不同掺杂浓度Tm3+：LiLuF4单晶的1800 nm荧光发射

采用坩埚下降法生长了Tm3+掺杂浓度为0.45%,0.90%,1.63%与3.25%(摩尔分数,x)的LiLuF4单晶.测试了样品的电感耦合等离子体原子发射光谱(ICP-AES)、X射线衍射(XRD)谱、吸收光谱(1400-2000 nm),并且分析比较了808 nm半导体激光器(LD)激发下荧光光谱.结果表明:当Tm3+的浓度从0.45%变化到3.25%时,1800 nm处的荧光强度呈现了先增后减的趋势,当掺杂浓度约为0.90%时达到最大值,而位于1470 nm处的荧光强度则呈现了相反的趋势.Tm3+:3F4能级的荧光衰减寿命随着掺杂浓度的增加不断减小.1800 nm处的这种荧光强度变化归结于Tm3+离子间的交叉驰豫效应(3H6,3H4→3F4,3F4)和自身的浓度猝灭效应.同时计算得到了浓度为0.90%的样品在1890 nm处的最大发射截面为0.392×10-20cm2.并且根据Judd-Ofelt理论所得寿命和测定的荧光寿命计算得到了3F4→3H6的最大量子效率约为120%.     

不同掺杂浓度Tm3+：LiLuF4单晶的1800 nm荧光发射

采用坩埚下降法生长了Tm³⁺掺杂浓度为0.45%,0.90%,1.63%与3.25%（摩尔分数,x）的LiLuF₄单晶.测试了样品的电感耦合等离子体原子发射光谱（ICP-AES）、X射线衍射（XRD）谱、吸收光谱（1400-2000 nm）,并且分析比较了808 nm半导体激光器（LD）激发下荧光光谱. 结果表明：当Tm³⁺的浓度从0.45%变化到3.25%时,1800 nm处的荧光强度呈现了先增后减的趋势,当掺杂浓度约为0.90%时达到最大值,而位于1470 nm处的荧光强度则呈现了相反的趋势. Tm³⁺：³F₄能级的荧光衰减寿命随着掺杂浓度的增加不断减小. 1800 nm处的这种荧光强度变化归结于Tm³⁺离子间的交叉驰豫效应（³H₆,³H₄→³F₄,³F₄）和自身的浓度猝灭效应. 同时计算得到了浓度为0.90%的样品在1890 nm处的最大发射截面为0.392×10^-20 cm². 并且根据Judd-Ofelt 理论所得寿命和测定的荧光寿命计算得到了³F₄→³H₆的最大量子效率约为120%.     

Tm3+掺杂锗镓酸盐玻璃的2 μm中红外光谱特性

用高温熔融法制备了Tm2O2掺杂浓度分别为1.526%,3.006%,5.836%,11.028%,15.678%(质量分数,以下同)的65GeO2-12Ga2O3-10BaO-8Li2O-5La2O3(摩尔比)玻璃.从其吸收光谱特性出发,应用Judd-Ofelt理论,计算了Tm3+离子的J-O强度参数(Ω2,Ω4,Ω6)及Tm3+离子各激发态能级的自发跃迁几率、荧光分支比以及辐射寿命等光谱参量.在808 nm波长光的激发下,研究了不同Tm3+掺杂浓度玻璃在～1.47 μm与～1.8 μm的荧光特性,发现当Tm2O3掺杂浓度约达到～3.006%时,在1.8 μm处的荧光强度达最大;然后随着掺杂浓度的增大,其荧光强度反而降低.本文从Tm3+离子间的能量交叉弛豫效应与浓度猝灭效应解释了这一荧光强度变化的现象.同时,根据Mc-Cumber理论,计算了Tm3+离子能级3F4→3H6(1.8 μm)跃迁的吸收截面和受激发射截面,该荧光的受激发射截面峰值比氟锆铝酸盐玻璃大.由于该玻璃材料表现出较好的光谱性能,因此该材料可望成为～2.0 μm波段中红外光纤激光器的候选基质材料.     

绿色荧光粉Ba2-xB2O5:xTb3+的制备及发光性能研究

采用高温固相法合成了Ba2-xB2O5:xTb3+绿色荧光粉。XRD图谱表明合成物质为纯相的Ba2B2O5晶体。该样品在256 nm(4f8→4f75d1)处有最强激发;有4个发射峰,分别位于489 nm(5D4→7F6),545 nm(5D4→7F5),585 nm(5D4→7F4)和622 nm(5D4→7F3);其中在545 nm处有最强发射。随着Tb3+掺杂浓度的不同,激发峰与发射峰的强度先增大后减小,当x=0.7时最佳。研究了电荷补偿剂Na+对发光性能的影响,样品的发射光谱强度随Na+掺杂浓度的增大而增大,当掺杂浓度达到或超过Tb3+浓度后发射光谱强度下降。     

一种上转换白光荧光粉的制备与发光性能研究

采用高温固相法制备了上转换白光荧光粉AlF3-YbF3:Er3+/Tm3+。通过XRD物相分析可知:上转换白光荧光粉AlF3-YbF3:Er3+/Tm3+是由三方AlF3相和正交YbF3相组成;利用发射光谱研究了该荧光粉的上转换发光性能,并且分析了当固定Er3+离子掺杂浓度时,Tm3+离子掺杂浓度对上转换白光荧光粉AlF3-YbF3:Er3+/Tm3+色度的影响,进而提出其上转换能量传递机制。结果表明:在980 nm激光激发下,波长为410 nm的紫光峰、550 nm的绿光峰和660 nm的红光峰分别对应于荧光粉中Er3+离子的2H9/2→4I15/2,4S3/2→4I15/2和4F9/2→4I15/2能级的跃迁,而波长为360 nm的紫外光峰、450 nm的蓝光峰、700 nm的红光峰,分别对应于荧光粉中Tm3+离子的1D2→3H6,1G4→3H6和1G4→3F4能级的跃迁,Er3+离子发出的光与Tm3+离子发出的光最终混合成色坐标为x=0.32,y=0.36的白光。此外,通过980 nm半导体激光器和EPM 2000 Dual-channel Joulemeter/Power meter测得该荧光粉最大上转换效率为6.90%。     

Dy~(3+)掺杂Ge-Ga-Se-KBr硫卤玻璃近红外和中红外发光特性研究

用熔融淬冷法制备了系列掺杂浓度的Dy3+∶Ge-Ga-Se-KBr硫卤玻璃样品,测试了样品的折射率、吸收光谱、近红外及中红外荧光谱。应用Judd-Ofelt理论计算了Dy3+离子的强度参数(Ωi,i=2,4,6)、自发辐射跃迁几率(A)、荧光分支比(β)和辐射寿命(τrad)等光谱参数。研究了810 nm激光泵浦下样品中红外荧光特性与掺杂浓度之间的关系,利用McCumber(MC)和Futchbauer-Ladenburg(FL)理论分别计算了常温Dy3+:6F5/2→6H9/2(2.17μm),6F11/2(6H9/2)→6H13/2(2.47)和6H13/2→6H15/2(2.86μm)中红外荧光的受激发射截面。     

Yb3+/Tm3+掺杂的NaY(WO4)2纳米晶的制备及发光特性

以聚乙二醇为配位剂,用水热法制备出纳米级上转换发光粉Yb3+和Tm3+共掺杂的NaY(WO4)2。研究了不同cYb/cTm对上转换发光强度的影响,实验表明当cYb/cTm=5∶1时,上转换发光强度最强。用XRD,SEM确定了Yb3+和Tm3+共掺杂的NaY(WO4)2是四方晶系,其粒径在25~35 nm范围,且分散均匀。用980 nm半导体激光器(LD)对其进行激发,在室温下观察到了365 nm附近紫外发射峰、456 nm,476 nm附近的蓝光发射峰和648 nm附近的红光发射峰,分别对应于Tm3+离子的1D2→3H6,1D2→3F4,1G4→3H6和1G4→3F4的跃迁。根据泵浦功率与发光强度的关系得出紫外发射峰、蓝光和红光发射均为双光子过程。     

铕掺杂硅钛柱撑蒙脱土的合成及发光性能研究

采用溶胶凝胶法制备了Eu3+掺杂的硅钛柱撑蒙脱土(Si-Ti-MT),运用XRD,SEM-EDX和FT-IR对其结构进行了表征。结果表明,Eu3+掺杂的硅钛柱撑剂插入蒙脱土层之间,保持了蒙脱土层状结构。经荧光发射光谱和激发光谱分析可知,Si-Ti-MT是Eu3+发光的有效基体,其发射能级主要为Eu3+613 nm(5D0→7F2);激发光谱中表现了Eu3+的5个特征激发带,分别为363 nm(7F0→5D4),382 nm(7F0→5G2),395 nm(7F0→5L6),415 nm(7F0→5D1)和465 nm(7F0→5D2);热处理促进了Eu3+掺杂的硅钛柱撑蒙脱土的发光,且样品的荧光强度随着Eu3+掺杂量的增加而增强,不会发生浓度猝灭现象。     

YVO_4:Eu~(3+),Al~(3+)荧光粉的制备及荧光性能研究

用高温固相法制备了Al3+掺杂的YVO4:Eu3+荧光粉。采用X射线粉末衍射(XRD)、环境扫描电镜(SEM)、荧光光谱(FL)等对样品进行了表征。分析了Al3+掺杂对YVO4:Eu样品晶体结构、晶胞参数和荧光性能的影响,并探讨了烧结温度对光谱性能的影响。研究结果表明:当Eu3+的浓度x(摩尔百分比)为4%,Al3+的浓度为1.5%时,在1100℃下烧结的样品其荧光性能最好,5D0→7F2处的发光强度约为未掺Al3+的2.5倍。由于Eu3+的7F2→5L6跃迁吸收,YVO4:Eu3+,Al3+荧光粉可在395 nm被有效激发。因此,YVO4:Eu3+,Al3+可以作为近紫外激发的白光LED红色荧光粉。     

Li+掺杂对TeO2:Tm3+/Er3+/Yb3+纳米材料上转换发光的增强作用

采用水热法制备了发白光的Li+掺杂α-TeO2∶Tm3+/Er3+/Yb3+和β-TeO2∶Tm3+/Er3+/Yb3+纳米上转换发光材料。采用X射线衍射、透射电镜和上转换发光光谱对制备的TeO2∶Tm3+/Er3+/Yb3+/Li+纳米材料进行表征,结果显示:Li+的掺入基本不改变纳米材料的晶型和结构;在980 nm近红外光的激发下,纳米材料发射出中心波长476 nm的蓝光,525 nm及545 nm的绿光和659 nm及675nm的红光,分别对应于Tm3+的1G4→3H6能级跃迁,Er3+的2H11/2→4I15/2和4S3/2→4I15/2能级跃迁,Er3+的4F9/2→4I15/2能级跃迁和Tm3+的3F2→3H6能级跃迁;Li+的掺入能够增大白光体系的发光强度,基本不改变纳米材料的白光颜色。此外,探讨了纳米材料的上转换发光机理。     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles by Curtius reaction in Morita-Baylis-Hillman derivatives

Synthesis of substituted pyrrolo[1,2-a]pyrazines and pyrazino[1,2-a]indoles from the Morita-Baylis-Hillman derivatives of acrylates via saponification followed by Curtius reaction is described.     

正丁胺对激光染料荧光谱影响的研究

用正丁胺作为碳源,采用射频辉光放电制备碳膜,选用激光染料R6G和聚乙二醇混合液作为蒸气源,采用单源热蒸发,在蒸发室与染料同时沉积得到混合膜,用拉曼光谱和红外光谱分析了碳膜的结构和键合方式,分析表明:碳膜中存在胺基团和氢原子.混合膜的荧光谱测量结果表明,认为正丁胺对染料荧光谱的影响是因为胺基和氢原子的存在.     

Cu0-catalysed 1,3-dipolar cycloadditions of α-amino acid derived N,N-cyclic azomethine imines to ynones

A series of 20 CuAIAC reactions between eight 4-acylamino substituted pyrazolidine-3-one-1-azomethine imines and four terminal ynones were performed using Cu⁰ as catalyst. The corresponding fluorescent cycloadducts were obtained in very high yields upon simple workup. Thus, Cu-metal turned out to be a better catalyst than Cu^I in terms of yield and ease of isolation. Availability of azomethine imines, mild reaction conditions, and simple workup enable a “click” access to libraries of densely substituted 2,3-dihydro-1H,5H-pyrazolo[1,2-a]pyrazol-1-ones. Reactivity of differently substituted dipoles was evaluated experimentally and by quantum chemical methods (DFT).     

Synthesis and antioxidative/anti-inflammatory activity of novel fullerene–polyamine conjugates

(E)-4-(Fullerenopyrrolidin-1-yl)-3-methylbut-2-enoic acid and its corresponding succinimidyl ester, readily obtained through Prato-type modification of C₆₀, were used for the selective N-acylation of polyamines. The thus obtained conjugates were evaluated for their antioxidative and anti-inflammatory activity and their cytotoxicity was determined. Members of this family of compounds showed interesting anti-lipid peroxidation, anti-lipoxygenase and anti-inflammatory activity and comparable cytocompatibility to spermidine.