Syntheses, Crystal Structure and Photoluminescence Properties of Piperidinium Tetrakis (1,3-Diphenyl-1,3-Propanedionato) Europate(III) Complex and Its Two Different Crystals

Treatment of 1,3-diphenyl-1,3-propanedione 1a with europium (III) chloride in the presence of piperidine results in the halide ligands exchange giving newly piperidinium tetrakis (1,3-diphenyl-1,3-propanedionato)europate(III) complex 2a. The complex was characterized by 1H-NMR, positive FAB-mass, and Elemental Analysis. The exact molecular structure of 2a was determined by single crystal X-ray diffraction with the monoclinic space group Cc (centrosymmetric, No.13). The large cavity sizes of the complex 2a facilitated the inclusion of water and benzene solvate molecules. The other two different crystals 2b, 2c having two water molecules and one benzene moleculewere obtained by the crystallization in different solvents and the exact molecular structures were determined by single crystal X-ray diffraction analysis with space groups P21/n (centrosymmetric, No.14), and P21/n (centrosymmetric, No.14), respectively. The eight coordinate structures of the complexes in the three crystals were slightly different due to the crystal packing and the existence of the solvent molecule(s). The photoluminescence studies indicated that four β-diketone ligands acted as strong antenna ligands and transferred the absorbed energy to europium (III) ion, consequently red luminescence was observed. These strong emissions wereattributed to the 5D0 → 7F2 transition of Europium (III) ions under UV excitation. The photoluminescence spectrum of the three crystals was almost same in solid as well as in solution.

INDIRECT VOLTAMMETRIC DETERMINATION OF TRACE SULFATE IN NATURAL WATERS WITH THE ADSORPTIVE COMPLEX WAVE OF LEAD(Ⅱ)-TETRAKIS (4-TRIMETHYLAMMONIUM PHENYL) PORPHYRIN

The indirect voltammetric determination of trace sulfate (2.0×10^(-6)～4.0×10^(-5) mol/L ) with the adsorptive complex wave of lead(Ⅱ)-tetrakis (4-trimethylammonium phenyl) porphyrin (PbTTMAPP) is reported.This method has been used for the analysis of natural waters with satisfactory results.

A NOVEL SYNTHETIC METHOD AND STRUCTURE OF TETRAKIS(BENZOATE)BIS(TRIPHENYLPHOSPHINE OXIDE)DICOPPER(II).OXIDATIVE ADDITION OF DIBENZOYL ON METALLIC COPPER

Dibenzoyl peroxide undergoes oxidative addition on metallic copper with triphenylphosphine in a mixed solvent(acetone,dichloromethane and trichloromethane),and affords the binuclear copper complex (Cu(C_6H_5COO)_2(OPPh_3))_2.Crystals are monoclinic,space group A_2/a,with cell parameters,a=24.337(3),b=10.566(1),c=21.579(2),β= 93.18(1)°, V=5540(1)~3,Z=4,R=0.042,and Rw=0.044 for 5872 observed reflections. Each copper ion is coordinated by four bridging benzoato ligands and one triphenylphosphine oxide group to form binuclear complexes.

STUDY AND APPLICATION OF SPECTROPHOTOMETRIC DETERMINATION OF MICRO AMOUNTS OF BISMUTH WITH MESO—TETRAKIS—(4—N—TRIMETHYL AMMONIUMPHENYL)PORPHINE

A new highly sensitive spectrophotometric method has been developed for the determination of micro amounts of bismuth (Ⅲ), based on the formation of Bi (Ⅲ)—meso—tetrakis—(4—N—trimethylammonium phenyl) porphine [T (4TMAP) P] complex. In the presence of Cd (Ⅱ), Bi(Ⅲ) reacts almost instantaneously with T (4TMAP)P in a 0. 6 mol/l NaAc—HAC buffer (PH5.8) at room temperature. The composition of the complex is T(4TMAP)P: Bi=1:1. The absorbance complex obeys Beer's law over the Bi(Ⅲ) concentration range 0.1—1.4 μg/ml. The linear relative coefficient γ is 0.9998. The apparent molar absorptivity was 1.75×10~5 1. mol^(-1). cm^(-1) at 463nm. The relative standard deviation of the method is 1.50％ for Bi(Ⅲ) 7ug/10ml (10 determinations). The interference of foreign ions has been examined. This simple and rapid method can be applied to the assay of Bi(Ⅲ) in some tablets directly.

STUDIES ON LANGMUIR-BLODGETT FILM OF METAL COMPLEXES(Ⅰ)-PREPARATION AND CHARACTERIZATION OF THE LB FILM OF N-HEXADECYL PYRIDINIUM TETRAKIS(1-PHENYL-3-METHYL-4-BENZOYL-PYRAZOL-5-ONE)EUROPIUM,C_5H_5NC_(16)H_(33)Eu(PMBP)_4

The LB film of the title complex was prepared by dropping a benzene solution of the title complex on the surfaceof water subphase at 25±1℃.The film was deposited in Z type on various hydrophilic pretreated substrates ofquartz,CaF;and electronic conductive glass for different purposes.The π-A curve of the film shows that thecross section per molecule is 125;,which indicates that the alkyl chain of the molecule is basically perpendiculalto the surface of the substrate.UV,IR spectra and transmission electronic microscopy of the film were also obtained.

Effects of tetrakis (hydroxymethyl) phosphonium sulfate pretreatment on characteristics of sewage sludge

Recently, tetrakis(hydroxymethyl)phosphonium sulfate(THPS) was found to play an important role in the sludge pretreatment process. However, the effects of THPS pretreatment on the characteristics of sewage sludge are still insufficiently understood.The properties of sludge after pretreatment with different concentrations of THPS were investigated in this study. The results showed that pH, dewatering ability, and particle size of sludge decreased with increase in THPS concentration. The volatile suspended solids(VSS) and total suspended solids(TSS) of sludge also decreased slightly with increase in THPS concentration. The specific oxygen uptake rate(SOUR) results suggested that lower THPS concentrations(≤ 1.87 mg/g VSS) enhanced the activity of sludge, but higher concentrations(≥ 1.87 mg/g VSS) inhibited it. Gram-negative bacteria with peritrichous flagellation(such as Pseudomonas, Escherichia, and Faecalibacterium) were extremely sensitive to THPS. The decrease in specific most probable numbers(MPNs) of pathogens(total coliforms and Escherichia coli) with the increase in THPS concentration also proved the sterilization ability of THPS in the sludge pretreatment process. Pretreatment of sludge with concentrations of THPS higher than 37.41 mg/g VSS would meet the pathogen requirements for land application of Class A biosolids.

Imaging assessment of photosensitizer emission induced by radionuclide-derived Cherenkov radiation using charge-coupled device optical imaging and long-pass filters

BACKGROUND Radionuclides produce Cherenkov radiation(CR),which can potentially activate photosensitizers(PSs)in phototherapy.Several groups have studied Cherenkov energy transfer to PSs using optical imaging;however,cost-effectively identifying whether PSs are excited by radionuclide-derived CR and detecting fluorescence emission from excited PSs remain a challenge.Many laboratories face the need for expensive dedicated equipment.AIM To cost-effectively confirm whether PSs are excited by radionuclide-derived CR and distinguish fluorescence emission from excited PSs.METHODS The absorbance and fluorescence spectra of PSs were measured using a microplate reader and fluorescence spectrometer to examine the photo-physical properties of PSs.To mitigate the need for expensive dedicated equipment and achieve the aim of the study,we developed a method that utilizes a chargecoupled device optical imaging system and appropriate long-pass filters of different wavelengths(manual sequential application of long-pass filters of 515,580,645,700,750,and 800 nm).Tetrakis(4-carboxyphenyl)porphyrin(TCPP)was utilized as a model PS.Different doses of copper-64(^(64)CuCl_(2))(4,2,and 1 mCi)were used as CR-producing radionuclides.Imaging and data acquisition were performed 0.5 h after sample preparation.Differential image analysis was conducted by using ImageJ software(National Institutes of Health)to visually evaluate TCPP fluorescence.RESULTS The maximum absorbance of TCPP was at 390-430 nm,and the emission peak was at 670 nm.The CR and CRinduced TCPP emissions were observed using the optical imaging system and the high-transmittance long-pass filters described above.The emission spectra of TCPP with a peak in the 645-700 nm window were obtained by calculation and subtraction based on the serial signal intensity(total flux)difference between^(64)CuCl_(2)+TCPP and^(64)CuCl_(2).Moreover,the differential fluorescence images of TCPP were obtained by subtracting the^(64)CuCl_(2)image from the^(64)CuCl_(2)+TCPP image.The experimental results considering different^(64)CuCl_(2)doses showed a dosedependent trend.These results demonstrate that a bioluminescence imaging device coupled with different longpass filters and subtraction image processing can confirm the emission spectra and differential fluorescence images of CR-induced TCPP.CONCLUSION This simple method identifies the PS fluorescence emission generated by radionuclide-derived CR and can contribute to accelerating the development of Cherenkov energy transfer imaging and the discovery of new PSs.

Synthesis and Crystal Structure of a New Complex Constructed from a Flexible Tetrapyridyl Ligand

The title complex [Cd2（NO3）2（OCH3）2（TPOM）2]·8H2O （TPOM = tetrakis（4-pyri- dyloxymethylene） methane） has been synthesized and characterized by IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. It crystallizes in the orthorhombic crystal system Ccca with a = 17.125（2）, b = 40.751（3）, c = 24.938（2）A, β = 90.00°, V= 17403（3）A3 C26H27N5O8Cd, Mr = 649.93, Z= 16, F（000） = 5280, Dc = 0.992 mg/m3,μ（MoKa） = 0.538 mm-1, S = 1.080, the final R = 0.0533 and wR = 0.1449 for 6627 observed reflections （I 〉 2σ（I））. The crystal structure shows that each Cd atom is coordinated to four pyridyl nitrogen atoms from four TPOM ligands and each tetrahedral TPOM ligand links up four Cd atoms into a 2-fold interpenetrating 3D framework. The TG analysis shows that the framework of the title complex is stable up to 300 ℃.

Spectral,Thermal and Structural Studies of Two 3D Coordination Polymers Based on Tetracarboxylic Ligand

Two new coordination polymers,[M6L3（DMA）3（H2O）]（M=Zn for 1,Cu for 2,L=tetrakis[3-（carboxyphenyl）oxamethyl]methane acid,DMA = N,N-dimethylacetamide） have been solvothermally synthesized. Single-crystal X-ray diffraction analysis reveals that compounds 1 and 2 are isostructural and crystallize in the trigonal space group R. The asymmetrical unit contains two metal ions,one L^4- ligand and two coordinated DMA molecules. The metal ions are connected through six aromatic rings into a linear trimetallic zinc building unit. The whole structure is connected through tetrehedral ligand and the trimetallic building units to form a 4,6-connected framework of the toc topology. Compounds 1 and 2 are further studied by IR spectroscopy,thermogravimetric analyses and PXRD. The solid-state UV-Vis and photoluminescent properties of compounds 1 are also investigated.

Design, Synthesis, Crystal Structure and Photoluminescence Properties of Four New Europium (III) Complexes with Fluorinated β-Diketone Ligand

The strong photoluminescence properties of europium complexes with organic ligands attracted the attention of many researchers and found a wide range of uses in medical, industrial and biological fields. In this article, four new Tetrakis europium complexes 3a, 3b, 3c and 3d have been prepared using 1-phenyl-4,4,4-trifluoro-1,3-butenedionato ligand and pyridinium, bipyridinium, piperazinium and piperidinium counter cations. These complexes have been characterized by negative FAB-mass. The crystal structures of 3a, 3b, 3c and 3d were determined by single crystal X-ray diffraction analysis. The complex 3a crystallized in monoclinic form, space group P21/n with four molecules in the unit cell. The complex 3b crystallized in monoclinic form, space group P2/n with two complex molecules in the unit cell. The complex 3c crystallized in monoclinic form, space group C2/c with sixteen molecules in the unit cell. The complex 3d crystallized in monoclinic form, space group P21/n with four complex molecules in the unit cell. The complex 3a has 1,2-alternative structure, 3b has 1,3-alternative structure, 3c has cone like structure and 3d has partial cone like structure. The photoluminescence properties of these complexes have been evaluated. Strong red emissions were observed in all four complexes due to 5D0 → 7F2 transition of Europium (III) ions under UV excitation. Four β-diketone ligands acted as strong antenna ligands and transferred the absorbed energy to europium (III) ion effectively;consequently strong red luminescence was observed.

Intracellular uptake of nanocrystals:Probing with aggregation-induced emission of fluorescence and kinetic modeling

Nanocrystal formulations have been explored to deliver poorly water-soluble drug molecules.Despite various studies of nanocrystal formulation and delivery,much more understanding needs to be gained into absorption mechanisms and kinetics of drug nanocrystals at various levels,ranging from cells to tissues and to the whole body.In this study,nanocrystals of tetrakis(4-hydroxyphenyl)ethylene(THPE)with an aggregation-induced emission(AIE)property was used as a model to explore intracellular absorption mechanism and dissolution kinetics of nanocrystals.Cellular uptake studies were conducted with KB cells and characterized by confocal microscopy,fow cytometry,and quantitative analyses.The results suggested that THPE nanocrystals could be taken up by KB cells directly,as well as in the form of dissolved molecules.The cellular uptake was found to be concentration-and timedependent.In addition,the intracellular THPE also could be exocytosed from cells in forms of dissolved molecules and nanocrystals.Kinetic modeling was conducted to further understand the cellular mechanism of THPE nanocrystals based on frst-order ordinary differential equations(ODEs).By ftting the kinetic model against experimental measurements,it was found that the initial nanocrystal concentration had a great infuence on the dynamic process of dissolution,cellular uptake,and exocytosis of THPE nanocrystals.As the nanocrystal concentration increased in the culture media,dissolution of endocytosed nanocrystals became enhanced,subsequently driving the effux of THPE molecules from cells.

Syntheses, Structures, Fluorescence and Magnetism of Six Lanthanide Metal-organic Frameworks Based on Silicon-centered Tetrahedral Ligand

Multifunctional lanthanide metal-organic frameworks（MOFs）, M（H4TCPS）（H20）l.5[M=Tb（JUC-95a）, Er（JUC-95b）, Dy（JUC-95c）, Tm（JUC-95d）, Y（JUC-95e） and Pr（JUC-95f）; H4TCPS=tetrakis（4-carboxyphenyl）silane] were synthesized via the reaction of the lanthanide metal ions（Ln3） with a rigid silicon-centered tetrahedral carbo- xylate ligand H4TCPS via a hydrothermal synthesis method. X-Ray diffraction（XRD） analyses reveal that they are extremely similar in structure and crystallized in a monoclinic system with space group C2/c. Two eight-coordinated metal centers and four tetrahedral H4TCPS groups constructed a paddle-wheel building block. The paddle-wheel buil- ding blocks assembled with each other via one oxygen bridge from a water molecule to lead to a 1D infinite inorganic rod-shaped chain, --Y--O--C--O--Y--, along the [001] direction. These 1D inorganic rod-shaped chains linked with the phenyl groups of the tetrahedral HaTCPS ligand to form a 3D framework. In addition, the luminescent and magnetic properties of these compounds show that they could be potential antiferromagnetic and fluorescent mate- rials.

Controllable photodynamic performance via an acidic microenvironment based on two-dimensional metal-organic frameworks for photodynamic therapy

Photodynamic therapy(PDT)is a widely-used technology for cancer therapy,but conventional photosensitizers still face some drawbacks,such as hydrophobicity,inadequate pharmacokinetics,low cell/tissue specificity,and uncontrollable photodynamic performance during the therapeutic process.Herein,we present a controllable photodynamic performance based on two-dimensional metal-organic frameworks(2D Zn-TCPP MOF)that displayed a week PDT effect under a neutral environment upon exposure to a 660 nm laser due to the degeneracy of Q bands of TCPP.However,the 2D Zn-TCPP MOF showed a significantly enhanced PDT effect in an acidic environment under irradiation with a 660 nm laser due to the released TCPP from decomposed MOF structure.From the in vitro outcomes,the 2D Zn-TCPP MOF showed controllable photodynamic performance from neutral to acidic environments.Due to the acidic tumor microenvironment,the 2D Zn-TCPP MOF presented the strongest antitumor effect in vivo under irradiation with a 660 nm laser.This work offers a promising strategy to develop a next-generation photosensitizer.

Synthesis, Structures, Fluorescence and Magnetism of Two Lanthanide Metal-organic Frameworks with CaF2 Topology Based on Silicon-centered Tetrahedral Ligand

Two 3D multifunctional lanthanide metal-organic frameworks（MOFs）, Pr（HTCPS）（H20）·2DMF·C2H2OH·5H2O（JUC-93） and Pr3（TCPS）2（NO3）（H2O）4（DMA）2.2DMA.C2H5OH.3H2O（JUC-94）[H4TCPS=tetrakis（4-carboxyphenyl）- silane, DMF=N,N＇-dimethylformamide, DMA=N,N＇-dimethylacetamide and JUC=Jilin University China] were synthe- sized by the self-assembly of a rigid silicon-centered tetrahedral carboxylate ligand H4TCPS and Pr（III） ions in different solvothermal reactions. X-Ray crystallography revealed that they exhibited a rare CaFE topology framework, constructed from the 4-connected tetrahedral TCPS unit with the 8-connected dinuclear praseodymium cluster unit and trinuclear praseodymium cluster unit, respectively. In addition, the luminescent and magnetic properties of the two compounds were investigated.