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Oil/water separation processes have garnered significant global attention due to the quick growth in industrial development, recurring chemical leakages, and oil spills. Hence, there is a significant demand for the development of inexpensive superwetting materials in an eco-friendly manner to separate oil/water mixtures and emulsions. In this study, a superwetting melamine sponge (SMS) with switchable wettabilities was prepared by modifying melamine sponge (MS) with sodium dodecanoate. The as-prepared SMS exhibited superhydrophobicity, superoleophilicity, underwater superoleophobicity, and underoil superhydrophobicity. The SMS can be utilized in treating both light and heavy oil/water mixtures through the prewetting process. It demonstrated fast permeation fluxes (reaching 108,600 L m -2 h -1 for a light oil/water mixture and 147,700 L m -2 h -1 for a heavy oil/water mixture) and exhibited good separation efficiency (exceeding 99.56%). The compressed SMS was employed in separating surfactant-stabilized water-in-oil emulsions (SWOEs), as well as surfactant-stabilized oil-in-water emulsions (SOWEs), giving high permeation fluxes (reaching 7210 and 5054 L m -2 h -1 , respectively). The oil purity for SWOEs' filtrates surpassed 99.98 wt% and the separation efficiencies of SOWEs exceeded 98.84%. Owing to their remarkable capability for separating oil/water mixtures and emulsions, eco-friendly fabrication method, and feasibility for large-scale production, our SMS has a promising potential for practical applications.

A hole array was fabricated via photolithography to wet the bottoms of holes using oxygen plasma. Amide-terminated silane, a water immiscible compound before hydrolysis, was evaporated for deposition on the plasma-treated hole template surface. The silane compound was hydrolyzed along the edges of circular sides of the hole bottom to form a ring of an initiator after halogenation. Poly(methacrylic acid) (PMAA) was grafted from the ring of the initiator to attract Ag clusters (AgCs) as AgC-PMAA hybrid ring (SPHR) arrays via alternate phase transition cycles. The SPHR arrays were modified with a Yersinia pestis antibody (abY) to detect the antigen of Yersinia pestis (agY) for plague diagnosis. The binding of the agY onto the abY-anchored SPHR array resulted in a geometrical change from a ring to a two-humped structure. The reflectance spectra could be used to analyze the AgC attachment and the agY binding onto the abY-anchored SPHR array. The linear range between the wavelength shift and agY concentration from 30 to 270 pg mL -1 was established to obtain the detection limit of ~12.3 pg mL -1 . Our proposed method provides a novel pathway to efficiently fabricate a ring array with a scale of less than 100 nm, which demonstrates excellent performance in preclinical trials.

Poly(methacrylic acid) (PMAA) brushes were tethered on a silicon surface possessing a 500-nm hole array via atom transfer radical polymerization after the modification of the halogen group. Dextran-biotin (DB) was sequentially immobilized on the PMAA chains to obtain a P(MAA-DB) brush surrounding the hole edges on the silicon surface. After loading antibiotics inside the holes, biphenyl-4,4'-diboronic acid (BDA) was used to cross-link the P(MAA-DB) chains through the formation of boronate esters to cap the hole and block the release of the antibiotics. The boronate esters were disassociated with reactive oxygen species (ROS) to open the holes and release the antibiotics, thus indicating a reversible association. The total amount of drug inside the chip was approximately 52.4 μg cm -2 , which could be released at a rate of approximately 1.6 μg h -1 cm -2 at a ROS concentration of 10 nM. The P(MAA-DB) brush-modified chip was biocompatible without significant toxicity toward L929 cells during the antibiotic release. The inflammation-triggered antibiotic release system based on a subcutaneous implant chip not only exhibits excellent efficacy against bacteria but also excellent biocompatibility, recyclability, and sensitivity, which can be easily extended to other drug delivery systems for numerous biomedical applications without phagocytosis- and metabolism-related issues.

Applications of cellulose nanofibers currently match the demands of biodegradable and renewable constituent biocomposites. In this study, we studied the process of preparing TEMPO-oxidized cellulose nanofibers (TOCNs). These nano-sized cellulose fibers (ca. 11 nm) can be fabricated to high transmittance and optically transparent paper (OP) films. Then the OP films can be facilely immobilized initiating sites for the subsequent surface-initiated atom transfer radical polymerization (SI ATRP). We investigated SI ATRP with styrene (St) kinetics and monitored chemical structure changes of the OP surfaces. The obtained OP- g -PSt significantly led to enhance thermal stability and alter the OP surface with hydrophobic compared to that of pristine OP film. Characterization was studied by Fourier transform infrared spectroscopy (FT-IR), powder X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), UV-Vis spectroscopy, thermogravimetric analyzer (TGA), and water contact angle (WCA) measurements.

Gelatin was immobilized selectively on the amide groups-modified bottom of a trench array of a photoresist template with 2 μm resolution by the ethyl(dimethylaminopropyl) carbodiimide/ N -hydroxysuccinimide reaction. The gelatin-immobilized line array was brominated to generate a macroinitiator for atom transfer radical polymerization. Poly(methacrylic acid) (PMAA) brushes were grafted from the macroinitiator layer as line arrays of one-dimensional diffraction gratings (DGs) for various grafting polymerization times. A laser beam system was employed to analyze the optical feature with a characteristic diffraction effect of the PMAA DGs at a 45° incident angle along the transverse magnetic and transverse electric polarization. The growth of the PMAA brush lines increased both their heights and widths, leading to a change in the reflective diffraction intensity. The PMAA brushes under various grafting polymerization times were cleaved from the substrate by digestion of gelatin with trypsin, and their molecular weights were obtained by gel permeation chromatography. The change degree of the diffraction intensity varied linearly with the molecular weight of the PMAA brushes over a wide range, from 135 to 1475 kDa, with high correlation coefficients. Molecular weight determination of polymer brushes using the reflective diffraction intensity provides a simple method to monitor their growth in real time without polymer brush cleavage.

To afford an intact double network (sample abbr.: DN) hydrogel, two-step crosslinking reactions of poly(2-acrylamido-2-methylpropanesulfonic acid) (i.e., PAMPS first network) and then poly(acrylic acid) (i.e., PAA second network) were conducted both in the presence of crosslinker ( N , N '-methylenebisacrylamide (MBAA)). Similar to the two-step processes, different contents of 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) oxidized cellulose nanofibers (TOCN: 1, 2, and 3 wt.%) were initially dispersed in the first network solutions and then crosslinked. The TOCN-containing PAMPS first networks subsequently soaked in AA and crosslinker and conducted the second network crosslinking reactions (TOCN was then abbreviated as T for DN samples). As the third step, various (T-)DN hydrogels were then treated with different concentrations of FeCl 3(aq) solutions (5, 50, 100, and 200 mM). Through incorporations of ferric ions into (T-)DN hydrogels, notably, three purposes are targeted: (i) strengthen the (T-)DN hydrogels through ionic bonding, (ii) significantly render ionic conductivity of hydrogels, and (iii) serve as a catalyst for the forth step to proceed with in situ chemical oxidative polymerizations of pyrroles to afford polypyrrole-containing (sample abbr.: Py) hydrogels [i.e., (T-)Py-DN samples]. The characteristic functional groups of PAMPS, PAA, and Py were confirmed by FT-IR. Uniform microstructures were observed by cryo scanning electron microscopy (cryo-SEM). These results indicated that homogeneous composites of T-Py-DN hydrogels were obtained through the four-step process. All dry samples showed similar thermal degradation behaviors from the thermogravimetric analysis (TGA). The T 2 -Py 5 -DN sample (i.e., containing 2 wt.% TOCN with 5 mM FeCl 3(aq) treatment) showed the best tensile strength and strain at breaking properties (i.e., σ Tb = 450 kPa and ε Tb = 106%). With the same compositions, a high conductivity of 3.34 × 10 -3 S/cm was acquired. The tough T 2 -Py 5 -DN hydrogel displayed good conductive reversibility during several "stretching-and-releasing" cycles of 50-100-0%, demonstrating a promising candidate for bioelectronic or biomaterial applications.

Polystyrene nanospheres (PNs) were embedded in bovine skin gelatin gels with a poly( N -isopropylacrylamide) (PNIPAAm) network, which were denoted as NGHHs, to generate thermoresponsive behavior. When 265 nm PNs were exploited to generate the pores, bovine skin gelatin extended to completely occupy the pores left by PNs below the lower critical solution temperature (LCST), forming a pore-less structure. Contrarily, above the LCST, the collapse of hydrogen bonding between bovine skin gelatin and PNIPAAm occurred, resulting in pores in the NGHH. The behavior of pore closing and opening below and above the LCST, respectively, indicates the excellent drug gating efficiency. Amoxicillin (AMX) was loaded into the NGHHs as smart antibiotic gating due to the pore closing and opening behavior. Accordingly, E. coli . and S. aureus were exploited to test the bacteria inhibition ratio (BIR) of the AMX-loaded NGHHs. BIRs of NGHH without pores were 48% to 46.7% at 25 and 37 °C, respectively, for E. coli during 12 h of incubation time. The BIRs of nanoporous NGHH could be enhanced from 61.5% to 90.4% providing a smart antibiotic gate of bovine skin gelatin gels against inflammation from infection or injury inflammation.

Atom transfer radical polyaddition (ATRPA) was utilized herein to synthesize a specific functional polyester. We conducted ATRPA of 4-vinylbenzyl 2-bromo-2-phenylacetate (VBBPA) inimer and successfully obtained a linear type poly(VBBPA) (PVBBPA) polyester with benzylic bromides along the backbone. To obtain a novel amphiphilic polymer bottlebrush, however, the lateral ATRP chain extension of PVBBPA with N -vinyl pyrrolidone (NVP) met the problem of quantitative dimerization. By replacing the bromides to xanthate moieties efficiently, we thus observed a pseudo linear first order reversible addition-fragmentation chain transfer (RAFT) polymerization to obtain novel poly(4-vinylbenzyl-2-phenylacetate)- g -poly(NVP) (PVBPA- g -PNVP) amphiphilic polymer bottlebrushes. The critical micelle concentration (CMC) and particle size of the amphiphilic polymer bottlebrushes were characterized by fluorescence spectroscopy, dynamic light scattering (DLS), and scanning electron microscopy (SEM) (CMCs < 0.5 mg/mL; particle sizes = ca. 100 nm). Toward drug delivery application, we examined release profiles using a model drug of Nile red at different pH environments (3, 5, and 7). Eventually, low cytotoxicity and well cell uptake of the Madin-Darby Canine Kidney Epithelial (MDCK) for the polymer bottlebrush micelles were demonstrated.

In this work, a unique hybrid system is proposed for one-dimensional gratings comprising of poly(glycidyl methacrylate) (PGMA) brushes and CdS quantum dots (CQDs). Generally, the emission of QDs is too weak to be observed in a dry state. Plasmonic resonances of the grating structures can be used to enhance the light emission or absorption of CQDs. The interaction between PGMA plasmonic nanostructures and inorganic CQDs plays a crucial role in engineering the light harvest, notably for optoelectronic applications. Extinction measurements of the hybrid system consisting of a PGMA grating and CQDs are reported. We designed one-dimensional gratings with various resolutions to tune the absorptance peaks of grating. PGMA grating grafted from a 1.5 µm resolution of trench arrays of photoresist exhibited absorptance peak at 395 nm, close to the absorption peak of CQDs, resulting in the photoluminescence enhancement of CQDs on the grating due to high charge carriers' recombination rate. Generally, the emission of quantum dots occurs under irradiation at characteristic wavelengths. Immobilizing QDs on the grating facilitates the emission of QDs under irradiation of full-wavelength light. Furthermore, the PGMA gratings with CQDs were immersed in various solvents to change the geometries resulting the shift of absorptance peak of grating. The proposed method could be applied for sensing the nature of the surrounding media and vice versa, as well as for various media of solvents.

The synthesis of novel branched/star copolymers which possess unique physical properties is highly desirable. Herein, a novel strategy was demonstrated to synthesize poly(ε-caprolactone) (PCL) based miktoarm star (μ-star) copolymers by combining ring-opening polymerization (ROP), styrenics-assisted atom transfer radical coupling (SA ATRC), and atom transfer radical polymerization (ATRP). From the analyses of gel permeation chromatography (GPC), proton nuclear magnetic resonance (¹H NMR), and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS), well-defined PCL-μ-PSt (PSt: polystyrene), and PCL-μ-PtBA (PtBA: poly( tert -butyl acrylate) μ-star copolymers were successfully obtained. By using atomic force microscopy (AFM), interestingly, our preliminary examinations of the μ-star copolymers showed a spherical structure with diameters of ca. 250 and 45 nm, respectively. We successfully employed combinations of synthetic techniques including ROP, SA ATRC, and ATRP with high effectiveness to synthesize PCL-based μ-star copolymers.

Enhancing drug loading efficacy and stability of polymeric micelles remains a grand challenge. Here we develop adamantane-based star copolymers adamantane-[poly(ε-caprolactone)- b -poly(2-(diethylamino)ethyl methacrylate)- b -poly(poly(ethylene glycol) methyl ether methacrylate)]₄ (Ad-(PCL- b -PDEAEMA- b -PPEGMA)₄) and their self-assembled micelles for controlled drug delivery. Results show that the polymers have excellent stability in solution with low critical micelle concentration (CMC) (0.0025⁻0.0034 mg/mL) and the apparent base dissociation constant (p K ) of the polymers is from 5.31 to 6.05. Dynamic light scattering analysis exhibits the great environmental response capability of the pH-sensitive micelles according to particle sizes and zeta potentials. With the synergy effect of the adamantane and hydrophobic block, the micelles display the high Doxorubicin (DOX) loading efficacy (up to 22.4%). The DOX release study shows that the micelles are capable of controlled release for drug. This work indicates the Ad-(PCL- b ) of the polymers is from 5.31 to 6.05. Dynamic light scattering analysis exhibits the great environmental response capability of the pH-sensitive micelles according to particle sizes and zeta potentials. With the synergy effect of the adamantane and hydrophobic block, the micelles display the high Doxorubicin (DOX) loading efficacy (up to 22.4%). The DOX release study shows that the micelles are capable of controlled release for drug. This work indicates the Ad-(PCL- b -PDEAEMA- b -PPEGMA)₄ micelles may provide new guidelines for drug control and release system in overcoming cancer treatment., Competing Interests: The authors declare no conflict of interest.

Considering the poor compatibility and water-resistance of sulfonate flame retardants for polycarbonate (PC), an efficient S/N-based flame retardant named 1,3,5,7-tetrakis(phenyl-4-sulfonyl-melamine)adamantane (ASN) has been developed. Fire properties studies of PC/ASN blends indicate that the addition of 0.10 wt % ASN imparts a V-0 rating and a limited oxygen index (LOI) value of 30.1% to PC specimens, and ASN can suppress the heat and toxic gas release of PC composites. Additionally, PC/ASN blends are believed to be exceptional materials for outdoor PC applications due to their superior water-resistance properties. Moreover, mechanical properties were further systematically investigated, and the correlative results indicate that the tensile strength and rigidity of specimens are improved with the addition of ASN., Competing Interests: The authors declare no conflict of interest. The founding sponsors had no role in the design of the study; in the collection, analyses, or interpretation of data; in the writing of the manuscript, and in the decision to publish the results.

This study developed multi-layered lidocaine- and epinephrine-eluting biodegradable poly[(d,l)-lactide- co -glyco lide] (PLGA)/collagen nanofibers. An electrospinning technique was employed to fabricate the multi-layer biodegradable drug-eluting nanofibers. After fabrication, the nanofibrous membranes were characterized. The drug release characteristics were also investigated. In addition, the in vivo efficacy of nanofibers for pain relief and hemostasis in palatal oral wounds of rabbits were evaluated. Histological examinations were also completed. The experimental results suggested that all nanofibers exhibited good biocompatibility and eluted effective levels of lidocaine and epinephrine at the initial stages of wound recovery., Competing Interests: The authors declare no conflict of interest.

Through the reversible addition⁻fragmentation chain transfer (RAFT) copolymerization of 3-ethyl-1-vinyl-2-pyrrolidone (C₂NVP) and N -vinylpyrrolidone (NVP), a series of well-defined P(C₂NVP- co -NVP) copolymers were synthesized ( M n = ca. 8000 to 16,000 and M w /M n <1.5) by using a difunctional chain transfer agent, S -(1-methyl-4-hydroxyethyl acetate) O -ethyl xanthate (MHEX). Copolymerizing kinetics and different monomer ratio in feeds were conducted to study the apparent monomer reaction rate and reactivity ratios of NVP and C₂NVP, which indicated similar reaction rates and predominantly ideal random copolymers for the two monomers. The T g s of the obtaining P(C₂NVP- co -NVP) copolymers significantly corresponded to not only molecular weights MWs but also copolymer compositions. These copolymers presented characteristic lower critical solution temperatures (LCST) behavior. We then studied the cloud points (CPs) of the copolymers with varying MWs and compositions. With different MWs, the CPs were linearly decreased from ca. 51 to 45 °C. With different compositions, the CPs of the copolymers decreased from ca. 48 to 29 °C with C₂NVP content (i.e., from 60.8 to 89.9 mol %). Fitting the CPs by the theoretical equation, the result illustrated that the introduction of more hydrophobic units of C₂NVP suppressed the hydrophilic interaction between the polymer chain and water. We then successfully proceeded the chain extension through the ring-opening polymerization (ROP) of ε-caprolactone (CL) to the synthesis of a novel P(C₂NVP- co -NVP)- b -PCL amphiphilic block copolymer ( M n,NMR = 14,730 and M w / M n = 1.59). The critical micelle concentration (CMC) of the block copolymer had a value of ca. 1.46 × 10 -4 g/L. The block copolymer micelle was traced by dynamic light scattering (DLS), obtaining thermosensitive behaviors with a particle size of ca. 240 nm at 25 °C and ca. 140 nm at 55 °C, respectively., Competing Interests: The authors declare no conflict of interest.

We grafted thermo-responsive poly( N -isopropylacrylamide) (PNIPAM) brushes from monodisperse SiO₂ microspheres through surface-initiated atom transfer radical polymerization (SI ATRP) to generate core-shell structured SiO₂@PNIPAM microspheres (SPMs). Regular-sized SPMs dispersed in aqueous solution and packed as photonic crystals (PCs) in dry state. Because of the microscale of the SPMs, the packing behavior of the PCs in water can be observed by optical microscopy. By increasing the temperature above the lower critical solution temperature (LCST) of PNIPAM, the reversible swelling and shrinking of the PNIPAM shell resulted in dispersion and precipitation (three-dimensional aggregation) of the SPM in aqueous solution. The SPMs were microdispersed in a water layer to accommodate the aggregation along two dimensions. In the microdispersion, the SPMs are packed as PCs with microscale spacing between SPMs below the LCST. When the temperature is increased above the LCST, the microdispersed PCs exhibited a close-packed arrangement along two dimensions with decreased spacing between SPMs. The change in spacing with increasing temperature above the LCST resulted in a color change from red to blue, which could be observed by the naked eye at an incident angle. Thus, the SPM array could be applied as a visual temperature sensor.