Dialdehyde cellulose (DAC) and polyethyleneimine (PEI) coated polyvinylidene fluoride (PVDF) membrane for simultaneously removing emulsified oils and anionic dyes.

Developing high-efficiency membrane for oil and dye removal is very urgent, because wastewater containing them can cause great damage to human and environment. In this study, a coated membrane was fabricated by applying DAC and PEI onto the commercial PVDF microfiltration membrane for supplying the demand. The coated membrane presents superhydrophlic and superoleophobic properties with a water contact angle of 0o and underwater oil contact angle exceed 150°, as well as excellent low underwater oil adhesion performance. The coated membrane shows high separation efficiency exceeded 99.0% and flux 350.0 L·m-2·h-1 when used for separating for six kinds of oil including pump oil, sunflower oil, n-hexadecane, soybean oil, diesel and kerosene in water emulsions. Additionally, the coated membrane can effectively remove anionic dyes, achieving rejection rates of 94.7%, 93.4%, 92.3%, 90.7% for the CR, MB, RB5, AR66, respectively. More importantly, the membrane was able to simultaneously remove emulsified oil and soluble anionic dyes in wastewater containing both of them. Therefore, this novel coated membrane can be a promising candidate for treating complex wastewater.

Synthesis of Water-Dispersible Poly(dimethylsiloxane) and Its Potential Application in the Paper Coating Industry as an Alternative for PFAS-Coated Paper and Single-Use Plastics.

Polyethylene-, polyvinylidene chloride-, and per- and polyfluoroalkyl substance-coated paper generate microplastics or fluorochemicals in the environment. Here, we report an approach for the development of oil-resistant papers using an environmentally friendly, fluorine-free, water-dispersible poly(dimethylsiloxane) (PDMS) coating on kraft paper. Carboxylic-functionalized PDMS (PDMS-COOH) was synthesized and subsequently neutralized with ammonium bicarbonate to obtain a waterborne emulsion, which was then coated onto kraft paper. The water resistance of the coated paper was determined via Cobb60 measurements. The Cobb60 value was reduced to 2.70 ± 0.14 g/m2 as compared to 87.6 ± 5.1 g/m2 for uncoated paper, suggesting a remarkable improvement in water resistance. Similarly, oil resistance was found to be 12/12 on the kit test scale versus 0/12 for uncoated paper. In addition, the coated paper retained 70-90% of its inherent mechanical properties, and more importantly, the coated paper was recycled via pulp recovery using a standard protocol with a 91.1% yield.

Supramolecular biomaterials for bio-imaging and imaging-guided therapy.

Benefiting from their unique advantages, including reversibly switchable structures, good biocompatibility, facile functionalization, and sensitive response to biological stimuli, supramolecular biomaterials have been widely applied in biomedicine. In this review, the representative achievements and trends in the design of supramolecular biomaterials (mainly those derived from biomacromolecules) with specific macromolecules including peptides, deoxyribonucleic acid, and polysaccharides, as well as their applications in bio-imaging and imaging-guided therapy are summarized. This review will serve as an important summary and "go for" reference for explorations of the applications of supramolecular biomaterials in bio-imaging and image-guided therapy, and will promote the development of supramolecular chemistry as an emerging interdisciplinary research area.

A Surface-Confined Gradient Conductive Network Strategy for Transparent Strain Sensors toward Full-Range Monitoring.

The development of transparent and flexible sensors suitable for the full-range monitoring of human activities is highly desirable, yet presents a daunting challenge due to the need for a combination of properties such as high stretchability, high sensitivity, and good linearity. Gradient structures are commonly found in many biological systems and exhibit excellent mechanical properties. Here, we report a novel surface-confined gradient conductive network (SGN) strategy to construct conductive polymer hydrogel-based stain sensors (CHSS). This CHSS showed an ultrahigh stretchability of 4000% strain, transparency above 90% at a wavelength of 600 nm, as well as skin-like Young's modulus of 40 kPa. Impressively, the sensitivity was improved to 3.0 and outstanding linear sensing performance was achieved simultaneously in the ultrawide range of 0% to 4000% strain with a high R-square value of 0.994. With the help of SGN strategy, this CHSS was able to monitor both large-scale and small-scale human motions and activities. This SGN strategy can open a new avenue for the development of novel flexible strain sensors with excellent mechanical, transparent, and sensing performance for full-range monitoring of human activities.

Smart Self-Cleaning Membrane via the Blending of an Upper Critical Solution Temperature Diblock Copolymer with PVDF.

Poly(2,2,2-trifluoroethyl methacrylate)-b-poly(imidazoled glycidyl methacrylate-co-diethylene glycol methyl ether methacrylate) (PTFEMA-b-P(iGMA-co-MEO2MA)) containing an upper critical solution temperature (UCST) polymer chain was prepared and blended with poly(vinylidene fluoride) (PVDF) to produce a thermoresponsive membrane with smart self-cleaning performance. The successful preparation of the membrane was demonstrated by attenuated total reflection-Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, and scanning electron microscopy characterization. The membrane shows UCST performance, and its flux changes with the filtrate temperature as the UCST polymer chain stretches out and contracts in response to various temperatures. In addition, the UCST polymer chain can disrupt the foulant and push it away from the membrane when the temperature is above the UCST and thus enables membranes to exhibit a smart self-cleaning behavior. To the best of our knowledge, this work is the first report of a smart self-cleaning membrane based on the blending of a diblock copolymer containing a UCST polymer chain with PVDF.

Cucurbit[8]uril-based supramolecular hydrogels for biomedical applications.

As a member of the cucurbit[n]uril family (where n denotes the number of glycoluril units), cucurbit[8]uril (CB[8]) possesses a large cavity volume and is able to accommodate two guests simultaneously. Therefore, CB[8] has been adapted as a dynamic noncovalent crosslinker to form various supramolecular hydrogels. These CB[8]-based hydrogels have been investigated for various biomedical applications due to their good biocompatibility and dynamic properties afforded by host-guest interactions. In this review, we summarize the hydrogels that have been dynamically fabricated via supramolecular crosslinking of polymers by CB[8] reported during the past decade, and discuss their design principles, innovative applications in biomedical science and their future prospects.

Topological cyclodextrin nanoparticles as crosslinkers for self-healing tough hydrogels as strain sensors.

Hydrogels have been widely used for various applications, and thus addressing the challenges associated with the design of sustainable hydrogels has become an important issue. However, little attention has been devoted toward the design of crosslinkers which are often toxic, lack self-healing capabilities, and derived from petrochemicals. Herein, novel cyclodextrin topological nanoparticles (TNPs) have been constructed. These TNPs were found to possess crosslinking capabilities and the corresponding TNPs-crosslinked hydrogels showed excellent mechanical performances with a high stretchability of 1860 % and stress of 180 kPa and good anti-fatigue abilities. These hydrogels could be readily recycled and used for modular assembly and disassembly in various shapes and could serve as flexible strain sensors to monitor human activities with a sensing range of 0-1800 %, controllable sensitivity, and good fatigue resistance. These topological nanoparticles can inspire the design of novel physical crosslinkers for novel flexible strain sensors, tough and self-healing hydrogels, and soft robotics.

Preparation of Multipurpose Polyvinylidene Fluoride Membranes via a Spray-Coating Strategy Using Waterborne Polymers.

As reported herein, the waterborne polymers poly(glycidyl methacrylate-co-poly(ethylene glycol) methyl ether methacrylate) P(GMA-co-mPEGMA) and polyethyleneimine (PEI) were used to prepare multipurpose polyvinylidene fluoride (PVDF) membranes via a direct spray-coating method. P(GMA-co-mPEGMA) and PEI were alternately sprayed onto the PVDF membrane to yield stable cross-linked copolymer coatings. The successful coating of polymers onto the membrane surface was verified by scanning electron microscopy, attenuated total reflectance-Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy characterization. The coated membrane exhibited oil rejection rates that exceeded 99.0% for oil water mixture separation and 98.0% for oil/water emulsion separation. The flux recovery ratio reached 96.7% after bovine serum albumin filtration and washing with water. The removal efficiencies of the coated membrane M3 for Congo red, methyl orange, methylene blue, and crystal violet, Pb(II), Cu(II), and Cd(II) were 82.4, 83.9, 6.3, 26.8, 90.6, 91.3, and 86.2%, respectively. Thus, it can be used for the removal of dyes and heavy metal ions from wastewater. The antibacterial activities of the coated membranes were also confirmed by the inhibition zone tests and confocal laser scanning microscopy analysis. In addition, the cross-linking strategy provides the coated membranes with excellent durability and repeatability. More importantly, the use of water as the solvent can ensure that the application of these membrane coatings proceeds via a very safe and environmentally friendly coating process.

Coexistence of Antiadhesion Performance, Intrinsic Stretchability, and Transparency.

Antiadhesion performance, stretchability, and transparency are highly desirable properties for materials and devices in numerous applications. However, the existing strategies for imparting materials with antiadhesion performance generally induce rigidity and opacity, and principle is yet to be provided for designing materials that combine these important parameters. Here, we show that four factors including a low surface energy, appropriate cross-linking, availability of a homogeneous and amorphous composite, and a smooth material surface can be used to design an intrinsically stretchable and transparent polymer film with antiadhesion performance against various liquids including water, diiodomethane, hexadecane, cooking oil, and pump oil. The film can be obtained via simply molding a waterborne polymer network at ambient temperature. Furthermore, the film can retain its antiadhesion performance and outstanding transparency even when it is subjected to large mechanical deformations reaching up to 1800%, and its maximal fracture strain exceeds 3000%. These design concepts offer a general platform for achieving multiple material functionalities, and may open new avenues for the surface functionalization of stretchable materials and devices.

Cucurbit[7]uril: an emerging candidate for pharmaceutical excipients.

Cucurbit[7]uril (CB[7]), belonging to the cucurbit[n]uril family (CB[n], n = 5-8, 10, or 13-15), may form host-guest complexes with a variety of small molecules of biomedical interest. The physical and chemical properties of the complexed drugs are often improved as a result of this complexation, suggesting the potential application of CB[7] as a pharmaceutical excipient. This review has summarized the most recent research progress reported between 2011 and early 2017 regarding the biocompatibility of CB[7] and the influence of CB[7] on the stability, solubility, biouptake, and biological activities (including therapeutic efficacies and toxicities) of guest drug molecules. Through this systemic summary and analysis, we intend to stimulate further research efforts in this area and promote the use of CB[7] as an emerging pharmaceutical excipient to improve various properties of drug molecules (or active pharmaceutical ingredients).

Anion Sensing with a Blue Fluorescent Triarylboron-Functionalized Bisbenzimidazole and Its Bisbenzimidazolium Salt.

A blue fluorescent p-dimesitylboryl-phenyl-functionalized 1,3-bisbenzimidazolyl benzene molecule (1) has been synthesized in high yield by Stille coupling of bisbenzimidazolyl bromobenzene with p-BMes2-SnBu3-benzene. Methylation of 1 led to the formation of the bisbenzimidazolium salt (2). The utility of both 1 and 2 in sensing CN- and halide (F-, Cl-, Br-, and I-) was examined, and it was found that only the small fluoride and cyanide anions were able to bind to the boron atom with binding constants in the range of 2.9 × 104 to 5 × 105 M-1. Computational studies provided insight into the photophysical properties of the molecules and verified that a charge-transfer process is quenched in these "turn-off" molecular sensors.

Inhibition of C(2)-H Activity on Alkylated Imidazolium Monocations and Dications upon Inclusion by Cucurbit[7]uril.

The inclusions of 1-methyl-3-alkylimidazolium cations (ICn+, n = 4, 6, and 8) and 3,3'-bis(3-(1-methylimidazolium))-1,n-alkane (DICn2+, n = 4, 6, and 8) in the macrocyclic cucurbit[7]uril result in a decrease (up to 25-fold) of the C(2)-H/D exchange rate constants and an increase in the C(2)-H pKa values (ΔpKa = 0.34 to 1.45). The alkyl chain lengths were found to play an important role in the extent of C(2)-H activity inhibition, upon complexation with cucurbit[7]uril.

Encapsulation of Vitamin B(1) and Its Phosphate Derivatives by Cucurbit[7]uril: Tunability of the Binding Site and Affinity by the Presence of Phosphate Groups.

Vitamin B1 (1) and its phosphate derivatives, thiamine monophosphate (2) and thiamine pyrophosphate (3), are shown to form stable 1:1 host-guest complexes with cucurbit[7]uril (CB[7]) in aqueous solution. The binding sites of CB[7] on these guests shift from the ethylthiazolium region of 1 to the pyrimidine moiety of 2 and 3 due to the presence of phosphate groups, leading to variations of binding affinities as well as C(2)-H/D exchange rate constants and C(2)-H pKa values with these guest molecules.

Supramolecular Nanostructures Based on Cyclodextrin and Poly(ethylene oxide): Syntheses, Structural Characterizations and Applications for Drug Delivery.

Cyclodextrins (CDs) have been extensively studied as drug delivery carriers through host⁻guest interactions. CD-based poly(pseudo)rotaxanes, which are composed of one or more CD rings threading on the polymer chain with or without bulky groups (or stoppers), have attracted great interest in the development of supramolecular biomaterials. Poly(ethylene oxide) (PEO) is a water-soluble, biocompatible polymer. Depending on the molecular weight, PEO can be used as a plasticizer or as a toughening agent. Moreover, the hydrogels of PEO are also extensively studied because of their outstanding characteristics in biological drug delivery systems. These biomaterials based on CD and PEO for controlled drug delivery have received increasing attention in recent years. In this review, we summarize the recent progress in supramolecular architectures, focusing on poly(pseudo)rotaxanes, vesicles and supramolecular hydrogels based on CDs and PEO for drug delivery. Particular focus will be devoted to the structures and properties of supramolecular copolymers based on these materials as well as their use for the design and synthesis of supramolecular hydrogels. Moreover, the various applications of drug delivery techniques such as drug absorption, controlled release and drug targeting based CD/PEO supramolecular complexes, are also discussed.

Supramolecular Inhibition of Neurodegeneration by a Synthetic Receptor.

Cucurbit[7]uril (CB[7]) was found in vitro to sequester the neurotoxins MPTP (N-methyl-4-phenyl-1,2,3,6-tetrahydropyridine) and MPP(+) (N-methyl-4-phenylpyridine). The CB[7]/neurotoxin host-guest complexes were studied in detail with (1)H NMR, electrospray ionization mass spectrometry, UV-visible spectroscopic titration, and molecular modeling by density functional theory. The results supported the macrocyclic encapsulation of MPTP and MPP(+), respectively, by CB[7] in aqueous solutions with relatively strong affinities and 1:1 host-guest binding stoichiometries in both cases. More importantly, the progression of MPTP/MPP(+) induced neurodegeneration (often referred to as a Parkinson's disease model) was observed to be strongly inhibited in vivo by the synthetic CB[7] receptor, as shown in zebrafish models. These results show that a supramolecular approach could lead to a new preventive and/or therapeutic strategy for counteracting the deleterious effects of some neurotoxins leading to neurodegeneration.

Selective sensitization of Eu(III) and Tb(III) emission with triarylboron-functionalized dipicolinic acids.

Three triarylboron- (Mes2BAr-) functionalized dipicolinic acids, namely, 4-(4-(dimesitylboranyl)-2,3,5,6-tetramethylphenyl)pyridine-2,6-dicarboxylic acid (H2L1), 4-(4-(4-dimesitylboranyl)-2,3,5,6-tetramethylphenyl)-1H-1,2,3-triazol-1-yl)pyridine-2,6-dicarboxylic acid (H2L2), and 4-(4-(4-dimesitylboranyl) phenyl)-1H-1,2,3-triazol-1-yl)pyridine-2,6-dicarboxylic acid (H2L3), have been designed and synthesized. Lanthanide(III) complexes with the general formula of [NBu4]3[LnL3] (Ln = Eu or Tb; L = L1, L2, or L3) were obtained. The new triarylboron-functionalized ligands were found to be effective in the selective sensitization of the emissions of Eu(III) and Tb(III) ions with a high quantum efficiency (e.g., 0.54 for [NBu4]3[TbL13] in the solid state) upon excitation at ∼330 nm. An intraligand charge-transfer (ILCT) transition from the mesityl or aryl group to the boron or boron-aryl unit was found to play a key role in the activation of the Eu(III) and Tb(III) emissions, based on TD-DFT computational data and luminescence titration experiments performed using fluoride and cyanide ions.

Robust superamphiphobic coatings based on silica particles bearing bifunctional random copolymers.

Reported herein is the growth of bifunctional random copolymer chains from silica particles through a "grafting from" approach and the use of these copolymer-bearing particles to fabricate superamphiphobic coatings. The silica particles had a diameter of 90 ± 7 nm and were prepared through a modified Stöber process before atom transfer radical polymerization (ATRP) initiators were introduced onto their surfaces. Bifunctional copolymer chains bearing low-surface-free-energy fluorinated units and sol-gel-forming units were then grafted from these silica particles by surface-initiated ATRP. Perfluorooctyl ethyl acrylate (FOEA) and 3-(triisopropyloxy)silylpropyl methacrylate (IPSMA) were respectively used as fluorinated and sol-gel-forming monomers in this reaction. Hydrolyzing the IPSMA units in the presence of an acid catalyst yielded silica particles that were adorned with silanol-bearing copolymer chains. Coatings were prepared by spraying these hydrolyzed silica particles onto glass and cotton substrates. A series of four different copolymer-functionalized silica particles samples bearing copolymers with similar FOEA molar fractions (fF) of ~80% but with different copolymer grafting mass ratios (gm) that ranged between 12.3 wt% and 58.8 wt%, relative to silica, were prepared by varying the polymerization protocols. These copolymer-bearing silica particles with a gm exceeding 34.1 wt% were used to coat glass and cotton substrates, yielding superamphiphobic surfaces. More importantly, these particulate-based coatings were robust and resistant to solvent extraction and NaOH etching thanks to the self-cross-linking of the copolymer chains and their covalent attachment to the substrates.

Host-guest complexations of local anaesthetics by cucurbit[7]uril in aqueous solution.

The cucurbit[7]uril (CB[7]) host molecule forms very stable host-guest complexes with the local anaesthetics procaine (K(CB[7]) = (3.5 +/- 0.7) x 10(4) dm(3) mol(-1)), tetracaine (K(CB[7]) = (1.5 +/- 0.4) x 10(4) dm(3) mol(-1)), procainamide (K(CB[7]) = (7.8 +/- 1.6) x 10(4) dm(3) mol(-1)), dibucaine (K(CB[7]) = (1.8 +/- 0.4) x 10(5) dm(3) mol(-1)) and prilocaine (K(CB[7]) = (2.6 +/- 0.6) x 10(4) dm(3) mol(-1)) in aqueous solution (pD = 4.75). The stability constants are 2-3 orders of magnitude greater than the values reported for binding by the comparably sized beta-cyclodextrin host molecule. The inclusion by CB[7] raises the first pK(a) values of the anaesthetics by 0.5-1.9 pK units, as the protonated forms are bound more strongly in acidic solution. The complexation-induced chemical shift changes in the guest proton resonances provide an indication of the site(s) of binding and the effects of protonation on the location of the binding sites.

Cucurbit[7]uril host-guest complexes of cholines and phosphonium cholines in aqueous solution.

The neutral host cucurbit[7]uril forms very stable complexes with a series of cationic cholines (R(3)NCH(2)CH(2)OR'(+)) and their phosphonium analogues (R(3)PCH(2)CH(2)OR'(+)) (R(3) = Me(3), Et(3), or Me(2)Bz, or R(3)N = quinuclidinium, and R' = H, COCH(3), CO(CH(2))(2)CH(3), or PO(3)H), and (+/-)-carnitine, in aqueous solution. The complexation behaviour has been investigated using (1)H and (31)P NMR spectroscopies, and ESI mass spectrometry. The complexation-induced chemical shift changes of the guests clearly indicate the effects of replacing the N(CH(3))(3)(+) end group by P(CH(3))(3)(+), and changing the nature of R on the position of the guest with respect to the CB[7] cavity and its polar portal-lining carbonyl groups. This study demonstrates that molecular recognition of cholines in aqueous solution is achievable with a neutral host without the need for aromatic walls for cation-pi interactions.