Solid Dye Lasers Based on 2-Hydroxypropyl Methacrylate and Methyl Methacrylate Copolymers

Polymers are a kind of attractive hosts for laser dyes because of their superior optical homogeneity, and high transparency in pumping and lasing range. Copolymers usually have higher damage threshold and better photostability than mono-polymers. Solid dye samples based on copolymer of methyl methacrylate （MMA） with 2-hydroxypropyl methacrylate （HPMA） doped with 1-, 3-, 5-, 7-, 8-pentamethyl-2, 6-diethylpyrromethene-BF2 （PM567） are prepared. Spectra and lasing properties of the samples are studied. Compared to the samples based on monopolymer polymethyl methacrylate （PMMA）, enhanced slope efficiency and photostability are obtained in the copolymers. The highest slope efficiency is 45.1%, and nearly one-fold increase of photostability is obtained. The longest useful lifetime of 4390 pumping pulses is presented with the pump energy as high as 183 mJ per pulse at repetition rate of 10 Hz. The results indicate that the laser performances of solid dye mediums can be greatly increased using copolymer of MMA with HPMA as host.     

聚甲基丙烯酸甲酯中乙酰丙酮铕水合物掺杂形成的差异化发光中心

制备了均匀且透明的乙酰丙酮铕水合物掺杂的聚甲基丙烯酸甲酯(PMMA)。Judd-Ofelt强场参数Ω2(19.73×10-20 cm2)和Ω4(2.19×10-20 cm2)表明在掺杂样品中三价铕离子周围环境具有较强共价性和反演非对称性。计算得5 D0→7 FJ(J=1,2和4)跃迁的最大发射截面分别为0.38×10-21,4.90×10-21和0.36×10-21 cm2。在365nm紫外光的激发下样品发出紫红色荧光,在254nm紫外光激发下则呈现明亮的红色,表明样品可作为紫外光敏感元件用于光学传感器。掺杂样品折射率与纯PMMA的折射率之间存在合理的差值,当其作为纤芯材料与包层材料纯PMMA结合制成标准尺寸9μm/125μm光纤时支持多模光传输,为进一步研发医疗照明光纤、柔性通讯光纤和光纤传感器提供基础。     

Eu(DBM)_3Phen掺杂聚甲基丙烯酸甲酯静电纺丝荧光纤维

通过静电纺丝技术获得直径约为700 nm,均匀且随机取向的亚微米级Eu(DBM)3Phen/PMMA纤维。在紫外光辐射下,亚微米级荧光纤维发出明亮的红色荧光。其激发光谱表明,荧光纤维有效激发波长范围为200~400 nm。利用积分球配以CCD探测器,在367 nm长波紫外LED激发下对荧光纤维开展绝对光谱功率测试。当LED泵浦功率为535.76#W时,厚度80#m的Eu(DBM)3Phen/PMMA纤维薄层对紫外辐射的吸收率高达89%,350~850 nm范围内发射的总绝对光谱功率、总光子数和总荧光量子产率分别为36.56#W、11.46×10~(13)cps和12.94%。亚微米级Eu(DBM)_3Phen/PMMA纤维薄层中,Eu~(3+)较高的跃迁发射几率及较大的发射截面使得纤维可以高效吸收紫外辐射并转变为可见光,在提高太阳能电池光电转换效率方面具有潜在应用价值。     

基于超分子结构共掺杂纳米复合薄膜的制备与荧光特性

为改善功能分了的特性,提出一种基于金属纳米粒子-偶氮染料复合物共掺杂超分子结构功能材料的设计新方法.并依照此方法制备出复合材料,观测了其显微结构,测量了其紫外-可见光吸收,研究了该超分子结构复合体系的荧光特性.实验发现,由于金属银纳米粒子的掺杂,使得超分子结构复合体系中功能分子甲基橙在溶液态体系的荧光强度增强近5倍,而在两种不同结构(共混结构和包覆结构)的薄膜态超分子结构体系中,其荧光强度分别被猝灭15%和20%.研究结果表明,复合膜中采用超分子结构完全能够改善功能分子的特性.     

Thermal Properties of Carboxymethylcellulose and Methyl Methacrylate Graft Copolymers

Carboxymethyl cellulose and methyl methacrylate graft copolymers (CMC-g-PMMA) were synthesized by using potassium persulphate (KPS) as initiator. These graft copolymers were characterized by Fourier transform infrared spectra (FTIR), thermogravimetric analyses (TGA), and differential scanning calorimeter analyses (DSC). In addition, the nonisothermal thermal decomposition kinetics of copolymers was studied. The experimental results indicated that in the temperature range from 300°C to 450°C, the copolymer had a mass loss. The activation energy was 41.96 kJ/mol, and the logarithm of the Arrhenius coefficient (lnA) was 17.31.     

基于三维荧光光谱的沥青老化行为研究

沥青在服役过程中暴露在自然环境里,受到光、热、氧等的作用,易出现老化从而引起的多种病害,如裂缝、龟裂和坑槽等,严重影响沥青混凝土路面的服役寿命。为了提高沥青混凝土路面的耐久性能,揭示沥青在老化过程中的成分与结构的变化规律,基于荧光光谱技术,从沥青的荧光猝灭现象出发,利用实验室内的紫外老化与热氧老化,针对两种不同沥青进行了老化实验,并研究了沥青在老化前后的性能和组分变化;借助荧光分光光度计采集了沥青的三维荧光光谱,并分析了沥青荧光光谱谱图的特征,获取了沥青荧光光谱的峰值强度坐标,计算了老化前后峰值坐标的偏移向量。实验结果表明,沥青避免出现荧光猝灭的理想浓度是0.1 g·L-1;沥青老化后其软化点增加,针入度与延度减小;其四组分中饱和分基本不变,芳香分减小,胶质与沥青质增加。结合三维荧光光谱发现,沥青的荧光强度峰值坐标出现了“蓝移”,且沥青组成中的芳香分的含量决定了荧光光谱峰值的偏移程度;通过向量计算表明,峰值坐标偏移的向量的模大于36时,沥青已经严重老化。通过对沥青三维荧光光谱特征值的分析,可以有效评价沥青的老化过程,对提高沥青的耐久性具有重要意义。     

8-羟基喹哪啶-丙烯酸-镓(Ⅲ)与甲基丙烯酸甲酯共聚物的光致发光研究

制备了8-羟基喹哪啶、丙烯酸与镓(Ⅲ)的三元配合物,将此配合物与甲基丙烯酸甲酯共聚后得到一种含镓(Ⅲ)的共聚物,这种共聚物易溶于氯仿、丙酮等普通低沸点溶剂,具有良好的成膜性能。通过红外光谱、元素分析、紫外光谱等方法对三元配合物和共聚物的组成进行了表征。三元配合物和共聚物的荧光光谱测试,表明共聚物在496 nm处能发出较强的荧光。     

Preparation and Characterization of an Organic/Inorganic Composite Based on Ferrospinel with Poly(Methyl Methacrylate) and Polyaniline

A novel organic/inorganic composite based on LiNi–ferrospinel with poly(methyl methacrylate) (PMMA) and polyaniline (PANI), PANI/PMMA/LiNi_0.5Fe₂O₄ composite, was synthesized via a facile in-situ polymerization process. The structures of the resulting samples were investigated by X-ray diffraction, Fourier transform infrared spectroscopy, and atomic force microscopy. The optical and thermal properties of the PANI/PMMA/LiNi_0.5Fe₂O₄ composite were studied by fluorescent spectroscopy and thermogravimetry analysis. It was indicated that the existence of LiNi_0.5Fe₂O₄ (LFNO) in the PANI/PMMA/LFNO composite resulted in changes in the fluorescence spectra. The as-obtained composite may have potential for electrical and electromagnetic applications in antistatic materials, electromagnetic shields, radar absorbers, and so forth.     

Synthesis, Structural, Thermal and Photo-Physical Properties of Triazine Based NLO Material

Three novel triazine based organic chromophores with D-π-A (Donor-π system- Acceptor) push-pull type have been synthesized from 2, 4-diamino-6-phenyl-1,3,5-triazine as a starting material. Structures of all the three compounds have been confirmed by UV-Visible absorption, FT-IR, NMR and Mass spectral techniques. Their photo physical and thermal properties have been investigated. Among the three compounds, 6-phenyl-2,4-((4-amino-1,5-dimethyl-2-phenyl pyrazol-3-ylidene)(4-nitro benzylidene))-diamino-1, 3, 5-triazine (NDP) showed positive solvatochromism compared to the other two compounds. The absorption in the UV region of these three compounds were found to be less dependent on solvent polarities, whereas the red shifted fluorescence was strongly dependent on solvent polarities. The TGA data indicates that all the three compounds are stable up to 160 °C. Measurement of non linear optical properties showed that there is an increased second harmonic generation (SHG) efficiency with respect to urea indicating the existence of high molecular nonlinearity in NDP.     

Effect of Individualized Cellulose Fibrils on Properties of Poly(Methyl Methacrylate) Composites

Cellulose fibrils were manufactured from flax fibers using chemical treatments followed by cryo-crushing and ultrasonication techniques. The fibrils, consisting mainly of cellulose free from lignin, pectin and hemicellulose, were exploited as a biofiller in preparing poly(methyl methacrylate) (PMMA) matrix composites. The effects of incorporating cellulose fibrils on the physical and mechanical properties of the polymer matrix were investigated. In particular, the influence of the fibrils on the thermal stability and degradation of the composites was studied by means of thermogravimetric analysis carried out in both inert and oxidative atmospheres. The runs performed under air flow revealed the efficiency of the cellulose fibrils in delaying the polymer decomposition during thermal oxidation. The weight loss was slowed down in the composites of all compositions and the temperature of degradation increased with increasing the amount of the fibrils. The combustion properties of the fibril-based composites were evaluated by means of pyrolysis combustion flow calorimetry. The addition of cellulose fibrils into the PMMA matrix resulted in a noticeable decrease of the primary combustion parameters.     

Switchable Diffraction Pattern Based on Cascaded Metasurfaces

Metasurfaces have great advantages in the field of laser detection because of their ability to generate large amounts of point sources or various diffraction patterns. Here,cascaded metasurfaces (CM) for generating switchable spatial light distributions is utilized, which can be used for optical scanning and identifications. The light distribution is composed of several distinct diffraction patterns, and the scanning of the diffraction space is realized by multiple pixel-scale alignment strategies between two pieces of CM. Through combining Dammann optimization and the gradient descent method, various diffraction patterns under different matching situations can be guaranteed by phase superposition. Various diffraction conditions with highly identifiable intensity distribution are guaranteed by using the optimization method. Such optical scanning devices based on CM have small footprints, high integration, flexible composition, and stable diffractive combination features. By manipulating CM to generate changeable spatial diffraction phenomenon may provide flexible modulation properties to optical scanning, measurement, and other applications.     

Preparation and Characterization of Poly(Methyl Methacrylate) Coated TiO2 Nanoparticles

Titanium dioxide (TiO₂) nanoparticles were modified with poly(methyl methacrylate) (PMMA) to improve the dispersion stability of the nanoparticles in a dielectric medium and to reduce the density mismatch between TiO₂ and a dielectric medium for a microcapsule‐type electrophoretic display application. Nanoparticles were coated with PMMA by in situ dispersion polymerization. The PMMA‐coated TiO₂ nanoparticles were characterized by fourier transform‐infrared spectrometrey (FT‐IR), electrophoretic light scattering (ELS), and scanning electron microscopy (SEM). Density of PMMA‐coated TiO₂ nanoparticles was found to be dependent on the thickness of the PMMA coating on the nanoparticles. An increase of thermal stability of the PMMA layer and the contents of PMMA on the surface of the nanoparticles were measured via thermogravimetric analysis (TGA).     

基于荧光光谱技术研究胶原蛋白溶液中分子的聚集行为

对胶原分子聚集行为的研究,不仅能改善其理化特性,同时也为其在食品、组织工程和生物医药等领域的应用提供理论指导。基于胶原分子中苯丙氨酸(Phe)和酪氨酸(Tyr)的内源荧光特性,采用常规波长、同步荧光和二维(2D)荧光光谱技术研究了不同浓度和温度下胶原分子的聚集行为。研究结果表明：(1)在激发波长275 nm条件下,胶原分子仅在发射波长303 nm处出现了归属于Tyr的特征峰;选取波长差(Δλ)为15 nm的同步荧光扫描胶原分子,发现其在261和282 nm处出现了分别归属于Phe和Tyr的特征峰。(2)特征峰的荧光强度与胶原浓度呈现良好的线性关系,表明了基于常规波长和同步荧光光谱技术对胶原定量分析的可行性。(3)随着胶原浓度的增加,Tyr和Phe的含量逐渐增大,且胶原分子间距逐渐降低并聚集成纤维束,使得Tyr和Phe相互靠近并参与形成大量的氢键,从而导致荧光强度不断增大。然而随着温度的升高,荧光基团与溶剂碰撞的猝灭机会增大,且胶原分子中Tyr和Phe的荧光量子产率逐渐降低,同时胶原分子动能增大,其聚集体逐渐松散,其三股螺旋结构逐渐坍塌,Tyr和Phe参与形成的氢键被破坏,从而导致荧光强度随温度的升高不断降低。(4)275 nm常规波长的2D荧光光谱分析表明,胶原分子在297,303和310 nm处出现了相关峰,其中303 nm归属于Tyr,297 nm归属于胶原分子聚集过程中参与氢键形成的Tyr;310 nm可能归属于Tyr的激发态,其不断的蓝移形成稳定的基团,以便参与氢键的形成,从而促进了胶原分子的聚集。以浓度为外扰的基团响应顺序为303 nm>297 nm>310 nm;以温度为外扰的基团响应顺序为297 nm>310 nm>303 nm。(5)2D同步荧光光谱分析表明,随着胶原浓度和温度的升高,Phe均比Tyr优先响应。综上,采用常规波长、同步荧光光谱技术均能较好的研究胶原分子在不同浓度和温度下的聚集行为,且为胶原的定量分析提供了一种新的方法,但同步荧光光谱技术可将量子产率较低的Phe显现出来,体现了其具有窄化谱带和提升分辨率的优点。此外,结合2D荧光分析技术,可进一步研究胶原分子基团的响应顺序。     

Solvatochromic and Fluorescence Behavior of Sulfisoxazole

The Fluorescence spectroscopic and solvatochromic behavior of Sulfisoxazole, a sulfa drug with antimicrobial activities, in various pure solvents of different polarity and hydrogen bonding capability is reported. The fluorescence emission spectrum of sulfisoxazole was found to be solvent polarity dependent, where a notable red shift in emission maximum was observed with increasing solvent polarity as well as hydrogen bonding capability. The effects of the latter two solvent parameters were quantitatively investigated using the methods of Lippert–Mataga and solvatochromic comparison method (SCM) that is based on the Kamlet-Taft equation. Particularly, the Lippert–Mataga method was applied to estimate the dipole moment of the excited state (μ_e) upon plotting Stokes shift versus solvent polarizability (Δf), where a value of 11.54 Debye was obtained. On the other hand, applying the multiple regression analysis to the SCM method revealed that solvent polarizability (π*) and hydrogen-bond donor capability (α) approximately equally stabilize sulfisoxazole in the excited state with minor destabilization contribution by the hydrogen-bond acceptor capability (β). These findings revealed that the excited state of sulfisoxazole is stabilized by polar solvents, indicating that this drug molecules exhibit larger dipole moment in the excited state than in the ground state, which in turn implies that a potential intramolecular charge transfer (ICT) occurs after excitation.     

Thermal Behavior of Polypropylene-g-glycidyl Methacrylate Prepared by Melt Grafting

The thermal behaviors of glycidyl methacrylate (GMA)-grafted polypropylene (PP) (PP-g-GMA) with two different grafting degrees, namely, GPP1 and GPP2, were investigated by differential scanning calorimetry (DSC), polarized optical microscopy (POM), wide-angle X-ray diffraction (WAXD), dynamic mechanical analysis (DMA), and thermogravimetrical analysis (TGA). DSC results suggested that the GMA grafted PP exhibited higher crystallization temperature T_c, higher melting temperature T_m, and higher crystallinity compared with the neat PP. The isothermal crystallization kinetics was analyzed with the Avrami equation and the total crystallization activation energy was calculated. It was concluded that the crystallization processes of PP and the grafted PP were controlled by nucleation and the values of the crystallization activation energy of PP and the grafted PP were almost identical. POM results suggested that the GMA grafted PP exhibited smaller spherulites size compared with the neat PP. WAXD patterns indicated that the neat PP encouraged the formation of γ phase, compared with the grafted PP, during the crystallization process. DMA results showed that melt grafting did not induce a clear effect on the γ-transition and β-transition of the amorphous phase but resulted in a decrease in mobility of the PP chains in the crystals. TGA curves suggested that the melt grafting slightly improved the thermal stability of PP.     

脱镁叶绿酸-a甲酯的合成及对牛血清白蛋白的结合作用

用荧光光谱和UV-Vis光谱研究了脱镁叶绿酸-a甲酯(Methyl pheo-phorbide-a)与牛血清白蛋白(Bovine Serium Albumin,BSA)的相互结合反应。实验表明叶绿酸-a甲酯与牛血清白蛋白的相互结合作用为单一的静态猝灭过程。在水溶液中脱镁叶绿酸-a甲酯发生自聚,它与蛋白质以表观摩尔比2∶1牢固结合,其结合常数K_B=6.7×104 L·mol-1。而在四氢呋喃与水的混合溶液中脱镁叶绿酸-a甲酯以单分子状存在, 其与BSA的结合摩尔比为1∶1。BSA分子与叶绿酸-a甲酯的结合点位为1。根据Frster非辐射能量转移机理,求算了给体(BSA)与受体(脱镁叶绿酸-a甲酯)间距离r=3.50 nm和能量转移效率E=0.39。     

Effect of Molecular Architecture on Physical Properties of Tree-Shaped and Star-Shaped Poly(Methyl Methacrylate)-Based Copolymers

The synthesis of star-like A(B)_n copolymers based on the hydrophilic poly(ethylene glycol) monomethyl ether (m-PEG, block A) and the hydrophobic poly(methyl methacrylate) (PMMA, blocks B) is reported. We obtained copolymers made of one m-PEG chain and 2 or 4 PMMA blocks using a combined “arm first”—“core first” approach. Such structures were called tree-shaped copolymers where the m-PEG was considered as the trunk and PMMA arms as the branches. Star-like copolymers (B)_nA-A(B)_n built by two tree-shaped fragments with a poly(propylene oxide) (PPO) as the central junction, were also synthesized according to a previously reported procedure. The latter were called star-shaped structures and the synthesis was performed to obtain architectures different from the tree-shaped one but characterized by a similar length of the PMMA arms. Microstructural analysis was carried out through ¹H-NMR and GPC, and the thermal and transport properties (sorption and diffusion) to liquid water were investigated and correlated to the molecular architecture of the two classes of copolymers.     

Fluorescence Spectral Properties of Methyl Orange in Homogeneous Media

Journal of Fluorescence - The methyl orange [C14H14N3SO3Na], an azo dye exhibited strong emission and large Stokes shift in various solvents, and the largest shift (Δλ = 125.51nm or...     

Morphological Effect on Fluorescence Behavior of Silver Nanoparticles

Effect of Silver nanoparticles (AgNPs) morphology on their fluorescence behavior is reported. AgNPs sol stabilized by Ethylene Diamine Tetra Acetic-Acid (EDTA) was prepared by chemical reduction method. Morphology of the AgNPs was tuned through changing the Ag⁺ ion concentration and P^H of reaction mixture. Additional peaks observed in surface Plasmon resonance spectra suggest the an-isotropic nature of AgNPs. Actual morphology was judged by Transmission Electron Microscopy. Emission spectra recorded using Spectrofluoremeter suggest the fluorescent nature of AgNPs, which also influenced by morphology of AgNPs and attributed to the variation in surface structure of an-isotropic AgNPs.

司帕沙星氯代物的制备及荧光性质研究

司帕沙星在酸性介质中与亚硝酸反应 ,其重氮盐在氯化亚铜存在下 ,继而与氢氯酸反应生成一种较司帕沙星荧光响应值高 1 1 0倍的强荧光物质 ,采用元素分析、红外光谱和质谱对其衍生物的结构进行了表征。结果表明 ,司帕沙星的荧光强度与其喹啉环 5 位上的氨基密切相关 ,本文还对司帕沙星的荧光自猝灭及氯代荧光增敏机理进行了探讨。