Quadruple-stranded Eu-helicate Assembled from Bis-β-diketonate： Its Stability Towards Metal Ions

Herein, we reported the synthesis and investigation of highly luminescent quadruple-stranded helicate （C6H 16N）4[Eu2（MBDA）4]2·3 C4H10O.4C2H 3N（ 1-Eu） [H2M B DA=N-methyl-4,4＇-b i s（4,4,4-tri fl uoro-1,3-dioxob utyl）di- phenylamine] for its stability toward metal ions in the solution. The material was characterized via X-ray crystallo- graphic technique, Fourier transform infrared（FTIR） spectroscopy and electrospray ionization quadrapole time-of- flight（ESI-TOF） mass spectrometry. The results on the luminescence quantum yields clearly demonstrate that the ligand can effectively sensitize the luminescence of the Eu3＋ ions（φoverall=15%）. Upon the addition of different metal ions（i, e., Ag＋, Cd2＋, Zn2＋, Fe3＋, A13＋ and Ni2＋） to the CH3CN solution of compound I-Eu, the emission intensities of Eu3＋ ions at 612 nm were affected to some extent, which could be attributed to the presence of ion exchanges between Eu3＋ ions and the metals ions, and the result was confirmed by ESI-TOF mass spectrometry.

3,6-Bis-β-Dicarbonylsubstituted Carbazoles Bearing N-Spacers and Their Eu(III) Complexes as Immunofluorescent Labelling Agents

New reagents for immunofluorescence analysis of carbazole series containing fluorinated β-dicarbonyl fragments and carboxylic substituent groups separated by spacers of different lengths from the light-gathering carbazole scaffold have been developed. The markers in complex with Eu3+ ions possess stability in the aqueous phase, intense and prolonged luminescence (τ 550 - 570 μs) with characteristic emission maxima in the region of 615 nm and excitation wavelengths in the region of 380 - 390 nm, which distinguishes them from most of the analogs used. In the study of marker conjugation with streptavidin, a reagent containing 4 - 5 europium labeling complexes based on spacer-containing carbazole tetraketone was obtained. The marker-doped silicate nanoparticles exhibit intense and long-lived luminescence in the characteristic region.

UV-Vis Spectrum and the Third-order Nonlinear Optical Properties of the Chiral Camphorderived β-diketonate Platinum Complexes

UV-Vis spectrum and the third-order nonlinear optical properties of the chiral camphor-derived β-diketonate have been studied at the B3LYP/6-31G＊ level. The results showed that the introduction of electron-drawing group -CF3 and -C3F7 on β-diketonate made the strongest absorption peak red-shift and the lowest energy absorption blue-shied. Introduction of -OC2H5 on the benzene or pyridine ring made the lowest energy absorption blue-shift. When the -C2H3 was introduced on the benzene or pyridine ring, the lowest energy absorption was red-shifted. Introduction of electron-donating group on β-diketonate can enlarge their nonlinear optical properties. On the contrary, the introduction of electron-drawing group dropped it down.

Mass Transport of β-Diketonate Precursors for MOCVD of YBa_2Cu_3O_(7-δ) High T_c Superconducting Thin Films

Mass transport of Y(dpm)2 Ba(dpm)5· OH· 2Ho and Cu (dpm)2 by a carrier gas(argon) was theoretically considered and experimentally studied as a function of the system with operating parameters including temperature, carrier gas flow rate and system pressure. The experimental results are in a good agreement with the theoretical prediction. The mechanism of mass transport of these organometallic precursors and their use for YBCO film stoichiometry control and reproducibility are discussed.

Investigation of the Solar Cells with Films of Porous Silicon and <i>β</i>-Diketonates

The experimental results of a research of the solar cells parameters covered with films InxSnyOz, and solar cells covered with films, obtained by dispersion of alcoholic solutions of three-chloride Indium acetyl acetonate of aluminum are represented. The spectral dependencies of reflection factor and open circuit voltage of the film-covered solar cells are obtained. The conditions of deriving and properties of porous silicon and parameters of the solar cells with films of porous silicon and covers, forming a potential barrier, are investigated. It is shown that for optimum parameters of films deriving the solar cells with efficiency 15.8% is possible.

Copper-Catalyzed C-C(O)C Bond Cleavage of Monoalkylated β-Diketone: Synthesis of α,β-Unsaturated Ketones

A new and simple route for the synthesis of α,β-unsaturated ketones via cleavage of the C-C(O)C single bond of monoalkylated β-diketone has been described. The reaction was catalyzed by copper, a cheap transition metal in a weakly basic medium (K3PO4) at room temperature. To carry out this study, we first had to synthesize the monoalkylated β-diketones 1. Afterwards, α,β-unsaturated ketones 2 were obtained with high yields around 80%. Finally, all the products were characterized by 1H NMR, 13C NMR, and HRMS spectra. .

BIS-丙泊酚闭环靶控输注全静脉麻醉在消化道肿瘤切除手术中的应用效果

研究BIS-丙泊酚闭环靶控输注全静脉麻醉在消化道肿瘤切除手术中的应用效果。方法 从2019年4月到2020年8月,本院收治的98例消化道肿瘤患者中,按照随机数字表法,将这98例患者分成两组,一组是观察组(n=49),另一组是对照组(n=49),观察组,给予异丙酚闭环靶控输注全静脉麻醉,对照组给予丙泊酚开环靶控输注全静脉麻醉,并进行10周的观察。观察两组患者在不同时间点的血液动力学指标, BIS值,丙泊酚血药浓度,麻醉恢复,术后并发症,术中知识等方面的差别。结果 两组间 MAP和 HR值无显著性差异(P>0.05);在T9时点,观察组 BIS值明显高于对照组(P<0.05),而在其它时点,两组 BIS值无显著性差异(P>0.05);观察组的睁眼时间、气管拔管时间和方向恢复时间均显著小于对照组,有显著性差异(P<0.05);观察组、对照组两组患者术后并发症的发生率分别为8.16%和22.45%,有显著性差异(P<0.05)。结论 BIS-丙泊酚闭环靶控输注全静脉麻醉,可维持满意的麻醉深度,以BIS值为反馈更好控制丙泊酚血药浓度,促进麻醉后患者的恢复,降低术中知晓及术后并发症的发生。

Synergistic extraction of zinc from ammoniacal solutions using β-diketone mixed with CYANEX923 or LIX84I

The extraction behaviors of zinc from ammoniacal solutions were investigated using β-diketone （HA） and their mixtures with CYANEX923 or LIX84I. The effects of pH, total ammonia concentration, extractant concentration, anion species and temperature on zinc extraction were examined. The synergistic mechanism was discussed with regard to the structure of extractant and the extracted zinc complexes. It is found that the increase of total ammonia concentration and pH inhibits zinc extraction for all extraction systems due to the formation of zinc ammine complexes in aqueous phase. This effect of HA with CYANEX923 is evidently smaller than that of HA with LIX84I or HA alone system. Effect of anion species on the zinc extraction by HA with CYANEX923 can be neglected, but this effect of HA alone and the mixture of HA with LIX84I decreases in the order of （NH4）2SO4 〉 NH4NO3 〉 NH4Cl.

硫脲基桥联双四苯乙烯有机荧光传感器的制备及在水介质中叶黄素检测上的应用

以4-羟基四苯乙烯与溴乙酸乙酯为起始原料设计并合成一种硫脲基桥联双四苯乙烯(Bis-S)有机荧光传感器。将Bis-S溶解在95%(体积分数)四氢呋喃溶液中制备Bis-S溶液,采用荧光光谱仪在激发波长360 nm、发射波长468 nm下测量叶黄素加入前后Bis-S体系的荧光强度。结果显示:在Bis-S溶液或含Bis-S的传感试纸中加入叶黄素,叶黄素与Bis-S按照物质的量比1∶1结合并被Bis-S空腔包裹,Bis-S体系亮蓝色荧光猝灭;在Bis-S溶液或含Bis-S的传感试纸中加入共存生物分子鸟嘌呤、色氨酸、果糖、胞嘧啶、腺嘌呤、胸腺嘧啶、维生素B1、维生素B2、淀粉、蔗糖、葡萄糖、咖啡因、脯氨酸后,Bis-S体系荧光强度无明显变化;在含叶黄素的Bis-S溶液中加入上述共存生物分子,体系荧光强度较未加入共存生物分子的变化不大,说明Bis-S传感器对于叶黄素具有良好的选择性和抗干扰性,且在比色法检测叶黄素方面具有一定应用前景。当Bis-S的浓度为1.00×10^(-5)mol·L^(-1)时,Bis-S体系荧光强度随叶黄素浓度的增加而减弱,检测范围为0~2.00×10^(-5)mol·L^(-1),线性定量检测范围为0~0.06μmol·L^(-1),检出限(2s/k)为1.21×10^(-9)mol·L^(-1);进行4个浓度水平的回收试验,叶黄素的回收率为94.0%~101%,测定值的相对标准偏差(n=6)为1.5%~4.1%。

Synthesis and fluorescent properties in complexes of Eu( Ⅲ), Tb( Ⅲ), and Sm( Ⅲ) with β-diketone and 2,2′-bipyridine

Three new rare earth ternary complexes, RE(PB)_3bpy (RE=Sm^(3+) , Eu^(3+) , and Tb^(3+) ), were synthesized by the reaction of 1-(p-phenylethynyl- phenyl)-1,3-butanedione (HPB) and 2,2′-bipyridine (bpy) with rare earth chloride RECl_3 , respectively, in alcohol solution. The compositions were characterized by means of infrared (IR) spectra, chemical analysis, elemental analysis, and thermodynamic analysis. Luminescent properties of the three complexes were studied. At room temperature, under UV light excitation, the Sm^(3+) , Eu^(3+) , and Tb^(3+) complexes exhibit characteristic emission of the central ions. The fluorescence spectra show that the fluorescence emission intensity of Eu^(3+) complex is the strongest. The narrow strongest emission band of Eu^(3+) complex is considered to be a valuable material with bright red fluorescence.

Synthesis and luminescence properties of rare earth ternary complexes consisting of Tb(Ⅲ), β-diketones and 1,10-phenanthroline (phen)

In order to study the luminescent properties of ternary rare earth complexes with fl-diketone ligand, three new β-diketone ligands, 1-phenyl-3-（p-phenylethynylphenyl）-1,3-propanedione（HPPP）, 1-（2-thienyl）-3-（p-phenylethynylphenyl）-1,3-propanedione （HTPP） and 1-（2-furyl）-3-（p-phenylethynylphenyl）-1,3-propanedione （HFPP）, were synthesized by Sonogashira coupling reaction and Claisen condensation. Three new ternary rare earth complexes, TbL3phen （L = PPP, TPP, or FPP）, were synthesized by the reaction of rare earth chloride TbCl3,1,10-phenanthroline （phen） with HPPP, HTPP, or HFPP respectively, in alcohol solution. The compositions were characterized by means of elemental analysis, chemical analysis, and IR spectra. Luminescent properties of the three new complexes have been studied. The results show that the ternary Yb（Ⅲ） complexes only emit the weak fluorescence of the Tb（Ⅲ） ion, which reveals the triplet state energy of the ligands does not match well with the excited state vibrating energy of Tb^3＋ ion.

Total synthesis of bis-(2,3-dibromo-4,5-dihydroxyphenyl)-methane as potent PTP1B inhibitor

Protein tyrosine phosphatase 1B （PTP1B） plays an important role as a negative regulator and has been proved to be an effective target for the treatment of type 2 diabetes mellitus. Bis-（2,3-dibromo-4,5-dihydroxyphenyl）-methane 7 was first reported as a natural bromophenol with significant inhibition against PTP1B which was isolated from red algae Rhodomela conrervoides. Intrigued by its astonishing activity （IC50 = 2.4 μmol/L）, compound 7 was synthesized with the overall yield of 24% and evaluated for its PTPIB inhibitory activity compared with natural compound.

Synthesis,fluorescence properties of Eu(Ⅲ) complexes with novel carbazole functionalized β-diketone ligand

A novel carbazole functionalized β-diketone, methyl 6-（9-ethylcarbazole-3-yl）-oxoacetyl-2-pyridinecarboxylate （MEP）, and its corresponding binary Eu（III） complexes Eu（MEP）y2H2O and ternary complex Eu（MEP）aPhen with 1,10-Phenanthroline （Phen） were prepared. The ligand was characterized based on elemental analysis, FT-IR, and ^1H NMR, and the complexes were characterized with elemental analysis, FT-IR and thermogravimetric and differential thermal analysis （TG-DTA）. The investigation of fluorescence properties of the complexes Eu（MEP）3·2H2O and Eu（MEP）3Phen showed that the Eu（III） ion could be sensitized efficiently by the ligand to some extent, in partitular, in the ternary system, the secondary ligand Phen acting as a light-harvesting center was involved in the highly efficient energy transfer process, and the emission was stronger than the binary complex. In addition, the introduction of the carbazole moiety enlarged the n-conjugated system of the ligand and enhanced the luminescent intensity of the complexes.

A mild,simple and efficient method for selectiveα-monobromination of 1,3-diketones and β-ketoesters using pyridinium bromochromate

Pyridinium bromochromate has been found to be a highly efficient and selective reagent for the α-monobromination of 1,3- diketones and β-keto-esters in the absence of base, Lewis acid, or other catalyst. The products were formed in high to excellent yields under mild reaction conditions and in short reaction times.

β-Diketones at Water/Supercritical CO2 Interface： A Molecular Dynamics Simulation

The structural and dynamical properties of hexafluoroacetylacetone(HFA) and acetylacetone(AA) at the water/supercritical CO2(Sc-CO2) interface at 20 MPa and 318.15 K are investigated by molecular dynamics simulations.The TIP3P potential is used for water and the EPM2 model is for CO2.The water phase and SC-CO2 phase form a distinct immiscible liquid-liquid interface.The two chelating molecules show interfacial preference.Comparatively,the AA molecules show somewhat more preference for interfacial region,whereas the HFA molecules are preferably near the Sc-CO2 phase.The orientational distribution of the β-diketone molecules and the radial distribution functions between β-diketones and solvents are obtained in order to study the microscopic structural properties of the β-diketones at the water-SC-CO2 interface.It is found that the translational diffusion and rotational diffusion of HFA and AA are obviously anisotropic and decrease as the β-diketone molecules approach the interface.The anisotropic dynamic behavior for the solute molecules is related to the corresponding structural properties.

Synthesis and luminescence properties of rare earth ternary complexes consisting of Eu(III), β-diketones and 1,10-phenanthroline

Three novel β-diketones （HPPP, HTPP, and HFPP） ligands were synthesized by Sonogashira coupling reaction and Claisen condensation. The structure of β-diketones was confirmed with elemental analysis, IR, NMR and MS spectra. Three new ternary complexes consisting of Eu（Ⅲ）, β-diketones, and 1,10-phenanthroline（phen） were synthesized and characterized as TbL3phen （L=PPP, TPP, FPP） with elemental analysis, chemical analysis, and IR spectra, and their luminescence properties were studied.

Solubility determination and thermodynamic modeling of bis-2-hydroxyethyl terephthalate(BHET)in different solvents

Studies on the degradation process of waste polyethylene terephthalate(PET)have become increasingly mature,but there are relatively few studies on the separation of degradation products.The products contain many components and the separation of which is difficult.Therefore,the study on phase equilibrium thermodynamics of bis-2-hydroxyethyl terephthalate(BHET)is of great theoretical significance and practical value to provide basic data for the BHET crystallization separation.In this work,the degraded products were purified and characterized.The solubility of BHET in methanol,ethanol,ethylene glycol,water and the mixture of ethylene glycol+water were determined by static method.The experimental results were correlated with different models,such as ideal solution(IS)model,λh equation,Apelblat equation and NRTL model.Based on the van’t Hoff equation,the mixing Gibbs energy,enthalpy and entropy were calculated.From this work,the basic data which can be used to guide the crystallization process of BHET were obtained,including solubility data,correlation model and thermodynamic properties.

Asymmetric Intramolecular Cyclopropanation Induced by (β-Diketone)-copper Complex

Asymmetric intramolecular cyclopropanation of allylic diazoacetate was investigated using a chiral (β-diketone)-copper complex as catalyst, excellent yield and enantioselectivity were achieved. Some factors influencing enantioselectivity were discussed.

Oxalic acid as a catalyst for efficient synthesis of bis-(indolyl)methanes,and 14-aryl-14H-dibenzo[a,j]xanthenes in water

A simple, efficient, and environment benign route was developed for the preparation of bis-（indolyl）methanes and 14-aryl-14H- dibenzo[aj]xanthenes from condensation of various aromatic aldehydes or ketones with indole, and 2-naphthol, respectively, using oxalic acid catalyst in aqueous medium. Use of cheap and easily available catalyst, better yields and simple reaction protocol are the advantages of the present method.

New Greener Alternative for Biocondensation of Aldehydes and Indoles Using Lemon Juice: Formation of Bis-, Tris-, and Tetraindoles

This work presents a new greener alternative for biocondensation of aldehydes and indoles for the synthesis of bis- and tris(indolyl)methanes catalyzed by lemon juice (Citrus limon) in good yields under ultrasound irradiation in aqueous ethanol. Various substituted aldehydes with indoles under this reaction condition are elucidated. Also, tetraindolyl compounds were prepared using terephthaldialdehyde by following the same protocol. This method is an environmentally benign, efficient reaction, which requires shorter reaction time and simple experimental and work-up procedures.