. Systemic injection of the nanoparticles into tumor-bearing mice not only prevented tumor immune escape but also significantly inhibited tumor growth and extended survival. In general, the podophyllotoxin-loaded nanoparticles exhibited both immunological effects and antitumor effects in addition to having better targeting activity and fewer side effects than free podophyllotoxin. We expect our findings to facilitate the development of therapies for lung cancer.

Structure-activity relationships of pH-responsive and ionizable lipids for gene delivery.

Ionizable lipids are the leading vectors for gene therapy. Understanding the effects of molecular structure on efficient gene delivery is one of the most important challenges for maximizing the utility of such lipid vectors. We synthesized an array of pH-responsive and ionizable lipids to investigate the relationship between lipid structure and activity. The optimized lipid (EDM) has double tertiary amines in the headgroup and an ester linker. EDM exhibited efficient DNA and siRNA delivery to, and gene silencing of, A549 cells. EDM has a pKa value of 6.67, which enabled it to quickly escape from the endosome after entering the cell; the ester linkages rapidly degraded and enabled gene release into the cytoplasm. EDM also delivered IGF-1R siRNA to inhibit tumor growth and induce cancer cell apoptosis by efficient inhibition of IGF-1R expression in mice. Our study on the structure-activity relationships of ionizable lipids will facilitate clinical applications.

Cephalopod-Inspired Chromotropic Ionic Skin with Rapid Visual Sensing Capabilities to Multiple Stimuli.

Biological skin systems can perceive various external stimuli through ion transduction. Especially, the skin of some advanced organisms such as cephalopods can further promptly change body color by manipulating photonic nanostructures. However, the current skin-inspired soft iontronics lack the rapid full-color switching ability to respond to multiple stimuli including tension, pressure, and temperature. Here, an intelligent chromotropic iontronics with these fascinating functions is developed by constructing a biomimetic ultrastructure with anisotropic electrostatic repulsion. This skin-like chromotropic iontronics can synchronously realize electrical response and optical visualization to mechanical strain and tactile sensation by adjusting the ultrastructure in cooperation with ionic mechanotransduction. Notably, it can perform instantaneous geometric changes to thermal stimuli via an anisotropic electrostatic repulsion interior. Such a capability allows bionic skin to transduce temperature or infrared light into ionic signals and color changes in real time. The design of anisotropic photonic nanostructures expands the intelligent application for soft iontronics at higher levels, providing a concise, multifunctional, interactive sensing platform that dynamically displays stimuli information on its body.

Novel amphiphilic cellulose nanocrystals for pH-responsive Pickering emulsions.

Development of a green, recyclable emulsifier for pH-responsive Pickering emulsion would be of great importance to many industries. To this end, a novel emulsifier, benzyl-polyethyleneimine modified cellulose nanocrystals (Ben-PEI-CNCs), was developed via the periodate oxidation of cellulose nanocrystals and reductive amination. Ben-PEI-CNCs possess pH-responsive amphiphilicity due to the existence of hydrophilic amino and hydrophobic benzyl groups. The Pickering emulsions stabilized by Ben-PEI-CNC2 and Ben-PEI-CNC18 are very responsive to pH changes, and adjusting the pH from 3 to 7 effectively triggers oil-water separation and emulsification. Additionally, cyclic testing establishes the robustness of this process. Overall, this study demonstrates that Ben-PEI-CNCs can promote the transition from a stable emulsion to an unstable emulsion by adjusting the pH, allowing the recovery of oil and the recycling of the emulsifier.

Preparation of thermoresponsive alginate/starch ether composite hydrogel and its application to the removal of Cu(II) from aqueous solution.

A novel polysaccharide-based thermoresponsive hydrogel containing sodium alginate (SA) and 2-hydroxy-3-isopropoxypropyl starch (HIPS) was developed for removing Cu(II) from aqueous solution. HIPS/SA hydrogel showed network and porous structure, as well as the abundant carboxy groups inside the structure, endowed it with sufficient binding sites for adsorption of Cu(II). The reversible thermoresponsive swelling-shrinking behavior of HIPS/SA hydrogel was discussed. The effects of pH and initial Cu(II) concentration on adsorption capacity were investigated. The adsorption isotherms and kinetics of HIPS/SA hydrogel demonstrated that the adsorption of Cu(II) was subjected to Langmuir and pseudo-second-order models respectively, and the maximum adsorption capacity was 25.81 mg/g. Additionally, HIPS/SA hydrogel could be successfully desorbed by only small amounts of dilute hydrochloric acid within a short time for its thermoresponsive property, it also exhibited the feasibility of regeneration, because the adsorption capacity for Cu(II) was still higher than 15.23 ±â€¯0.27 mg/g even after five cycles.

Thermoresponsive 2-hydroxy-3-isopropoxypropyl hydroxyethyl cellulose with tunable LCST for drug delivery.

Thermoresponsive polymer 2-hydroxy-3-isopropoxypropyl hydroxyethyl celluloses (HIPECs) were successfully synthesized, characterized, and applied for thermoresponsive drug delivery. The lower critical solution temperature (LCST) of HIPEC could be easily tuned from 21.1 to 56.1 °C as the molar substitution (MS) increased from 1.21 to 2.88. Dynamic light scattering and transmission electron microscopy experiments revealed that HIPEC can self-assemble into nano-sized aggregates, and their size could be changed by variation in temperature. Additionally, the critical aggregation concentration (CAC) ranged from 0.101 to 0.805 g L-1 by changing MS of HIPEC. In vitro drug delivery studies indicated that the amphotericin B (AmpB) release rate was much faster at temperatures above LCST; approximately 95% of the drug was released from aggregates in 40 h. MTT assays were conducted to evaluate the cytotoxicity of HIPEC, and the observation of the Hoechst 33342 living cell stain using confocal laser scanning microscopy confirmed the high cell viability as HIPECs were used.

A green l-cysteine modified cellulose nanocrystals biosorbent for adsorption of mercury ions from aqueous solutions.

Using a green biosorbent to remove toxic mercury ions from aqueous solutions is a significant undertaking. In the present study, a novel biosorbent, l-cysteine modified cellulose nanocrystals (Lcys-CNCs), was prepared by functionalizing high surface area cellulose nanocrystals with l-cysteine through periodate oxidation and reductive amination reaction. Lcys-CNCs were characterized by FT-IR, 13C CP-MAS NMR, elemental analysis, XPS, zeta potential and SEM. As cellulose nanocrystals are the natural nanomaterial, and l-cysteine contains strong mercury chelating groups, Lcys-CNCs show excellent adsorption capacity for mercury ions. The experimental conditions such as pH, contact time, and initial mercury ion concentration are discussed. The pseudo-second order model can describe the removal kinetics of Hg(ii) more accurately than the pseudo-first order model. The adsorption isotherm study of Hg(ii) followed the Langmuir model of monolayer adsorption. The maximum uptake capacity of Lcys-CNCs was determined to be 923 mg g-1. Lcys-CNCs can remove mercury ions with 93% removal efficiency within 5 min from a 71 mg L-1 solution. For Cd(ii), Pb(ii), Cu(ii) and Zn(ii) ions, Lcsy-CNCs can selectively adsorb Hg(ii) ions and the removal efficiency is 87.4% for Hg(ii). This study suggests Lcsy-CNCs are a green and highly efficient biosorbent for adsorption of mercury ions from aqueous solutions.

Biomimetic Structural Color Films with a Bilayer Inverse Heterostructure for Anticounterfeiting Applications.

The unique brilliant and angle-independent structural colors of morpho butterfly wings were derived from the multilayer interference, diffraction, and scattering of light with a composite structure including ordered and quasiamorphous arrays. Inspired by the biological heterostructure of ordered and quasiamorphous arrays in the wings, a bilayer inverse heterostructure (BLIHS) containing ordered array layers inverse structure (OALIS) and quasiamorphous array layers inverse structure (Q-AALIS) of polyvinylidene fluoride were successfully prepared through the template method. The BLIHS films selectively displayed iridescent structural color derived from Bragg diffraction of OALIS, whereas the color states transform to noniridescent color because of Q-AALIS just by rotating the sample. Furthermore, the patterning process could be realized by using the spray-coating method on the BILIS films as quasiamorphous array layers. By virtue of this novel photonic structure, the switch between hiding and displaying patterns could be easily realized by changing the viewing angles, and the as-prepared films exhibited inherent excellent durability, which is crucial to their potential for practical applications as anticounterfeiting materials.

Synthesis of pH-responsive N-acetyl-cysteine modified starch derivatives for oral delivery.

In this study, a novel type of pH-responsive polymer PyHES-NAC (2-hydroxy-3-(2-propynyloxy) propyl hydroxyethyl starch (PyHES)) - (N-acetyl-cysteine (NAC)) was synthesized. First, PyHES was prepared via hydrophobic modification of hydroxyl groups in hydroxyethyl starch (HES) with propynylglycidyl ether (PGE), and then pH-responsive carboxylic acid group was connected to propynyl group via thiol-yne click reaction with NAC. Aqueous PyHES-NAC solutions exhibited a good transference between hydrophobic (or self-assembly) and hydrophilic static along with the change of pH value and protective properties of drugs under acidic conditions. 10.0% DOX was released under artificial gastric fluid after 2 h, whereas an immediate release (above 80%) was observed under artificial intestinal fluid. Drug loading capacity of PyHES-NAC was increased by the increase of degree of substitution (DS) of hydrophobic propynyl groups in PyHES, and 41 wt% DOX Loading capacity was the highest value in our study area.

Multiple Colors Output on Voile through 3D Colloidal Crystals with Robust Mechanical Properties.

Distinguished from the chromatic mechanism of dyes and pigments, structural color is derived from physical interactions of visible light with structures that are periodic at the scale of the wavelength of light. Using colloidal crystals with coloring functions for fabrics has resulted in significant improvements compared with chemical colors because the structural color from colloidal crystals bears many unique and fascinating optical properties, such as vivid iridescence and nonphotobleaching. However, the poor mechanical performance of the structural color films cannot meet actual requirements because of the weak point contact of colloidal crystal particles. Herein, we demonstrate in this study the patterning on voile fabrics with high mechanical strength on account of the periodic array lock effect of polymers, and multiple structural color output was simultaneously achieved by a simple two-phase self-assembly method for printing voile fabrics with 3D colloidal crystals. The colored voile fabrics exhibit high color saturation, good mechanical stability, and multiple-color patterns printable. In addition, colloidal crystals are promising potential substitutes for organic dyes and pigments because colloidal crystals are environmentally friendly.

Thermoresponsive cellulose ether and its flocculation behavior for organic dye removal.

A thermoresponsive polymer, 2-hydroxy-3-butoxypropyl hydroxyethyl cellulose (HBPEC), was prepared by grafting butyl glycidyl ether (BGE) onto hydroxyethyl cellulose (HEC). The lower critical solution temperature (LCST) and critical flocculation temperature (CFT) of HBPEC were varied by changing the molar substitution (MS) and salt concentrations. Transmission electron microscopy (TEM) images and fluorescence spectroscopy showed that HBPEC can assemble into micelles. Additionally, using Nile Red as a model dye, the performance of HBPEC for the removing Nile Red from aqueous solutions via cloud point extraction procedures was investigated in detail. The encapsulation behavior of dye in the aqueous solution of HBPEC was studied by fluorescence spectroscopy and fluorescence microscope. The experimental results indicated that 99.4% of dye was removed from the aqueous solutions, and the HBPEC was recycled and reused easily, Furthermore, the recycle efficiency (RE) and maximum loading capacity portrayed little loss with the number of cycles.

Easy approach to assembling a biomimetic color film with tunable structural colors.

The self-assembly of silica microspheres into a close-packed array is a simple method of fabricating three-dimensional photonic crystal structural color films. However, the color is very dull because of the interferences of scattering and background light. In this study, we added a small quantity of surface-modified carbon black (CB) to the system of colloidal silica in n-propanol. The use of n-propanol as a dispersant is beneficial to the rapid development of photonic crystal films during the process of dip-coating. The doping of CB into silica microspheres can absorb background and scattering light, resulting in vivid structural colors.