Selective adsorption of zearalenone by a novel magnetic molecularly imprinted carbon nanomaterial.

In this paper, the objective is to immobilize molecularly imprinted polymers (MIPs) onto the surface of magnetic carbon nanoparticles (Fe3O4@SiO2@C) to develop an effective method for the adsorption of zearalenone (ZEN). The prepared products were characterized by FT-IR, SEM, TEM, XRD, VSM, TGA, and BET. The content of zearalenone in corn samples was monitored by HPLC. The results indicate that the particle size of magnetic molecularly imprinted polymers (MMIPs) is approximately 200 nm. The adsorption mechanism of MMIPs was confirmed by static adsorption and dynamic adsorption experiments. The maximum adsorption capacity was 1.56 mg/g, and the adsorption equilibrium was reached within 50 min. The scatchard model showed that MMIPs had two binding sites, a high-affinity binding site and a low-affinity site. Kinetic second-order fitting indicates that MMIPs are mainly through chemisorption. In the actual sample application, the limit of detection (LOD) and limit of quantitation (LOQ) were 0.3 mg/L and 0.9 mg/L, respectively. The recovery of corn with the standard addition of ZEN was 73.6-88.1%, and the relative standard deviation (RSD) was 2.86-5.63%. The results demonstrated that MMIPs possess the advantages of straightforward operation, high precision, and cost-effectiveness, rendering them suitable for rapid ZEN detection.

Preparation of a hydrophilic nanofiber membrane by electrospinning for application in the detection of NO2 by chemiluminescence.

The strong hydrophobicity of the PVDF membrane is prone to contamination that is hard to clean for long-term usage. In this study, hydrophilic and antifouling nanofiber membranes (NMs) were prepared with the hydrophilic polymer PVP and inorganic nanoparticles TiO2NPS. This NM was found to have excellent cleanability and good recyclability. Within 30 minutes, the residual ions could be removed by cleaning with deionized water. In alkaline solutions with the power of hydrogen (PH) ≤10, NM exhibits good alkaline resistance and recycling performance. It was also found, for the first time, that TiO2NPS could enhance the sensitivity of Luminol-NO2 (L-NO2) by 4 times. The detection of NO2 concentration by NM presents an excellent linear relationship with the chemiluminescence reading. This linear relationship would aid quick and convenient detection of NO2 using chemiluminescence.

Ozone-3,6-dihydroxynaphtha-2,7-disulphonate chemiluminescence system is used for online ozone detection.

The chemiluminescence (CL) reaction between ozone and 3,6-dihydroxynaphtha-2,7-disulphonate (DNDS) was found under alkaline conditions. Therefore, a novel CL system for ozone detection was established. The CL signal of the CL system is weak, and the CL signal is enhanced by adding nonionic surfactants. It was found that adding 16.4 g/l Triton X-100 can enhance the CL signal. The CL reagent activated by ultraviolet (UV) light produced a CL signal was nearly 10 times stronger than the CL reagent not activated by UV light; the CL signal was enhanced by adding 8 g/l NaHCO3 to the CL reagent irradiated by UV light. Through the optimization of these test conditions, a high-selectivity, high-sensitivity online detection method for ozone CL was established. The linear range was 0.5-150 ppbv, and the limit of detection (LOD) was 0.092 ppbv (S/N = 3).

[Treatment of open middle and lower tibial fractures with bridge link combined fixation system external by means of external fixation].

OBJECTIVE: To explore clinical effect of bridge-link combined fixation system(BCFS) in treating open middle and lower tibial fractures by external fixation. METHODS: From October 2016 to September 2017, 11 patients with open middle and lower tibial fractures were treated with BCFS by external fixation, including 7 males and 4 females aged from 23 to 65 years old with an average of 44.2 years old;the course of disease ranged from 7 to 10 days. All fractures were open, middle and lower tibiofibular fractures. According to AO classification, 5 patients were type A, 5 patients were type B, and 1 patient was type C. All fractures were classified as typeⅡaccording to Gustilo-Anderson classification. The time of fracture healing, postoperative complications were observed, Johner-Wruhs standard were used to evaluate clinical effect. RESULTS: All patients were followed up from 7 to 13 months with an average of 10.1 months. Fracture healing time ranged from 4 to 8 months with an average of 6.2 months. The removal time of BCFS ranged from 5 to 11 months with an average of 7.8 months. No screws loosening and BCFS breakage occurred after operation, while 1 patient occurred infection of proximal and distal tibia after operation which was healed by anti-inflammatory treatment and dressing change. According to Johner-Wruhs standard, 8 patients were excellent and 3 patients good at the latest follow-up. CONCLUSION: BCFS could be used to treat open middle and lower tibial fractures by external fixation, which had features of small size, flexible use, solid and elastic fixation. It could not effectively reduce tissue injury and promote fracture healing, but also have advantages of less postoperative complications and better recovery of limb function.

Nanoscale kinetics of asymmetrical corrosion in core-shell nanoparticles.

Designing new materials and structure to sustain the corrosion during operation requires better understanding on the corrosion dynamics. Observation on how the corrosion proceeds in atomic scale is thus critical. Here, using a liquid cell, we studied the real-time corrosion process of palladium@platinum (Pd@Pt) core-shell nanocubes via transmission electron microscopy (TEM). The results revealed that multiple etching pathways operatively contribute to the morphology evolution during corrosion, including galvanic etching on non-defected sites with slow kinetics and halogen-induced etching at defected sites at faster rates. Corners are the preferential corrosion sites; both etching pathways are mutually restricted during corrosion. Those insights on the interaction of nanostructures with reactive liquid environments can help better engineer the surface structure to improve the stability of electrocatalysts as well as design a new porous structure that may provide more active sites for catalysis.

Strain-induced Stranski-Krastanov growth of Pd@Pt core-shell hexapods and octapods as electrocatalysts for methanol oxidation.

Bimetallic nanocrystals with a branched shape have received great interest as catalysts due to their unique structures and fascinating properties. However, the conventional synthetic approaches based on the island growth mode often lead to the dendritic nanostructures with inhomogeneous and uncontrolled branches. Here precise control over the number of branches has been realized in the deposition of Pt on Pd seeds through the Stranski-Krastanov growth mechanism. Based on such a growth mode, Pd@Pt core-shell hexapods and octapods have been generated by a seeded growth with Pd octahedra and cubes as the seeds, respectively. We found that Pt atoms are initially deposited on the side faces of Pd seeds through a layer-by-layer epitaxial growth in the presence of oleylamine (OAm), leading to a local strain focused at their corners. These strain-concentrated sites promote the subsequent island growth of Pt atoms at the corners of the Pd seeds, resulting in the Pd@Pt core-shell hexapods or octapods. Both the Pd@Pt core-shell hexapods and octapods exhibit the substantially enhanced catalytic properties in terms of activity and stability towards a methanol oxidation reaction (MOR) relative to the commercial Pt/C. Specifically, the Pd@Pt core-shell hexapods show the highest specific (1.97 mA cm-2) activity and mass activity (0.52 mA µgPt-1) for the MOR, which are 5.8 and 2.6 times higher than those of the commercial Pt/C, respectively. This enhancement can probably be attributed to their unique structures and the synergistic effect between Pt and Pd.

An In situ TEM study of the surface oxidation of palladium nanocrystals assisted by electron irradiation.

The surface oxidation of palladium nanocrystals plays an important role in changing the active sites and subsequently influencing the catalytic reactivity. Such a microscopy study on surface oxidation, down to the atomic scale, is essential for understanding the structure-property correlations of palladium nanocrystal based catalysts. Herein, we present an in situ atomic scale study on the surface oxidation behavior of palladium nanocrystals, which is induced by electron beam irradiation under low oxygen partial pressure and at room temperature inside an environmental transmission electron microscope. We found that: (i) surface oxidation initially started at the edge sites with atomic steps or vertex sites, which served as active sites for oxidation; (ii) the oxidation reaction proceeded with a much faster rate on the {111} surface, indicating a certain crystallography preference; (iii) nanometer-sized palladium monoxide islands were formed on the surfaces eventually. The results from our in situ studies provide insightful knowledge, and will be of certain importance for the design of improved functional catalysts in future.

Tuning Surface Structure and Strain in Pd-Pt Core-Shell Nanocrystals for Enhanced Electrocatalytic Oxygen Reduction.

Icosahedral, octahedral, and cubic Pd@Pt core-shell nanocrystals with two atomic Pt layers are epitaxially generated under thermodynamic control. Such icosahedra exhibit remarkably enhanced catalytic properties for oxygen reduction reaction compared to the octahedra and cubes as well as commercial Pt/C, which can be attributed to ligand and geometry effects, especially twin-induced strain effect that is revealed by geometrical phase analysis.

Developing an aqueous approach for synthesizing Au and M@Au (M = Pd, CuPt) hybrid nanostars with plasmonic properties.

Anisotropic Au nanoparticles show unique localized surface plasmon resonance (LSPR) properties, which make them attractive in optical, sensing, and biomedical applications. In this contribution, we report a general and facile strategy towards aqueous synthesis of Au and M@Au (M = Pd, CuPt) hybrid nanostars by reducing HAuCl4 with ethanolamine in the presence of cetyltrimethylammonium bromide (CTAB). According to electron microscopic observations and spectral monitoring, we found that the layered epitaxial growth mode (i.e., the Frank-van der Merwe mechanism) contributes to the enlargement of the core, while the random attachment of Au nanoclusters onto the cores accounts for the formation of the branches. Both of them are indispensable to the formation of the nanostars. The LSPR properties of the Au nanoparticles have been well investigated with morphology control via the precursor amount and growth temperature. The Au nanostars showed improved surface-enhanced Raman spectroscopy (SERS) performance for rhodamine 6G due to their sharp edges and tips, which were therefore confirmed as good SERS substrates to detect trace amounts of molecules.

Millisecond phase kinetic analysis of elongation catalyzed by human, yeast, and Escherichia coli RNA polymerase.

Strategies for assembly and analysis of human, yeast, and bacterial RNA polymerase elongation complexes are described, and methods are shown for millisecond phase kinetic analyses of elongation using rapid chemical quench flow. Human, yeast, and bacterial RNA polymerases function very similarly in NTP-Mg2+ commitment and phosphodiester bond formation. A "running start, two-bond, double-quench" protocol is described and its advantages discussed. These studies provide information about stable NTP-Mg2+ loading, phosphodiester bond synthesis, the processive transition between bonds, and sequence-specific effects on transcription elongation dynamics.

A tunable ratchet driving human RNA polymerase II translocation adjusted by accurately templated nucleoside triphosphates loaded at downstream sites and by elongation factors.

When nucleoside triphosphate (NTP) substrates and alpha-amanitin are added to a human RNA polymerase II elongation complex simultaneously, the reaction becomes stalled in the core of the bond synthesis mechanism. The mode of stalling is influenced by NTP substrates at the active site and at downstream sites and by transcription factor IIF (TFIIF) and TFIIS. NTP substrates templated at i+2, i+3, and i+4 downstream DNA sites can reverse the previously stable binding of an NTP loaded at the i+1 substrate site. Deoxy-(d)NTPs and NDPs (nucleoside diphosphates) do not substitute for NTPs at the i+2 and i+3 positions (considered together) or the i+4, i+5, and i+6 positions (considered together). The mode of stalling is altered by changing the number of downstream template sites that are accurately occupied by NTPs and by changing NTP concentration. In the presence of the translocation blocker alpha-amanitin, a steady state condition is established in which RNA polymerase II stably loads an NTP substrate at i+1 and forms a phosphodiester bond but cannot rapidly complete bond synthesis by releasing pyrophosphate. These observations support a role for incoming NTP substrates in stimulating translocation; results appear inconsistent with the secondary pore being the sole route of NTP entry for human RNA polymerase II, and results indicate mechanisms of dynamic error avoidance and error correction during rapid RNA synthesis.

NTP-driven translocation and regulation of downstream template opening by multi-subunit RNA polymerases.

Multi-subunit RNA polymerases bind nucleotide triphosphate (NTP) substrates in the pretranslocated state and carry the dNMP-NTP base pair into the active site for phosphoryl transfer. NTP-driven translocation requires that NTP substrates enter the main-enzyme channel before loading into the active site. Based on this model, a new view of fidelity and efficiency of RNA synthesis is proposed. The model predicts that, during processive elongation, NTP-driven translocation is coupled to a protein conformational change that allows pyrophosphate release: coupling the end of one bond-addition cycle to substrate loading and translocation for the next. We present a detailed model of the RNA polymerase II elongation complex based on 2 low-affinity NTP binding sites located in the main-enzyme channel. This model posits that NTP substrates, elongation factors, and the conserved Rpb2 subunit fork loop 2 cooperate to regulate opening of the downstream transcription bubble.