The base-free oxidation of lignin into valuable aromatic chemicals is a promising pathway for biomass valorization. Developing efficient LaBO3-based catalysts and elucidating the structure-activity relationship of B-site metal substitution is the key to improving the yield/selectivity of aromatic chemicals. In view of this, a series of LaFeO3-based catalysts with different strengths of oxygen vacancies and acid-base sites were tailored by replacing high valence Fe ions with low valence Ni ions to varying degrees. Afterwards, these catalysts performance were tested for the wet aerobic oxidation of corncob alkali lignin (CAL) in individual alcohol or alcoholwater co-solvent system. Extraordinary catalytic performance was achieved when the Ni substitution degree was 0.8 in iPrOH-H2O (v/v = 1:1) co-solvent system, affording a 14.52 % yield of six aromatic aldehydes and acids. Electron paramagnetic resonance (EPR) measurements and radical quenching experiments confirmed the involvement of center dot O2- and center dot OH radicals in CAL catalytic oxidation system. Mechanism studies pronounced that the oxidative dehydrogenation of C alpha H-OH by center dot O2- that originated from O2 adsorbed on oxygen vacancies of catalyst was the initially step. Subsequently, the formed C alpha HO* was adsorbed on Fe delta+ acidic active sites with strong oxygen affinity, while activating the cleavage of C alpha-C beta, C beta-O-4 and C beta-C gamma linkages. Moreover, the existence of synergistic effect between Fe and Ni cations, where Fe4+ species obtaining electrons from Ni2+ species and transformed into Fe3+ species, resulting in an increase in oxygen vacancy concentration, thereby promoting the production of aromatic aldehydes and acids. This work provided fundamental guidance for a deeper understanding of the relationship between surface properties and activity to design efficient perovskite-based catalysts for lignin valorization.

Renewable energy has attracted widespread interest for fuel resources and environmental concerns. In this work, an eco-friendly novel catalyst (VSCS) was prepared from Vernicia montana seed shell via direct sulfonation. Subsequently, the catalytic performance was evaluated through the transesterification. The catalyst was characterized in order to elucidate the relationship between its catalytic performance and physicochemical structure. The VSCS catalyst achieved a high biodiesel yield (>90%) for glyceryl trioleate and Waste Cooking Oil (WCO). The catalyst possesses a considerable number of stable -SO3H, a sufficient quantity of -COOH, and exhibits a high acid content. Consequently, a 98.58% yield of biodiesel for WCO was obtained via VSCS 450 degrees C catalysis, and it reached 99.70% at the optimal conditions (catalyst amount of 9.6 wt.%, WCO/MeOH molar ratio of 1:30, at 120 degrees C for 8 h). Furthermore, an artificial neural network (ANN) model demonstrated the excellent performance for the prediction of FAME yield. Mechanism analysis shows that the synergistic effect of oxygen-containing group and sulfonic acid group, as well as facilitate physical adsorption, greatly facilitates transesterification. Green metrics indicated its sustainability, with low E-factor (0.609), high atom economy (90.60%) and desirable RME (0.621).

Furoin and furil, the high-value C10 fuel precursors, could be obtained by upgrading the biomass-based furfural. In this work, a feasible strategy for coupling furfural to furoin and further oxidizing it to furil was proposed. Results showed that the surrounding structure of the diimidazolium IL was the key to the furfural coupling, and the furoin yield could increase from 26 % to 91 % by adjusting the structure of ILs. Moreover, Ce/TiO2-ZrO2 exhibited promising catalytic performance for obtaining furil from furoin with a 97 % yield. Meanwhile, it could be recycled six times with only a 20 % decrease in furil yield. Mechanistic studies revealed that Ti4+ conducted the oxidation of furoin, and Olatt played a significant role in electronic transfer between the catalyst and O2, thus facilitating the oxidation of Ce3+ and the cycling of Ti3+/Ti4+. Overall, this work may provide some insights into the utilization of biomass resources.

It is essential for accelerating the development and deployment of advanced lignocellulosic biorefineries to utilize industrial lignin availably. Herein, rare earth lanthanum ferrite (LaFeO3) perovskite fabricated via coprecipitation method employed as a catalyst in an ex-situ mode for the microwave-assisted pyrolysis of softwood kraft pulp lignin (SKPL), aiming to evaluate its applicability and delve deeply into understanding the underlying mechanisms that govern the catalytic action during the pyrolysis process. The results showed that LaFeO3 catalyst exhibited outstanding activity for affording monophenols with a selectivity of 83.71%, and the product selectivity remained above 94% after six consecutive cycles. Mechanism studies declared that the catalytic pyrolysis was initiated by the electrons loss of Fe2+ species in LaFeO3 catalyst, and the subsequent active oxygen vacancies (after obtaining the electrons) contributed to adsorbing oxygen-containing motifs in SKPL, thus promoting the breakage of C-O bonds and aromatization reactions. Concurrently, the augmentation in Fe3+ species facilitated the cleavage of beta-O-4 aryl ether bonds and beta-beta linkages (pinoresinol structures), thereby contributing to the generation of monophenols. In essence, LaFeO3 perovskite emerged as an adept catalyst for the ex-situ microwave-assisted pyrolysis of SKPL, enabling the production of high value-added monophenols.

(E) omega-formylcamphene was synthesized from alpha-pinene, the main component of turpentine, and then reacted with thiosemicarbazide to obtain (E) omega-formylcamphene thiosemicarbazide 3, which was reacted with 14 alpha-bromoacetophenone compounds to obtain 14 (E) omega-formylcamphene thiazole hydrazone compounds 5a-5n; the yields were all above 80%. The structures of the target compounds were characterized by IR, H-1-NMR, C-13-NMR, and HR-MS analyses. Then, 500, 250, 125, 62.5, and 31.25 mg/L drug solutions were prepared. Free radical scavenging experiments of 1, 1-diphenyl-2-picrylhydrazyl (DPPH) and 2, 2-bis (3-ethyl-benzothiazole-6-sulfonic acid) diammonium salt (ABTS) were carried out with Trolox and L-ascorbic acid as the control samples. The scavenging rates of 14 compounds for DPPH and ABTS free radicals were obtained; the IC50 values of scavenging free radicals were fitted using SPSS software. The results show that 14 (E) omega-formylcamphene-based thiazole hydrazone compounds exhibited good scavenging effects on the two free radicals, especially when the concentration of the drug solution was 125 and 62.5 mg/L; most compounds exceeded the scavenging efficiency of Trolox and L-ascorbic acid.

With the help of active substructure splicing strategy, 36 novel pyridine ring pyrazolamide derivatives were designed and synthesized. The structures of those compounds were confirmed and characterized by 1 H NMR, 13 C NMR, FT-IR, and HRMS. The compound 2i was identified by X-ray crystal diffraction. The fungicidal effects of the pyrazolamide derivates against four plant pathogenic fungi, Colletotrichum gloeosporioides, Fusarium oxysporum, Sphaeropsis sapinea and Fusarium moniliforme , was determined by the mycelial growth rate. The results showed that the designed compounds had certain antifungal activity at the concentration of 200 mg/L. Compared with the positive control carbendazim, compounds 1e , 1g and 1h exhibited stronger antifungal activity on Sphaeropsis sapinea and Fusarium moniliforme . The antifungal activity of compound 1a- 1s (R 1 = H ) was better than that of compound 2a-2p (R 1 = CH 3 ). Compounds 1d, 1e , 1g, 1h, 1i , 2g and 2i showed good antifungal activity, and the introduction of halogen groups (except F) on benzene ring may have an important effect on biological activity. Compound 1g had a good inhibitory effect on the growth of a variety of plant pathogenic fungi. Molecular docking revealed that the -CH 3 group at R 1 position would reduce the binding affinity between these compounds and receptor, which would reduce the antifungal activity of the compound. Compound 1g is promising to become the lead compound of pesticide in the future, which is worthy of further study.(c) 2022 Elsevier B.V. All rights reserved.

Biomass-based platform compound furfural can be upgraded to C10 furoin, which is significant to the development and utilization of biomass energy. In this work, a series of diimidazole ILs were applied to explore a feasible way for upgrading of furfural to furoin. The results showed that the catalytic performance of diimidazole ILs were affected by the solvent and the structure of the anion and cation. Furoin yield could increase from 14.8% to 45.0% with the extension of the side chain, and it could be greatly enhanced by the transformation of ethyl group into unsaturated vinyl group. Theoretical calculations revealed it was due to the higher absorption energy and shorter distance between the di (vinylimidazole) ILs and furfural. Furthermore, the anion of diimidazole ILs also displayed influence by affecting the acidity and the electron distribution on the imidazole ring. Finally, the optimized yields of 84.4%, 82.0% and 84.8% were obtained by optimizing the BV4, FV4 and SV4 catalytic systems, respectively. Mechanistic studies suggested that C-2 deprotonation was the key to the reaction, and both the σ hyperconjugation and π-π conjugation with the imidazole ring could facilitated the reaction. This work may provide some reference in upgrading biomass energy

In this study, a fluorescent labeling reagent 4-hydrazino-7-nitrobenzo [c] [1,2,5] oxadiazole (NBD-NHNH2) was synthesized and used for fluorescence detection of clobetasol propionate in cosmetics by high performance liquid chromatography. In the presence of acidic catalyst (pH = 6.0), NBD-NHNH2 reacted at 45 degrees C for 30 min, and clobetasol propionate can be labeled quickly and efficiently. These derivatives have excellent stability and fluorescent properties. The maximum excitation wavelength was 450 nm, and the emission wavelength was 550 nm. The four cosmetic formulations were completely separated on a Waters e2695 HPLC C18 column by gradient elution. Under the optimal conditions, the standard curve showed a good linear response, and the correlation coefficient of r(2) = 0.9999. The LOD and LOQ were 0.01 ng/mL and 0.03 ng/mL, respectively. Therefore, NBD-NHNH2 was successfully applied in the detection of clobetasol propionate illegal added in cosmetics.

C12H20ClN3O, monoclinic, C2/c (no. 15), a = 27.228(5) Å, b = 11.380(2) Å, c = 9.3775(16) Å, β = 95.733(2)°, V = 2891.1(9) Å3, Z = 8, Rgt(F) = 0.0372, wRref(F2) = 0.1058, T = 296(2) K.

Two Zn(II)/Cd(II) complexes, [Zn(CMOPAA)( Phen)(H2O)](n) (1) and [Cd(CMOPAA)(Phen)](n) ( 2), (H(2)CMOPAA = 4.carboxymethoxy-3-phenylpropenoate and Phen=1,10-phenanthroline) were synthesized with H(2)CMOPAA ligand by solvothermal condition and structurally characterized by element analysis, IR, TGA (thermogravimetric analysis) and single crystal X-ray diffraction. Complex 1 crystalizes in the monoclinic system, space group P2(1)/ n with a= 0.698 84(8) nm, b=1.751 16(19) nm, c=1.655 49(18) nm, beta=95.165(10)degrees, V=2.017 7(4) nm(3). The asymmetric unit of complex 1 consists of one Zn(II)ion, one CMOPAA2- ligand, one Phen ligand and one coordinated H2O. Zn(II) ion is a six-coordinated distorted octahedral configuration. The carboxyl group of CMOPAA(2-) ligand connects the adjacent zinc ions to form a helical one-dimensional chain. Hydrogen bonds link the adjacent one.dimensional chains to form a two.dimensional network. Complex 2 crystalizes in the triclinic system, space group P1 with a=0.988 28( 16) nm, b = 1.040 08(17) nm, c=1.096 15(18) nm, alpha=72.213(2)degrees, beta= 74.439(2)degrees, gamma=71.265(2)degrees, V= 0.997 8(3) nm(3). The asymmet. ric unit of complex 2 consists of one Cd(II) ion, one CMOPAA(2-) ligand and one Phen ligand. Cd(II) ion is a seven. coordinated twisted single.cap triangular prism configuration. The carboxyl group of CMOPAA(2-) ligand connects the adjacent cadmium ions to form a parallelogram 26.membered large ring structure. The 26.membered large rings are linked to a one.dimensional band. like structure. The thermal stabilities and antibacterial activities of complexes 1 and 2 were studied. CCDC: 2054460, 1; 2068057, 2.

以莰烯为原料,经Vilsmeier-Haack反应、氧化反应得到莰烯酸,再经酰氯化、酯化反应,合成了一个新化合物莰烯酸薄荷酯,其结构经X-射线单晶衍射表征.莰烯酸属三斜Triclinic晶系,P-1空间群,晶胞参数为a=0.60659(13)nm,b=0.74231(17)nm,c=1.2062(3)nm,α=86.896(4)°,β=79.298(3)°,γ=76.083(3)°,V=0.5180(2)nm3,Z=1.在莰烯酸的不对称单元中有1个莰烯酸分子,相邻的莰烯酸分子通过分子间O—H…O氢键相互连接.莰烯酸薄荷酯属正交晶系,P212121空间群,晶胞参数为a=1.19226(13)nm,b=1.72351(19)nm,c=1.9577(2)nm,α=90°,β=90°,γ=90°,V=4.0228(7)nm3,Z=1.在莰烯酸薄荷酯中存在1个莰烯酸分子和1个薄荷醇分子,莰烯酸和薄荷醇通过酯基相连.

In this work, functionalized alkyl imidazolium hexafluorophosphate ILs were synthesized and characterized; then, they were applied in the conversion of xylose to furfural under the microwave method. The results showed that when C n MF was used as a catalyst, an acidic environment was provided to promote the formation of furfural. In addition, the heating method, the solvent, and the different structures of cations in the ionic liquid influenced their catalytic activity. In an aqueous solution, the yield of furfural obtained using the microwave method was better than that of the conventional heating method, and the catalytic activity of diimidazole hexafluorophosphate was better than that of monoimidazole. Meanwhile, for the diimidazole hexafluorophosphate, the change of the carbon chain length between the imidazole rings also slightly influenced the yield. Finally, the optimal yield of 49.76% was obtained at 205°C for 8 min using 3,3′-methylenebis(1-methyl-1H-imidazol-3-ium), C 1 MF, as a catalyst. Mechanistic studies suggested that the catalytic activity of C 1 MF was mainly due to the combined effect of POF n (OH) 3-n and imidazole ring. Without a doubt, the catalytic activity of C 1 MF was still available after five cycles, which not only showed its excellent catalytic activity in catalyzing the xylose to prepare the biomass platform compound furfural but also could promote the application of functionalized ionic liquids.

: Course teaching not only imparts theoretical knowledge, but also trains students to apply theoretical knowledge to practice. Based on this, we study organic chemistry teaching of agronomy education major in agricultural and forestry universities, put forward integration pattern of classroom teaching and laboratory teaching, and design teaching content and teaching process. The students’ active thinking, the ability to analyze and solve problems, the ability to work with people and to query data are fully mobilized through practice. Finally, course teaching effect is appraised through questionnaire survey and pupil performances.

有机化学实验是高等农业院校农科专业一门重要的基础实验课.针对农科专业有机化学实验课程思政建设的现状,作者从加强顶层设计,完善制度保障;提升育人意识,提高政治素养;挖掘思政元素,优化教学内容等方面进行探索与尝试.将有机化学实验教学与课程思政有机融合,构建有机化学实验课程思政教学,可以实现了知识传授,能力培养和价值塑造的"三位一体".

以5种含氢化诺卜基的叔胺分别与氯化氢、溴化氢、碘化氢反应,合成了14个氢化诺卜基叔胺的氢卤酸盐:二甲基氢化诺卜基胺盐酸盐(2a)、二甲基氢化诺卜基胺氢溴酸盐(2b)、二甲基氢化诺卜基胺氢碘酸盐(2c)、二乙基氢化诺卜基胺盐酸盐(2d)、二乙基氢化诺卜基胺氢溴酸盐(2e)、二正丙基氢化诺卜基胺盐酸盐(2f)、二正丙基氢化诺卜基胺氢溴酸盐(2g)、二正丙基氢化诺卜基胺氢碘酸盐(2h)、N-氢化诺卜基哌啶盐酸盐(2i)、N-氢化诺卜基哌啶氢溴酸盐(2j)、N-氢化诺卜基哌啶氢碘酸盐(2k)、N-氢化诺卜基吗啉盐酸盐(2l)、N-氢化诺卜基吗啉氢溴酸盐(2m)、N-氢化诺卜基吗啉氢碘酸盐(2n).对所合成的化合物进行了1 H NMR、13 C NMR和LC-MS分析,表征了它们的结构.采用菌丝生长速率法测试了化合物2a、2b、2f、2h对5种植物病原菌生长的抑制率,结果表明它们均有较好的抑菌活性.当药液质量浓度为500 mg·L-1时,2a、2b、2f、2h对烟草黑胫病菌的抑制率均在83％以上,其中2a的抑制率为100％;对西瓜枯萎病菌和苦瓜尖孢镰刀病菌的抑制率均在65％以上,部分高达85％;对轮枝镰刀病菌的抑制率均在75％以上.

Abstract C18H20F12N4P2, monoclinic, P21/n (no. 14), a = 8.3185(9) Å, b = 21.883(2) Å, c = 13.4345(15) Å, β = 103.4730(10)°, V = 2378.3(5) Å3, Z = 4, R gt (F) = 0.0470, wRref (F 2) = 0.1305, T = 296(2) K.

将E型莰烯醛与盐酸羟胺在碳酸钠作用下反应合成了E型莰烯醛肟,将E型莰烯醛肟用乙酸酐脱水得到E型莰烯腈,产品得率和纯化均在90％以上.产物结构均经MS和NMR分析方法进行了表征.采用菌丝生长速率法,将E型莰烯醛肟和莰烯腈对12种植物病原真菌的生长进行了抑制活性试验,实验结果表明:在药液质量浓度为500 mg·L-1时,E型莰烯醛肟对油茶炭疽病菌(GlomerellaCingulata,A)、玉米赤霉病菌(Gibberellazeae,B)、梨链格孢菌(Alternariakikuchiana,C)、辣椒菌核病菌(Sclerotiniasclerotiorum,D)、水稻纹枯病菌(Thanatephoruscucumeris,E)、辣椒疫霉病菌(Phytophthoracapsici,F)、毛竹枯梢病菌(Cer-atosphaeriaphyllostachydis,G)、猕猴桃果实拟茎点霉(Botryisphariadothide,H)、葡萄炭疽病菌(Colletorichum-gloeosporioides,K)的抑制率均达100％;E型莰烯腈对所试植物病原真菌的抑制率均高于98.5％,多数为100％.当药液质量浓度为250 mg·L-1时,E型莰烯醛肟对A、B、E、F、G、H、K等7种植物病原真菌的抑制率仍达95％以上.抑制效果超过甚至远超过百菌清的抑制效果.

挥发物因分子量小、易挥发、能在空气和土壤中自由扩散,在植物病害防治中可通过熏蒸方式防治温室作物病害、土传病害、果蔬采后病害等,具有独特的应用价值(陈利军等,2016).土荆芥Chenopodium ambrosioides挥发油对植物病原真菌有明显的抑制作用,且其熏蒸抑菌效果优于触杀(陈利军等,2015),开发应用潜力巨大.目前,关于土荆芥挥发油对植物病原真菌抑制机制的研究较少.本研究以农业生产上重要的植物病原真菌灰葡萄孢Botrytis cinerea为对象,从细胞内含物、核酸类物质和蛋白质的外渗等方面分析土荆芥挥发油的熏蒸作用对细胞膜通透性的影响,观察土荆芥挥发油的熏蒸作用机制,以期为土荆芥挥发油的应用提供理论依据.

Abstract C18H16O8, monoclinic, P21/c (no. 14), a = 5.3210(8) Å, b = 5.1825(8) Å, c = 29.598(5) Å, β = 93.875(2)°, V = 814.3(2) Å3, Z = 2, R gt(F) = 0.0340, wR ref(F 2) = 0.1011, T = 296(2) K.

分析了目前有机化学理论和实验的教学现状,并通过调整有机化学理论和实验课程的开设时间、 教学内容选择和内容衔接三个方面,尝试有机化学理论和实验同步教学.对比同一院系2015级和2016级两批学生的卷面成绩,发现同步教学后,成绩在高于90分和低于60分这两个区间的人数有明显变化,但大部分学生可能更关注整合了平时成绩和卷面成绩的总评成绩.因此,为了更好地提高教学效果,还需要多方共同努力,改变学生的学习态度.