紫精基光敏配位聚合物的制备与光色-荧光性质研究的综合实验教学设计

金属-有机光敏配位聚合物因其在光敏器件方面的研究价值和应用前景而受到广泛关注。本实验合成了一例紫精基光敏金属-有机配位聚合物,并围绕其制备、晶体结构、光致变色-荧光变色等性质设计了综合性实验教学。以甲基紫精阳离子为模板,5-((3,5-二羧基苄基)氧基)间苯二甲酸和锌离子配位形成具有孔道的负电性Zn-MOF框架,构建了一例荧光-光色化合物[Zn_(3)(MV^(2+))(L^(4-))_(2)]·2H_(2)O。光照后,化合物颜色由土黄色变为深绿色,荧光发射强度发生明显的衰减,对于信号存储、光控开关等领域具有很好的潜在应用价值。该实验有助于学生理解“无机化学”中的重难点知识和科学素养的培养。

Laser-induced Fluorescence and Dispersed Fluorescence Spectroscopy of NiB： Identification of a New 2П State in 19000-22100 cm^-1

The laser-induced fluorescence excitation spectra of jet-cooled NiB radicals have been recorded in the energy range of 19000-22100 cm-1. Eleven bands have been assigned to the [20.77]2П-X2∑＋ transition system for the first time. The dispersed fluorescence spectra related to most of these bands have been investigated. Vibrationally excited levels of the ground electronic state, with v＂ up to 6, have been observed. In addition, the lifetimes for almost all the observed bands have also been measured.

Fluorescent vital staining of plant sexual cell nuclei with DNA-specific fluorochromes and its application in gametoplast fusion

DNA-binding fluorochromes are often used for vital staining of plant cell nuclei. However, it is not always sure whether the cells after staining still remain in living state. We chose several criteria to estimate the validity of real vital staining for sexual cell nuclei. These were: the cytoplasmic streaming in pollen tubes whose nuclei were stained, the simultaneous visualization of fluo-rochromatic reaction and nucleus staining in isolated generative cells, and the capability of isolated, prestained generative or sperm cells to fuse with other protoplasts. The results confirmed that 4',6-diamidino-2-phenylindole (DAPI), Hoechst 33258 and mithramycin could be used as real vital stains, though their efficiency varied from case to case; among them DAPI showed best effect. The fluorescent vital staining technique offered a useful means fori-dentification and selection of heterokaryons in gametoplast manipulation studies.

The Three-region Method of Color Matching in the Presence of Fluorescent Whitening Agents

An expression of reflectance of fluorescent dyes in emission region was used in this article. Through the analysis of the spectral radiance factor of fluorescent whitening agents(FWA), the color matching of FWA was studied and the three-region method of color matching method was put forward. The method was proved to be reliable for the dyes used and was easy to apply for the color matching of FWAs.

Thermochromism of 1,4-Bis[2-(4-pyridyl)ethenyl]-benzene Derivatives

Three kinds of thermochromic materials(DC8,DC12,DC16)were synthesized by linking the rigid 1,4-bis[2-(4-pyridyl)ethenyl]-benzene(bpeb)with different lengths of alkyl chains.They exhibit remarkable fluorescent color changes under the irradiation of 365 nm light with elevating temperature,which is supposed to be caused by the transition between the crystal state and the amorphous state.Interestingly,the DC16 solid also has a photochromic character.It should be noticed that the phase transition temperatures of three materials measured by differential scanning calorimetry are higher than those of the fluorescence color changes during the heating process.Thus,the allochroic effect is attributed to the synergistic effect of both heating and photo-inducement(365 nm).Ethanol can turn the heated powder into the initial crystal again which indicates that their thermochromic behavior is reversible and makes the fluorescence recover.

Expression and characterization of Mac-1-FP fusion protein in CHO cells

Objective: To construct mammalian cell expression vectors for Mac-1 with CFP and YFP and apply FRET to study the dimerization and function of CD11 b( Mac-1 α subunit) and CD18(Mac-1 β subunit). Methods: The mammalian cell expression vector for CD11b fused with CFP at the carboxyl terminal was constructed to create recombinant plasmid of pCD11b-CFP. Then pCD11b-CFP was co-transfected with pYFP-CD18 into CHO cell, a fibroblast like cell line, as a target cell within which there are some signal pathways involved in inflammatory stimulation but without endogenous Mac-1. Then CHO cells stably expressing both CD11b-CFP and YFP-CD18 fusion proteins were selected by Western blot and laser scanning confocal microscope. Results: The cyan and yellow fluorescence in co-transfected positive CHO cells were observed under a fluorescence microscope. CHO-Mac-1-FP cells stably expressing both CD11b-CFP and YFP-CD18 fusion proteins were obtained as demonstrated by Western blot successfully. The adhesive activity of CHO-Mac-1-FP cells with CHO-1CAM-1 cells was increased markedly by treatment with PMA, suggesting the translocation of GD11b-CFP and YFP-CD18 to the plasma membrane in CHO-Mac-1-FP cells and dimerization of CD11b-CFP and YFP-CD18 just as the function of the wild type Mac-1. Conclusion: CHO-Mac-1-FP cells with adhesive activity are established successfully, thus CHO-Mac-1-FP cells may be useful for the study of Mac-1 by FRET and for other purposes.

Mechanistic Insights into the Photophysics of Ortho-hydroxyl GFP Core Chromophores

Herein we have employed the MS-CASPT2//CASSCF method to study the S1 excited-state intramolecular proton transfers （ESIPTs） of recently synthesized ortho-hydroxyl GFP core chromophores, i.e. OHIM, CHBDI, and MHBID, and their excited-state relaxation pathways. We have found that in OHIM and CHBDI, the ESIPT process is associated with small barriers of 3.4 and 4.2 kcal/mol; while, in MHBDI, it becomes essentially barrierless. Moreover, we have found two main S1 excited-state radiationless channels. In the first one, the enol S1 species decays to the So state via the enol S1/S0 conical intersection after overcoming considerable barriers of 7.0 and 7.7 kcal/mol in OHIM and CHBDI （however, in MHBDI, it is nearly barrierless）. In the second one, the keto S] species is first generated through the ESIPT event; then, it is de-excited into the So state in the vicinity of the keto S1/S0 conical intersection. These energetically allowed excited-state decay channels rationalize ex- perimentally observed ultralow fluorescence quantum yields. The insights gained from the present work may help to guide the design of new ortho-hydroxyl GFP core chromophores with improved fluorescence emission and brightness.

Luminescence Properties of Green-emitting Phosphors-Sr4Al14O25：Eu2＋ for LED Applications

A highly intense green-emitting phosphor of Eu2＋-doped Sr4Al14O25 （SAE：Eu2＋） was synthesized by a solid state reaction. In this study, XRD, PL/PLE, QE, thermal stability and LED package tests are systematically carried out and investigated. The optimized-composition of （Sro 92Eu0.08）4Al14025 exhibited a green emission peak at 497 nm under excitation wavelength of 400 nm, giving the chromaticity coordinates of （0.14, 0.35） with excellent quantum efficiency （98%） compared to those of other green-commodities, such as Ba2SiO4：Eu2＋ （90%） and BaMgAl10O17：EU2＋, Mn2＋ （92%）. The results demonstrated that SAE：Eu2＋ could be a potential candidate as the NUV-pumping phosphor for applications in light-emitting diodes （LEDs）.

Switchable 2,3-dithienylmaleimide bonded to different fluorophores: synthesis and photochromic properties

A series of photochromic diarylethene derivatives containing different fluorophores was synthesized by the Sonogashira coupling reaction and characterized by 1H nuclear magnetic resonance (NMR), 13C NMR and mass spectroscopy. Photochromic conversion of Cz-MS was observed and its structural change was confirmed by proton NMR. Switchable absorption and emission phenomena were observed for these molecules. These phenomena were attributed to the reversible photochromic fluorescence resonance energy transfer (pcFRET) process. The design of this novel photochromic system of Py-4MS enables information to be processed in a non-destructive manner. This overcomes the problem of the destructive nature of tracking photochromism using ultraviolet (UV)-vis spectroscopy.

Efficient production of transgenic chickens using self-inactive HIV-based lentiviral vectors

We demonstrated the simple and effective production of transgenic chickens, in which the enhanced green fluorescence protein （EGFP） was expressed by using third-generation self-inactive HIV-based lentiviral vectors. In our experiments, lentiviruses were injected into 204 fertilized eggs, from which 30 （15%） chickens were hatched. The exogenous gene was detected in the genomes of 16 out of 30 （53%） chickens. The green fluorescence signal was observed directly in various body parts, and was particularly significant in the testes. The transgenes were also found in the offspring of these chickens. The results indicate that HIV-based lentiviral vectors can be used to generate transgenic birds economically and effectively [ Current Zoology 55 （5）： 383 - 387,2009].

Synthesis and Luminescence Properties of Tb^3＋-Activated Silicate Oxyapatite Phosphor

A green-emitting phosphor Ca（Tb1-xLax）4（SiO4）3O （CTLS） was synthesized by a solid state reaction. X-ray diffraction, photoluminescence （PL） spectroscopy, reflectance spectra and chromaticity coordinates were carried out in this study. The CaTb4（SiO4）3O host has been known to crystallize in a hexagonal structure with disordering found in the Ca2＋ and Tb3＋ cation sites. The phosphors exhibited highly green-emitting band centered at 541 nm under ultraviolet excitation, which corresponds to the 5D4→7F5 transition. The optimal doping concentration of Tb3＋ was observed to be at 20 mol%, and the PL intensity was found to decline dramatically when the content of Tb3＋ exceeds 20m01% due to concentration quenching. Based on the results, we are currently evaluating the potential application of Ca（Tb,La）4（SiO4）30 as a new green-emitting near-UV LED convertible phosphor.

Simultaneous determination mercury species of Su-He-Xiang-Wan in rat tissues by HPLC-CVG-AFS

A simple and sensitive high performance liquid chromatography-chemical vapour generation-atom fluorescent spectrometry （HPLC-CVG-AFS） method was developed and validated for simultaneous determination mercury species in Su-He-Xiang-Wan （SHXW） and in tissues of rats, respectively. The species of mercury were separated by a Venusil MP-C 18 （5μm, 150 mm×4.6 ram） column with the optimized mobile phase containing 5% （w/v） acetonitrile, 0.01 mol/L L-cysteine and 0.06 moL/L ammonium acetate. The tissues of rats were freeze-dried after giving the medicine for 10 d, and then added into the solution containing 10% （w/v） HC1, 1% （w/v） sulfocarbamide and 0.15% （w/v） KC1 for increasing extraction rate. The resolutions of Hg2＋, MeHg and EtHg were 1.5 and 2.9, respectively. The detection limits of Hg2＋, MeHg and EtHg were 2.0, 1.0 and 0.9 ng/mL, respectively. The relative standard deviation （RSD） of inter- and intra-day precisions ranged from 1.56% to 2.86%. The recovery rates of three different adding level were 87%-101% （n=6）, and the RSDs were smaller than 8.2%. The results show that no MeHg and EtHg were detected in rat tissues. Only soluble mercury （Hg2＋） was determined for the mercury species of SHXW in rat tissues.

Luminescent properties of Lu_2MoO_6:Eu^(3+) red phosphor for solid state lighting

The Eu^3＋ activated Lu2MoO6 phosphors were synthesized by high-temperature solid-state reaction method. The X-ray diffraction （XRD）, excitation spectra, emission spectra and decay lifetime of the phosphors were measured to characterize the structure and luminescent properties. The XRD results show that all the prepared phosphors can be assigned to the monoclinic structure. The experimental results indicate efficient absorption of near ultraviolet light from the Mo^6＋O^2- group followed by intensive emission in the visible spectral range. The optimal content of Eu3＋ is 10% （mole fraction）. The critical distance Rc and energy transfer mechanism were also discussed in detail. This red emitting material may be applied as a promising red phosphor for the near ultraviolet excited white light emitting diodes.

Effects of Homologous Genome 7 on Gas Exchange and Chlorophyll Fluorescence Parameters of Wheat

[Objective]To study the effects of homologous chromosomes 7 （7A,7B and 7D） on wheat photosynthesis and provide theoretical basis for breeding high photosynthetic efficiency wheat by genetic,physiological and biochemical means. [Method]The Triticum asetivum cultivar Chinese Spring wheat and nullisomic wheat （N7A,N7B and N7D） were planted in greenhouse. The photosynthetic indexes were determined at early filling stage. [Result]The photosynthetic rate （Pn）,stomatal conductance （Gs）,primary photochemical efficiency （Fv/Fm）,actual chemical efficiency of photosystem II （ФPS II） and apparent electron transfer rate of photosystem II （ETR） were significantly lower in the N7A and N7B than in the Chinese Spring （P0.05）. The photosynthetic rate and stomatal conductance was significantly lower in the N7D than in the Chinese Spring （P0.05）. The Fv/Fm,ФPS II,ETR of N7D were higher than that of the Chinese Spring without significant difference. [Conclusion]The homologous chromosomes 7A and 7B have positive effects on photosynthetic rate and have relationship with stomatal conductance and photoreaction （chlorophyll fluorescence parameters）. The homologous chromosome 7D has negative effects on photosynthetic rate,which is mainly related to stomatal conductance rather than photoreaction.

Experimental Determination of the Vibrational Constants of FeS（X5 △） by Dispersed Fluorescence Spectroscopy

Based on previous laser-induced fluorescence excitation spectroscopy work, the vibrational constants of neutral FeS in the X5 △ electronic state were obtained by directly mapping the ground-state vibrational levels up to v＂=3 using conventional laser-induced dispersed fluorescence spectroscopy. The vibrational frequency of FeS（X5 △） （518±5 cm-1） agrees well with that reported in a recent PES measurement （520±30 cm-1） [J. Phys. Chem. A 107, 2821 （2003）] which is the only one prior experimental vibrational frequency value for the 5 △ state of FeS. Careful comparisons of our experimental results and those documented in the literature （mainly from theoretical predictions） suggest that the ground state of FeS is 5 △ state.

Hypertonic stimulation induces synthesis and release of glutamate in cultured rat hypothalamic astrocytes and C6 cells

Objective To investigate whether hypertonic saline （HS） can induce the synthesis and release of glutamate in cultured hypothalamic astrocytes or C6 cell line. Methods Astrocytes were isolated, cultured, purified and identified from the hypothalamus of newborn rat （1 day）. The astrocytes were randomly divided into five groups： isotonic （IS） and HS groups, astrocytes were incubated by IS and HS （320 mosM NaCl） medium, respectively, for 1, 3, 5, 10 or 15 rain; carbenoxolone （CBX） ＋IS and CBX＋HS groups, astrocytes were pre-treated with CBX （100 mmol/L） for 1 h at 37℃ in a 5% CO2 / 95% atmosphere, then removed to IS and HS medium, respectively, for 1, 3, 5, 10 or 15 min; Ca2＋＋HS group, astrocytes were pre-incubated with Ca2＋ （1 000 μmol/L） for 1 h at 37℃ in a 5% CO2 / 95% atmosphere, followed by a wash with isotonic FBS/DMEM, and then removed to hypertonic saline for 1, 3, 5, 10 or 15 min. The media of five groups were collected to analyze the medium glutamate concentration with high performance liquid chromatography. The astrocytes were fixed and double immunofluorescent stained with anti-glial fibrillary acidic protein （GFAP） and anti-glutamate. The C6 cells were divided into four groups： IS, HS, CBX＋IS and CBX＋HS groups, and used for quantitative measurement of glutamate in cells by flow cytometry （FCM）. Results （1） Anti-GFAP immunofluorescent signal revealed no significant difference among various time points in each group, or among the five groups. （2） The anti-glutamate immunofluorescent signal was increased in HS group and peaked at 5 min, and decreased and returned to the level of IS group at 15 rain （P 〈 0.01 vs the 5 min of HS group）. In CBX＋HS group, the glutamate intensity was higher than that in CBX＋IS and HS groups. （3） The medium glutamate concentration had no change after treatment with HS for 1 and 3 min, while increased markedly after treatment for 5 min to 15 min （P 〈 0.01 vs 1 min and 3 min）. On the contrary, the medium glutamate concentrations in the CBX＋HS or Ca2＋＋HS group were significant lower than that in the HS group （P 〈 0.01）. （4） FCM showed HS and CBX＋HS induced glutamate increase in C6 cells. Conclusion HS induced cultured rat hypothalamic astrocytes or C6 cells to synthesize and release glutamate; CBX could block glutamate release, but could not disrupt glutamate synthesis.

Spectral Properties of Yellow Fluorescent Powder for White LEDs

Much attention has been paid to white LEDs because of their potential applications in the illumination.The doping of rare earth ions plays an important role in the optical properties of yellow fluorescent powder.And mainly aiming to raise the intensity and the luminous rate of the white LEDs and by photoluminescence and electroluminescence,the luminescence spectrum of yellow fluorescent powder bought from different places is measured.Furthermore, the luminous intensity in the normal direction and the angle distribution of half maximum power for the white LEDs packed with cylindrical Φ 5 epoxy on the same blue GaN chips are also measured under the same manufacture conditions. The results show that the yellow fluorescent powder bought from China mainland has higher optical output rate than that bought from China Taiwan and hence is more suitable to fabricate the white LEDs for practical use.

Extraction of nickel from molybdenum leaching residue of metalliferous black shale by segregation roasting and acid leaching

The recovery of nickel from molybdenum leach residue by the process of segregation roasting-sulfuric acid leaching-solvent extraction was investigated. The residue was characterized by microscopic investigations, using X-ray fluorescence spectrometry （XRF） and X-ray diffractometry （XRD） techniques and the residue after segregation roasting was characterized by chemical phase analysis method. A series of experiments were conducted to examine the mass ratio of activated carbon （AC） to the residue, segregation roasting time and temperature, sulfuric acid concentration, liquid-to-solid ratio, leaching time, leaching temperature, addition amount of 30% H2O2, stirring speed （a constant） on the leaching efficiency of nickel. A maximum nickel leaching efficiency of 90.5% is achieved with the mass ratio of AC to the residue of 1：2.5, segregation roasting time of 2 h, segregation roasting temperature of 850 ℃, sulfuric acid concentration of 4.5 mol/L, liquid-to-solid ratio of 6：1, leaching time of 5 h, leaching temperature of 80 ℃, addition of 30% H202 of 0.6 mL for 1 g dry residue. Under these optimized conditions, the average leaching efficiency of nickel is 89.3%. The nickel extraction efficiency in the examined conditions is about 99.6%, and the nickel stripping efficiency in the examined conditions is about 99.2%.

Preparation of Luminescent Tb^3＋ Doped CaO Green Phosphor

CaCO3 was chosen as main raw material and Solid State method was used to prepare the sample. The precursor was directly sintered at 1100 ℃ with reducing atmosphere for 3 h to obtain new green CaO：Tb^3＋, Li^＋ Phosphors. The effects of the content of the doping ions Tb^3＋ on the luminescent properties have been studied. The structure, morphology and luminescent properties of the phosphors were characterized by XRD, SEM, UV and PL-PLE spectra respectively. The results showed that the CaO：Tb^3＋, Li^＋ was a single face-centered cubic crystals, the phosphor particle distributed uniformly. The phosphor has a strong absorptive capacity excited by 282 nm ultraviolet ray, and could emit the strong green light with the wavelength of 543 nm （^5D4→^7F5）. The CaO：Tb^3＋, Li^＋ is a new type of green fluorescent material.

The distribution and variation of elements in sediments off the Huanghe (Yellow) River mouth

Surface sediment samples collected off the Huanghe （Yellow） River mouth during the period 2007-2009 were analyzed for major and trace element concentrations. Concentrations of 16 elements were measured using X-ray fluorescence spectrometry. Results demonstrate that sediment grain size is the dominant factor controlling the spatial variations of elemental concentrations. Correlation and cluster analyses allowed classification of the study area into four geochemical regions： Regions Ⅰ and Ⅲare characterized by high concentrations ofAl2O3, Fe2O3, MgO, Na2O, K2O, Cr, Cu, Mn, Ni, Pb, V, and Zn, and contain fine-grained sediments with mean grain size （Mz）〈22 μm; and; Regions Ⅱ and Ⅳcontain mostly coarse-grained sediments, and are characterized by high concentrations of SiO2, Na2O, and Zr. The sediment entering the sea from the Huanghe River and its tributaries is enriched in Ca. Thus, the Ca/Al ratio was used as an indicator of the proportion of sediments in the study area that originated from the Huanghe River. Ca/Al ratios decrease from Regions Ⅰ and Ⅱ（located in the nearshore zone of the Huanghe River delta） to Regions Ⅲand Ⅳ（distributed in the offshore zone of the northern Huanghe River delta, southern and southeastern Laizhou Bay area）.