Urethane Methacrylate Research Articles

Evaluation of Monomer-containing Isocyanate Groups on Stabilizing Demineralized Dentin Matrix Against Bond Interface Degradation.

To evaluate the effect of urethane methacrylate precursor (UMP) on the enzymatic resistance of demineralized dentin (DD) matrices. Experimental treatments containing 0 (control), 1, and 5 mmol/L UMP dissolved in an acetone (Ace) solution were formulated. Dentin matrix specimens were demineralized in vitro and immersed in the experimental treatments for 1 h. The treated specimens were then stored in 0.1 mg/mL collagenase solution for 24 h, after which their dry mass loss and hydroxyproline (HYP) release were assessed. The swelling ratios of specimens in each group were also evaluated. The interaction between UMP and the dentin matrix was observed using field-emission scanning electron microscopy (FE-SEM). Endogenous enzyme activity in dentin was evaluated using confocal laser scanning microscopy (CLSM). Compared with the other treatment groups, treatment with 1 mM and 5 mM UMP-Ace significantly decreased the dry mass loss, HYP release and swelling ratio of the DD matrix (p < 0.05). FE-SEM and CLSM observations showed that treatment with UMP-Ace protected the structure of the dentin matrix and decreased porosity within the dentin-collagen network. Treatment with 1 mM and 5 mM UMP-Ace protects DD matrix against collagenase degradation and may be clinically useful for improving the durability of the hybrid layer.

Functionalization of calcium-deficient nanohydroxyapatite improves the mechanical properties of 3D printed biopolymer nanocomposites

Agglomerations of nanoparticles in a polymer matrix can drastically reduce the mechanical properties of a polymer nanocomposite, especially its strength. The grafting of nanoparticle surfaces with suitable functional groups can provide improved dispersion and stronger interfacial bonding, improving the fracture resistance of the nanocomposite. In this study, calcium-deficient nanohydroxyapatite (nHA) particles were functionalized with an amino acid-based urethane methacrylate (lysine urethane methacrylate, LUM) and subsequently reacted with hydroxyethyl methacrylate. We mixed these functionalized nHA particles with resin, composed of methacrylated acrylated epoxidized soybean oil, methacrylated isosorbide, and triethylene glycol dimethacrylate, and 3D-printed nanocomposites using masked stereolithography. We hypothesized that the functionalized nanoparticles would enhance the mechanical performance of the 3D-printed nanocomposites due to the greater dispersion and stronger interface. Flexural, tensile, compression and Mode-I fracture toughness test specimens were fabricated using a mSLA printer and tested following ASTM standards. The LUM functionalization of nHA improved the dispersion and increased the viscosity of the uncured nanocomposite ink. The flexural fracture strength, yield strength, and mode-I fracture toughness values were increased by 10 %, 30 %, and 11 %, respectively. The LUM improved the strength and fracture toughness by providing a stronger, more stable interface, resisting debonding between the matrix and particles, allowing for greater plastic deformation.

Effects of aging on attachment of Candida albicans to conventional heat-polymerized, CAD-CAM milled, and CAD-CAM 3D-printed acrylic resin bases.

The aim of this study was to assess Candida albicans attachment on conventionally fabricated (polymethylmethacrylate, PMMA), CAD-CAM milled, and 3D-printed acrylic resin bases pre- and post-simulated thermal aging, along with examining material surface changes after aging. Forty-six samples (10mm×10mm×2mm) for each of four material groups (conventional heat-polymerized PMMA, CAD-CAM milled acrylic resin base, CAD-CAM 3D-printed methacrylate resin base, CAD-CAM 3D-printed urethane methacrylate resin base) were subjected to 0, 1, or 2 years of simulated thermal aging. Microscopic images were taken before and after aging, and C. albicans attachment was quantified using cell proliferation assay (XTT). Statistical analysis employed analysis of variance (α = 0.05). Two-way factorial analysis showed no significant differences based on acrylic resin type or thermal aging (p=0.344 and p=0.091 respectively). However, C. albicans attachment significantly differed between 0- and 2-year thermally aged groups (p=0.004), mainly due to elevated initial attachments on CAD-CAM milled acrylic resin base and CAD-CAM 3D-printed urethane methacrylate resin base. Regardless of the fabrication technique and material combination, no significant differences were found in C. albicans adhesion pre- or post- thermal aging. Milled and 3D-printed bases compared favorably with heat- polymerized PMMA in their affinity for C. albicans attachment and surface characteristics after aging. These findings indicate that the risk of patients developing denture stomatitis might not be linked to the type of acrylic resin or fabrication method used.

Enhanced Mechanical Properties of PUMA/SiO2 Ceramic Composites via Digital Light Processing.

This study aims to enhance the mechanical properties of additively manufactured polymer parts by incorporating ceramic particles (SiO2) into diluted urethane methacrylate (UDMA) photopolymer resin using digital light processing (DLP) technology. The resulting PUMA/SiO2 composites, featuring varying SiO2 contents (16.7, 28.5, and 37.5 wt%) and processed under different conditions, underwent a comprehensive series of mechanical, thermal, and chemical tests. Hardness tests showed that composites with 37.5 wt% SiO2 demonstrated superior hardness with low sensitivity to processing conditions. Bending tests indicated that elevated vat temperatures tended to degrade flexural properties, yet this degradation was mitigated in the case of the 37.5 wt% SiO2 composition. Tensile tests revealed a transition from viscoelastic to linear elastic behaviors with increasing SiO2 content, with high tensile strength sustained at low vat temperatures (<35 °C) when the SiO2 content exceeded 28.5 wt%. Thermogravimetric analysis supported these findings, indicating that increased SiO2 content ensured a more uniform dispersion, enhancing mechanical properties consequently. Thermal tests showed augmented thermal conductivity and diffusivity with reduced specific heat in SiO2-inclusive composites. This study provides guidelines for optimal PUMA/SiO2 composite utilization that emphasizes high SiO2 content and low vat temperature, offering comprehensive insights for high-performance ceramic composite fabrication in functional applications.

Tailoring of Silicone Urethane Methacrylate Resin for Vat Photopolymerization-Based 3D Printing of Shape Memory Polymers.

Polydimethylsiloxane (PDMS) or silicone elastomers have garnered considerable attention in the field of medical device applications due to their superior thermal stability. However, conventional manufacturing techniques for silicone elastomers suffer from drawbacks such as cost, lengthy production time, and inherent difficulties in fabricating complex structures. To address these limitations, photosensitive polydimethylsiloxane urethane methacrylate (PDMSUMA) oligomers were synthesized, and their curing behaviors were specifically investigated for vat photopolymerization 3D printing applications. The study focused on exploring the impact of weight ratios between poly(ethylene glycol) dimethacrylate (PEGDMA) and 2-hydroxyethyl methacrylate (HEMA) in the PDMSUMA resin formulation. The addition of PEGDMA as a reactive diluent was found to enhance the printability of the PDMSUMA resin and decrease its viscosity. Thermal, mechanical, and shape memory properties of the 3D-printed specimens were examined. Our findings demonstrate the potential of PDMSUMA resins for developing customizable shape memory materials with tailored properties.

Biodegradation of Urethane Dimethacrylate-based materials (CAD/CAM resin-ceramic composites) and its effect on the adhesion and proliferation of Streptococcus mutans

ObjectiveTo investigate whether urethane dimethacrylate (UDMA) -based dental restorative materials biodegrade in the presence of Streptococcus mutans (S. mutans) and whether the monomers affect the adhesion and proliferation of S. mutans in turn. MethodsCholesterol esterase and pseudocholinesterase-like activities in S. mutans were detected using p-nitrophenyl substrate. Two UDMA-based CAD/CAM resin-ceramic composites, Lava Ultimate (LU) and Vita Enamic (VE), and a light-cured UDMA resin block were co-cultured with S. mutans for 14 days. Their surfaces were characterized by scanning electron microscopy and laser microscopy, and the byproducts of biodegradation were examined by Ultra Performance Liquid Chromatography-Tandem Mass Spectrometry (UPLC-MS/MS). Then, the antimicrobial components (silver nanoparticles with quaternary ammonium salts) were added to the UDMA resin block to detect whether the biodegradation was restrained. Finally, the effect of UDMA on biofilm formation and virulence expression of S. mutans was assessed. ResultsFollowing a 14-day immersion, the LU and UDMA resin blocks' surface roughness increased. The LU and VE groups had no UDMA or its byproducts discovered, according to the UPLC-MS/MS data, whereas the light-cured UDMA block group had UDMA, urethane methacrylate (UMA), and urethane detected. The addition of antimicrobial agents showed a significant reduction in the release of UDMA. Biofilm staining experiments showed that UDMA promoted the growth of S. mutans biofilm and quantitative real-time polymerase chain reaction results indicated that 50 μg/mL UDMA significantly increase the expression of gtfB, comC, comD, comE, and gbpB genes within the biofilm. ConclusionsUDMA in the light-cured resin can be biodegraded to produce UMA and urethane under the influence of S. mutans. The formation of early biofilm can be promoted and the expression of cariogenic genes can be up-regulated by UDMA. Clinical significanceThis study focuses for the first time on whether UDMA-based materials can undergo biodegradation and verifies from a genetic perspective that UDMA can promote the formation of S. mutans biofilms, providing a reference for the rational use of UDMA-based materials in clinical practice.

Photocurable High-Energy Polymer-Based Materials for 3D Printing

Digital light processing (DLP) or stereolithography is the most promising method of additive manufacturing (3D printing) of products based on high-energy materials due to, first of all, the absence of a high-temperature impact on the material. This paper presents research results of an ultraviolet (UV)-cured urethane methacrylate polymer containing 70 wt.% of high-energy solid powder based on ammonium salts, which is intended for digital light processing. Polymerization of the initial slurry is studied herein. It is shown that the addition of coarse powder transparency for the UV radiation to resin increases its curing depth. The thickness of the layer, which can polymerize, varies from 600 µm to 2 mm when the light power density ranges from 20 to 400 mJ/cm2, respectively. In DLP-based 3D printing, the obtained material density is 92% of the full density, while the compressive strength is 29 ± 3 MPa, and the ultimate tensile strength is 13 ± 1.3 MPa. The thermogravimetric analysis shows the decrease in the thermal decomposition temperature of UV-cured resin with high-energy additives compared to the thermal decomposition temperatures of the initial components separately. Thermal decomposition is accompanied by intensive heat generation. The burning rate of obtained samples grows from 0.74 to 3.68 mm/s, respectively, at the pressure growth from 0.1 to 4 MPa. Based on the results, it can be concluded that DLP-based 3D printing with the proposed UV photocurable resin is rather promising for the fabrication of multicomponent high-energy systems and complex profile parts produced therefrom.

UV LED Curable Perfluoropolyether (PFPE)-Urethane Methacrylate Transparent Coatings for Photonic Applications: Synthesis and Characterization.

The contribution aims to bring forth a novel synthesis route in developing transparent UV LED-curable coatings accounting for various exposure options. A selection of perfluoropolyether (PFPE)-urethane methacrylate and acrylate resins, free-radical photo-initiator Omnirad 2100, and two distinct silane-based crosslinking agents were blended under a weight ratio of 75:20:5 (without crosslinker) and 70:15:5:10, respectively. The coatings were cured under a UV LED 4 × 3 matrix light emitting source, in a chamber under a controlled atmosphere, by means of an in-house developed conveyor belt type platform, at different conveyor belt speeds (5, 50, 150, 250, and 500 mm/s). The morphologies of fabricated coatings were characterized by FTIR revealing high conversion rates (e.g., from 98 to 100%) for increased exposure time as a result of the 5 or 50 mm/s values, on all combinations. Dynamic-mechanical and optical properties of UV LED-cured transparent coatings were also investigated. A negative shift of the glass transition temperature values with a decrease in exposure time, in all combinations, from about 60 °C to 30 °C, along with storage moduli lowering in the glassy plateau further favors higher exposure times for curing. The refractive indices of poly-mers were from 1.38 to 1.40, whereas the thermo-optic coefficients are showing minor changes around the value of 2.55∙10-4 K-1.

UV–thermally dual-curable 1K clearcoat via urethane and radical reactions

Conventional polyurethane-based automotive clearcoat systems have mainly consisted of a polyol and an isocyanate crosslinker, requiring a metal catalyst and high-temperature curing conditions. Herein, we report a UV–thermally dual-curable 1K clearcoat that contains isocyanate crosslinkers blocked by methacrylate-functionalized pyrazole (BIPyA-3) and a photoactive benzophenone containing a polyol (BP–polyol). The blocked isocyanate can form a urethane bond with the polyol after deblocking, and the self-initiation of methacrylate in the blocking agent can participate in the radical reaction. In addition, under UV irradiation, the benzophenone group can generate radicals that can propagate the methacrylate functional group of BIPyA-3 as well as form CC bonds with the polyol, thereby increasing the overall crosslinking density in the clearcoat. Rheological behaviors of the novel clearcoat were investigated by oscillatory rheometry under combined thermal and UV curing conditions. The thermal and surface mechanical properties of the films cured under different conditions—(i) thermal, (ii) thermal–UV, (iii) UV–thermal, and (iv) UV—were compared, and their relationship with the overall crosslinking density was investigated. This novel dual-curable, urethane–methacrylate clearcoat cured via a UV–thermal process can not only contribute to enhancing the surface hardness of clearcoats without modifying their chemistry but also effectively consume unreacted methacrylate functional groups in the cured films.

Stereospecific radical polymerization of methacrylate bearing oxazolidone structure and improvement of glass transition temperature of urethane methacrylate copolymers

AbstractWe synthesized the novel methacrylate monomer bearing an oxazolidone structure (M1) and performed radical polymerization of M1 by traditional procedures. The glass transition temperature (Tg) of the obtained polymer (P1) was a significantly high value compared to that of poly(methyl methacrylate) and typical poly(urethane methacrylate)s. The copolymers of M1 and monofunctional urethane methacrylate derived from 2‐hydroxyethyl methacrylate and phenyl isocyanate (M2) exhibited a linear rise of the Tg values depending on the composition ratio of M1. The NMR analysis and the estimation of monomer reactivity ratio and Q–e values suggested that the improvement of glass transition temperature resulted from a stereoregularity, meaning a syndiotacticity of the copolymers improved with increasing the composition ratio of M1. Furthermore, the thermal curing reaction of M1 or M2 with bifunctional urethane acrylate successfully proceeded, then the Tg value of the cured product from M1 was much higher than that from M2.

Synthesis and Characterization of Polyglycidol Based Hyperbranched Urethane Methacrylate/ POSS/ Silver Nanoparticle Nanocomposites

Bu çalışmada çok dallanmış poliglisidol oligomeri (PG) ve poliglisidol esaslı çok dallanmış üretan metakrilat (PGUM) oligomeri glisidol ve 2-izosiyanatoetil metakrilat (IEM) kullanılarak sentezlenmiştir. Oligomerlerin yapıları FT-IR ile aydınlatılmıştır. Daha sonra PGUM, Metakril-POSS, fotobaşlatıcı (Irg-184), çapraz bağlayıcı olarak trimetilolpropan triakrilat (TMPA) ve AgNO3 karıştırılarak hibrit nanokompozit film hazırlanmıştır. Hibrit nanokompozit filmlerin mekanik ve termal özelliklerinin yanısıra kaplama performansları incelenmiştir. Metakrilik grupların çapraz bağlanması, gümüş iyonlarının kararlı nanopartiküllere (AgNP) indirgenmesi ve AgNP'lerin nanokompozitlere dahil edilmesi için UV ışığı kullanılmıştır. AgNP'lerin oluşumu TEM analizi ile doğrulanmıştır. Hibrit nanokompozit filmlerin Gram-pozitif ve Gram-negatif bakterilere karşı antibakteriyel aktiviteside ayrıca gözlenmiştir.

Evaluation of a novel primer containing isocyanate group on dentin bonding durability.

To evaluate the benefits of a novel dentin-bonding primer, namely, isocyanate-terminated urethane methacrylate precursor (UMP), which can form covalent bonds with demineralized dentin collagen. The synthesized and purified UMP monomer was characterized and tested its effects on the degree of conversion (DC) and wettability of an acetone-based dental adhesive. Then UMP primers of different concentrations were formulated and used to prepare adhesive specimens, which were compared with solvent-treated groups. Primer-treated specimens with and without aging were also compared. To evaluate the bonding interface, microtensile strength tests, nano-indentation tests and nanoleakage- eavaluation were performed using a field-emission scanning electron microscope and nano-indenter. Data were analyzed using SPSS 20.0 software with significance set at α=0.05 using one-way analysis of variance (ANOVA) and two-way ANOVA to characterize the effects of the primer. Treatment with the UMP primer promoted the DC and wettability of the adhesive on the demineralized dentin surface (P<0.05); it also increased the bond strength of the aged dentin bonding interface (P<0.05). Nanoleakage was reduced; the bonding interface became more stable, and the continuity and strength of the hybrid layer improved (P<0.05) following UMP treatment. The application of 5mM UMP as a primer for dentin bonding could lead to a stable bonding interface and long-lasting bonding effects. The use of 5mM UMP primer developed in this study could improve dentin bonding durability and has excellent clinical application prospects.

A smart polymer electrolyte coordinates the trade-off between thermal safety and energy density of lithium batteries

In this article, we develop a smart polymer electrolyte through in-situ radical random polymerization of the cyclic carbonate urethane methacrylate monomer and the 2-isocyanatoethyl methacrylate monomer, which coordinates the trade-off between thermal safety and energy density of lithium batteries. It is demonstrated that the as-developed polymer electrolyte can incur the battery thermal shutdown before reaching the thermal runaway temperature. This originates from the highly crosslinking network caused by the nucleophilic addition of carbamate to isocyanate in the polymer matrix under the elevated temperature exceeding 170 °C. Besides, superior cycle performance of 4.5 V-class LiNi0.6Co0.2Mn0.2O2/Li batteries can be achieved, with a capacity retention of 80% after 200 cycles at 0.5 C and 30 °C, owing to enhanced interface compatibility of this polymer electrolyte. Noting that this polymer electrolyte possesses a superior water-scavenging ability, which helps improve the moisture resistance and battery cycle performance. Impressively, this polymer electrolyte can achieve improved energy density and superior safety characteristic of lithium batteries under high cut-off voltage.

Facile Fabrication of Flexible Polymeric Membranes with Micro and Nano Apertures over Large Areas.

Freestanding, flexible and open through-hole polymeric micro- and nanostructured membranes were successfully fabricated over large areas (>16 cm2) via solvent removal of sacrificial scaffolds filled with polymer resin by spontaneous capillary flow. Most of the polymeric membranes were obtained through a rapid UV curing processes via cationic or free radical UV polymerisation. Free standing microstructured membranes were fabricated across a range of curable polymer materials, including: EBECRYL3708 (radical UV polymerisation), CUVR1534 (cationic UV polymerisation) UV lacquer, fluorinated perfluoropolyether urethane methacrylate UV resin (MD700), optical adhesive UV resin with high refractive index (NOA84) and medical adhesive UV resin (1161-M). The present method was also extended to make a thermal set polydimethylsiloxane (PDMS) membranes. The pore sizes for the as-fabricated membranes ranged from 100 µm down to 200 nm and membrane thickness could be varied from 100 µm down to 10 µm. Aspect ratios as high as 16.7 were achieved for the 100 µm thick membranes for pore diameters of approximately 6 µm. Wide-area and uniform, open through-hole 30 µm thick membranes with 15 µm pore size were fabricated over 44 × 44 mm2 areas. As an application example, arrays of Au nanodots and Pd nanodots, as small as 130 nm, were deposited on Si substrates using a nanoaperture polymer through-hole membrane as a stencil.

Facile fabrication of biobased porous material via the photocuring technique and a template-assisted approach for oil/water separation

In this study, we developed a facile, low-cost and eco-friendly approach to prepare a sustainable, porous, polymeric sorbent for oil/water separation by using photocurable soybean oil-based urethane methacrylate and inexpensive salt porogen as raw materials. By combining UV curing technology and a salt template-assisted method, a biobased porous sorbent with good hydrophobicity, lipophilicity, and recyclability was prepared. The effects of particle size and content of salt porogen on the density, morphology, porosity and surface wettability of porous sorbent were analyzed and discussed in detail to optimize the preparation conditions. Due to its unique three-dimensional porous structure and large specific surface area, the prepared biobased porous material exhibits the ability of rapid organic solvent absorption and could serve as sorbents that effectively realized the separation of oil/water mixtures. Moreover, all of the key materials are almost low cost and available in large quantities, meaning that this biobased porous material is expected to be used in oil/water separation on a large scale.

Thermal crosslinking characteristics of dual-curable isocyanate blocked with methacrylate-functionalized amine derivatives for eco-friendly automotive clearcoats

A novel isocyanate blocked with an amine derivative blocking agent (2-(tert-butylamino) ethyl methacrylate, TBEMA) was designed as a thermal crosslinker for an eco-friendly automotive clearcoat system. New dual-curable blocked isocyanate (BITBEMA) was effectively deblocked at curing temperatures of 120 and 130 °C, which are lower than the conventional curing temperature of 150 °C. The deblocking features of BITBEMA were verified through experimental measurements and density functional theory simulations. The amine-based blocking agent with the methacrylate functionality directly participated in free radical polymerization with CC double bonds in the main resin (hydroxyl functionalized urethane methacrylate oligomer) during thermal curing, leading to enhanced crosslinking networks as well as reduced emissions of volatile organic compounds. The real-time crosslinking behaviors and mechanical properties of the clearcoat with BITBEMA were compared to those of clearcoats with mono-curable amine-based blocked isocyanate and a commercial crosslinker, confirming the excellent crosslinking characteristics of the dual-curable isocyanate crosslinker.

Reusable catalysts based on CeO2/cellulose derivative with visible light photocatalytic activity tuned by noble metal nanoparticles inclusion

For environmental preservation, it is crucial to effectively remove organic waste from water. Several approaches have been put forth, but photocatalysis stands out as a quick and effective solution. In this study, some hybrid polymeric structures that were created by photopolymerizing cellulose acetate/castor oil urethane methacrylates with embedded CeO2 nanoparticles (NPs) and in situ photogenerated noble metal nanoparticles (Ag, Au, Pd) are characterized, and photochemically thoroughly evaluated. The effective modification of cellulose acetate with urethane methacrylate sequences and the degree of functionalization were first observed using 1H NMR and FTIR spectra. Additionally, scanning and transmission electron microscopy, X-ray diffraction, FT-IR and UV–visible spectroscopy were utilized to analyse the resultant nanocomposites. The homogeneous dispersion of CeO2 NPs (10–40 nm) into an organic matrix with the suitable functionalities, namely urethane and hydroxyl groups, favour the interfacial charge transfer reducing the Eg up to 2.85 eV. Moreover, noble metal nanoparticles (5–15 nm), such as Ag, Au and Pd introduction in nanocomposites, significantly lowered the Eg: 2.1 eV for CeAg samples, 1.7 eV for CeAu films and 1.5 eV for CePd films, respectively. This opens up new avenues for the creation of flexible cellulose-based photocatalysts that are active in visible light.

Improved Functional Assessment of Ischemic Severity Using 3D Printed Models.

ObjectiveTo develop a novel in vitro method for evaluating coronary artery ischemia using a combination of non-invasive coronary CT angiograms (CCTA) and 3D printing (FFR3D).MethodsTwenty eight patients with varying degrees of coronary artery disease who underwent non-invasive CCTA scans and invasive fractional flow reserve (FFR) of their epicardial coronary arteries were included in this study. Coronary arteries were segmented and reconstructed from CCTA scans using Mimics (Materialize). The segmented models were then 3D printed using a Carbon M1 3D printer with urethane methacrylate (UMA) family of rigid resins. Physiological coronary circulation was modeled in vitro as flow-dependent stenosis resistance in series with variable downstream resistance. A range of physiological flow rates (Q) were applied using a peristaltic steady flow pump and titrated with a flow sensor. The pressure drop (ΔP) and the pressure ratio (Pd/Pa) were assessed for patient-specific aortic pressure (Pa) and differing flow rates (Q) to evaluate FFR3D using the 3D printed model.ResultsThere was a good positive correlation (r = 0.87, p < 0.0001) between FFR3D and invasive FFR. Bland-Altman analysis revealed a good concordance between the FFR3D and invasive FFR values with a mean bias of 0.02 (limits of agreement: −0.14 to 0.18; p = 0.2).Conclusions3D printed patient-specific models can be used in a non-invasive in vitro environment to quantify coronary artery ischemia with good correlation and concordance to that of invasive FFR.

In situ generated polymer electrolyte coating-based Janus interfaces for long-life LAGP-based NMC811/Li metal batteries

NASCION-type Li+ conductor Li1.5Al0.5Ge1.5P3O12 (LAGP) has been well considered as a promising solid-state electrolyte for solid-state lithium mental batteries (SSLMBs) by virtue of several strengths (e.g., high ionic conductivities, good stability under ambient conditions, and wide electrochemical stability windows). However, there are rare reports concerning the utilization of LAGP-based solid electrolytes in the high-voltage LiNi0.8Mn0.1Co0.1O2 (NMC811)/Li metal cell. This can be ascribed to the fact that the mechanochemically stable interface toward Li metal anodes and compatible interface close to NMC811 cathodes cannot be simultaneously achieved. To address this, herein, a LAGP-type solid electrolyte with in situ generated polymer electrolyte coating-based Janus interfaces is developed. The as-developed solid electrolyte is prepared by coating LAGP with in situ crosslinked polymethyl methacrylate and poly(cyclic carbonate urethane methacrylate)-based polymer electrolytes toward lithium anode and NMC811 cathode, respectively. It is demonstrated that the as-developed solid electrolyte can achieve both compatible electrode–electrolyte interphases. As a result, this solid electrolyte endows 4.3 V and 4.5 V-class NMC811/Li batteries with superior cycling stability. Our work provides a good paradigm to address the interfacial issues confronting solid state electrolyte chemistries.

Direct-Ink Write 3D Printing Multistimuli-Responsive Hydrogels and Post-Functionalization Via Disulfide Exchange.

Herein, we describe a multi-stimuli-responsive hydrogel that can be 3D printed via a direct-ink write process to afford cross-linked hydrogel networks that can be post-functionalized with thiol-bearing molecules. Poly(alkyl glycidyl ether)s with methacrylate groups at their termini were synthesized and self-assembled into hydrogels with three key stimuli-responsive behaviors necessary for extrusion based 3D printing: a sol-gel temperature response, shear-thinning behavior, and the ability to be photochemically crosslinked. In addition, the chemically crosslinked hydrogels demonstrated a temperature dependent swelling consistent with an LCST behavior. Pyridyl disulfide urethane methacrylate (PDS-UM) monomers were introduced into the network as a thiol-reactive handle for post-functionalization of the hydrogel. The reactivities of these hydrogels were investigated at different temperatures (5, 25, 37 °C) and swelling statuses (as-cured versus preswollen) using glutathione as a reactive probe. To illustrate the versatility of the platform, a number of additional thiol-containing probes such as proteins, polymers, and small molecules were conjugated to the hydrogel network at different temperatures, pH's, and concentrations. In a final demonstration of the multi-stimuli-responsive hydrogel platform, a customized DIW 3D printer was used to fabricate a printed object that was subsequently conjugated with a fluorescent tag and displayed the ability to change in size with environmental temperature.