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The iron catalyst (POM-Fe) could combine with chloride ions to form a supramolecular aggregate FeMo6·Cl, which was used in the oxidation of alcohols to carboxylic acids under mild conditions and can tolerate 40 substrates with moderate to high yield.

Single-atom catalysts on supported silicomolybdic acid for CO2 electroreduction.

The site-blocking effect (SBE) of nonelectro-chemical steps (nonECS) gives the sluggish kinetics in alkaline hydrogen evolution reaction (HER), but remains rather challenging in electrocatalysis. Herein, we explored nonECS on the highly amorphized NiMoN/NC(500-R) nanoarrays, in which Ni0.76Mo1.24 and Mo2N with the crystallinity of only 13.3% were embedded into nitrogen-rich derived carbons (NC) at 500oC, then followed by electrochemical surface reconstruction. The amorphization and hydroxylation induce the coupled dual-centers of Ni-Mo species to circumvent SBE through separating H*- and H2-involved elementary steps from nonECS, and deliver efficient transfer of individual species and heavy charge accumulation to actuate the whole HER. Resultantly, the exceptional catalytic activity is demonstrated by ultra-low overpotentials of 5.8 and 200.6mV at 10 and 1000mA cm-2, respectively. Importantly, NiMoN/NC(500-R) survive in lasting alkaline HER for 50 days at 500mA cm-2 almost without degeneration. This work presents the key to get rid of SBE in electrocatalysis, and the inspiration to rationally design the amorphized nanoarrays of electrocatalysts.

Highly efficient removal of Hg(ii) has been previously achieved through the adsorption by functionalized covalent organic frameworks (COFs). Among these COFs, thioether groups need to be deliberately introduced into the pores of COFs through either a bottom-up synthesis or post-synthesis strategy. Herein, we report a simple mercury removal strategy that used a stable alkynyl (-C[triple bond, length as m-dash]C-) based covalent organic framework (TP-EDDA COF) as an adsorbent for Hg(ii) removal. Sulfur vapor was first adsorbed by the TP-EDDA COF due to the van der Waals interaction between adsorbed sulfur and alkynyl groups. The Hg(ii) removal capability was then evaluated for the sulfur loaded TP-EDDA COF. Our results exhibited a good Hg(ii) removal performance for the sulfur loaded TP-EDDA COF. It was deduced that s⋯π interaction between sulfur atom and the alkynyl groups of the COF skeleton caused an increase in the electron density of sulfur and the electronegative sulfur atoms acted as a soft acid to accept soft-basic Hg(ii). This strategy provides a convenient platform for COFs to cope with environmental issues.

The hydroisomerization of n-hexadecane over Pt-Pd bimetallic catalysts is an effective way to produce clean fuel oil. This work reports a useful preparation method of bimetallic bifunctional catalysts by a co-impregnation or sequential impregnation process. Furthermore, monometallic catalysts with loading either Pt or Pd are also prepared for comparison. The effects of the metal species and impregnation order on the characteristics and catalytic performance of the catalysts are investigated. The catalytic test results indicate that the maximum iso-hexadecane yield over different catalysts increases as follows: Pt/silicoaluminophosphate SAPO-41 < Pd/SAPO-41 < Pt*-Pd/SAPO-41 (prepared by sequential impregnation) < Pt-Pd/SAPO-41 (prepared by co-impregnation). Owing to the synergic effects between Pt and Pd, the Pt-Pd/SAPO-41 catalyst prepared by the co-impregnation method demonstrates the effective promotion of (de)hydrogenation activity. Therefore, this catalyst exhibits the highest iso-hexadecane yield of 89.4% when the n-hexadecane conversion is 96.3%. Additionally, the Pt-Pd/SAPO-41 catalyst also presents the highest catalytic activity and best stability even after 150 h long-term tests.

Abstract Three nanosized ZSM-5 zeolites were successfully prepared from reactive gels with the same Si/Al ratios by different synthetic procedures that included the use of tetrapropylammonium hydroxide or n-butylamine as a template and a seeding method that did not use an organic additive. The effect of the synthetic method on the physicochemical properties of the prepared samples was investigated by XRD, XRF, XPS, N2 physisorption, SEM, TEM, 27Al MAS NMR, NH3-TPD, and Py-FTIR. The catalytic performance of the nanosized ZSM-5 zeolites in the alkylation of naphthalene with methanol was compared. The prepared samples were phase-pure, highly crystalline ZSM-5 zeolites, but they had different bulk and surface Si/Al ratios as well as textural and acidic properties. The study of the prepared catalysts in naphthalene methylation revealed that both the acid characteristics of the ZSM-5 nanosized zeolites and their textural properties were responsible for their activity in the reaction. A difference in the composition of monomethylnaphthalenes and dimethylnaphthalenes was attributed to the ability of the catalyst to isomerize the primary reaction products on acid sites located on the external surface of the zeolite crystals. 2,7-DMN was found to be the preferred reaction product over 2,6-DMN when formed at pore entrances to ZSM-5 channels due to the differences in their dimensions. In contrast, 2,6-dimethylnaphthalene could be produced on weaker external Brønsted acid sites, which are hydroxyls attached to octahedral Al atoms. The presented results show that the method used to synthesize nanoscale ZSM-5 zeolites is a critical factor that determines the physicochemical properties and catalytic performance of the resulting crystals.

Supported single-atom catalysts have become one of the most exciting frontiers in heterogeneous catalysis. The physicochemical properties of these materials are highly interesting; however, the gen...

The preparation of bifunctional catalysts with high catalytic selectivity for the n-alkanes hydroisomerization still remains challenging for the production of bio-diesel. Herein, two series of Pd/SAPO-41 bifunctional catalysts are prepared by the ultrasonic-assisted impregnation (xPd/S41-U) with different treating time and conventional incipient wetness impregnation methods (0.30Pd/S41-I) on the SAPO-41 molecular sieve, respectively. The physico-chemical property of the synthesized SAPO-41 and prepared catalysts were studied by XRD, SEM, ICP, N2 physical adsorption, H2 chemisorption and Py-IR measurements. The catalytic performance for the n-hexadecane hydroisomerization over all catalysts is also studied. The characteristic results indicate that the xPd/S41-U catalysts show stronger Bronsted acidity compared with the 0.30Pd/S41-I catalyst. In addition, the Pd dispersion of the xPd/S41-U catalysts is almost two times higher than that of the 0.30Pd/S41-I catalyst, which leads more Pd cluster to enter into the micropores of the SAPO-41 molecular sieve. Furthermore, the 0.30Pd/S41-U catalyst with 0.30 wt % Pd loading shows promoted catalytic performance than that of the 0.30Pd/S41-I catalyst with the same Pd loading because of the stronger metal function and more favourable metal-acid balance caused by the larger CPd/CH+ ratio. Therefore, the ultrasonic-assisted impregnation prepared Pd/SAPO-41 catalysts are potential to be widely employed for the n-alkane hydroisomerization.

Nanosized ZSM-5 zeolites were synthesized by an in situ seed-induced hydrothermal method, and samples modified with an Fe promoter were prepared by the traditional wet impregnation-thermal decomposition and dielectric barrier discharge plasma (DBD) methods, respectively. The physico-chemical properties of the catalysts were studied by XRD, SEM, TEM, BET, XPS, H2-TPR, NH3-TPD and Py-IR techniques. The catalytic performance was eValuated by the methanol-to-olefin (MTO) reaction. The results showed that the acidity of the catalysts, the dispersity of the Fe promoter and the interaction degree with the ZSM-5 zeolite are closely related to product selectivity in the MTO reaction. Compared with the Fe-NZ5 sample prepared by the traditional impregnation-calcination method, the FeD-NZ5 samples prepared by the DBD method exhibited the higher selectivity of C2—C4 light olefins and the lower coke deposition during long-term eValuation (100 h), which can be attributed to the weaker acid strength, more uniform Fe promoter dispersion and strong interaction with the ZSM-5 zeolite. The developed Fe-modified catalysts have high potential for application in the MTO reaction.

Background: Accumulating studies have suggested the airway microbiota of lung cancer was significantly different from healthy controls. However, little was known about the relationship between airway microbiota and important clinical parameters of lung cancer. In this study, we aimed to explore the association between sputum microbiota and lung cancer stage, lymph node metastasis, intrathoracic metastasis, and Epidermal growth factor receptor (EGFR) gene mutation. Methods: The microbiota of sputum samples from 85 newly diagnosed NSCLC patients were sequenced via 16S rRNA sequencing with V3-V4 region. Sequencing reads were filtered using QIIME2 and clustered against UPARSE. Results: The α diversity and β diversity was significantly different between patients in stage I to II (early stage, ES) and patients in stage III to IV (advanced stage, AS). Lefse identified that genera Granulicatella and Actinobacillus were significantly enriched in ES, and genus Actinomyces were significantly enriched in AS. PICRUSt2 identified NAD salvage pathway was significantly enriched in AS, which was positively associated with Granulicatella. Patients with intrathoracic metastasis were associated with increased genus Peptostreptococcus and incomplete reductive TCA cycle, which was associated with increased Peptostreptococcus. Genera Parvimonas, Pseudomona and L-valine biosynthesis were positively associated with lymph node metastasis. L-valine biosynthesis was related with increased Pseudomona. Finally, genus Parvimonas were significantly upregulated in adenocarcinoma patients with EGFR mutation. Conclusion: Taxonomy structure differed between different lung cancer stage. The tumor stage, intrathoracic metastasis, lymph node metastasis, and EGFR mutation were associated with alteration of specific airway genera and metabolic function of sputum microbiota.

The Olefin aromatization is an important method for the upgrade of catalytic cracking (FCC) gasoline and production of fuel oil with high octane number. The nano-ZSM-5 zeolite was synthesized via a seed-induced method, a series of modified nano-ZSM-5 zeolite samples with different Ga deposition amount were prepared by Ga liquid deposition method. The XRD, N2 physical adsorption, SEM, TEM, XPS, H2-TPR and Py-IR measurements were used to characterize the morphology, textural properties and acidity of the modified ZSM-5 zeolites. The catalytic performance of the Hexene-1 aromatization was evaluated on a fixed-bed microreactor. The effects of Ga modification on the physicochemical and catalytic performance of nano-ZSM-5 zeolites were investigated. The Ga species in the modified nano-ZSM-5 zeolites mainly exist as the form of Ga2O3 and GaO+, which provide strong Lewis acid sites. The aromatics selectivity over Ga modified nano-ZSM-5 zeolite in the Hexene-1 aromatization was significantly increased, which could be attributed to the improvement of the dehydrogenation activity. The selectivity for aromatics over the Ga4.2/NZ5 catalyst with suitable Ga deposition amount reached 55.4%.

Background: Accumulating studies have suggested the airway microbiota of lung cancer was significantly different from healthy controls. However, little was known about the relationship between airway microbiota and important clinical parameters of lung cancer. In this study, we aimed to explore the association between sputum microbiota and lung cancer stage, lymph node metastasis, intrathoracic metastasis, and Epidermal growth factor receptor (EGFR) gene mutation. Methods: The microbiota of sputum samples from 85 newly diagnosed NSCLC patients were sequenced via 16S rRNA sequencing with V3-V4 region. Sequencing reads were filtered using QIIME2 and clustered against UPARSE. Results: The α diversity and β diversity was significantly different between patients in stage I to II (early stage, ES) and patients in stage III to IV (advanced stage, AS). Lefse identified that genera Granulicatella and Actinobacillus were significantly enriched in ES, and genus Actinomyces were significantly enriched in AS. PICRUSt2 identified NAD salvage pathway was significantly enriched in AS, which was positively associated with Granulicatella. Patients with intrathoracic metastasis were associated with increased genus Peptostreptococcus and incomplete reductive TCA cycle. Enrichment of TCA cycle was associated with increased Peptostreptococcus. Genera Parvimonas, Pseudomona and L-valine biosynthesis were positively associated with lymph node metastasis. L-valine biosynthesis was related with increased Pseudomona. Finally, genus Parvimonas were significantly upregulated in adenocarcinoma patients with EGFR mutation. Conclusion: In conclusion, the taxonomy structure differed between different lung cancer stage. The tumor stage, intrathoracic 1 metastasis, lymph node metastasis, and EGFR mutation were associated with alteration of specific airway genera and metabolic function of sputum microbiota.

Nano-Ga/Al-ZSM-5 zeolites are synthesized by the in situ isomorphous substitution method (I-series) and a secondary synthesis method in a Ga(NO3)3/NH4F solution (S-series). The effects of the Ga in...

Two series of pure nanosized ZSM-22 zeolites (Z-22 (xD) and Z-22 (xS)) with different SiO2/Al2O3 molar ratios are synthesized with 1,6-diaminohexane (DAH) template by the hydrothermal method under dynamic and static crystallization conditions, respectively. The effects of crystallization conditions on the characteristic properties of ZSM-22 zeolites are investigated by XRD, SEM, HR-TEM, N2 adsorption, 29Si and 27Al MAS NMR, NH3-TPD, Py-IR and H2 chemisorption measurements. The results show that Z-22 (xD) samples reveal smaller crystal size, larger mesoporosity, weaker Bronsted acid strength and lower Bronsted acid density compared with Z-22 (xS) samples. The Pd/Z-22 (xD) and Pd/Z-22 (xS) bifunctional catalysts are prepared by loading 0.5 wt% Pd on the corresponding zeolite samples, respectively, and the catalytic performance over all bifunctional catalysts is tested in the hydroisomerization of n-decane. The catalytic test results indicate that the Pd/Z-22 (xD) catalysts show higher selectivity for both mono-branched and multi-branched iso-decanes than those of Pd/Z-22 (xS) catalysts, because of the smaller crystal size and lower Bronsted acidity. Therefore, the dynamic hydrothermal crystallization is an effective way to synthesize ZSM-22 zeolites with improved catalytic behaviors for the n-alkane hydroisomerization.

Nanosized ZSM-5 zeolites (NZ5(x) series) with different SiO2/Al2O3 ratios as well as samples isomorphously substituted by Fe ([Fe,Al]NZ5(x) series) with various SiO2/(Al2O3+Fe2O3) ratios were synthesized by an in situ seed-induced hydrothermal method. The structure, morphology, textural and acidity of catalysts were characterized via XRD, SEM, 27Al and 29Si MAS NMR, UV–vis spectroscopy, XPS, N2 physical adsorption, NH3-TPD and Py-IR. The catalytic performance was assessed by methanol-to-olefins (MTO) reaction and the effect of the textural and acidity of the two series of samples on the catalytic performance was also investigated. The results showed that the catalyst acidity is closely related to the product selectivity in the MTO reaction. Compared with NZ5(x), the [Fe,Al]NZ5(x) samples with smaller particle size, weaker acid strength and fewer Bronsted acid sites displayed a higher selectivity towards C2∼C4 light olefins. Highest selectivity of 82.7% for C2∼C4 light olefins and lowest coke amount of 0.71% after reaction for 50 h was obtained for the [Fe,Al]NZ5(300) catalyst due to the appropriate acidity and improved diffusion properties.

A series of bifunctional catalysts are prepared by loading Pd, Ni2P and bimetallic Pd–Ni2P on di-n-butylamine(DBA)-templated SAPO-31 molecular sieves through either impregnation or impregnation combined with temperature-programmed reduction methods. All bifunctional catalysts are characterized using XRD, N2 adsorption, 27Al and 31P MAS NMR, SEM, TEM, IR spectroscopy of adsorbed pyridine, XPS, H2 chemisorption, ICP, and TG–DTG measurements. The catalytic performance over all prepared bifunctional catalysts is compared for n-hexadecane hydroisomerization. The obtained results demonstrate that the 0.05Pd–4Ni2P/S31 catalyst produces a higher iso-C16 yield of 72.7% with n-C16 conversion of 83.1% compared with the other two catalysts. This result is attributed to two reasons: i) the bimetallic Pd–Ni2P component possesses stronger (de)hydrogenation functionality than Ni2P does, and ii) the bimetallic bifunctional catalyst has a better balance between metal and acid functionality than the monometallic catalysts do. Moreover, the 0.05Pd–4Ni2P/S31 catalyst also shows the best catalytic stability among all catalysts, since the n-C16 conversion and iso-C16 selectivity are still above 80% and 90%, respectively, even after 100 h of long-term testing. Therefore, the present study has provided a novel idea for the design of bimetallic bifunctional catalysts for long-chain n-alkane hydroisomerization.

The effect of the method of introduction of zinc cations and the zinc content in a nanocrystalline zeolite of the ZSM-5 type on the physicochemical and catalytic properties of the material in DME conversion to a mixture of liquid synthetic hydrocarbons has been studied. Zinc is introduced into the catalysts both during the zeolite synthesis and the ion exchange (Zn n Al m NZ5 and ZnNZ5, respectively). The use of nanocrystalline Zn n Al m NZ5 zeolites provides the formation of a mixture of liquid hydrocarbons with a high selectivity of no less than 90%; the liquid hydrocarbons contain more than 70% of isoparaffins and a small amount of aromatic compounds. An increase in the zinc loading of the Zn n Al m NZ5 zeolite from 0.9 to ~3% leads to an increase in the methanol content in the aqueous phase of the liquid product, an increase in the selectivity for liquid hydrocarbons, and a slight increase in the concentration of aromatic and unsaturated hydrocarbons in the mixture. In the presence of the ZnNZ5/Al2O3 catalyst with Zn introduced by ion exchange, the methanol content in the aqueous phase and the aromatics content in the liquid hydrocarbon mixture are significantly higher. The Zn n Al m NZ5 nanozeolites are characterized by a more developed external surface, a higher concentration of mesopores, and higher acidity.

We propose an ultra-thin planar reflective metalens with sub-diffraction-limited and multifunctional focusing. Based on the equal optical path principle, the specific phase distributions for multifunction focusing are derived. Following the formulas, on-center focusing with the characteristics of sub-diffraction-limited, high focusing efficiency (85%) and broadband focusing is investigated in detail. To demonstrate the flexibility of the reflective metalens, off-center and dual spots focusing (at the horizontal and longitudinal directions) are demonstrated. Note that all these focusings are sub-diffraction-limited due to the evanescent-filed enhancement mechanism in our elaborately designed structure. The designed reflective metalens will find important applications in super-resolution imaging, microscopes, and spectroscopic designs.

Nanosized Ga-containing ZSM-5 zeolites were prepared via isomorphous substitution and impregnation followed by characterized using various techniques. The catalytic performance of the zeolites for the aromatization of 1-hexene was investigated. The results indicate that isomorphous substitution promotes the incorporation of Ga heteroatoms into the framework along with the formation of extra-framework GaO+ species ([GaO+]a) that have stronger interactions with the negative potential of the framework. In addition, based on the Py-IR results and catalytic performance, the [GaO+]a species with stronger Lewis acid sites produced a better synergism with moderate Bronsted acid sites and thus improved the selectivity to aromatic compounds. However, the impregnation results in the formation of Ga2O3 phase and small amounts of GaO+ species that are mainly located on the external surface ([GaO+]b), which contribute to weaker Lewis acid sites due to weaker interactions with the zeolite framework. During 1-hexene aromatization, the nanosized Ga isomorphously substituted ZSM-5 zeolite samples (Gax-NZ5) exhibited better catalytic performance compared to the impregnated samples, and the highest aromatic yield (i.e., 65.4 wt%) was achieved over the Ga4.2-NZ5 sample, which contained with the highest Ga content.

Silicoaluminophosphate molecular sieves (SAPO-41) with different SiO2/Al2O3 ratios were synthesized using di-n-butylamine (DBA) as template. All of the samples were characterized by XRD, SEM, TEM, N2 adsorption, 29Si MAS NMR and IR spectroscopy of adsorbed pyridine. Based on the SAPO-41 molecular sieve, a series of nPd/S41(x) bifunctional catalysts with different SiO2/Al2O3 molar ratios (x = 0.2–0.7) and Pd loadings (n = 0.1–1.0 wt%) were prepared. Their catalytic performance was investigated in n-hexadecane hydroisomerization using a fixed-bed flow reactor system. The influence of the acidity and ratio between the accessible Pd sites and Bronsted acid sites $$\left( {{{{{C}_{{Pd}}}} \mathord{\left/ {\vphantom {{{{C}_{{Pd}}}} {{{C}_{{{H}^{+}}}}}}} \right. \kern-\nulldelimiterspace} {{{C}_{{{H}^{+}}}}}}} \right)$$ on the catalytic performance of the prepared samples was studied by adjusting the composition of the initial gel in the synthesis of SAPO-41 molecular sieves and the Pd loadings during preparation process. The results indicated that the 0.8Pd/S41(0.6) catalyst exhibited excellent catalytic performance due to a suitable acidity, high Pd dispersion and appropriate $${{{{C}_{{Pd}}}} \mathord{\left/ {\vphantom {{{{C}_{{Pd}}}} {{{C}_{{{H}^{+}}}}}}} \right. \kern-\nulldelimiterspace} {{{C}_{{{H}^{+}}}}}}$$ ratio (0.58), which was beneficial for the synergetic effect between the (de)hydrogenating and acid functions of the bifunctional catalyst. The highest iso-hexadecane yield of 89% was obtained at an n-hexadecane conversion of 94% over the 0.8Pd/S41(0.6) catalyst.

Nanocrystalline SAPO-11 silicoaluminophosphate molecular sieves with appropriate acidic sites were successfully synthesized by a hydrothermal method using di-n-butylamine (DBA) as a template. A series of bifunctionalPd/SAPO-11 catalysts with different ratios between the accessible metal Pd sites and acid sites was prepared by adjusting the Pd loading, and the catalytic performance of the prepared samples was tested in the hydroisomerization of n-C10. The results showed that the activity of xPd/S11 in the hydroisomerization of n-C10 and the selectivity to i-C10 were dependent upon both the ratio between the metal and acid sites (CPd/CH+) and the effective acid sites number between two metal Pd sites (nas) in the xPd/S11 catalysts. It was concluded that the appropriate values of CPd/CH+ (0.09 ≤ CPd/CH+ ≤ 0.27) and nas values of ∼1.5, observed for the 0.1Pd/S11 and 0.3Pd/S11 bifunctional catalysts, were beneficial for the synergetic effect between hydrogenating/dehydrogenation and acid functions. The highest selectivity of 89.8% to i-C10 was obtained at n-C10 conversion of 90.8% over the 0.3Pd/S11 catalyst, which could be considered as an ideal Pd/SAPO-11 catalyst for n-C10hydroisomerization.

Recently, metamaterial absorbers have received tremendous amount of interest because of their remarkable ability to manipulate the amplitude, phase, and polarization of light. However, most absorbers rely on the direct coupling of electric or magnetic field with external excitation, which lead to inevitable energy leakage to the surrounding environment and depress the quality factor of the structure. In this work, we investigate the multiband absorption property by exciting dark plasmonic modes in reflective symmetric and asymmetric metamaterials. Theoretically, the existence of dark plasmonic modes in asymmetric metamaterials is unambiguously illustrated by the improved eigen-mode theory. With the introduction of asymmetry, dark modes in metamaterials can be easily excited by normal incident plane wave. Moreover, we also directly excite the dark modes in symmetric absorber with oblique incidence. The dark modes splitting mechanism is also clarified with the excitation of designer surface plasmon. Dominated by magnetic dipole or higher-order multipole, these dark modes possess high quality factors (Q). Numerical results indicate that the metamaterial absorber maintains high absorbance within a wide-angle incidence (0~50°). The high Q asymmetric metamaterial absorber can be an excellent candidate for multiband plasmonic sensor.

Microscale and nanoscale HZSM-5 zeolites, MZ5 and NZ5, have been successfully synthesized by using a template-free and an in situ seed-induced method, respectively; the synthesized zeolites were then modified by Zn impregnation to obtain Zn-modified catalysts, Zn/MZ5 and Zn/NZ5. Various techniques, including XRD, SEM, 27Al MAS NMR, N2 adsorption, H2-TPR, XPS, NH3-TPD, Py-IR and TG/DTA, were used in the characterization of the catalysts, and their catalytic performance in the aromatization of 1-hexene was investigated to correlate the particle size, acidity and catalytic behavior. Compared to MZ5, the NZ5 sample exhibited better catalytic stability due to its smaller particle size and weaker acid strength. Both Zn-modified catalysts showed increased BTX yield because of the smaller B/L ratio and newly formed stronger Lewis acid sites provided by the [ZnOZn]2+ species, which effectively facilitated the dehydrogenation process in the aromatization. The highest BTX yield of 57.93 wt% was obtained for the Zn/NZ5 sample.

We propose a dielectric metasurface of 34 phase level, to reproduce the holographic image in the visible region. With normal incident circular polarized illumination, imaging efficiency as high as 59.72% is achieved at 560 nm wavelength. Consisting of non-resonant meta-cells, the proposed polarization-insensitive dielectric metasurface performs well in a broad band from 480 nm to 660 nm. Numerical results also indicate that the metasurface hologram maintains high fidelity within a wide-angle incidence (0–25°), and show high tolerance to fabrication errors. The high efficiency, broadband, wide-angle, and high fabrication tolerance metasurface based on the hologram, can be used in the fields of display, security, data storage, and information processing.

Defatted soybean meal is a popular raw material for soybean protein products. Thermal properties of soybean meal, which is vital for its application in extruded texturized soybean protein, are influenced by storage time and processing temperature. Thus, low-temperature defatted soybean meal (LSM), low-temperature defatted one-year-stored-soybean meal (LSSM) and high-temperature defatted soybean meal (HSM) were selected to investigate the thermal transition and decomposition properties by pH induction with phosphate using differential scanning calorimetry and thermal gravimetric analysis. The results showed that the peak temperature of 11S (glycinin) in phosphate buffer at pH 7 is significantly higher than that in deionized water. Break temperatures of LSM and LSSM at around 110 °C in deionized water are significantly higher than that in phosphate buffer at pH 7; however, the break temperature of LSM at 300 °C in deionized water is significantly lower than that in phosphate buffer at pH 7. In contrast to LSM, ∆H of LSSM in phosphate buffer at pH 7 is significantly lower than in deionized water. It is thus concluded that phosphate stabilizes the soybean protein quaternary structure, enhances protein–protein interactions and weakens protein-water interactions. Protein association occurs in LSSM during soybean storage, while HSM protein appears to be insensitive to these changes.

There were few knowledge concerned correlation between lung microbiome and different clinicopathology of lung cancer. Bronchial washing fluid (BWF) and sputum are commonly used sample types but there was no study comparing difference of microbiome between these two in lung cancer. In this study, we aimed to compare difference of microbiome between these two sample types and characterize lung microbiome in squamous cell lung carcinoma with (SCC_M1) or without distant metastasis (SCC_M0) and lung adenocarcinoma with (AD_M1) or without distant metastasis (AD_M0). We collected 40 BWF samples and 52 sputum samples from newly diagnosed lung cancer patients. Bacterial species were sequenced via 16S rRNA sequencing. Phylum Proteobacteria in BWF samples were significantly higher than sputum samples (Wilcoxon test, P = 0.003). At phylum level, microbiome of BWF samples was more similar to that of lung cancer tissues reported in the previous literature. LEFse analysis showed that in BWF group, genera Veillonell, Megasphaera, Actinomyces and Arthrobacter in AD_M0 were significantly higher than those in SCC_M0, and genera Capnocytophaga and Rothia in AD_M1 were significantly lower than that in SCC_M1. Compared with AD_M0, genus Streptococcus of AD_M1 was significantly lower, and genera Veillonella and Rothia in SCC_M1 were significantly higher than that in SCC_M1. Our study suggested that BWF samples might better reflect the microbiome of lung cancer tissues. In different metastatic states of lung cancer, differential genera between squamous cell carcinoma and adenocarcinoma were different. And in different histologic types of lung cancer, distant metastasis-related genera were not the same.