Multistate Luminescent Solar Concentrator “Smart” Windows

A supertwist liquid crystalline luminescent solar concentrator (LSC) “smart” window is fabricated which can be switched electrically between three states: one designed for increased light absorption and electrical generation (the “dark” state), one for transparency (the “light” state), and one for enhanced haziness (“scattering” state). In the scattering state, the absorption and edge emissions decrease while the face emissions are enhanced. This new LSC “smart” window state can find application as a privacy feature in housing, but could also allow for a new “smart” window application as a diffuse glazing to increase plant growth in horticultural applications.     

Preparation,characterization and luminescent properties of dense nano‐silica hybrids loaded with 1,8‐naphthalic anhydride

Novel luminescent dense nano‐silica hybrid materials (DNSS) modified with different amounts of (3‐aminopropyl)triethoxysilane (APTES) and 1,8‐naphthalic anhydride (NA) were successfully synthesized via two steps combined with post‐grafting methods. Powder X‐ray diffraction (XRD), N₂‐sorption analysis, Fourier transform infrared (FT‐IR) spectroscopy, transmission electron microscopy (TEM), thermogravimetric analysis (TGA), photoluminescence (PL) spectroscopy and elemental analysis, as well as time‐resolved decays were employed to characterize the resultant hybrid materials. The results revealed that luminescent organic molecules had been successfully loaded onto the amine‐modified surface of nano‐silica spheres. In addition, their fluorescence intensity and characteristic peak of emission spectra changed with increasing amount of APTES and NA additive. In particular, the characteristic peak showed a red shift from 390 to 450 nm, however, this was inconsistent with results calculated on the basis of the elemental analysis data, most probably because of the dispersion behaviors of NA molecules from the aggregating to the monolayer state. These observations demonstrated the existence of a quantum confinement effectiveness of NA–DNSS samples, and therefore a possible mechanism was put forward. Copyright © 2013 John Wiley & Sons, Ltd.     

Synthesis and luminescent properties of Eu(TTA)3·3H2O nanocrystallines

Nanocrystallines of rare earth complex, Eu(TTA)₃·3H₂O, were synthesized by the chemical precipitation method and were characterized by elemental analysis, ultraviolet visible absorption spectroscopy (UV–vis), infrared spectroscopy (IR), differential thermal analysis–thermogravimetry (TG‐DTA), X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The size of the nanocrystallines was tunable by selecting the proper buffer system, which was used to control the pH of the solution. A small polydispersity in particle size ranging from 70 to 250 nm was obtained when ammonia was used. The nanocrystallines showed the characteristic fluorescence of europium ions and energy transfer from the organic ligand to central ions was observed by fluorescence excitation and emission spectroscopy. These nanoparticles of rare earth complexes have potential application in luminescent materials due to their excellent fluorescence properties. Copyright © 2009 John Wiley & Sons, Ltd.     

Stereoselective Synthesis of (R)‐3‐Methylthalidomide by Piperidin‐2‐one Ring Assembly Approach

A simple and stereoselective synthesis of 3‐methylthalidomide, a configurationally stable thalidomide analog, is presented. Herein we describe the synthesis of (R)‐3‐methylthalidomide starting from (S)‐alanine by piperidin‐2‐one ring assembly approach in high yield and enantiomeric purity without using a chiral auxiliary or reagent. Starting from (R)‐alanine, the corresponding (S)‐3‐methylthalidomide can be prepared using the same methodology. Chirality 27:619–624, 2015. © 2015 Wiley Periodicals, Inc.     

Taking into account the conformational dynamics of macromolecules when analyzing luminescent probe signals

A mathematical model is proposed that takes into account the specific features of electronic excitation energy transfer between the molecular probes sorbed on a polymeric chain in a liquid solution. The kinetics of the process is described from the standpoint of the stochastic changes in macromolecular conformations. The results of numerical solution of the problem are described, as well as the analytical expressions obtained in the context of perturbation theory for a low transfer rate and/or fast conformational dynamics of the macrochain. A channel of nonlinear (with respect to excitation) deactivation resulting from binary annihilation of closely spaced excited centers is considered. Expressions for the efficient rate of mutual quenching and delayed annihilation fluorescence of the probe are obtained. The time dependences of characteristic luminescent signals and the parametric curves of relative fluorescence quantum yield are given.     

Necessary and sufficient conditions for the asymmetric synthesis of chiral amines using ω‐aminotransferases

The half reactions of ω‐aminotransferase (ω‐AT) from Vibrio fluvialis JS17 (ω‐ATVf) were carried out using purified pyridoxal 5′‐phosphate‐enzyme (PLP‐Enz) and pyridoxamine 5′‐phosphate‐enzyme (PMP‐Enz) complexes to investigate the relative activities of substrates. In the reaction generating PMP‐Enz from PLP‐Enz using L ‐alanine as an amine donor, L ‐alanine showed about 70% of the initial reaction rate of (S)‐α‐methylbenzylamine ((S)‐α‐MBA). However, in the subsequent half reaction recycling PLP‐Enz from PMP‐Enz using acetophenone as an amine acceptor, acetophenone showed nearly negligible reactivity compared to pyruvate. These results indicate that the main bottleneck in the asymmetric synthesis of (S)‐α‐MBA lies not in the amination of PLP by alanine, but in the amination of acetophenone by PMP‐Enz, where conformational restraints of the enzyme structure is likely to be the main reason for limiting the amine group transfer from PMP‐Enz to acetophenone. Based upon those half reaction experiments using the two amino acceptors of different activity, it appears that the relative activities of the two amine donors and the two acceptors involved in the ω‐AT reactions can roughly determine the asymmetric synthesis yield of the target chiral amine compound. Predicted conversion yields of several target chiral amines were calculated and compared with the experimental conversion yields. Approximately, a positive linear correlation (Pearson's correlation coefficient = 0.92) was observed between the calculated values and the experimental conversion yields. To overcome the low (S)‐α‐MBA productivity of ω‐ATVf caused by the possible disadvantageous structural constraints for acetophenone, new ω‐ATs showing higher affinity to benzene ring of acetophenone than ω‐ATVf were computationally screened using comparative modeling and protein‐ligand docking. ω‐ATs from Streptomyces avermitilis MA‐4680 (SAV2612) and Agrobacterium tumefaciens str. C58 (Atu4761) were selected, and the two screened ω‐ATs showed higher asymmetric synthesis reaction rate of (S)‐α‐MBA and lower (S)‐α‐MBA degradation reaction rate than ω‐ATVf. To verify the higher conversion yield of the variants of ω‐ATs, the reaction with 50 mM acetophenone and 50 mM alanine was performed with coupling of lactate dehydrogenase and two‐phase reaction system. SAV2612 and Atu4761 showed 70% and 59% enhanced yield in the synthesis of (S)‐α‐MBA compared to that of ω‐ATVf, respectively. Biotechnol. Bioeng. 2011;108: 253–263. © 2010 Wiley Periodicals, Inc.     

基于金属配合物的生物小分子发光探针研究进展

生物体内存在各种内源性活性物质,帮助生物进行信号传递与代谢调控。正常条件下,细胞环境不断变化,内源性小分子的时 空分布在生物体内保持动态平衡。但当它们的种类和浓度超过生理过程所需的限定范围时,就会影响细胞活性,进而导致疾病,甚至 是肿瘤和癌症的发生。因此,这些活性物质在体内活动的实时追踪及可视化对人们理解生命现象、研究疾病发生机制十分重要。与传 统有机染料相比,金属配合物发光(荧光/磷光)探针因光稳定性好、生理功能易调控等优势,已成为生物体系小分子活性物质示踪和 成像的研究热点。依照不同的作用靶点,对应用于生物体系的金属配合物探针的最新进展进行分类和总结,并展望金属配合物在生物 成像中的未来应用,以期可以为人们继续设计出新的具有良好示踪成像性能金属配合物探针提供参考,并从分子水平理解探针作用及 癌症治疗的机制。     

Luminescent and hydrophilic LaF3–polymer nanocomposite for DNA detection

Luminescent LaF₃–Ce³⁺/Tb³⁺ nanocrystals have been successfully prepared via a simple wet chemical technique. For the next bioapplication, these nanoparticles dispersed in cyclohexane have also been functionalized with poly(St‐co‐MAA), based on a designed oil‐in‐water microemulsion system. These polymer‐coated nanospheres are water‐soluble and bioconjugable. Unlike semiconductor quantum dots, the as‐prepared lanthanum fluoride nanocrystals possess non‐size‐dependent emissions and completely stable photocycles. With functionalized LaF₃ nanospheres as fluorescence probes, a fluorescence method was developed for the rapid quantitative analysis of DNA, due to the quenching effect of fluorescence by the DNA. Under optimum conditions, the fluorescence intensity was proportional to the concentration of the introduced DNA over the range 2.5–35 µg/mL for calf thymus DNA (ctDNA) and 2.5–30 µg/mL for fish sperm DNA (fsDNA), respectively. Copyright © 2008 John Wiley & Sons, Ltd.     

Syntheses and luminescent properties of a copolymer of terbium‐p‐aminobenzoic acid–methacrylic acid and styrene

A reactive Tb(III) complex with p‐aminobenzoic acid (p‐ABA) and methacrylic acid (MAA) as ligands was synthesized. A novel copolymer was synthesized by free radical copolymerization of styrene and the reactive Tb(III) complex in dimethyl sulfoxide (DMSO) with 2,2′‐azobis(2‐methylpropionitrile) (AIBN) as the initiator. IR and UV/Vis spectra indicate that the copolymer exhibited absorption from polystyrene and the complex. Thermogravimetric analysis indicates that the copolymer remained stable up to 357°C and the thermal stability was significantly improved in comparison with polymer matrix and the Tb(III) complex. The luminescent intensity of the synthetic terbium macromolecular complexes increased with increasing complex monomer content. Moreover, concentration quenching was not observed. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis,characterization and luminescent properties of lanthanide complexes with an unsymmetrical tripodal ligand

Solid complexes of lanthanide nitrates with an novel unsymmetrical tripodal ligand, butyl‐N,N‐bis[(2′‐benzylaminofomyl)phenoxyl)ethyl]‐amine ( L ) have been synthesized and characterized by elemental analysis, infrared spectra and molar conductivity measurements. At the same time, the luminescent properties of the Sm(III), Eu(III), Tb(III) and Dy(III) nitrate complexes in solid state were also investigated. Under the excitation of UV light, these complexes exhibited characteristic emission of central metal ions. Copyright © 2010 John Wiley & Sons, Ltd.     

Luminescent thermometer based on Eu3+/Tb3+‐organic‐functionalized mesoporous silica

In this work we investigate a mesoporous silica (MS) decorated with dipyridyl‐pyridazine (dppz) ligands and further grafted with a mixture of Eu³⁺/Tb³⁺ ions (28.45%:71.55%), which was investigated as a potential thermometer in the 10–360 K temperature range. The MS material was prepared employing a hetero Diels–Alder reaction: 3,6‐di(2‐pyridyl)‐1,2,4,5‐tetrazine was reacted with the double bonds of vinyl‐silica (vSilica) followed by an oxidation procedure. We explore using the dppz‐vSilica material to obtain visible emitting luminescent materials and for obtaining a luminescent thermometer when grafted with Eu³⁺/Tb³⁺ ions. For the dppz‐vSilica@Eu,Tb material absolute sensitivity S_a of 0.011 K^?1 (210 K) and relative sensitivity S_r of 1.32 %K^?1 (260 K) were calculated showing good sensing capability of the material. Upon temperature change from 10 K to 360 K the emission color of the material changed gradually from yellow to red.     

Multifunctional Luminescent Down‐Shifting Fluoropolymer Coatings: A Straightforward Strategy to Improve the UV‐Light Harvesting Ability and Long‐Term Outdoor Stability of Organic Dye‐Sensitized Solar Cells

A new multifunctional coating for photovoltaic cells incorporating light‐management, UV‐protection, and easy‐cleaning capabilities is presented. Such coating consists of a new photocurable fluorinated polymer embedding a luminescent europium complex that acts as luminescent down‐shifting (LDS) material converting UV photons into visible light. The combination of this system with ruthenium‐free organic dye‐sensitized solar cells (DSSCs) gives a 70% relative increase in power conversion efficiency as compared with control uncoated devices, which is the highest efficiency enhancement reported to date on organic DSSC systems by means of a polymeric LDS layer. Long‐term (>2000 h) weathering tests in real outdoor conditions reveal the excellent stabilizing effect of the new coating on DSSC devices, which fully preserve their initial performance. This excellent outdoor stability is attributed to the combined action of the luminescent material that acts as UV‐screen and the highly photostable, hydrophobic fluoropolymeric carrier that further prevents photochemical and physical degradation of the solar cell components. The straightforward approach presented to simultaneously improve performance and outdoor stability of DSSC devices may be readily extended to a large variety of sensitizer/luminophore combinations, thus enabling the fabrication of highly efficient and extremely stable DSSCs in an easy and versatile fashion.     

Virulence of luminescent and non-luminescent isogenic vibrios towards gnotobiotic Artemia franciscana larvae and specific pathogen-free Litopenaeus vannamei shrimp

Aims:  This study was conducted to test the virulence of luminescent (L) and non-luminescent (NL) isogenic strains of Vibrio campbellii LMG21363, Vibrio harveyi BB120 (wild type) and quorum-sensing mutant strains derived from the wild type such as Vibrio harveyi BB152, BB170, MM30 and BB886.
Methods and Results:  The NL strains could be obtained by culturing rifampicin-resistant luminescent strains in the dark under static condition. The virulence of the L and NL strains was tested in gnotobiotic Artemia franciscana larvae challenged with 10⁴ CFU ml⁻¹ of bacteria. All luminescent isogenic tested strains showed higher virulence compared to the NL strains. The virulence of L and NL V. campbellii and V. harveyi BB120 was also tested in specific pathogen-free juvenile shrimp upon intramuscular injection with 10⁶ CFU of bacteria. In contrast with Artemia , there was no significant difference in mortality between the groups challenged with L and NL strains ( P  > 0·05). The non-luminescent strains were not able to revert back to the luminescent state and quorum sensing did not influence this phenotypic shift.
Conclusions:  Luminescent Vibrio strains can switch to a non-luminescent state by culturing them in static conditions. The NL strains become less virulent as verified in Artemia .
Significance and Impact of the Study:  The luminescent state of Vibrio cells in a culture needs to be verified in order to assure maintenance of virulence.     

Relationship between ultra‐weak bioluminescence and vigour or irradiation dose of irradiated wheat

Ultra‐weak luminescent analysis is a new way to detect the irradiation dose and the vigour of irradiated wheat. Wheat grain and wheat flour were used in this research for ultra‐weak luminescent analysis. The experimental data showed that the bioluminescence intensity of wheat grain sample was different with increasing storage time and increasing dose, and a similar trend appeared in the germination rates of irradiated wheat grain. It was found that the differences in bioluminescence intensities and germination rates of irradiated wheat grain at different doses and storage times were due to the effect of irraditation on the wheat embryo and self‐repair during storage. As a result, ultra‐weak luminescent analysis cannot be used to detect the irradiation dose of irradiated wheat, but it can be used to determine vigour. Experiments showed that the irradiation dose had a highly significant effect on the bioluminescence intensities of wheat flour when cane sugar was added. Copyright © 2009 John Wiley & Sons, Ltd.     

铽(Ⅲ)离子及其复合物:从发光特性到传感应用

稀土元素也称镧系元素,因其独特的发光性质和配位性质,其发光复合物被广泛研究于生物技术领域。其中稀土铽(Ⅲ)离子复合物因具有优异的光谱特性,关于其研究呈现出快速的发展趋势。主要从其发光特性的角度出发,探讨了其发光机理,并对铽(Ⅲ)离子与不同有机化合物结合形成的发光铽配合物以及铽(Ⅲ)离子及其配合物与不同纳米材料形成的复合物进行了分类综述。此外,还详细地阐述了铽离子及其复合物在荧光探针、生物传感器、药物递送、细胞成像、癌症治疗等相关领域的应用。最后,对其今后发展趋势和潜在的研究价值进行了展望。     

Molecular tweezers for enantiodiscrimination in NMR: Di‐(R,R)‐1‐[10‐(1‐hydroxy‐2,2,2‐trifluoroethyl)‐9‐anthryl]‐2,2,2‐trifluoroethyl benzenedicarboxylates

A series of new chiral molecular tweezers, di‐(R,R)‐1‐[10‐(1‐hydroxy‐2,2,2‐trifluoroethyl)‐9‐anthryl]‐2,2,2‐trifluoroethyl phthalate (2), isophthalate (3) and terephthalate (4), were synthesized and their structure studied by NMR and molecular mechanics. Their effectiveness as chiral solvating agents for the determination of the enantiomeric purity of chiral compounds using NMR was demonstrated. Chirality 2010. © 2009 Wiley‐Liss, Inc.     

Synthesis,characterization and luminescent properties of europium complexes with 2,4,6‐tris‐(2‐pyridyl)‐s‐triazine as highly efficient sensitizers

Using 2,4,6‐tris‐(2‐pyridyl)‐s‐triazine (TPTZ) as a neutral ligand, and p‐hydroxybenzoic acid, terephthalic acid and nitrate as anion ligands, five novel europium complexes have been synthesized. These complexes were characterized using elemental analysis, rare earth coordination titrations, UV/vis absorption spectroscopy and infrared spectroscopy. Luminescence spectra, luminescence lifetime and quantum efficiency were investigated and the mechanism discussed in depth. The results show that the complexes have excellent emission intensities, long emission lifetimes and high quantum efficiencies. The superior luminescent properties of the complexes may be because the triplet energy level of the ligands matches well with the lowest excitation state energy level of Eu³⁺. Moreover, changing the ratio of the ligands and metal ions leads to different luminescent properties. Among the complexes, Eu₂(TPTZ)₂(C₈H₄O₄)(NO₃)₄(C₂H₅OH)·H₂O shows the strongest luminescence intensity, longest emission lifetime and highest quantum efficiency. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis of reserve polyhydroxyalkanoates by luminescent bacteria

The ability of marine luminescent bacteria to synthesize polyesters of hydroxycarboxylic acids (polyhydroxyalkanoates, PHA) as reserve macromolecules was studied. Twenty strains from the collection of the luminescent bacteria CCIBSO (WDCM839) of the Institute of Biophysics, Siberian Branch, Russian Academy of Sciences, assigned to different taxa (Photobacterium leiognathi, Ph. phosphoreum, Vibrio harveyi, and V. fischeri) were analyzed. The most productive strains were identified, and the conditions ensuring high polymer yields in batch culture (40–70% of the cell dry mass weight) were determined. The capacity for synthesizing two-and three-component polymers containing hydroxybutyric acid as the main monomer and hydroxyvaleric and hydroxyhexanoic acids was revealed in Ph. leiognathi and V. harveyi strains. The results allow luminescent microorganisms to be regarded as new producers of multicomponent polyhydroxyalkanoates.     

Enantioselective resolution of 4‐chloromandelic acid by liquid–liquid extraction using 2‐chloro‐N‐carbobenzyloxy‐L‐amino acid

A liquid–liquid extraction resolution of 4‐chloro‐mandelic acid (4‐ClMA) was studied by using 2‐chloro‐N‐carbobenzyloxy‐L‐amino acid (2‐Cl‐Z‐AA) as a chiral extractant. Important factors affecting the extraction efficiency were investigated, including the type of chiral extractant, pH value of aqueous phase, initial concentration of chiral extractant in organic phase, initial concentration of 4‐ClMA in aqueous phase, and resolution temperature. It was observed that the concentration of (R)‐4‐ClMA was much higher than that of (S)‐4‐ClMA in organic phase due to a higher stability of the complex formed between (R)‐4‐ClMA and 2‐Cl‐Z‐AA. A separation factor (α) of 3.05 was obtained at 0.02 mol/L 2‐Cl‐Z‐Valine dissolved in dichloromethane, pH of 2.0, concentration of 4‐ClMA of 0.11 mmol/Land T of 296.7K.     

Luminescent properties of Ca3SiO4Cl2 co‐doped with Ce3+ and Eu2+ for near‐ultraviolet light‐emitting diodes

Ca₃SiO₄Cl₂ co‐doped with Ce³⁺,Eu²⁺ was prepared by high temperature reaction. The structure, luminescent properties and the energy transfer process of Ca₃SiO₄Cl₂: Ce³⁺,Eu²⁺ were investigated. Eu²⁺ ions can give enhanced green emission through Ce³⁺ → Eu²⁺ energy transfer in these phosphors. The green phosphor Ca_2.9775SiO₄Cl₂:0.0045Ce³⁺,0.018Eu²⁺ showed intense green emission with broader excitation in the near‐ultraviolet light range. A green light‐emitting diode (LED) based on this phosphor was made, and bright green light from this green LED could be observed by the naked eye under 20 mA current excitation. Hence it is considered to be a good candidate for the green component of a three‐band white LED. Copyright © 2015 John Wiley & Sons, Ltd.