Multi-functional terahertz metasurface for a vortex beam, multi-channel focusing, polarization conversion, and broadband absorption based on vanadium dioxide.

Although terahertz metasurface devices have been widely studied, thus far, metasurfaces can rarely manipulate both circularly and linearly polarized incident waves. In this paper, taking advantage of the phase transition characteristics of vanadium dioxide (V O 2), a multi-functional terahertz metasurface for a vortex beam, multi-channel focusing, polarization conversion, and broadband absorption is proposed. When V O 2 is in the insulating state, a vortex beam is generated at 1.2 THz when the circularly polarized wave is incident on the metasurface. Meanwhile, the multi-channel focusing is realized at 1.0 THz, and the cross-polarization conversion rate can reach more than 90% at the frequencies of 0.6 THz, 1.1 THz, and 1.6 THz when the y-polarized wave is incident vertically. When V O 2 is in the metallic state, the metasurface achieves close to 95% absorption in the range of 0.8-1.5 THz. The designed metasurface has tunability and multi-functional characteristics, which have potential applications in wireless communication.

Self-Assembled Modified Soy Protein/Dextran Nanogel Induced by Ultrasonication as a Delivery Vehicle for Riboflavin.

A simple and green approach was developed to produce a novel nanogel via self-assembly of modified soy protein and dextran, to efficiently deliver riboflavin. First, modified soy protein was prepared by heating denaturation at 60 °C for 30 min or Alcalase hydrolysis for 40 min. Second, modified soy protein was mixed with dextran and ultrasonicated for 70 min so as to assemble nanogels. The modified soy protein-dextran nanogels were characterized by Fourier-transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) and ζ-potential studies to confirm the formation of NGs. Transmission electron microscopy (TEM) revealed the NGs to be spherical with core-shell structures, in the range of 32-40 nm size. The nanogels were stable against various environmental conditions. Furthermore, the particle size of the nanogels hardly changed with the incorporation of riboflavin. The encapsulation efficiency of nanogels was found to be up to 65.9% at a riboflavin concentration of 250 µg/mL. The nanogels exhibited a faster release in simulated intestine fluid (SIF) compared with simulated gastric fluid (SGF). From the results obtained it can be concluded that modified soy protein-dextran nanogels can be considered a promising carrier for drugs and other bioactive molecule delivery purposes.

Salinity decreases methane concentrations in Chinese lakes.

Lakes are important sources of methane (CH4), and understanding the influence of environmental factors on CH4 concentration in lake water is crucial for accurately assessing CH4 emission from lakes. In this study, we investigated CH4 concentration in two connected Tibetan Plateau lakes, Lake Keluke (an open freshwater lake) and Lake Tuosu (a closed saline lake), through in-situ continuous measurements taken in different months from 2021 to 2023. The results show substantial spatial and seasonal variations in CH4 concentrations in the two lakes, while the CH4 concentrations in Lake Keluke are consistently higher than those in Lake Tuosu for each month. Despite sharing similar environmental conditions due to connected (e.g. pH, water temperature, dissolved oxygen content, and total organic carbon content), the critical difference between the two lakes is their salinity. This implies that salinity is the critical factor contributing to the decrease in CH4 concentrations in Lake Tuosu, possibly due to the changes in microbial species between freshwater and brackish/saline lakes. Additionally, to further validate the effect of salinity on CH4 concentrations in lake water, we compared the CH4 concentrations of 33 lakes (including 5 saline lakes and 28 freshwater lakes) from the Tibetan Plateau, Chinese Loess Plateau, and Yangtze Plain, and found that saline lakes consistently exhibit lower CH4 concentrations (avg. 0.08 µmol/L), while freshwater lakes generally display higher CH4 concentrations (avg. 1.25 µmol/L) with considerable fluctuations. Consequently, freshwater and saline lakes exhibit distinct CH4 emissions, which could be used for more accurate estimation of global CH4 emission from lakes.

High-precision zinc isotopic characterization of twenty soil reference materials from China determined by MC-ICP-MS.

Zinc isotopic ratios serve as powerful tools for tracing biochemical cycling of metals at Earth's surface, including the distribution, transportation, and enrichment of zinc (Zn) in soil. To conduct such studies and enable inter-laboratory comparisons, high-precision Zn isotopic measurements require the use of soil reference materials (RMs). However, there have been limited reports on the high-precision Zn isotope ratios of soil RMs thus far. In this study, we have developed a two-step Zn chemical separation protocol utilizing Bio-Rad AG MP-1M resin columns. This method has demonstrated excellent reproducibility for measuring the external δ66Zn values (relative to JMC-Lyon) of standard soil reference materials over an extended time period, with a better than 0.06‰ (2SD) precision. Remarkably, this study is the first to report the Zn isotopic compositions of 20 soil reference materials from various soil types in China. With the exception of one sample obtained from a mining area, the Zn isotopic compositions of all the analyzed soil reference materials exhibit remarkable similarity, with an average δ66Zn value of 0.31 ± 0.12‰, which aligns closely with the values observed in igneous rocks. The exceptional sample, with a higher δ66Zn value of 0.61 ± 0.02‰, indicates potential contamination during mining activities.

Alpine permafrost could account for a quarter of thawed carbon based on Plio-Pleistocene paleoclimate analogue.

Estimates of the permafrost-climate feedback vary in magnitude and sign, partly because permafrost carbon stability in warmer-than-present conditions is not well constrained. Here we use a Plio-Pleistocene lacustrine reconstruction of mean annual air temperature (MAAT) from the Tibetan Plateau, the largest alpine permafrost region on the Earth, to constrain past and future changes in permafrost carbon storage. Clumped isotope-temperatures (Δ47-T) indicate warmer MAAT (~1.2 °C) prior to 2.7 Ma, and support a permafrost-free environment on the northern Tibetan Plateau in a warmer-than-present climate. Δ47-T indicate ~8.1 °C cooling from 2.7 Ma, coincident with Northern Hemisphere glacial intensification. Combined with climate models and global permafrost distribution, these results indicate, under conditions similar to mid-Pliocene Warm period (3.3-3.0 Ma), ~60% of alpine permafrost containing ~85 petagrams of carbon may be vulnerable to thawing compared to ~20% of circumarctic permafrost. This estimate highlights ~25% of permafrost carbon and the permafrost-climate feedback could originate in alpine areas.

The differences in the nitrogen isotope composition between a maize hybrid and its parents.

Understanding of nitrogen stable isotope variation in maize hybrids might help obtaining information on nitrogen absorption and distribution in different maize hybrids. In this study, we examined the nitrogen isotopic composition of different parts of maize hybrids under a laboratory culture experiment. The results showed that the δ15N values of different parts of the maize hybrid and its parents were ordered as follows: δ15Nstem>δ15Nleaf>δ15Nroot. The variation pattern of δ15N between the roots and leaves(Δδ15Nroot-leaf) of the maize hybrid was the same as that of δ15N between the roots and stems (Δδ15Nroot-stem). Therefore, the order of Δδ15Nroot-leaf as well as Δδ15Nroot-stem was as follows: Δδ15Nroot-leaf of the maize hybrid>Δδ15Nroot-leaf of the female parent (T4)>Δδ15Nroot-leaf of the male parent (803) and Δδ15Nroot-stem of the maize hybrid>Δδ15Nroot-stem of the female parent (T4)>Δδ15Nroot-stem of the male parent (803). This order is consistent with heterosis, indicating that differences in δ15N reflect the phenomenon of heterosis. The present study provides data in support of using the isotope technique to determine nitrogen distributions inside a plant and guide crossbreeding.

Inhibitory effect of small interfering RNA on dengue virus replication in mosquito cells.

BACKGROUND: Dengue viruses (DENs) are the wildest transmitted mosquito-borne pathogens throughout tropical and sub-tropical regions worldwide. Infection with DENs can cause severe flu-like illness and potentially fatal hemorrhagic fever. Although RNA interference triggered by long-length dsRNA was considered a potent antiviral pathway in the mosquito, only limited studies of the value of small interfering RNA (siRNA) have been conducted. RESULTS: A 21 nt siRNA targeting the membrane glycoprotein precursor gene of DEN-1 was synthesized and transfected into mosquito C6/36 cells followed by challenge with DEN. The stability of the siRNA in cells was monitored by flow cytometry. The antiviral effect of siRNA was evaluated by measurement of cell survival rate using the MTT method and viral RNA was quantitated with real-time RT-PCR. The presence of cells containing siRNA at 0.25, 1, 3, 5, 7 days after transfection were 66.0%, 52.1%, 32.0%, 13.5% and 8.9%, respectively. After 7 days incubation with DEN, there was reduced cytopathic effect, increased cell survival rate (76.9 ± 4.5% vs 23.6 ± 14.6%) and reduced viral RNA copies (Ct value 19.91 ± 0.63 vs 14.56 ± 0.39) detected in transfected C6/36 cells. CONCLUSIONS: Our data showed that synthetic siRNA against the DEN-1 membrane glycoprotein precursor gene effectively inhibited DEN-1 viral RNA replication and increased C6/36 cell survival rate. siRNA may offer a potential new strategy for prevention and treatment of DEN infection.

Effects of key reaction parameters on the reductive dechlorination of chloroform with Pd/Fe0 bimetal in aqueous solution.

In this study, bimetallic Pd/Fe(0) particles were synthesized and employed to reduce chloroform in aqueous solution. The investigation emphasized on the effects of some key reaction parameters including Pd/Fe(0) dosage, pH, oxidation-reduction potential (ORP) and presence of anions on the reductive dechlorination reaction. The experimental results showed that high Pd/Fe(0) dosage, low initial pH and low ORP benefited the reductive dechlorination of chloroform. The ORP values in the aqueous chloroform solution bubbled with different gases of N(2), O(2) and air varied significantly and the efficiency of chloroform degradation under different atmospheres followed an order from high to low as N(2) > air > O(2). The experiments also demonstrated that SO(4)(2 -) and NO(3)(-) ions inhibited the dechlorination reaction significantly, while H(2)PO(4)(-) ion had no significant influence on the dechlorination.

Microbial fuel cell with an azo-dye-feeding cathode.

Microbial fuel cells (MFCs) were constructed using azo dyes as the cathode oxidants to accept the electrons produced from the respiration of Klebsiella pneumoniae strain L17 in the anode. Experimental results showed that a methyl orange (MO)-feeding MFC produced a comparable performance against that of an air-based one at pH 3.0 and that azo dyes including MO, Orange I, and Orange II could be successfully degraded in such cathodes. The reaction rate constant (k) of azo dye reduction was positively correlated with the power output which was highly dependent on the catholyte pH and the dye molecular structure. When pH was varied from 3.0 to 9.0, the k value in relation to MO degradation decreased from 0.298 to 0.016 micromol min(-1), and the maximum power density decreased from 34.77 to 1.51 mW m(-2). The performances of the MFC fed with different azo dyes can be ranked from good to poor as MO>Orange I>Orange II. Furthermore, the cyclic voltammograms of azo dyes disclosed that the pH and the dye structure determined their redox potentials. A higher redox potential corresponded to a higher reaction rate.

Effects of structure of anodic TiO(2) nanotube arrays on photocatalytic activity for the degradation of 2,3-dichlorophenol in aqueous solution.

In this study titanium dioxide nanotube (TNT) arrays were prepared by an anodic oxidation process with post-calcination. The morphology and structure of the TNT films were studied by field-emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Photocatalytic activity of the TNT films was evaluated in terms of the degradation of 2,3-dichlorophenol in aqueous solution under UV light irradiation. The effects of the nanotube structure including tube length and tube wall thickness, and crystallinity on the photocatalytic activity were investigated in detail. The results showed that the large specific surface area, high pore volume, thin tube wall, and optimal tube length would be important factors to achieve the good performance of TNT films. Moreover, the TNT films calcined at 500 degrees C for 1h with the higher degree of crystallinity exhibited the higher photocatalytic activity than other TNT films calcined at 300 and 800 degrees C. Consequently, these results indicate that the optimization of TiO(2) nanotube structures is critical to achieve the high performance of photocatalytic reaction.

Aqueous oxidation of dimethyl phthalate in a Fe(VI)-TiO(2)-UV reaction system.

The application of a combined ferrate-photocatalysis process for the aqueous degradation of dimethyl phthalate (DMP) has been studied. The behaviour of the Fe(VI)-TiO(2)-UV process at pH 9 in the presence and absence of dissolved oxygen (DO) has been compared and significant differences have been found. In comparative tests under N(2) and O(2) bubbling, the chemical reduction rate of ferrate as conduction band electron acceptor was similar, but the resulting degradation of DMP was substantially lower in the presence of oxygen. It is speculated that the presence of oxygen leads to the formation of Fe-O-(organic) complex species that adsorb to, and deactivate, the surface of the photocatalyst. The presence of surface-adsorbed complex species was indicated by FTIR spectroscopy and a reduced TiO(2) adsorption capacity for DMP. In the presence of typical environmental levels of DO ( approximately 9mgL(-1)), the Fe(VI)-TiO(2)-UV process achieved a modest degree of DMP degradation (40% in 120min).

Reaction pathways of dimethyl phthalate degradation in TiO2-UV-O2 and TiO2-UV-Fe(VI) systems.

The photocatalytic degradation of dimethyl phthalate (DMP) in aqueous TiO2 suspension under UV illumination has been investigated using oxygen (O2) and ferrate (Fe(VI)) as electron acceptors. The experiments demonstrated that Fe(VI) was a more effective electron acceptor than O2 for scavenging the conduction band electrons from the surface of the catalyst. Some major intermediate products from DMP degradation were identified by HPLC and GC/MS analyses. The analytical results identified dimethyl 3-hydroxyphthalate and dimethyl 2-hydroxyphthalate as the two main intermediate products from the DMP degradation in the TiO2-UV-O2 system, while in contrast phthalic acid was found to be the main intermediate product in the TiO2-UV-Fe(VI) system. These findings indicate that DMP degradation in the TiO2-UV-O2 and TiO2-UV-Fe(VI) systems followed different reaction pathways. An electron spin resonance analysis confirmed that hydroxyl radicals existed in the TiO2-UV-O2 reaction system and an unknown radical species (most likely an iron-oxo species) is suspected to exist in the TiO2-UV-Fe(VI) reaction system. Two pathway schemes of DMP degradation in the TiO2-UV-O2 and TiO2-UV-Fe(VI) reaction systems are proposed. It is believed that the radicals formed in the TiO2-UV-O2 reaction system preferably attack the aromatic ring of the DMP, while in contrast the radicals formed in the TiO2-UV-Fe(VI) reaction systems attack the alkyl chain of DMP.

Effects of dissolved oxygen, pH, and anions on the 2,3-dichlorophenol degradation by photocatalytic reaction with anodic TiO(2) nanotube films.

In this study, the highly-ordered TiO(2) nanotube (TNT) arrays on titanium sheets were prepared by an anodic oxidation method. Under UV illumination, the TNT films demonstrated the higher photocatalytic activity in terms of 2,3-dichlorophenol (2,3-DCP) degradation in aqueous solution than the conventional TiO(2) thin films prepared by a sol-gel method. The effects of dissolved oxygen (DO) and pH on the photocatalytic degradation of 2,3-DCP were investigated. The results showed that the role of DO in the 2,3-DCP degradation with the TNT film was significant. It was found that 2,3-DCP in alkaline solution was degraded and dechlorinated faster than that in acidic solution whereas dissolved organic carbon removal presented an opposite order in dependence of pH. In the meantime, some main intermediate products from 2,3-DCP degradation were identified by a (1)H NMR technique to explore a possible degradation pathway. A major intermediate, 2-chlororesorcinol, was identified from the 2,3-DCP decomposition as a new species compared to the findings in previous reports. Photocatalytic deactivation was also evaluated in the presence of individual anions (NO(3)(-), Cl(-), SO(4)(2-), and H(2)PO(4)(-)). The inhibition degree of photocatalytic degradation of 2,3-DCP caused by these anions can be ranked from high to low as SO(4)(2-)>Cl(-)>H(2)PO(4)(-)>NO(3)(-). The observed inhibition effect can be attributed to the competitive adsorption and the formation of less reactive radicals during the photocatalytic reaction.

Effects of peptizing conditions on nanometer properties and photocatalytic activity of TiO2 hydrosols prepared by H2TiO3.

TiO2 hydrosols were prepared from metatitanic acid (H2TiO3) by chemical precipitation-peptization method under various peptizing conditions. The effects of peptizing conditions on nanosized properties and photocatalytic activity of TiO2 hydrosols were investigated. The crystal structure, crystallinity, particle size distribution, and transparency (T%) of as-obtained hydrosols were characterized by means of X-ray diffraction, transmission electron microscopy, light-scattering size analyzer, and UV-vis transmittance spectra. The results showed that the properties of hydrosols depended on peptizing conditions including a molar ratio of H+/Ti, temperature, and solid content. The photoactivity of TiO2 hydrosols was evaluated in terms of the degradation of rhodamine B (RhB) in aqueous solution, and formaldehyde (HCHO) and methyl mercaptan (CH3SH) in gaseous phase. The results showed that increase in H+/Ti ranging 0.19-0.75 led to the decrease in particle size and the increase in transparency. With increasing of temperature, particle sizes increased while the transparency and photoactivity decreased steadily when the temperature was higher than 65 degrees C. The particle size, transparency and photoactivity of the hydrosols hardly depended on solid content when it was not less than 2%. It should be confirmed that the hydrosols with higher crystallinity, smaller particle size and higher transparency could have the higher photoactivity for the degradation of RhB, CH3SH, and HCHO. In this study, the optimal peptizing conditions were determined to be H+/Ti=0.75, temperature=65 degrees C and solid content=2-6%.

TiO2 hydrosols with high activity for photocatalytic degradation of formaldehyde in a gaseous phase.

Two types of TiO2 hydrosols (TOSO and HTO) were prepared from titanium sulfate (TiOSO4) and metatitanic acid (H2TiO3) by a chemical precipitation-peptization method, respectively. The prepared hydrosols were characterized by means of X-ray diffraction, particle size distribution, scanning electron microscopy, UV-vis spectroscopy, Fourier transform infrared spectroscopy, Brunauer-Emmett-Teller and Barret-Joyner-Halender methods. The results showed that the TiO2 hydrosols with an anatase crystal structure had smaller particle sizes, higher surface areas, larger pore volume, and higher transparence than Degussa P-25 suspension. The photocatalytic activity of the TiO2 hydrosols was evaluated for formaldehyde degradation under UVA illumination in a gaseous phase. The results demonstrated that the photocatalytic activity with the catalyst loading of 2mgcm(-2) was ranked as an order of HTO>TOSO>P-25. The photocatalytic activity was further studied using the HTO catalyst under different experimental conditions. The results showed that catalyst loading, relative humidity, and initial concentration could influence the efficiency of HCHO photocatalytic degradation. It was found that a catalyst loading of more than 2mgcm(-2) and a relative humidity of 55% were two essential conditions for achieving the best performance under these experimental conditions. The repeated experiments indicated that the HTO catalyst was reasonably stable and could be repeatedly used for the HCHO oxidation under UVA irradiation. This investigation would be helpful to promote the application of TiO2 photocatalytic technique for indoor air purification.

The oxidative degradation of 2-mercaptobenzothiazole at the interface of beta-MnO2 and water.

To investigate the oxidative degradation of organic pollutants at the interface of manganese oxides and water, beta-MnO2 was prepared and its crystal structure and the specific surface area were examined by X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET) methods, respectively. 2-Mercaptobenzothiazole (MBT) as a model chemical was used to study its oxidative degradation reaction in beta-MnO2 suspension. The experimental results showed that MBT was effectively degraded and mineralized into SO4(2-) and NO3- by beta-MnO2. In the meantime, it was found that beta-MnO2 could be reductively dissolved, and aqueous and adsorbed Mn2+ was generated. The kinetics of MBT degradation by beta-MnO2 is a function of initial MBT concentration, beta-MnO2 dosage and pH value. At pH 4.6, apparent reaction orders with respect to initial MBT concentration and beta-MnO2 dosage were determined to be 0.88 and 0.27, respectively. The initial reaction rate (rinit) is of pH dependence with a reaction order of -0.36. The thermodynamics of MBT degradation by beta-MnO2 was also investigated, and the apparent activation energy was calculated to be 5.62 kJ/mol. The inhibited effect of carboxylic acids (oxalic, citric, tartaric, and malic acids) or metal ions (Ni2+, Ca2+, Mn2+ and Cr3+) on the oxidative degradation of MBT by beta-MnO2 was also investigated. This investigation will give some new insights for understanding the interaction of organic pollutants with manganese oxides in natural soils and sediments.

Synthesis, characterization and re-activation of a Fe0/Ti system for the reduction of aqueous Cr(VI).

The conventionally employed zero-valent iron (Fe0) particles suffer a formation of surface oxides to lower their activity prior to use. During their using process for contaminant remediation, such oxide formation is also encountered, while the cumbersome handling of particles impedes the Fe0 recovery. To conquer the drawbacks, a Fe0 film was synthesized by electrodepositing ferrous ion cathodically on titanium (Ti) substrate to form a new Fe0/Ti system. X-ray diffraction (XRD) revealed that the freshly electrodeposited (FED) Fe0 film was free of oxides, which was attributed to the particularity of electrodeposition procedure. Reduction results of 10.0 mg/L chromium [Cr(VI)] indicated that the FED Fe0 film had higher activity than the oxide-covered counterpart. Further analysis of the pH-dependent Cr(VI) reduction reaction indicated that the Fe0/Ti system kept its activity and could be reused for further Cr(VI) reduction at pH 3.0 and 4.0, while it was inactivated at pH 5.0 and 7.0. Due to the easy handling of Fe0/Ti system, the inactivated Fe0 was recovered significantly through a cathodic reduction.

Quantifying biodegradable organic matter in polluted water on the basis of coulombic yield.

Biodegradable organic matter (BOM) in polluted water plays a key role in various biological purification technologies. The five-day biochemical oxygen demand (BOD5) index is often used to determine the amount of BOM. However, standard BOD5 assays, centering on dissolved oxygen detection, have long testing times and often show severe deviation (error ≥ 15%). In the present study, the coulombic yield (Q) of a bio-electrochemical degradation process was determined, and a new index for BOM quantification was proposed. The Q value represents the quantity of transferred electrons from BOM to oxygen, and the corresponding index was defined as BOMQ. By revealing Q-BOM stoichiometric relationship, we were able to perform a BOMQ assay in a microbial fuel cell involved technical platform. Experimental results verified that 5-500mgL-1 of BOMQ toward artificial wastewater samples could be directly obtained without calibration in several to dozens of hours, leaving less than 5% error. Moreover, the BOMQ assay remained accurate and precise in a wide range of optimized operational conditions. A ratio of approximately 1.0 between the values of BOMQ and BOD5 toward artificial and real wastewater samples was observed. The rapidity, accuracy, and precision of the measurement results are supported by a solid theoretical foundation. Thus, BOMQ is a promising water quality index for quantifying BOM in polluted water.

The first calibration of an aminiumyl radical ion clock: why N-cyclopropylanilines may be poor mechanistic probes for single electron transfer.

Using direct and indirect electrochemical methods, the rate constant for ring opening of the radical cation generated from N-cyclopropyl-N-methylaniline was found to be 4.1 x 10(4) s(-1).

Degradation of 2,4-dichlorophenol with a novel TiO2/Ti-Fe-graphite felt photoelectrocatalytic oxidation process.

Degradation of 2,4-dichlorophenol (2,4-DCP) was studied in a novel three-electrode photoelectrocatalytic (PEC) integrative oxidation process, and the factors influencing the degradation rate, such as applied current, flow speed of O2, pH, adscititious voltage and initial 2,4-DCP concentration were investigated and optimized. H2O2 was produced nearby cathode and Fe2+ continuously generated from Fe anode in solution when current and O2 were applied, so, main reactions, H2O2-assisted TiO2 PEC oxidation and E-Fenton reaction, occurred during degradation of 2,4-DCP in this integrative system. The degradation ratio of 2,4-DCP was 93% in this integrative oxidation process, while it was only 31% in E-Fenton process and 46% in H2O2-assisted TiO2 PEC process. So, it revealed that the degradation of 2,4-DCP was improved greatly by photoelectrical cooperation effect. By the investigation of pH, it showed that this integrative process could work well in a wide pH range from pH 3 to pH 9.