Iron Nanoparticles Protected by Chainmail-structured Graphene for Durable Electrocatalytic Nitrate Reduction to Nitrogen

The electrochemical nitrate reduction reaction (NO₃RR) is an appealing technology for regulating the nitrogen cycle. Metallic iron is one of the well-known electrocatalysts for NO₃RR, but it suffers from poor durability due to leaching and oxidation of iron during the electrocatalytic process. In this work, a graphene-nanochainmail-protected iron nanoparticle (Fe@Gnc) electrocatalyst is reported. It displays superior nitrate removal efficiency and high nitrogen selectivity. Notably, the catalyst delivers exceptional stability and durability, with the nitrate removal rate and nitrogen selectivity remained ≈96 % of that of the first time after up to 40 cycles (24 h for one cycle). As expected, the conductive graphene nanochainmail provides robust protection for the internal iron active sites, allowing Fe@Gnc to maintain its long-lasting electrochemical nitrate catalytic activity. This research proposes a workable solution for the scientific challenge of poor lasting ability of iron-based electrocatalysts in large-scale industrialization.     

Nickel-Catalyzed Markovnikov-Selective Hydrodifluoromethylation of Alkynes Using BrCF2H

A Markovnikov-selective hydrodifluoromethylation of alkynes with BrCF₂H via nickel catalysis is described. This protocol proceeds via a migratory insertion of nickel hydride to alkyne followed by a CF₂H-coupling, enabling straightforward access to diverse branched CF₂H-alkenes with high efficiency and exclusive regioselectivity. The mild condition applies to a wide array of aliphatic and aryl alkynes with good functional group compatibility. Mechanistic studies are presented to support the proposed pathway.     

钯（II）-克林霉素-卤代荧光素体系的共振瑞丽散射光谱及其分析应用

在pH为5.0-5.4的乙酸-乙酸钠缓冲溶液中,克林霉素（Clin）与钯(Ⅱ)形成螯合阳离子,它能进一步与二碘荧光素（DIF）,赤藓红（Ery）,曙红Y（EY）等卤代荧光素类染料反应形成1：1：1的三元离子缔合物,此时将引起吸收光谱变化和荧光猝灭,同时还导致共振瑞利散射(RRS)的急剧增强并产生新的RRS光谱,钯(Ⅱ)-克林霉素与DIF,Ery和EY形成产物的最大散射波长分别位于285,287,32 1nm处,另外还有些较弱的散射峰存在。散射增强（ΔI）与克林霉素浓度在一定范围内成正比,可用于克林霉素的定量测定。对于DIF,Ery和EY体系的线性范围和检出限分别为0.025-2.1μg•mL-1和7.8 ng•mL-1,0.053-2.4μg•mL-1和16.0 ng•mL-1;以及0.038-2.4μg•mL-1和11.0 ng•mL-1。本文研究了适宜的反应条件,考察了共存物质的影响,表明方法有较好的选择性,基于三元离子缔合物的RRS光谱,发展了一种高灵敏、简便快速测定克林霉素的新方法。文中还对离子缔合物的组成,结构和反应机理,以及离子缔合物对吸收,荧光和RRS光谱的影响进行了讨论。     

Direct electron transfer of Mb on chitosan/single-wall carbon nanotubes film modified Au electrode and its interaction with cimetidine

Three methods were used to immobilize myoglobin (Mb) on chitosan/single-wall carbon nanotubes (SWNTs) film, and direct electrochemistry of the immobilized Mb was extensively investigated. Immobilized Mb displayed a couple of stable and well-defined redox peaks with the formal potential (E’) is at about −0.27 V (vs. SCE) in 0.1 M phosphate buffer solution (pH 7.0). The E′ was shifted linearly with pH in the range of 3.0 to 9.0 with a slope of −54.1 mV pH⁻¹, denoting that one-electron accompanies with one-proton transfer in electrode reaction process. The FT-IR spectroscopy and UV-vis spectroscopy showed that Mb on the film retained its secondary structure similar to its native state. The experimental results demonstrated that the immobilized Mb exhibited excellent electrocatalytic activity to reduction of cimetidine with a significant lowering of overpotential. The electrocatalytic current was proportional to the concentration of cimetidine over the range from 9.80 × 10⁻⁶ to 1.1 × 10⁻⁴ M; the detection limit is 8.40 × 10⁻⁶ M (signal-to-noise ratio of 3). The proposed method exhibits good sensitivity, stability and reproducibility. Published in Russian in Elektrokhimiya, 2008, Vol. 44, No. 2, pp. 235–243. The text was submitted by the authors in English     

Cyclometalated platinum(II) complex with strong and broadband nonlinear optical response

A cyclometalated platinum(II) 4,6-diphenyl-2,2'-bipyridyl pentynyl complex (1) has been synthesized and structurally characterized. Its photophysical and third-order nonlinear optical properties have been systematically investigated. This complex exhibits a metal-to-ligand charge-transfer (1MLCT) absorption band between 400 and 500 nm and a 3MLCT emission band at approximately 591 nm at room temperature with a lifetime of approximately 100 ns. At 77 K, the emission band blue shifts. Both UV-vis absorption and emission spectra show solvent dependence. Low-polarity solvents cause a bathochromic shift of the absorption and emission bands. This complex also exhibits a broad and strong transient absorption from the near-UV to the near-IR spectral region, with a triplet absorption coefficient of 4933 L mol(-1) cm(-1) at 585 nm and a quantum yield of 0.51 for the formation of the triplet excited state. Nonlinear transmission and Z-scan techniques were employed to characterize the third-order nonlinearities of this complex. A strong and broadband reverse saturable absorption was observed for nanosecond and picosecond laser pulses due to the reduced ground-state absorption in the visible spectral range. It also exhibits a self-defocusing effect at 532 nm for nanosecond laser pulses. The excited-state absorption cross section deduced from the open-aperture Z-scan increases at longer wavelengths, with an exceptionally large ratio of excited-state absorption to ground-state absorption of 160 at 570 nm for picosecond laser pulses.     

Approximately solving multiobjective linear programmes in objective space and an application in radiotherapy treatment planning

In this paper, we propose a modification of Benson’s algorithm for solving multiobjective linear programmes in objective space in order to approximate the true nondominated set. We first summarize Benson’s original algorithm and propose some small changes to improve computational performance. We then introduce our approximation version of the algorithm, which computes an inner and an outer approximation of the nondominated set. We prove that the inner approximation provides a set of -nondominated points. This work is motivated by an application, the beam intensity optimization problem of radiotherapy treatment planning. This problem can be formulated as a multiobjective linear programme with three objectives. The constraint matrix of the problem relies on the calculation of dose deposited in tissue. Since this calculation is always imprecise solving the MOLP exactly is not necessary in practice. With our algorithm we solve the problem approximately within a specified accuracy in objective space. We present results on four clinical cancer cases that clearly illustrate the advantages of our method.     

Interfacial Assembly of Nanocrystals on Nanofibers with Strong Interaction for Electrocatalytic Nitrate Reduction

One-dimensional fiber architecture serves as an excellent catalyst support. The orderly arrangement of active materials on such a fiber substrate can enhance catalytic performance by exposing more active sites and facilitating mass diffusion; however, this remains a challenge. We developed an interfacial assembly strategy for the orderly distribution of metal nanocrystals on different fiber substrates to optimize their electrocatalytic performance. Using electrochemical nitrate reduction reaction (NO₃⁻RR) as a representative reaction, the iron-based nanofibers (Fe/NFs) assembly structure achieved an excellent nitrate removal capacity of 2317 mg N/g Fe and N₂ selectivity up to 97.2 %. This strategy could promote the rational design and synthesis of fiber-based electrocatalysts.     

Synchronous Dual Electrolyte Additive Sustains Zn Metal Anode with 5600 h Lifespan

Despite conspicuous merits of Zn metal anodes, the commercialization is still handicapped by rampant dendrite formation and notorious side reaction. Manipulating the nucleation mode and deposition orientation of Zn is a key to rendering stabilized Zn anodes. Here, a dual electrolyte additive strategy is put forward via the direct cooperation of xylitol (XY) and graphene oxide (GO) species into typical zinc sulfate electrolyte. As verified by molecular dynamics simulations, the incorporated XY molecules could regulate the solvation structure of Zn²⁺, thus inhibiting hydrogen evolution and side reactions. The self-assembled GO layer is in favor of facilitating the desolvation process to accelerate reaction kinetics. Progressive nucleation and orientational deposition can be realized under the synergistic modulation, enabling a dense and uniform Zn deposition. Consequently, symmetric cell based on dual additives harvests a highly reversible cycling of 5600 h at 1.0 mA cm⁻²/1.0 mAh cm⁻².     

Effects of sintering atmospheres on sintering behavior, electrical conductivity and oxygen permeability of mixed-conducting membranes

Effects of sintering atmospheres on properties of SrCo_0.4Fe_0.5Zr_0.1O_3−δ mixed-conducting membranes were in detail studied in terms of sintering behavior, electrical conductivity and oxygen permeability. The sintering atmospheres were 100% N₂, 79% N₂–21% O₂, 60% N₂–40% O₂, 40% N₂–60% O₂, 20% N₂–80% O₂ and 100% O₂ (in vol.%), and the prepared membranes were correspondingly denoted as S-0, S-21, S-40, S-60, S-80 and S-100, respectively. It was found that the properties of membranes were strongly dependent on the sintering atmosphere. As the oxygen partial pressure in the sintering atmosphere (P_O2) increased, sintering ability, electrical conductivity and oxygen permeability decreased at first, which was in the order of S-0 > S-21 > S-40. However, as P_O2 increased further, sintering ability, electrical conductivity and oxygen permeability increased gradually: S-40 < S-60 < S-80 < S-100. And the S-100 membrane had the best sintering ability, electrical conductivity and oxygen permeability in all membranes.     

Protective role of exogenous nitric oxide against oxidative-stress induced by salt stress in barley (Hordeum vulgare)

To probe into the potential of relieving the oxidative damage of salt stress, we investigated the protective role of nitric oxide on barley under salt stress. Salt stress resulted in increased ion leakage, lipid peroxidation and protein oxidation in barley leaves. Simultaneous treatments of barley leaves with 50 microM sodium nitroprusside, a nitric oxide donor, alleviated the damage of salt stress, reflected by decreased ion leakage, and malendialdehyde (MDA), carbonyl, and hydrogen peroxide content in barley leaves. The presence of the nitric oxide donor increased the activities of superoxide dismutases (SOD), ascorbate peroxidases (APX), and catalases (CAT). Meantime, sodium nitroprusside addition increased accumulation of ferritin at the protein level, indicating that nitric oxide directly regulated ferritin accumulation. These results suggested that nitric oxide can effectively protect seedlings from salt stress damage by enhancing activities of antioxidant enzymes to quench the excessive reactive oxygen species caused by salt stress and inducing the increase of ferritin accumulation to chelate larger number of ferrous ion. Information from this study can be used to improve soil management practices for sustainable use of salt-affected soils in the future.