Tributyl citrate (TBC) is an environmentally friendly plasticizer with low toxicity, good compatibility and degradability. Compared to the traditional catalysts of the concentrated H,SO, to produce TBC, heteropolyacid (HPA), as solid superacid, are non-volatile and no-corrosive to equipment, but are expensive and difficult to recycle. In order to recycle HPA, supported heteropolyacid catalysts using different carriers exhibit promising potential in the preparation of TBC owing to Their large surface area and easy separability. This review summarizes summariz the research progress in preparing TBC using supported HPA catalysts. Those catalysts are loaded on the carriers such metal oxides, carbon materials, molecular sieves, and ionic liquids through surface loading, internal encapsulation and ion-ic bonding. A key challenge in advancing these materials toward industrial application is strengthening the interac-tion between the HPAs and their supporting carriers. Polyoxometalate-based metal-organic frameworks (POMOFs) and polyoxometalate-based covalent organic frameworks (POMCOFs), which employ metal-organic frameworks (MOFs) and covalent organic frameworks (COFs) as carriers to support HPAs, effectively reduce the leaching of HPA catalysts through internal encapsulation. The characteristics and limitations of different carrier systems in terms of catalytic activity, structure-activity relationships, and compatibility with novel processes are systematically summarized, which can provide some references to develop efficient, stable, and eco-friendly catalysts for TBC syn-thesis.

Abstract Five octanuclear homometallic or heterometallic clusters based on thiacalix[4]arene (TC4A): {[Ni8(TC4A)2(μ6-CO3)2(μ2-CH3CO2)3(μ2-CO3)(DMA)4]}∙(CH3CN)2 (1) (DMA = N,N-Dimethylamine), {[Ni5.81Co2.19(TC4A)2(μ6-CO3)2(μ2-HCO2)2(μ2-Cl)2(DMA)4]}∙2DMF∙2CH3CN (2) (DMF = N,N-Dimethylformamide), {[Ni4.06Co3.94(TC4A)2(μ6-CO3)2(μ2-HCO2)2(μ2-Cl)2(DMA)4]}∙2DMF∙2CH3CN (3), {[Ni2Co6(TC4A)2(μ6-CO3)2(μ2-HCO2)2(μ2-Cl)2(DMA)4]}∙2DMF∙2CH3CN (4), {[Co8(TC4A)2(μ6-CO3)2(μ2-HCO2)3(μ2-CO3)2(DMA)4]}∙6DMF (5) have been synthesized via the solvothermal method. Single crystal X-ray diffraction structural analyses indicate that all compounds consisted of two badminton-like secondary building units (SBUs) [M4(TC4A)], (M = Co, Ni, Co/Ni), which are linked by two μ6-CO32- anions in a tail-to-tail manner, forming a chair-like octanuclear metal cluster. Their structures were further evidenced by FT-IR, UV-Vis, XPS, PXRD and so on. Magnetism studies of compounds 1-5 indicate that there is an antiferromagnetic interaction between their metal ions, and the measured magnetic susceptibility χMT of compounds 1 to 5 increases as the cobalt content rises in the range of 50-300 K. The structures and magnetic properties of the Co(II)/Ni(II) cluster supported by TC4A can be conveniently tuned by varying the molar ratio of Ni(II) to Co(II), providing a straightforward approach to construct heterometallic clusters based on TC4A.

Herein, we describe a method employing an arylthianthrenium salts strategy for the direct skeletal transformation of the benzene rings commonly found in drugs into indoles via two consecutive site-selective C-H functionalizations. This method features a broad substrate scope and is applicable for the late-stage skeletal transformation of pharmaceuticals. For example, the insect growth regulator Pyriproxyfen, the antifungal agent Bifonazole, the nonsteroidal anti-inflammatory drug Flurbiprofen, and the natural product Salicin can all be rapidly transformed into the desired indole derivatives. As for the mechanistic studies, DFT calculations demonstrated that the nitrogen insertion proceeds through a reductive elimination involving an eight-membered ring intermediate, rather than a nitrene pathway.

Abstract Aimed at exploring new organically derivatized POMs, three heterocyclic hydrazides functionalized hexamolybdates (TBA)3[Mo6O18(=N=NCOC5H4N)] (1) (TBA = tetrabutylammonium), (TBA)3[Mo6O18(=N=NCOC4H3S)] (2) and (TBA)3[Mo6O18(=N=NCOC4H3N2)] (3) were prepared via the reflux reaction of corresponding heterocyclic hydrazides and octamolybdates in the dry acetonitrile. Their structures were determined by single crystal X-ray diffraction, all compounds can be viewed as one terminal oxo atom of hexamolybdates being substituted by corresponding heterocyclic hydrazides via the Mo=N multiple bond. There are three conformational isomers of [Mo6O18(=N=NCOC5H4N)]3- with the approximate symmetry of Cs or C1 in the asymmetric unit of compound 1, but only one anion cluster of [Mo6O18(=N=NCOC4H3S)]3- with the approximate symmetry of Cs in the asymmetric unit of compound 2. Their structures are further evidenced by FT-IR, UV-Vis, ESI MS, 1H NMR spectroscopy and so on. Antitubercular activity tests manifest that all compounds demonstrate enhanced inhibitory activities compared to that of hexamolybdates and L2, but it still inferior to L1 and L3. Considering their large molecular weight, their molar inhibitory activity is close or superior to the ligands of L1 and L3. Our current work provides a promising way to develop POMs with biological activities through the molecular hybridization of organic medicines and POMs via covalent bond.

This study systematically examines the effect of the morphology of cerium oxide (CeO2) on the flame retardancy, thermal stability, and mechanical properties of polypropylene composites with intumescent flame retardant (PP/IFR). Layer-CeO2 (L-CeO2) outperforms Particulate-CeO2 (P-CeO2) in enhancing the flame retardancy of PP/IFR composites, showing higher limiting oxygen index (LOI) and greater reductions in the total heat release rate (THR) and total smoke production (TSR). The substitution of 1% IFR with 1% L-CeO2 significantly increased the LOI from 29.4% to 32.6%, while reducing the THR and TSR by 38.9% and 74.3%, respectively. L-CeO2 incorporation improves thermal stability, increasing the residual char yield to 8.53% at 800 °C under air (vs. 3.87% for PP/IFR). Additionally, L-CeO2 improved the mechanical properties of the composites, increasing tensile strength and rigidity. The synergistic flame-retardant mechanism is hypothesized to involve CeO2 catalyzing the formation of a P-O-C crosslinked network in the carbon layer, leading to a denser carbon structure and improved flame-retardant performance in the PP/IFR composites. These findings demonstrate the efficacy of L-CeO2 as a flame-retardant synergist, providing a foundation for developing fire-safe polymeric materials.

The crystal size and uniformity of zeolites are crucial for their excellent performance in various industrial applications. Here, by utilizing commercial micrometer-sized zeolites as seeds and adjusting the weight percentage of seeds from 0 % to 5 %, the crystal sizes of silicoaluminophosphate SAPO-34 samples first decrease from 12.47 mu m (S0) to 3.04 mu m (S4), then increase to 5.34 mu m (S5). Correspondingly, their relative crystal size deviations first decrease from 183.32 % to 60.53 %, then increase to 115.17 %, and the crystal size uniformity factors first increase from 0.33 to 1, then decrease to 0.53. The crystal size uniformity factor of sample S4 equals 1, indicating that it exhibits the best crystal size uniformity. This method is also applicable to aluminosilicate zeolites. By adjusting the weight percentage of seeds from 0 % to 3 %, the crystal sizes of ZSM-5 samples first decrease from 13.61 mu m (Z0) to 2.49 mu m (Z2), then increase to 4.46 mu m (Z3); correspondingly, their crystal size uniformity factors first increase from 0.42 to 1, then decrease to 0.71. In addition, this route significantly enhances the yields and relative crystallinities of both SAPO-34 and ZSM-5 zeolites. Specifically, the yield and relative crystallinity of SAPO-34 zeolite increase by 40.71 % and 8.45 % respectively, while the yield and relative crystallinity of ZSM-5 zeolite improve by 24.05 % and 12.55 % individually. Notably, in the methanol to olefins (MTO) reaction, the propylene selectivity to butene selectivity ratio is inversely related to the crystal size; this suggests that crystal size may play a primary role in the formation of propylene and butene, with smaller crystal sizes being more favorable for the formation of propylene compared to butene. Furthermore, sample S4, which has a crystal size uniformity factor of 1 and a crystal size of 3.04 mu m, exhibits excellent MTO performance; its catalytic lifetime increases by 69 %, and selectivity for ethylene plus propylene increases by 6.3 % in comparison to conventional sample S0.

Two novel Cd(II) Metal-Organic Frameworks (MOFs), namely, {[Cd(bimphtpy)(m-bdc)(H2O)]·(H2O)3}n (Cd-MOF-1) and {[Cd(bimphtpy)(tdc)(H2O)]·(H2O)3}n (Cd-MOF-1), have been assembled from two unique dicarboxylate ligands (m-H2bdc = meta-benzenedicarboxylic acid, H2tdc = 2,5-thiophenedicarboxylic acid) and 4'-(4-(1H-benzimidazol-1-yl)phenyl)-3,2':6',3″-terpyridine (bimphtpy), featuring two dimensional (2D) frameworks. Cd-MOF-1 and Cd-MOF-2 are isostructural, exhibiting undulated 2D layers with 4-connected sql topology. Within this structure, 1D channels (void fraction: 21.6 % for Cd-MOF-1 and 20.6 % for Cd-MOF-2) arise from parallelogram windows formed by vertex-sharing [Cd4] nodes. Both Cd-MOF-1 and Cd-MOF-2 are promising quintuple-functional fluorescent sensors of Fe3+, Cr2O72-, Sulfathiazole (STZ), Oxytetracycline (OTC) and Nitrofurantoin (NFT) with high selectivity and sensitivity through luminescence quenching effects. The limits of detection (LOD) of Cd-MOF-1 and Cd-MOF-2 are 4.11 × 10-6 mol·L-1 and 7.84 × 10-6 mol·L-1 for Fe3+, 2.12 × 10-6 mol·L-1 and 1.32 × 10-6 mol·L-1 for Cr2O72-, 9.17 × 10-7 mol·L-1 and 1.79 × 10-7 mol·L-1 for STZ, 3.73 × 10-7 mol·L-1 and 5.51 × 10-7 mol·L-1 for OTC and 1.92 × 10-7 mol·L-1 and 5.58 × 10-7 mol·L-1 for NFT, respectively. Investigations into the plausible pathways for fluorescence quenching phenomena have integrated PXRD, UV-vis, fluorescence lifetime studies, and theoretical calculations. Moreover, CO2 adsorption capacities quantified as 15.1 cm3 g-1 for Cd-MOF-1 and 7.99 cm3 g-1 for Cd-MOF-2 at 273 K and 1 bar have been determined. The dual-functional frameworks serve as gas separation materials and multi-analyte sensing platforms, enabling synchronous detection of Fe3+, Cr2O72-, STZ, OTC and NFT via analyte-specific quenching pathways.

Background: The design and synthesis of catalysts with high stability, activity and selectivity in Fischer-Tropsch synthesis (FTS) have been attracting extensive research attention. Maintaining high catalytic stability and activity is the best strategy for improving the catalyst efficiency and economic benefits. Methods: In this study, graphitic carbon nitride (g-C3N4)-coated SBA-15 was utilised as a support material to prepare cobalt-based FTS catalysts. The catalysts coated with g-C3N4 were studied via TEM, XPS, XRD, H2-TPR, TG, N2 adsorption-desorption, and tested in a fixed-bed reactor. Significant findings: The catalysts coated with g-C3N4 were considerably more stable than the Co/SBA-15 catalyst without g-C3N4 coating during a 100 h test period. Furthermore, the CO-conversion performance of the Co/SBA15 catalyst decreased continuously. Notably, the activity of the Co/SBA-15@0.5C3N4 catalyst with a low g-C3N4 loading was higher than that of the Co/SBA-15@1C3N4 catalyst with a relatively high g-C3N4 loading. g-C3N4 can significantly strengthen the interaction between the cobalt species and the support, thereby increasing the catalyst stability. Therefore, a highly stable catalyst with good activity can be achieved by employing a small amount of g-C3N4 for surface modification. The results highlight the effectiveness of the proposed strategy for preparing highly stable, cobalt-based catalysts with good activity.

Four new POM-based coordination complexes [Cu(TPP)2(CH3CN)2]2{[Cu(TPP)2]2(beta-Mo8O26)}2CH3CN (1) (TPP = triphenylphosphine), {[Ag(TPP)]2[Ag(TPP)2]2(beta-Mo8O26)}6DMF (2), {[Cu2(DPPM)2(CH3CN)]2(beta-Mo8O26)}2CH3CN2DCM (3) (DPPM = bis(diphenylphosphino)methane), and {[Ag2(DPPM)2(CH3CN)]2(beta-Mo8O26)}2CH3CN2DCM (4) were prepared through the self-assembly of alpha-octamolybdates and the corresponding Cu/Ag phosphine building blocks. Single crystal X-ray diffraction reveals that compound 1 consists of two cations of [Cu(TPP)2(CH3CN)2]+ and one anion of {[Cu(TPP)2]2(beta-Mo8O26)}2-; the anion of {[Cu(TPP)2]2(beta-Mo8O26)}2- can be viewed in such a way that the central cluster of beta-Mo8O26 are coordinated with two Cu(TPP)2 units via terminal oxygen atoms to form a linear trimer; compound 2 is a neutral cross-like pentamer which is made up of the central beta-Mo8O26 coordinated with two equatorial Ag(TPP)2 units and two Ag(TPP) units above and below the beta-Mo8O26 cluster via the terminal oxygen atoms; compounds 3 and 4 can be viewed as a trimer consisting of two binuclear metal clusters of {[Cu2(DPPM)2(CH3CN)]2}2+ or {[Ag2(DPPM)2(CH3CN)]2}2+ bridged by one beta-Mo8O26 cluster via terminal oxygen atoms. Their structures are further evidenced by FT-IR and PXRD. TGA study indicates that the skeleton of compounds 1-4 is stable up to 250-290 degrees C and then a rapid weight loss followed. Their band gaps can be calculated (Eg value: 2.27 eV for 1, 3.14 eV for 2, 2.66 eV for 3, and 3.16 eV for 4) using the Tauc's method according to their solid state UV diffuse reflection spectra. Upon irradiation at 211 nm, compounds 1-4 exhibit a series of successive emissions around 360 nm, 380 nm and 400 nm, which demonstrate a similar solid state emission compared to their corresponding Cu/Ag phosphine building blocks. Four POM-based coordination compounds were obtained by the self-assembly of alpha-octamolybdates and luminescent Cu/Ag phosphine units, which maintain the luminescence feature of their precursors of Cu/Ag phosphine units.

Aimed at energy conservation and water saving for the lab, we have designed and constructed one kind of lab-scale small recirculating device of cooling water utilizing a water recirculator coupled to a solar energy system via a self-made multifunctional voltage regulator, which is equipped with an active heat radiator and powered by a solar energy system. It can provide cooling water for 1–3 sets of ordinary refluxing setups in series without additional consumption of water and electricity. The temperature difference between the water in the bucket and the environment is less than 4 °C for eight common solvents in single refluxing set-up or three combined refluxing setups with different solvents in series. In the performance assessment experiments for the refluxing of eight common solvents with different boiling point, the largest solvent loss is less than 6% if the condenser is open to the air in the refluxing time of 8 h, but none obvious solvent loss are found if the condensers were equipped with an oil bubbler. Control experiments indicates that the preparation of bromoethane/ethyl acetate/propyl hexanoate using our water recirculator can achieve almost unanimous yields in relative to those reactions using tap water as cooling water.

One inclusion complex H 4 BTC 4 A·CH 3 OH ( I ) and one ionic complex [Ag(PPh 3 ) 4 ](H 3 BTC 4 A)· DMF ( II ) (H 4 BTC 4 A = p - tert -butylthiacalix[4]arene) were obtained through solvothermal reaction. Their structures were determined by single crystal X-ray diffraction (CCDC nos. 2203699 ( I ) and 2203700 ( II )), and further evidenced by FT-IR, 1 H NMR, UV–Vis spectra, elemental analyses and so on. For complex I , there is one molecule of H 4 BTC 4 A in the asymmetric unit cell, in whose cavity one guest molecule of methanol was included. In the asymmetric unit of complex II , there are one cation of [Ag(PPh 3 ) 4 ] + , one deprotonated thiacalix[4]arene anion of [H 3 BTC 4 A] − and one DMF solvent molecule. Upon the irradiation of UV light in their acetonitrile solution, complex I demonstrate an emission at 294 nm, and [Ag(P(Ph 3 ) 4 )]NO 3 show an emission at 304 nm. Complex II not only showed the characteristic strong emissions of complex I (294 nm) and [Ag(P(Ph 3 ) 4 )]NO 3 (305 nm), but also produced a new weak emission at 368 nm, which further verified the formation of complex II .

The preparation of cyclohexanone is one important organic chemistry teaching experiment.In this paper,we modified the experimental operation to prepare cyclohexanone using K 2 Cr 2 O 7 instead of Na 2 Cr 2 O 7 ·2H 2 O as oxidizing agent.The solids of K 2 Cr 2 O 7 were directly added to the round flask with the mixture of cyclohexanol and diluted sulfuric acid in one/two/three portions,the reaction temperature is controlled between 55～60℃ through heating or cooling,the reaction time is controlled in the range of 20～30 min,cyclohexanone can be obtained in good yields.The distillate from the simplified steam distillation can be extracted directedly using methyl tertiary-butyl ether （MTBE）.The combined organic phase is easier to dry and easily separated from the drying agent.The modified experiment procedure has a good reproducibility and stable yield and can be promoted in other universities.

A class of iodobenzoyldiazenido-functionalized POMs (TBA)3 [Mo6O18(=N=NCOAr)] (Ar = Ph-o-I (1); Ph-m-I (2); Ph-p-I (3); Ph-3,4-I2(4); Ph-2,3,5-I3(5) (TBA = tetrabutylammonium) were prepared via the refluxing reaction of α-octamolybdates, DCC, and corresponding hydrazides in dry acetonitrile. Their structures were determined by Fourier-transform infrared spectroscopy, ultraviolet–visible spectra, X-ray photoelectron spectroscopy, hydrogen-1 nuclear magnetic resonance, and high-resolution mass spectrometry. Research on the biological activity of title compounds shows that L3, L5, 3, and 5 demonstrate potent inhibitory activity against coxsackievirus B3 and low in vitro cytotoxic activity against Hep-2 cell lines. The covalent linkage between the iodobenzoyldiazenido components and POMs can enhance the molecular inhibitory efficiency of iodobenzohydrazides.

Nowadays, large amounts of aluminosilicophosphate SAPO-34 zeolite are produced in industrials annually. Here, a green strategy is developed to increase SAPO-34 crystal’s yield and its catalytic performance in methanol-to-olefin (MTO) reaction. Tuning the pH value of mother liquor from alkaline to acid by rationally decreasing the environmentally unfriendly organic amine to only 57%, surprisingly the yield of SAPO-34 zeolite increases from 31% to 78%; the weak acid environment at the initial stage generates more AlPO4 precursors, which then are converted into the zeolite framework. For the first time, we found that the yield and crystallinity of the SAPO-34 crystal are positively correlated with the pH difference between gels before and after crystallization. Furthermore, the sample with the largest pH difference of about 2, showing hierarchical pore structure and mild acidity, presents excellent MTO performance: a longer lifetime of 381 min and a higher selectivity for ethylene plus propylene of 84.91%, compared to the conventional microporous sample of 131 min and 78.89%. This green approach uses less environmentally detrimental amine but enhances the yield of zeolite, in favor of the completion of the world’s carbon neutrality.

Two new cobalt(II) coordination complexes [Co(Phtpy)(HBTC)0.5]n·nH2O (I) and [Co(Meophtpy)(HBTC)0.5]n·nH2O (II) (Phtpy = 4'-(4-phenyl)-3,2':6',3''-terpyridine, Meophtpy = 4'-(4-methoxyphenyl)-3,2':6',3''-terpyridine,H3BTC = trimesic acid) were synthesized under solvothermal conditions. The structures of complexes I, II have been characterized by elemental analysis, FT-IR, TG analysis, PXRD and single crystal X-ray diffraction techniques (CCDC nos. 2123289 (I) and 2123290 (II)). For complex I, a two-dimensional (2D) layered structure is formed parallel to the bc plane and the adjacent layers are connected by Phtpy ligand along a direction to form a three-dimensional (3D) structure. It is represented as 2-nodal (3, 5)-connected {4.6.8}{4.66.83} by Schläfli symbol. For complex II, one-dimensional (1D) ladder chains along two almost perpendicular directions are formed and these chains are connected by Meophtpy ligands to form a 3D structure. It is represented as 2-nodal (3, 5)-connected {42.65.83}{42.6} by Schläfli symbol. In both complexes, dominant antiferromagnetic interactions between Co(II) ions were observed.

Several polyoxomolybdovanadates with tunable structures and NLO properties, and their application as superbroadband optical limiters utilizing POM-doped gel glasses.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

综合性实验就是在实验过程中,采用多步反应、 多种实验手段和多种实验技术来协同完成实验目的的实验.包括异烟肼的制备,异烟肼和β-环糊精包合物的制备,异烟肼和β-环糊精包合作用的研究三部分.通过异烟肼的制备、异烟肼与β-环糊精包合物的制备和包结常数的研究,让学生了解质谱、核磁、熔点仪、紫外可见光谱仪、荧光光谱仪的使用和数据处理,使学生能够掌握经典药物异烟肼的合成,异烟肼与β-环糊精包合物的制备及其包结常数的研究方法,涵盖了有机合成、仪器分析及物理化学等不同学科的知识,可以作为一个综合性实验对高年级化学类专业和制药专业的本科生及研究生开放.

Mucin 1 (MUC1), a well-known tumor-associated antigen and attractive target for tumor immunotherapy, is overexpressed in most human epithelial adenomas with aberrant glycosylation. However, its low immunogenicity impedes the development of MUC1-targeted antitumor vaccines. In this study, we investigated three liposomal adjuvant systems containing toll-like receptor 4 (TLR4) agonist monophosphoryl lipid A (MPLA) and auxiliary lipids of different charges: cationic lipid dimethyldioctadecylammonium (DDA), neutral lipid distearoylglycerophosphocholine (DSPC) or anionic lipid dioleoylphosphatidylglycerol (DOPG), respectively. ELISA assay evidenced that the positively charged DDA/MPLA liposomes are potent immune activators, which induced remarkable levels of anti-MUC1 antibodies and exhibited robust Th1-biased immune responses. Importantly, the antibodies induced by DDA/MPLA liposomes efficiently recognized and killed MUC1-positive tumor cells through complement-mediated cytotoxicity. In addition, antibody titers in mice immunized with P-2-MUC1 vaccine were significantly higher than those from mice immunized with P-1-MUC1 or MUC1 vaccine, which indicated that the lipid conjugated on MUC1 antigen also played important role for immunomodulation. This study suggested that the liposomal DDA/MPLA with lipid-MUC1 is a promising antitumor vaccine, which can be used for the immunotherapy of various epithelial carcinomas represented by breast cancer.

湖北某电厂是一个新建超临界热电厂,其配套超纯水水厂的水处理面临一系列工程难题:所用水源为市政中水,具有含盐量较高的特点,夏季高温,补给水含盐量和硬度较高,且pH值时高时低等一系列复杂工程问题.我们在双膜法水处理工艺基础上通过引入纳滤膜、阴离子交换树脂、脱气膜工艺和PLC自动加药系统,进行了一系列的水处理工艺改进,控制了水厂的出水品质,保证了超临界发电机组长期稳定运行.