Laser Patterning of Porous Support Membranes to Enhance the Effective Surface Area of Thin-Film Composite-Facilitated Transport Membranes for CO2 Separation.

Although thin-film composite membranes have achieved great success in CO2 separation, further improvements in the CO2 permeance are required to reduce the size and cost of the CO2 separation process. Herein, we report the fabrication of composite membranes with high CO2 permeability using a laser-patterned porous membrane as the support membrane. High-aspect-ratio micropatterns with well-defined micropores on their surface were carved on microporous polymer supports by a direct laser writing process using a short-pulsed laser. By using a Galvano scanner and optimizing the laser conditions and target materials, in-plane micropatterns, such as microhole arrays, microline grating, microlattices, and out-of-plane hierarchical micropatterns, were created on porous membranes. An aqueous suspension of hydrogel microparticles doped with an amine-based mobile carrier was sprayed onto the patterned surface to form a defect-free thin separation layer. The surface area of the separation layer on the patterned support is up to 80% larger than that of flat pristine membranes, resulting in a 52% higher CO2 permeance (1106 GPU) with a CO2/N2 selectivity of 172. The laser-patterned porous membranes allow the development of inexpensive and high-performance functional membranes not only for CO2 separation but also for other applications, such as water treatment, cell culture, micro-TAS, and membrane reactors.

Critical role of lattice vacancies in pressure-induced phase transitions of baroplastic diblock copolymers.

Baroplastic diblock copolymers exhibit order-disorder transitions and melt upon compression at low temperatures, in some cases even at ambient temperatures. Their unique low-temperature processability makes them promising candidates for sustainable polymeric materials. Despite their potential, however, the molecular mechanisms governing the pressure-induced phase transitions of these copolymers remain largely unexplored. This study develops a compressible self-consistent field theory for baroplastic copolymers based on a simple lattice vacancy model that explicitly incorporates voids to account for compressibility. The theory shows that the selective presence of voids in compressible domains stabilizes the ordered phase, while a reduction of voids under compression leads to the order-disorder transition. In addition, this work demonstrates for the first time the critical role of gas absorption rates in each segment in the pressure-induced order-disorder transition of baroplastic diblock copolymers. These findings have significant implications for the rational design of baroplastic polymers with tailored low-temperature processability.

Deep-Sea-Inspired Chemistry: A Hitchhiker's Guide to the Bottom of the Ocean for Chemists.

The ocean constitutes approximately 70% of Earth's surface. Its average depth is 3688 m, of which depths beyond 200 m are classified as the deep sea. The deep sea is distinct from the surface of the ocean in terms of pressure, temperature, and sunlight. The unique physicochemical processes under the extreme environment of the deep sea and the specialized biochemical mechanisms developed by organisms to survive in the deep sea can serve as a vast source of inspiration for scientific and technological advancements. In this Perspective, we discuss three examples of deep-sea-inspired chemistry: (1) soft materials that respond to high pressures such as those observed in the deep sea; (2) molecular self-assembly inspired by the chemistry of hot and compressed water in deep-sea hydrothermal vents; and (3) nanobiotechnology and biomimetics inspired by survival strategies of deep-sea organisms. Finally, we provide an outlook on deep-sea-inspired chemistry. This Perspective aims to promote the sustainable utilization of the ocean based on knowledge, as opposed to the conventional utilization of the ocean solely based on resources. We hope that this Perspective will encourage chemists to harness their inspiration gleaned from the deep sea.

Why does 2-(2-aminoethylamino)ethanol have superior CO2 separation performance to monoethanolamine? A computational study.

Our computational reaction analysis shows that 2-(2-aminoethylamino)ethanol (AEEA) has superior performance to monoethanolamine for CO2 separation, in terms of its ability to sorb CO2 by its primary amine and desorb CO2 by its secondary amine.

Glycine amino acid transformation under impacts by small solar system bodies, simulated via high-pressure torsion method.

Impacts by small solar system bodies (meteoroids, asteroids, comets and transitional objects) are characterized by a combination of energy dynamics and chemical modification on both terrestrial and small solar system bodies. In this context, the discovery of glycine amino acid in meteorites and comets has led to a hypothesis that impacts by astronomical bodies could contribute to delivery and polymerization of amino acids in the early Earth to generate proteins as essential molecules for life. Besides the possibility of abiotic polymerization of glycine, its decomposition by impacts could generate reactive groups to form other essential organic biomolecules. In this study, the high-pressure torsion (HPT) method, as a new platform for simulation of impacts by small solar system bodies, was applied to glycine. In comparison with high-pressure shock experiments, the HPT method simultaneously introduces high pressure and deformation strain. It was found that glycine was not polymerized in the experimental condition assayed, but partially decomposed to ethanol under pressures of 1 and 6 GPa and shear strains of < 120 m/m. The detection of ethanol implies the inherent availability of remaining nitrogen-containing groups, which can incorporate to the formation of other organic molecules at the impact site. In addition, this finding highlights a possibility of the origin of ethanol previously detected in comets.

Assembly of Defect-Free Microgel Nanomembranes for CO2 Separation.

The development of robust and thin CO2 separation membranes that allow fast and selective permeation of CO2 will be crucial for rebalancing the global carbon cycle. Hydrogels are attractive membrane materials because of their tunable chemical properties and exceptionally high diffusion coefficients for solutes. However, their fragility prevents the fabrication of thin defect-free membranes suitable for gas separation. Here, we report the assembly of defect-free hydrogel nanomembranes for CO2 separation. Such membranes can be prepared by coating an aqueous suspension of colloidal hydrogel microparticles (microgels) onto a flat, rough, or micropatterned porous support as long as the pores are hydrophilic and the pore size is smaller than the diameter of the microgels. The deformability of the microgel particles enables the autonomous assembly of defect-free 30-50 nm-thick membrane layers from deformed ∼15 nm-thick discoidal particles. Microscopic analysis established that the penetration of water into the pores driven by capillary force assists the assembly of a defect-free dense hydrogel layer on the pores. Although the dried films did not show significant CO2 permeance even in the presence of amine groups, the permeance dramatically increased when the membranes are adequately hydrated to form a hydrogel. This result indicated the importance of free water in the membranes to achieve fast diffusion of bicarbonate ions. The hydrogel nanomembranes consisting of amine-containing microgel particles show selective CO2 permeation (850 GPU, αCO2/N2 = 25) against post-combustion gases. Acid-containing microgel membranes doped with amines show highly selective CO2 permeation against post-combustion gases (1010 GPU, αCO2/N2 = 216) and direct air capture (1270 GPU, αCO2/N2 = 2380). The membrane formation mechanism reported in this paper will provide insights into the self-assembly of soft matters. Furthermore, the versatile strategy of fabricating hydrogel nanomembranes by the autonomous assembly of deformable microgels will enable the large-scale manufacturing of high-performance separation membranes, allowing low-cost carbon capture from post-combustion gases and atmospheric air.

Ideonella sakaiensis, PETase, and MHETase: From identification of microbial PET degradation to enzyme characterization.

Few reports have described the biological degradation or utilization of poly(ethylene terephthalate) (PET) to support microbial growth. We screened environmental samples from a PET bottle recycling site and identified the microbial consortium no. 46, which degraded amorphous PET at ambient temperature; thereafter, we isolated the resident Ideonella sakaiensis 201-F6 strain responsible for the degradation. We further identified two hydrolytic enzymes from I. sakaiensis, PET hydrolase (PETase) and mono(2-hydroxyethyl) terephthalate hydrolase (MHETase), which synergistically converted PET into its monomeric building blocks. Here, we provide original methods of microbial screening and isolation of PET degrading microbe(s). These novel approaches can be adapted for exploring microorganisms that degrade PET and other plastics. Furthermore, our enzyme assay protocols to characterize PETase and MHETase can be applied to evaluate new enzymes that target PET and its hydrolysates.

Effect of Alkali Treatment on the Mechanical Properties of Anion-Exchange Membranes with a Poly(vinyl Chloride) Backing and Binder.

An alkali treatment under various operating conditions is conducted on a commercial anion-exchange membrane containing poly(vinyl chloride) (PVC) as a backing and binder to study the effect of the treatment on the mechanical properties by both Müllen burst and tensile tests. Contrary to our expectations, the Müllen burst pressure and tensile strain at break improved significantly after the alkali treatment in comparison to the pristine membrane and then decreased as the treatment period progressed. A good correlation is observed between the area below the stress-strain curve and burst pressure. To understand the obtained results, the PVC degradates are recovered by Soxhlet extraction and characterized via nuclear magnetic resonance and gel permeation chromatography. It is discovered that the PVC main chains degraded in the alkali solution. We propose a composite model to explain the burst pressure improvement mechanism by the change in the chemical structure of the PVC binder.

Biodegradation of waste PET: A sustainable solution for dealing with plastic pollution.

The discovery of Ideonella sakaiensis, a plastic-degrading bacterium, creates possibilities for a sustainable "bioeconomy" for recycling plastic waste.

The beneficial effects of long-term enzyme replacement therapy on cardiac involvement in Japanese Fabry patients.

Fabry disease is a hereditary disorder that occurs due to the reduction or absence of alpha-galactosidase A activity, which leads to cardiac involvement including left ventricular hypertrophy (LVH). Enzyme replacement therapy (ERT) provides better patient outcomes by preventing serious complications. However, there have been very few studies on the long-term effects of ERT on the cardiac manifestations in Japanese Fabry patients. We retrospectively analyzed the data from the medical records of 42 Fabry patients (male, n = 17; female, n = 25) who were followed at Jikei University Hospital, and in whom the long-term effects of ERT could be evaluated (median follow-up period: male, 11 years; female, 8 years). The slope of the left ventricular mass (LVM) increase was 3.02 ±â€¯3.41 g/m2/year in males and 1.69 ±â€¯2.73 g/m2/year in females. In a subgroup analysis, the slopes of males with and without LVH did not differ to a statistically significant extent; however, the slope in female patients without LVH was significantly smaller than that of female patients with LVH. We then compared our data to the natural historical data that have previously been reported. In comparison to the previously reported data, we found a significant reduction in the LVM changes (g/height2.7/year) of patients who received long-term ERT (male, 4.07 ±â€¯1.03 to 1.25 ±â€¯1.39; female, 2.31 ±â€¯0.81 to 0.78 ±â€¯1.23). Long-term ERT effectively prevents LVH in Fabry patients. This effect was also observed in the patients with LVH prior to the initiation of ERT.

Effect of amine structure on CO2 capture by polymeric membranes.

Poly(amidoamine)s (PAMAMs) incorporated into a cross-linked poly(ethylene glycol) exhibited excellent CO2 separation properties over H2. However, the CO2 permeability should be increased for practical applications. Monoethanolamine (MEA) used as a CO2 determining agent in the current CO2 capture technology at demonstration scale was readily immobilized in poly(vinyl alcohol) (PVA) matrix by solvent casting of aqueous mixture of PVA and the amine. The resulting polymeric membranes can be self-standing with the thickness above 3 µm and the amine fraction less than 80 wt%. The gas permeation properties were examined at 40 °C and under 80% relative humidity. The CO2 separation performance increased with increase of the amine content in the polymeric membranes. When the amine fraction was 80 wt%, the CO2 permeability coefficient of MEA containing membrane was 604 barrer with CO2 selectivity of 58.5 over H2, which was much higher than the PAMAM membrane (83.7 barrer and 51.8, respectively) under the same operation conditions. On the other hand, ethylamine (EA) was also incorporated into PVA matrix to form a thin membrane. However, the resulting polymeric membranes exhibited slight CO2-selective gas permeation properties. The hydroxyl group of MEA was crucial for high CO2 separation performance.

Tissue thrombin is associated with the pathogenesis of dilated cardiomyopathy.

BACKGROUND: Thrombin is a serine protease known to be the final product of the coagulation cascade. However, thrombin plays other physiological roles in processes such as gastric contractions and vessel wound healing, and a state of coagulability is increased in patients with dilated cardiomyopathy (DCM). In this study, we investigate the role of thrombin in the pathogenesis of DCM. The purpose of this study is to clarify the role of thrombin in the pathogenesis of DCM and investigate the possibility of treatment against DCM by thrombin inhibition. METHODS: We investigated the expression of thrombin in the left ventricles of five patients with DCM who underwent the Batista operation and four patients without heart disease. Furthermore, we investigated the involvement of thrombin in the development of DCM using knock-in mice with a deletion mutation of cardiac troponin T that causes human DCM (∆K210 knock-in mouse) (B6;129-Tnnt2tm2Mmto) and assessed the effects of a direct thrombin inhibitor, dabigatran on ∆K210 knock-in mice using echocardiographic examinations, the Kaplan-Meier method and Western blotting. RESULTS: The immunohistochemical analysis showed a strong thrombin expression in the DCM patients compared to the patients without heart disease. In immunohistochemical analysis, a strong thrombin expression was observed in the heart tissues analysis in the ∆K210 knock-in mice. Dabigatran administration significantly improved fractional shortening according to the echocardiographic examination and the survival outcomes in ∆K210 knock-in mice. CONCLUSION: Tissue thrombin is involved in the pathogenesis of DCM and thrombin inhibition can be beneficial for the treatment of DCM.

Response to Comment on "A bacterium that degrades and assimilates poly(ethylene terephthalate)".

Yang et al suggest that the use of low-crystallinity poly(ethylene terephthalate) (PET) exaggerates our results. However, the primary focus of our study was identifying an organism capable of the biological degradation and assimilation of PET, regardless of its crystallinity. We provide additional PET depolymerization data that further support several other lines of data showing PET assimilation by growing cells of Ideonella sakaiensis.

Low-Temperature Processable Block Copolymers That Preserve the Function of Blended Proteins.

Low-temperature processable polymers have attracted increasing interest as ecological materials because of their reduced energy consumption during processing and suitability for making composites with heat-sensitive biomolecules at ambient temperature. In the current study, low-temperature processable biodegradable block copolymers were synthesized by ring-opening polymerization of l-lactide (LLA) using polyphosphoester as a macroinitiator. The polymer films could be processed under a hydraulic pressure of 35 MPa. The block copolymer films swelled in water because the polyphosphoester block was partially hydrated. Interestingly, the swelling ratio of the films changed with temperature. The pressure-induced order-to-disorder transition of the block copolymers was characterized by small-angle X-ray scattering; a crystallinity reduction in the block copolymers was observed after application of pressure. The crystallinity of the block copolymers was recovered after removing the applied pressure. The Young's modulus of the block copolymer films increased as the LLA unit content increased. Moreover, the modulus did not change after multiple processing cycles and the recyclability of the block copolymers was also confirmed. Finally, polymer films with embedded proteinase K as a model protein were prepared. The activity of catalase loaded into the polymer films was evaluated after processing at different temperatures. The activity of catalase was preserved when the polymer films were processed at room temperature but was significantly reduced after high-temperature processing. The suitability of low-temperature processable biodegradable polymers for making biofunctional composites without reducing protein activity was clarified. These materials will be useful for biomedical and therapeutic applications.

A bacterium that degrades and assimilates poly(ethylene terephthalate).

Poly(ethylene terephthalate) (PET) is used extensively worldwide in plastic products, and its accumulation in the environment has become a global concern. Because the ability to enzymatically degrade PET has been thought to be limited to a few fungal species, biodegradation is not yet a viable remediation or recycling strategy. By screening natural microbial communities exposed to PET in the environment, we isolated a novel bacterium, Ideonella sakaiensis 201-F6, that is able to use PET as its major energy and carbon source. When grown on PET, this strain produces two enzymes capable of hydrolyzing PET and the reaction intermediate, mono(2-hydroxyethyl) terephthalic acid. Both enzymes are required to enzymatically convert PET efficiently into its two environmentally benign monomers, terephthalic acid and ethylene glycol.

Nanoconfinement and Chemical Structure Effects on Permeation Selectivity of Self-Assembling Graft Copolymers.

Permeation of small molecule solutes through thin films is typically described by the solution-diffusion model, but this model cannot predict the effects of nanostructure due to self-assembly or additives. Other models focusing on diffusion through isolated nanopores indicate that confining permeation to channels slightly larger than the size of the solute can lead to an increased influence of solute-pore wall interactions on permeation rate. In this study, we analyze how differences in polymer nanostructure affect the relative contributions of solute size and polymer-solute interactions on transport rate. We compared the diffusion rates of several small molecules through two polymer thin films: A cross-linked, homogeneous film of poly(ethylene glycol phenyl ether acrylate) (PEGPEA) and a graft copolymer with a poly(vinylidene fluoride-co-chlorotrifluoroethylene) (P(VDF-co-CTFE)) backbone and PEGPEA side chains that self-assemble into continuous ∼1-3 nm PEGPEA domains through which transport occurs. We correlated these rates with the size of each solute and its chemical affinity to PEGPEA, as measured by the difference between their solubility parameters. Diffusion rate through the homogeneous polymer film was controlled by solute size, whereas diffusion rate through the copolymer was strongly controlled by the difference between the solubility parameters. Furthermore, permeation selectivity between two selected molecules was 2.5× higher for the nanostructured copolymer, likely enhanced by the nanoconfinement effects. These initial results indicate that polymer self-assembly is a promising tool for designing polymeric membranes that can differentiate between solutes of similar size but differing chemical structures.

Cardiac tamponade as an independent condition affecting the relationship between the plasma B-type natriuretic peptide levels and cardiac function.

Plasma B-type natriuretic peptide (BNP) is finely regulated by the cardiac function and several extracardiac factors. Therefore, the relationship between the plasma BNP levels and the severity of heart failure sometimes seems inconsistent. The purpose of the present study was to investigate the plasma BNP levels in patients with cardiac tamponade and their changes after pericardial drainage. This study included 14 patients with cardiac tamponade who underwent pericardiocentesis. The cardiac tamponade was due to malignant diseases in 13 patients and uremia in 1 patient. The plasma BNP levels were measured before and 24-48 h after drainage. Although the patients reported severe symptoms of heart failure, their plasma BNP levels were only 71.2 ± 11.1 pg/ml before drainage. After appropriate drainage, the plasma BNP levels increased to 186.0 ± 22.5 pg/ml, which was significantly higher than that before drainage (P = 0.0002). In patients with cardiac tamponade, the plasma BNP levels were low, probably because of impaired ventricular stretching, and the levels significantly increased in response to the primary condition after drainage. This study demonstrates an additional condition that affects the relationship between the plasma BNP levels and cardiac function. If inconsistency is seen in the relationship between the plasma BNP levels and clinical signs of heart failure, the presence of cardiac tamponade should therefore be considered.

Low-Temperature Processable Degradable Polyesters.

Block copolymers composed of a low-T(g) and high-T(g) block, with suitable pressure miscibility characteristics, can be formed at low-temperature through the application of pressure. Aliphatic block copolyesters composed of poly(ε-caprolactone) derivatives and poly(L-lactide) show room temperature processability under hydraulic pressure of 34.5 MPa without polymer degradation. Mechanism of the pressure-induced flow is investigated by small-angle X-ray scattering. A scattering associated with a lamellae structure observed at ambient conditions decreases with elevating hydrostatic pressures, indicating pressure-induced phase mixing. Traces of the pressure-induced phase transition are studied by differential scanning calorimetry and X-ray diffraction. Tensile test of the block copolymers reveals that the mechanical properties can be readily controlled by changing composition, molecular weight, and chemical structure of the blocks. Among them, the hard segment PLLA fraction is the key factor to characterize the properties. Young's modulus of the block copolyesters is similar to that of polyethylene.