Dark background-surface enhanced Raman spectroscopic detection of nanoplastics: Thermofluidic strategy.

This study aims to develop a cost-effective and time-efficient method for detecting nanoplastics, which have recently garnered significant attention due to their potential harmful impact on the water environment (XiaoZhi, 2021; Gigault et al., 2021; Mitrano et al., 2021; Ferreira et al., 2019). Although several techniques are available to accumulate data on microplastics, there is currently no universally accepted analytical technique for detecting nanoplastics (Gigault et al., 2021; Mitrano et al., 2021; Mitrano et al., 2019; Cai et al., 2021a; Allen et al., 2022). In this study, we have developed a substrate that exhibits Surface-enhanced Raman scattering (SERS) (Zhou et al., 2021; Lv et al., 2020; Lê et al., 2021; Hu et al., 2022; Chang et al., 2022; Yang et al., 2022; Xu et al., 2020; Jeon et al., 2021; Lee and Fang, 2022; Vélez-Escamilla and Contreras-Torres, 2022; Liu et al., 2022; Xie et al., 2023) activity over a large area and a dark background in optical (darkfield mode) vision, enabling the detection of sparkling nanoplastics on the substrate. This darkfield-based strategy allows for the point-by-point detection of single nanoplastics, offering cost and time-saving advantages over other resource-intensive analytical techniques. Our findings reveal the presence of PP nanoplastics in commonly used laboratory equipment, individual PE nanoplastics from a hot water-contained commercial paper cup, and the first detection of natural nanoplastics in coastal seawater. We believe that this technique will have a universal application in establishing a global map of nanoplastics and advancing our understanding of the environmental life cycle of plastics.

Fabrication of a PVA-Based Hydrogel Microneedle Patch.

The degree of saponification, which is a dissolution characteristic of poly(vinyl alcohol) (PVA), is used to blend PVA to prepare a hydrogel microneedle (MN) patch. The MN patch was manufactured with an adjustable disassembly time using a molding process, and it was confirmed to have morphological stability and excellent needle formation. The permeability of the gelatin sheet, which is analogous to the skin elasticity coefficient of a real human, was confirmed. The penetration ratio had a very high value of 100% and sufficient physical properties to penetrate the skin. In the disassembly experiment, the MN patch was produced with ratios of lower:higher saponification of 6:4 (PVA6), 7:3 (PVA7), 8:2 (PVA8), 9:1 (PVA9), and 10:0 (PVA10). Degradation did not occur for PVA6 and PVA7 but occurred for PVA8, PVA9, and PVA10. A cytotoxicity test to investigate its suitability for use in the human body confirmed the cell viability of 80% or more and nontoxic properties. Therefore, sufficient cell viability was confirmed when compared to the existing products.

Polyurethane Sponge with a Modified Specific Surface for Repeatable Oil-Water Separation.

Oil spill accidents contaminate the oceanic environment and cause economic distress, and they continue to occur. Many methods have been developed to restore waters contaminated with spilled oil. However, still most commercially available methods are not environmentally or economically sustainable solutions. Therefore, there is a need for the development of sustainable materials with running water treatment capabilities. In recent years, a polyurethane (PU) sponge-based adsorbent has been reported as an oil-water separation and reusable adsorbent. This is because the porous 3D structure of the PU sponge provides a large surface area. However, as the PU sponge has a carboxyl group and an amino group, it exhibits hydrophilicity, so surface modification is essential for oil-water separation. Therefore, to modify the surface of PU to have hydrophobic/oleophilic properties, a hydrophobic/oleophilic adsorbent (HOA) was prepared using graphite and polydimethylsiloxane. On the basis of this, a PU sponge, a porous material, was used to manufacture an adsorbent that can be used in a sustainable and environmentally friendly way. The prepared HOA can selectively adsorb water or oil and can be reused. Furthermore, continuous oil-water separation is possible through a simple flow of fluid. Therefore, it is confirmed that the studied HOA can have great potential for ocean restoration in the future as an adsorbent that mitigates the disadvantages of the currently commercialized method.

Development of a Tough, Self-Healing Polyampholyte Terpolymer Hydrogel Patch with Enhanced Skin Adhesion via Tuning the Density and Strength of Ion-Pair Associations.

Polyampholyte (PA) hydrogels have great potential for biomedical applications, owing to their high toughness and good self-recovery and self-healing (SELF) behavior in addition to their physical properties similar to human tissue. However, their implementation as practical biomedical skin patches or wearable devices has so far been limited by their insufficient transdermal adhesion strength. In this work, a new polyampholytic terpolymer (PAT) hydrogel with enhanced skin adhesion was developed using a novel and simple strategy that tunes the structure of ion-pair associations (IPAs), acting as cross-links, in the hydrogel via adding an extra neutral monomer component into the network without changing the total charge balance. The PAT hydrogels were synthesized by the terpolymerization of the neutral monomer N,N-dimethylacrylamide (DMAAm) (or 2-hydroxyethyl methacrylate (HEMA)) as well as the cationic monomer 3-(methacryloylamino) propyl-trimethylammonium chloride (MPTC) and the anionic monomer sodium p-styrenesulfonate (NaSS). Their IPA, which determines their network structure, was modulated by varying the feed concentration of the neutral monomer, Cnm. An increase of Cnm within an optimized Cnm window (0.3-0.4 M) decreased the cross-linking density (strength and density of the IPAs) of the PAT hydrogels, reducing the softening temperature and Young's modulus, which increased compliance but maintained sufficient mechanical strength and thereby maximized the contact surface and enhanced skin adhesion. The DMAAm monomers, compared to the HEMA monomers, produced the higher skin adhesion of the PAT hydrogel, which was explained by the difference in their reactivity to the MPTC and NaSS. This study demonstrated this new method to develop the PAT hydrogels with excellent skin adhesion and biocompatibility while maintaining good toughness, compliance, and SELF behavior and the potential of the PAT hydrogels for biomedical skin patches and wearable devices.

Efficient Inverted Solar Cells Using Benzotriazole-Based Small Molecule and Polymers.

We synthesized medium-band-gap donor-acceptor (D-A) -type conjugated polymers (PBTZCZ-L and PBTZCZ-H) consisting of a benzotriazole building block as an acceptor and a carbazole unit as a donor. In comparison with the polymers, a small conjugated molecule (BTZCZ-2) was developed, and its structural, thermal, optical, and photovoltaic properties were investigated. The power conversion efficiency (PCE) of the BTZCZ-2-based solar cell devices was less than 0.5%, considerably lower than those of polymer-based devices with conventional device structures. However, inverted solar cell devices configured with glass/ITO/ZnO:PEIE/BTZCZ-2:PC71BM/MoO3/Ag showed a tremendously improved efficiency (PCE: 5.05%, Jsc: 9.95 mA/cm2, Voc: 0.89 V, and FF: 57.0%). We believe that this is attributed to high energy transfer and excellent film morphologies.

Interlayer structure and magnetic field-induced orientation of modified nanoclays in polymer aqueous solution.

Structural changes and orientation of organically modified montmorillonite (Mt) were investigated by employing synchrotron small-angle X-ray scattering. Mt was modified with various cationic compound [3-(methacryloylamino)propyl]-trimethyl ammonium chloride (MPTC) contents (1.5, 3, 6, 12, and 18 CEC (cation exchange capacity) per 1 CEC of Mt). There are two types of modified Mt structures, lateral monolayer and paraffin type monolayer, in accordance with the MPTC contents. A paraffin-type monolayer is more dominant than a lateral monolayer for efficient packing of MPTC between Mt layers as the MPTC contents increase. In 10 wt% of the modified Mt series oriented in 1 M of polyacrylamide aqueous solution using a magnetic field (1.2 Tesla), the modified Mt series oriented parallel to the magnetic field within 200 s.

Electrically induced deformation in chiral smectic elastomers with different domain structures.

Electrical actuation is investigated in two kinds of chiral smectic liquid-crystal elastomers (LCEs) with different domain structures LCE1 and LCE2: The latter is better than the former in orientational order. Tracking fluorescent beads dispersed on the samples enables us to measure the two-dimensional strain tensors in ferroelectric elastomer films. It turns out that the electric-field-induced strain is polarity dependent and the type of molecular orientation responsible for the strain is specified. In LCE1 the shear strain is dominant, whereas in LCE2 it is comparable to the elongation strain, which is explained by the rotation of the principal axes. The essential differences of the two elastomers are observed in the eigenvalues of the strain tensors. The absolute values for LCE1 are larger than those for LCE2. The difference is discussed on the basis of the domain structures.

Apparent viscosity of p-methoxybenzylidene-p'-n-butylaniline in the presence of electrohydrodynamic convection.

The apparent shear viscosity of p-methoxybenzylidene-p'-n-butylaniline in the presence of electrohydrodynamic convection (EHC) is investigated experimentally. In the absence of an electric field, directors are almost aligned along the flow direction such that the viscosity is close to the minimum of the Miesowicz viscosities. Since EHC disturbs the flow-aligned director configuration, the viscosity increases as the applied voltage is increased in the low-voltage regime. In the high-voltage regime, however, further increasing the voltage leads to a decrease in viscosity. Microscope observations using a rheometer reveal that the decrease in viscosity occurs in the dynamic scattering mode 2 (DSM2) state, whose spatial director distribution is anisotropic due to the shear flow. By adopting the Ericksen-Leslie theory for the shear flow under the electric field, we find that the viscosity decrease can be attributed to the negative contribution of the electric stress caused by the anisotropic director distribution of the DSM2 state.

Influence of shear flow on the linear response of a nematic liquid crystal to external electric fields.

We have investigated the linear response of shear stress to ac electric fields under shear flow in a nematic liquid crystal. The experimental results were compared with the theoretical results derived from the Ericksen-Leslie theory. Although close agreement was obtained at low shear rates, discrepancies were observed at high shear rates. By introducing a two-mode coupling model the experimental results were well reproduced for the entire range of shear rates, and nonconservative forces were found to play an important role in determining the fluctuation dynamics, which is a characteristic of nonequilibrium steady states.

Measurement of electrically induced shear strain in a chiral smectic liquid-crystal elastomer.

The mechanical response to electrical stimulation was investigated in a chiral smectic elastomer. The two-dimensional strain tensor in an elastomer film was precisely measured by tracking fluorescent beads dispersed on the film. Shear deformation in the film was clearly observed when an electric field was applied perpendicular to the film surface. The temperature dependence of the strain tensor was also investigated, and the origin of the electric-field-induced shear strain in the chiral smectic-C phase was mainly attributed to the Nambu-Goldstone mode.

Three-dimensional observation of an immiscible polymer blend subjected to a step electric field under shear flow.

We have investigated the structural change of an immiscible blend consisting of two polymers with equal viscosity subjected to a step electric field under shear flow. During the process, three-dimensional images were successfully acquired with a confocal scanning laser microscope, and at the same time, the transient shear stress was also measured. From the images, the interface tensor was calculated. In a blend of polymers with equal viscosity, the total shear stress may consist of the viscous, interfacial, and electric stresses. An experiment was performed to separate these stresses, and the results are discussed in terms of the interface tensor.

Droplet coalescence process under electric fields in an immiscible polymer blend.

The droplet coalescence process was investigated in immiscible polymer blends when subjected to a step electric field. We present sequential three-dimensional images captured during the process with a confocal scanning laser microscope. Characteristic lengths parallel and perpendicular to the electric field were obtained from the spatial correlation functions of the images. It was found that the droplet growth rate increased with both the electric field and the volume fraction of droplets. A function describing the droplet growth rate was derived from theory using the "hierarchical model" and was found to be in good agreement with the experimental results.

Storage shear modulus of columnar structure formed in an immiscible polymer blend under electric fields.

Oscillatory measurements of a columnar structure were performed, which was formed in an immiscible polymer blend subjected to an electric field. The formation process was observed through a confocal scanning laser microscope and the structure for the measurements was confirmed to be well defined. The storage shear modulus at low frequencies increased with increasing the electric field. A linear relation was found between the storage shear modulus and the square of the electric field. The static modulus calculated on the basis of the Maxwell stress exerted on the interface and interfacial tension was in good agreement with the experimental result.

Response of shear stress to ac electric fields under steady shear flow in a droplet-dispersed phase.

We have measured the response of shear stress to ac electric fields under steady shear flow in the droplet-dispersed phase of an immiscible polymer blend. A characteristic mode was found under steady shear flow, the relaxation frequency of which increased with increasing the shear rate. In the frequency dispersion, a scaling relation derived from dimensional analysis was confirmed to hold. The origin of the mode was investigated on the basis of the Maffettone-Minale (MM) model, in which the droplet shape is described by a second-rank tensor. The frequency dispersion of the response was also calculated using a modified MM model.

Stripe formation in an immiscible polymer blend under electric and shear-flow fields.

We found a stripe formation in an emulsion of a liquid crystalline polymer (LCP) and a machine oil (OIL) in electric and shear fields. Through the simultaneous measurement with a confocal scanning laser microscope and a rheometer, it was clearly shown that the formation of stripes, which are periodically arrayed, leads to the increase of the shear stress. The droplets, which are one component of the emulsion, start to be connected at low electric fields and then change into the stripes with the increase of electric field. Finally, a three-dimensional network is formed at high electric fields. The period and fluctuation of the stripe structure were also investigated in detail.

Structural analysis of polyelectrolyte film absorbing metal ion by SAXS utilizing with X-ray anomalous dispersion effect.

A distribution of Cu ions in polyelectrolyte film (Nafion) is directly observed with a small-angle X-ray scattering (SAXS) method utilizing an X-ray anomalous dispersion effect. A partial structure factor of the Cu ions, GAA(q), can be derived from the SAXS profiles obtained by scanning the incident X-ray energy around the Cu K absorption edge. GAA(q) has two peaks, indicating that the Cu ions hierarchically distribute in Nafion film. In addition, a standard SAXS also shows that Nafion film has a hierarchical structure. These results mean that the Cu ions locate in the domain where the hydrophilic bases aggregate.

Determination of fracture energy of high strength double network hydrogels.

The fracture energy G of double network (DN) gels, consisting of poly(2-acrylamido-2-methylpropanesulfonic acid) (PAMPS) as the first network and poly(acrylamide) (PAAm) as the second network, was measured by the tearing test as a function of the crack velocity V. The following results were obtained: (i) The fracture energy G ranges from 10(2) to approximately 10(3) J/m2, which is 100-1000 times larger than that of normal PAAm gels (10(0) J/m2) or PAMPS gels (10(-1) J/m2) with similar polymer concentrations to the DN gels. (ii) G shows weak dependence on the crack velocity V. (iii) G at a given value of V increases with decreasing of cross-linking density of the 2nd network. The measured values of G were compared with three theories that describe different mechanisms enhancing the fracture energy of soft polymeric systems. A mechanism relating to a heterogeneous structure of the DN gel is convincing for the remarkable large values of G.

Effect of polymer entanglement on the toughening of double network hydrogels.

The mechanical strength of double network (DN) gels consisting of highly cross-linked poly(2-acrylamido-2-methylpropanesulfonic acid) (PAMPS) as the first component and linear polyacrylamide (PAAm) as the second component has been investigated by varying the molecular weight of the second polymer PAAm, M(w). The experimental results reveal that, for toughening of the DN gels, (1) M(w) is one of the dominant parameters; (2) there is a critical value of M(w) = 10(6) for a remarkable enhancement; (3) the fracture energy of DN gels with a M(w) larger than 10(6) reaches a value as high as 10(3) J/m(2). By plotting the strength of DN gels (fracture stress sigma and fracture energy G) against a characteristic parameter of c[eta], where c is the average concentration of PAAm in the DN gels and [eta] is the intrinsic viscosity of PAAm, it is found that the dramatic increase in the mechanical strength of the DN gels occurs above the region where linear PAAm chains are entangled with each other. Thus, we conclude that the entanglement between the second component PAAm plays an important role of the toughening mechanism of DN gels. This result supports the heterogeneous model, which predicts the presence of "voids" of the first network PAMPS with a size much larger than the radius of the second polymer PAAm.

Compatibilization effect of poly(epsilon-caprolactone)-b-poly(ethylene glycol) block copolymers and phase morphology analysis in immiscible poly(lactide)/poly(epsilon-caprolactone) blends.

The miscibility and phase behavior of two stereoisomer forms of poly(lactide) (PLA: poly (L-lactide) (PLLA) and poly(DL-lactide) (PDLLA)) blends with poly(epsilon-caprolactone)-b-poly(ethylene glycol) (PCL-b-PEG) and PCL-b-monomethoxy-PEG (PCL-b-MPEG) block copolymers have been investigated by differential scanning calorimetry (DSC). The DSC thermal behavior of both the blend systems revealed that PLA is miscible with the PEG segment phase of PCL-b-(M)PEG but is still immiscible with its PCL segment phase although PCL was block-copolymerized with PEG. On the basis of these results, PCL-b-PEG was added as a compatibilizer to PLA/PCL binary blends. The improvement in mechanical properties of PLA/PCL blends was achieved as anticipated upon the addition of PCL-b-PEG. In addition, atomic force microscopy (AFM) measurements have been performed in order to study the compositional synergism to be observed in mechanical tests. AFM observations of the morphological dependency on blend composition indicate that PLA/PCL blends are immiscible but compatible to some extent and that synergism of compatibilizing may be maximized in the compositional blend ratio before apparent phase separation and coarsening.