Enhancement of Electrical and Optical Properties of Sodium Bromide Doped Carboxymethyl Cellulose Biopolymer Electrolyte Films

Abstract

Biodegradable ion conducting solid polymer electrolyte films of carboxymethyl cellulose (CMC) doped with sodium bromide (NaBr) with various weight percentages were prepared by a solution casting technique. Their structural, optical and electrical properties were studied by various experimental techniques in order to understand the impact of the sodium metal salt on the biopolymer CMC’s properties. The optical parameters namely the optical bandgap energy and the refractive index, showed a significant variable variation with the metal salt concentration. The maximum dc conductivity was found to be ～5.15?×?10^?4 S cm^?1 at room temperature for the sample with 20?wt% of NaBr content in the CMC matrix. The ionic conductivity and dielectric constant in general, increased with increase in metal salt content, affirming the increase in ion concentration. The calculated transference number showed that the conductivity was mainly due to ions. The increase in conductivity was due to an increase in degree of amorphousness of the polymer upon doping, as analyzed by their XRD spectra.     

Ce3+—高分子络合物发光的激发过程

本文研究了Ce3+-PMMA及Ce3+—PMA18·C·6两个高分子络合物发光材料的荧光激发过程以及激发过程与高分子结构的关系。通过荧光寿命、荧光光谱以及时间分辨光谱分析表明,在Ce3+—PMMA络合物体系中,Ce3+的荧光发射主要是来自高分子配体的能量传递,而对于Ce3+—PMA18·C·6粉末络合物体系,Ce3+发光的能量主要是来自入射光的直接激发。文章对上述两个稀土高分子络合物的激发机制的差异也做了较为详细地描述。     

溶液中稀土(Eu、Tb)络合物的敏化荧光

本文应用荧光滴定法研究了稀土络合物的敏化荧光,比较了某些稀土的二元络合物的激发光谱和荧光光谱,讨论了一些因素如配位体的配比、络合物浓度、酸碱度及其它络合剂对稀土络合物荧光的影响。对三元络合物的能量转移途径也进行了考查,了解到三元络合物中同时存在两个敏化剂配位体时,由于配位体络合力的不同,光能的吸收主要是通过与稀土结合较强的配位体向稀土离子作能量转移,所研究络合物的能量转移机理属于Dexter型的短程交换相互作用。     

The Dependence of Benzo-15-Crown-5 Ether-Containing Oligo Paraphenylene Vinylene (CE-OPV) Emission Upon Complexation with Metal Ions in Solution

The effects of metal salts (NaCl, CaCl₂·2H₂O, EuCl₃·6H₂O and Eu(OAc)₃) on the steady state and time resolved fluorescence behaviour of poly(para phenylene vinylene) oligomers containing benzo-15-crown-5 ether units (CE-OPV) have been investigated. The presence of EuCl₃ causes a significant (8–9 fold) increase in the fluorescence emission intensity of the OPV segments, as compared to pure CE-OPV, in 99:1 methanol/chloroform solution and a small (9 nm) red shift in the emission maximum. The presence of Na⁺ or Ca²⁺ results in less marked increases in fluorescence intensity compared to Eu³⁺. In the presence of Eu³⁺ and Na⁺, the fluorescence intensity increases approximately linearly with metal ion concentration up to a metal ion/CE-OPV molar ratio of 10. The emission enhancement is not related to a simple 1:1 (CE-OPV:metal ion) complex formation process. In contrast, in acetonitrile, CE-OPV shows complex fluorescence quenching behaviour as a function of EuCl₃ concentration. This solvent dependence suggests that the emission changes with metal concentration are related to the formation of charge-transferred complexes. The marked changes in fluorescence quantum yield of the PPV backbone due to complexation with metal ions makes CE-OPV a sensitive fluorescent probe for metal ions, or may be exploited for improving the quantum yield of PPV-based devices.     

Fabrication of rare-earth/quantum-dot nanocomposites for color-tunable sensing applications

We developed a new fluorescent nanocomposite by using a layer-by-layer approach to link NaYF₄:Ce,Tb rare-earth (RE) nanocrystals and CdSe/ZnSe semiconductor quantum dots (QDs) with opposite charges. Under ultraviolet light excitation, the nanocomposites exhibited both the green Tb emission centered at 550 nm, and the red QD emission at 650 nm. Sensing applications showed that the red QD emission was quenched by trace amount of Cu²⁺ (or Ag⁺) ions due to the ion displacement mechanism, while the green RE emission kept constant. Thus, the nanocomposites with the decreased QD/RE emission intensity ratio and changed fluorescence output color provided a visible “indicator” to detect metal ions quantificationally. In comparison with single emission materials, the dual emission nanocomposites can be a more reliable probe for various sensing applications.     

A-site and B-site substitutions and the emission properties of Eu3+ ions in ABO3 –type cubic perovskite: A case study of BaZrO3

The emission properties of the rare earth (RE) elements have been found to be sensitive to the local lattice environment around them, and could be employed for probing the local lattice environment. Because each constituent ion of a material should have its own particular structural environment, the emission profiles in RE elements depend strongly on the doping sites of RE elements inside the host crystals. We investigated the emission properties of the Eu³⁺ ion doped BaZrO₃ (BaZrO₃:Eu) with doping site dependence (A-site vs. B-site), as well as ambient dependence in the post-annealing process. The site-selective doping was identified from the Rietveld refinement analysis on the XRD patterns of our BaZrO₃:Eu samples. Photoluminescence and photoluminescence excitation measurements showed that the emission properties of the samples with the Eu³⁺ ions substituted at Zr sites revealed much greater emission properties than those at the Ba sites. This behavior was found to accord with the change in intensity ratio of ⁵D₀ → ⁷F_0,2 to ⁵D₀ → ⁷F₁ in Eu ions, which should be a measure of the local lattice asymmetry around the Eu ions. We also found that with post-annealing in H₂ atmosphere, the emission intensities of the Eu ions increased significantly, while with post-annealing in O₂ atmosphere, they were suppressed. Our findings indicated that the cation/oxygen vacancies could change the local lattice environment around the Eu ions, as well as the valence states of Eu ions, depending on the doping site in the cubic perovskite.     

A functionalized dianthryl tetraaza macrocycle having the recognizing and switching ability

The synthesized macrocycle L is the novel fluorescent receptor having the switching ability by the external stimuli as well as having the recognizing ability of various metal ions. In particular, this macrocycle L shows the possibility of the selectivity of metal ions even in the same charge ions of a different metal, and the values of association constant (M⁻¹) of that for metal ions are consistent with the tendency of increasing charge number of metal ion. In addition, the values of quantum yield (Φ_F) of metal complexes of macrocycle L were ranged from 0.021 to 0.111 enough to recognize the metal ions in macrocycle L. We know from the fluorescent pH titration of macrocycle L by acid/base that the change of fluorescence intersects at about pH=5.     

Synthesis and optical properties of silver nanoparticles in ORMOCER

Experimental results on synthesis of metal nanoparticles in ORMOCER by ion implantation are presented. Silver ions were implanted into organic/inorganic matrix at an accelerating energy of 30?keV and doses in the range of 0.25?10¹⁷ to 0.75?10¹⁷?ion/cm². The silver ions form metal nanoparticles, which demonstrate surface plasmon absorption at the wavelength of 425?C580?nm. The nonlinear absorption of new composite materials is measured by Z-scan technique using 150?fs laser pulses at 780?nm wavelength. ORMOCER matrix shows two-photon nonlinear absorption, whereas ORMOCER with silver nanoparticles demonstrates saturated absorption. Some optical applications of these composite materials are discussed.     

Rare-earth ion distribution in sol–gel glasses co-doped with Al3+

Terbium spectroscopy is used to probe clustering of rare earth (RE) ions in sol–gel glasses. We use pulsed laser experiments to study energy transfer among Tb³⁺ dopants, and analyze the fluorescence decay curves using the Inokuti–Hirayama model. The analysis yields new insights about the role of Al³⁺ co-doping. Assuming a multipolar interaction, we derive an effective Tb³⁺ concentration for a series of samples with varying amounts of RE. When actual doping concentration is varied over 2 orders of magnitude, the effective Tb³⁺ concentration of centers that emit light changes by only a factor of 10. The results indicate that Al³⁺ co-doping is only effective at dispersing RE ions when the ratio of Al:RE is 10:1 or greater. At higher RE concentrations, most ions reside in clusters; ⁵D₃ fluorescence is observed from a minority of isolated ions. This interpretation contradicts earlier work that used fluorescence line narrowing to demonstrate that Al³⁺ co-doping caused RE dispersal at high doping levels.     

RE(POA)3phen配合物的合成、表征及荧光性能

合成了以稀土离子Sm³⁺、Eu³⁺、Tb³⁺、Dy³⁺及Tb³⁺为发光中心,以苯氧乙酸(HPOA)和邻菲罗啉(phen)为配体,掺杂La³⁺、Gd³⁺、 Y³⁺的7种稀土配合物, 对配合物进行了C、H、N元素分析、稀土络合滴定、红外光谱、紫外光谱和发光光谱的研究。结果表明配合物的组成分别为SmL₃L'·1/2H₂O,EuL₃L'·1/2H₂O,TbL₃L'· 1/2H₂O,DyL₃L'·1/2H₂O,掺杂配合物组成分别为Tb_0.5Gd_0.5L₃L'·1/2H₂O,Tb_0.5Y_0.5L₃L'·1/2H₂O,Tb_0.5La_0.5L₃L'·1/2H₂O(L=C₆H₅OCH₂COO^-, L'=phen)。配合物中的稀土离子与苯氧乙酸中羧基的一个氧原子和苯氧基的氧原子配位,与邻菲罗啉中的两个氮原子配位成键;荧光光谱表明,铽三元配合物的发射强度要远大于其它三元配合物的发光强度,掺杂发光惰性稀土离子La³⁺、Gd³⁺、Y³⁺的铽配合物中,Y³⁺掺杂配合物的发光强度有所增强。     

稀土茜素黄R配合物的合成、表征及荧光性质

合成了 4种茜素黄R稀土配合物 ,通过对元素分析、红外光谱、紫外光谱和核磁共振氢谱的分析 ,确定它们的组成为 :Na[REL2 ]·2H2 O(RE =Sm ,Eu ,Tb ,Y ,NaHL =茜素黄R)。红外光谱表明 :配体以羧羰基的氧与稀土离子以单齿配位 ;配体的酚羟基离解 ,脱去质子后羟基氧与稀土离子配位 ;即酚氧和羧羰基的氧与稀土离子形成一个六元螯合环。配体的吸收峰 398nm在形成配合物后移于 35 1～ 35 5nm ,发生了较大位移 ,这说明稀土离子与配体成键 ;配合物IR在 4 15～ 4 35cm-1之间出现的新吸收峰归属为RE—O键的伸缩振动 ,佐证了配合物的形成 ;硝基中的氧和偶氮的氮原子未参与配位 ;IR还说明有两个水分子配位于稀土离子。紫外灯下可以看到Eu(Ⅲ )的配合物很强的红色荧光 ;荧光光谱测定 :Na[EuL2 ]·2H2 O有两个荧光发射峰分属于Eu的 5D0 → 7F1和5D0 → 7F2 跃迁。     

A Multifunctional Fluorescence Probe for the Detection of Cations in Aqueous Solution: the Versatility of Probes Based on Peptides

We synthesized a tetra-functional fluorescence probe based on dansyl and peptide motif, dansyl-Gly-Trp (DGT, 1), that efficiently bound several metal ions and showed distinguishing optical properties. The probe 1 could respond to Hg²⁺ with enhanced and blue-shifted fluorescence emission but to Cu²⁺ with obvious fluorescence quenching. In addition, 1 was sensitive to pH ranging from 2.0 to 5.0 and precipitated in the presence of Pb²⁺ at neutral conditions. The combination of these intrinsic properties with the selective responses to different chemical inputs allows this system to be implemented as an ionic switch. Furthermore, 1 could penetrate the cell membrane and accumulated well in intracellular region. The underlying mechanisms of the probe to different kind of metal ion were explored successfully by using either ¹H NMR, NOESY, electron paramagnetic resonance (EPR) or FT-IR spectra. In addition, to investigate the binding model of 1/Hg²⁺ and 1/Cu²⁺, simulations were also performed by using density functional theory (DFT) and reasonable binding configurations were achieved for these two complexes.     

An ab initio molecular orbital study comparing the bonding of the NH3 and the H2O in the monoammines and the monohydrates of main group and transition metal ions

It is common knowledge that some metal ions prefer to bond to nitrogen atoms, others prefer oxygen and others select sulfur, although the mechanistic origin of this behaviour is not well understood. To provide quantitative data that can illuminate this characteristic difference, we have been performing ab initio molecular orbital calculations on complexes of a wide variety of main group and transition metal ions with simple ligands. In this paper we concentrate on metal ion complexes of NH₃ and compare them with the corresponding complexes with H₂O (Trachtman et al., 1998, Inorg. Chem., 37, 4221). The results reported here show that for each metal ion the bonding to ammonia in monoammines is intrinsically stronger than that to water in monohydrates, but that the enthalpy of formation of the amine complexes has a greater sensitivity to the nature of the metal ion. For both mono- and divalent transition metal cations the ligand-field stabilization energy (LFSE) in the monoammine complexes is larger than that in the monohydrates, although the larger enthalpies of formation, ΔH ⁰ ₂₉₈, for the monoammines are due only in part to the larger LFSE values. The formation of both monoammines and monohydrates is accompanied by a transfer of charge from the ligand hydrogen atoms to the metal ion so that there is relatively little change in the net charge on the oxygen or nitrogen atoms. Hence the increased acidity of the ligand in the metal ion complex is not the result of net electron depletion of the atom that is directly bonded to the metal ion, but rather reflects weakening of the bond of that ligand atom to its proton (O-H or N-H). This characteristic is used by many enzymes to promote catalytic activity.     

Emergence of the half-metallic performance in transition-metal doped BAs semiconductor: a first-principles study

ABSTRACT

A spin density functional study of structural, electronic and magnetic properties of BAs semiconductor doped with different transition metals is reported. Cr is favourable to dope in BAs semiconductor. Transition metal dopants increase the lattice parameters and their volumes. The net magnetisation is mainly donated from transition metal, As and B, respectively. The computations remark that the transition metals introduce the d orbitals inside host band gap. The magnetism is formed by the hybridisation between d orbitals of transition metal and p orbitals of As, called p-d hybridisation. Fe and Cu doping in BAs semiconductor become metallic. The semiconductor to dilute magnetic semiconductor transformation by doping with Cr, Mn and Co is important for exploring the possibilities of the spintronic applications. Finally, this research offers the innovative perception into the nature of transition metals doping in BAs semiconductor at a quantitative level and envisages a new spintronic materials.     

Hydrophilic surface formation on polymers and its applications

A new surface modification technique, so-called ion assisted reaction (IAR) has been developed at the Korea Institute of Science and Technology (KIST) Ion Beam Laboratory while modifying the surface of polymer results in many of industrial applications. The IAR, in which a keV ion beam is irradiated on the surface of polymer in reactive gases environment, has been developed for improving wettability of polymer surface and enhancing adhesion of other materials. The contact angles of water drops with modified polymers were significantly reduced by Ar⁺ ion irradiation with flowing oxygen gas environment than without flowing oxygen gas. Change of contact angles for the modified polymers was explained by a two-step chemical reaction among polymer matrix, energetic ions and oxygen gas. X-ray photoelectron analysis showed that hydrophilic groups were formed on the surface of polymers by chemical reaction between the unstable chains induced by ion irradiation and the oxygen gas, and the hydrophilic groups were identified as –(C–O)–, –(CO)– and –(CO)–O– bonds. The enhanced adhesion between metal and modified polymers was explained by the formation of charge transfer complex in polymer and electron donors in metal. Possible industrial applications of the IAR are to be discussed.     

Exafs studies of LiYF 4 -LiREF 4 solid solutions

In this work we are investigating dopant environments in LiYF 4 -LiREF 4 (RE=rare-earth cations) solid solutions, via EXAFS. The main aims are to identify the local environmental symmetry and the average lattice distortion as a function of the concentration and the type of the RE ion. LiY 1 m x RE x F 4 (RE=Gd or Lu) (0< x <1) single crystals were grown by the Czochralski technique under argon or CF 4 atmosphere, crystal-pulling rates were 0.6-1 v mm/h for <100>-oriented boules, with 8-25 v rpm rotation rates. Most of the crystals were also codoped with 2.7 v mol% of neodymium in the melt. EXAFS measurements were performed in transmission and fluorescence modes in the synchrotron XAS line of the LNLS, Campinas, Brazil, in and above the L III absorption edges of the RE ions. The samples were prepared as powder films, for the transmission mode measurements, and as powder or single crystals for fluorescence mode measurements. The WINXAS program was used for data reduction and fitting, and the FEFF6 package was used for the simulations of the spectra. The EXAFS oscillation curves were obtained by standard procedure.     

Interaction studies of cysteine with Li+, Na+, K+, Be2+, Mg2+, and Ca2+ metal cation complexes

The coordination geometries, electronic features, metal ion affinities, entropies, and the energetics of Li⁺, Na⁺, K⁺, Be²⁺, Mg²⁺, and Ca²⁺ metal cations with different possible conformations of cysteine complexes were studied. The complexes were optimized using density functional theory (B3LYP) and second order Moller–Plesset Perturbation (MP2) theory methods using 6‐311 + +G** basis set. The interactions of the metal cations at different nucleophilic sites of cysteine conformations were considered after a careful selection among several binding sites. All the metal cations coordinate with cysteine in a tridentate manner and also the most preferred position for the interaction. It is found that, the overall structural parameters of cysteine are not altered by metal ion substitution, but, the metal ion‐binding site has undergone a noticeable change. All the complexes were characterized by an electrostatic interaction between ligand and metal ions that appears slightly more pronounced for lithium and beryllium metal complexes. The metal ion affinity (MIA) and basis set superposition error (BSSE) corrected interaction energy were also computed for all the complexes. The effect of metal cations on the infrared (IR) stretching vibrational modes of amino N? H bond, side chain thiol group S? H bond, hydroxyl O? H bond, and Carbonyl C?O bond in cysteine molecules have also been studied. The nature of the metal ion‐ligand bond and the coordination properties were examined using natural bond order (NBO) at bond critical point (electron density and their Laplacian of electron density) through Atoms in Molecules (AIM) analyses. Copyright © 2010 John Wiley & Sons, Ltd.     

稀土配合物RE(TPTZ)Cl_3的合成、表征及荧光性能研究

首次以2,4,6-三吡啶基三嗪（TPTZ）与Sm, Eu, Tb和Dy氯化物反应,合成四种单一稀土配合物以及Tb分别1∶1掺Gd, Y, La的三种异核配合物。经元素分析、稀土络合滴定、摩尔电导率、红外光谱、紫外光谱和差热-热重测定表明,配合物的组成分别为RE（TPTZ）Cl3&#183;3H2O（RE=Sm, Eu, Tb, Dy）和Tb0.5Ln0.5（TPTZ）Cl3&#183;3H2O（Ln=Gd, Y, La）;TPTZ作为三齿配体与稀土离子配位,即中心环提供一个N原子,两个吡啶环分别提供一个N原子;配合物中3个水分子与稀土离子配位,1个Cl-在外界,2个在内界,为1∶1型电解质;配合物内外界可能为[RE（TPTZ）（H2O）3Cl2] Cl,稀土离子的配位数为8。配合物的荧光光谱测试表明,四种单一稀土配合物中,Tb配合物发光最强;三种1∶1掺杂异核Tb配合物荧光强度大于纯Tb配合物,表明Y3＋, La3＋和Gd3＋都可以敏化Tb3＋的发光,其中Gd3＋的敏化作用最强,Y3＋次之,La3＋最差。     

Computer modelling of defects and dopants in mixed metal fluorides

This paper describes a computer modelling study of rare earth doping in the mixed metal fluorides LiCaAlF 6 , LiSrAlF 6 and LiYF 4 . All these materials have potential technological applications, providing the motivation to improve understanding of their defect chemistry; in particular the energetics of doping and the sites occupied by dopant ions. Computer modelling is used to calculate the effect of rare earth dopant concentration on the structure of LiYF 4 , and to predict the sites occupied by rare earth dopants and the corresponding form of charge compensation, in LiCaAlF 6 and LiSrAlF 6 .     

Solvatochromic Studies of Fluorescent Azo Dyes: Kamlet-Taft (π*, α and β) and Catalan (Spp, SA and SB) Solvent Scales Approach

A new metal ion-responsive azo-based fluorescent probes have been synthesized and characterized by NMR spectral techniques. Steady-state fluorometric study has been used to analyze the spectroscopic and photophysical characteristics of dye derivatives in various solvents. The fluorescence properties of these dyes are strongly solvent dependent, the wavelength of maximum fluorescence emission shifts to the red. The Kamlet-Taft and Catalan’s solvent scales were found to be the most suitable for describing the solvatochromic shifts of the absorption and fluorescence emission. The hydroxy substituted azo dye formed complexes with several metal ions (Co²⁺, Hg²⁺, Ni²⁺ and Cu²⁺) and fluorescence quenching with metal ions reveal that it can be used as a new fluorescence sensor to detect the Cu²⁺ ion.