Highly efficient dual photoredox/copper catalyzed atom transfer radical polymerization achieved through mechanism-driven photocatalyst design.

Atom transfer radical polymerization (ATRP) with dual photoredox/copper catalysis combines the advantages of photo-ATRP and photoredox-mediated ATRP, utilizing visible light and ensuring broad monomer scope and solvent compatibility while minimizing side reactions. Despite its popularity, challenges include high photocatalyst (PC) loadings (10 to 1000 ppm), requiring additional purification and increasing costs. In this study, we discover a PC that functions at the sub-ppm level for ATRP through mechanism-driven PC design. Through studying polymerization mechanisms, we find that the efficient polymerizations are driven by PCs whose ground state oxidation potential-responsible for PC regeneration-play a more important role than their excited state reducing power, responsible for initiation. This is verified by screening PCs with varying redox potentials and triplet excited state generation capabilities. Based on these findings, we identify a highly efficient PC, 4DCDP-IPN, featuring moderate excited state reducing power and a maximized ground state oxidation potential. Employing this PC at 50 ppb, we synthesize poly(methyl methacrylate) with high conversion, narrow molecular weight distribution, and high chain-end fidelity. This system exhibits oxygen tolerance and supports large-scale reactions under ambient conditions. Our findings, driven by the systematic PC design, offer meaningful insights for controlled radical polymerizations and metallaphotoredox-mediated syntheses beyond ATRP.

Tailoring the Degradation of Cyano-arene based Photocatalysts for Enhanced Visible-Light-Driven Halogen Atom Transfer Reactions.

We present the strategic design of donor-acceptor cyanoarene-based photocatalysts (PCs) aiming to augment beneficial PC degradation for halogen atom transfer (XAT)-induced dehalogenation reactions. Our investigation reveals a competitive nature between the catalytic cycle and the degradation pathway, with degradation becoming dominant, particularly for less activated alkyl halides. The degradation behavior of PCs significantly impacts the efficiency of the XAT process, leading to exploration into manipulating the degradation behavior in a desirable direction. Recognizing the variation in the nature and rate of PC degradation, as well as its influence on the reaction across the range of PC structures, we carefully engineered the PCs to develop a pre-catalyst, named 3DP-DCDP-IPN. This pre-catalyst undergoes rapid degradation into an active form, 3DP-DCDP-Me-BN, exhibited an enhanced reducing ability in its radical anion form to induce better PC regeneration and consequently effectively catalyzes the XAT reaction, even with a challenging substrate.

Multifunctional and Flexible Neural Probe with Thermally Drawn Fibers for Bidirectional Synaptic Probing in the Brain.

Synapses in the brain utilize two distinct communication mechanisms: chemical and electrical. For a comprehensive investigation of neural circuitry, neural interfaces should be capable of both monitoring and stimulating these types of physiological interactions. However, previously developed interfaces for neurotransmitter monitoring have been limited in interaction modality due to constraints in device size, fabrication techniques, and the usage of flexible materials. To address this obstacle, we propose a multifunctional and flexible fiber probe fabricated through the microwire codrawing thermal drawing process, which enables the high-density integration of functional components with various materials such as polymers, metals, and carbon fibers. The fiber enables real-time monitoring of transient dopamine release in vivo, real-time stimulation of cell-specific neuronal populations via optogenetic stimulation, single-unit electrophysiology of individual neurons localized to the tip of the neural probe, and chemical stimulation via drug delivery. This fiber will improve the accessibility and functionality of bidirectional interrogation of neurochemical mechanisms in implantable neural probes.

Ultraviolet light blocking optically clear adhesives for foldable displays via highly efficient visible-light curing.

In developing an organic light-emitting diode (OLED) panel for a foldable smartphone (specifically, a color filter on encapsulation) aimed at reducing power consumption, the use of a new optically clear adhesive (OCA) that blocks UV light was crucial. However, the incorporation of a UV-blocking agent within the OCA presented a challenge, as it restricted the traditional UV-curing methods commonly used in the manufacturing process. Although a visible-light curing technique for producing UV-blocking OCA was proposed, its slow curing speed posed a barrier to commercialization. Our study introduces a highly efficient photo-initiating system (PIS) for the rapid production of UV-blocking OCAs utilizing visible light. We have carefully selected the photocatalyst (PC) to minimize electron and energy transfer to UV-blocking agents and have chosen co-initiators that allow for faster electron transfer and more rapid PC regeneration compared to previously established amine-based co-initiators. This advancement enabled a tenfold increase in the production speed of UV-blocking OCAs, while maintaining their essential protective, transparent, and flexible properties. When applied to OLED devices, this OCA demonstrated UV protection, suggesting its potential for broader application in the safeguarding of various smart devices.

Structurally Aligned Multifunctional Neural Probe (SAMP) Using Forest-Drawn CNT Sheet onto Thermally Drawn Polymer Fiber for Long-Term In Vivo Operation.

Neural probe engineering is a dynamic field, driving innovation in neuroscience and addressing scientific and medical demands. Recent advancements involve integrating nanomaterials to improve performance, aiming for sustained in vivo functionality. However, challenges persist due to size, stiffness, complexity, and manufacturing intricacies. To address these issues, a neural interface utilizing freestanding CNT-sheets drawn from CNT-forests integrated onto thermally drawn functional polymer fibers is proposed. This approach yields a device with structural alignment, resulting in exceptional electrical, mechanical, and electrochemical properties while retaining biocompatibility for prolonged periods of implantation. This Structurally Aligned Multifunctional neural Probe (SAMP) employing forest-drawn CNT sheets demonstrates in vivo capabilities in neural recording, neurotransmitter detection, and brain/spinal cord circuit manipulation via optogenetics, maintaining functionality for over a year post-implantation. The straightforward fabrication method's versatility, coupled with the device's functional reliability, underscores the significance of this technique in the next-generation carbon-based implants. Moreover, the device's longevity and multifunctionality position it as a promising platform for long-term neuroscience research.

Visible-Light-Driven Rapid 3D Printing of Photoresponsive Resins for Optically Clear Multifunctional 3D Objects.

Light-driven 3D printing is gaining significant attention for its unparalleled build speed and high-resolution in additive manufacturing. However, extending vat photopolymerization to multifunctional, photoresponsive materials poses challenges, such as light attenuation and interference between the photocatalysts (PCs) and photoactive moieties. This study introduces novel visible-light-driven acrylic resins that enable rapid, high-resolution photoactive 3D printing. The synergistic combination of a cyanine-based PC, borate, and iodonium coinitiators (HNu 254) achieves an excellent printing rate and feature resolution under low-intensity, red light exposure. The incorporation of novel hexaarylbiimidazole (HABI) crosslinkers allows for spatially-resolved photoactivation upon exposure to violet/blue light. Furthermore, a photobleaching mechanism inhibited by HNu 254 during the photopolymerization process results in the production of optically-clear 3D printed objects. Real-time Fourier transform infrared spectroscopy validates the rapid photopolymerization of the HABI-containing acrylic resin, whereas mechanistic evaluations reveal the underlying dynamics that are responsible for the rapid photopolymerization rate, wavelength-orthogonal photoactivation, and observed photobleaching phenomenon. Ultimately, this visible-light-based printing method demonstrates: (i) rapid printing rate of 22.5 mm h-1, (ii) excellent feature resolution (≈20 µm), and (iii) production of optically clear object with self-healing capability and spatially controlled cleavage. This study serves as a roadmap for developing next-generation "smart" 3D printing technologies.

Ultraviolet Light Debondable Optically Clear Adhesives for Flexible Displays through Efficient Visible-Light Curing.

With growing sustainability concerns, the need for products that facilitate easy disassembly and reuse has increased. Adhesives, initially designed for bonding, now face demands for selective removal, enabling rapid assembly-disassembly and efficient maintenance across industries. This need is particularly evident in the display industry, with the rise of foldable devices necessitating specialized adhesives. A novel optically clear adhesive (OCA) is presented for foldable display, featuring a unique UV-stimulated selective removal feature. This approach incorporates benzophenone derivatives into the polymer network, facilitating rapid debonding under UV irradiation. A key feature of this method is the adept use of visible-light-driven radical polymerization for OCA film fabrication. This method shows remarkable compatibility with various monomers and exhibits orthogonal reactivity to benzophenone, rendering it ideal for large-scale production. The resultant OCA not only has high transparency and balanced elasticity, along with excellent resistance to repeated folding, but it also exhibits significantly reduced adhesion when exposed to UV irradiation. By merging this customized formulation with strategically integrated UV-responsive elements, an effective solution is offered that enhances manufacturing efficiency and product reliability in the rapidly evolving field of sustainable electronics and displays. This research additionally contributes to eco-friendly device fabrication, aligning with emerging technology demands.

Characterization of the Reversible Intersystem Crossing Dynamics of Organic Photocatalysts Using Transient Absorption Spectroscopy and Time-Resolved Fluorescence Spectroscopy.

Thermally activated delayed fluorescence (TADF) emitters are molecules of interest as homogeneous organic photocatalysts (OPCs) for photoredox chemistry. Here, three classes of OPC candidates are studied in dichloromethane (DCM) or N,N-dimethylformamide (DMF) solutions, using transient absorption spectroscopy and time-resolved fluorescence spectroscopy. These OPCs are benzophenones with either carbazole (2Cz-BP and 2tCz-BP) or phenoxazine/phenothiazine (2PXZ-BP and 2PTZ-BP) appended groups and the dicyanobenzene derivative 4DP-IPN. Dual lifetimes of the S1 state populations are observed, consistent with reverse intersystem crossing (RISC) and TADF emission. Example fluorescence lifetimes in DCM are (5.18 ± 0.01) ns and (6.22 ± 1.27) µs for 2Cz-BP, (1.38 ± 0.01) ns and (0.32 ± 0.01) µs for 2PXZ-BP, and (2.97 ± 0.01) ns and (62.0 ± 5.8) µs for 4DP-IPN. From ground state bleach recoveries and time-correlated single photon counting measurements, triplet quantum yields in DCM are estimated to be 0.62 ± 0.16, 0.04 ± 0.01, and 0.83 ± 0.02 for 2Cz-BP, 2PXZ-BP, and 4DP-IPN, respectively. 4DP-IPN displays similar photophysical behavior to the previously studied OPC 4Cz-IPN. Independent of the choice of solvent, 4DP-IPN, 2Cz-BP, and 2tCz-BP are shown to be TADF emitters, whereas emission by 2PXZ-BP and 2PTZ-BP depends on the molecular environment, with TADF emission enhanced in aggregates compared to monomers. Behavior of this type is representative of aggregation-induced emission luminogens (AIEgens).

Conductance stable and mechanically durable bi-layer EGaIn composite-coated stretchable fiber for 1D bioelectronics.

Deformable semi-solid liquid metal particles (LMP) have emerged as a promising substitute for rigid conductive fillers due to their excellent electrical properties and stable conductance under strain. However, achieving a compact and robust coating of LMP on fibers remains a persistent challenge, mainly due to the incompatibility of conventional coating techniques with LMP. Additionally, the limited durability and absence of initial electrical conductivity of LMP restrict their widespread application. In this study, we propose a solution process that robustly and compactly assembles mechanically durable and initially conductive LMP on fibers. Specifically, we present a shearing-based deposition of polymer-attached LMP followed by additional coating with CNT-attached LMP to create bi-layer LMP composite with exceptional durability, electrical conductivity, stretchability, and biocompatibility on various fibers. The versatility and reliability of this manufacturing strategy for 1D electronics are demonstrated through the development of sewn electrical circuits, smart clothes, stretchable biointerfaced fiber, and multifunctional fiber probes.

Non-thermal plasma coupled with a wet scrubber for removing odorous VOC.

Odorous volatile organic compounds (VOCs) deteriorate the quality of life and affect human health. In this study, a process was developed to remove an odorous VOC using a combined non-thermal plasma (NTP) and wet scrubber (WS) system. The low removal efficiency of WSs and the large amount of ozone generated by NTP were resolved. Compared to the decomposition effects when using a WS and NTP separately, the NTP + WS system improved the removal efficiency of ethyl acrylate (EA) and significantly reduced ozone emissions. The maximum EA removal efficiency was 99.9%. Additionally, an EA removal efficiency of over 53.4% and a 100% ozone removal efficiency were achieved even at discharge voltages lower than 4.5 kV. Ozone catalysis was confirmed to occur in the NTP + WS system. Furthermore, we verified the removal of by-products such as residual ozone and formaldehyde, which is a representative organic intermediate of EA. This study demonstrates that the NTP + WS system is a green technology for removing odorous VOCs.

Antiviral Lipid Nanocarrier Loaded with Remdesivir Effective Against SARS-CoV-2 in vitro Model.

Introduction: The ongoing SARS-CoV-2 pandemic has affected public health, the economy, and society. This study reported a nanotechnology-based strategy to enhance the antiviral efficacy of the antiviral agent remdesivir (RDS). Results: We developed a nanosized spherical RDS-NLC in which the RDS was encapsulated in an amorphous form. The RDS-NLC significantly potentiated the antiviral efficacy of RDS against SARS-CoV-2 and its variants (alpha, beta, and delta). Our study revealed that NLC technology improved the antiviral effect of RDS against SARS-CoV-2 by enhancing the cellular uptake of RDS and reducing SARS-CoV-2 entry in cells. These improvements resulted in a 211% increase in the bioavailability of RDS. Conclusion: Thus, the application of NLC against SARS-CoV-2 may be a beneficial strategy to improve the antiviral effects of antiviral agents.

Development of a long-acting tablet with ticagrelor high-loaded nanostructured lipid carriers.

Ticagrelor (TCG), an antiplatelet agent, has low solubility and permeability; thus, there are many trials to apply the pharmaceutical technology for the enhancement of TCG solubility and permeability. Herein, we have developed the TCG high-loaded nanostructured lipid carrier (HL-NLC) and solidified the HL-NLC to develop the oral tablet. The HL-NLC was successfully fabricated and optimized with a particle size of 164.5 nm, a PDI of 0.199, an encapsulation efficiency of 98.5%, and a drug loading of 16.4%. For the solidification of HL-NLC (S-HL-NLC), the adsorbent was determined based on the physical properties of the S-HL-NLC, such as bulk density, tap density, angle of repose, Hausner ratio, Carr's index, and drug content. Florite R was chosen because of its excellent adsorption capacity, excellent physical properties, and solubility of the powder after manufacturing. Using an S-HL-NLC, the S-HL-NLC tablet with HPMC 4 K was prepared, which is showed a released extent of more than 90% at 24 h. Thus, we have developed the sustained release tablet containing the TCG-loaded HL-NLC. Moreover, the formulations have exhibited no cytotoxicity against Caco-2 cells and improved the cellular uptake of TCG. In pharmacokinetic study, compared with raw TCG, the bioavailability of HL-NLC and S-HL-NLC was increased by 293% and 323%, respectively. In conclusion, we successfully developed the TCG high-loaded NLC tablet, that exhibited a sustained release profile and enhanced oral bioavailability.

Bottom-up plasma-enhanced atomic layer deposition of SiO2 by utilizing growth inhibition using NH3 plasma pre-treatment for seamless gap-fill process.

The design-rule shrinkage in semiconductor devices is a challenge at every step of the integration process. In the gap-fill process for isolation, the seam and void formation cannot be suppressed by using a deposition process, which even has excellent step coverage. To achieve seamless gap fill in the high-aspect-ratio structure, which has a non-ideal etch profile such as a negative slope, the deposition process should be able to realize the "bottom-up growth" behavior. In this work, the bottom-up growth of a SiO2 plasma-enhanced atomic layer deposition (PE-ALD) process in a trench structure was investigated by using a growth inhibition process employing plasma treatment. N2 and NH3 plasma pre-treatments were employed to suppress the growth of the SiO2 PE-ALD process without any contamination, and the inhibition mechanism was investigated by performing surface chemistry analyses using X-ray photoelectron spectroscopy. Furthermore, the gap-fill characteristics of the SiO2 PE-ALD process were examined, depending on the process conditions of NH3 plasma pre-treatment, by performing cross-sectional field emission scanning electron microscopy measurements. Finally, a seamless gap-fill process in a high-aspect-ratio trench pattern was achieved by the bottom-up growth behavior of SiO2 PE-ALD using NH3 plasma pre-treatment.

Mannosylated poly(acrylic acid)-coated mesoporous silica nanoparticles for anticancer therapy.

Although mesoporous silica nanoparticles (MSNs) are widely used as anticancer drug carriers, unmodified MSNs induce off-target effects and at high doses, there are adverse effects of hemolysis because of the interaction with the silanol group on the surface and cells. In this study, we developed doxorubicin (DOX)-loaded MSNs coated with mannose grafted poly (acrylic acid) copolymer (DOX@MSNs-man-g-PAA) to enhance the hemocompatibility and target efficacy to cancer cells. This uniform nanosized DOX@MSNs-man-g-PAA showed sustained and pH-dependent drug release with improved hemocompatibility over the bare MSNs. The uptake of the DOX@MSN-man-g-PAA in breast cancer cells was significantly improved by mannose receptor-mediated endocytosis, which showed significant increasing intracellular ROS and changes in mitochondrial membrane potential. This formulation exhibited superior tumor-suppressing activity in the MDA-MB-231 cells inoculated mice. Overall, the present study suggested the possibility of the copolymer-coated MSNs as drug carriers for cancer therapy.

Hard-Cation-Soft-Anion Ionic Liquids for PEDOT:PSS Treatment.

A promising conducting polymer poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) experiences significant conductivity enhancement when treated with proper ionic liquids (ILs). Based on the hard-soft-acid-base principle, we propose a combination of a hydrophilic hard cation A+ (instead of the commonly used 1-ethyl-3-methyl imidazolium, EMIM+) and a hydrophobic soft anion X- (such as tetracyanoborate, TCB-) as the best ILs for this purpose. Such ILs would decouple hydrophilic-but-insulating PSS- from conducting-but-hydrophobic PEDOT+ most efficiently by strong interactions with hydrophilic A+ and hydrophobic X-, respectively. Such a favorable ion exchange between PEDOT+:PSS- and A+:X- ILs would allow the growth of conducting PEDOT+ domains decorated by X-, not disturbed by PSS- or A+. Using density functional theory calculations and molecular dynamics simulations, we demonstrate that a protic cation- (aliphatic N-alkyl pyrrolidinium, in particular) combined with the hydrophobic anion TCB- indeed outperforms EMIM+ by promptly leaving hydrophobic TCB- and strongly binding to hydrophilic PSS-.

Preparation and evaluation of rapid disintegrating formulation from coated microneedle.

Microneedles (MNs), one of the transdermal drug delivery systems, have received extensive interest as an alternative to parenteral or parenteral administrations. For the successful drug delivery of coated MNs, the coated drug or chemical of MNs should be dissolved by skin's interstitial fluid and completely released from the MNs. Thus, the rapid disintegration of the drug from MNs plays a crucial role in ideal drug delivery of MNs. In this study, we developed the rapid disintegration coating formulation to reduce the application time of MN. The rapid disintegration MN was developed using polymers (PVA or HPMC), glycerol, croscarmellose sodium, tween 80, and Brij, as thickener, plasticizer, disintegrating agent, and surfactants, respectively. HPMC MN showed the burst release and rapid disintegration. Moreover, the drug from HPMC MN was successfully delivered into porcine skin within 1 min. In toxicological evaluation, the HPMC MN did not alter the liver and kidney function. Besides, HPMC MN did not induce the acute inflammation and change of skin structure after the application on rat skin. Thus, the coating formulation in this study could be one of the options for the development of safe and rapid disintegration MN.

Discovery of µ,δ-Opioid Receptor Dual-Biased Agonists That Overcome the Limitation of Prior Biased Agonists.

Morphine is widely used in pain management although the risk of side effects is significant. The use of biased agonists to the G protein of µ-opioid receptors has been suggested as a potential solution, although oliceridine and PZM21 have previously failed to demonstrate benefits in clinical studies. An amplification-induced confusion in the process of comparing G protein and beta-arrestin pathways may account for previously biased agonist misidentification. Here, we have devised a strategy to discover biased agonists with intrinsic efficacy. We computationally simulated 430 000 molecular dockings to the µ-opioid receptor to construct a compound library. Hits were then verified experimentally. Using the verified compounds, we performed simulations to build a second library with a common scaffold and selected compounds that showed a bias to µ- and δ-opioid receptors in a cell-based assay. Three compounds (ID110460001, ID110460002, and ID110460003) with a dual-biased agonistic effect for µ- and δ-opioid receptors were identified. These candidates are full agonists for the µ-opioid receptor and show specific binding modes. On the basis of our findings, we expect our novel compounds to act as more biased agonists compared to existing drugs, including oliceridine.

Improved Properties of the Atomic Layer Deposited Ru Electrode for Dynamic Random-Access Memory Capacitor Using Discrete Feeding Method.

Ruthenium (Ru) thin films deposited via atomic layer deposition (ALD) with a normal sequence and discrete feeding method (DFM) and their performance as a bottom electrode of dynamic random-access memory (DRAM) capacitors were compared. The DFM-ALD was performed by dividing the Ru feeding and purge steps of the conventional ALD process into four steps (shorter feeding time + purge time). The surface morphology of the Ru films was improved significantly with the DFM-ALD, and the preferred orientation of the Ru films was changed from relatively random to a <101>-oriented direction. Under the DFM-ALD condition, the higher susceptibility of oxygen atoms to the Ru electrode resulted in a higher proportion of the RuO2 formation on the Ru film surface during the subsequent TiO2 ALD process. This higher RuO2 portion leads to higher crystallinity of the local-epitaxially grown TiO2 films with a rutile phase. Such improvement also decreased the interfacial component of equivalent oxide thickness (EOTi) by ∼0.1 nm compared with the cases on sputtered Ru film, which showed an even smoother surface morphology. Consequently, the minimum EOT values when the Ru bottom electrodes deposited via DFM-ALD were adopted were 0.76 and 0.48 nm for TiO2 and Al-doped TiO2 films, respectively, while still satisfying the DRAM leakage current density specification (<10-7 A/cm2 at a capacitor voltage of 0.8 V).

Computational and Histological Analyses for Investigating Mechanical Interaction of Thermally Drawn Fiber Implants with Brain Tissue.

The development of a compliant neural probe is necessary to achieve chronic implantation with minimal signal loss. Although fiber-based neural probes fabricated by the thermal drawing process have been proposed as a solution, their long-term effect on the brain has not been thoroughly investigated. Here, we examined the mechanical interaction of thermally drawn fiber implants with neural tissue through computational and histological analyses. Specifically, finite element analysis and immunohistochemistry were conducted to evaluate the biocompatibility of various fiber implants made with different base materials (steel, silica, polycarbonate, and hydrogel). Moreover, the effects of the coefficient of friction and geometric factors including aspect ratio and the shape of the cross-section on the strain were investigated with the finite element model. As a result, we observed that the fiber implants fabricated with extremely softer material such as hydrogel exhibited significantly lower strain distribution and elicited a reduced immune response. In addition, the implants with higher coefficient of friction (COF) and/or circular cross-sections showed a lower strain distribution and smaller critical volume. This work suggests the materials and design factors that need to be carefully considered to develop future fiber-based neural probes to minimize mechanical invasiveness.

A visible-light phototransistor based on the heterostructure of ZnO and TiO2 with trap-assisted photocurrent generation.

Visible-light phototransistors have been fabricated based on the heterojunction of zinc oxide (ZnO) and titanium oxide (TiO2). A thin layer of TiO2 was deposited onto the spin-coated ZnO film via atomic layer deposition (ALD). The electrical characteristics of the TiO2 layer were optimized by controlling the purge time of titanium isopropoxide (TTIP). The optimized TiO2 layer could absorb the visible-light from the sub-gap states near the conduction band of TiO2, which was confirmed via photoelectron spectroscopy measurements. Therefore, the heterostructure of TiO2/ZnO can absorb and generate photocurrent under visible light illumination. The oxygen-related-states were investigated via X-ray photoelectron spectroscopy (XPS), and the interfacial band structure between TiO2 and ZnO was evaluated via ultraviolet photoelectron spectroscopy (UPS). Oxygen-related states and subgap-states were observed, which could be used to generate photocurrent by absorbing visible light, even with TiO2 and ZnO having a wide bandgap. The optimized TiO2/ZnO visible-light phototransistor showed a photoresponsivity of 99.3 A W-1 and photosensitivity of 1.5 × 105 under the illumination of 520 nm wavelength light. This study provides a useful way to fabricate a visible-light phototransistor based on the heterostructure of wide bandgap oxide semiconductors.