Charge selective encapsulation by polymeric micelles with cationic,anionic, or zwitterionic cores

Polymeric micelles showing charge selective and pH‐reversible encapsulation are reported. It is found that for a guest mixture of organic cationic–anionic dyes, a unimolecular micelle (PEI@PS) with a polystyrene (PS) as shell and a hyperbranched polyethylenimine (PEI) as core can exclusively entrap the anionic one; and a physical micelle consisting of brush‐like macromolecule (mPS‐PAA) with multi PS‐b‐polyacrylic acid (PAA) as grafts can exclusively entrap the cationic one. A covalent micelle (PEI‐COOH@PS) bearing a zwitterionic core, that is, PEI covalently derived with dense carboxylic acids, can undergo highly pH‐switchable charge selective and pH‐reversible encapsulation. Both PEI@PS and mPS‐PAA can be used for highly charge‐selective separation of ionic dyes but the pH‐reversibility of the encapsulation is relatively limited. In contrast, PEI‐COOH@PS is less effective to differentiate the anionic–cationic dyes but is well recyclable. A physical micelle obtained from the self‐assembly of PEI and mPS‐PAA shows similar property to PEI‐COOH@PS. The combination of these micelles in mixture separation can enhance the recyclability of the micelle and widen the spectrum of mixtures that can be well separated. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Dye-labeled polystyrene latex microspheres prepared via a combined swelling-diffusion technique

A series of water-insoluble, biologically compatible dyes, meso-tetraphenylchlorin, meso-tetraphenylporphyrin and chlorophyll-a, were successfully incorporated into beads composed of linear polystyrene (PS) via a tunable combined swelling-diffusion process. Dyed PS beads were prepared by the addition of a dye solution in tetrahydrofuran to an aqueous suspension of 10 μm PS beads in the presence of a poly((ethylene glycol)-b-(propylene glycol)-b-(ethylene glycol)) block copolymer surfactant. The presence of surfactant was found to be beneficial to prevent particle aggregation, especially at tetrahydrofuran contents above 30%. Dye loading was shown to be tunable by simple adjustments in dye composition. Confocal fluorescence microscopy indicated that dyes were distributed uniformly throughout the entire PS bead, but heterogeneously with ~500 nm diameter droplets, indicative of a separate dye phase within the PS matrix. The stability of dyed beads, indicated by resistance to dye leaching in solvent, was found to be governed by the degree of swelling of PS in the solvent medium. Hence, no leaching was observed even when a good solvent for the dye was used (ethanol), as long as that solvent did not swell the carrier particle, PS. No leaching of dyes from the beads was observed during long-term (2 years) storage in water.     

THE ROLE OF CYCLIC ELECTRON FLOW AROUND PHOTOSYSTEM I and EXCITATION ENERGY DISTRIBUTION BETWEEN THE PHOTOSYSTEMS UPON ACCLIMATION TO HIGH IONIC STRESS IN Dunaliella salina

Abstract— The distribution of excitation energy between the two photosystems in the halophylic alga Dunaliella salina has been analyzed under ionic stress. In the transition from state 1 to state 2, it was found that a, the absorption cross-section of photosystem (PS) I increased from 42 to 49% until an equal distribution between PS I and PS II was obtained in state 2. Acclimation of the algae to different salt concentrations did not change the fractions of light absorbed in PS II and PS I, but slowed down the transition time from state 1 to state 2. A large increase in ΔpH induced fluorescence quenching was observed which was abolished by the uncoupler nigericin. Photoacoustic quantum yield spectra of energy storage indicated a larger energy storage at 700 nm induced upon stress. The additional ΔpH quenching of fluorescence and the additional quantum yield of energy storage at 700 nm, in the stressed algae, are consistent with the operation of a cyclic, energy-storing pathway in PS I which is uncoupler sensitive.     

Effect of the excitation source on the quantum-yield measurements of rhodamine B laser dye studied using thermal-lens technique.

A dual-beam transient thermal-lens technique was employed for the determination of absolute fluorescence quantum-yield measurements of Rhodamine B laser dye in different solvents. We investigated the effect of excitation on the absolute fluorescence quantum yield of Rhodamine B. 514 nm radiation from an argon ion laser was used as a cw excitation source and 532 nm pulses from a Q-switched Nd:YAG laser were used as a pulsed excitation source. The fluorescence quantum-yield values were found to be strongly influenced by environmental effects as well as the transient nature of the excitation beam. Our results also indicate that parameters, like the concentration of the dye solution, aggregate formation and excited state absorption, affect the absolute values of the fluorescence yield significantly.     

Synthesis of Water‐Soluble Red‐Emitting Thienyl–BODIPYs and Bovine Serum Albumin Labeling

Thesynthesis of three red‐emitting and water‐soluble thienyl‐BODIPYs has beenachieved. The trimethyl(propargyl)ammonium group was chosen as a vector forwater solubility. One or two cationic arms were introduced either on the2‐position of the thienyl unit or on the 4‐position on the boron atom. Thesedyes have pronounced absorption around 600 nm and intense emission at 650 nmwith quantum yield of about 60% in water. Grafting of such BODIPYs via a flexible arm to BSA is veryefficient, allowing attachment of 1 to 30 labels in a controlled manner.  Very strong fluorescence (quantum yield 56%)without aggregation of the dye at a low loading ratio (1:5 BSA/label) in PBSbuffer is measured.     

Constitution and energetics of photosystem I and photosystem II in the chlorophyll d-dominated cyanobacterium Acaryochloris marina

This mini review presents current topics of discussion about photosystem (PS) I and PS II of photosynthesis in the Acaryochloris marina. A. marina is a photosynthetic cyanobacterium in which chlorophyll (Chl) d is the major antenna pigment (>95%). However, Chl a is always present in a few percent. Chl d absorbs light with a wavelength up to 30 nm red-shifted from Chl a. Therefore, the chlorophyll species of the special pair in PS II has been a matter of debate because if Chl d was the special pair component, the overall energetics must be different in A. marina. The history of this field indicates that a purified sample is necessary for the reliable identification and characterization of the special pair. In view of the spectroscopic data and the redox potential of pheophytin, we discuss the nature of special pair constituents and the localization of the enigmatic Chl a.     

Vapor phase excitation transfer from pyrene to perylene

Excitation transfer from optically pumped pyrene to perylene has been investigated to determine its applicability to dye vapor lasers. A quenching distance of 9 ± 1 Å and a quantum yield of transfer of 30–40% have been measured and an overall energy conversion efficiency of 20% has been obtained.     

Facile preparation of Au nanoparticle-embedded polydopamine hollow microcapsule and its catalytic activity for the reduction of methylene blue

Abstract

Development of novel supported catalysts with high activity and stability is still a challenge. In this study, the Au-polydopamine (Au-PDA) hollow microcapsules with Au nanoparticles embedded into the PDA microcapsule shell have been synthesized through a simple template-induced covalent assembly method, where polystyrene (PS) nanospheres were used as templates to form core/shell structured PS/Au-PDA composites, followed by core removal through tetrahydrofuran etching. Their morphology and composition were characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), Fourier transform infrared spectra (FT-IR), UV-Vis spectrophotometer and X-ray diffraction (XRD), respectively. Results showed that the Au-PDA microcapsules possessed well-fined hollow structure and uniform sizes with inner diameter of about 385?nm, shell thickness of about 30?nm, and Au nanoparticles with diameter of about 17?nm incorporated. The catalytic performance of Au-PDA hollow microcapsules was evaluated through the reduction of methylene blue (MB) dye with NaBH₄ as a reducing agent. Compared to PDA/Au composites with Au nanoparticles loaded on the surface of PDA microspheres, as-prepared Au-PDA hollow microcapsules show good stability and recyclability in the catalytic experiments as the Au nanoparticles were firmly wrapped in PDA matrix, which makes the Au-PDA hollow microcapsules a practicable catalyst candidate for advanced catalytic systems.     

6-Dialkylaminobenzimidazole Nonlinear Optical Dyes

A new 6-dialkylaminobenzimidazole nonlinear optical dye was synthesized in eight linear steps with an overall yield of 16%.     

Photochemical electrocyclization and leaving group expulsion with a naphthothiophene-2-carboxanilide linked to a chromophore

A naphthiothiophene-2-carboxanilide bearing a leaving group at the C-3 position undergoes efficient electrocyclic ring closure and leaving group expulsion upon direct photolysis. The reaction occurs in the triplet excited state and can be sensitized by thioxanthone. Thioxanthone as chromophore can also be covalently attached to amide nitrogen by a trimethylene linker, and the photoreaction is equally efficient. Quenching studies show that the triplet excitation is localized primarily on the naphthothiophene moiety, due to rapid exothermic energy transfer from the thioxanthone chromophore. Acriflavin dye is capable of sensitizing the photoreaction at 450?nm, but the quantum yield is low in this case.     

Surface modification of thin polystyrene films

 The sulfonation of polystyrene (PS) films with 50 and 96% sulfuric acid as a function of time is presented. In contrast to previous literature reports, we showed that the treatment of PS films even with dilute sulfuric acid yields sulfonated surfaces after reaction times of 30 s–1 h. The hydrophilicity of the modified PS increased considerably in comparison to the unreacted PS films. X-ray photoelectron spectroscopy yielded evidence for the sulfonation of PS at the surface. Unreacted spin-coated PS films were very smooth, while modified PS showed some clumps dispersed on a flat surface, as analyzed by atomic force microscopy. The surface morphology was identified as a phase-separated system composed of domains of unreacted PS and a matrix of sulfonated PS by fluorescence microscopy using the positively charged dye rhodamine B. The adsorption of the polycation diallyldimethylammonium chloride on the sulfonated PS surface could be detected. The thickness of the adsorbed polycation was 2.2 nm. Received: 3 November 1998 Accepted in revised form: 23 February 1999     

Time-resolved two-photon spectroscopy of photosystem I determines hidden carotenoid dark-state dynamics

We present time-resolved fs two-photon pump-probe data measured with photosystem I (PS I) of Thermosynechococcus elongatus. Two-photon excitation (lambda(exc)/2 = 575 nm) in the spectral region of the optically forbidden first excited singlet state of the carotenoids, Car S1, gives rise to a 800 fs and a 9 ps decay component of the Car S1 --> S(n) excited-state absorption with an amplitude of about 47 +/- 16% and 53 +/- 10%, respectively. By measuring a solution of pure beta-carotene under exactly the same conditions, only a 9 ps decay component can be observed. Exciting PS I at exactly the same spectral region via one-photon excitation (lambda(exc) = 575 nm) also does not show any sub-ps component. We ascribe the observed constant of 800 fs to a portion of about 47 +/- 16% beta-carotene states that can potentially transfer their energy efficiently to chlorophyll pigments via the optically dark Car S1 state. We compared these data with conventional one-photon pump-probe data, exciting the optically allowed second excited state, Car S2. This comparison demonstrates that the fast dynamics of the optically forbidden state can hardly be unravelled via conventional one-photon excitation only because the corresponding Car S1 populations are too small after Car S2 --> Car S1 internal conversion. A direct comparison of the amplitudes of the Car S1 --> S(n) excited-state absorption of PS I and beta-carotene observed after Car S2 excitation allows determination of a quantum yield for the Car S1 formation in PS I of 44 +/- 5%. In conclusion, an overall Car S2 --> Chl energy-transfer efficiency of approximately 69 +/- 5% is observed at room temperature with 56 +/- 5% being transferred via Car S2 and probably very hot Car S1 states and 13 +/- 5% being transferred via hot and "cold" Car S1 states.     

Enhanced molecular fluorescence near thick Ag island film of large pseudotabular nanoparticles

A highly reflective thick Ag island film (TAIF) sputter-grown on mica, consisting of unique large pseudotabular nanoislands, 60-200 nm across and 30-60 nm thick, produced an unusually strong surface enhanced fluorescence (SEF) for rhodamine dyes situated very close to (only approximately 10 A away from) the metal surface. A significantly greater part of the enhanced fluorescence was emitted into the back half space through TAIF and the mica substrate. The detailed fluorescence angular distribution was very similar to that of the light scattering by TAIF, suggesting that the enhanced emission originated from some large induced dipoles in TAIF. For reference, we also present a quantitative analysis of the fluorescent behavior of the same dye but directly coated on a reference glass surface. TAIF showed no distinct dipolar surface plasmon-like bands for excitation at normal incidence, and the light absorption by dye-coated TAIF could be described by simple superposition of the contribution of TAIF and that of the surface-bound dyes. However, the net dye absorptance was increased by 4-5 times due to the strong interactions of the dye transition dipoles with the TAIF-scattered fields. The estimated SEF quantum yield in the low dye coverage limit suggests a markedly high radiative yield of the induced dipole in TAIF around approximately 0.5.     

Theoretical studies on triaryamine‐based p‐type D‐D‐π‐A sensitizer

Development of triaryamine‐based nonmetallic dye sensitizers is a hot topic in the solar cell research. A series of triaryamine‐based dyes WS1 – WS7 were designed with W1 as the prototype. Density functional theory (DFT) and time‐dependent‐DFT calculations were used to investigate the effects of the attached donor D on the absorption spectra and electronic properties of the dyes. The light‐harvesting efficiency (LHE), hole injection force (ΔG_inj), dye regeneration force (ΔG_reg), and charge recombination force (ΔG_CR) for all the dyes were predicted. The insertion of D not only results in a red shift in the absorption spectra for all dyes but also achieves a broader absorption for visible light. Compared with that of the prototype, the absorption peak of the dye WS7 has a red shift of 95 nm and an oscillator strength increase of 29%. The absorption peak of WS7 is wider and stronger, and the absorption range extends to 900 nm. The LHE and ΔG_reg values of WS7 are 0.991 and ?1.49 eV, respectively. On overall evaluation, WS7 is a promising candidate of a p‐type dye sensitizer with good light absorption and dye regeneration efficiency.     

Solid-phase synthesis of 7-acylamino-1,4-benzodiazepine-2,5-diones

A method for the synthesis of polymer-bound 7-acylamino-benzodiazepine-2,5-diones is described. The amino group of an alpha-amino acid is linked to polystyrene or TentaGel resin via reductive amination of polymer-bound 4-alkoxy-2,6-dimethoxybenzaldehyde. Acylation with unprotected 5-nitroanthranilic acid is followed by base-catalyzed ring closure. Reduction of the nitro group yields enantiomerically pure 7-aminobenzodiazepin-2,5-dione attached via the N-4 atom to the resin. Acylation of the amino group on the aromatic ring with acid chlorides in N-methylpyrrolidone (no DMF, no base!) followed by cleavage from the resin using TFA/Me(2)S/water (90:5:5) provides the acylated benzodiazepinones in 52-69% (PS resin) and 41-48% (TG resin) yield (based on the theoretical loading) and >70% purity (HPLC, 210 nm). Using Fmoc-protected tyrosine fluoride in NMP gives the amino acid-coupled benzodiazepinones in 24% (PS resin) and 31% (TG resin) yield.     

一种含聚乙二醇非离子亲水基团的新型水溶性荧光染料的合成及细胞成像

通过向吲哚环“N”位上引入一个含聚乙二醇(PEG)醚链的非离子亲水基团,合成了一种新型水溶性不对称五甲川吲哚菁染料。 用核磁(¹H NMR)和高分辨质谱(HRMS)表征染料的结构,测试了染料的光谱性能,标记牛血清白蛋白(BSA),并对固定细胞和活细胞分别染色。 结果表明,该染料在水中的最大紫外吸收波长和荧光发射波长分别为648和668 nm,斯托克斯(stokes)位移为20 nm,荧光量子产率(Ф)为0.13,以碘钨灯为光源光照8 h后,染料光降解率为5.8%。 用染料的NHS活性酯标记牛血清白蛋白,标示率(D/P)为1.16。 对固定细胞染色发现,染料可对细胞整体着色,对细胞核染色最明显,能清晰看到核仁。 对活细胞染色发现,有少量染料跨膜进入细胞内部,对细胞质和细胞核有微弱染色,但在活细胞膜上聚集明显。     

超细荧光聚合物纳米微球的制备

合成了具有较高荧光量子产率(0.69)和良好光稳定性的可聚合荧光染料单体,该荧光染料的光稳定性高于商品化的染料罗丹明B。 通过氧化还原引发剂引发乳液聚合制备了超细荧光聚合物纳米微球,将染料分子共价连接在聚合物链上。 使用非离子表面活性剂Triton X-100作为乳化剂、甲基丙烯酸甲酯(MMA)作为单体和助乳化剂,制备的超细纳米微球平均粒径为22 nm,而不加MMA时制备出的纳米微球平均粒径在150 nm左右。 由于微球表面带有苄氯基团,为进一步的微球功能化提供了途径。     

4',5'-Dichloro-2',7'-dimethoxy-5(6)-carboxyfluorescein (JOE): synthesis and spectral properties of oligonucleotide conjugates

A convenient procedure for the preparation of the fluorescent dye 4',5'-dichloro-2',7'-dimethoxy-5(6)-carboxyfluorescein (JOE) is reported; the overall yield achieved starting from isovanillin is 10 times higher (40% vs 4%) compared to the known procedure. Isomers (5- and 6-) are easily chromatographically separable as pentafluorophenyl esters of 3',6'-O-bis(cyclohexylcarbonyl) derivatives. Four non-nucleoside JOE phosphoramidites based on 5- and 6-isomers and flexible 6-aminohexanol (AH) or rigid 4-trans-aminocyclohexanol (ACH) linkers have been prepared and used for oligonucleotide labeling. Spectral and photophysical properties of 5'-JOE-modified oligonucleotides have been studied. Fluorescence quantum yield of the dye correlates with the nature of the linker (rigid vs flexible) and with the presence of dG nucleosides in close proximity to a JOE residue.     

A chiral cyclotrisazobiphenyl: synthesis and photochemical properties

A chiral cyclotrisazobiphenyl macrocycle was synthesized conveniently in three steps from the literature known 3,3'-diaminobimesityl in 37-38% overall yield. Irradiation with 302 nm, 365 nm or visible light allows access to different photostationary states (PSSs). These PSSs can be conveniently read out by CD-spectroscopy as each of them exhibits a positive, a negative, or no signal, respectively, at 275 nm.     

Strategies for selective cancer photochemotherapy: antibody-targeted and selective carcinoma cell photolysis

A principle objective in chemotherapy is the development of modalities capable of selectively destroying malignant cells while sparing normal tissues. One new approach to selective photochemotherapy, antibody-targeted photolysis (ATPL) uses photosensitizers (PS) coupled to monoclonal antibodies (MAbs) which bind to cell surface antigens on malignant cells. Selective destruction of human T leukemia cells (HBP-ALL) was accomplished by coupling the efficient PS chlorin e(6) to an anti-T cell MAb using dextran carriers. Conjugates with chlorin: MAb ratios of 30:1 retained > 85% MA b binding activity, and had a quantum yield for singlet oxygen production of 0.7 +/- 0.1, the same as that of free chlorin e(6). Cell killing was dependent on the doses of both MAb-PS and 630-670 nm light and occurred only in target cell populations which bound the MAb. On the order of 10(10) singlet oxygen molecules were necessary to kill a cell. A second approach to specific photochemotherapy, selective carcinoma cell photolysis (SCCP), relies on preferential accumulation of certain cationic PS by carcinoma cell mitochondria. We have evaluated several classes of cationic dyes, and in the case of N,N'-bis-(2-ethyl-1,3-dioxolane)-kryptocyanine (EDKC) and some of its analogs, have demonstrated highly selective killing of human squamous cell, bladder and colon carcinoma cells in vitro. In isolated mitochondria, EDKC uptake and fluorescence depended on membrane potential, and the dye specifically photosensitized damage to Complex I in the electron transport chain. N,N'-bis-(2-ethyl-1,3-dioxolane)-kryptocyanine and some of its analogs accumulated within subcutaneous xenografts of human tumors in nude mice with tumor:skin ratios > 8. Photoirradiation caused significant inhibition of tumor growth, without cutaneous phototoxicity.