Synthesis of new tripodal receptors—a ‘PET’ based ‘off-on’ recognition of Ag

A new set of tripodal receptors based upon an aromatic platform have been synthesized in high yields. The compounds have been characterized by spectroscopic techniques and by single crystal X-ray crystallography. These receptors are found to have good extraction ability and high transport rate for Ag(I). The receptor with imine linkages exhibits weak fluorescence emission bands at λ_max=413 and 540 nm, upon excitation at λ_max=365 nm. The fluorescence spectrum of the receptor shows enhancement in the intensity of the signal at 413 nm on binding with the Ag⁺ cation. No such significant changes are observed with other metal ions. An absorption at ∼365 nm is typical of an intraligand (π-π^∗) transition involving the imine chromophore, which produces a weak emission band at 413 nm due to quenching caused by PET from a neighboring -OH group. Participation of OH group in coordination to the metal ion reduces PET and an enhancement of fluorescence intensity is observed, signaling recognition of the metal ion.     

A potential visual fluorescence probe for ultratrace arsenic (III) detection by using glutathione-capped CdTe quantum dots

The interaction between mercaptoacetic acid (MA)-capped CdTe QDs, MA-capped CdTe/ZnS QDs or glutathione (GSH)-capped CdTe QDs with As(III) was studied using fluorescence spectrometry. As (III) has a high-affinity to reduced-GSH to form As(SG)₃, and the emission of the GSH-capped CdTe QDs (λ_em. = 612 nm) is quenched effectively. Thus, a novel fluorescence spectrometric method was developed for As (III) determination by using GSH-CdTe QDs. Under optimal conditions, the quenched fluorescence intensity (F₀/F) increased linearly with the concentration of As (III) ranging from 5.0 × 10⁻⁶ to 25 × 10⁻⁵ mol L⁻¹. The limit of detection (3σ) for As (III) was found to be 2 × 10⁻⁸ mol L⁻¹. This method is potentially useful in visual detection of As (III) under irradiation of the ultraviolet light.     

Synthesis of azobenzene‐containing polymers via RAFT polymerization and investigation on intense fluorescence from aggregates of azobenzene‐containing amphiphilic diblock copolymers

The well‐defined azobenzene‐containing homopolymers, poly{6‐(4‐phenylazophenoxy)hexyl methacrylate (AHMA)} (PAHMA), were synthesized via reversible addition fragmentation chain transfer polymerization (RAFT) in anisole solution using 2‐cyanoprop‐2‐yl 1‐dithionaphthalate (CPDN) as the RAFT agent and 2,2′‐azobisisobutyronitrile (AIBN) as the initiator. The first‐order kinetic plot of the polymerization and the linear dependence of molecular weights of the homopolymers with the relatively low polydispersity index values (PDIs ≤ 1.25) on the monomer conversions were observed. Furthermore, the amphiphilic diblock copolymer, poly{6‐(4‐phenylazophenoxy)hexyl methacrylate (AHMA)}‐b‐poly{2‐(dimethylamino)ethyl methacrylate (DMAEMA)} (PAHMA‐b‐PDMAEMA), was prepared with the obtained PAHMA as the macro‐RAFT agent. The structures and properties of the polymers were characterized by ¹H NMR and GPC, respectively. Interestingly, the amphiphilic diblock copolymers in chloroform (CHCl₃) solution (PAHMA₂₃‐b‐PDMAEMA₉₇ (4 × 10^?5 M, M_n(GPC) = 18,400 g/mol, PDI = 1.48) and PAHMA₂₈‐b‐PDMAEMA₁₁₇ (6 × 10^?5 M, M_n(GPC) = 19,300 g/mol, PDI = 1.51) exhibited the intense fluorescence emission at ambient temperature. Moreover, the fluorescent intensity of PAHMA‐b‐PDMAEMA in CHCl₃ was sensitive to the ultraviolet irradiation at 365 nm, which increased within the first 10 min and later decreased when irradiation time was prolonged to 30 min or longer. The well distributed, self‐assembled micelles composed of azobenzene‐containing amphiphilic diblock copolymers, (PAHMA‐b‐QPDMAEMA)s (QPDMAEMA is quaternized PDMAEMA), in the mixed N,N‐dimethyl formamide (DMF)/H₂O solutions were prepared. Their fluorescent intensities decreased with the increasing amount of water. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5652–5662, 2008     

Controlled synthesis and fluorescent properties of poly(9-(4-vinylbenzyl)-9H-carbazole) via nitroxide-mediated living free-radical polymerization

The functional polymer containing carbazole unit, [(poly(9-(4-vinylbenzyl)-9H-carbazole) (PVBK)], was successfully prepared via nitroxide-mediated living free-radical polymerization of 9-(4-vinylbenzyl)-9H-carbazole (VBK). The controlled features of the polymerization were confirmed by the linear increase in the molecular weight with the monomer conversion while keeping the relative narrow molecular weight distribution (M_w/M_n ? 1.51), and successful chain extension with styrene. The resulting polymer absorbed light in the 305-355 nm range and exhibited fluorescent emission at 350 nm. The fluorescent intensity of the polymer was lower than that of monomer and was affected by the properties of the different solvents, which decreased in the following order: DMF > THF > CHCl₃ at the same concentration of carbazole units. The fluorescence intensity of the polymer was apparently influenced by chromophore concentration, and the maximum value was obtained when the carbazole unit concentration was around 8 × 10⁻⁵ mol/L. Moreover, it was shown that the strong fluorescence of PVBK can be quenched by methyl acrylate (MA).     

Fluorescence resonance energy transfer between acridine orange and rhodamine 6G and its analytical application for vitamin B12 with flow-injection laser-induced fluorescence detection

By coupling flow-injection with laser-induced fluorescence detection, a setup was developed and a novel method combining fluorescence resonance energy transfer (FRET) and flow-injection analysis (FIA) was proposed for the determination of vitamin B₁₂ (VB₁₂) based on its fluorescence quenching on the system of acridine orange (AO)/rhodamine 6G (R6G). The effective energy transfer could occur between AO and R6G in the dodecyl benzene sodium sulfonate (DBS) while 454 nm argon laser was used as the excitation source, and as a result, the fluorescence emission of R6G has been increased significantly. It was found that the fluorescence of the above system could be sharply diminished by VB₁₂. By using the mixed solution AO-R6G-DBS and the same solution containing VB₁₂ as the carrier and sample, respectively, a series of negative peaks which could be applied for the quantification of VB₁₂ were obtained. The detection limit for VB₁₂ was 1.65 × 10⁻⁶ mol/L. The linear range for determining VB₁₂ was 4 × 10⁻⁴ to 2 × 10⁻⁶ mol/L (correlation coefficient, r = 0.9923). The method was applied to measure VB₁₂ injections with satisfactory results.     

Preparation of reversibly photo-cross-linked nanogels from pH-responsive block copolymers and use as nanoreactors for the synthesis of gold nanoparticles

Reversibly photo-cross-linkable pH-responsive block copolymer poly(ethylene oxide)-b-poly((2-(diethylamino)ethyl methacrylate-co-4-methyl-[7-(methacryloyl)oxyethyloxy] coumarin)) (PEO-b-P(DEA-co-CMA)) was synthesized via atom transfer radical polymerization (ATRP). Block copolymer nanogels could be easily prepared by first photo-cross-linking of the micelles at pH > 7 and then adjusting the solution to pH < 7. The photo-cross-linking was proved to be reversibly controlled under alternative irradiation of UV light at 365 nm and 254 nm. As a result, the cross-linking degrees and sizes of the nanogels can be easily controlled by alternatively UV light irradiation. Finally, the nanogels can serve as nanoreactors for the synthesis of gold nanoparticles. The protonated DEA units were first coordinated with HAuCl₄, and then the electrostatically bounded AuCl⁴⁻ anions were reduced to gold nanoparticles by NaBH₄. The nanogel-supported gold nanoparticles were used in chemical catalysis. The pH-responsive photo-cross-linked nanogels have been characterized using dynamic light scattering, transmission electron microscopy, UV-vis spectra and ¹H NMR spectroscopy measurements, respectively.     

Photophysical properties and photostability of novel unsymmetric polycyclicphenazine-type D-π-A fluorescent dyes and the dye-doped films

Structural isomers of unsymmetric polycyclicphenazine-type D-π-A fluorescent dyes have been newly synthesized and characterized in both solution and polymer films. The dyes exhibited two strong absorption bands at around 328-401 nm and 516-532 nm, and an intense fluorescence band at around 595-629 nm (Φ = 0.32-0.84) in 1,4-dioxane. The dye-doped polymer films showed good ability of wavelength conversion; the films can efficiently convert ultraviolet and green-yellow lights into red light (Φ = 0.43-0.86). Moreover, the photostability of the dyes-doped PS, PMMA, and PLA films has been investigated.     

Synthesis of well‐defined naphthalene and photo‐labile group‐labeled polystyrene via ATRP

The atom transfer radical polymerizations of styrene were successfully carried out in bulk and solution, respectively, at 115 °C, with a novel photoiniferter reagent, (1‐naphthyl)methyl N,N‐diethyldithiocarbamate (NMDC), as an initiator in the presence of copper (I) bromide and N,N,N′,N″,N″‐pentamethyldiethylenetriamine. The results showed that NMDC was an effective initiator with high initiation efficiency for ATRP of St. The polymerization rate was first‐order with respect to the monomer concentration and the molecular weights of the obtained polystyrene (PS) increased linearly with the monomer conversion, with very narrow molecular weight distributions (M_w/M_n = 1.07–1.29). The functionalized naphthalene‐labeled PS bearing N,N‐(diethylamino)dithiocarbamoyl group which was confirmed by ¹H NMR analysis, and chain extension of the PS exhibited fluorescence and ultraviolet absorption in chloroform (CHCl₃). © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 510–518, 2006     

Fluorescence properties of novel rare earth complexes using carboxyl-containing polyaryletherketones as macromolecular ligands

The fluorescence properties of a series of rare earth (Re³⁺ = Eu³⁺, Tb³⁺) polymeric complexes (PEK-Re³⁺-HLs) using three high-T_g novel carboxyl-containing polyaryletherketones (PEK) as macromolecular ligands and small molecules (HL) such as 1,10-phenanthroline (Phen), dibenzoylmethane (DBM) and 8-hydroxyquinoline (HQ) as co-ligands were investigated by means of fluorescence excitation and emission spectroscopy as well as fluorescence lifetime measurement methods. Among them, PEK-1-Re³⁺-Phens, in which the Re³⁺ ions were coordinated simultaneously with Phen and PEK-1 containing both carboxyl and bulky isopropyl groups on the polymer backbone, exhibited strong fluorescence intensities, long lifetimes, and good film-formation properties. The smooth films of PEK-1-Eu³⁺-Phen and PEK-1-Tb³⁺-Phen, cast from their DMF solutions, could emit bright red and green light under the UV lamp of 365 nm, respectively, which characteristics are of great significance for their potential applications in the large area display material fields. The excellent fluorescence properties of complexes in this study were attributed to the synergistic effects of PEK-1 ligand and Phen co-ligand. Especially, the rigid twisted structure and the bulky isopropyl substituents on PEK-1 backbone forced the coordinated rare earth ion moieties apart, and thus the probability of non-radiative decay rate of Re³⁺ ions at the excited levels were decreased to a large extent.     

Photoresponsive peptide and polypeptide systems. VIII. Synthesis and reversible photochromism of azo aromatic poly(L-ornithine)

Poly(L -ornithine) having azo aromatic side chain was synthesized by the water-soluble carbodiimide procedure. The photochemical properties of the azo polypeptide poly[N^δ-p-(phenylazo)benzoyl-L -ornithine] (PPABLO) was investigated by absorption and circular dichroism spectroscopy in hexafluoro-2-propanol (HFIP). The photochromism of the dichroic bands in the visible and ultraviolet wavelength regions was found to be reversible as a function of irradiation time at different wavelengths due to the photostationary state (about 70% trans)–cis photoisomerization of the azo aromatic moieties. The reversible photoinduced solubility change was also studied. On irradiation PPABLO is soluble under ultraviolet light (cis) and precipitate under visible light (70% trans) in HFIP–water. A discussion was presented that includes results on azo aromatic poly(L -lysine).     

Fluorescence switching of photochromic vinylpyrene-substituted 2′-deoxyguanosine

We synthesized C8-vinylpyrene-substituted 2′-deoxyguanosine ^VPyG and studied the photoregulated reversible E-Z isomerization. When E-isomer was irradiated with visible light (>420 nm), E- toZ-isomerization took place very rapidly, while upon irradiation with UV-light (∼365 nm), Z-isomer was converted to E-isomer. When Z-isomer was illuminated with 365-400 nm light, no fluorescence was observed, while E-isomer showed a very strong fluorescence emission, indicating that ^VPyG could be a useful fluorescence switching molecule.     

Composition dependent frequency upconversion of Er/Yb-codoped lead chloride tellurite glasses

The green and red upconversion luminescence of Er³⁺ in lead chloride tellurite glasses excited at 980 nm is investigated. Three intense emission bands centered at 530, 545, and 658 nm corresponding to the transitions ⁴S_3/2→⁴I_15/2, ²H_11/2→⁴I_15/2 and ⁴F_9/2→⁴I_15/2, respectively, were simultaneously observed at room temperature. With increasing PbCl₂ content, the intensity of green (530 nm) emissions increase slightly, while the green (545 nm) and red (658 nm) emissions increase significantly. The results indicate that PbCl₂ has more influence on the green (545 nm) and red (658 nm) emissions than the green (530 nm) emission. The dependence of upconversion intensities on excitation power and possible upconversion mechanisms are discussed and evaluated.     

Photoluminescence of new red phosphor SrZnO2:Eu

SrZnO₂:Eu³⁺ has been synthesized by solid-state reaction and its photoluminescence in ultraviolet (UV)-vacuum ultraviolet (VUV) range was investigated. The broad bands around 254 nm are assigned to CT band of Eu³⁺-O²⁻. With the increasing of Eu³⁺ concentration, Eu³⁺ could occupy different sites, which leads to the broadening of CT band. A sharp band is observed in the region of 110-130 nm, which is related to the host absorption. The phosphors emit red luminescence centered at about 616 nm due to Eu³⁺⁵D₀→⁷F₂ both under 254 and 147 nm, but none of Eu²⁺ blue emission can be observed.     

Trifluoroacetyl-chlorin as a new chemosensor for alcohol/amine detection

Chlorophyll derivative possessing a trifluoroacetyl group at the 3-position was synthesized as a new chemosensor for alcohols and amines. Intense Q_y peak of the trifluoroacetyl-chlorin (701 nm in CHCl₃) showed blue shifts to 667 nm in MeOH and 665 nm in n-BuNH₂ due to the formation of the corresponding hemiacetal and hemiaminal with visible color changes. Thermodynamic parameters for the complexation between trifluoroacetyl-chlorin and n-BuNH₂ in CDCl₃ were determined to be ΔH = −48 kJ mol⁻¹ and ΔS = −147 J K⁻¹ mol⁻¹. Ratiometric fluorescence sensing of n-BuNH₂ in THF was also demonstrated.     

Excitation-wavelength-dependent fluorescent organohydrogel for dynamic information anti-counterfeiting

Anti-counterfeiting labels with various fluorescent colors are of great importance in information encryption-decryption, but are still limited to static information display. Therefore, it is urgent to develop new materials and encryption-decryption logic for improving the security level of secret information. In this study, an organohydrogel made up of poly(N,N-dimethylacrylamide) (pDMA) hydrogel network and polyoctadecyl methacrylate (pSMA) organogel network that copolymerized with two fluorophores, 6-acrylamidopicolinic acid moieties (6APA, fluorescent ligand) and spiropyran units (SPMA, photochromic monomer), was prepared by a two-step interpenetrating method. As UV light of 365 nm and 254 nm can both cleave C_spiro-O bonds of SPMA, and the green fluorescence of 6APA-Tb³⁺ can only be excited by 254 nm light, the organohydrogel displays yellow and red under the irradiation of 254 nm and 365 nm, respectively. In addition to wavelength selectivity, these two fluorophores are thermal-responsive, leading to the fluorescence variation of the organohydrogel during heating process. As a result, secret information loaded on the organohydrogel can be decrypted by the irradiation of UV light, and the authenticity of the information can be further identified by thermal stimulation. Our fluorescent organohydrogel can act as an effective anti-counterfeiting label to improve the information security and protect the information from being cracked.     

Synthesis of tetrazole‐containing azo polymers with properties of photo‐induced birefringence and surface‐relief‐gratings via RAFT polymerization

A novel optically active monomer, 6‐{4‐[4‐(1‐phenyl‐1H‐tetrazol‐5‐yloxy)‐phenylazo] ‐phenoxy}‐hexyl methacrylate (PTPPHMA) bearing tetrazole and azobenzol moieties, was synthesized and polymerized by reversible addition‐fragmentation chain transfer (RAFT) polymerization using 2‐cyanoprop‐2‐yl dithiobenzoate (CPDB) as the RAFT agent and 2, 2′‐azobis(isobutyronitrile) (AIBN) as the initiator. Well‐defined optically active photochromic polyPTPPHMA(PPTPPHMA) was obtained. “Living”/controlled characteristics were observed in the polymerization: well‐controlled molecular weights (M_ns), narrow molecular weight distributions (M_w/M_n) of the polymers and successful chain‐extension of PPTPPHMA with styrene (St) as the second monomer. The photochemical interconversion between trans and cis isomers of PPTPPHMA in N,N′‐dimethyl formamide (DMF) solution was explored under irradiation of ultraviolet light. The photoinduced birefringence on the thin films of PPTPPHMA was investigated. A maximum birefringence of 0.1 was obtained, and no significant change of profiles of the birefringence after several cycles of writing/erasing/rewriting sequences was observed. The surface‐relief‐gratings (SRGs) were induced on the polymer films by interference of Kr⁺ laser beams at 413.1 nm with 35 mW/cm² intensity, the diffraction efficiencies from SRGs were measured to be in the range of 2.0–2.5%. The atomic force microscopy (AFM) results showed the gratings produced on the surfaces of the polymer film. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 682–691, 2008     

Enhanced ultraviolet up-conversion emissions of Tm/Yb codoped YF3 nanocrystals

Tm³⁺/Yb³⁺ codoped rod-like YF₃ nanocrystals were synthesized through a facile hydrothermal method. After annealing in an argon atmosphere, the nanocrystals emitted bright blue and intense ultraviolet (UV) light under a 980-nm continuous wave diode laser excitation. Up-conversion emissions centered at ∼291 nm (¹I₆ → ³H₆), ∼347 nm (¹I₆ → ³F₄), ∼362 nm (¹D₂ → ³H₆), ∼452 nm (¹D₂ → ³F₄), ∼476 nm (¹G₄ → ³H₆), ∼642 nm (¹G₄ → ³F₄), and ∼805 nm (³H₄ → ³H₆) were recorded using a fluorescence spectrophotometer. Especially, enhanced UV emissions were studied by changing Yb³⁺/Tm³⁺ doping concentrations, the annealing temperatures, and the excitation power densities. A possible mechanism, energy transfer-cross relaxation-energy transfer (ET-CR-ET), was proposed based on a simple rate-equation model to elucidate the process of the enhanced UV emissions.     

Star-shaped electrochemiluminescent metallodendrimers with central polypyridyl Ru(II) complexes: Synthesis and their photophysical and electrochemical properties

Several dendritic bridging ligands were designed and synthesized to develop more sensitive and efficient electrochemiluminescent (ECL) polynuclear Ru(II) complexes. Various types of novel two-armed, four-armed and six-armed tris(bipyridyl)ruthenium core dendrimers were synthesized by coordinating dendritic polybipyridyl ligands with Ru(II) complexes, and the effect of the ligand and the dendritic network on the ECL characteristics were studied. Their electrochemical redox potentials, UV, photoluminescence (PL), and relative ECL intensities were also investigated in detail. The synthesized metallodendrimers exhibited strong metal-to-ligand charge transfer (MLCT) absorption at 428-451 nm and emission at 591-601 nm. Most of the newly synthesized metallodendrimers showed enhanced ECL intensities compared to the reference complex, [Ru(o-phen)₃](PF₆)₂. In particular, the ECL intensities of the six-armed heptanuclear ruthenium complexes were almost four times greater than that of [Ru(o-phen)₃]²⁺. These metallodendrimers could be utilized as efficient ECL materials and light emitting devices.     

Tweezers-like aromatic molecules and their luminescent properties depending on the structures

Di(hydroxyphenyl)pyrimidine with two anthryl substituents 1a was synthesized and characterized by X-ray crystallography and NMR spectroscopy. The molecule prefers ‘U’-shaped conformation supported by intramolecular O-H···N hydrogen bonds in the solid state and in solution. The CHCl₃-solvated compound binds two CHCl₃ molecules between the two parallel anthryl planes. Hexylation of the OH groups of 1a produces 1c whose diarylpyrimidine core contains these aromatic planes with O···H-C interaction and helical alignment. Compound 1c shows strong emission from the anthryl groups (410 nm, φ = 0.39), while luminescence is not observed for 1a partly due to quenching via PET (photo-induced electron transfer) process.     

A unique ‘ON-OFF-ON’ switch with two perturbations at two different concentrations of Ag

The dipod 1,2-bis(8-quinolinoxymethyl)benzene 3 and tetrapod 1,2,4,5-tetrakis(8-quinolinoxymethyl)benzene 4 show two perturbations in fluorescence with Ag⁺, (i) fluorescence quenching with <1.0 equiv of AgNO₃ at λ_max 395 nm and (ii) fluorescence enhancement at λ_max 500 nm with >3 equiv of AgNO₃. This ‘ON-OFF-ON’ switching of 3 and 4 in comparison with simultaneous fluorescence quenching and enhancement in the case of 8-methoxyquinoline 1 and the tripod 1,3,5-trimethyl-2,4,6-tris(8-quinolinoxymethyl)benzene 2 point to the unique role of molecular architectures arising due to the number and spatial positions of quinoline units in the fluorescence behaviour of an 8-alkoxyquinoline moiety towards Ag⁺.