Excitation-independent emission carbon nanoribbon polymer as a ratiometric photoluminescent probe for highly selective and sensitive detection of quercetin.

In this study, sulfur-nitrogen co-doped carbon nanoribbon (SNCNR) polymers with stable dual-emission fluorescence were synthesized using a one-step traditional hydrothermal method of 6-mercaptopurine in an aqueous methanol solution. Unexpectedly, the as-prepared SNCNRs with excitation-independent emission, as carbon nanomaterial derivatives, showed stable dispersions of a reticular-like shape and different lengths in the skeleton diameter. Compared with other carbon nanomaterials, the SNCNRs dramatically improved the electronic properties and surface chemical reactivities, and exhibited a sensitive ratiometric response to quercetin (Que) because of the Meisenheimer-like complexes formed through π-π stacking and electrostatic interaction. By using this SNCNR sensor, excellent ratiometric linear relationships (FL345 nm/FL420 nm) existed between the degree of quenching of the SNCNRs and the concentrations of Que in the range of 50.0 nM to 200 µM, and the limit of detection was 21.13 nM (3σ/k). Meanwhile, this sensor shows high selectivity for Que over other biomolecules, most amino acids and metal ions under the same conditions. Finally, this fluorescent probe was successfully applied to the direct analysis of Que in bovine serum and some beverage samples, which showed that it has potential for use in applications in clinical diagnosis and food analysis, and may pave the way for the design of effective fluorescent probes for other biologically related targets and food protection.

Photoluminescent coral-like carbon-branched polymers as nanoprobe for fluorometric determination of captopril.

The authors describe the synthesis of fluorescent coral-like carbon nano-branched polymers (PCNBPs) co-doped with nitrogen and phosphorus. Uric acid and phosphoric acid act as nitrogen and phosphorus sources, respectively. The PCNBPs have a coral-like branched structure, are cross-connected, and < 20 nm in skeleton diameter. Their blue fluorescence, best measured at excitation/emission wavelengths of 330/425 nm, is quenched by mercury (II) ions due to the specifically restricted rigid conformation caused by the interaction of phosphorus, nitrogen, and oxygen groups on the surface of the PCNBPs. Fluorescence is selectivity quenched by Hg(II) but restored in addition of the hypertension drug captopril (CAP) in the range 50 nM to 40 µM concentration range. Fluorescence recovery is attributed to the effectively specific interactions between the thiol group of CAP and Hg(II). The method was applied to the determination of the concentration of Cap in pharmaceutical samples, and recoveries were between 97.6 and 105.1%. Graphical abstract Fluorescent coral-like carbon nano-branched polymers (PCNBPs) co-doped with nitrogen and phosphorus are described. Their fluorescence is selectivity quenched by Hg(II) but restored in addition of the hypertension drug captopril (Cap) in the range 50 nM to 40 µM concentration range.

An ultrasensitive electrochemiluminescent biosensor for the detection of concanavalin A based on poly(ethylenimine) reduced graphene oxide and hollow gold nanoparticles.

A highly sensitive electrochemiluminescent (ECL) biosensor was designed for the detection of concanavalin A (ConA) based on glucose oxidase (GOx) as a recognition element by carbohydrate-lectin biospecific interaction, and poly(ethylenimine) (PEI) reduced graphene and hollow gold nanoparticles (HAuNPs) as supporting matrix and signal amplifier. The modification process and detection principle of the biosensor are briefly described as follows. First, PEI reduced graphene oxide with abundant amino groups was cast onto the surface of glassy carbon electrode to adsorb HAuNPs for improving the signal intensity in luminol/H2O2 ECL system. Next, GOx was further assembled onto the electrode by the interaction between Au and -NH2. In the presence of glucose in the detection solution, GOx catalyzed glucose to generate H2O2 in situ, which served as a co-reactant of luminol to enhance ECL signal of luminol. Based on the fact that ConA could result in a decrease in ECL signal when immobilized on the electrode, an ECL biosensor was prepared for the determination of ConA. The ECL signal intensity was linear with the logarithm of ConA concentration and the linear range was from 1.0 to 20 ng/mL with a low detection limit of 0.31 ng/mL (signal to noise ratio =3). This strategy led to a nearly 1000-fold improvement in detection limit for ConA assays compared with previously reported method, thus exhibiting a great potential application in sensitive bioassays of ConA.

A comparison of different dilute solution explosions pretreatment for conversion of distillers' grains into ethanol.

In order to improve the efficiency of distillers' grains converting to ethanol, 13 dilute solution explosions were evaluated based on the optimization of pure water explosion. To decrease residual inhibitor content, the exploded slurry was dried at 105°C. Using a 1.1 mol/L butanone solution explosion, with the explosion temperature set at 160°C (pressure at 1.9 MPa), the residence time at 10 min, and the dried distillers' grains-to-water ratio at 1:2 (w/w), the yields of total sugar, glucose, and xylose were 86%, 89%, and 84% (w/w), respectively, and the ethanol yield was 25.3 g/100 g distillers' grains dry matter. Moreover, the eight other reagent solution explosions improved the efficiency of enzymatic hydrolysis, and of simultaneous saccharification and co-fermentation, and the residual contents of furfural, 5-hydroxymethylfurfural, and acetic acid decreased to an acceptable concentration range after detoxification by drying. The results suggested that compared with pure water explosions, the use of volatile solutions lowered the explosive temperature and improved the sugar yield. This study offers a reference for the further study of lignocellulosic materials with higher starch and hemicelluloses contents as raw materials for converting biomass to bioethanol.

Lipid nanoparticle-encapsulated mRNA antibody provides long-term protection against SARS-CoV-2 in mice and hamsters.

Monoclonal antibodies represent important weapons in our arsenal to against the COVID-19 pandemic. However, this potential is severely limited by the time-consuming process of developing effective antibodies and the relative high cost of manufacturing. Herein, we present a rapid and cost-effective lipid nanoparticle (LNP) encapsulated-mRNA platform for in vivo delivery of SARS-CoV-2 neutralization antibodies. Two mRNAs encoding the light and heavy chains of a potent SARS-CoV-2 neutralizing antibody HB27, which is currently being evaluated in clinical trials, were encapsulated into clinical grade LNP formulations (named as mRNA-HB27-LNP). In vivo characterization demonstrated that intravenous administration of mRNA-HB27-LNP in mice resulted in a longer circulating half-life compared with the original HB27 antibody in protein format. More importantly, a single prophylactic administration of mRNA-HB27-LNP provided protection against SARS-CoV-2 challenge in mice at 1, 7 and even 63 days post administration. In a close contact transmission model, prophylactic administration of mRNA-HB27-LNP prevented SARS-CoV-2 infection between hamsters in a dose-dependent manner. Overall, our results demonstrate a superior long-term protection against SARS-CoV-2 conferred by a single administration of this unique mRNA antibody, highlighting the potential of this universal platform for antibody-based disease prevention and therapy against COVID-19 as well as a variety of other infectious diseases.

Fabrication of chitosan/poly(ε-caprolactone) composite hydrogels for tissue engineering applications.

The aim of this study was to fabricate three-dimensional (3D) porous chitosan/poly(ε-caprolactone) (PCL) hydrogels with improved mechanical properties for tissue engineering applications. A modified emulsion lyophilisation technique was developed to produce 3D chitosan/PCL hydrogels. The addition of 25 and 50 wt% of PCL into chitosan substantially enhanced the compressive strength of composite hydrogel 160 and 290%, respectively, compared to pure chitosan hydrogel. The result of ATR-FTIR imaging corroborated that PCL and chitosan were well mixed and physically co-existed in the composite structures. The composite hydrogels were constructed of homogenous structure with average pore size of 59.7 ± 14 µm and finer pores with average size of 4.4 ± 2 µm on the wall of these larger pores. The SEM and confocal laser scanning microscopy images confirmed that fibroblast cells were attached and proliferated on the 3D structure of these composite hydrogels. The composite hydrogels acquired in this study possessed homogeneous porous structure with improved mechanical strength and integrity. They may have a high potential for the production of 3D hydrogels for tissue engineering applications.

Highly Sensitive Photoelectrochemical Biosensor Based on Quantum Dots Sensitizing Bi2Te3 Nanosheets and DNA-Amplifying Strategies.

In this work, Bi2Te3 nanosheets treated with N-vinyl-pyrrolidinone showed highly sufficient and stable photocurrent for being used as a novel photoactive material. Accordingly, with CdTe quantum dots (QDs) sensitizing Bi2Te3 nanosheets, photoelectrochemical (PEC) biosensor coupling of DNA-amplifying strategies was constructed for sensitive miRNA-21 detection. Initially, the Bi2Te3 nanosheets on the electrode have conductive surface states with dissipationless electronic property, thus providing a highly stable photocurrent and a large surface-to-volume ratio. Then, with the participation of target miRNA-21 and auxiliary DNA, strand displacement amplification took place, thereby opening substantial DNA hairpins for triggering the next hybridization chain reaction (HCR). Through the HCR, long DNA tails decorated with CdTe QDs could thus be assembled on the electrode for enhancing the photocurrent of Bi2Te3 nanosheets. As a result, the proposed PEC biosensor showed a wide detection range from 10 fM to 100 pM with a detection limit of 3.3 fM, displaying a promising avenue to construct simple, ultrasensitive, and stable analytical techniques and tremendous potential in bioanalysis and early clinical diagnosis.

Machinability: Zirconia-reinforced lithium silicate glass ceramic versus lithium disilicate glass ceramic.

Diamond grinding used in dental adjustment of high-strength zirconia-reinforced lithium silicate glass ceramic (ZLS) and lithium disilicate glass ceramic (LDGC) is challenging in restorative dentistry. This study aimed to compare the machinability of ZLS and LDGC in diamond grinding in terms of machining forces and energy, debris, surface and edge chipping damage. Grinding experiments in simulation of dental adjustment were conducted using a computer-assisted high-speed dental handpiece and coarse diamond burs. A piezoelectric force dynamometer and a high-speed data acquisition system were used for on-processing monitoring for assessment of grinding forces and energy. Grinding debris and grinding-induced surface and edge chipping damage were examined using scanning electron microscopy. The results show that grinding of ZLS required higher tangential and normal forces and energy than LDGC (p < 0.05). ZLS was ranked the most difficult to machine among dental glass ceramics based on a machinability index associated with the material mechanical properties. The higher machinability indices of ZLS and LDGC pose a challenge for clinicians to conduct high-efficient material removal for dental adjustment and repair. Both ZLS and LDGC debris were micro fractured particles but the former were smaller than the latter due to the finer microstructure of ZLS. Ground ZLS surfaces contained more irregular microchipping and microfracture in comparison with LDGC surfaces with intergranular fracture or grain dislodgement. Grinding-induced edge chipping damage remained a serious issue for both ZLS and LDGC, which depths ranged approximately 20-100 µm and significantly increased with the material removal rate (p < 0.01). As the zirconia-reinforcement in ZLS only slightly reduced edge chipping damage (p > 0.05), continued efforts are required to explore new reinforcement technologies for optimized LDGC.

The unique calcium chelation property of poly(vinyl phosphonic acid-co-acrylic acid) and effects on osteogenesis in vitro.

There is a clear clinical need for a bioactive bone graft substitute. Poly(vinyl phosphonic acid-co-acrylic acid) (PVPA-co-AA) has been identified as a promising candidate for bone regeneration but there is little evidence to show its direct osteogenic effect on progenitor or mature cells. In this study mature osteoblast-like cells (SaOS-2) and human bone marrow-derived mesenchymal stem cells (hBM-MSCs) were cultured with PVPA-co-AA polymers with different VPA:AA ratio and at different concentrations in vitro. We are the first to report the direct osteogenic effect of PVPA-co-AA polymer on bone cells and, more importantly, this effect was dependent on VPA:AA ratio and concentration. Under the optimized conditions, PVPA-co-AA polymer not only has an osteoconductive effect, enhancing SaOS-2 cell mineralization, but also has an osteoinductive effect to promote hBM-MSCs' osteogenic differentiation. Notably, the same PVPA-co-AA polymer at different concentrations could lead to differential osteogenic effects on both SaOS-2 and hBM-MSCs in vitro. This study furthers knowledge of the PVPA-co-AA polymer in osteogenic studies, which is critical when utilizing the PVPA-co-AA polymer for the design of novel bioactive polymeric tissue engineering scaffolds for future clinical applications. © 2017 The Authors Journal of Biomedical Materials Research Part A Published by Wiley Periodicals, Inc. J Biomed Mater Res Part A: 106A: 168-179, 2018.

New amperometric and potentiometric immunosensors based on gold nanoparticles/tris(2,2'-bipyridyl)cobalt(III) multilayer films for hepatitis B surface antigen determinations.

Two generic, fast, sensitive and novel electrochemical immunosensors have been developed. Initially, a layer of plasma-polymerized Nafion film (PPF) was deposited on the platinum electrode surface, then positively charged tris(2,2'-bipyridyl)cobalt(III) (Co(bpy)(3)(3+)) and negatively charged gold nanoparticles were assembled on the PPF-modified Pt electrode by layer-by-layer technique. Finally, hepatitis B surface antibody (HBsAb) was electrostatically adsorbed on the gold nanoparticles surface. Electrochemical behavior of the {Au/Co(bpy)(3)(3+)}(n) multilayer film-modified electrodes was studied. Cyclic voltammetry, electrochemical impedance spectroscopy (EIS) were adopted to monitor the regular growth of the multilayer films. The performance and factors influencing the performance of the resulting immunosensors were studied in detail. The multilayer film-modified immunosensor was used for hepatitis B surface antigen (HBsAg) determination via the amperometric and potentiometric immunosensor systems, and both systems provided the same linear ranges from 0.05 to 4.5 microg/mL with different detection limits for the amperometric system 0.005 microg/mL and for the potentiometric system 0.015 microg/mL. The immunosensors were used to analyse HBsAg in human serum samples. Analytical results of clinical samples show that the developed immunoassay is comparable with the enzyme-linked immunosorbent assays (ELISAs) method, implying a promising alternative approach for detecting HBsAg in the clinical diagnosis. In addition, the multilayer films also showed better stability for 1 month at least.

A novel immunosensor based on immobilization of hepatitis B surface antibody on platinum electrode modified colloidal gold and polyvinyl butyral as matrices via electrochemical impedance spectroscopy.

Hepatitis B surface antibody (HBsAb) was immobilized to the surface of platinum electrode modified with colloidal gold and polyvinyl butyral (PVB) as matrices to detect hepatitis B surface antigen (HBsAg) via electrochemical impedance spectroscopy (EIS). The electrochemical measurements of cyclic voltammetry and impedance spectroscopy showed that K(4)[Fe(CN)(6)]/K(3)[Fe(CN)(6)] reactions on the platinum electrode surface were blocked due to the procedures of self-assembly of HBsAb-Au-PVB. The binding of a specific HBsAb to HBsAg recognition layer could be detected by measurements of the impedance change. A new strategy was introduced for improving the sensitivity of impedance measurements via the large specific surface area and high surface free energy of Au nanoparticles and the encapsulated effect of polyvinyl butyral. The results showed that this strategy caused dramatic improvement of the detection sensitivity of HBsAg and had good linear response to detect HBsAg in the range of 20-160 ng.ml(-1) with a detection limit of 7.8 ng.ml(-1). Moreover, the studied immunosensor exhibited high sensitivity and long-term stability.

Novel potentiometry immunoassay with amplified sensitivity for diphtheria antigen based on Nafion, colloidal Ag and polyvinyl butyral as matrixes.

A novel potentiometry immunoassay with amplified sensitivity has been developed for the detection of diphtheria antigen (Diph) via immobilizing diphtheria antibody (anti-Diph) on a platinum electrode based on Nafion, colloidal Ag (Ag), and polyvinyl butyral (PVB) as matrixes in this study. The modified procedure was further characterized by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The influence and factors influencing the performance of resulting immunosensor were studied in detail. The resulting immunosensor exhibited sigmoid curve with log Diph concentrations, high sensitivity (51.4 mV/decade), wide linear range from 8 to 800 ng ml(-1) with a detection limit of 1.5 ng ml(-1), rapid potentiometric response (<3 min) and long-term stability (>6 months). Analytical results of clinical samples show that the developed immunoassay is comparable with the enzyme-linked immunosorbent assays (ELISAs) method, implying a promising alternative approach for detecting diphtheria antigen in the clinical diagnosis.

Dinuclear magnesium, zinc and aluminum complexes supported by bis(iminopyrrolide) ligands: synthesis, structures, and catalysis toward the ring-opening polymerization of ε-caprolactone and rac-lactide.

Synthesis and characterization of novel dinuclear magnesium, zinc and aluminum complexes supported by bis(iminopyrrolide) ligands and their catalysis toward the ring-opening polymerization (ROP) of ε-caprolactone (ε-CL) and rac-lactide (rac-LA) were carried out. The ligand precursors [(5-Bu(t)-2-C4H2NH)CH=N(CH2)2]2NH (H2L(Bu), 1) and [(2-C4H3NH)CH=N(CH2)2]2NH (H2L(H), 2) were prepared by condensation of diethylene triamine with 5-tert-butyl-1H-pyrrole-2-carbaldehyde and 1H-pyrrole-2-carbaldehyde, respectively. Treatment of 1 with 2 equiv. of Bu(n)MgOBn in toluene at 70 °C produced dinuclear magnesium complex [(µ-OBn)2Mg2L(Bu)] (3). Similar treatment of 1 with EtZnOBn generated [(µ-OBn)2Zn2L(Bu)] (4). Reaction of 2 with 2 equiv. of Me2AlOBn in toluene at 70 °C afforded aluminum complex [Me2Al(µ-OBn)2AlL(H)] (5). Complexes 3-5 were characterized by (1)H and (13)C NMR spectroscopy, elemental analyses, and single crystal X-ray diffraction techniques. Each of complexes 3-5 is active for the ROP of ε-CL and rac-LA. Kinetic studies of the polymerization reactions were performed.

Delicate refinement of surface nanotopography by adjusting TiO2 coating chemical composition for enhanced interfacial biocompatibility.

Surface topography and chemistry have significant influences on the biological performance of biomedical implants. Our aim is to produce an implant surface with favorable biological properties by dual modification of surface chemistry and topography in one single simple process. In this study, because of its chemical stability, excellent corrosion resistance, and biocompatibility, titanium oxide (TiO2) was chosen to coat the biomedical Ti alloy implants. Biocompatible elements (niobium (Nb) and silicon (Si)) were introduced into TiO2 matrix to change the surface chemical composition and tailor the thermophysical properties, which in turn leads to the generation of topographical features under specific thermal history of plasma spraying. Results demonstrated that introduction of Nb2O5 resulted in the formation of Ti0.95Nb0.95O4 solid solution and led to the generation of nanoplate network structures on the composite coating surface. By contrast, the addition of SiO2 resulted in a hairy nanostructure and coexistence of rutile and quartz phases in the coating. Additionally, the introduction of Nb2O5 enhanced the corrosion resistance of TiO2 coating, whereas SiO2 did not exert much effect on the corrosion behaviors. Compared to the TiO2 coating, TiO2 coating doped with Nb2O5 enhanced primary human osteoblast adhesion and promoted cell proliferation, whereas TiO2 coatings with SiO2 were inferior in their bioactivity, compared to TiO2 coatings. Our results suggest that the incorporation of Nb2O5 can enhance the biological performance of TiO2 coatings by changing the surface chemical composition and nanotopgraphy, suggesting its potential use in modification of biomedical TiO2 coatings in orthopedic applications.

Nanoscale chemical interaction enhances the physical properties of bioglass composites.

Bioglasses are favorable biomaterials for bone tissue engineering; however, their applications are limited due to their brittleness. In addition, the early failure in the interface is a common problem of composites of bioglass and a polymer with high mechanical strength. This effect is due to the phase separation, nonhomogeneous mixture, nonuniform mechanical strength, and different degradation properties of two compounds. To address these issues, in this study a nanoscale interaction between poly(methyl methacrylate) (PMMA) and bioactive glass was formed via silane coupling agent (3-trimethoxysilyl)propyl methacrylate (MPMA). A monolith was produced at optimum composition from this hybrid by the sol-gel method at 50 °C with a rapid gelation time (<50 min) that possessed superior physicochemical properties compared to pure bioglass and physical mixture. For instance, the Young's modulus of bioglass was decreased 40-fold and the dissolution rate of silica was retarded 1.5-fold by integration of PMMA. Prolonged dissolution of silica fosters bone integration due to the continuous dissolution of bioactive silica. The primary osteoblast cells were well anchored and cell migration was observed on the surface of the hybrid. The in vivo studies in mice demonstrated that the integrity of the hybrids was maintained in subcutaneous implantation. They induced mainly a mononuclear phagocytic tissue reaction with a low level of inflammation, while bioglass provoked a tissue reaction with TRAP-positive multinucleated giant cells. These results demonstrated that the presence of a nanoscale interaction between bioglass and PMMA affects the properties of bioglass and broadens its potential applications for bone replacement.

Surface modification of poly(propylene carbonate) by aminolysis and layer-by-layer assembly for enhanced cytocompatibility.

Poly(propylene carbonate) (PPC) is a biodegradable polymer with desirable mechanical properties for bone and cartilage repair. However, the poor biocompatibility impedes its applications in tissue engineering. The aim of this study was to evaluate the effect of surface modification of PPC on the improvement of its cytocompatibility. The combination of aminolysis and layer-by-layer (LBL) assembly techniques was used to modify the PPC surface. The results of ATR-FTIR measurement demonstrated that PPC was aminolyzed by polyethylenimine (PEI) at specific reaction conditions and the degree of aminolyzation was quantitatively determined by ninhydrin method. Positively charged PEI and negatively charged gelatin were alternatively deposited on the aminolyzed PPC membranes at pH 7.4, which formed polyelectrolyte multilayers surface with gelatin as the outermost layer. The presence of amino groups on the aminolyzed PPC and gelatin on the multilayers had significant impact on enhancing the hydrophilicity of PPC. Fibroblast and primary human osteoblasts (HOBs) were used to assess the cytocompatibility of PPC. The deposition of PEI and gelatin bilayers on PPC remarkably promoted both fibroblast and HOBs cell attachment, spreading and growth. In particular, the osteogenic gene expression of HOBs cultured on the multilayers modified PPC was substantially increased. The aminolysis followed by LBL assembly is a convenient and cost effective technique for enhancing cell attachment and proliferation. The product has high potential for musculoskeletal tissue engineering applications due to its desirable mechanical strength and tunable cytocompatibility.

Ultrasensitive potentiometric immunosensor based on SA and OCA techniques for immobilization of HBsAb with colloidal Au and polyvinyl butyral as matrixes.

A novel potentiometric immunosensor for detection of hepatitis B surface antigen (HBsAg) has been developed by means of self-assembly (SA) and opposite-charged adsorption (OCA) techniques to immobilize hepatitis B surface antibody (HBsAb) on a platinum electrode. A cleaned platinum electrode was first pretreated in the presence of 10% HNO3 and 2.5% K2CrO4 solution and held at -1.5 V (vs SCE) for 1 min to make it negatively charged and then immersed in a mixing solution containing hepatitis B surface antibody, colloidal gold (Au), and polyvinyl butyral (PVB). Finally, HBsAb was successfully immobilized onto the surface of the negatively charged platinum electrode modified nanosized gold and PVB sol-gel matrixes. The modified procedure was characterized by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). The immobilized hepatitis B surface antibody exhibited direct electrochemical behavior toward hepatitis B surface antigen (HBsAg). The performance and factors influencing the performance of the resulting immunosensor were studied in detail. More than 95.7% of the results of the human serum samples obtained by this method were in agreement with those obtained by enzyme-linked immunosorbent assays (ELISAs). The resulting immunosensor exhibited fast potentiometric response (<3 min) to HBsAg. The detection limit of the immunosensor was 2.3 ng.mL(-1), and the linear range was from 8 to 1280 ng.mL(-1). Moreover, the studied immunosensor exhibited high sensitivity, good reproducibility, and long-term stability (>6 months).