Affinity Adsorption Solid Substrate‐Room Temperature Phosphorimetry for the Determination of Alkaline Phosphatase

Abstract

In the presence of Pb(Ac)₂, the silicon dioxide nanoparticle containing rhodamine 6G (R‐SiO₂) can emit strong and stable solid substrate‐room temperature phosphorescence (SS‐RTP) signal on the surface of acetyl cellulose membrane (ACM) at λ_ex/λ_em=482/649 nm. It was found in the research that specific affinity adsorption reaction between triticum vulgare lectin (WGA) (which was labeled with luminescent silicon dioxide nanoparticle) and alkaline phosphatase (AP) can be carried out on the surface of ACM. The product of the reaction can emit stronger SS‐RTP signal. A new method of SS‐RTP for the determination of AP was established, based on an affinity adsorption reaction between AP and WGA labeled with nanoparticles containing rhodanime 6G luminescent molecules. The linear range of this WGA‐AP‐WGA‐R‐SiO₂ method is 1.00–360.00 ag AP spot^?1 (sample volume: 0.40 µL spot^?1, corresponding concentration range: 2.50–900.00 fg mL^?1). The regression equation of working curve is ΔIp=16.24+0.8856 m_AP (ag spot^?1), r=0.9993. Detection limit of this method calculated by 3S_b/k is 0.14 ag spot^?1. After 11‐fold replicate measurements, RSD are 3.9% and 3.1% for the systems containing 1.00 and 360.00 ag AP spot^?1, respectively. Compared with R‐SiO₂‐WGA‐AP method (detection limit: 0.45 ag spot^?1, corresponding concentration range: 2.00–320.00 ag spot^?1), the sensitivity of WGA‐AP‐WGA‐R‐SiO₂ method was obviously improved and the linear range was wider. The sensitivity, accuracy, and precision of this method are high. It has been successfully applied to determine AP in human serum.     

Determination of Glucose by Affinity Adsorption Solid Substrate‐room Temperature Phosphorimetry Based on Triticum Vulgare Lectin Labeled with Silicon Dioxide Nanoparticle Containing Fluorescein Isothiocyanate

In the presence of heavy atom perturber Pb2＋, silicon dioxide nanoparticle containing fluorescein isothiocyanate (FITC-SiO2) could emit a strong and stable room temperature phosphorescence (RTP) signal on the surface of acetyl cellulose membrane (ACM). It was found in the research that a quantitative specific affinity adsorption (AA) reaction between triticum vulgare lectin (WGA) labeled with luminescent nanoparticle and glucose (G) could be carried on the surface of ACM. The product (WGA-G-WGA-FITC-SiO2) of the reaction could emit a stronger RTP signal, and the ΔIp had linear correlation to the content of G. According to the facts above, a new method to determine G by affinity adsorption solid substrate room temperature phosphorimetry (AA-SS-RTP) was established, based on WGA labeled with FITC-SiO2. The detection limit (LD) of this method calculated by 3Sb/k was 0.47 pg•spot－1 (corresponding to a concentration value 1.2×10－9 g•mL－1, namely 5.3×10－9 mol•L－1), the sensitivity was high. Meanwhile, the mechanism for the determination of G by AA-SS-RTP was discussed.     

A purely organic D-π-A-π-D emitter with thermally activated delayed fluorescence and room temperature phosphorescence for near-white OLED

A purely organic D-π-A-π-D type emitter showing thermally activated delayed fluorescence(TADF) and room temperature phosphorescence(RTP) was designed and synthesized by utilizing the benzophenone as an acceptor and the N-phenyl-2-napthylamine as a donor moiety.It exhibits considerable TADF character in doped PMMA film and room temperature phosphorescence with a long lifetime of 74 ms at466 nm in solid state.The devices with the configuration of ITO/Mo_2 O_3(4 nm)/mCP(30 nm)/mCP:x wt%NP2 BP/TmTyPB(60 nm)/LiF(1.5 nm)/AI(100 nm) were prepared by vacuum evaporation to explore their electroluminescent performance.Intere stingly,the non-doped device has obtained near-white emission with a fluorescence emission peak at 475 nm and a phosphore scence emission peak at 563 nm having the CIE coordinate of(0.23,0.32) and the maximum external quantum efficiency of 1.09%.     

Tailoring Intermolecular Interactions for Efficient Room‐Temperature Phosphorescence from Purely Organic Materials in Amorphous Polymer Matrices

Herein we report a rational design strategy for tailoring intermolecular interactions to enhance room‐temperature phosphorescence from purely organic materials in amorphous matrices at ambient conditions. The built‐in strong halogen and hydrogen bonding between the newly developed phosphor G1 and the poly(vinyl alcohol) (PVA) matrix efficiently suppresses vibrational dissipation and thus enables bright room‐temperature phosphorescence (RTP) with quantum yields reaching 24 %. Furthermore, we found that modulation of the strength of halogen and hydrogen bonding in the G1–PVA system by water molecules produced unique reversible phosphorescence‐to‐fluorescence switching behavior. This unique system can be utilized as a ratiometric water sensor.     

12种嘌呤类化合物的滤纸基质室温燐光法研究

较为详细地研究了１２种嘌呤类化合物以滤纸为基质的室温燐光（ＲＴＰ）光谱特性与分子结构的关系，以及重原子效应和酸度效应对ＲＴＰ的影响。     

若干香豆素衍生物在滤纸基质上的RTP和RTF特性

详细考察了各种基质、重原子微扰剂和实验条件的影响之后,成功地实现了多种香豆素衍生物的室温磷光(RTP)发射。在滤纸基质上,以1mol/L的Pb(Ac)_2作重原子微扰剂时,近20种香豆素衍生物大都能产生较强的RTP发射。而且某些衍生物的RTP强度和λ_(ex)/λ_(em)等特性间呈现出明显的取代基效应。本文还对这些衍生物在滤纸基质上的室温荧光(RTF)和其混和光谱(在重原子微扰剂存在下以荧光方式测得的光谱)等特性作了对比测定,发现其间亦呈现类似的取代基效应。有关香豆素衍生物的RTP特性,迄今尚未报道。这类衍生物RTP发射的实现,预示着它们用作RTP标记物的可能性。     

Crystal‐State Photochromism and Dual‐Mode Mechanochromism of an Organic Molecule with Fluorescence,Room‐Temperature Phosphorescence,and Delayed Fluorescence

A D‐A‐D′ type pure organic molecule, named ODFRCZ, has unique triple‐emission character covering fluorescence, phosphorescence, and delayed fluorescence (DF). The phosphorescence of ODFRCZ has a rather long lifetime of about 350 ms at room temperature. One dimer of ODFRCZ with enhanced parallel molecular packing acts more effectively to prompt ISC processes, which further generates room‐temperature phosphorescence (RTP), owing to the larger transition dipole moment and closer energy level between S₁ and T_n. ODFRCZ is a rare example of an organic RTP molecule that shows dual‐stimuli responsiveness of dual‐mode mechanochromism (fluorescence red‐shift and RTP/DF on‐off switch) and reversible crystal‐state photochromism. This work may broaden the knowledge for stimuli‐responsive RTP organic molecules and lay the foundation for their wide‐scale applications.     

Crystal‐State Photochromism and Dual‐Mode Mechanochromism of an Organic Molecule with Fluorescence,Room‐Temperature Phosphorescence,and Delayed Fluorescence

A D‐A‐D′ type pure organic molecule, named ODFRCZ, has unique triple‐emission character covering fluorescence, phosphorescence, and delayed fluorescence (DF). The phosphorescence of ODFRCZ has a rather long lifetime of about 350 ms at room temperature. One dimer of ODFRCZ with enhanced parallel molecular packing acts more effectively to prompt ISC processes, which further generates room‐temperature phosphorescence (RTP), owing to the larger transition dipole moment and closer energy level between S₁ and T_n. ODFRCZ is a rare example of an organic RTP molecule that shows dual‐stimuli responsiveness of dual‐mode mechanochromism (fluorescence red‐shift and RTP/DF on‐off switch) and reversible crystal‐state photochromism. This work may broaden the knowledge for stimuli‐responsive RTP organic molecules and lay the foundation for their wide‐scale applications.     

导数-固体基质室温燐光法同时测定痕量对位三联苯和间位三联苯

本文提出间三联苯和对三联苯的二阶导数-固体基质室温燐光法(d²SS-RTP)。本法在λ_ax=288nm,用448nm处正峰和460nm处负峰的峰峰高度值定量测定间三联苯,对三联苯不干扰测定.线性范围0.46～46ng.检出限为0.1ng/斑点.对三联苯用526nm处正峰和548nm处负峰的峰峰高度值测定.间三联苯不干扰.线性范围0.46～46ng.检出限0.07ng/斑点.     

以滤纸为基质室温磷光法测定痕量多环芳烃的研究

1 前言 固体基质室温磷光法(SS-RTP)是一种发展很快的微量技术与痕量分析相结合的新技术.SS -RTP法以其简便、快速、灵敏的特点在环境污染物及药物分析方面得到了广泛的应用 [1],尤其对于痕量多环芳烃的分析十分有效.文献报道过应用环糊精诱导室温磷光法 [2]和胶束增稳室温磷光法[3]测定的方法.本文用国产快速定量滤纸作固体基质,探讨了测定萘、苊和屈磷光发光的条件,建立了以滤纸为基质的测定痕量萘、苊和屈的SS-RTP法.     

Strong Luminescence Catalytic Solid Substrate Room Temperature Phosphorescence for the Determination of Trace Copper

Under the conditions of reacting at 100°C for 8 min and irradiating with the infrared light for 15 min, methylene blue (MEB) could emit weak room temperature phosphorescence (RTP) on the cellulose acetate membrane (CAM) using Pb²⁺ as the ion perturber in the NH₃‐NH₄Cl (pH=9.80) solution. MEB was oxidized by H₂O₂, which caused the RTP of the system to enhance. Cu²⁺ could catalyze the reaction of H₂O₂ oxidizing MEB, which caused the RTP of the system to enhance sharply. The ΔI_p (I_p0?I_p, the I_p0 and I_p were RTP intensity of the blank reagent and RTP intensity of the test reagent, respectively) of the catalytic system was 133.6, which was 4.1 times larger than that without infrared light irradiation (33.1). Its ΔI_p was proportional to the content of Cu²⁺. Thus, a new catalytic solid substrate room temperature phosphorimetry (SSRTP) for the determination of trace copper has been established. The limit of quantization (LOQ) of this method was 0.12 ag·spot^?1 (sample volume: 0.40 µL·spot^?1, corresponding concentration: 3.0×10^?16 g·mL^?1), showing high sensitivity. This method not only has been successfully applied to the determination of trace copper in the tobacco, tea and human serum, but also could predict human diseases. The catalytic reaction was first order reaction, whose activation energy (E) was 18.17 kJ·mol^?1 and rate constant (k) was 3.4×10^?4 s^?1. At the same time, the mechanism of catalytic SSRTP for the determination of trace copper was discussed.     

CaCl2作为异硫氰酸曙红固体基质室温磷光增强剂及其在免疫分析中的应用

有关荧光素的溴和碘取代物的低温磷光性质与取代度关系的研究表明，随着取代度的增大，磷光量子产率与荧光量子产率之比呈现先增大继而减小的趋势，即溴和碘的充分取代物的磷光反而减弱，故用eosin-ITC作标记物的报道很少．化学结构和环境等因素对磷光发射有重要影响；某些已被重原子(Br或／和I)高度取代的试剂，     

Stimuli‐Responsive Circularly Polarized Organic Ultralong Room Temperature Phosphorescence

Purely organic materials showing room temperature phosphorescence (RTP) and ultralong RTP (OURTP) have recently attracted much attention. However, it is challenging to integrate circularly polarized luminescence (CPL) into RTP/OURTP. Here, we show a strategy to realize CPL‐active OURTP (CP‐OURTP) by binding an achiral phosphor group directly to the chiral center of an ester chain. Engineering of this flexible chiral chain enables efficient chirality transfer to carbazole aggregates, resulting in strong CP‐OURTP with a lifetime of over 0.6 s and dissymmetry factor of 2.3×10^?3 after the conformation regulation upon photo‐activation. The realized CP‐OURTP is thus stable at room temperature but can be deactivated quickly at 50 °C to CP‐RTP with high CPL stability during the photo‐activation/thermal‐deactivation cycles. Based on this extraordinary photo/thermal‐responsive and highly reversible CP‐OURTP/RTP, a CPL‐featured lifetime‐encrypted combinational logic device has been successfully established.     

ZnS:Mn/ZnS量子点在DNA定量分析中的应用

以巯基乙酸为稳定剂,采用成核掺杂的方法在水溶液中一步制备得到具有核壳结构的ZnS:Mn/ZnS量子点.研究了荧光、室温磷光产生的机理.基于DNA对量子点发光的增强效应,以ZnS:Mn/ZnS量子点作为标记探针建立了测定DNA的荧光、室温磷光的分析方法.考察了量子点浓度、EDC/NHS用量和反应时间等条件对DNA测定的影...     

Triple‐Mode Emission of Carbon Dots: Applications for Advanced Anti‐Counterfeiting

Photoluminescence (PL), up‐conversion PL (UCPL), and phosphorescence are three kinds of phenomena common to light‐emitting materials, but it is very difficult to observe all of them simultaneously when they are derived from a single material at room temperature. For the first time, triple‐mode emission (that is, PL, UCPL, and room temperature phosphorescence (RTP)) is reported, which relies on a composite of the luminescent carbon dots (CDs) prepared from m‐phenylenediamine and poly(vinyl alcohol) (PVA). Moreover, the CDs‐PVA aqueous dispersion is nearly colorless and demonstrates promise as a triple‐mode emission ink in the field of advanced anti‐counterfeiting.     

Cyclic Triimidazole Derivatives: Intriguing Examples of Multiple Emissions and Ultralong Phosphorescence at Room Temperature

The performance of solid luminogens depends on both their inherent electronic properties and their packing status. Intermolecular interactions have been exploited to achieve persistent room‐temperature phosphorescence (RTP) from organic molecules. However, the design of organic materials with bright RTP and the rationalization of the role of interchromophoric electronic coupling remain challenging tasks. Cyclic triimidazole has been shown to be a promising scaffold for such purposes owing to its crystallization‐induced room‐temperature ultralong phosphorescence (RTUP), which has been associated with H‐aggregation. Herein, we report three triimidazole derivatives as significant examples of multifaceted emission. In particular, dual fluorescence, RTUP, and phosphorescence from the molecular and supramolecular units were observed. H‐aggregation is responsible for the red RTUP, and Br substituents favor yellow molecular phosphorescence while halogen‐bonded Br⋅⋅⋅Br tetrameric units are involved in the blue‐green phosphorescence.     

Study on the phosphorescence characterizations of palmatine chloride on the solid substrate and its interaction with ctDNA

The spectroscopic characterizations of solid substrate room temperature phosphorescence (SS-RTP) of palmatine (Pal) have been studied. Strong RTP signal at 615 nm can be induced on filter paper in the presence of TIAc. The interaction between calf thymus DNA (ctDNA) and Pal has been investigated at pH 6.90 using fluorescence, UV-vis, SS-RTP and cyclic voltammogram spectroscopy. Strong binding affinity of Pal with DNA is revealed from the absorption and fluorescence studies in the liquid state. With the addition of ctDNA, the fluorescence intensity of Pal is enhanced greatly and UV-vis spectra show no apparent hypochromicity and red shift, which indicates that Pal intercalates into ctDNA bases. However, this conclusion could not explain the phenomena from fluorescence polarization and denatured DNA measurements, which indicate that groove binding is at least the main binding mode. Binding constant and binding site size have been calculated to be 2.57 × 10⁴ L/mol and 0.16 based on Scatchard plot from fluorescence titration data. Groove binding has also been supported by phosphorescence lifetime and anion quenching experiments. Above studies demonstrate that there should exist intercalative binding and groove binding in the interaction of Pal and DNA. Furthermore, cyclic voltammogram study suggests that electrostatic binding exists at the same time exactly. Taken together, the binding model obtained in this study is mixed-mode.     

Proton‐Activated Amorphous Room‐Temperature Phosphorescence for Humidity Sensing and High‐Level Data Encryption

Supramolecular co‐assembling terpyridine‐derivatives with nanoclay ( LP ) are exploited to acquire efficient amorphous room‐temperature phosphorescence (RTP). Experimental and theoretical investigations reveal that this co‐assembly not only brings about a configuration transformation from the trans‐trans ( a ) to the cis‐trans ( a′′ ) form via the protonating process, significantly narrowing the singlet‐triplet energy gap, thereby effectively facilitating the single‐triplet ISC processes, but also well protects the triplet state and suppresses the nonradiative transitions via restricting molecular rotation and vibration by the hydrogen‐bond interactions between them. Additionally, the flexible and transparent films, through co‐assembling 1 @ LP (or 2 @ LP ) with polyvinyl alcohol (PVA), also display excellent phosphorescence performance. Owing to their distinctive RTP performances, the RH sensing and high‐level data encryption are achieved.     

Kalman filtering-aided time-resolved solid-surface room temperature phosphorimetry for simultaneous determination of tetracyclines in solution

Tetracycline, chlortetracycline and oxytetracycline react with Eu (III) to form complexes which exhibit analytically useful room temperature phosphorescence (RTP). The RTP features of the three complexes are similar and the RTP spectra completely overlap. However, their three phosphorescence decay rates are quite different. These differences are utilized here to analyze the time-resolved RTP data by Kalman filtering. Simultaneous quantification of all the three complexes is demonstrated and a method is proposed for the simultaneous determination of the three tetracyclines in mixtures by RTP optosensing. Analytical errors observed are within ± 5%.     

A Simple Organic Molecule Realizing Simultaneous TADF,RTP, AIE,and Mechanoluminescence: Understanding the Mechanism Behind the Multifunctional Emitter

Aggregation‐induced emission (AIE), thermally activated delayed fluorescence (TADF), room‐temperature phosphorescence (RTP), and mechanoluminescence (ML) have attracted widespread interest. However, a multifunctional organic emitter exhibiting simultaneous AIE, TADF, RTP, and ML has not been reported. Now, two multifunctional blue emitters with very simple structures, mono‐DMACDPS and Me‐DMACDPS, exhibit typical AIE, TADF, and RTP properties but different behavior in mechanoluminescence. Crystal structure analysis reveals that large dipole moment and multiple intermolecular interactions with tight packing mode endow mono‐DMACDPS with strong ML. Combined with the data of crystal analysis and theoretical calculation, the separated monomer and dimer in the crystal lead to the typical TADF and RTP properties, respectively. Simple‐structure mono‐DMACDPS is the first example realizing TADF, RTP, AIE, and ML simultaneously.