Circularly polarized emission studies on Tb3+ and Eu3+ complexes with potentially terdentate amino acids in aqueous solution.

Circularly polarized emission (CPE) and total emission (TE) spectra are reported for Eu3+ and Tb3+ complexes of L-aspartic acid (L-asp), L-serine (L-ser), L-threonine (L-thr) and L-histidine (L-his) in D2O solution under various pH conditions. Variations in TE and CPE intensities and in CPE splittings and sign patterns as functions of solution pH are correlated with lanthanide ion/ligand binding characteristics and with structural changes in the coordination environment of the metal ion. In the Eu3+/amino acid systems, the emission bands associated with the 5D0 leads to 7F1 and 7F2 Eu3+ transitions are monitored, and in the Tb3+/amino acid systems the 5D4 leads to 7F5 Tb3+ emission is examined.     

Protein and cellular engineering with unnatural amino acids

Proteins are the central functional constituents in all living organisms ranging from viruses, bacteria, yeast, and plants to mammals. All of these biopolymers that are formed by natural biosynthetic pathways are composed of a genetically determined sequence of the 20 so-called natural amino acids. The physical and chemical properties of proteins are a reflection of the side chains of each of the component amino acids. However, for some purposes it would be very desireable to have amino acids with side chains of various selected physical chemical properties, such as a keto group, a crosslinker, or a NMR probe group, incorporated into the protein. Although chemical and biochemical methods for modifying amino acid moieties in proteins have been achieved, recent successes in incorporating unnatural amino acids in vivo open entirely new avenues for determining protein functions in vivo and for the creation of unnatural proteins with novel functionalities. Several examples by employing the novel activity of unnatural amino acids have shown significant roles in both basic research and biotechnology.     

Intramolecular cyclization of isothiocyanyl amino acids/peptide: arrival at unnatural thioxoimidazolidinyl/thioxooxazolidinyl amino acids

Amino Acids - A novel intramolecular cyclization of isothiocyanyl amino acids/peptide is reported to arrive at unnatural thioxoimidazolidinyl (TOI)/thioxooxazolidinyl (TOO) amino acids for the...     

Combustion synthesis and luminescence properties of SrAl2O4:Eu2+, Dy3+, Tb3+ phosphor.

Eu(2+), Dy(3+) and Tb(3+) co-doped strontium aluminate phosphor with high brightness and long afterglow was synthesized by a combustion method, using urea as a reducer. The properties of SrAl(2)O(4):Eu(2+),Dy(3+),Tb(3+) phosphor with a series of initiating combustion temperatures, urea concentrations and boric acid molar fractions were investigated. The sample at initiating combustion temperature of 600 degrees C exhibited an intense emission peak at 513 nm, in which the phosphor existed as a single-phase monoclinic structure. The experimental results showed that the optimum ratio of urea is 2.0 times higher than theoretical quantities and that the suitable molar fraction of H(3)BO(3) is 0.08. The average particle size of the phosphor was 50-80 nm and its luminescence properties were studied systematically. Compared with SrAl(2)O(4):Eu(2+),Dy(3+) phosphor, the initial luminescence brightness improved from 2.50 candela (cd)/m(2) to 3.55 cd/m(2) and the long afterglow time was prolonged from 1290 s to 2743 s.     

Preparation and luminescence properties of KLaSiO4:Tb3+ phosphors

KLaSiO₄:Tb³⁺ phosphors were synthesized using the sol–gel method. The structure and luminescence properties of the materials were characterized using X-ray diffraction, Fourier transform infrared (FTIR) spectroscopy, thermogravimetry–differential thermal analysis, fluorescence spectra and calculated Commission Internationale de l'éclairage coordinates. The results showed that the material had a hexagonal structure, and that doping of Tb³⁺ did not change the crystal structure of KLaSiO₄. FTIR spectroscopy confirmed the existence of stretching vibrations of Si–O, bending vibrations of Si–O–Si, and asymmetric tensile vibrations of Si–O in KLaSiO₄. The excitation spectrum of the sample consisted of 4f⁷→5d¹ broadband absorption and the characteristic excitation peak of Tb³⁺, the excitation peak at 232 nm belongs to the spin allowed ⁷F_J→⁷D_J transition of Tb³⁺, the excitation peak at 268 nm belongs to the spin forbidden ⁷F_J→⁹D_J transition of Tb³⁺, and the absorption band of ⁷F_J→⁷D_J transition is split. Under excitation at 232 nm, the emission peak of the sample was composed of the ⁵D₄→⁷F_J (J = 6, 5, 4, 3) energy level transition of Tb³⁺. The highest emission peak is located at 543 nm, which belongs to the ⁵D₄→⁷F₅ transition and emits green light. Concentration quenching occurred when the Tb³⁺ doping concentration was greater than 1% mol, the quenching mechanism was an electric dipole–electric dipole action. When the ratio of citric acid to total metal ions was 1:1 and the annealing temperature was 800°C, the surface defects of the phosphors were greatly reduced, the quenching effect was reduced, and the luminous intensity reached the maximum.     

Antagonists of luteinizing hormone releasing hormone with novel unnatural amino acids at position six

Five new antagonists of luteinizing hormone releasing hormone (LHRH) containing novel unnatural amino acids at position six are reported. They are very effective in the rat antiovulatory assay. Using saline as vehicle, antagonist-[N-Ac-D-2-Nal1, D-4-Cl-Phe2, D-3-Pal3, Arg5, D-A26, D-Ala10]-LHRH inhibited ovulation completely at 1 micrograms/rat and three of the other antagonists showed some antiovulatory activity at 0.5 micrograms/rat.     

Absorption and luminescence spectroscopy of Eu3+ in lead silicate glasses

The absorption and luminiscence spectra of a lead silicate glass containing Eu³⁺ as impurity have been measured. The doping ion was found to occupy two classes of non-centrosymmetric sites. The intensities of the 4f⁶→4f⁶ transitions are perturbed by the interaction with low-lying charge-transfer states. The quantum yield of the luminescence from the ⁵D₀ level of Eu³⁺ is usually low, probably because of the presence of a strong ion-phonon coupling.     

Synthesis and luminescence characterization of Y2BaZnO5:RE (RE = Eu3+, Tb3+, Pr3+ and Sm3+) phosphors

Modified synthesis and luminescence of Y₂BaZnO₅ phosphors activated with the rare earths (RE) Eu³⁺, Tb³⁺, Pr³⁺ and Sm³⁺ are reported. RE₂BaZnO₅ phosphors have attracted attention because of their interesting magnetic and optical properties; and are usually prepared using a two‐step solid‐state reaction. In the first step, carbonates or similar precursors are thoroughly mixed and heated at 900°C to decompose them to oxides. To eliminate the unwanted phases like BaRE₂O₄, the resulting powders are reheated at 1100°C for a long time. We prepared Y₂BaZnO₅ phosphors activated with various activators by replacing the first step with combustion synthesis. The photoluminescence results are presented. The photoluminescence results for Eu³⁺, Tb³⁺ and Pr³⁺ are in good agreement with the literature. However, photoluminescence emission from Sm³⁺ has not been documented previously. The excitation spectrum of Eu³⁺ is dominated by a charge transfer band around 261 nm, and an additional band around 238 nm is always present, irrespective of the type of activator. The presence of this band for all these different types of activators was interpreted as host absorption.     

Rare earth Eu3+/Tb3+-doped hollow microspheres (LaPO4) and core-shell nanocomposite luminescent materials with different transmittance (SiO2@LaPO4 Eu3+) preparation and research on luminescence performance

For the manufacture of hollow nanospheres that had different shapes, three distinct templates—urea, carbon microspheres, and polyethylene glycol 20,000—were used. The relationship between microspheres with various hollow structures and their luminescent properties were investigated. Furthermore, the effects of annealing temperature and the proportion of rare earth Eu³⁺/Tb³⁺ions in the reaction were investigated using the structural characteristics of the microspheres and fluorescent materials. The fluorescent materials were wrapped on the outer surface of the microspheres. The ideal balance between the best structure and superior luminescent performance was found, to create reasonably good white light.     

Synthesis and luminescence properties of Ca3Ga2Si3O12:RE3+ (RE = Eu/Tb) powder phosphors

Rare earth ions (Eu³⁺ or Tb³⁺)‐activated Ca₃ Ga₂ Si₃O₁₂ (CaGaSi) phosphors were synthesized by using a sol–gel method. Photoluminescence spectra of Eu³⁺:CaGaSi phosphors exhibited five emission bands at 578, 592, 612, 652 and 701 nm, which were assigned to the transitions (⁵D₀ → ⁷F₀, ⁷F_1, ⁷F₂, ⁷F₃ and ⁷F₄), respectively, with an excitation wavelength of λ_exci = 392 nm. Among these, the transition ⁵D₀ → ⁷F₂ (612 nm) displayed bright red emission. In the case of Tb³⁺:CaGaSi phosphors, four emission bands were observed at 488 (⁵D₄ → ⁷F₆), 543 (⁵D₄ → ⁷F₅), 584 (⁵D₄ → ⁷F₄) and 614 nm (⁵D₄ → ⁷F₃) from the measurement of PL spectra with λ_exci = 376 nm. Among these, the transition ⁵D₄ → ⁷F₅ at 543 nm displayed bright green emission. The structure and morphology of the phosphors were studied from the measurements of X‐ray diffraction (XRD), scanning electron microscopy (SEM) and energy‐dispersive X‐ray analysis (EDAX) results. Copyright © 2011 John Wiley & Sons, Ltd.     

非天然氨基酸细胞工厂的构建与应用

非天然氨基酸在医药、农药、材料等领域得到广泛应用,其绿色、高效合成越来越受到关注.近年来,随着合成生物学的快速发展,微生物细胞工厂为非天然氨基酸的制造提供了重要手段.文中从合成途径的重构、关键酶的设计改造及与前体的协同调控、竞争性旁路途径的敲除、辅因子循环系统的构建等方面介绍了 一系列非天然氨基酸细胞工厂构建与应用的研...     

The determination of the Mg2+.ATP dissociation constant by competition with Eu3+ ion using laser-induced Eu3+ ion luminescence spectroscopy

A direct spectroscopic method for the determination of the submicromolar dissociation constant of Eu3+. ATP using laser-induced Eu3+ ion luminescence spectroscopy is described. The dissociation constant of Mg2+.ATP is then determined by the competition of Mg2+ with Eu3+ for the binding of ATP. The experiments were performed in 2H2O to mitigate the significant quenching of the Eu3+ luminescence that occurs in 1H2O. Values for the effective dissociation constants of the 1:1 ATP metal ion complexes of 1.2 +/- 0.3 X 10(-7) and 2.7 +/- 0.7 X 10(-4) M are obtained for Eu3+ and Mg2+, respectively, at p2H 5.8.     

Tunable luminescence properties and energy transfer in LaAl11O18:Eu,Tb phosphor

Eu²⁺ and Tb³⁺ singly doped and co‐doped LaAl₁₁O₁₈ phosphors were prepared by a combustion method using urea as a fuel. The phase structure and photoluminescence (PL) properties of the prepared phosphors were characterized by powder X‐ray diffraction (XRD), scanning electron microscopy (SEM), and photoluminescence excitation and emission spectra. When the content of Eu²⁺ was fixed at 0.01, the emission chromaticity coordinates could be adjusted from blue to green region by tuning the contents of Tb³⁺ ions from 0.01 to 0.03 through an energy transfer (ET) process. The fluorescence data collected from the samples with different contents of Tb³⁺ into LaAl₁₁O₁₈: Eu, show the enhanced green emission at 545 nm associated with ⁵D₄ –⁷F₅ transitions of Tb³⁺. The enhancement was attributed to ET from Eu²⁺ to Tb³⁺, and therefore Eu²⁺ ion acts as a sensitizer (an energy donor) while Tb³⁺ ion as an activator. The ET from Eu²⁺ to Tb³⁺ is performed through dipole–dipole interaction. The ET efficiency and critical distance were also calculated. The present Eu²⁺–Tb³⁺ co‐doped LaAl₁₁O₁₈ phosphor will have potential application for UV convertible white light‐emitting diodes. Copyright © 2015 John Wiley & Sons, Ltd.     

White light emission and energy transfer of LaMgAl11O19:Eu3+, Tb3+ phosphors

White-light-tunable LaMgAl₁₁O₁₉:x%Tb³⁺, y%Eu³⁺ series phosphors were prepared using the gel-combustion method. The structure and luminescence properties were studied, and the energy transfer of Eu³⁺ and Tb³⁺ in the LaMgAl₁₁O₁₉ system was also discussed. The results showed that the LaMgAl₁₁O₁₉ matrix exhibited strong emission in the blue-light region under the excitation of ultraviolet light, which resulted in conditions suitable for the preparation of white-light-tunable phosphors. The emission spectra of LaMgAl₁₁O₁₉:2%Tb³⁺, y%Eu³⁺ (y = 2%–9%) series phosphors were obtained through optimization experiments. It could be seen from the CIE diagram that by adjusting the doping quantities of Eu³⁺ and Tb³⁺ in the LaMgAl₁₁O₁₉ host, multicolor luminescence and white light emission in a single host could be achieved. By calculating the energy transfer efficiency and critical distance between Eu³⁺ and Tb³⁺ series phosphors, the mechanism of energy transfer between Tb³⁺ and Eu³⁺ was found to be the interaction between electric quadruples.     

Catalytic Ca2+-binding site of pancreatic phospholipase A2: laser-induced Eu3+ luminescence study

7F0----5D0 excitation spectroscopy of Eu3+ has been used to study the catalytic Ca2+-binding site of pancreatic phospholipases A2. Eu3+ binds competitively with Ca2+ to the enzyme with retention of about 5% of the activity found with Ca2+. The dissociation constants for the Eu3+-enzyme complexes of bovine phospholipase A2 and porcine isophospholipase A2 are 0.22 mM and 0.16 mM, respectively. Results obtained with the porcine phospholipase A2 at neutral pH indicate aggregation of this enzyme at protein concentrations above 0.18 mM. The Eu3+ bound at the catalytic site of pancreatic phospholipase A2 is coordinated to four or five water molecules, which, in conjunction with binding constant data, suggests the involvement of two or three protein ligands. Addition of a monomeric substrate analogue to the enzyme-Eu3+ complex results in the loss of an additional water molecule from the first coordination sphere of the bound Eu3+. This result suggests an interaction between the negative charge of the polar head group of the substrate analogue and the Eu3+. Binding of the enzyme-Eu3+ complex to micelles results in a nearly complete dehydration of the Eu3+ bound to the catalytic center. In the phospholipase A2-Eu3+-micelle complex, only one H2O molecule is coordinated to Eu3+. This dehydration at the active site of phospholipase A2 in the protein-lipid complex can be an important reason for the enhanced activity of this enzyme at lipid-water interfaces.     

Red‐ and green‐emitting nano‐clay materials doped with Eu3+ and/or Tb3+

Trivalent europium (Eu³⁺) and terbium (Tb³⁺) ions are important activator centers used in different host lattices to produce red and green emitting materials. The current work shows the design of new clay minerals to act as host lattices for rare earth (RE) ions. Based on the hectorite structure, nano‐chlorohectorites and nano‐fluorohectorites were developed by replacing the OH^? present in the hectorite structure with Cl^? or F^?, thus avoiding the luminescence quenching expected due to the OH^? groups. The produced matrices were characterized through X‐ray powder diffraction (XPD), transmission electron microscopy (TEM), FT‐IR, ²⁹Si MAS (magic angle spinning) NMR, nitrogen sorption, thermogravimetry‐differential scanning calorimetry (TGA‐DSC) and luminescence measurements, indicating all good features expected from a host lattice for RE ions. The nano‐clay materials were successfully doped with Eu³⁺ and/or Tb³⁺ to yield materials preserving the hectorite crystal structure and showing the related luminescence emissions. Thus, the present work shows that efficient RE³⁺ luminescence can be obtained from clays without the use of organic ‘antenna’ molecules.     

Optically stimulated luminescence in LiCaAlF6:Eu2+ phosphor

Results on optically stimulated luminescence (OSL) in LiCaAlF₆:Eu²⁺ are reported. Continuous wave OSL signal as recorded using blue (470 nm) stimulation was found to be ~31% that of standard phosphor lithium magnesium phosphate. The rate of OSL depletion for standard phosphor lithium magnesium phosphate is only three times less as compared with that of LiCaAlF₆:Eu²⁺. Strong photoluminescence (PL) in the near ultraviolet region is observed for LiCaAlF₆:Eu²⁺ with the characteristic Eu²⁺ emission at 369 nm for 254 nm excitation. The thermoluminescence (TL) glow peak for LiCaAlF₆:Eu²⁺ was observed at around 180°C. The glow peak was about six times more intense compared with the dosimetric peak of the well known thermoluminescence dosimetric (TLD) phosphor LiF‐TLD 100. Thus this phosphor deserves much more attention than it has received until now and may be useful as a dosimetric material in radiation dosimetry. Copyright © 2015 John Wiley & Sons, Ltd.     

Site-specific coupling and sterically controlled formation of multimeric antibody fab fragments with unnatural amino acids

Immunoconjugates and multispecific antibodies are rapidly emerging as highly potent experimental therapeutics against cancer. We have developed a method to incorporate an unnatural amino acid, p-acetylphenylalanine (pAcPhe) into an antibody antigen binding fragment (Fab) targeting HER2 (human epidermal growth factor receptor 2), allowing site-specific labeling without disrupting antigen binding. Expression levels of the pAcPhe-containing proteins were comparable to that of wild-type protein in shake-flask and fermentation preparations. The pAcPhe-Fabs were labeled by reaction with hydroxylamine dye and biotin species to produce well-defined, singly conjugated Fabs. We then coupled a hydroxylamine biotin to the pAcPhe-Fab and demonstrated controlled assembly of Fabs in the presence of the tetrameric biotin-binding protein, NeutrAvidin. The position of Fab biotinylation dictates the geometry of multimer assembly, producing unique multimeric Fab structures. These assembled Fab multimers differentially attenuate Her2 phosphorylation in breast cancer cells that overexpress the Her2 receptor. Thus, an encoded unnatural amino acid produces a chemical “handle” by which immunoconjugates and multimers can be engineered.     

Synthesis and luminescence study of Eu3+‐doped SrYAl3O7 phosphor

Rare‐earth ions play an important role in eco‐friendly solid‐state lighting for the lighting industry. In the present study we were interested in Eu³⁺ ion‐doped inorganic phosphors for near ultraviolet (UV) excited light‐emitting diode (LED) applications. Eu³⁺ ion‐activated SrYAl₃O₇ phosphors were prepared using a solution combustion route at 550°C. Photoluminescence characterization of SrYAl₃O₇:Eu³⁺ phosphors showed a 612 nm emission peak in the red region of the spectrum due to the ⁵D₀→⁷F₂ transition of Eu³⁺ ions under excitation at 395 nm in the near‐UV region and at the 466 nm blue excitation wavelength. These red and blue emissions are supported for white light generation for LED lighting. Structure, bonding between each element of the sample and morphology of the sample were analysed using X‐ray diffraction (XRD) and scanning electron microscopy (SEM), which showed that the samples were crystallized in a well known structure. The phosphor was irradiated with a ⁶⁰Co‐γ (gamma) source at a dose rate of 7.2 kGy/h. Thermoluminescence (TL) studies of these Eu³⁺‐doped SrYAl₃O₇ phosphors were performed using a Nucleonix TL 1009I TL reader. Trapping parameters of this phosphor such as activation energy (E), order of kinetics (b) and frequency factor (s) were calculated using Chen's peak shape method, the initial rise method and Ilich's method.     

Enhancing the luminescence of Eu3+/Eu2+ ion‐doped hydroxyapatite by fluoridation and thermal annealing

This paper reports a novel way for the synthesis of a europium (Eu)‐doped fluor‐hydroxyapatite (FHA) nanostructure to control the luminescence of hydroxyapatite nanophosphor, particularly, by applying optimum fluorine concentrations, annealed temperatures and pH value. The Eu‐doped FHA was made using the co‐precipitation method followed by thermal annealing in air and reducing in a H₂ atmosphere to control the visible light emission center of the nanophosphors. The intensities of the OH^? group decreased with the increasing fluorine concentrations. For the specimens annealed in air, the light emission center of the nanophosphor was 615 nm, which was emission from the Eu³⁺ ion. However, when they were annealed in reduced gas (Ar + 5% H₂), a 448 nm light emission center from the Eu²⁺ ion of FHA was observed. The presence of fluorine in Eu‐doped FHA resulted in a significant enhancement of nanophosphor luminescence, which has potential application in light emission and nanomedicine.