pH-degradable, bisphosphonate-loaded nanogels attenuate liver fibrosis by repolarization of M2-type macrophages.

Immune-suppressive (M2-type) macrophages can contribute to the progression of cancer and fibrosis. In chronic liver diseases, M2-type macrophages promote the replacement of functional parenchyma by collagen-rich scar tissue. Here, we aim to prevent liver fibrosis progression by repolarizing liver M2-type macrophages toward a nonfibrotic phenotype by applying a pH-degradable, squaric ester­based nanogel carrier system. This nanotechnology platform enables a selective conjugation of the highly water-soluble bisphosphonate alendronate, a macrophage-repolarizing agent that intrinsically targets bone tissue. The covalent delivery system, however, promotes the drug's safe and efficient delivery to nonparenchymal cells of fibrotic livers after intravenous administration. The bisphosphonate payload does not eliminate but instead reprograms profibrotic M2- toward antifibrotic M1-type macrophages in vitro and potently prevents liver fibrosis progression in vivo, mainly via induction of a fibrolytic phenotype, as demonstrated by transcriptomic and proteomic analyses. Therefore, the alendronate-loaded squaric ester­based nanogels represent an attractive approach for nanotherapeutic interventions in fibrosis and other diseases driven by M2-type macrophages, including cancer.

Interlayer and Phase Engineering Modifications of K-MoS2@C Nanoflowers for High-Performance Degradable Zn-Ion Batteries.

2D transition metal dichalcogenides (TMDs) have garnered significant interest as cathode materials for aqueous zinc-ion batteries (AZIBs) due to their open transport channels and abundant Zn2+ intercalation sites. However, unmodified TMDs exhibit low electrochemical activity and poor kinetics owing to the high binding energy and large hydration radius of divalent Zn2+. To overcome these limitations, an interlayer engineering strategy is proposed where K+ is preintercalated into K-MoS2 nanosheets, which then undergo in situ growth on carbon nanospheres (denoted as K-MoS2@C nanoflowers). This strategy stimulates in-plane redox-active sites, expands the interlayer spacing (from 6.16 to 9.42 Å), and induces the formation of abundant MoS2 1T-phase. The K-MoS2@C cathode demonstrates excellent redox activity and fast kinetics, attributed to the potassium ions acting as a structural "stabilizer" and an electrostatic interaction "shield," accelerating charge transfer, promoting Zn2+ diffusion, and ensuring structural stability. Meanwhile, the carbon nanospheres serve as a 3D conductive network for Zn2+ and enhance the cathode's hydrophilicity. More significantly, the outstanding electrochemical performance of K-MoS2@C, along with its superior biocompatibility and degradability of its related components, can enable an implantable energy supply, providing novel opportunities for the application of transient electronics.

Chiral Acetal-Based Stereo-Controlled Degradable Polymer Synthesis.

The precise synthesis of chiral polymers remains a significant challenge in polymer chemistry, particularly for applications in advanced biomedical and electronic materials. The development of degradable polymers is important for eco-friendly and advanced materials. Here, we introduce a stereo-controlled degradable polymer via cascade enyne metathesis polymerization and enantioselective acetal synthesis through Pd-catalyzed asymmetric hydroamination. This approach allows for the creation of chiral acetal-based polymers with controlled stereochemistry and degradability, highlighting their potential for use in drug delivery and electronic applications. This concept article reviews the background, development, and potential applications of these stereo-controlled degradable polymers.

Advance Technologies in Biodegradable Flexible Solid-State Supercapacitors: A Mini Review on Clean and Sustainable Energy.

In the recent times research towards solid state supercapacitors (SSS) have increased drastically due to the promising performance in futuristic technologies particularly in portable and flexible electronics like smart watches, smart fabrics, foldable smartphones and tablets. Also, when compared to supercapacitors using liquid electrolyte, solid electrolyte has several advantages like high energy density, safety, high cycle life, flexible form factor, and less environmental impact. The crucial factor determining the sustainability of a technology is the eco-friendliness since the natural resources are being exploited in a wide scale. Numerous studies have focused on biodegradable materials for supercapacitor electrodes, electrolytes, and other inactive components. Making use of these biodegradable materials to design a SSS enables the technology to sustain for a very long time since biodegradable materials are not only environment friendly but also, they show relatively high performance. This review focuses on recent progress of different biodegradable electrodes, and electrolytes along with their properties, electrochemical performance and biodegradable capabilities for SSS have been analyzed and provides a concise summary enabling readers to understand the importance of biodegradable materials and to narrow down the research in a more rational way.

Relationship between Composition and Environmental Degradation of Poly(isosorbide-co-diol oxalate) (PISOX) Copolyesters.

To reduce the global CO2 footprint of plastics, bio- and CO2-based feedstock are considered the most important design features for plastics. Oxalic acid from CO2 and isosorbide from biomass are interesting rigid building blocks for high Tg polyesters. The biodegradability of a family of novel fully renewable (bio- and CO2-based) poly(isosorbide-co-diol) oxalate (PISOX-diol) copolyesters was studied. We systematically investigated the effects of the composition on biodegradation at ambient temperature in soil for PISOX (co)polyesters. Results show that the lag phase of PISOX (co)polyester biodegradation varies from 0 to 7 weeks. All (co)polyesters undergo over 80% mineralization within 180 days (faster than the cellulose reference) except one composition with the cyclic codiol 1,4-cyclohexanedimethanol (CHDM). Their relatively fast degradability is independent of the type of noncyclic codiol and results from facile nonenzymatic hydrolysis of oxalate ester bonds (especially oxalate isosorbide bonds), which mostly hydrolyzed completely within 180 days. On the other hand, partially replacing oxalate with terephthalate units enhances the polymer's resistance to hydrolysis and its biodegradability in soil. Our study demonstrates the potential for tuning PISOX copolyester structures to design biodegradable plastics with improved thermal, mechanical, and barrier properties.

Azomethine-Containing Pyrrolo[3,2-b]pyrrole Copolymers for Simple and Degradable Conjugated Polymers.

Conjugated polymers have received significant attention as potentially lightweight and highly tailorable alternatives to inorganic semiconductors, but their synthesis is often complex, produces toxic byproducts, and they are not typically designed to be degradable or recyclable. These drawbacks necessitate dedicated efforts to discover materials with design motifs that enable targeted and efficient degradation of conjugated polymers. In this vein, the synthetic simplicity of 1,4-dihydropyrrolo[3,2-b]pyrroles (DHPPs) is exploited to access azomethine-containing copolymers via a benign acid-catalyzed polycondensation protocol. Polymerizations involve reacting a dialdehyde-functionalized dihydropyrrolopyrrole with p-phenylenediamine as the comonomer using p-toluenesulfonic acid as a catalyst. The inherent dynamic equilibrium of the azomethine bonds subsequently enabled the degradation of the polymers in solution in the presence of acid. Degradation of the polymers is monitored via NMR, UV-vis absorbance, and fluorescence spectroscopies, and the polymers are shown to be fully degradable. Notably, while absorbance measurements reveal a continued shift to higher energies with extended exposure to acid, fluorescence measurements show a substantial increase in the fluorescence response upon degradation. Results from this study encourage the continued development of environmentally-conscious polymerizations to attain polymeric materials with useful properties while simultaneously creating polymers with structural handles for end-of-life management or/and recyclability.

In vivo study of the utility of selective intra-arterial injection of thiopental for neuroprotection in reversible cerebral ischemia.

BACKGROUND: Neuroprotective agents are needed to reduce cerebral damage during surgical or neurointerventional procedures including stroke patients. PURPOSE: To evaluate if thiopental can be used as a neuroprotective agent when injected intra-arterially in a transient ischemia model. MATERIAL AND METHODS: In total, 24 rabbits were studied as four groups of six animals. Group 1 served as the control group. In group 2, transient ischemia was obtained by intracarotid administration of degradable starch microspheres (DSM). Group 3 was administered thiopental intra-arterially via the carotid artery. Group 4 (experimental group) received both thiopental and DSM intra-arterially. DSM and thiopental were administered through a microcatheter placed into the common carotid artery via the central ear artery access. After sacrifice, apoptotic cells in the cerebral tissues of the animals were evaluated in H&E and TUNEL stained slides. RESULTS: There was a significant increase in the number of apoptotic glial or neuronal cells in group 2 compared to the control group and group 3. The mean number of both the apoptotic neuronal cells (6.8 ± 2.1 vs. 2.5 ± 1.3, P < 0.001) and the apoptotic glial cells (9.4 ± 3.1 vs. 4.6 ± 1.6, P < 0.001) were higher in group 2 compared to group 4. In addition, a higher level of neurological improvement was observed in group 4 compared to group 2 based on neurological assessment score. CONCLUSION: The intra-arterial administration of thiopental has a protective effect on both glial and neuronal cells during temporary cerebral ischemia in low doses.

Synthesis and Characterization of Graft Copolymers with Poly(ε-caprolactone) Side Chain Using Hydroxylated Poly(ß-myrcene-co-α-methyl styrene).

Graft copolymers have unique application scenarios in the field of high-performance thermoplastic elastomers, resins and rubbers. ß-myrcene (My) is a biomass monomer derived from renewable plant resources, and its homopolymer has a low glass transition temperature and high elasticity. In this work, a series of tapered copolymers P(My-co-AMS)k (k = 1, 2, 3) were first synthesized in cyclohexane by one-pot anionic polymerization of My and α-methyl styrene (AMS) using sec-BuLi as the initiator. PAMS chain would fracture when heated at high temperature and could endow the copolymer with thermal degradation property. The effect of the incorporation of AMS unit on the thermal stability and glass transition temperature of polymyrcene main chain was studied. Subsequently, the double bonds in the linear copolymers were partially epoxidized and hydroxylated into hydroxyl groups to obtain hydroxylated copolymer, which was finally used to initiate the ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) to synthesize the graft copolymer with PCL as the side chain. All these copolymers before and after modifications were characterized by proton nuclear magnetic resonance (1H NMR), gel permeation chromatography (GPC), thermogravimetry analysis (TGA), and differential scanning calorimeter (DSC).

Poly(silyl ether)s as Degradable and Sustainable Materials: Synthesis and Applications.

Polymer research is currently focused on sustainable and degradable polymers which are cheap, easy to synthesize, and environmentally friendly. Silicon-based polymers are thermally stable and can be utilized in various applications, such as columns and coatings. Poly(silyl ether)s (PSEs) are an interesting class of silicon-based polymers that are easily hydrolyzed in either acidic or basic conditions due to the presence of the silyl ether Si-O-C bond. Synthetically, these polymers can be formed in several different ways, and the most effective and environmentally friendly synthesis is dehydrogenative cross coupling, where the byproduct is H2 gas. These polymers have a lot of promise in the polymeric materials field due to their sustainability, thermal stability, hydrolytic degradability, and ease of synthesis, with nontoxic byproducts. In this review, we will summarize the synthetic approaches for the PSEs in the recent literature, followed by the properties and applications of these materials. A conclusion and perspective will be provided at the end.

Biodegradable Microspheres for Transarterial Chemoembolization in Malignant Liver Disease.

Transarterial chemoembolization (TACE) has revolutionized the treatment landscape for malignant liver disease, offering localized therapy with reduced systemic toxicity. This manuscript delves into the use of degradable microspheres (DMS) in TACE, exploring its potential advantages and clinical applications. DMS-TACE emerges as a promising strategy, offering temporary vessel occlusion and optimized drug delivery. The manuscript reviews the existing literature on DMS-TACE, emphasizing its tolerability, toxicity, and efficacy. Notably, DMS-TACE demonstrates versatility in patient selection, being suitable for both intermediate and advanced stages. The unique properties of DMS provide advantages over traditional embolic agents. The manuscript discusses the DMS-TACE procedure, adverse events, and tumor response rates in HCC, ICC, and metastases.

Digital Light Processing to Afford High Resolution and Degradable CO2-Derived Copolymer Elastomers.

Vat photopolymerization 3D printing has proven very successful for the rapid additive manufacturing (AM) of polymeric parts at high resolution. However, the range of materials that can be printed and their resulting properties remains narrow. Herein, we report the successful AM of a series of poly(carbonate-b-ester-b-carbonate) elastomers, derived from carbon dioxide and bio-derived ϵ-decalactone. By employing a highly active and selective Co(II)Mg(II) polymerization catalyst, an ABA triblock copolymer (Mn=6.3 kg mol-1, ÐM=1.26) was synthesized, formulated into resins which were 3D printed using digital light processing (DLP) and a thiol-ene-based crosslinking system. A series of elastomeric and degradable thermosets were produced, with varying thiol cross-linker length and poly(ethylene glycol) content, to produce complex triply periodic geometries at high resolution. Thermomechanical characterization of the materials reveals printing-induced microphase separation and tunable hydrophilicity. These findings highlight how utilizing DLP can produce sustainable materials from low molar mass polyols quickly and at high resolution. The 3D printing of these functional materials may help to expedite the production of sustainable plastics and elastomers with potential to replace conventional petrochemical-based options.

Recent Advances in Environmentally Friendly Dual-crosslinking Polymer Networks.

Environmentally friendly crosslinked polymer networks feature degradable covalent or non-covalent bonds, with many of them manifesting dynamic characteristics. These attributes enable convenient degradation, facile reprocessibility, and self-healing capabilities. However, the inherent instability of these crosslinking bonds often compromises the mechanical properties of polymer networks, limiting their practical applications. In this context, environmentally friendly dual-crosslinking polymer networks (denoted EF-DCPNs) have emerged as promising alternatives to address this challenge. These materials effectively balance the need for high mechanical properties with the ability to degrade, recycle, and/or self-heal. Despite their promising potential, investigations into EF-DCPNs remain in their nascent stages, and several gaps and limitations persist. This Review provides a comprehensive overview of the synthesis, properties, and applications of recent progress in EF-DCPNs. Firstly, synthetic routes to a rich variety of EF-DCPNs possessing two distinct types of dynamic bonds (i.e., imine, disulfide, ester, hydrogen bond, coordination bond, and other bonds) are introduced. Subsequently, complex structure- and dynamic nature-dependent mechanical, thermal, and electrical properties of EF-DCPNs are discussed, followed by their exemplary applications in electronics and biotechnology. Finally, future research directions in this rapidly evolving field are outlined.

Aldehyde End-Capped Degradable Polyethylenes from Hydrogen-Controlled Ethylene/CO Copolymerization.

To access degradable polyolefin plastic, non-alternating copolymerization of ethylene (E) and carbon monoxide (CO) for producing polyethylene (PE) with in-chain ketones is particularly appealing; however, it still presents significant challenges such as molecular weight modulation (hydrogen response) and chain endgroup control (functional terminal). In this study, we achieved hydrogen-controlled E/CO non-alternating copolymerization using late transition metal catalysts. This process results in linear PEs containing the desired non-alternating in-chain keto groups (1.0-9.3 mol%) and with tunable molecular weights ranging from 43 to 195 kDa. In this reaction, H2 serves as a chain transfer agent, modulating the polymer's molecular weight, forming unique aldehyde endgroups and eliminating usual olefinic endgroups; CO undergoes non-alternating insertion into the PE chain, resulting in a strictly non-alternating structure (> 99%) for the keto-PE. The dispersed incorporation of in-chain keto groups retains bulk properties of PE and makes PE susceptible to photodegradation, which produces significantly lower molecular weight polymers and oligomers with unambiguous vinyl and acetyl terminals.

Water-Degradable Oxygen-Rich Polymers with AB/ABB Units from Fast and Selective Copolymerization.

Researchers have been chasing plastics that can automatically and fully degrade into valuable products under natural conditions. Here, we develop a series of water-degradable polymers from the first reported fast and selective cationic copolymerization of formaldehyde (B) with cyclic anhydrides (A). In addition to readily accessible monomers, the method is performed at industrially relevant temperatures (~100 °C), takes tens or even minutes, and uses common acid as the catalyst. Interestingly, such polymers possess tunable AB/ABB-type repeating units, which are considered to be thermodynamic and kinetic products, respectively, resulting in low carbon content ([O] : [C] up to 1 : 1). Notably, the polymers can completely degrade to valuable diacids within 150 days in water at ambient temperature owing to the incorporation of carboxyl terminals and acid-responsive acetal units. By washing with aqueous sodium carbonate, the polymers are relatively stable over several months.

Ring-Opening Terpolymerisation of Elemental Sulfur Waste with Propylene Oxide and Carbon Disulfide via Lithium Catalysis.

Elemental sulfur, a waste product of the oil refinement process, represents a promising raw material for the synthesis of degradable polymers. We show that simple lithium alkoxides facilitate the polymerisation of elemental sulfur S8 with industrially relevant propylene oxide (PO) and CS2 (a base chemical sourced from waste S8 itself) to give poly(monothiocarbonate-alt-Sx) in which x can be controlled by the amount of supplied sulfur. The in situ generation of thiolate intermediates obtained by a rearrangement, which follows CS2 and PO incorporation, allows to combine S8 and epoxides into one polymer sequence that would otherwise not be possible. Mechanistic investigations reveal that alkyl oligosulfide intermediates from S8 ring opening and sulfur chain length equilibration represent the better nucleophiles for inserting the next PO if compared to the trithiocarbonates obtained from the competing CS2 addition, which causes the sequence selectivity. The polymers can be crosslinked in situ with multifunctional thiols to yield reprocessable and degradable networks. Our report demonstrates how mechanistic understanding allows to combine intrinsically incompatible building blocks for sulfur waste utilisation.

Photocatalytic Cracking of non-Biodegradable Plastics to Chemicals and Fuels.

Plastic pollution is worsening the living conditions on Earth, primarily due to the toxicity and stability of non-biodegradable plastics (NBPs). Photocatalytic cracking of NBPs is emerging as a promising way to cleave inert C-C bonds and abstract the carbon atoms from these wastes into valuable chemicals and fuels. However, controlling these processes is a huge challenge, ascribed to the complicated reactions of various NBPs. Herein, we summarize recent advances in the CO2 and carbon-radical-mediated photocatalytic cracking of NBPs, with an emphasis on the pivotal intermediates. The CO2-mediated cracking proceeded with indiscriminate C-H/C-C bond cleavage of NBPs and tandem photoreduction of CO2, while carbon-radical-mediated cracking was realized by the prior activation of C-H bonds for selective C-C bond cleavage of NBPs. Catalytic generation and conversion of different intermediates greatly depend on the kinds of active species and the structure of photocatalysts under irradiation. Meanwhile, the fate of a specific intermediate is compared with small molecule activation to reveal the key problems in the cracking of NBPs. Finally, the challenges and potential directions are discussed to improve the overall efficiency in the photocatalytic cracking of NBPs.

[Thoughts on the Biological Evaluation of Biodegradable Cardiovascular Implants].

In recent years, new degradable materials have been applied to cardiovascular implants. Cardiovascular implants with different physicochemical properties and degradation properties have special endpoints for their biological evaluation. In this study, the end points of biological evaluation of degradable cardiovascular implants were reviewed by taking vascular stents and occluders as examples.

Feasibility of repairing skin defects by VEGF165 gene-modified iPS-HFSCs seeded on a 3D printed scaffold containing astragalus polysaccharide.

The preparation of biodegradable scaffolds loaded with cells and cytokine is a feature of tissue-engineered skin. IPSCs-based tissue-engineered skin treatment for wound repair is worth exploring. Healthy human skin fibroblasts were collected and reprogrammed into iPSCs. After gene modification and induction, CK19+ /Integrinß1+ /CD200+ VEGF165 gene-modified iPS-HFSCsGFP were obtained and identified by a combination of immunofluorescence and RT-qPCR. Astragalus polysaccharide-containing 3D printed degradable scaffolds were prepared and co-cultured with VEGF165 gene-modified iPS-HFSCsGFP , and the biocompatibility and spatial structure of the tissue-engineered skin was analysed by cell counting kit-8 (CCK8) assay and scanning electron microscopy. Finally, the tissue-engineered skin was transplanted onto the dorsal trauma of nude mice, and the effect of tissue-engineered skin on the regenerative repair of total skin defects was evaluated by a combination of histology, immunohistochemistry, immunofluorescence, RT-qPCR, and in vivo three-dimensional reconstruction under two-photon microscopy. CK19+ /Integrinß1+ /CD200+ VEGF165 gene-modified iPS-HFSCsGFP , close to the morphology and phenotype of human-derived hair follicle stem cells, were obtained. The surface of the prepared 3D printed degradable scaffold containing 200 µg/mL astragalus polysaccharide was enriched with honeycomb-like meshwork, which was more conducive to the proliferation of the resulting cells. After tissue-engineered skin transplantation, combined assays showed that it promoted early vascularization, collagen and hair follicle regeneration and accelerated wound repair. VEGF165 gene-modified iPS-HFSCsGFP compounded with 3D printed degradable scaffolds containing 200 µg/mL astragalus polysaccharide can directly and indirectly participate in vascular, collagen, and hair follicle regeneration in the skin, achieving more complete structural and functional skin regenerative repair.

Cell-Like Capsules with "Smart" Compartments.

Eukaryotic cells have inner compartments (organelles), each with distinct properties and functions. One mimic of this architecture, based on biopolymers, is the multicompartment capsule (MCC). Here, MCCs in which the inner compartments are chemically unique and "smart," i.e., responsive to distinct stimuli in an orthogonal manner are created. Specifically, one compartment alone is induced to degrade when the MCC is contacted with an enzyme while other compartments remain unaffected. Similarly, just one compartment gets degraded upon contact with reactive oxygen species generated from hydrogen peroxide (H2 O2 ). And thirdly, one compartment alone is degraded by an external, physical stimulus, namely, by irradiating the MCC with ultraviolet (UV) light. All these specific responses are achieved without resorting to complicated chemistry to create the compartments: the multivalent cation used to crosslink the biopolymer alginate (Alg) is simply altered. Compartments of Alg crosslinked by Ca2+ are shown to be sensitive to enzymes (alginate lyases) but not to H2 O2 or UV, whereas the reverse is the case with Alg/Fe3+ compartments. These results imply the ability to selectively burst open a compartment in an MCC "on-demand" (i.e., as and when needed) and using biologically relevant stimuli. The results are then extended to a sequential degradation, where compartments in an MCC are degraded one after another, leaving behind an empty MCC lumen. Collectively, this work advances the MCC as a platform that not only emulates key features of cellular architecture, but can also begin to capture rudimentary cell-like behaviors.

A Photo-degradable Crosslinker for the Development of Light-responsive Protocell Membranes.

The achievement of light-responsive behaviours is an important target for protocell engineering to allow control of fundamental protocellular processes such as communication via diffusible chemical signals, shape changes or even motility at the flick of a switch. As a step towards this ambitious goal, here we describe the synthesis of a novel poly(ethylene glycol)-based crosslinker, reactive towards nucleophiles, that effectively degrades with UV light (405 nm). We demonstrate its utility for the fabrication of the first protocell membranes capable of light-induced disassembly, for the photo-generation of patterns of protocells, and for the modulation of protocell membrane permeability. Overall, our results not only open up new avenues towards the engineering of spatially organised, communicating networks of protocells, and of micro-compartmentalised systems for information storage and release, but also have important implications for other research fields such as drug delivery and soft materials chemistry.