Catalytic hydrodeoxygenation (HDO) of aromatic aldehydes represents a core research direction in the efficient utilization of lignin. In this study, a cost-effective catalyst was constructed by incorporating rich lattice defects into Ni nanoparticles. The catalyst was synthesized via a uniform precipitation method, employing urea as the precipitant. By introducing aluminum nitrate during the precipitation process, nickel was effectively segregated to inhibit its growth and the generation of well-crystallized, defect-free Ni nanoparticles, thereby generating a substantial quantity of defective Ni nanoparticles with abundant lattice defects. The catalyst was characterized using XRD, TEM, HRTEM, EDS line and mapping scanning, XPS and H-2-TPD, confirming the formation of Ni nanoparticles with a narrow size distribution of similar to 5 nm with numerous lattice defects. The hydrodeoxygenation of vanillin was employed to evaluate the catalyst's activity, with investigations into the effects of Al content, solvents, temperature, H-2 pressure, and reaction time. The reaction was successfully conducted at 363 K in water. The catalyst demonstrated excellent hydrodeoxygenation activity across a series of other aromatic aldehyde compounds. Cycle experiments confirmed the catalyst's stability, maintaining its activity over at least five consecutive uses.

Single crystals of a family of 3 d -4 f Ln-Mn (Ln=lanthanide element) hetero nuclear bimetallic [Ln Mn] complexes [Ln 2 Mn(2,6-dipic) 4 (H 2 O) 8 ]·10H 2 O (Ln = La, Ce, Pr, Nd), (2, 6-dipic = pyridine-2, 6-dicarboxylic acid anion) were designed and synthesized. Unique novel structure of the complexes is a Z -shaped one-dimensional chain. In one unit, the carboxyl group (-COO) of the anion in pyridine dicarboxylic acid chelates one Ln 3+ ion ( trans ) and one bridged Mn 2+ ion ( cis ) in a cis-trans chelation mode, respectively. As a result, one Mn 2+ ion connects two Ln 3+ units in the form of a cis-cis bridge. The magnetic properties of the complexes were studied, the antiferromagnetic exchange interaction between adjacent paramagnetic ions was discovered. The magnetic data of the complexes were fitted using the Least Squares Method, and the estimated strength of the antiferromagnetic exchange interaction was obtained. At the same time, the spin orbit coupling phenomenon was explained.

Lanthanide-based 3d metals and aromatic dicarboxylic acids complexes (Ln-3d-MOFs) as a new family of crystalline materials have fascinating structures. Much attention has been paid on the rational design and construction of the new functional Ln-3d-MOFs. Bridging of the different metals ions is achieved through the O atoms of the dicarboxylic acid units to build Ln-O-M units and to construct one-, two- or three-dimensional topological structures by the linking action of ligands. The constructed Ln-3d-MOFs exhibit superior performance in optics, magnetism, and catalysis. Especially, these materials have unique magnetic properties due to the combination of lanthanides ions and 3d metals (Fe, Ni, Mn, Zn, Co) with stronger magnetism. Simultaneously, Ln3+ of the MOFs produces characteristic luminescence under the sensitizing effect of the spin-orbit interaction, crystal fields and transitional metal. With the effect of the unstable ligands or 3d metal ions that is prone to oxidize and reduce in some MOFs, Ln3+ is also used in organic chemical reactions as a catalytic active site. In this work, the synthesis and properties of Ln-3d-MOFs and their application in optics, magnetism and catalysis are summarized. Moreover, structure-activity relationships are discussed and the design strategy for these new materials is presented.

In this work, we report a pseudo-circular DNA walker (PDW) integrated with G-quadruplex (G4) and triplex DNA to construct an electrochemical biosensor for ultrasensitive detection of apolipoprotein E4 (T-e4). PDW contains double embedded DNAzyme sequences, leveraging the intrinsic advantages of enhanced structural rigidity for stable spatial conformation, continuous autonomous rolling capability, and efficient cyclic cleavage of hairpin probes due to its closed-loop topology. After binding to the target, the catalytic domain of the PDW is activated, rolling and cutting the hairpin probe in the presence of Mg2+. The triplex helix hairpin orbital (THO) serves as a rigid scaffold to immobilize hairpin DNA probes, enhancing interfacial stability and signal probe loading efficiency. The cleavage releases G-rich DNA fragments, which subsequently self-assemble into hemin/G-quadruplex (HG4) nanostructures. This design achieves label-free detection with exceptional sensitivity, exhibiting a linear range of 0.05-10 pM and a detection limit of 27 fM. This strategy opens up a new way for the sensitive detection of neurodegenerative disease biomarkers and shows broad application prospects in the fields of early disease screening and clinical monitoring.

Single crystal of 3 d -4 f hetero-metallic complexes [Ln 2 Ni(2, 6-DPA) 4 (H 2 O) 8 ] ∙4H 2 O (Ln = Ce, Pr, Nd, Sm), (2, 6-H 2 DPA = pyridine-2, 6-dicarboxylic acid) were designed and synthesized, featuring a Ln-Ni double hetero-nuclear structure, one Ni 2+ ion connects two units of Ln 3+ as a syn-syn bridge forming a chain. The carboxyl (-COO) groups chelated one Ln 3+ ion ( anti ) and one bridging Ni 2+ ion ( syn ), which conform a syn-anti chelating mode. The magnetic data were fitted by different equations with a least-squares refinement method to get an estimate on the strength of the antiferromagnetic exchange interaction, and to describe the spin-orbit coupling. Antiferromagnetic interaction between adjacent paramagnetic ions were found by the magneto-structural study. Pyridine-2, 6-dicarboxylic acid has the ability to sensitize luminescence emission from lanthanide ions.

A new family of 3d-4f Ln-TM (Ln = lanthanide TM = transition metal) heterometallic [Ln & horbar;Co] complexes [Ln2Co(2,6-dipic)4(H2O)8]center dot 8H2O (Ln = La, Ce, Pr, Nd, Sm), (2,6-dipic = pyridine-2,6-dicarboxylic acid anion) were synthesized, featuring a unique new Ln-Co double heteronuclear structure. Structural analyses reveal that the complexes crystallize in monoclinic, space group C 2/c. The carboxyl(& horbar;COO) groups chelated one Ln3+ ion (anti) and one bridging Co2+ ion (syn), which conformed a syn-anti chelating mode. As a result, one Co2+ ion connected two units of Ln3+ as a syn-syn bridge forming a Z-shaped 1D chain. From the study of the magneto-structural, antiferromagnetic interaction between adjacent paramagnetic ions were found. The magnetic data of the complexes were fitted by different equations with a least-squares refinement method to get an estimate on the strength of the antiferromagnetic exchange interaction, and to describe the spin-orbit coupling.

Maltol (MA) is a common additive used in many fields, and its detection is of great importance to human health. Here, we synthesized a bimetallic MOF (CuNiMOF) based on graphite paper by a fast, simple, and green electrodeposition method. Then, we constructed a self-calibrated MOF to detect maltol. CuNiMOF was based on graphite paper by a fast, simple, and green electrodeposition method, and then constructed a self-calibrated flexible biosensor for the detection of maltol. In this work, we utilized the amperometric i-t curve (IT), cyclic voltammetry (CV), and multipotential step (STEP) methods to electrosynthesize three modified electrodes (Gp/ CuNiMOF/IT, Gp/CuNiMOF/CV, Gp/CuNiMOF/STEP). The MA was characterized by differential pulse voltammetry electrochemical reactions on the electrode surface were investigated. The results showed that compared with the other two electrodeposition processes, the IT method was used to the sensor prepared by the IT method exhibits superior performance compared to the other two electrodeposition processes. The nonlinear response of the sensor to MA was in the concentration range of 0.5-450 mu M with a detection limit of 0.17 mu M.

M951 alloy is a cast nickel-based super-alloy widely used in gas turbines and aircraft engines, thus a suitable high temperature protective coating must be applied on its surface to enhance the corrosion resistance. In this research, NiCrAlY coating was deposited on M951 by arc ion plating. TGA at 1100 degrees C, cyclic oxidation at 1000 degrees C and hot corrosion in molten Na2SO4+25 wt% K2SO4 salt at 850 degrees C of M951 bare alloy and NiCrAlY coating specimens were investigated respectively. After TGA and cyclic oxidation, mixed oxides of NiO, NiAl2O4, Nb2O5 and Al2O3 formed on M951 surface, which spalled seriously during cyclic oxidation process. Thin, continuous and adhesive alpha- Al2O3 formed on the surface of NiCrAlY coating after both oxidation process. In molten Na2SO4+25 wt%K2SO4 salt at 850 degrees C, catastrophic corrosion occurred for the M951 alloy only after 10 hours, while thin and continuous theta- Al2O3 film formed on the surface of the NiCrAlY coating. In a word, NiCrAlY coating greatly improved the high temperature oxidation and hot corrosion resistance of the M951 superalloy. This study will further refine the oxidation and corrosion behaviors of M951 superalloy under different high temperature protective coatings and provides theoretical and experimental basis for the application of M951 superalloy in corrosive environments.

Alkaline phosphatase (ALP) is integral to a diverse array of biological processes, consequently, its presence is frequently linked to the onset of various pathologies. In the current investigation, 1-naphthyl phosphate (1-Npp) served as a substrate, with the catalytic hydrolysis of phosphate groups by ALP being leveraged to engender a detectable current at an applied potential of 0.277 V. Initially, carbon nanotubes (SWCNTs) were deposited via drop-coating onto graphite paper (Gp), a material characterized by exceptional electrical conductivity. Subsequently, Cu-MOF was uniformly deposited on Gp/SWCNTs composites by rapid electrodeposition technique, that is, chronocurrent method (i-t), at a potential of -1.1 V for 240 s, thereby fabricating an electrochemical sensor platform denominated Gp/SWCNTs/Cu-MOF. This platform enabled the ratiometric electrochemical quantification of ALP, utilizing the signal from Cu-MOF as an internal standard. This platform's integrated design facilitates signal amplification and provides an inbuilt reference, which was instrumental in mitigating the impact of environmental fluctuations and enhancing the precision of the obtained data. The ratiometric signals exhibited strong linear correlations within the 0.014-14.29 U mL- 1 concentration, with a detection limit of 0.005 U mL-1. Moreover, the sensor exhibited robust selectivity, repeatability, and excellent detection performance in realworld samples, with recovery rates spanning 99.3 %-103.5 %, making it a suitable candidate for the expedient and precise quantification of ALP in serum.

The iron-based metal-organic framework (NH2-MIL-101(Fe)) nanoparticles exhibited excellent conductivity, exceptional catalytic effect, sturdy stability flexible structure, etc. Consequently, it has been exploited in various applications. Herein, NH2-MIL-101(Fe) nanoparticles were successfully synthesized via the hydrothermal method and were grown in situ onto the pencil core electrode (PCE) for simultaneous determination of caffeic acid (CA) and acetaminophen (AP). The PCE decorated by NH2-MIL-101(Fe) as electrode substrate, combined with the dual effects of the excellent electrocatalytic activity of NH2-MIL-101(Fe) and the commendable electrical conductivity of PCE, the constructed sensor exhibits superior electrochemical sensing activity. The electrochemical behavior of CA and AP at the electrodes were investigated mainly by differential pulse voltammetry (DPV) and cyclic voltammetry (CV), exhibiting broad linear responses from 0.1 to 500 mu M, and 0.08 to 800 mu M for simultaneous detection of CA and AP, with detection limits of 29 nM and 24 nM, respectively. Moreover, the results of CA and AP in drug and human urine using this sensor were satisfactory, which proved that the sensor is feasible to simultaneously detect CA and AP.

Two 3d-4f heterometallic coordination polymers H3O[LnMn2(2,6-dipic)3Ac2(H2O)6]·3H2O (Ln: Ho, Dy) were synthesized through hydrothermal synthesis method and characterized by single-crytal X-ray diffraction. The isostructural complexes crystallize in C2/c space group (Ln: Ho, a = 2.22782(10) nm, b = 1.02640(5) nm, c = 2.34038(8) nm, V = 3.6680 (3) nm3, Z = 4) and (Ln: Dy, a = 2.23161(9) nm, b = 1.02809(4) nm, c = 1.79538(7) nm, V = 3.6941 (3) nm3, Z = 4). A special semi-staggered network was constructed by LnIII, MnII ions, and the oxygen atoms on the flat of the a and b axes. From the c-axis direction, the networks were piled up by the π-π force from the coordinated pyridine-2,6-dicarboxylic acid. Magnetic susceptibility measurements were carried out, and the magnetic behavior of the complexes revealed the lack of magnetic coupling and the occurrence of weak antiferromagnetic interactions within the HoIII − HoIII (1) and DyIII − DyIII (2) ions.

采用水热合成法,制备了铕/钕?2,6?吡啶二甲酸配合物[Ln(2,6?dipic)(2,6?Hdipic)(H2O)2]·4H2O(Ln代表Eu及Nd),并通过单晶结构测定、磁化率测试、热重分析及差示扫描量热分析,研究了稀土吡啶羧酸类配合物的结构、磁性、热力学性质.结果表明,2个配合物为异质同构体,属于单斜晶系,P21/c空间群;晶体中的2,6?吡啶二甲酸采用了两种不同的配位模式;配合物呈现反铁磁性,有明显的轨道耦合作用;配合物具有较高的热稳定性.

采用缓慢蒸发法合成了具有三维结构的稀土-过渡金属配合物[LaCu6(OH)3(ClO4)3(Gly)6(Im)6]-(ClO4)2·3(MeOH)(Gly=甘氨酸,Im=咪唑),配合物属三方晶系,R3空间群,a=1.591 99(12)nm,b=1.591 99(12)nm,c=2.354 20(2)nm,α=β=90°,γ=120°.配合物的配位单元经由多种形式的氢键延伸为三维结构.通过红外光谱分析、热重分析、荧光分析、磁性分析对配合物的性质进行了表征.结果表明,配合物失重大致分为3步,热稳定性较好;配合物的荧光发射光谱存在3个特征峰,具有较弱的荧光性;配合物中金属离子间存在反铁磁相互作用.

The catalytic conversion of furan derivatives, furfural and 5-hydroxymethylfurfural (HMF), to valuable chemicals is of great importance due to the increase in carbon emissions and decrease in fossil fuels. In this manuscript, 1,2,5-hexanetriol was transformed to HMF through a two steps procedure. The HMF was first hydrogenated to 1-hydroxyhexane-2,5-dione (HHD). The reaction scale could be enlarged from 1 mmol to 50 mmol of the reactant with a similar yield of HHD, and the purity of HHD was over 95 % after a simple extraction. Then the HHD was hydrogenated to 1,2,5-hexanetriol on Ru/C at very mild reaction conditions. The parameters of pressure, solvent, the concentration of HHD, reaction time and temperature on the hydrogenation of HHD were investigated to find the optimal reaction conditions. The 1,2,5-hexanetriol could be obtained from HMF in a one-pot reaction by removing the Pd/C and adding Ru/C after the HMF hydrogenation step. The fresh and used Pd/C and Ru/C were characterized by XRD, TEM, XPS, and the Ru/C was further characterized by EDS mappings. The characterization showed partial agglomeration of Pd occurred after the Pd/C was used. The Ru/C had a narrow Ru distribution and was stable under the reaction conditions. The Ru/C could be used at least 5 times. This manuscript showed an easy route for the production of valuable chemicals from renewable biomass furan derives.

为提高环氧氯丙烷胺型絮凝剂的脱色性能,以二乙烯三胺为交联改性剂,环氧氯丙烷和二甲胺为原料合成改性的环氧氯丙烷-二甲胺型絮凝剂,并用于活性红X-3B模拟染料废水脱色絮凝实验.研究了投料比、反应温度、水温、pH值、染料质量浓度和絮凝剂投入量等因素对絮凝剂脱色性能的影响,探讨了与聚丙烯酰胺复配使用情况.得到改性絮凝剂制备优化条件:环氧氯丙烷 、 二甲胺、 二乙烯三胺的量比为1:0.95:0.05,反应温度为90℃.同时,得到絮凝脱色的优化条件:水温为20℃,pH值为4,染料质量浓度为200 mg/L,絮凝剂投入量为125 mg/L;在此脱色优化条件下,改性絮凝剂对染料废水的脱色率达到91.0％.研究结果表明:改性絮凝剂比未改性絮凝剂有更好的脱色效果;改性剂提高了改性絮凝剂的电中和作用和架桥网捕作用;与聚丙烯酰胺的复配提高改性絮凝剂的脱色性能和耐盐性.

Biomass is viewed as an important renewable carbon source, in which 5-hydroxymethylfurfural (HMF) plays an important role as platform compound. 2, 5-dihydroxymethylfuran (DHMF) and 2, 5-dimethylfuran (DMF) could be obtained by the hydrogenation of HMF under certain conditions. The DHMF and DMF are chemicals of high added value with wide application.The catalysts played a key role in the conversion of HMF to DHMF and DMF. This review paid attentions on the hydrogenation of HMF to DHMF and the hydrogenolysis of HMF to DMF via kinds of catalytic systems. The recent progress were summarized according to catalytic system, including noble metal catalysts and non-noble metal catalysts and a perspective on the transformation was given based on the recent progress.

By changing the simulation incineration conditions of municipal solid waste incineration experiment (nickel catalyst, water), analysing the reaction temperature, incineration exhaust gas flow, concentration of exhaust gas composition, the dioxin concentrations, the toxicity of dioxin equivalent of absorbing liquid, and the change of the absorption liquid organic matter concentration, to explore the effect of different combustion conditions on dioxins from simulated municipal solid waste incineration. The results showed that the addition of nickel catalyst and water could promote the conversion of macromolecule organic matter to small molecule organic matter during the incineration process, and effectively inhibited the precursor synthesis of dioxins, the suppression ratio of dioxins were decreased by 80.7% and the total equivalent toxicity of dioxins were decreased by 98%.

Dicyandiamide-formaldehyde condensation product shows excellent decolorization performance for dyeing wastewater.The cross-linking agent plays an important role in the decolorization performance.In this work, a three-dimensional modified dicyandiamide-formaldehyde decolorizing decolorant (defined as DF 1 ) was synthesized using hexamethylenetetramine as the three-dimensional cross-linking agent.The influences of dosage of DF 1 , settling time, settling temperature, pH value and inorganic salt on the flocculation ability of DF 1 were investigated.The existence of inorganic salt has a slight effect on the color removal of DF 1 .The maximum color removal of 98.8% was achieved with the DF 1 dosage of 35 mg/L.The infrared spectra of samples demonstrate that chemical reactions occurred between DF 1 and Reactive Brilliant Red X-3B.