Modulating the selectivity of solid-phase microextraction fibers based on morphological, compositional, and size-depended control of bimetallic oxide nanostructures grown on nickel-titanium alloy substrates.

Nickel-titanium oxide nanotubes (NiTiONTs), nanoparticles, and nanopores were in situ grown on NiTi fiber substrates by controlling anodization parameters. The adsorption performance of different bimetallic oxide nanostructures was evaluated using typical aromatic compounds including chlorophenols, phthalic acid esters, ultraviolet filters (UVFs), and polycyclic aromatic hydrocarbons (PAHs) coupled to HPLC-UV. The results clearly indicate that these NiTiO nanostructures show good extraction capability for UVFs and PAHs. The extraction performance of UVFs and PAHs greatly depends on the surface morphologies and sizes of the grown NiTiO nanostructures along with their elemental compositions. Compared with NiTiO nanoparticle and nanopore coatings, the longer well-aligned NiTiONT coating exhibits better extraction capability and selectivity for PAHs than for UVFs. Therefore, the extraction parameters of the NiTi@NiTiONT fiber for PAHs were investigated and optimized. Under optimized conditions, the proposed method was linear in the range 0.05-200 µg L-1 with correlation coefficients above 0.999. Limits of detection were between 0.008 and 0.124 µg L-1. Relative standard deviations (RSDs) of the intra-day and the inter-day analyses with the single fiber varied from 4.09 to 6.33%. RSDs for fiber-to-fiber reproducibility of the proposed method with five fibers prepared in different batches were between 5.75 and 7.43%. The applicability of the proposed method was investigated by the enrichment and determination of target PAHs in environmental water samples and relative recoveries of 84.5 ± 6.5 - 116 ± 7.8% were achieved. Notably, the prepared fiber was stable up to 250 times. Graphical abstract.

A physically constrained Monte Carlo-Neural Network coupling algorithm for BNCT dose calculation.

BACKGROUND: In boron neutron capture therapy (BNCT)-a form of binary radiotherapy-the primary challenge in treatment planning systems for dose calculations arises from the time-consuming nature of the Monte Carlo (MC) method. Recent progress, including the use of neural networks (NN), has been made to accelerate BNCT dose calculations. However, this approach may result in significant dose errors in both the tumor and the skin, with the latter being a critical organ in BNCT. Furthermore, owing to the lack of physical processes in purely NN-based approaches, their reliability for clinical dose calculations in BNCT is questionable. PURPOSE: In this study, a physically constrained MC-NN (PCMC-NN) coupling algorithm is proposed to achieve fast and accurate computation of the BNCT three-dimensional (3D) therapeutic dose distribution. This approach synergizes the high precision of the MC method with the speed of the NN and utilizes physical conservation laws to constrain the coupling process. It addresses the time-consuming issue of the traditional MC method while reducing dose errors. METHODS: Clinical data were collected from 113 glioblastoma patients. For each patient, the 3D dose distributions for both the coarse and detailed dose grids were calculated using the MC code PHITS. Among these patients, the data from 14 patients were allocated to the test set, 9 to the validation set, and the remaining to the training set. A neural network, 3D-Unet, was built based on the coarse grid dose and patient CT information to enable fast and accurate computation of the 3D detailed grid dose distribution of BNCT. RESULTS: Statistical evaluations, including relative deviation, dose deviation, mean absolute error (MAE), and mean absolute percentage error (MAPE) were conducted. Our findings suggested that the PCMC-NN algorithm substantially outperformed the traditional NN and interpolation methods. Furthermore, the proposed algorithm significantly reduced errors, particularly in the skin and GTV, and improved computational accuracy (hereinafter referred to simply as 'accuracy') with a MAPE range of 1.6%-4.0% and a maximum MAE of 0.3 Gy (IsoE) for different organs. The dose-volume histograms generated by the PCMC-NN aligned well with those obtained from the MC method, further validating its accuracy. CONCLUSIONS: The PCMC-NN algorithm enhanced the speed and accuracy of BNCT dose calculations by combining the MC method with the NN algorithm. This indicates the significant potential of the proposed algorithm for clinical applications in optimizing treatment planning.

Performance evaluation of a 71Ga(n,γ)72Ga reaction-based epithermal neutron flux detector at an AB-BNCT device.

The 71Ga(n,γ)72Ga reaction-based epithermal neutron flux detectors are novel instruments developed to measure the epithermal neutron flux of boron neutron capture therapy (BNCT) treatment beams. In this study, a spherical epithermal neutron flux detector using 71Ga(n,γ)72Ga reaction was prototyped. The performance of the detector was experimentally evaluated at an accelerator-based BNCT (AB-BNCT) device developed by Lanzhou University, China. Based on the experimental results and related analysis, we demonstrated that the detector is a reliable tool for the quality assurance of BNCT treatment beams.

Squamous cell carcinoma of ascending colon with pMMR/MSS showed a partial response to PD-1 blockade combined with chemotherapy: A case report.

Primary colon squamous cell carcinoma (SCC) is extremely rare and associated with a poor prognosis. Moreover, there is no treatment guideline for this disease. Proficient mismatch repair/microsatellite-stable (pMMR/MSS) colorectal adenocarcinoma is refractory to immune monotherapy. Although the combination of immunotherapy with chemotherapy in pMMR/MSS colorectal cancer (CRC) is currently under investigation, the clinical activity of this approach in colorectal SCC remains unknown. In this article, we report the case of a pMMR/MSS CRC patient with ascending colon SCC who had high programmed cell death-ligand 1 (PD-L1) expression and the a missense mutation in codon 600 of the B-Raf proto-oncogene (BRAF V600E) mutation. The patient exhibited a significant response to the combination of immunotherapy and chemotherapy. After eight cycles of treatment with the combination of sintilimab and mFOLFOX6 (oxaliplatin, fluorouracil, and leucovorin), computed tomography-guided microwave ablation of the liver metastasis was performed. The patient achieved excellent durable response and continues to experience a good quality of life. The present case indicates that programmed cell death 1 blockade combined with chemotherapy may be an effective therapy for patients with pMMR/MSS colon SCC and high PD-L1 expression. Furthermore, PD-L1 expression may be a biomarker for immunotherapy in patients with colorectal SCC.

Controllable in situ growth of novel octahedral TiO2 nanoparticles on nickel/titanium alloy fiber substrate for selective solid-phase microextraction of ultraviolet filters in water samples.

The nature and fabrication of fiber coatings with good adsorption capacity and selectivity play a decisive role in solid-phase microextraction (SPME). In this work, a novel SPME fiber was fabricated through hydrothermal in situ growth of octahedral TiO2 nanoparticles (TiO2NPs) on a superelastic nickel/titanium alloy (NiTi) wire substrate in acid solution. The resulting fiber coatings were characterized by scanning electron microscopy and energy dispersive X-ray spectroscopy. Acid types, acid concentration as well as hydrothermal temperature and time were found to be effective route to manipulate the morphologies and composition of TiO2-based nanoflakes grown on the NiTi fiber substrates. At the concentration of 0.4 mol L-1 HCl as well as hydrothermal temperature of 150 °C and hydrothermal time of 12 h, TiO2NPs were in situ grown on the NiTi wire substrates. The obtained NiTi wire with the TiO2NPs coating (NiTi@TiO2NPs fiber) was employed to investigate the adsorption of some representative aromatic analytes in water samples coupling with high-performance liquid chromatography with UV detection (HPLC/UV). The results clearly demonstrate that the fiber exhibits good extraction selectivity for ultraviolet filters (UVFs). In view of good extraction selectivity for the selected UVFs, the key experimental parameters were optimized. Under the optimum conditions, the calibration curves were linear in the ranges of 0.05-100 µg L-1 with the correlation coefficients greater than 0.998. Limits of detection (LODs) were 0.007 to 0.064 µg L-1. Furthermore, the intra-day and inter-day repeatability of the proposed method with the single fiber varied from 4.3% to 6.1% and from 4.5% to 6.8%, respectively. The fiber-to-fiber reproducibility ranged from 5.8% to 8.2%. The developed SPME-HPLC/UV method was applied to selective preconcentration and sensitive determination of target UVFs from real water samples. Moreover, the fabricated fiber showed precisely controllable growth and 150 extraction and desorption cycles.

Development of a novel porous cobalt, phosphorus and nitrogen co-doped carbonaceous coating by phosphiding ZIF-67 grown on nitinol fiber for selective solid-phase microextraction of polycyclic aromatic hydrocarbons from water samples.

The nature and fabrication of the fiber coatings with good adsorption capacity and selectivity play a decisive role in solid-phase microextraction (SPME). In this work, a facile strategy was proposed to fabricate a cobalt, phosphorus and nitrogen co-doped carbonaceous (Co-P-NC) coating on superelastic nitinol (NiTi) substrate as a binder-free fiber for SPME. In particular, direct electrochemical in situ growth of ZIF-67 crystals served as the N-containing carbon precursor and sacrificial template for subsequent controllable conversion of ZIF-67 into a novel porous Co-P-NC coating on the NiTi wire substrate via a phosphiding process in a N2 atmosphere. The obtained NiTi wire with the Co-P-NC coating (NiTi@Co-P-NC) was employed to investigate the adsorption of some representative aromatic analytes in water samples for the first time coupling with high-performance liquid chromatography with UV detection (HPLC/UV). The results proved that the resulting fiber showed superior adsorption selectivity for polycyclic aromatic hydrocarbons (PAHs). Therefore, the key parameters were further examined for the adsorption and preconcentration of PAHs. Under the obtained conditions, linear chromatographic responses were achieved over the concentration ranges of 0.03-100 µg L-1 with the correlation coefficients ranging from 0.9980 to 0.9991. Limits of detection (LODs) were between 0.007 and 0.149 µg L-1 (S/N = 3). The developed SPME-HPLC/UV method was applied to selective preconcentration and sensitive determination of PAHs in water. Moreover, this fiber had good fiber preparation reproducibility and presented 120 adsorption and desorption cycles at the same time in practical SPME application.

Coupling Coordination Measurement and Evaluation of Urban Digitalization and Green Development in China.

The coordinated promotion of urban digitalization and green development is an inevitable requirement for sustainable development in the digital age. Based on the coupling mechanism of urban digitalization and green development, in this study, we took 282 cities at the prefecture level and above in China from 2011 to 2019 as the research object, and we constructed the evaluation index system and calculated the coupling coordination degree (CD&GDD) of the two through the coupling coordination degree model. We further used the Dagum Gini coefficient, kernel density estimation, Markov chain and Moran's I to assess the spatial effects of the regional differences, dynamic evolution trends and degree of coupling coordination. The results show the following: (1) The level of urban digitalization and green development show a fluctuating upward trend, and the interaction between the two is obvious. (2) Although the CD&GDD of most cities is continuously improving, it is still at a low level. There are large differences in the levels between the regions. (3) The inter-regional differences are the main source of the large overall differences in the CD&GDD in China, and these are mainly composed of the hypervariable density and net differences between the regions. (4) The phenomenon of "club convergence" exists in the CD&GDD. (5) The coupling coordination relationship between cities has a substantial spatial effect, and the spatial effect has obvious regional heterogeneity. The results and conclusions provide a reference for developing countries to promote green and low-carbon urban development.

A novel grey spatial extension relational model and its application to identify the drivers for ambient air quality in Shandong Province, China.

The ambient air quality is a complex dynamical system that is shocked by a number of subsystems, such as government policies, industry regulation adjustment and internationalization. To identify the drivers for ambient air quality, a grey spatial extension relational analysis model is proposed. Firstly, a spatial extension method for one-dimensional time series of complex systems is introduced, and the two key parameters are obtained based on the grey similarity and proximity relational analysis models. Secondly, grey relational coefficient is calculated by the difference of the three-dimensional vector, and a grey spatial extension relational analysis model is presented. Furthermore, the properties of the proposed model were investigated. Finally, the model is used to identify the drivers of the ambient air quality in eastern coastal Shandong Province, China. Results suggest that the drivers of the ambient air quality vary among cities, but with some common ones. Therefore, this paper provides an important reference for the improvement of ambient air quality.

Controllable growth of flower-like hierarchical CoNiO2 nanoflakes anchored on Nitinol fiber substrate with good selectivity for highly efficient solid-phase microextraction of polycyclic aromatic hydrocarbons in water.

The flower-like hierarchical cobalt nickel oxide nanoflakes (CoNiO2NFs) with a porous structure were fabricated on Nitinol (NiTi) fiber substrate by a hydrothermal reaction and subsequent annealing treatment. The morphology affected by the molar ratios of Ni to Co and counter ions in starting precursors as well as hydrothermal reaction temperature and time was investigated in detail. The obtained CoNiO2NFs coating exhibited outstanding performance for the selective extraction of PAHs. After optimizing the main parameters that affected extraction through orthogonal experiments, the developed method showed good linearity in the ranges of 0.05 µg L-1 - 200 µg L-1 with the determination coefficient >0.999. LODs were between 0.006 µg L-1 and 0.114 µg L-1, LOQs were in the ranges of 0.020-0.376 µg L-1 and RSDs were below 5.19% and 5.71% for intra-day and inter-day analyses, respectively. The developed method was successfully applied to selective enrichment and determination of target PAHs in real water samples. Moreover, the fabricated fiber exhibited high chemical and mechanical stability, and could withstand more than 260 extraction-desorption cycles without loss of its extraction efficiency.

Temperature and time-controlled hydrothermal growth and sorption selectivity of titania nanowires on titanium fiber for highly efficient solid-phase microextraction.

Two kinds of TiO2 nanowires (TiO2NWs) with different orientation were in-situ grown on Ti substrates by controlling temperature and time during the hydrothermal process. The adsorption performance was evaluated by using typical aromatic compounds as model analytes coupled to HPLC with UV detection. The results demonstrated that the TiO2NWs coating grown at higher temperature within longer time had better affinity towards PAHs. For this purpose, the key experimental factors affecting the adsorption performance of the TiO2NWs coating fabricated at 200 °C for 10 h were further investigated and optimized for the extraction of PAHs. Under the optimized conditions, the proposed method presented linear responses in the concentration ranges of 0.05 to 200 µg·L-1 PAHs with correlation coefficients more than 0.998. LODs (S/N=3) were 0.008 to 0.034 µg·L-1. Moreover, RSDs for the single fiber repeatability of the intra-day and the inter-day analyses were less than 5.6% (n=5) and 5.8%, respectively. RSDs for the fiber-to-fiber reproducibility were between 5.1% and 6.5%. Finally, the proposed method was successfully applied to the selective preconcentration and determination of trace PAHs in environmental water samples. In addition, The fabricated Ti fiber can be used at least 200 times due to its high mechanical and chemical stability.

Effective allocation of resources in water pollution treatment alternatives: a multi-stage gray group decision-making method based on hesitant fuzzy linguistic term sets.

With the significant economic shift, water pollution treatment has gradually become a key problem which needs to be deeply investigated for the sustainable development of China. In the face of specific water pollution incidents, multiple alternatives are often required to work together in order to achieve better results. However, due to the limitation of resources, alternatives must be ranked to realize the effective allocation of resources, which means the more highly ranked ones should possess more disposable resources. Furthermore, the water pollution treatment process is a multi-stage and multi-objective process. In each stage, decision-makers may have different emphasis and thus have different preferences for the treatment alternatives. How to effectively aggregate decision-makers' preferences in different stages into an overall preference so as to form a ranking of treatment alternatives under global constraints has turned into a problem worthy of discussion. Under such background, this paper proposes a multi-stage gray group decision-making method, where decision-makers use Group-G1 to rank and weight the criteria, and in this way, the weights of decision-makers and criteria in each stage could be determined. Considering the difference and deficiency of the cognitive level of decision-makers, this paper adopts the form of hesitant fuzzy linguistic term sets (HFITS) to express the evaluation information of decision-makers. And then, gray incidence analysis is selected to rank the alternatives. After ranking the alternatives in each stage, the multi-stage rankings will be aggregated into an overall ranking and the resource allocation is made according to the priorities of the alternatives. Finally, an example of water pollution treatment alternatives ranking based on a cyanobacterial bloom in Taihu Lake, China, is given to illustrate the proposed approach.

Template-directed fabrication of zeolitic imidazolate framework-67-derived coating materials on nickel/titanium alloy fiber substrate for selective solid-phase microextraction.

Novel solid-phase microextraction fibers were fabricated by electrochemical deposition of cobalt on the pretreated nickel/titanium alloy (NiTi) fiber substrate and subsequent in situ growth of zeolitic imidazolate framework-67 (ZIF-67) followed by annealing treatment. The Co@ZIF-67 coating was used as a precursor and template for controlled fabrication of the Co@ZIF-67-derived coatings including Co@ZIF-67-Co3O4 and carbonaceous composite coatings. . The extraction performance of the Co@ZIF-67-derived coatings was evaluated using typical aromatic compounds coupled to high-performance liquid chromatography with UV detection. The results clearly demonstrate that the extraction selectivity is subject to the surface elemental composition of the ZIF-67-derived coatings. In view of long-term stability and good extraction selectivity, the Co@ZIF-67-C coating was selected for the enrichment and determination of polycyclic aromatic hydrocarbons (PAHs). Under the optimized conditions, the calibration curves were linear in the range of 0.05-100 µg•L-1 with the correlation coefficients above 0.998. Limits of detection were 0.005-0.042 µg•L-1. Furthermore, the intra-day and inter-day repeatability of the proposed method with the single fiber varied from 2.3% to 5.8% and from 3.3% to 6.9%, respectively. The fiber-to-fiber reproducibility ranged from 4.1% to 8.5%. The proposed method was suitable for selective enrichment and determination of target PAHs from real water samples. Moreover, the fabricated fiber showed precisely controllable growth and 150 extraction and desorption cycles.

Selective and efficient solid-phase microextraction of polycyclic aromatic hydrocarbons in water by robust two-dimensional zinc oxide nanosheets grown on a superelastic nickel-titanium alloy fiber prior to determination by HPLC-UV.

Oriented zinc oxide nanosheets (ZnONSs) were directly grown on pretreated nickel-titanium alloy (NiTi) fiber substrates without a traditional seeding layer of ZnO by electrochemical deposition for the first time. The fiber coatings were characterized by scanning electron microscopy and energy dispersive X-ray spectrometry. Direct growth of ZnONSs on the NiTi fiber substrate was dependent on the type of zinc salt. The adsorption performance of the ZnONSs coatings was evaluated using representative aromatic compounds as model analytes together with high performance liquid chromatography with ultraviolet detection. The as-prepared fiber shows higher extraction capability for the selected polycyclic aromatic hydrocarbons (PAHs) than for ultraviolet filters in water samples, and better extraction selectivity for PAHs. For this purpose, the important experimental parameters were optimized for the extraction of PAHs. Under the optimized conditions, the calibration curves are linear in the range of 0.03-200 µg L-1 with correlation coefficients greater than 0.999. Limits of detection ranged from 0.011 µg L-1 to 0.082 µg L-1. Intra-day and inter-day relative standard deviations (RSDs) of the developed method with a single fiber ranged from 2.69% to 4.18% and from 4.44% to 5.40%, respectively. RSDs for the fiber-to-fiber reproducibility varied between 5.57% and 7.66%. The developed method was successfully applied for selective preconcentration and determination of trace PAHs in five real water samples. Relative recoveries varied from 84.5% to 104% with RSDs between 1.65% and 8.30%. Furthermore, the as-prepared fiber is highly stable.

An interactive group decision model for selecting treatment schemes for mitigating air pollution.

Air pollution has caused huge losses of life and property. So, how to choose a practically effective scheme to m.itigate air pollution is of great significance. However, such a selection problem of treatment schemes represents really a group negotiation process of many decision makers (DMs), involving a variety of fuzzy information and preferences. To successfully address this selection problem, this paper proposes a novel group negotiation decision model by jointly employing various approaches, such as hesitant fuzzy set, grey target, grey incidence analysis, and graph model for conflict resolution (GMCR). Then, this model is used to determine the equilibrium schemes for treating air pollution. It is expected that this work provides a method for Chinese government to introduce programs to target air pollution control.

Assessing Regional Differences in Green Innovation Efficiency of Industrial Enterprises in China.

Green technology innovation is an important means to break out of the constraints of resources and the environment, enhance the competitiveness of enterprises, and achieve the upgrading of industrial structures, and promote high-quality economic growth. In order to realize the overall improvement of the green technology innovation capability of Chinese enterprises, it is necessary to measure the efficiency of industrial enterprises' green technology innovation and explore their regional differences. In this paper, from the perspective of a two-stage innovation value chain, by introducing the industrial carbon emissions per unit of Gross Domestic Product (GDP) and the "three wastes" pollutants into the research framework of green technology innovation efficiency, we established a novel green innovation efficiency evaluation indicator system for industrial enterprises. Furthermore, we used a two-stage network DEA with shared input to measure the efficiency of regional enterprises' green technology innovation and explored the regional differences in industrial enterprises' green technology R&D and the efficiency of green technology achievement transformation. Finally, we provide some suggestions for improving China's industrial enterprises' green innovation efficiency, so that they can ameliorate the significant regional imbalances and differences and realize high-quality economic growth.

Inclusion complex formation of ionic liquids with cucurbit[7]uril studied by competitive binding of methylene blue fluorescent probe.

Methylene blue (MB) was used as a fluorescent probe to study the encapsulation of three kinds of 1-butyl-3-methylimidazolium ionic liquids in cucurbit[7]uril (CB7) at pH 3. Addition of ionic liquids to the aqueous solution of MB-CB7 inclusion complexes brought about considerable fluorescence intensity quenching, and it was because that MB was extruded from the cavity of CB7 into the aqueous phase by the ionic liquid. NMR and AM1 semi-empirical calculations indicated that the 1-butyl-imidazolium moiety of ionic liquid was responsible for the complexation with CB7.