Interaction between the end groups and the main chain of conjugated polymers by time-resolved EPR and fluorescence spectroscopy

ABSTRACT

Interaction between a zinc porphyrin (ZnPor) as the end-group and poly(9,9-di-n-octylfluorene-2,7-vinylene) (PFV) as the main chain in a porphyrin end-modified fluorescent conjugated polymer, ZnPFV, was studied by time-resolved electron paramagnetic resonance (EPR) and fluorescence spectroscopy. While fluorescence from the PFV part of ZnPFV showed a spectral profile almost identical to that of a PFV oligomer without end-modification, the emission spectrum of the ZnPor part exhibited a much broader profile compared to that of the reference zinc porphyrin monomer. Based on the analysis of lifetimes and quantum yields, it was found that radiative rate constant of the ZnPor part was enhanced by nearly three times. The observed unusual enhancement in the radiative rate constant was rationalised in terms of a partial π-conjugation between the end group and the main chain, as a result of co-planarisation in fluid solution. On the other hand, the time-resolved EPR spectrum of ZnPFV at 100?K basically showed a similar spectral pattern to that of the reference zinc porphyrin, but with significant differences in zero-field spitting parameters and initial population ratios. The π-system of the excited triplet state is deduced to deviate from D_4h symmetry in the end zinc porphyrin groups. The obtained results show that interaction of the porphyrin end group with the main chain of the polymer significantly influences the excited singlet state properties of the porphyrin, while its triplet state properties were affected to a lesser extent.     

大斯托克斯位移远红光至近红外荧光探针用于检测肝损伤过程中过氧化亚硝酸盐的动态变化

肝损伤是影响公众健康的重大问题之一, 已经引起了人们越来越多的关注. 而过表达的过氧化亚硝酸盐(ONOO^?)在肝损伤等疾病的发病机制中起着重要作用, 被认为是一种与早期肝损伤密切相关的生物活性分子. 因此, 为了探究ONOO^?在肝损伤过程中的作用, 开发可以实现肝损伤过程中ONOO^?高选择性和实时检测的分析方法具有重要意义. 本文报道了一种具有大斯托克斯位移的远红光至近红外(FR-NIR)ONOO^?荧光探针. 由于该探针具有大的斯托克斯位移, 可以有效消除光谱重叠和自吸收的干扰, 从而显著提高成像的信噪比. 此外, 该探针对ONOO^?具有高的灵敏度(检出限为25.8 nmol/L)和良好的选择性, 被成功用于药物诱导肝损伤过程中ONOO^?信号的成像检测.     

Aerial electrostatic spray deposition and canopy penetration in cotton

Daylight visible fluorescent dye (10% v/v) mixed with water was aerially applied on mature field cotton with electrostatic and rotary atomizer nozzles. The spray rates for the electrostatic and rotary atomizer nozzles were 9.4 and 28 L/ha, respectively. Images of spray droplets on cotton leaves were digitally analyzed with ImageJ software. Charged spray cloud increased deposition nearly two to three times on adaxial and abaxial surfaces, respectively, of top canopy leaves compared to uncharged spray. Canopy penetration of the spray into the lower layers of the plant foliage was unaffected by spray application method.     

Immobilization of Antibodies on Magnetic Carbonaceous Microspheres for Selective Enrichment of Lysine‐acetylated Proteins and Peptides

Lysine acetylation is a dynamic and reversible modification, which has been proved to be a key posttranslational modification in cellular regulation. However, the low amounts of the acetylated proteins could hardly be detected before enrichment. In this study, for the first time, antibody‐immobilized magnetic carbonaceous microspheres were developed for selective enrichment of acetylated proteins and peptides. At first, standard proteins composed of acetylated bovine serum albumin, myoglobin, α‐casein and ovalbumin were used as model proteins to verify the enrichment efficiency. Then, the synthesized peptide was employed to confirm the selectivity of the method. Besides, the antibody‐immobilized magnetic particles were successfully applied to analyze mouse mitochondrial proteins. After database search, 29 acetylated sites in 26 proteins were identi?ed.     

Squaraine dyes: The hierarchical synthesis and its application in optical detection

Squaraine dyes, a four-membered ring system with structural rigidity, possess unique photoelectrical properties and are marked by their exceptionally sharp and intense absorption associated with a strong fluorescent emission in solution. These favorable characteristics have prompted their exploitation in a number of state of the art applications including photoconductivity, data storage, light-emitting field-effect transistors, solar cells and fluorescent histological probes. In this review, we first summarize the recently proposed novel methods in the synthesis of these versatile derivatives. Subsequently, their extensive applications in the prevalent optical detection of the surrounding medium such as ions, pH, thiol-based compounds, biomolecules and cell over the past decades are covered and discussed. In addition, different categories for the synthesis and sensing mechanisms for various squaric acid-based chemo-/bio- sensors are illustrated. Finally, the challenges and opportunities in the synthesis and application of these derivatives are also briefly discussed.     

Viscometric Estimation of Unperturbed Chain Dimensions of Polymers

A new expression is proposed to determine the unperturbed dimensions of coil-like polymers viscometrically by use of the Flory and Kratky expression. The unperturbed dimensions so estimated are compared with the results obtained by using different expressions available in the literature. The results are comparable even for stiff chain polymers. The data obtained under theta conditions also fit this expression very well. The effect of molecular weight, its distribution, and that of the solvent has also been studied. It is concluded that the unperturbed dimensions are independent of molecular weight and solvent but depend on the heterogeneity of the system.     

Sequence Dependence of Fluorescent Quenching of Chromophores Covalently Bonded to Oligo-DNAs before and after Duplex Formation

The labeling of oligo- and polynucleotides with fluorescent probes is an important technique for the analysis of DNAs and RNAs. The effect of duplex formation with complementary oligo-DNA on the quenching behavior of two fluorescent chromophores (eosin, Eo and tetramethylrhodamine, TMR) attached to the 5′-terminal of various 10mer oligo-DNAs was investigated and the dependence of the quenching on DNA base sequence is discussed. We found that guanine residues played a major role in the quenching of the fluorescence of the chromophores. Guanine residues on the complementary DNA near the chromophores, in particular, had a significant influence on the quenching.     

Syntheses and structures of tetranuclear Zn（Ⅱ） complexes with in situ generated macrocyclic Schiff base ligands:Applications in Zn2+ sensing

Three novel Zn（II） complexes,[Zn₄L¹Cl₄]-3H₂O（1）,[Zn₄L²Cl₄]-2DMF（2） and[Zn₄L³Cl₄]H₂O（3）,have been synthesized and structurally characterized.In these complexes,interesting 32-membered dodecadentate macrocyclic ligands were generated in situ by ’2 + 2’ type condensation reactions between a tetraamine and various dialdehydes.All the complexes are isostructurally tetranuclear Zn（Ⅱ） complexes,containing endogenous alkoxo and phenoxo bridges.Applications of the macrocyclic ligands as Zn²⁺ sensors have been investigated.Take H₄L¹ for example,it exhibits a 4-fold fluorescence enhancement upon the addition of 2 equiv.of Zn²⁺ in MeOH.     

Design of Sensitive Biocompatible Quantum‐Dots Embedded in Mesoporous Silica Microspheres for the Quantitative Immunoassay of Human Immunodeficiency Virus‐1 Antibodies

A novel sandwich‐type electrochemiluminescence (ECL) immunosensor was developed to enable the sensitive detection of HIV‐1 antibodies. This system incorporated mesoporous silica (mSiO₂) complexed with quantum dots (QDs) and nano‐gold particles, which were assembled to enhance signal detection. Magnetic beads were used by immobilizing the secondary anti‐IgG antibody. This was first employed to capture HIV‐1 antibody (Ab) to form a Fe₃O₄/anti‐IgG/Ab complex. A high loading and signal‐enhanced nanocomposite (hereafter referred to as Au‐mSiO₂‐CdTe) was used as a HIV‐1 antigen label. The Au‐mSiO₂‐CdTe nanocomposite was conjugated with the Fe₃O₄/anti‐IgG/Ab complex to form an immunocomplex (hereafter referred to as Fe₃O₄/anti‐IgG/Ab/HIV‐1/CdTe‐mSiO₂‐Au). This complex could be further separated by an external magnetic field to produce ECL signals. Due to the large specific surface area and pore volume of mSiO₂, the loading of the CdTe QDs was markedly increased. Thus, the loaded QDs released a powerful chemiluminescent signal with a concordantly increased sensitivity of the immunosensor. The immunosensor was highly sensitive, and displayed a linear range of responses for HIV‐1 antibody across a dilution range of 1 : 1500 through 1 : 50 with the detection limit of 1 : 4500. The immunoassay can be a promising candidate in early diagnosis of HIV infection.