Robust estimation for varying index coefficient models

Varying index coefficient models (VICMs) proposed by Ma and Song (J Am Stat Assoc, 2014. doi: 10.1080/01621459.2014.903185) are a new class of semiparametric models, which encompass most of the existing semiparametric models. So far, only the profile least squares method and local linear fitting were developed for the VICM, which are very sensitive to the outliers and will lose efficiency for the heavy tailed error distributions. In this paper, we propose an efficient and robust estimation procedure for the VICM based on modal regression which depends on a bandwidth. We establish the consistency and asymptotic normality of proposed estimators for index coefficients by utilizing profile spline modal regression method. The oracle property of estimators for the nonparametric functions is also established by utilizing a two-step spline backfitted local linear modal regression approach. In addition, we discuss the bandwidth selection for achieving better robustness and efficiency and propose a modified expectation–maximization-type algorithm for the proposed estimation procedure. Finally, simulation studies and a real data analysis are carried out to assess the finite sample performance of the proposed method.     

Carleson measures and balayage for Bergman spaces of strongly pseudoconvex domains

Given a bounded strongly pseudoconvex domain D in with smooth boundary, we characterize ‐Bergman Carleson measures for , , and . As an application, we show that the Bergman space version of the balayage of a Bergman Carleson measure on D belongs to BMO in the Kobayashi metric.     

Porous graphene oxide-based carbon artefact with high capacity for methylene blue adsorption

A three-dimensional porous graphene oxide (PGO) material prepared by hydrothermal method was selected to adsorb methylene blue (MB), which demonstrates a high MB adsorption capacity, up to 1100 mg g^?1 in alkaline solution at room temperature. The influences of different pore structures and different contents of oxygen-containing functional groups on MB adsorption behaviors were studied in detail, which indicated that the high MB adsorption capacity is mainly ascribed to the synergistic effect of the large number of oxygen-containing functional groups and the interconnected 3D porous network. Moreover, based on the investigation on the adsorption kinetics and the effect of pH value on MB adsorption, we propose a two-step adsorption kinetics for PGO, which involved in two interactions between MB molecular and porous graphene oxide-based carbon: electrostatic force and π-π stacking. Besides, the calculation of the activation energies indicates that chemisorption dominates the adsorption for PGO in comparison with physisorption for three-dimensional porous graphene materials which has low adsorption capacity because of the removal of functional groups. The results are of great significance for the design and environmental applications of PGO as a promising adsorbent material for water purification.     

Copper-catalyzed efficient dithiocyanation of styrenes: Synthesis of dithiocyanates

A novel Cu-catalyzed intermolecular chemoselectivity dithiocyanation of styrenes with ammonium thiocyanate has been developed under mild conditions. This reaction exhibits a wide range of functional-group tolerance in styrenes to afford various dithiocyanates. The reaction mechanism was primarily investigated and a radical process was proposed.     

Ultrasensitive photometric and visual determination of organophosphorus pesticides based on the inhibition of enzyme-triggered formation of core-shell gold-silver nanoparticles

The authors describe a colorimetric assay for the determination of organophosphorous pesticides (OPPs) based on enzyme-triggered deposition of silver nanoparticles on the surface of gold nanoparticles (AuNP). In this method, alkaline phosphatase (ALP) catalyzes the dephosphorylation of the substrate p-aminophenyl phosphate (p-APP) to form p-aminophenol (p-AP) which is capable of reducing Ag(I) ion to Ag metal which is spontaneously deposited on the surface of AuNP to form Au@Ag NPs. As a result, the color of the colloidal solution first changes from red to yellow, and then to gray with further increases in the thickness of the Ag shell. This can be detected visually or by spectrophotometry. OPPs act as inhibitors of ALP so that the dephosphorylation of p-APP is blocked and silver deposition on the AuNP is retarded or completely suppressed. As a result, the color change from red to yellow is less distinct. This finding forms the basis for the determination of OPPs. Under optimum conditions, the absorbance at 370 nm depends linearly on the logarithm of inhibitor concentration over the ranges from 0.05 to 500 μg?L^?1 and from 0.1 to  500 μg?L^?1, with detection limits of 0.025 μg?L^?1 for methamidophos and 0.036 μg?L^?1 for malathion (at an S/N ratio of 3). Both values are much lower than the maximum residue limits specified in the U.S. Department of Agriculture and European Union pesticide regulations. The validation and practicability of this method for the measurement of OPPs was demonstrated by analyzing (spiked) tap water and lake water.

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Graphical abstract The alkaline phosphatase (ALP) activity is inhibited by organophosphorus pesticides (OPPs). As a result, the ALP-trigged formation of core-shell gold-silver nanoparticles depends on the amount of OPPs, which showed different absorbances and colors.

     

Rapid screening,identification, and purification of neuraminidase inhibitors from Lithospermum erythrorhizon Sieb.et Zucc. by ultrafiltration with HPLC–ESI‐TOF‐MS combined with semipreparative HPLC

We put forward an efficient strategy based on bioassay guidance for the rapid screening, identification, and purification of the neuraminidase inhibitors from traditional Chinese medicines, and apply to the discovery of anti‐influenza components from Lithospermiun erythrorhizon Sieb.et Zucc. Ultrafiltration with high‐performance liquid chromatography and electrospray ionization time‐of‐flight mass spectrometry was employed for the rapid screening and preliminarily identification of anti‐influenza components from Zicao. Semipreparative high‐performance liquid chromatography was used for the rapid separation and purification of the target compounds. NMR spectroscopy, mass spectrometry, and UV spectroscopy were used for further structural identification, and the activity of the compounds was verified by in vitro assay. Five compounds were found to have neuraminidase inhibitory activity by this method. Subsequently, the five compounds were separated by semipreparative high‐performance liquid chromatography with the purity over 98% for all of them by high‐performance liquid chromatography test. Combined with the NMR spectroscopy, mass spectrometry, and UV spectroscopy data, they were identified as alkannin, acetylalkannin, isobutyrylalkannin, β,β‐dimethylacryloylalkannin and isovalerylalkannin. The in vitro assay showed that all five compounds had good neuraminidase inhibitory activities. These results suggested that the method is highly efficient, and it can provide platform and methodology supports for the rapid discovery of anti‐influenza active ingredients from complex Chinese herbal medicines.     

Environmentally friendly solid‐phase microextraction coupled with gas chromatography and mass spectrometry for the determination of biogenic amines in fish samples

In this work, a facile and environmentally friendly solid‐phase microextraction assay based on on‐fiber derivatization coupled with gas chromatography and mass spectrometry was developed for determining four nonvolatile index biogenic amines (putrescine, cadaverine, histamine, and tyramine) in fish samples. In the assay, the fiber was firstly dipped into a solution with isobutyl chloroformate as derivatization reagent and isooctane as extraction solvent. Thus, a thin organic liquid membrane coating was developed. Then the modified fiber was immersed into sample solution to extract four important bioamines. Afterwards, the fiber was directly inserted into gas chromatography injection port for thermal desorption. 1,7‐Diaminoheptane was employed as internal standard reagent for quantification of the targets. The limits of detection of the method were 2.98–45.3 μg/kg. The proposed method was successfully applied to the detection of bioamines in several fish samples with recoveries ranging 78.9–110%. The organic reagent used for extraction was as few as microliter that can greatly reduce the harm to manipulator and environment. Moreover, the extraction procedures were very simple without concentration and elution procedures, which can greatly simplify the pretreatment process. The assay can be extended to the in situ screening of other pollutant in food safety by changing the derivatization reagent.     

Metabolomics method based on ultra high performance liquid chromatography with time‐of‐flight mass spectrometry to analyze toxins in fresh and dried toad venom

Drying is a critical step to prolong the storage time in natural medicine processing but it changes the chemical characteristics of the product. In this study, research was performed to characterize the metabolomic changes in toad venom induced by vacuum‐drying at 60°C and air‐drying at room temperature by ultra high performance liquid chromatography coupled with pattern recognition approaches. In total 52 metabolites, down‐regulated or up‐regulated, were identified as potential chemical markers. Compared with fresh toad venom, vacuum‐drying at 60°C succeeded in raising the conjugated‐type bufadienolide content significantly, while the content of free‐type bufadienolides were slightly reduced. On the other hand, toad venom air‐dried at room temperature presented a relatively low amount of bufadienolides compared with fresh venom. For example, the content of several known anti‐tumor components (gamabufotalin, bufotalin, cinobufagin, etc.) were significantly reduced. The 3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyltetrazolium bromide bioassay further showed that venom air‐dried at room temperature had weaker anti‐tumor activity on human hepatocellular carcinoma SMMC‐7721 proliferation in vitro than samples vacuum‐dried at 60°C. These results showed that the great metabolomic changes of toad venom occurred during the drying process, suggesting that a proper drying procedure is important for sustaining the chemical quality of natural medicines.     

Fabrication of Thickness‐Controllable Micropatterned Polyelectrolyte‐Film/Nanoparticle Surfaces by Using the Plasma Oxidation Method

We have demonstrated a novel way to form thickness‐controllable polyelectrolyte‐film/nanoparticle patterns by using a plasma etching technique to form, first, a patterned self‐assembled monolayer surface, followed by layer‐by‐layer assembly of polyelectrolyte‐films/nanoparticles. Octadecyltrimethoxysilane (ODS) and (3‐aminopropyl)triethoxysilane (APTES) self‐assembled monolayers (SAMs) were used for polyelectrolyte‐film and nanoparticle patterning, respectively. The resolution of the proposed patterning method can easily reach approximately 2.5 μm. The height of the groove structure was tunable from approximately 2.5 to 150 nm. The suspended lipid membrane across the grooves was fabricated by incubating the patterned polyelectrolyte groove arrays in solutions of 1,2‐dioleoyl‐sn‐glycero‐3‐phosphocholine (DOPC) giant unilamellar vesicles (GUVs). The method demonstrated here reveals a new path to create patterned 2D or 3D structures.     

Superelastic,Macroporous Polystyrene‐Mediated Graphene Aerogels for Active Pressure Sensing

Three‐dimensional (3D) graphene‐based polymer/graphene aerogels with excellent mechanical properties are crucial for broad applications. The creation of such polymer/graphene aerogels remains challenging because of the poor dispersion and compatibility of polymer within the graphene matrix. By using the freezing‐directed assembly of graphene under the assistance of surfactant, 3D macroporous polystyrene/graphene aerogels (MPS‐GAs) with lightweight, superelastivity (80 % strain), high strength (80 kPa), and good electrical properties have been achieved in this study. The as‐prepared MPS‐GAs shows excellent electromechanical performance with stable cyclic resilient properties and sensitive resistance responses, thus making the MPS‐GAs promising candidates for applications in actuators, elastic conductors, strain/pressure sensors, and wearable devices.