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Three xanthophylls [(3R,3'R,6'R)-lutein (1), (3R,3'S)-zeaxanthin (2), and (3R,3'S)-astaxanthin (3)] were used for the first time as initiators in the ring-opening polymerization (ROP) of ε-caprolactone (CL) catalyzed by tin(ii) 2-ethylhexanoate [Sn(Oct)2] for the synthesis of novel sustainable xanthophyll-containing poly(ε-caprolactone)s (xanthophylls-PCL). The obtained polyesters were characterized by 1H and 13C NMR, FT-IR, DSC, SEC, and MALDI-TOF MS, and their use as additives in green lubricants was evaluated using a sliding friction test under boundary conditions. Xanthophylls-PCL were obtained with good conversions and with molecular weights determined by SEC to be between 2500 and 10 500 Da. The thermal properties of xanthophyll-polyesters showed a crystalline domain, detected by DSC. Lastly, the green lubricant activity of these polymers was evaluated and the results showed that xanthophylls-PCL could be employed as additives for biodegradable lubricant applications since they have better tribological behavior than current additives, which demonstrates their potential as future commercial materials with interesting eco-friendly properties for diverse applications.

A biomimetic of endogenous tissue inhibitors of metalloproteinases (TIMPs) was engineered by introducing three binding elements to a synthetic tetrapolymer. We evaluated the contribution of composition, size, and shape of the TIMP-mimicking polymers to the inhibition of BaP1, a P-I class snake venom metalloproteinase (SVMP). Inhibition was achieved when the size of the linear polymer (LP) was comparable to or greater than that of the enzyme, indicating the efficacy requires binding to a significant portion of the enzyme surface in the vicinity of the active site. The efficacy of a low cross-linked polymer hydrogel nanoparticle (NP) of substantially greater molecular weight was comparable to that of the LPs despite differences in size and shape, an important finding for in vivo applications. The abiotic TIMP was effective against two classes of SVMPs in whole snake venom. The results can serve as a design principle for biomimetic polymer inhibitors of enzymes.

As the most representative family of proteinases related to tumorigenesis, matrix metalloproteinase-9 (MMP-9) represents a key player in cancer cell migration and regulation of the tumor microenvironment. The inhibition of MMP-9 activity has been pursued as a target for anticancer therapy. However, most synthetic MMP-9 inhibitors have failed in clinical trials because of their lack of selectivity. Here, an abiotic mimic based on molecularly imprinted nanoparticles has been designed as an inhibitor for MMP-9. To attain fast mass transfer and facilitate multifunctional roles, we synthesized the imprinted polymer thin layer on the surface of gold nanorods by reversible addition-fragmentation chain transfer polymerization using MMP-9 as the template, which captures MMP-9 selectively and inhibits its activity by providing steric hindrance to the activity-related domain of MMP-9. In vitro cell experiments and in vivo studies in mice demonstrate that the imprinted artificial antibody suppresses the migration and growth of metastatic tumors. The tumor growth inhibition rate reaches up to 54 ± 15%. Compared with the typical photothermal therapy induced by gold nanorods, the use of MMP-9-imprinted synthetic antibody could better inhibit the lung tumor metastasis by quenching the enzyme activity of MMP-9. This study offers a new paradigm in the engineering of imprinted nanoparticles as inhibitors for cancer therapy.

We report a metal free synthetic hydrogel copolymer with affinity and selectivity for His6-tagged peptides and proteins. Small libraries of copolymers incorporating charged and hydrophobic functional groups were screened by an iterative process for His6 peptide affinity. The monomer selection was guided by interactions found in the crystal structure of an anti-His tag antibody-His6 peptide antigen complex. Synthetic copolymers incorporating a phenylalanine-derived monomer were found to exhibit strong affinity for both His6-containing peptides and proteins. The proximity of both aromatic and negatively charged functional groups were important factors for the His6 affinity of hydrogel copolymers. His6 affinity was not compromised by the presence of enzyme cleavage sequences. The His6-copolymer interactions are pH sensitive: the copolymer selectively captured His6 peptides at pH 7.8 while the interactions were substantially weakened at pH 8.6. This provided mild conditions for releasing His6-tagged proteins from the copolymer. Finally, a synthetic copolymer coated chromatographic medium was prepared and applied to the purification of a His6-tagged protein from an E. coli expression system. The results establish that a synthetic copolymer-based affinity medium can function as an effective alternative to immobilized metal ion columns for the purification of His6-tagged proteins.

The photonic crystals (PhCs) have a bright structural color, but their angular dependence and naked-eye observation subjectivity only apply for qualitative analysis. The HSB color space is a three-channel color analysis technology based on hue (H)-saturation (S)-brightness (B). We use the HSB color space to analyze the structural color of the AM/NIPAM PhCs hydrogel sensor in response to temperature and organic solvents. We proved that the structural color analysis based on the hue value (H) could achieve an analysis accuracy close to the spectrum analysis. In addition, we have obtained stimulus-responsive PhCs structure color images from references and quantitatively analyzed them through the HSB color space. The results show that the H of the structural color can establish a high correlation with the specified target. In some cases, its best fitness exceeds traditional spectroscopy methods. This analysis method will provide a general and quantitative analysis technology for the structural color of PhCs by consumer-grade computers and smartphones.

Konjac tofu is a traditional Chinese food whose main ingredient is the water-soluble polysaccharide from konjac tubers-konjac glucomannan (KGM). Herein we report an interpenetrating double network polymeric film by crosslinking KGM and polyvinyl alcohol (PVA) with glutaraldehyde under acidic conditions. PVA was introduced into the hydrogel system as a hard skeleton, which not only maintained the biocompatibility of KGM, but also gave the hydrogel superior mechanical properties and solvent resistance. Implanting a colloidal array inside the above film, we obtained a new type of biomass based photonic crystal that is sensitive to a variety of physical and chemical stimulus, especially for methanol. This photonic crystal responds to methanol and methanol vapor, and has the ability to detect methanol in gasoline, which has a good application prospect.

The determination of lactic acid content has a guiding significance for disease diagnosis or food supervision. Herein, a hydrogel-based three-dimensional photonic crystal (PC) sensor for specific detection of lactic acid is introduced. The hydrogel was prepared by one-step copolymerization of N-isopropylacrylamide and acrylamide in the presence of oxamate derivative 2-((6-acrylamidohexyl) amino)-2-oxoacetic acid (AOA). An obvious color change from orange-red to purple and a 45-nm redshift of the reflection peak were obtained in 3 min when lactic acid concentration increased from 0 to 20 mM. The detection limit was confirmed as 0.1 mM, and the prepared sensor can be reused more than 20 times. Moreover, the affinity and selectivity of AOA to lactic acid were proven by both the interaction energy from density functional theory (DFT) study and the comparison to those of pyruvate and propionic acid. This sensor was proven to be cost-effective and convenient with rapid response time, good reusability, and selectivity.

We report the synthesis of polymethylene waxes, a surrogate of PE waxes, by a controlled polymerization reaction in water at or near r.t. and under atmospheric pressure. The monomer, dimethylsulfoxonium methylide, is generated in situ from a salt, trimethylsulfoxonium halide. The carbon sources for the polymerizations are C1 molecules, which can be derived from nonpetroleum feedstock. DMSO serves as the C1 carrier and is not consumed. The reaction is initiated and catalyzed by trialkylboranes, compounds that are stable in water. A certain degree of molecular weight control is achieved by adjusting the stoichiometry of “salt” to organoborane. Polymethylene, the simplest hydrocarbon polymer, is a semicrystalline material. The room temperature polymerization produces a linear polymer approximately 100 °C below its melting temperature (Tm). The supercooled polymers rapidly crystallize into flat nanoparticles comprised of stacked lamellae.

We report the first synthesis of a gradient methylidene-ethylidene copolymer via a living C1 polymerization. The copolymer has a similar chemical structure as the corresponding ethylene-propylene copolymer. To achieve this goal a new and convenient source of the ethylide monomer, diethylsulfoxonium ethylide, was developed for the introduction of the methyl branch in the polymer backbone. The gradient copolymer contains a gradual change of instantaneous methyl branch content from 0% on one end of the polymer chain to 63% on the other end. Thermal analysis revealed that the gradient copolymers have a narrow glass transition temperature range with values intermediate between those of linear polyethylene and atactic polypropylene.

Peptide – polymer complementary pairs can provide useful tools for isolating, organizing and separating biomacromolecules. We describe a procedure for selecting a high affinity complementary peptide-polymer nanoparticle (NP) pair using phage display. A hydrogel copolymer nanoparticle containing a statistical distribution of negatively charged and hydrophobic groups was used to select a peptide sequence from a phage displayed library of >10(10) peptides. The NP has low nanomolar affinity for the selected cyclic peptide and exhibited low affinity for a panel of diverse proteins and peptide variants. Affinity arises from the complementary physiochemical properties of both NP and peptide as well as the specific peptide sequence. Comparison of linear and cyclic variants of the peptide established that peptide structure also contributes to affinity. These findings offer a general method for identifying polymer-peptide complementary pairs. Significantly, precise polymer sequences (proteins) are not a requirement, a low information statistical copolymer can be used to select for a specific peptide sequence with affinity and selectivity comparable to that of an antibody. The data also provides evidence for the physiochemical and structural contributions to binding. The results confirm the utility of abiotic, statistical, synthetic copolymers as selective, high affinity peptide affinity reagents.

In this paper, soft thermosensitive photonic crystals are immobilized via a reversible temperature-triggered in situ sol–gel transition above their phase transition temperature (Tp), which may be a significant advance in the field. Specifically, a library of thermosensitive poly(N-isopropylacrylamide)/poly(acrylic acid) (PNIPAm/PAA) interpenetrating nanogels (IPNs) is synthesized, which can achieve a reversible temperature-induced sol–gel transition at a low concentration (1.1 wt%). More interestingly, as the temperature is increased above Tp, the photonic crystals assembled by these IPNs do not disappear but are “immobilized” in the in situ formed hydrogel matrix. Moreover, these colorful IPN dispersions exhibit outstanding syringe-injectability, immediately turning from an aqueous solution into an insoluble hydrogel as they are injected into PBS at 37 °C. Plus, a protein-release study showed that these injectable hydrogels show extended release times and slower release rates in comparison with dilute nanogel dispersions. In brief, these in situ formed hydrogels with brilliant structural colors have potential in optical applications, e.g., color displays, crystal immobilization, and biological applications, e.g., 3D cell culture and drug delivery.

Sepsis is a life-threatening condition caused by the extreme release of inflammatory mediators into the blood in response to infection (e.g., bacterial infection, COVID-19), resulting in the dysfunction of multiple organs. Currently, there is no direct treatment for sepsis. Here we report an abiotic hydrogel nanoparticle (HNP) as a potential therapeutic agent for late-stage sepsis. The HNP captures and neutralizes all variants of histones, a major inflammatory mediator released during sepsis. The highly optimized HNP has high capacity and long-term circulation capability for the selective sequestration and neutralization of histones. Intravenous injection of the HNP protects mice against a lethal dose of histones through the inhibition of platelet aggregation and migration into the lungs. In vivo administration in murine sepsis model mice results in near complete survival. These results establish the potential for synthetic, nonbiological polymer hydrogel sequestrants as a new intervention strategy for sepsis therapy and adds to our understanding of the importance of histones to this condition., Sepsis caused by the release of inflammatory mediators into the blood is a life threatening disease. Here, the authors report on the development of hydrogel nanoparticles for the capture and neutralisation of histones, major inflammatory mediators, and demonstrate sepsis treatment in a murine model.

We describe a process for engineering a synthetic polymer nanoparticle (NP) that functions as an effective, broad-spectrum metalloproteinase inhibitor. Inhibition is achieved by incorporating three functional elements in the NP: a group that interacts with the catalytic zinc ion, functionality that enhances affinity to the substrate-binding pocket, and fine-tuning of the chemical composition of the polymer to strengthen NP affinity for the enzyme surface. The approach is validated by synthesis of a NP that sequesters and inhibits the proteolytic activity of snake venom metalloproteinases from five clinically relevant species of snakes. The mechanism of action of the NP mimics that of endogenous tissue inhibitors of metalloproteinases. The strategy provides a general design principle for synthesizing abiotic polymer inhibitors of enzymes.

Linear aliphatic oligoesters derived from δ-valerolactone (VL) and e-caprolactone (CL) were synthesised by ring-opening polymerisation (ROP) using 1-docosanol (C22H45OH, C22OH) and aluminum isopropoxide [Al(OiPr)3] as initiator and catalyst, respectively. Monodisperse species such as monomers, dimers, trimers, and tetramers with terminal groups α-hydroxyl-ω-docosyl (C22)-(C22VL and C22CL) were isolated by flash column chromatography (FCC). Characterisation by MALDI-TOF and 1H NMR spectroscopy corroborated the chemical nature of the samples. This work represents the first time in the literature that monodisperse species derived from VL are isolated. The thermal properties of C22VL and C22VL showed a pattern suggesting that the crystallinity was proportional to the length of the chain. The presence of C22 groups promoted the nucleation of the crystalline domain in the monomers (C22VL1 and C22CL1), increasing their respective melting temperatures (Tm) relative to those of their non-monodisperse oligomers (C22PVL or C22PCL). Finally, monodisperse species and non-monodisperse oligomers were analysed by POM.

The affinity of a synthetic polymer nanoparticle (NP) to a target biomacromolecule is determined by the association and dissociation rate constants (kon, koff) of the interaction. The individual rates and their sensitivity to local environmental influences are important factors for the on-demand capture and release a target biomacromolecule. Positively charged NPs for small interfering RNA (siRNA) delivery is a case in point. The knockdown efficacy of siRNA can be strongly influenced by the binding kinetics to the NP. Here, we show that kon and koff of siRNA to NPs can be individually engineered by tuning the chemical structure and composition of the NP. N-Isopropylacrylamide-based NPs functionalized with hydrophobic and amine monomers were used. koff decreased by increasing the amount of amine groups in the NP, whereas kon did not change. Importantly, NPs showing a low koff at pH 5.5 together with a high koff at pH 7.4 showed high knockdown efficiency when NP/siRNA complexes were packaged in lipid nanoparticles. These results provide direct evidence for the premise that the efficacy of an siRNA delivery vector is linked with the strong affinity to the siRNA in the endosome and low affinity in the cytoplasm.

Stimuli-responsive polymers are an efficient means of targeted therapy. Compared to conventional agents, they increase bioavailability and efficacy. In particular, polymer hydrogel nanoparticles (NPs) can be designed to respond when exposed to a specific environmental stimulus such as pH or temperature. However, targeting a specific metabolite as the trigger for stimuli response could further elevate selectivity and create a new class of bioresponsive materials. In this work we describe an N-isopropylacrylamide (NIPAm) NP that responds to a specific metabolite, characteristic of a hypoxic environment found in cancerous tumors. NIPAm NPs were synthesized by copolymerization with an oxamate derivative, a known inhibitor of lactate dehydrogenase (LDH). The oxamate-functionalized NPs (OxNP) efficiently sequestered LDH to produce an OxNP–protein complex. When exposed to elevated concentrations of lactic acid, a substrate of LDH and a metabolite characteristic of hypoxic tumor microenvironments, OxNP–LDH complexes swelled (65%). The OxNP–LDH complexes were not responsive to structurally related small molecules. This work demonstrates a proof of concept for tuning NP responsiveness by conjugation with a key protein to target a specific metabolite of disease.

We describe an approach for the discovery of protein affinity reagents (PARs). Abiotic synthetic hydrogel copolymers can be "tuned" for selective protein capture by the type and ratios of functional monomers included in their polymerization and by the polymerization conditions (i.e., pH). By screening libraries of hydrogel nanoparticles (NPs) containing charged and hydrophobic groups against a protein target (IgG), a stimuli-responsive PAR is selected. The robust carbon backbone synthetic copolymer is rapidly synthesized in the chemistry laboratory from readily available monomers. The production of the PAR does not require living cells and is free from biological contamination. The capture and release of the protein by the copolymer NP is reversible. IgG is sequestered from human serum at pH 6.5 and following a wash step, the purified protein is released by elevating the pH to 7.3. The binding and release of the protein occur without denaturation. The abiotic material functions as a selective PAR for the F(ab')2 domain of IgG for pull-down and immunoprecipitation experiments and for isolation and purification of proteins from complex biological mixtures.

Metal nanoparticle-incorporated metal–organic framework (MOF) nanosheets have been deemed as a promising heterogeneous catalyst. We report the synthesis of ultra-thin two-dimensional MOF nanosheets and loading of Pd nanoparticles through an in situ reduction strategy under mild conditions. The obtained Pd@MOF showed high catalytic activity in hydrogenation reactions.

In this paper, a library of multi-functional linear poly-N-isopropylacrylamide (pNIPAm) polymers having a range of molecular weights and functional groups were synthesized and their interaction with the hemolytic peptide, melittin, was examined. The linear pNIPAm (LPs) containing both tert-butyl group and carboxylic acids bound with the peptide by a combination of hydrophobic and electrostatic interactions and neutralized its toxicity. The melittin binding capacity and affinity of each LP was quantified and further compared with cross-linked multi-functional nanogel particles (NPs) having same combination of functional groups. The binding capacity of the LPs (weight of captured melittin/weight of LP) was independent of their molecular weight and was three times higher than that of previously reported NPs. The binding constant depended on the molecular weight of the LPs, showing the highest value of 1.1 × 108 (M−1) for a ∼1000 mer linear polymer with 40% tert-butyl group and 20% carboxylic acid. Comparison of the interactions of the LPs and NPs suggested the importance of the flexibility of the polymer chain in order to achieve high binding capacity and affinity.

In this work, we demonstrated a nano-decorated porous impedance electrode sensor for efficient capture, rapid killing and ultrasensitive detection of bacteria. The multi-functional sensor was prepared by a facile sonochemical method via in situ deposition of antibacterial prickly Zn-CuO nanoparticles and graphene oxide (GO) nanosheets on a Ni porous electrode. Due to the surface burr-like nanostructures, the nano-decorated impedance sensor exhibited very good bacterial-capture efficiency (70 - 80% in 20min) even at a low concentration of 50 CFU mL-1, rapid antibacterial rate (100% killing in 30min) and high detection sensitivity (as low as 10 CFU mL-1). More importantly, the nano-decorated sensor has proven to be highly effective in quantitative detection of bacteria in a biological sample, for example, a rat blood sample spiked with E. coli. Despite the complexity of blood, the sensor still exhibited excellent detection precision within 30min at bacteria concentrations ranging from 10 - 105 CFU mL-1. The simplicity, rapidity, sensitivity, practicability and multifunctionality of this impedance sensor would greatly facilitate applications in portable medical devices for on-the-spot diagnosis and even the possibility for simultaneous therapy of diseases caused by bacterial infections.

A series of redox- and photo-responsive copolymers, poly(2-(methacryloyloxy)ethyl ferrocenecarboxylate-co-4-methacryloylamino-4′-nitroazobenzene) (P(FcEMA-co-MAAzo)s) were synthesized using free radical polymerization. The synthesized copolymers were characterized by 1H NMR, FT-IR, gel permeation chromatography (GPC) and thermogravimetric analysis (TGA). Cyclic voltammetry (CV) and Ultraviolet–visible (UV–vis) absorption studies showed redox- and photo-responsive properties of the synthesized copolymers in the solution. P(FcEMA-co-MAAzo)s films were prepared by spin-coating or drop-coating method and these films were found to be redox- and photo-responsive. The color of the prepared films could be adjusted by the redox stimulus, while UV–vis absorption properties of the prepared films could be adjusted by changing wavelength of light. It was found that these synthesized films show potential application for high density information storage.

Porous membranes have been used for many applications, including separations in biotechnology, the food industry, water purification, and even energy storage devices. The benefit of polymers of intrinsic microporosity (PIMs) is their consistently sized nanopore channels. Inherent functionalities of the PIM structure not only create these channels but are also available for further modifications that can change the interactions of ions and molecules inside of the pore. Here we design solid state nanopores on which are drop-casted two different PIMs, functionalized with either a cyano group or a carboxylic acid. Ionic transport through the membranes is investigated based on pore size and charge-charge interactions, as well as steric and hydrophobic interactions. Achieving specific ion selectivity with easily processable porous membranes opens new avenues for water purification strategies and energy storage.

Redox/temperature responsive poly(N-isopropylacrylamide/N-hydroxyethylacrylamide) (P(NIPA/HEAA)) nonionic nanogels (NP-BAC) crosslinked with N,N′-Bis(acryloyl)cystamine (BAC) have been prepared. An analogous nanogel incorporating N,N′-methylenebisacrylamine (BIS), a reduction-insensitive nanogel (NP-BIS), was chosen as a control nanogel. Compared to the nondegradable NP-BIS nanogel, NP-BAC nanogel particles were found to swell and become less dense due to cleavage of disulfide bonds in BAC. Interestingly, the NP-BAC nanogels preserved their spherical shape after reduction. When loaded with the drug propranolol, NP-BAC nanogels showed accelerated drug release in the presence of 1,4-dithiothreitol (DTT), with rate of release controlled by the DTT concentration. Furthermore, the liquid-crystal-glass phase behavior of these nanogel suspensions were investigated relative to polymer concentration and temperature. Following the liquid-crystal-glass phase diagram, these nanogels can be fabricated into hydrogel by crosslinking with divinylsulfone (DVS). These crosslinked hydrogels exhibited optical diffractions sensitive to temperature and DTT concentration. Several unexpected and distinguishing differences between NP-BAC and NP-BIS nanogels were noted. For example, NP-BAC nanogel formed colloidal crystalline structures faster than NP-BIS nanogels and their reflection signals were much stronger. The reflection peaks of NP-BAC crosslinked hydrogel were blue shifted with rising temperature while that of NP-BIS hydrogel remained unchanged.

Traditional artificial opals are assembled from silica or polystylene colloidals which have poor swellability and a lower response to stimuli. A novel three-dimensional photonic crystal array sensor which has a high stability and desired structural colour was fabricated from the self assembly of nano hydrogel colloids. The nano hydrogel colloids were prepared by co-polymerisation of N-isopropylacrylamide, functional monomer acrylic acid and N-tert-butylacrylamide. The relative humidity from 20% to 100% could be detected rapidly via the reflection spectrum of the nano hydrogel colloidal array with a maximum amount of red shift of 24 nm. The response kinetics for humidity of the nano hydrogel colloidal array were investigated, and correspondingly, a rational response mechanism of the compactness of the close-packed structure caused by the swelling of the nano hydrogel colloidal array was discussed. The nano hydrogel colloidal array sensor presented good reversibility and can be reused for at least five rounds.

Diblock copolymers of poly(methylene-b-e-caprolactone) (PM-b-PCL) were synthesized in two steps: (a) polyhomologation, to obtain, following oxidative cleavage of the carbon–boron (PM, block1), an α-hydroxyl-ω-methyl polymethylene (PMOH, CH3–[CH2]m–OH) and, following the transfer reaction to the ring-opening polymerization catalyst, (b) ring-opening polymerization (ROP) of e-caprolactone (CL) (PCL, block2). In addition, a series of homopolymers derived from poly(e-caprolactone) (PCL) oligoesters containing an end group of docosyl (CH3–[CH2]21– or C22; C22–PCL) were obtained as a model to compare their physical properties by DSC with those of PM-b-PCL. The oligomers derived from PM-b-PCL and C22–PCL were characterized by 1H and 13C NMR, AFM, DSC, GPC, and MALDI-TOF. PM-b-PCL and C22–PCL were evaluated as compatibilizers for PE/PCL polymer blends. Identification and analysis of optimized blocks of PM-b-PCL by POM and SEM showed improved mixing of PE/PCL blends.

Protein affinity reagents are widely used in basic research, diagnostics and separations and for clinical applications, the most common of which are antibodies. However, they often suffer from high cost, and difficulties in their development, production and storage. Here we show that a synthetic polymer nanoparticle (NP) can be engineered to have many of the functions of a protein affinity reagent. Polymer NPs with nM affinity to a key vascular endothelial growth factor (VEGF165) inhibit binding of the signalling protein to its receptor VEGFR-2, preventing receptor phosphorylation and downstream VEGF165-dependent endothelial cell migration and invasion into the extracellular matrix. In addition, the NPs inhibit VEGF-mediated new blood vessel formation in Matrigel plugs in vivo. Importantly, the non-toxic NPs were not found to exhibit off-target activity. These results support the assertion that synthetic polymers offer a new paradigm in the search for abiotic protein affinity reagents by providing many of the functions of their protein counterparts.

A wearable silk fibroin/cellulose composite is reported. It is structurally dyed and functionalized by embedding three-dimensional (3D) or two-dimensional poly(methyl methacrylate) and polystyrene nanocolloidal arrays to form opal and inverse opal silk methylcellulose photonic crystal films (SMPCF). The brilliant color of SMPCF is utilized for naked-eye detection of humidity and a trace amount (0.02%) of H2O content in organic solvents. Volatile organic compounds gases of 5 types were detected. By alternately exposed to organic solvents of methanol, acetonitrile, acetone, ethanol, isopropanol, n-butanol, carbon tetrachloride, and toluene, 3D inverse opal SMPCF displayed an excellent sensing performance with instantaneously color changes from green to red. The organic solvent sensitive SMPCF are wearable by integrated into a rubber glove. This composite has the potential to be used in wearable real-time sensing materials.

Specific cell adhesion and osteogenicity are both crucial factors for the long-term success of titanium implants. In this work, two mussel-derived bioactive peptides were designed to one-step dual-biofunctionalization of titanium implants via robust catechol/TiO2 coordinative interactions. The highly biomimetic peptides capped with integrin-targeted sequence or osteogenic growth sequence could efficiently improve the biocompatibilities of titanium implants and endow the implants with abilities to induce specific cell adhesion and enhanced osteogenicity. More importantly, rationally combined use of the two biomimetic peptides indicated an enhanced synergism on osteogenicity, osseointegration and finally the mechanical stability of Ti implants in vivo. Therefore, the highly biomimetic mussel-derived peptides and the dual-functional strategy in this study would provide a facile, safe, and effective means for improving clinical outcome of titanium-based medical implants.

A facile controlled-release nanogels delivery system has been developed by using hydroxypropyl methylcellulose (HPMC) hybrid nanogels as encapsulation shell materials, which were synthesized by surfactant-free polymerization in aqueous solution. The effects of reaction time and cross-linker concentration on the size of the nanogels have been studied. The results showed that in a certain range, the particle size decreased with increasing reaction time and increasing concentration of cross-linker. Meanwhile, at the feeding ratio 0.05/1 of HPMC/methacrylic acid (MAA), the LCST of prepared nanogels at pH = 6 was close to the body temperature, which can be used as sustained insulin delivery system. Besides, the HPMC nanogels loaded with insulin had a high drug loading of 21.3% and a high entrapment efficiency of 95.7%. The release behavior of the insulin nanogels can be adjusted by pH and temperature which will have potential applications in controlled release delivery system.

The insertion of long hydrocarbon chains between ester groups in polyester allows for introduction and modulation of crystallinity, which can result in enhanced performance approaching high-density polyethylene. We report a convenient synthesis of building blocks for long-chain aliphatic polyesters via an aqueous C1 polymerization. The macromonomers include ω-hydroxyacid esters, α,ω-diols and α,ω-diacids. The length of hydrocarbon chain segment (C20-C60) can be controlled by the ratio of monomer/initiator in the C1 polymerization. The obtained polyesters from condensation of the long-chain ω-hydroxyacid esters have thermal and mechanical properties indistinguishable from related materials derived from biomass.

Nanomaterials, when introduced into a complex, protein-rich environment, rapidly acquire a protein corona. The type and amount of proteins that constitute the corona depend significantly on the synthetic identity of the nanomaterial. For example, hydrogel nanoparticles (NPs) such as poly(N-isopropylacrylamide) (NIPAm) have little affinity for plasma proteins; in contrast, carboxylated poly(styrene) NPs acquire a dense protein corona. This range of protein adsorption suggests that the protein corona might be "tuned" by controlling the chemical composition of the NP. In this Account, we demonstrate that small libraries of synthetic polymer NPs incorporating a diverse pool of functional monomers can be screened for candidates with high affinity and selectivity to targeted biomacromolecules. Through directed synthetic evolution of NP compositions, one can tailor the protein corona to create synthetic organic hydrogel polymer NPs with high affinity and specificity to peptide toxins, enzymes, and other functional proteins, as well as to specific domains of large proteins. In addition, many NIPAm NPs undergo a change in morphology as a function of temperature. This transformation often correlates with a significant change in NP-biomacromolecule affinity, resulting in a temperature-dependent protein corona. This temperature dependence has been used to develop NP hydrogels with autonomous affinity switching for the protection of proteins from thermal stress and as a method of biomacromolecule purification through a selective thermally induced catch and release. In addition to temperature, changes in pH or buffer can also alter a NP protein corona composition, a property that has been exploited for protein purification. Finally, synthetic polymer nanoparticles with low nanomolar affinity for a peptide toxin were shown to capture and neutralize the toxin in the bloodstream of living mice. While the development of synthetic polymer alternatives to protein affinity reagents is in its early stages, these recent successes using only small libraries of functional monomers are most encouraging. It is likely that by expanding the chemical diversity of functional hydrogels and other polymers, a much broader range of NP-biomacromolecule affinity pairs will result. Since these robust, nontoxic polymers are readily synthesized in the chemistry laboratory, we believe the results presented in this Account offer a promising future for the development of low cost alternatives to more traditional protein affinity reagents such as antibodies.

Molecularly imprinted polymers (MIPs) are highly cross-linked polymers with high binding capacity and selectivity to the target molecules. MIPs become increasingly important because of the potential applications in drug delivery, purification and separation. In spite of the tremendous progress that has been made in the molecular imprinting field, many challenges remain to be addressed, especially in transforming the binding event into a detectable optical signal. The combination of photonic crystal and molecular imprinting technique is becoming a popular research idea. Compared to the conventional MIPs, the molecularly imprinted photonic crystal sensors (MIPCB) have the advantage of directly convert the molecule recognition process into optical signal. This review comprehensively summarizes various MIPCB, including the principle of molecular imprinted photonic crystal sensors, recent development, some challenges and effective strategies for MIPCB.

It is significant to detect lysozyme both in fundamental research and in clinical practice, since its concentration in body fluid is associated with many diseases. In this study, a new kind of sensor for rapid screening the lysozyme was fabricated based on the two-dimensional (2D) polystyrene colloidal crystal array together with the optimized hydrogel containing acrylamide-based functional groups. Distinct hydrogel volume shrink was observed due to the hydrogel crosslink induced by the functional ligand–protein interactions while the protein bound to the sensor. Therefore, the analyte concentration could be accessed by of the lattice spacing of the 2D colloidal crystal array, which was detected by a change in the Debye diffraction ring diameter. The lysozyme concentration could be easily monitored by measuring the diameter of the Debye diffraction ring in the pathophysiologic range. The particle spacing of 2D colloidal crystal hydrogel sensor increased to about 22 nm while lysozyme concentration increased from zero to 1.0 mg/mL, meanwhile the structural color of the sensor blue shifted from red to yellow. The detection limit was confirmed as 1.38 × 10−3 mg/mL. The selective response to other common proteins in body fluids was also exhibited, indicating the great selective response properties to lysozyme. In addition, the 2D colloidal crystal hydrogel sensor was reusable to detect the lysozyme solution reversibly due to its thermal sensitivity. Moreover, the determination of lysozyme in artificial tears and human urine samples by this sensor demonstrated its feasibility in potential clinical analysis diagnosis.

Protein affinity reagents (PARs), frequently antibodies, are essential tools for basic research, diagnostics, separations and for clinical applications. However, there is growing concern about the reproducibility, quality and cost of recombinant and animal-derived antibodies. This has prompted the development of alternatives that could offer economic, and time-saving advantages without the use of living organisms. Synthetic copolymer nanoparticles (NPs), engineered with affinity for specific protein targets, are potential alternatives to PARs. Although there are now a number of examples of abiotic protein affinity reagents (APARs), most have been evaluated in vitro limiting a realistic assessment of their potential for more demanding, practical in vivo applications. We demonstrate for the first time that an abiotic copolymer hydrogel nanoparticle (NP1) engineered to bind a key signaling protein, vascular endothelial growth factor (VEGF165), functions in vivo to suppress tumor growth by regulating angiogenesis. Lightly cross-linked N-isopropylacrylamide based NPs that incorporate both sulfated N-acetylglucosamine and hydrophobic monomers were optimized by dynamic chemical evolution for VEGF165 affinity. NP1 efficacy in vivo was evaluated by systemic administration to tumor-bearing mice. The study found that NP1 suppresses tumor growth and reduces tumor vasculature density. Combination therapy with doxorubicin resulted in increased doxorubicin concentration in the tumor and dramatic inhibition of tumor growth. NP1 treatment did not show off target anti-coagulant activity. In addition, >97% of injected NPs are rapidly excreted from the body following IV injection. These results establish the use of APARs as inhibitors of protein-protein interactions in vivo and may point the way to their broader use as abiotic, cost effective protein affinity reagents for the treatment of certain cancers and more broadly for regulating signal transduction.

We report a novel strategy for creating abiotic Bacillus thuringiensis (Bt) protein affinity ligands by biomimicry of the recognition process that takes place between Bt Cry1Ab/Ac proteins and insect receptor cadherin-like Bt-R1 proteins. Guided by this strategy, a library of synthetic polymer nanoparticles (NPs) was prepared and screened for binding to three epitopes 280FRGSAQGIEGS290, 368RRPFNIGINNQQ379 and 436FRSGFSNSSVSIIR449 located in loop α8, loop 2 and loop 3 of domain II of Bt Cry1Ab/Ac proteins. A negatively charged and hydrophilic nanoparticle (NP12) was found to have high affinity to one of the epitopes, 368RRPFNIGINNQQ379. This same NP also had specific binding ability to both Bt Cry1Ab and Bt Cry1Ac, proteins that share the same epitope, but very low affinity to Bt Cry2A, Bt Cry1C and Bt Cry1F closely related proteins that lack epitope homology. To locate possible NP-Bt Cry1Ab/Ac interaction sites, NP12 was used as a competitive inhibitor to block the binding of 865NITIHITDTNNK876, a specifi...

The self-assembled fabrication of large-area opal photonic crystals (PCs) that are free of cracks has remained a challenge which greatly limits the practicality of such a structure in optical and electronic applications. We report a new route in this paper for fabricating centimeter scale crack-free opal PC films in which the latex spheres are bound together through coordination bonds. The elimination of cracks in the PCs is attributed to the formation of metal ion–polymer latex spheres coordination complexes which is confirmed by shifts of the binding energy of the metal ion after the reaction. The coordination bonds enhance the interactions between the polymer latex spheres, which can neutralize the adhesion stress caused by the substrate and tension stress caused by the shrinkage of the latex spheres during the evaporation of solvent. The as-prepared PC films show a uniform diffraction color and excellent reflection properties, which proves that the formation of coordination bonds does not weaken the contrasts of the refractive index or the optical quality of the PCs. This facile fabrication of large area, crack-free opal PCs will offer significant insight into the preparation and applications of PCs in optical devices.

Poly(1,4-butanediol dimethacrylate) microcapsules containing dementholized peppermint oil (DPO) were prepared by interfacial free-radical polymerization. The influence of the composition of the core material on the morphology of the fragrance microcapsules was investigated by scanning electron microscopy (SEM). Response surface methodology (RSM) was applied to optimize the effects of curing temperature, homogenization time, ratio of core/shell and homogenization rate on the encapsulation efficiency. The thermal stability of the fragrance microcapsules was studied by thermogravimetric analysis (TGA). The prepared fragrance microcapsule, under optimal conditions, possessed spherical shape, good thermal stability below 100 °C and high encapsulation efficiency of 91%. In addition, the fragrance microcapsules coated onto cotton fabric displayed good washing durability after 15 cycles, which will be beneficial for their future application in textiles, daily necessities and so on.

Surfactant-free hydroxypropylcellulose (HPC) nanogels were synthesized by using thermo-sensitive HPC as a template to form HPC/PMAA nanoscale complex. The formation mechanism was owing to the interpolymer hydrogen bonding between HPC and PMAA induced phase transition of HPC in aqueous media. The average size of the resulting HPC nanogels ranges from about 98 to 241 nm. It was found that the average size of HPC nanogels changed little with increasing polymerization temperature below 26 °C, whereas it greatly increased above 26 °C. When the concentration of HPC was increased from 0.1 to 0.9 wt.%, the diameter of nanogels decreased firstly and then increased. Besides, an increasing crosslinker BIS concentration led to a reduced size of HPC nanogels, and the nanogels had the narrowest size distribution when its concentration was 0.1 wt.%. In addition to intrinsic thermo-sensitivity, HPC nanogels also display pH-induced phase transition due to pH-responsive PMAA contained in HPC nanogels. Surfactant-free, dual-responsive HPC nanogels would have promising applications in biotechnology and nanomedicine.

A new kind of phase change material n-octadecane microcapsules containing peppermint fragrance scent has been synthesized through the interfacial polymerization of isophorone diisocyanate (IPDI) and hexamethylenediamine (HMDA). The average size, morphology, and chemical components of the microcapsules were characterized by laser particle size analyzer, scanning electron microscope (SEM), and Fourier transform infrared (FTIR), respectively. The thermal characterizations of the microcapsules were studied by differential scanning calorimetry (DSC) and thermal gravity analysis (TGA). The results show that the average size of the microcapsules was in the range of 4.0 to 7.0 μm and decreased with increasing emulsifier. The microcapsulated phase change materials (MicroPCMs) are spherical, and their surface is dented. The MicroPCMs without nucleating agents demonstrated high heat storage capacity but had supercooling phenomena. It was found that the addition of approximately 8.3 wt % nucleating agents 1-tetradeca...

Following its resolution by diastereomeric complexation, 5,5',6,6'-tetrahydroxy-3,3,3',3'-tetramethyl-1,1'-spirobisindane (TTSBI) was used to synthesize a chiral ladder polymer, (+)-PIM-CN. (+)-PIM-COOH was also synthesized by the acid hydrolysis of (+)-PIM-CN. Following characterization, both (+)-PIM-CN and (+)-PIM-COOH were solvent cast directly into semipermeable membranes and evaluated for their ability to enable the selective permeation of a range of racemates, including mandelic acid (Man), Fmoc-phenylalanine, 1,1'-bi-2-naphthol (binol), and TTSBI. High ee values were observed for a number of analytes, and both materials exhibited high permeation rates. A selective diffusion-permeation mechanism was consistent with the results obtained with these materials. Their high permeability, processability, and ease of chemical modification offer considerable potential for liquid-phase membrane separations and related separation applications.

In this paper, a pseudo-ternary phase diagram was drawn according to the phase separation theory to decide if O/W capsules can be formed by using poly(ethylene glycol dimethacrylate) as shell material and fragrance dementholized peppermint oil as model core material. Within a certain ratio range of reaction reagents, the nanocapsule was first synthesized by the precipitation of crosslinking agent on the surface of a nanoemulsion. The encapsulation efficiency of dementholized peppermint oil in the nanocapsules was above 86.3%, the average diameter was 261 nm, the particle size distribution was 0.195 and the final conversion rate of ethylene glycol dimethacrylate reached up to 92%. It was also demonstrated that the nanocapsules' sizes can be tuned by the number of carbons in the polyol dimethyl acrylate.

Three-dimensional photonic crystal sensors are attractive platforms for autonomous chemical sensing and colorimetric bioassays. At present, the photonic crystal sensors with inverse opal structure were extensively studied, which swells or shrinks in response to the analytes. However, the fabrication of inverse opal sensors still remains a major challenge. Herein, we propose a simple and versatile approach to fabricate 3D opal photonic sensors. This photonic crystal is fabricated via assembly of monodispersed silica particles grafted with linear polymeric ligands (SiO2@LPs). Acrylic acid (negatively charged monomer) and N-tert-butylacrylamide (hydrophobic monomer) were incorporated with N-isopropylacrylamide to achieve strong affinity between the designed polymer ligands and proteins. The proposed photonic crystal displays a maximum redshift of 23 nm in response to 2 mg/mL lysozyme, accompanied by the structure color change from blue to green. Compared to the cross-linked polymers, the linear polymer with flexible structure allows the colloidal array to recognize lysozyme with higher sensitivity (as low as 5 μg/mL) and broader linearity (from 5 to 2000 μg/mL in aqueous media). In the future, this photonic crystal sensor can be used as universal tools for the detection of a broad range of analytes.