Controlled Carbon Dioxide Terpolymerizations to Deliver Toughened yet Recyclable Thermoplastics.

Using CO2 polycarbonates as engineering thermoplastics has been limited by their mechanical performances, particularly their brittleness. Poly(cyclohexene carbonate) (PCHC) has a high tensile strength (40 MPa) but is very brittle (elongation at break <3%), which limits both its processing and applications. Here, well-defined, high molar mass CO2 terpolymers are prepared from cyclohexene oxide (CHO), cyclopentene oxide (CPO), and CO2 by using a Zn(II)Mg(II) catalyst. In the catalysis, CHO and CPO show reactivity ratios of 1.53 and 0.08 with CO2, respectively; as such, the terpolymers have gradient structures. The poly(cyclohexene carbonate)-grad-poly(cyclopentene carbonate) (PCHC-grad-PCPC) have high molar masses (86 < Mn < 164 kg mol-1, DM < 1.22) and good thermal stability (Td > 250 °C). All the polymers are amorphous with a single, high glass transition temperature (96 < Tg < 108 °C). The polymer entanglement molar masses, determined using dynamic mechanical analyses, range from 4 < Me < 23 kg mol-1 depending on the polymer composition (PCHC:PCPC). These polymers show superior mechanical performance to PCHC; specifically the lead material (PCHC0.28-grad-PCPC0.72) shows 25% greater tensile strength and 160% higher tensile toughness. These new plastics are recycled, using cycles of reprocessing by compression molding (150 °C, 1.2 ton m-2, 60 min), four times without any loss in mechanical properties. They are also efficiently chemically recycled to selectively yield the two epoxide monomers, CHO and CPO, as well as carbon dioxide, with high activity (TOF = 270-1653 h-1, 140 °C, 120 min). The isolated recycled monomers are repolymerized to form thermoplastic showing the same material properties. The findings highlight the benefits of the terpolymer strategy to deliver thermoplastics combining the beneficial low entanglement molar mass, high glass transition temperatures, and tensile strengths; PCHC properties are significantly improved by incorporating small quantities (23 mol %) of cyclopentene carbonate linkages. The general strategy of designing terpolymers to include chain segments of low entanglement molar mass may help to toughen other brittle and renewably sourced plastics.

Antibacterial polylactic acid fabricated via Pickering emulsion approach with polyethyleneimine and polydopamine modified cellulose nanocrystals as emulsion stabilizers.

Antibacterial biodegradable plastics are highly demanded for food package and disposable medical plastic consumables. Incorporating antibacterial nanoagents into polymer matrices is an effective method to endow polymers with antibacterial activity. However, synthesis of sustainable antibacterial nanoagents with high antibacterial activity via facile approach and well dispersion of them in polymer matrices are still challenging. In this study, polyethyleneimine (PEI) was grafted on surface of cellulose nanocrystals (CNCs) via the oxidation self-polymerization of dopamine (DA) and the Michael addition/Schiff base reaction between DA and PEI. The resulted PEI and polydopamine modified CNCs (PPCs) showed substantially enhanced antibacterial activity and reduced cytotoxicity for NIH3T3 than PEI due to increased local concentration and anchoring of PEI. The minimum concentration of PPCs to achieve antibacterial rate of 99.99 % against S. aureus and E. coli were about 50 and 20 µg/mL, respectively. PPCs displayed outstanding emulsifying ability, and PPC coated polylactic acid (PLA) microspheres were obtained by drying PPC stabilized PLA Pickering emulsion, leading to a well dispersion of PPCs in PLA. PPC/PLA film prepared by hot-pressing displayed great antibacterial performance and enhanced mechanical properties. Therefore, this study proposed a facile approach to fabricate biocompatible antibacterial nanoagents and plastics.

Toughening CO2 -Derived Copolymer Elastomers Through Ionomer Networking.

Utilizing carbon dioxide (CO2 ) to make polycarbonates through the ring-opening copolymerization (ROCOP) of CO2 and epoxides valorizes and recycles CO2 and reduces pollution in polymer manufacturing. Recent developments in catalysis provide access to polycarbonates with well-defined structures and allow for copolymerization with biomass-derived monomers; however, the resulting material properties are underinvestigated. Here, new types of CO2 -derived thermoplastic elastomers (TPEs) are described together with a generally applicable method to augment tensile mechanical strength and Young's modulus without requiring material re-design. These TPEs combine high glass transition temperature (Tg ) amorphous blocks comprising CO2 -derived poly(carbonates) (A-block), with low Tg poly(ε-decalactone), from castor oil, (B-block) in ABA structures. The poly(carbonate) blocks are selectively functionalized with metal-carboxylates where the metals are Na(I), Mg(II), Ca(II), Zn(II) and Al(III). The colorless polymers, featuring <1 wt% metal, show tunable thermal (Tg ), and mechanical (elongation at break, elasticity, creep-resistance) properties. The best elastomers show >50-fold higher Young's modulus and 21-times greater tensile strength, without compromise to elastic recovery, compared with the starting block polymers. They have wide operating temperatures (-20 to 200 °C), high creep-resistance and yet remain recyclable. In the future, these materials may substitute high-volume petrochemical elastomers and be utilized in high-growth fields like medicine, robotics, and electronics.

Tannic acid-coated cellulose nanocrystals with enhanced mucoadhesive properties for aquaculture.

Mucoadhesion can be exploited as a strategy to target drug and nutrient delivery to the outer mucosal layers of fish in aquaculture farms. Cellulose nanocrystals (CNC) derived from cellulose pulp fibers can interact with the mucosal membranes via hydrogen bonding, however, their mucoadhesive properties are weak and should be enhanced. In this study, CNC were coated with tannic acid (TA), a plant polyphenol with excellent wet-resistant bioadhesive properties, to strengthen their mucoadhesive capability. The optimal CNC:TA mass ratio was determined to be 20:1. The modified CNCs were 190 ± 40 nm in length and 21 ± 4 nm wide and displayed excellent colloidal stability, with a zeta potential of -35 mV. Turbidity titrations and rheological measurements revealed that the modified CNC possessed superior mucoadhesive properties compared to pristine CNC. Modification with tannic acid introduced additional functional groups for stronger hydrogen bond formation and hydrophobic interactions with mucin, which was confirmed by a large reduction in viscosity enhancement values in the presence of chemical blockers (urea and Tween80). The enhanced mucoadhesion of the modified CNC could be utilized for the fabrication of a mucoadhesive drug delivery system to promote sustainable aquaculture practices.

Changes in Expression of Tumor Suppressor Gene RKIP Impact How Cancers Interact with Their Complex Environment.

Tumor microenvironment (TME) is the immediate environment where cancer cells reside in a tumor. It is composed of multiple cell types and extracellular matrix. Microenvironments can be restrictive or conducive to the progression of cancer cells. Initially, microenvironments are suppressive in nature. Stepwise accumulation of mutations in oncogenes and tumor suppressor genes enables cancer cells to acquire the ability to reshape the microenvironment to advance their growth and metastasis. Among the many genetic events, the loss-of-function mutations in tumor suppressor genes play a pivotal role. In this review, we will discuss the changes in TME and the ramifications on metastasis upon altered expression of tumor metastasis suppressor gene RKIP in breast cancer cells.

RKIP localizes to the nucleus through a bipartite nuclear localization signal and interaction with importin α to regulate mitotic progression.

Raf kinase inhibitor protein (RKIP) is a multifunctional modulator of intracellular signal transduction. Although most of its functions have been considered cytosolic, we show here that the localization of RKIP is primarily nuclear in both growing and quiescent Madin-Darby canine kidney epithelial cells and in Cal-51 and BT-20 human breast cancer cells. We have identified a putative bipartite nuclear localization signal (NLS) in RKIP that maps to the surface of the protein surrounding a known regulatory region. Like classical NLS sequences, the putative NLS of RKIP is rich in arginine and lysine residues. Deletion of and point mutations in the putative NLS lead to decreased nuclear localization. Point mutation of all the basic residues in the putative NLS of RKIP particularly strongly reduces nuclear localization. We found consistent results in reexpression experiments with wildtype or mutant RKIP in RKIP-silenced cells. A fusion construct of the putative NLS of RKIP alone to a heterologous reporter protein leads to nuclear localization of the fusion protein, demonstrating that this sequence alone is sufficient for import into the nucleus. We found that RKIP interacts with the nuclear transport factor importin α in BT-20 and MDA-MB-231 human breast cancer cells, suggesting importin-mediated active nuclear translocation. Evaluating the biological function of nuclear localization of RKIP, we found that the presence of the putative NLS is important for the role of RKIP in mitotic checkpoint regulation in MCF-7 human breast cancer cells. Taken together, these findings suggest that a bipartite NLS in RKIP interacts with importin α for active transport of RKIP into the nucleus and that this process may be involved in the regulation of mitotic progression.

A Negative Regulatory Role for RKIP in Breast Cancer Immune Response.

Raf-1 kinase inhibitor protein was first identified as a negative regulator of the Raf signaling pathway. Subsequently, it was shown to have a causal role in containing cancer progression and metastasis. Early studies suggested that RKIP blocks cancer progression by inhibiting the Raf-1 pathway. However, it is not clear if the RKIP tumor and metastasis suppression function involve other targets. In addition to the Raf signaling pathway, RKIP has been found to modulate several other signaling pathways, affecting diverse biological functions including immune response. Recent advances in medicine have identified both positive and negative roles of immune response in cancer initiation, progression and metastasis. It is possible that one way that RKIP exerts its effect on cancer is by targeting an immune response mechanism. Here, we provide evidence supporting the causal role of tumor and metastasis suppressor RKIP in downregulating signaling pathways involved with immune response in breast cancer cells and discuss its potential ramification on cancer therapy.

Electroconductive cellulose nanocrystals - Synthesis, properties and applications: A review.

There is a growing interest in the synthesis of electrically conductive cellulose nanocrystal (CNC) for advanced applications, such as supercapacitor, batteries, sensor, and printed electronics. CNC is recognized as an attractive template for the fabrication of functional nanomaterials. Since CNC possesses many attractive properties, it is a sustainable template to prepare conductive nanomaterials, by either coating it with a conductive material or transforming it into carbon nanorods. This review summarizes the utilization of a sustainable and low-cost CNC to produce conductive nanocomposites via an environmentally friendly process. Electroconductive CNCs with enhanced electrical properties, lower electrical percolation threshold, and better mechanical properties can be produced and are attractive systems for many new applications.

Bile Acid Sequestrants for Hypercholesterolemia Treatment Using Sustainable Biopolymers: Recent Advances and Future Perspectives.

Bile acids, the endogenous steroid nucleus containing signaling molecules, are responsible for the regulation of multiple metabolic processes, including lipoprotein and glucose metabolism to maintain homeostasis. Within our body, they are directly produced from their immediate precursors, cholesterol C (low-density lipoprotein C, LDL-C), through the enzymatic catabolic process mediated by 7-α-hydroxylase (CYP7A1). Bile acid sequestrants (BASs) or amphiphilic resins that are nonabsorbable to the human body (being complex high molecular weight polymers/electrolytes) are one of the classes of drugs used to treat hypercholesterolemia (a high plasma cholesterol level) or dyslipidemia (lipid abnormalities in the body); thus, they have been used clinically for more than 50 years with strong safety profiles as demonstrated by the Lipid Research Council-Cardiovascular Primary Prevention Trial (LRC-CPPT). They reduce plasma LDL-C and can slightly increase high-density lipoprotein C (HDL-C) levels, whereas many of the recent clinical studies have demonstrated that they can reduce glucose levels in patients with type 2 diabetes mellitus (T2DM). However, due to higher daily dosage requirements, lower efficacy in LDL-C reduction, and concomitant drug malabsorption, research to develop an "ideal" BAS from sustainable or natural sources with better LDL-C lowering efficacy and glucose regulations and lower side effects is being pursued. This Review discusses some recent developments and their corresponding efficacies as bile removal or LDL-C reduction of natural biopolymer (polysaccharide)-based compounds.

Emulsions undergoing phase transition: Effect of emulsifier type and concentration.

Pickering emulsion stabilized by cellulose nanocrystals (CNCs) during the phase transition of the dispersed oil is poorly understood. We investigated the capability of CNC in stabilizing Pickering emulsions during the temperature-induced phase transition. Paraffin wax emulsions stabilized by sodium dodecyl sulfate (SDS) were less stable than CNC stabilized emulsions. The relationship between droplet size and emulsifier content was examined, and a new model describing this relationship is proposed. The droplet size of CNC-based systems was not affected by temperature variation, even at low CNC concentrations. The minimum CNC content required to stabilize the paraffin wax emulsion was lower than SDS. DSC results indicated that higher droplet surface coverage with emulsifiers enhanced the deformation resistance of the crystallized droplets, which enhanced the emulsion stability. Temperature sweep viscosity measurements showed that the stability of CNC-based systems was not significantly impacted by the phase transition of the paraffin wax. Rheological amplitude sweep analysis indicated that emulsions above the melting point of paraffin wax were more stable at all strain levels. However, the SDS-based systems displayed substantial heterogeneity after the liquid-solid transition. Frequency sweep tests revealed that CNC-stabilized emulsions were more stable than SDS-stabilized emulsions.

Effect of Oil Phase Transition on the Stability of Pickering Emulsions Stabilized by Cellulose Nanocrystals.

Emulsifier design is one of the key strategies in interfacial engineering for emulsion stability. In this study, cellulose nanocrystals (CNCs) were used as an interfacial stabilizer to improve the stability of coconut oil (CO)-in-water emulsions. A Pickering emulsion consisting of CO and water was optimized based on four parameters using the response surface methodology and the central composite design. The droplet coverage remained stable during the crystallization of the oil phase when the temperature was reduced below the melting temperature of CO. Fluorescent-labeled CNCs were used to monitor the partitioning of CNC at the O/W interface during the crystallization of CO. The Generation 6 polyamidoamine (G6 PAMAM) dendrimer covalently grafted on the surface of CNC was used as an intrinsic fluorescent dye. Since it displayed similar properties as the emulsifier, it could be used to monitor the CNC coverage on the oil droplets at various temperatures. The fluorescence micrographs showed that the emission of PAMAM CNCs at the O/W interface remained on both the liquid and solid CO droplets, confirming that oil crystallization did not affect the fluorescent CNC coverage on the oil droplets.

The RhoA dependent anti-metastatic function of RKIP in breast cancer.

Raf-1 kinase inhibitor protein was initially discovered as a physiological kinase inhibitor of the MAPK signaling pathway and was later shown to suppress cancer cell invasion and metastasis. Yet, the molecular mechanism through which RKIP executes its effects is not completely defined. RhoA has both a pro- and anti-metastatic cell-context dependent functions. Given that Rho GTPases primarily function on actin cytoskeleton dynamics and cell movement regulation, it is possible that one way RKIP hinders cancer cell invasion/metastasis is by targeting these proteins. Here we show that RKIP inhibits cancer cell invasion and metastasis by stimulating RhoA anti-tumorigenic functions. Mechanistically, RKIP activates RhoA in an Erk2 and GEF-H1 dependent manner to enhance E-cadherin membrane localization and inhibit CCL5 expression.

Encapsulation and controlled release of vitamin C in modified cellulose nanocrystal/chitosan nanocapsules.

Vitamin C (VC), widely used in food, pharmaceutical and cosmetic products, is susceptible to degradation, and new formulations are necessary to maintain its stability. To address this challenge, VC encapsulation was achieved via electrostatic interaction with glycidyltrimethylammonium chloride (GTMAC)-chitosan (GCh) followed by cross-linking with phosphorylated-cellulose nanocrystals (PCNC) to form VC-GCh-PCNC nanocapsules. The particle size, surface charge, degradation, encapsulation efficiency, cumulative release, free-radical scavenging assay, and antibacterial test were quantified. Additionally, a simulated human gastrointestinal environment was used to assess the efficacy of the encapsulated VC under physiological conditions. Both VC loaded, GCh-PCNC, and GCh-Sodium tripolyphosphate (TPP) nanocapsules were spherical with a diameter of 450 â€‹± â€‹8 and 428 â€‹± â€‹6 â€‹nm respectively. VC-GCh-PCNC displayed a higher encapsulation efficiency of 90.3 â€‹± â€‹0.42% and a sustained release over 14 days. The release profiles were fitted to the first-order and Higuchi kinetic models with R2 values greater than 0.95. VC-GCh-PCNC possessed broad-spectrum antibacterial activity with a minimum inhibition concentration (MIC) of 8-16 â€‹µg/mL. These results highlight that modified CNC-based nano-formulations can preserve, protect and control the release of active compounds with improved antioxidant and antibacterial properties for food and nutraceutical applications.

Fishing for the right probiotic: host-microbe interactions at the interface of effective aquaculture strategies.

Effective aquaculture management strategies are paramount to global food security. Growing demands stimulate the intensification of production and create the need for practices that are both economically viable and environmentally sustainable. Importantly, pathogenic microbes continue to be detrimental to fish growth and survival. In terms of host health, the intestinal mucosa and its associated consortium of microbes have a critical role in modulating fitness and present an attractive opportunity to promote health at this interface. In light of this, the administration of probiotic microorganisms is being considered as a means to restore and sustain health in fish. Current evidence suggests that certain probiotic strains might be able to augment immunity, enhance growth rate and protect against infection in salmonids, the most economically important family of farmed finfish. This review affirms the relevance of host-microbe interactions in salmonids in light of emerging evidence, with an emphasis on intestinal health. In addition, the current understanding of the mode of action of probiotics in salmonid fish is discussed, along with delivery systems that can effectively carry the living microbes.

Product line transformation, foreign sales, and firm value: Evidence from COVID-19 pandemic governance in urban China.

Using a sample of Chinese firms, we examine stock market reaction to firms that announce a change in their product lines to those related to COVID-19 management (medical masks and ventilators, among others). We find the market reacts positively to the announcements. In addition, when a firm ordinarily has a large share of export sales, the stock market reaction is more salient, indicating that export sales provide a certification effect that positively signals investors. Additional analysis on moderating effects suggest that, conditional on foreign sales, prior experience with medical product lines or less uncertainty about supply availability enhances the cumulative announcement returns (CARs), while the adverse impact of firm size on CAR magnifies.

Effect of Molecular Architecture and Composition on the Aggregation Pathways of POEGMA Random Copolymers in Water.

Understanding of the temperature-induced phase transition of poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) random copolymers with varied composition remains largely incomplete. Upon heating they can form either macroscopically phase-separated aggregates or micelles. We examined the effect of polymer architecture by rationally designing and synthesizing various POEGMA copolymer structures via atom transfer radical polymerization using OEGMA monomers of different EO lengths. Micelle formation occurred for copolymers with a small fraction of long side chains counterbalanced by an appropriate number of short side chains, while macroscopic phase separation occurred for other copolymer compositions. In some copolymer compositions and architectures, micelle formation followed by macroscopic phase separation occurred, and the temperature of these phase transitions could be tailored accordingly. This new strategy allows the control over the microstructure and specific transition temperatures enabling, for instance, the preparation of nanocarriers for encapsulating hydrophobic compounds.

Interfacial Control of the Synthesis of Cellulose Nanocrystal Gold Nanoshells.

Cellulose nanocrystal (CNC) gold nanoshell was prepared using a polymer-coated CNC as a template. A seed-mediated shell growth approach (ex situ) was employed, gold nanoparticles (AuNPs) of two sizes were prepared, and the effect of the size of AuNP on the shell quality (smoothness, evenness, and continuity) was elucidated. Additionally, a novel one-pot synthesis approach (in situ) was evaluated for the preparation of the gold nanoshell, where polymer-coated CNCs with adsorbed ascorbic acid were used to reduce Au ions to form a metallic gold shell on CNC. The surface coverage was manipulated by adding different amounts of plating solutions. The formation and morphology of gold nanoshells were evaluated by zeta potential measurements, dynamic light scattering, UV-vis spectroscopy, and transmission electron microscopy (TEM). The catalytic performance of the CNC-gold nanostructures for the reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) was governed by the surface area of gold shells.