Toward Tailored Xerogel Composites: Local Dipolarity and Nanosecond Dynamics within Binary Composites Derived from Tetraethylorthosilane and ORMOSILs,Oligomers or Surfactants

We explore the potential of xerogel composites to tailor the behavior of active dopants that are sequestered within the xerogel. Toward this end, we report on the local dipolarity and dynamics of two fluorescent probes (pyrene and rhodamine 6G, R6G) each co-doped at low concentration directly into a series of binary xerogel composites. The composites that we have investigated are composed of tetraethylorthosilicate (Si(OCH₂CH₃)₄,TEOS) plus one of several organically-modified silanes (ORMOSILs), organic oligomers, or a common surfactant. For convenience we divide these xerogel composites into two classes: (1) xerogels wherein the organic character arises from the addition of an ORMOSIL co-monomer, possessing a non-hydrolyzable organic functional group, that becomes covalently incorporated with in the xerogel and (2) xerogels wherein the organic content is adjusted by adding organic oligomers or a surfactant. Six organically-modified silylalkoxides of the form R _n Si(OR)_4–n were investigated as ORMOSILs. Poly(ethylene glycol), Nafion, and Ionene 6,2 were tested as oligomers. Triton X-100 was used as the surfactant. To estimate the local dipolarity within these composites we used the static fluorescence from pyrene molecules that were sequestered within the composites. These experiments showed that the local dipolarity surrounding the average pyrene molecule can be tuned significantly, but this depends on the actual organic species that one uses to prepare the xerogel composite. Time-resolved fluorescence anisotropy measurements were used to quantify the R6G mobility within the same composites. These results demonstrate that certain organic additive scan be used to adjust the R6G mobility within the xerogel composite.     

Multiple fluorescence spectra of fluorescein molecules encapsulated in the silica xerogel prepared by the sol-gel reaction

The fluorescence and fluorescence-excitation spectra of fluorescein molecules during the sol-gel-xerogel transitions of tetraethyl orthosilicate (TEOS) solutions have been observed as functions of doped concentration, in the order of 10^-2 and 10^-5 mol dm^-3, and of the sol-gel-xerogel transition time. It was shown that with a lower initial concentration only the cation was encapsulated in the pores of the silica xerogel state during the sol-gel reaction processes. On the other hand, with a high concentration four species, i.e., cation, monoanion, dianion, and dimer, were encapsulated in the silica xerogel during the sol-gel reaction processes. These results have the potential to open the way to the development of simultaneous multiple-band solid-state laser emitting materials.     

A Spectroscopic Study of the Effects of Various Solvents and Sol-Gel Hosts on the Chemical and Photochemical Properties of Thionin and Nile Blue A

Tetraethyl orthosilicate (TEOS)-based gels were doped with two optically active organic indicators, thionin and nile blue A. Before trapping in a sol-gel host, thionin and nile blue A were both evaluated for solvent and protonation effects on their spectral properties. Only extreme pH values provided by HCl, NaOH, and NH₄OH produced new absorption and/or fluorescence bands. Introduction of nile blue A into alkaline environments (0.1N NaOH, NH₄OH) results in the appearance of a broad absorption band centered near 520 nm whereas highly acidic environments (1N HCl) show a reduction of the 635 nm absorption peak accompanied by an absorption band located near 460 nm. A marked decrease is observed in the optical density of thionin in 1N HCl solution which results in a reduction in the fluorescence intensity. The absorption and fluorescence spectra also reveal a decrease in a pH 11 solution of NH₄OH as compared to neutral conditions. Both dyes formed dimers when the sol-gel host, initially synthesized with TEOS, was organically modified with methyltrimethoxysilane (MTMS). However, thionin dimers were present in all silica-based sol-gel compositions, as evidenced by the absorption and fluorescence spectra. Substitution of MTMS for some of the TEOS in the gel matrix resulted in blue shifts in the absorption and fluorescence spectra of nile blue A. The absorption peak shifted 50 nm to 596 nm whereas the fluorescence shifted around 40 nm to 635 nm. These blue shifts resulted from the reduced polarity of the silica-based xerogel. Thionin also exhibited shifts in its absorption and fluorescence spectra with organic modification by MTMS. The absorption shifted approximately 3 nm to 595 nm while the fluorescence maximum decreased 7 nm to 630 nm. The blue shifts in the spectra of thionin with additions of MTMS were attributed to surface sites that altered the molecular structure of the adsorbed thionin molecules.     

上转换荧光响应性复合纳米凝胶的制备及荧光能量传递行为

采用水热法合成NaYF₄∶Yb³⁺,Er³⁺稀土纳米晶, 再经3-苄基三硫代碳酸酯基丙酸(BSPA)修饰, 制得功能化纳米晶体; 以罗丹明6G(R6G)为母体荧光染料, 经一系列反应合成了乙烯基功能化单体罗丹明6G酰基邻羧基苯甲肼腙(R6GHA); 将功能化纳米晶体与R6GHA构成荧光共振能量传递(FRET)的“给体/受体”对, 通过可逆加成断裂链转移(RAFT)聚合和“点击化学”反应, 合成具有多重响应性复合荧光纳米凝胶NaYF₄∶Yb³⁺,Er³⁺/PNIPAm-co-R6GHA. 采用TEM, XRD, FTIR和DSC对产物的微观结构进行了表征; 采用上转换荧光光谱(PL)研究了该复合纳米凝胶对pH值、 环境温度和不同金属离子的荧光响应行为, 并对相关机理进行了探讨. 结果表明, 环境温度变化对复合纳米凝胶的荧光发射具有显著影响, 且该复合纳米凝胶对Hg²⁺具有选择性荧光响应; 在H⁺或Hg²⁺作用下, 复合纳米凝胶中纳米晶和R6GHA之间会发生荧光共振能量传递; 通过纳米凝胶中纳米晶与R6GHA特征荧光发射峰比率的变化, 实现对Hg²⁺的检测.     

Characterization of rhodamine 6G aggregates intercalated in solid thin films of laponite clay. 2 Fluorescence spectroscopy

The photoluminescence response of Rhodamine 6G (R6G) laser dye intercalated into solid thin films of Laponite (Lap) clay is studied as a function of dye loading. Fluorescence spectroscopy (steady-state and time-resolved techniques) was used to characterize the R6G species adsorbed into the solid films. For very diluted R6G loadings (40% CEC), with a reminiscent fluorescence band at around 600 nm.     

A spectroscopic analysis of blue and ultraviolet upconverted emissions from Gd3Ga5O12:Tm3+, Yb3+ nanocrystals

The spectroscopic behavior of gadolinium gallium garnet (Gd3Ga5O12, GGG) nanocrystals codoped with 1% each of Tm3+ and Yb3+ prepared via a solution combustion synthesis procedure was investigated. Initial excitation of the codoped nanocrystals with 465.8 nm (into the 1G4 state) showed a dominant blue-green emission ascribed to the 1G4-3H6 transition as well as red and NIR emissions from the 1G4-3F4 and 1G4-3H5/3H4-3H6 transitions, respectively. Excitation at this wavelength (465.8 nm) showed the existence of a Tm3+ --> Yb3+ energy transfer process evidenced by the presence of the 2F5/2-2F7/2 Yb3+ emission in the NIR emission spectrum. The decay time constants proved that the transfer of energy occurred via the 3H4 state. Following excitation of the Yb3+ ion with 980 nm, intense upconverted emission was observed. Emissions in the UV (1D2-3H6), blue (1D2-3F4), blue-green (1G4-3H6), red (1G4-3F4), and NIR (1G4-3H5/3H4-3H6) were observed and were the direct result of subsequent transfers of energy from the Yb3+ ion to the Tm3+ ion. Power dependence studies showed a deviation from expected values for the number of photons involved in the upconversion thus indicating a saturation of the upconversion process. An energy transfer efficiency of 0.576 was determined experimentally.     

Effect of Microstructural Change on the Optical Property of Ormosil Embedded with Organic Molecules

An organically modified silicate (Ormosil) for a dye laser was produced with a 90/10 ratio of Tetraethyl orthosilicate and Polydimethyl silanol (TEOS/PDMS) by sol-gel method. The optical properties of a dye incorporated in Ormosil were studied as a function of the amount of catalyst. In the xerogel doped with Rhodamine 6G perchlorate, a dimer peak near 500 nm appeared with increases of HCl amounts. The dimer peak was affected by enlarged pore size of the Ormosil and increased porosity due to the increased HCl concentration. Also, the increase of HCl concentration led to gradually lower transmittance values of the dye host. The dimer peak was identified by measuring optical absorption by ultraviolet/visible spectrophotometer. The changes of pore structure and porosity were investigated by SEM and BET.     

新型复合介孔材料HPMo/SBA-15的合成与表征

合成了一种新型复合介孔材料HPMo/SBA-15, 通过XRD, TEM, UV-Vis和IR等方法表征证明HPMo均匀且稳定地包藏到介孔材料SBA-15的由SiO2网络组成的孔壁中. 催化实验结果表明, 该材料在大分子催化裂化反应中具有很高的活性, 在大分子催化氧化反应中连续循环使用未发现活性组分流失, 显示了其在大分子催化和均相催化反应多相化中具有很好的应用前景.     

Effects of Poly(ethylene glycol) Doping on the Behavior of Pyrene, Rhodamine 6G, and Acrylodan-Labeled Bovine Serum Albumin Sequestered within Tetramethylorthosilane-Derived Sol-Gel-Processed Composites

We investigate the effects of controlled poly(ethylene glycol) (PEG) doping on the behavior of pyrene, rhodamine 6G (R6G), and acrylodan-labeled bovine serum albumin (BSA-Ac) sequestered within tetramethylorthosilicate (TMOS)-derived sol-gel-processed materials. To probe the dipolarity of the local environment within the composite we performed static fluorescence measurements on pyrene as the composites aged. We found that small levels of PEG loading effected significant enhancements in the local dipolarity surrounding the average pyrene molecule. Time-resolved fluorescence anisotropy measurements were used to follow the rotational reorientation dynamics of R6G as the composites aged. As the PEG loading increased, the R6G reorientational mobility increased. Nitrogen adsorption techniques were used to quantify the effects of PEG doping level on the surface area and final xerogel pore features. A large reduction in surface area was observed with PEG doping, but no detectable change in pore size was noted. The effects of PEG doping on a biomolecule were probed by following the time-resolved fluorescence anisotropy decay of BSA-Ac. These results showed that PEG doping resulted in increased biomolecule dynamics relative to that found for a neat, undoped TMOS-derived composites. Together these results show that PEG doping can be used to tune the sol-gel-processed composite dipolarity, alter the mobility of dopants sequestered within the composite, control analyte acessibility to the sensing chemistry, and modulate the internal dynamics within a biodopant.     

V-P-O/TiO~2-SiO~2催化剂的制备、表征及其在丙烷氧化制取丙 烯酸反应中的应 用研究

通过湿磨法,将钒-磷-氧(V-P-O)氧化物负载于钛硅干凝胶(TiO~2-SiO~2)上,制备了V-P-O/TiO~2-SiO~2氧化物催化剂,并运用BET,XRD,TEM及XPS等技术考察了润湿剂,V-P-O的含量及焙烧条件对催化剂结构的影响。由BET方法发现,以异丁醇为润湿剂对催化剂表面积影响较小。XRD和TEM考察结果表明,所制备的催化剂有较高的热稳定性。通过XPS分析,证实钒元素主要以V(IV)价态存在于催化剂的表面。V-P-O/TiO~2-SiO~2催化剂在丙烷氧化反应中显示了良好的催化性能。     

Luminescence spectroscopy of matrix-isolated z 6P state atomic manganese

The relaxation of electronically excited atomic manganese isolated in solid rare gas matrices is observed from recorded emission spectra, to be strongly site specific. z 6P state excitation of Mn atoms isolated in the red absorption site in Ar and Kr produces narrow a 4D and a 6D state emissions while blue-site excitation produces z 6P state fluorescence and broadened a 4D and a 6D emissions. MnXe exhibits only a single thermally stable site whose emission at 620 nm is similar to the broad a 6D bands produced with blue-site excitation in Ar and Kr. Thus in Ar(Kr), excitation of the red site at 393 (400) nm produces narrow line emissions at 427.5 (427.8) and 590 (585.7) nm. From their spectral positions, linewidths, and long decay times, these emission bands are assigned to the a 4D72 and a 6D92 states, respectively. Excitation of the blue site at 380 (385.5) nm produces broad emission at 413 (416) nm which, because of its nanosecond radiative lifetime, is assigned to resonance z 6P --> a 6S fluorescence. Emission bands at 438 (440) and 625 (626.8) nm, also produced with blue-site excitation, are broader than their red-site equivalents at 427.5 and 590 nm (427.8 and 585.7 nm in Kr) but from their millisecond and microsecond decay times are assigned to the a 4D and a 6D states. The line features observed in high resolution scans of the red-site emission at 427.5 and 427.8 nm in MnAr and MnKr, respectively, have been analyzed with the W(p) optical line shape function and identified as resolved phonon structure originating from very weak (S=0.4) electron-phonon coupling. The presence of considerable hot-phonon emission (even in 12 K spectra) and the existence of crystal field splittings of 35 and 45 cm(-1) on the excited a 4D72 level in Ar and Kr matrices have been identified in W(p) line shape fits. The measured matrix lifetimes for the narrow red-site a 6D state emissions (0.29 and 0.65 ms) in Ar and Kr are much shorter than the calculated (3 s) gas phase value. With the lifetime of the metastable a 6D92 state shortened by four orders of magnitude in the solid rare gases, it is clear that the probability of the "forbidden" a 6D --> a 6S atomic transition is greatly enhanced in the solid state. A novel feature identified in the present work is the large width and shifted 4D and 6D emissions produced for Mn atoms isolated in the blue sites of Ar and Kr. In contrast, these states produce narrow, unshifted (gas-phase-like) 4D and 6D state emissions from the red site.     

溶胶-凝胶法制备Ni-SiO2催化剂的表征与性能

以正硅酸乙酯和硝酸镍为原料,采用溶胶-凝胶法,将硝酸镍分别溶于水和乙醇制得凝胶,分别经超临界干燥和常规干燥制备了一系列Ni-SiO2气凝胶和干凝胶催化剂,运用BET、XRD、TPR、IR、H2-TPD和活性评价等方法对催化剂的物理化学性质和催化间二硝基苯加氢性能进行研究.结果表明,Ni-SiO2气凝胶催化剂均具有较高的比表面积,但由于金属镍烧结导致活性比表面积较小,加氢性能较差;以乙醇为溶剂制备的干凝胶催化剂的镍物种分散度较高,但镍与载体之间的相互作用过强,致使催化剂的还原度降低,活性组分利用率下降;以水为溶剂制备的干凝胶催化剂具有较高的活性比表面积,表现出很高的催化活性和选择性.     

两个二维Cd(Ⅱ)配位聚合物的合成、晶体结构和荧光性质

具有d^10电子结构的简单金属配合物是不发光的。然而,采用具有π共轭芳香类有机物为配体所构建的Zn(Ⅱ)和Cd(Ⅱ)配合物,特别是具有重复单元结构的配位超分子和配位聚合物,能够发射较强的荧光,由于它们的配位数和结构的多样性,如[Cd4(betc)2(phen)2(H2O)]n(bete=1,2,4,5-benzenetetracarboxyl),[Cd(isonicotinate)2(EtOH)](EtOH),使这类化合物往往显示出一些新奇的功能。本文分别采用均苯四甲酸根和烟酸根为桥配体,合成了两种具有二维无限结构的Cd(Ⅱ)配位聚合物,它们在紫外光照射下,可以发出较强的蓝色荧光。     

一种近红外花菁染料的合成及其应用于生物大分子的测定

光谱性质;蛋白质;核酸测定;一种近红外花菁染料的合成及其应用于生物大分子的测定     

V-P-O／TiO2-SiO2催化剂的制备、表征及其在丙烷氧化制取丙烯酸反应中的应用研究

通过湿磨法,将钒-磷-氧(V-P-O)氧化物负载于钛硅干凝胶(TiO_2-SiO_2)上,制备了V-P-O/TiO_2-SiO_2氧化物催化剂,并运用BET,XRD,TEM及XPS等技术考察了润湿剂,V-P-O的含量及焙烧条件对催化剂结构的影响.由BET方法发现,以异丁醇为润湿剂对催化剂表面积影响较小.XRD和TEM考察结果表明,所制备的催化剂有较高的热稳定性.通过XPS分析,证实钒元素主要以V(Ⅳ)价态存在于催化剂的表面.V-P-O/TiO_2-SiO_2催化剂在丙烷氧化反应中显示了良好的催化性能.     

Solvent Effects on the Spectral Properties of Rhodamine 6G: Estimation of Ground and Excited State Dipole Moments

Spectroscopic and photophysical behavior of Rhodamine 6G (R6G) in seven solvents are reported in this work. R6G monomers exhibit strong electronic absorptions (due to π*←π transitions) in the 529–539-nm region, and the band positions were shown to depend on the refractive indices of the respective solvents. The Stokes’ shifts displayed a linear dependence on solvent polarity, with values ranging between 19 nm (in benzene) and 28 nm (in water). R6G’s fluorescence quantum yields (Φ_F) are generally high (> 0.90), and this was ascribed to structural features (rigidity, planarity and presence of condensed rings) in the R6G molecule. These Φ_F values are shown to vary with solvent viscosity in accordance with the Förster–Hoffmann model. Fluorescence quenching of R6G by 1,4-benzoquinone was diffusion controlled and occurred via an electron transfer mechanism. Theoretical treatment of the fluorescence quenching data yielded fluorescence lifetime values, which were also shown to be solvent viscosity dependent. Ground-state and excited-state dipole moments of R6G were obtained semi-empirically via the analysis of solvatochromic data, and the values are found to be 0.69 D and 1.97 D, respectively.     

非表面活性剂溶胶凝胶法制备介孔干胶包埋活酵母

通过非表面活性剂溶胶凝胶法,采用海藻糖和甘油既作为保护剂又作为造孔剂,并使用羟乙基纤维素(HEC)作为添加剂以减轻凝胶过程中的收缩,成功地将酵母原位包埋在具有介孔结构的干胶中,维持了酵母的存活并探索了包埋酵母的代谢动力学与材料孔径参数改良的相关性.选择四乙氧基硅烷(TEOS)和甲基三乙氧基硅烷(MTES)共同作为前驱体,并将湿胶(含水量60%)转变为干胶(含水量10%)以增强材料,部分实现了游离酵母的抑制.通过单轴抗压强度测试说明干胶的单轴压缩强度整体上是湿胶的13倍,最低可达7.13 MPa.由平板计数法算得溶胶中的酵母浓度为1.5×108mL-1,折算成干胶粉末则为6.4×108g-1.通过对材料进行比表面积及孔隙分析和代谢动力学表征,发现了包埋酵母的代谢动力学与材料孔径参数的相关性.通过非表面活性剂法制得的干胶的比表面积可达800 m2g-1,孔体积可达0.44 cm3g-1,孔径可达2.7 nm.在此条件下,采用独立取样的统计方法,对无游离酵母的样品点进行代谢动力学表征,包埋酵母60 h内可以代谢掉发酵液中89%的葡萄糖.     

Luminescence properties of rhodamine 6G intercalated in surfactant/clay hybrid thin solid films

To develop the solid-state laser oscillator based on laser dye compounds, the incorporation of rhodamine 6G (R6G, a laser dye) in cetyltrimethylammonium (CTA+) cationic surfactant/montmorillonite clay hybrid (HpC) thin solid films was investigated. The R6G/HpC samples were prepared by immersing the HpC films into a R6G aqueous solution with various concentration. X-ray diffraction patterns of the films of HpC, measured before and after the intercalation of R6G, proved the coexistence of both the dye and surfactant in clay interlayer spaces. All prepared thin films exhibited luminescence. It indicates that CTA+ molecules play a role as a partial suppressor of the aggregation of R6G molecules which prevents fluorescence. Moreover, the luminescence property of the present thin films was observed to be dependent on the co-intercalated degree of R6G molecules, indicating that the R6G intercalating in HpC interlayer space molecules exist as two or more luminescence species in the clay interlayer space.     

Conformations and fluorescence of encapsulated stilbene

Absorption and emission spectra of free and encapsulated stilbene in two different capsules were calculated using the DFT and the TDDFT methodology at the B3LYP, CAM-B3LYP, M06-2X, PBE0, and ωB97X-D/6-31G(d,p) levels of theory. The present work is directed toward the theoretical interpretation of recent experimental results on control of stilbene conformation and fluorescence in capsules [Ams, M. R.; et al. Beilstein J. Org. Chem. 2009, 5, 79]. The results of the calculations are in agreement with experiment and show that fluorescence of trans-stilbene persists in the large cage while it is quenched in the small one. It is found that the geometry of trans-stilbene in the ground as well as in the first excited singlet state is unaffected by encapsulation in the large cage, and consequently the absorption and emission spectra are similarly unaffected. In the small cage, the ground state of encapsulated trans-stilbene is distorted, with the two phenyl groups twisted, while the geometry of the excited state, after relaxation, lies at the conical intersection with the ground state. Consequently, there is no emission similar to that of free trans-stilbene, and the state decays nonradiatively to the ground state.     

Fe-P-O超细非晶态催化剂的制备与表征

共沉淀法;乙烷化学吸附;Fe-P-O超细非晶态催化剂的制备与表征