Multifunctional Molecularly Imprinted Receptor-Based Polymeric Membrane Potentiometric Sensor for Sensitive Detection of Bisphenol A.

Molecularly imprinted polymer (MIP)-based polymeric membrane potentiometric sensors have become an attractive tool for detection of organic species. However, the MIP receptors in potentiometric sensors developed so far are usually prepared by only using single functional monomers. This may lead to low affinities of the MIP receptors due to the lack of diversity of the functional groups, thus resulting in low detection sensitivity of the potentiometric sensors. Additionally, these classical MIP receptors are nonconductive polymers, which are undesirable for the fabrication of an electrochemical sensor. Herein, we describe a novel multifunctional MIP receptor-based potentiometric sensor. The multifunctional MIP receptor is prepared by using two functional monomers, methacrylic acid, and 3-vinylaniline with a dual functionality of both recognition and conduction properties. The poly(aniline) groups are introduced into the methacrylic acid-based MIP by postoxidation of the aniline monomer. Such poly(aniline) groups not only serve as the additional functional groups for selective recognition, but also work as a conducting polymer. The obtained multifunctional MIP receptor shows a high binding capacity and an excellent electron-transfer ability. By using bisphenol A as a model, the proposed multifunctional MIP sensor exhibits a largely improved sensitivity and low noise levels compared to the conventional MIP sensor. We believe that the proposed MIP-based sensing strategy provides a general and facile way to fabricate sensitive and selective MIP-based electrochemical sensors.

Co-delivery of paclitaxel and gemcitabine by methoxy poly(ethylene glycol)-poly(lactide-coglycolide)-polypeptide nanoparticles for effective breast cancer therapy.

Traditional chemotherapeutic drugs have shown limited clinical curative effects in antitumor therapy. The application of multidrug combination and adjuvant-drug carriers is a feasible strategy to overcome the limitations while minimizing the dosage of single drug and acquiring the synergistic effects in tumor therapy. However, the systemic toxicity, drug resistance, and tumor recurrence are still unavoidable. Here we develop core-shell nanoparticles (NPs) to encapsulate paclitaxel (PTX) and gemcitabine (GEM) for breast cancer therapy. We find that the NPs could encapsulate PTX and GEM, with an encapsulation efficiency of 96.3 and 95.13%, respectively. Moreover, the drug loading of these NPs is 2.71% (PTX) and 2.64% (GEM). Notably, the co-delivery of GEM and PTX performs enhanced anticancer effect compared with the PTX alone or GEM alone therapy at the same concentration, which indicates a synergistic effect. Moreover, encapsulation of PTX and GEM by methoxy poly(ethylene glycol)-poly(lactide-coglycolide) also shows enhanced anticancer effects (81.5% tumor inhibition) and reduced systemic toxicity in vivo compared with free drugs (65% tumor inhibition). Together with those results, co-delivery of PTX and GEM by methoxy poly(ethylene glycol)-poly(lactide-coglycolide) might have important potencies in clinical applications for breast cancer therapy.

An Antisweat Interference and Highly Sensitive Temperature Sensor Based on Poly(3,4-ethylenedioxythiophene)-Poly(styrenesulfonate) Fiber Coated with Polyurethane/Graphene for Real-Time Monitoring of Body Temperature.

Body temperature is an important indicator of human health. The traditional mercury and medical electronic thermometers have a slow response (≥1 min) and can not be worn for long to achieve continuous temperature monitoring due to their rigidity. In this work, we prepared a skin-core structure polyurethane (PU)/graphene encapsulated poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) temperature-sensitive fiber in one step by combining wet spinning technology with impregnation technology. The composite fiber has high sensitivity (-1.72%/°C), super-resolution (0.1 °C), fast time response (17 s), antisweat interference, and high linearity (R2 = 0.98) in the temperature sensing range of 30-50 °C. The fiber is strong enough to be braided into the temperature-sensitive fabric with commercial cotton yarns. The fabric with good comfort and durability can be arranged in the armpit position of the cloth to realize real-time body temperature monitoring without interruption during daily activities. Through Bluetooth wireless transmission, body temperature can be monitored in real-time and displayed on mobile phones to the parents or guardians. Overall, the fiber-based temperature sensor will significantly improve the practical applications of wearable temperature sensors in intelligent medical treatment due to its sensing stability, comfort, and durability.

A molecularly imprinted polymer-based potentiometric sensor based on covalent recognition for the determination of dopamine.

Polymeric membrane potentiometric sensors based on molecularly imprinted polymers (MIPs) have been successfully designed for the detection of organic compounds both in ionic and neutral forms. However, most of these sensors are based on the non-covalent recognition interactions between the functional groups of the MIP in the polymeric sensing membrane and the target. These weak non-covalent interactions are unfavorable for the detection of hydrophilic organic compounds (e.g., dopamine). Herein novel MIP potentiometric sensor based covalent recognition for the determination of protonated dopamine is described. Uniform-sized boronate-based MIP beads are utilized as the recognition receptors. These receptors can covalently bind with dopamine with a cis-diol group to form a five-membered cyclic ester and thus provide a higher affinity because of the stronger nature of the covalent bonds. It has been found that the proposed electrode shows an excellent sensitivity towards dopamine with a detection limit of 2.1 µM, which could satisfy the needs for in vivo analysis of dopamine in the brain of living animals. We believe that the covalent recognition MIP-based sensing strategy provides an appealing way to design MIP-based electrochemical and optical sensors with excellent sensing properties.

Facile fabrication of a controlled polymer brush-type functional nanoprobe for highly sensitive determination of alpha fetoprotein.

As robust functional polymers, polymer brush-based hybrid nanomaterials have potential application in the highly sensitive determination of tumor markers (TMs). Currently, there are plentiful reports on the polymerization methods of functional polymer brushes. Low ppm ATRP (activators (re)generated by electron transfer for atom transfer radical polymerization (A(R)GET ATRP), initiators for continuous activator regeneration atom transfer radical polymerization (ICAR ATRP) and electrochemically mediated atom transfer radical polymerization (eATRP)) is a facile and robust methodology with the advantages of simplicity, eco-friendliness and wide applicability to prepare well-defined polymeric materials. In this work, a controlled polymer brush-type functional nanoprobe is successfully fabricated by functional AGET ATRP and used as a sandwich-type electrochemical immunosensor for precise detection of TMs (alpha-fetoprotein, AFP). Using graphene oxide (GO) as an excellent conductive matrix, a GO-based poly-heterozygosis pyridine nanomaterial (GO@PHPY) is obtained by surface-initiated AGET ATRP and photocatalytic modification. The nanoprobe is assembled using GO@PHPY and a detection antibody (Ab2) to detect AFP, in which Cu(ii) serves as a signal label to coordinate with the pyridyl group. Under optimized conditions, the electrochemical sensor exhibits a good detection effect on AFP, with a detection range of 0.1 pg mL-1 to 100 ng mL-1 and a low detection limit of 0.08 pg mL-1. It is worth noting that the detection platform can be applied to the detection of real human serum samples. Thus, it is a desirable platform for AFP detection in clinical diagnosis and practical applications. Meanwhile, this work proves that designing and constructing functional polymer brushes is one of the most effective methods for developing new materials for analytical scientific applications.

A bionic stretchable nanogenerator for underwater sensing and energy harvesting.

Soft wearable electronics for underwater applications are of interest, but depend on the development of a waterproof, long-term sustainable power source. In this work, we report a bionic stretchable nanogenerator for underwater energy harvesting that mimics the structure of ion channels on the cytomembrane of electrocyte in an electric eel. Combining the effects of triboelectrification caused by flowing liquid and principles of electrostatic induction, the bionic stretchable nanogenerator can harvest mechanical energy from human motion underwater and output an open-circuit voltage over 10 V. Underwater applications of a bionic stretchable nanogenerator have also been demonstrated, such as human body multi-position motion monitoring and an undersea rescue system. The advantages of excellent flexibility, stretchability, outstanding tensile fatigue resistance (over 50,000 times) and underwater performance make the bionic stretchable nanogenerator a promising sustainable power source for the soft wearable electronics used underwater.

Surface state-controlled C-dot/C-dot based dual-emission fluorescent nanothermometers for intra-cellular thermometry.

Fluorescence-based nanothermometers have potential to offer accuracy in the measurement of temperature using non-contact approaches. Herein, a C-dot/C-dot based dual-emission temperature sensing platform is fabricated through the electrostatic self-assembly of two kinds of fluorescent CDs with opposite charges. This dual-emission platform consists of several nearly-spherical CDs with two emission centers in blue (440 nm) and orange (590 nm) regions. The orange fluorescence exhibits discernible response to external temperatures in the range of ∼15 to 85 °C; on the other hand, the blue fluorescence remains nearly constant. A continuous fluorescence color change in response to temperature from orange to blue can be clearly observed by the naked eye. Thus, the as-prepared C-dot based dual-emission nanospheres can be used for optical thermometry with high reproducibility and sensitivity (0.93%/°C). Detailed characterization shows that temperature (in the 15-85 °C window) impacts the surface states of orange emissive CDs, leaving the blue emissive CDs unaffected. A model is proposed to explain the observations. Finally, by taking advantage of the excellent biocompatibility and stability, the CD based fluorescent nanothermometer is successfully used for the visual measurement of intracellular temperature variations.

Interfacial synthesis of polyethyleneimine-protected copper nanoclusters: Size-dependent tunable photoluminescence, pH sensor and bioimaging.

The copper nanoclusters (CuNCs) offer excellent potential as functional biological probes due to their unique photoluminescence (PL) properties. Herein, CuNCs capped with hyperbranched polyethylenimine (PEI) were prepared by the interfacial etching approach. The resultant PEI-CuNCs exhibited good dispersion and strong fluorescence with high quantum yields (QYs, up to 7.5%), which would be endowed for bioimaging system. By changing the reaction temperatures from 25 to 150 °C, the size of PEI-CuNCs changed from 1.8 to 3.5 nm, and thus tunable PL were achieved, which was confirmed by transmission electron microscopy (TEM) imagings and PL spectra. Besides, PEI-CuNCs had smart absorption characteristics that the color changes from colorless to blue with changing the pH value from 2.0 to 13.2, and thus they could be used as color indicator for pH detection. In addition, the PEI-CuNCs exhibited good biocompatibility and low cytotoxicity to 293T cells through MTT assay. Owing to the positively charged of PEI-CuNCs surface, they had the ability to capture DNA, and the PEI-CuNCs/DNA complexes could get access to cells for efficient gene expression. Armed with these attractive properties, the synthesized PEI-CuNCs are quite promising in biological applications.

Protein-directed synthesis of pH-responsive red fluorescent copper nanoclusters and their applications in cellular imaging and catalysis.

The development of functional copper nanoclusters (Cu NCs) is becoming increasingly widespread in consumer technologies due to their applications in cellular imaging and catalysis. Herein, we report a simple protein-directed synthesis of stable, water-soluble and fluorescent Cu NCs, using BSA as the stabilising agent. Meanwhile, in this study, hydrazine hydrate (N2H4·2H2O) was used as the reducing agent. N2H4·2H2O was a mild reducing agent suggesting that all processes could be operated at room temperature. The as-prepared Cu NCs showed red fluorescence with a peaking center at 620 nm (quantum yield 4.1%). The fluorescence of the as-prepared BSA-Cu NCs was responsive to pH in that the intensity of fluorescence increased rapidly by decreasing the pH from 12 to 6. Besides, with an arresting set of features including water-dispersibility, red fluorescence, good biocompatibility, surface-bioactivity and small size, the resultant BSA-Cu NCs could be used as probes for cellular imaging and catalysis. In this study, CAL-27 cells and the reaction of oxidation of styrene are used as models to achieve fluorescence imaging and elucidate the catalytic activity of the as-prepared BSA-Cu NCs.

A nano-silver composite based on the ion-exchange response for the intelligent antibacterial applications.

As a kind of antimicrobial agent, nano-silver composites have attracted a great deal of interest in biomedical applications. However, the typical loadings of silver nanoparticles (AgNPs) in such composites could result in dose-related cytotoxicity. In this study, a nano-silver composite leading to antimicrobial activity without cytotoxicity was fabricated by loading AgNPs into a dried alginate hydrogel. The biological performance of this composite mainly depended on the release of AgNPs, which needed to be triggered by the ion-exchange response and was further influenced by the loadings of AgNPs in the composite. The antimicrobial activity against E. coli and S. aureus demonstrated that the released silver no less than 678 ppb in the medium caused a reduction of 7log10CFU/mL (100%) bacteria. Significantly, the dose (~1.10×10(3) ppb) of released silver was not toxic and allowed attachment, and growth of MC3T3-E1 pre-osteoblast cells. These results supported that the composite was compatible with in vitro mammalian cells yet exhibited antimicrobial activity by carefully designing the loadings of AgNPs within the alginate. Thus, it indicated that the performance of this composite might permit management of bacterial infection in wound beds without impairment of wound healing.

[Clinical effect of modified forsus appliance to children with mandibular retrusion].

OBJECTIVE: To evaluate the effects of modified Forsus appliance in the treatment of Class II mandibular retrusion. METHODS: 18 children with mandibular retrusion were selected and treated with modified Forsus appliance. Cephalometric radiographs were taken and analyzed at pre-treatment and post-treatment. Students' t-test was used to determine if there were significant differences between pre-treatment and post-treatment. RESULTS: After 6-8 months of therapy, profiles were obviously improved. B moved forward (2.9+/-3.1) mm. ANB decreased (2.5+/-1.2) degrees. The overjet decreased (5.0+2.8) mm. The molar relationship was corrected to Class I from Class II. SN-OL increased (4.3+2.2) degrees. There was significant difference between pre-treatment and post-treatment. CONCLUSION: Combined with straight wire appliance, modified Forsus appliance can effectively stimulate the mandibular growth, balance the jaw relationship, and correct mandibular retrusion.