Dual-Temperature/pH-Sensitive Hydrogels with Excellent Strength and Toughness Crosslinked Using Three Crosslinking Methods.

Hydrogels are widely used as excellent drug carriers in the field of biomedicine. However, their application in medicine is limited by their poor mechanical properties and softness. To improve the mechanical properties of hydrogels, a novel triple-network amphiphilic hydrogel with three overlapping crosslinking methods using a one-pot free-radical polymerization was synthesized in this study. Temperature-sensitive and pH-sensitive monomers were incorporated into the hydrogel to confer stimulus responsiveness, making the hydrogel stimuli-responsive. The successful synthesis of the hydrogel was confirmed using techniques, such as proton nuclear magnetic resonance spectroscopy (1H NMR), Fourier-transform infrared spectroscopy (FT-IR), and X-ray diffraction (XRD). In order to compare and analyze the properties of physically crosslinked hydrogels, physically-chemically double-crosslinked hydrogels, and physically-chemically clicked triple-crosslinked hydrogels, various tests were conducted on the gels' morphology, swelling behavior, thermal stability, mechanical properties, and drug loading capacity. The results indicate that the triple-crosslinked hydrogel maintains low swelling, high mechanical strength, and good thermal stability while not significantly compromising its drug delivery capability.

Design and Synthesis of a Robust and Multifunctional Superhydrophobic Coating with a Three-Dimensional Network Structure on a Paper-Based Material.

A fundamental challenge in artificial superhydrophobic papers is their poor resistance to mechanical abrasion, which limits their practical application in different fields. Herein, a robust and multifunctional superhydrophobic paper is successfully fabricated via a facile spraying method by combining silver nanowires and fluorinated titania nanoparticles through a common paper sizing agent (alkyl ketene dimer) onto paper. It is shown that the surface of the paper-based material presents a three-dimensional network structure due to the cross-linking of silver nanowires with a high aspect ratio. Further hydrophilic and hydrophobic performance test results show that it exhibits exceptional water repellency, with a desirable static contact angle of 165° and roll-off angle of 6.2°. The superhydrophobic paper showcases excellent mechanical durability and maintains its superhydrophobicity even after enduring 130 linear sandpaper abrasion cycles or high-velocity water jetting impact benefited from interfacial van der Waals and hydrogen bonding. Simultaneously, the robust superhydrophobic surface can effectively prevent the penetration of acid or alkali solutions, as well as UV light, resulting in excellent chemical stability. Additionally, the superhydrophobic paper offers supplementary features such as self-cleaning, electrical conductivity, and antibacterial capability. Further development of this strategy paves a way toward next-generation superhydrophobic paper composed of nanostructures and characterized by multiple (or additional) functionalities.

Palladium-Catalyzed Selective γ-Monoarylation of Free Amines Containing Symmetric γ-C-H Controlled by a Transient Directing Group.

We developed a new transient directing group, N-(2-benzoyl-4-chlorophenyl)-1,1,1-trifluoromethanesulfonamide, which can facilitate the γ-monoarylation of free amines containing symmetric γ-C-H bonds. A variety of amines containing symmetric and identical γ-C(sp3)-H and γ-C(sp2)-H reacted with a diverse range of aryl and heteroaryl iodides to provide γ-monoarylated products exclusively.

Photoinduced Lignin C α -C ß Bond Cleavage and Chemodivergent Functionalization via Iron Catalysis.

The photocatalytic conversion of lignin into value-added chemicals especially those functionalized molecules represent one of the most important strategies for sustainable and environmental-friendly development. Cleavage of C-C bonds in lignin under mild photocatalytic conditions for refining lignin into useful molecules is meaningful but challenging. Meanwhile, the assembly of diverse functional groups into active lignin fragments during the depolymerization is of great challenging. Herein, using cheap iron catalysts under visible light irradiation, the highly selective and efficient cleavage of Cα-Cß bond in lignin is realized via ligand-to-metal charge transfer (LMCT) and hydrogen atom transfer (HAT) processes. The subsequent divergent functionalization of generated lignin fragment-based radical intermediates enables an efficient formation of diverse functionalized molecules. This method is also effective for cleavage of Cα-Cß bond in native lignin, yielding two identified benzaldehyde monomers in a total yield of 8.7 wt%.

Dual-key-based adaptive watermark embedding for light field 3D images.

The existing methods fail to effectively utilize the viewpoint information of light field 3D images for watermark embedding which results in a serious decrease in both invisibility and robustness of the watermark. Therefore, we propose a novel, to the best of our knowledge, light field 3D dual-key-based watermarking network (3D-DKWN). Our method employs a pixel mapping algorithm to obtain the disparity sub-image of the light field 3D image and generates an encoding key (EK). Adaptive watermark embedding is then performed on the disparity sub-image and a steganographic key (SK) is generated. Finally, the light field 3D image with the embedded watermark is reconstructed. Compared with previous approaches, our method reasonably utilizes the viewpoint information of light field 3D images, resulting in the significant improvement of invisibility and robustness of the watermark.

Magnetic molecularly imprinted polymers using ternary deep eutectic solvent as novel functional monomer for hydroxytyrosol separation.

In this work, magnetic molecularly imprinted polymers (MIPs) for specific recognition of Hydroxytyrosol (HT) were designed by vinyl-modified magnetic particles (Fe3O4@SiO2@VTEOs) as carrier, ternary deep eutectic solvent (DES) as functional monomer, while ethylene glycol dimethacrylate (EGDMA) as crosslinker. The optimum amount of DES was obtained by adsorption experiments (molar ratio, caffeic acid: choline chloride: formic acid = 1:6:3) which were 140 µL in total. Under the optimized amount of DES, the maximum adsorption capacity of the MIPs particles was 42.43 mg g-1, which was superior to non-imprinted polymer (4.64 mg g-1) and the imprinting factor (IF) is 9.10. Syringin and Oleuropicrin were used as two reference molecules to test the selectivity of the DES-MIPs particles. The adsorption capacity of HT was 40.11 mg g-1. Three repeated experiments show that the polymer has high stability and repeatability (RSD = 5.50).

Use of Interfacial Interactions and Complexation of Carbon Dots to Construct Ultra-Robust and Efficient Photothermal Film From Micro-Carbonized Polysaccharides.

Solar energy conversion technologies, particularly solar-driven photothermal conversion, are both clean and manageable. Although much progress has been made in designing solar-driven photothermal materials, significant challenges remain, not least the photobleaching of organic dyes. To tackle these issues, micro-carbonized polysaccharide chains, with carbon dots (CDs) suspended from the chains, are conceived, just like grapes or tomatoes hanging from a vine. Carbonization of sodium carboxymethyl cellulose (CMC) produces just such a structure (termed CMC-g-CDs), which is used to produce an ultra-stable, robust, and efficient solar-thermal film by interfacial interactions within the CMC-g-CDs. The introduction of the CDs into the matrix of the photothermal material effectively avoided the problem of photobleaching. Manipulating the interfacial interactions (such as electrostatic interactions, van der Waals interactions, π-π stacking, and hydrogen bonding) between the CDs and the polymer chains markedly enhances the mechanical properties of the photothermal film. The CMC-g-CDs are complexed with Fe3+ to eliminate leakage of the photothermal reagent from the matrix and to solve the problem of poor water resistance. The resulting film (CMC-g-CDs-Fe) has excellent prospects for practical application as a photothermal film.

Type†I Photoinitiator Based on Sustainable Carbon Dots.

Sustainable carbon dots comprising surficial oxime ester groups following homolytic bond cleavage exhibit potential as photoinitiators for traditional free radical photopolymerization. Carbon dots were made following a solvothermal procedure from sustainable furfural available from lignocellulose. Surficial aldehyde moieties reacted with hydroxylamine to the respective oxime while reaction with benzoyl chloride resulted in a biobased Type I photoinitiator comprising sustainable carbon dot (CD-PI). Photoinitiating ability was compared with the traditional photoinitiator (PI) ethyl (2,4,6-trimethyl benzoyl) phenyl phosphinate (TPO-L) by real-time FTIR with UV exposure at 365 nm. Photopolymer composition based on a mixture of urethane dimethacrylate (UDMA) and tripropylene glycol diacrylate (TPGDA) resulted in a similar final conversion of about 70 % using either CD-PI or TPO-L. Nevertheless, it appeared homogeneous in the case of compositions processed with CD-PI, while those made with TPO-L were heterogeneous as shown by two glass transition temperatures. Moreover, the migration rate of CD-PI in the cured samples was lower in comparison with those samples using TPO-L as PI.

Discovery of novel peptide-dehydroepiandrosterone hybrids inducing endoplasmic reticulum stress with effective in vitro and in vivo anti-melanoma activities.

Steroid hybrids have emerged as a type of advantageous compound as they could offer improved pharmacological and pharmaceutical properties. Here, we report a series of novel peptide-dehydroepiandrosterone hybrids, which would effectively induce endoplasmic reticulum stress (ERS) and lead to apoptosis with outstanding in vitro and in vivo anti-melanoma effects. The lead compound IId among various steroids conjugated with peptides and pyridines showed effective in vivo activity in B16 xenograft mice: in medium- and high-dose treatment groups (60 and 80 mg/kg), compound IId would significantly inhibit the growth of tumours by 98%-99% compared to the control group, with the highest survival rate as well. Further mechanism studies showed that compound IId would damage the endoplasmic reticulum and upregulate the ERS markers C/EBP homologous protein (CHOP) and glucose-regulated protein 78 (GRP78), which could further regulate caspase and Bcl-2 family proteins and lead to cell apoptosis. The compound IId was also proven to be effective in inhibiting B16 cell migration and invasion.

Biobased and biodegradable films exhibiting circularly polarized room temperature phosphorescence.

There is interest in developing sustainable materials displaying circularly polarized room-temperature phosphorescence, which have been scarcely reported. Here, we introduce biobased thin films exhibiting circularly polarized luminescence with simultaneous room-temperature phosphorescence. For this purpose, phosphorescence-active lignosulfonate biomolecules are co-assembled with cellulose nanocrystals in a chiral construct. The lignosulfonate is shown to capture the chirality generated by cellulose nanocrystals within the films, emitting circularly polarized phosphorescence with a 0.21 dissymmetry factor and 103 ms phosphorescence lifetime. By contrast with most organic phosphorescence materials, this chiral-phosphorescent system possesses phosphorescence stability, with no significant recession under extreme chemical environments. Meanwhile, the luminescent films resist water and humid environments but are fully biodegradable (16 days) in soil conditions. The introduced bio-based, environmentally-friendly circularly polarized phosphorescence system is expected to open many opportunities, as demonstrated here for information processing and anti-counterfeiting.

Photocured room temperature phosphorescent materials from lignosulfonate.

Photocured room temperature phosphorescent (RTP) materials hold great potential for practical applications but are scarcely reported. Here, we develop photocured RTP materials (P-Lig) using a combination of lignosulfonate, acrylamide, and ionic liquid (1-ethyl-3-methylimidazolium bromide). With this design, lignosulfonate simultaneously serves as RTP chromophore and photoinitiator. Specifically, lignosulfonate in the ionic liquid generates radicals to polymerize the acrylamide upon UV irradiation. The resulting lignosulfonate is automatically confined in an as-formed crosslinked matrix to provide RTP. As such RTP with an emission lifetime of ~110 ms is observed from the confined lignosulfonate in P-Lig. Additionally, energy transfer occur between P-Lig and Rhodamine B (RhB), triggering red afterglow emission when P-Lig is in situ loaded with RhB (P-Lig/RhB). As a demonstration of potential applications, the P-Lig and P-Lig/RhB are used as photocured RTP coatings and RTP inks for fabricating 3D materials and for information encryption.

Photocatalytic Conversion of Lignin Models into Functionalized Aromatic Molecules Initiated by the Proton-Coupled Electron Transfer Process.

A mild and efficient method for lignin ß-O-4 cleavage and functionalization was achieved via photocatalysis. This protocol exhibits a broad scope of lignin models and excellent compatibility of functionalization reagents, constructing a series of functionalized lignin-based aromatic compounds. Highly selective formation of alkyl radical species through a proton-coupled electron transfer and ß-scission process provides the opportunity to form new C-C and C-N bonds by reaction with electrophilic reagents.

A Sustainable and Versatile Cellulose-based CO Surrogate for Carbonylative Reactions.

The highly toxic and flammable nature of CO lead to high handling demand for its use and storage, undoubtedly constricting its further academic exploration for carbonylative reactions in laboratory. Although many CO surrogates have been developed and applied in carbonylative reactions instead of CO gas, exploration of more versatile CO surrogates for diverse carbonylations is still highly desirable. Here we report a cellulose-based CO surrogate (cellulose-CO), which prepared from cheap and abundant cellulose through a simple and green process. The very mild and efficient CO release makes this reagent a highly competitive candidate for providing CO in carbonylation. This surrogate is compatible with a wide variety of functional groups in various carbonylative reactions due to the excellent compatibility of cellulose-CO. Moreover, the cellulose-CO exhibits excellent chemical stability which can be stored exposed to air for 12 months, making this CO surrogate a robust and general reagent in CO chemistry.

Biopolymers for Hygroscopic Material Development.

The effective management of atmospheric water will create huge value for mankind. Diversified and sustainable biopolymers that are derived from organisms provide rich building blocks for various hygroscopic materials. Here, a comprehensive review of recent advances in developing biopolymers for hygroscopic materials is provided. It is begun with a brief introduction of species diversity and the processes of obtaining various biopolymer materials from organisms. The fabrication of hygroscopic materials is then illustrated, with a specific focus on the use of biopolymer-derived materials as substrates to produce composites and the use of biopolymers as building blocks to fabricate composite gels. Next, the representative applications of biopolymer-derived hygroscopic materials for dehumidification, atmospheric water harvesting, and power generation are systematically presented. An outlook on future challenges and key issues worthy of attention are finally provided.

Light-Mediated Polymerization Catalyzed by Carbon Nanomaterials.

Carbon nanomaterials, specifically carbon dots and carbon nitrides, play a crucial role as heterogeneous photoinitiators in both radical and cationic polymerization processes. These recently introduced materials offer promising solutions to the limitations of current homogeneous systems, presenting a novel approach to photopolymerization. This review highlights the preparation and photocatalytic performance of these nanomaterials, emphasizing their application in various polymerization techniques, including photoinduced i) free radical, ii) RAFT, iii) ATRP, and iv) cationic photopolymerization. Additionally, it discusses their potential in addressing contemporary challenges and explores prospects in this field. Moreover, carbon nitrides, in particular, exhibit exceptional oxygen tolerance, underscoring their significance in radical polymerization processes and allowing their applications such as 3D printing, surface modification of coatings, and hydrogel engineering.

Assembly of porous filaments by interfacial complexation of nanochitin-based Pickering emulsion and seaweed alginate.

Interfacial polyelectrolyte complexation spinning is an all-water, easy-to-operate method for production of composite filaments. Herein, this concept is extended to interfacial polyelectrolyte-emulsion complexation (IPEC) that better encodes structural and functional attributes of biomass substances into the filaments. This allows for formation of composite filaments by drawing contacting oppositely-charged chitin nanofiber-stabilized Pickering emulsion and seaweed alginate solution. The parameters affecting spinnability of the system including water-to-oil ratio, alginate concentration, and pH are comprehensively elucidated to support the design and application of IPEC. The composite filaments exhibit varied diameters and diverse porous structures that are adjustable by properties of Pickering droplets. The droplet diameter of precursor emulsion and pore size in the filaments are well correlated, revealing controllability of the IPEC spinning. The filaments are mechanically robust in dry condition and show stable performance even in wet condition. The release rate of filaments that is pre-loaded with hydrophilic drug is regulated by the internal pore size, showing capability on sustained release. This study offers a new perspective toward dry spinning via interfacial complexation of complicated nanochitin-based structural building blocks, aiming at developing high-performance fiber materials for advanced applications.

Multisite photocatalytic depolymerization of lignin model compound utilizing full-spectrum light over magnetic microspheres.

Photocatalytic depolymerization is a high value-added approach for utilization of lignin. In this study, magnetic microspheres of FeCoRu@SiO2-TiO2 were synthesized by a co-precipitation method. Doping with CoOx and RuOx was used to improve the response to visible light, and doping with TiO2 was used to improve the response to ultraviolet light (λ < 380 nm). The lignin model compound depolymerization rate was >90%. The electron paramagnetic resonance results showed that the reaction occurred in two steps (aerobic phase and oxygen-free phase). Most of the O2- was produced in the first step by cleavage of C-O bonds. The second step was inhibited in an oxygen-free atmosphere. This research provides a valid method for enhancing the photocatalytic properties using full-spectrum light and exploring the lignin photocatalytic depolymerization mechanism. Further research is required to develop the catalyst properties and performance to produce radicals.

An ultra-thin and highly efficient electromagnetic interference shielding composite paper with hydrophobic and antibacterial properties.

Facing the increasing electromagnetic interference (EMI) pollution in the living environment, it is a new trend to explore an efficient EMI shielding material with facile fabrication and a wide range of application scenarios. A hydrophobic composite paper composed of silver nanowires (AgNWs) and kapok microfibers cellulose (MFC) was modified by methyl trimethoxy silane (MTMS) through a simple method. As a result, the composite paper has a good EMI shielding effectiveness (EMI SE) of 61.7 dB with electrical conductivity of 695.41 S/cm. The modification of MTMS improved the thermal stability performance of composite paper, which also increased its water contact angle to 113°. The free silver ions (Ag+) released from AgNWs can kill surrounding microbial bacteria, endowing the composite paper with good antibacterial property. Water resistance and antibacterial property enable MTMS/AgNWs/MFC composite paper to cope with complex application environments.

3D salient object detection based on light field integral imaging.

Potent usage of the multi-scale light field information for salient object detection (SOD) is the essential requirement of three-dimensional (3D) SOD. On this basis, a light field 3D-SOD scheme is proposed that employs the pixel mapping algorithm to achieve a more distinct representation of spatial and angular information in the four-dimensional (4D) light field, collaboratively mining the global saliency cues via the co-salient object detection (CoSOD) network. Compared with the previous method, our scheme filters out most of the noise by thoroughly leveraging the global dependence of the 4D light field, offering significant enhancements in saliency extraction performance and efficiency. Additionally, the 3D reconstruction results demonstrate the integral retention of the spatial and angular information of the original light field.

Room-temperature phosphorescent materials derived from natural resources.

Room-temperature phosphorescent (RTP) materials have enormous potential in many different areas. Additionally, the conversion of natural resources to RTP materials has attracted considerable attention. Owing to their inherent luminescent properties, natural materials can be efficiently converted into sustainable RTP materials. However, to date, only a few reviews have focused on this area of endeavour. Motivated by this lack of coverage, in this Review, we address this shortcoming and introduce the types of natural resource available for the preparation of RTP materials. We mainly focus on the inherent advantages of natural resources for RTP materials, strategies for activating and enhancing the RTP properties of the natural resources as well as the potential applications of these RTP materials. In addition, we discuss future challenges and opportunities in this area of research.