4.0代树枝状分子-卟啉标记伴刀豆凝集素亲和吸附固体基质室温磷光法测定人血清中甲胎蛋白异质体

提出一种4．0代树枝状分子（4.0G-D）-卟啉（P）双发光分子新的磷光标记试剂（4．0G-D-P）．基于4．0G-D-P标记伴刀豆凝集素（ConA）的产物（4.0G-D-P-Con A）能在聚酰胺素膜（PAM）上发射强而稳定的室温磷光（RTP）,而且该标记产物能与甲胎蛋白异质体（AFP-V）发生特异性的亲和吸附（AA）反应,其反应产物保持了4．0G-D-P双发光分子RTP的优良特性,且△Ip值与AFP-V的含量呈线性关系,加入Tween-80可以提高△Ip值,据此建立了Tween-80—4．0G-D-P双发光分子标记Con A亲和吸附固体基质室温磷光法（AA-SS-RTP）测定人血清中AFIP-V的新方法．直接法的检出限为0．31pg／mL（4．0G-D）和0．43pg／mL（P）,灵敏度较高．无论用4．0G-D或P的激发／发射波长测定人血清中AFP-V的含量,结果与酶联免疫法（ELISA）相吻合．     

Determination of trace glucose and forecast of human diseases by affinity adsorption solid substrate room temperature phosphorimetry based on Triticum valgaris lectin labeled with 4.0-generation dendrimers

A new phosphorescence labeling reagent Triton-100X-4.0G-D (4.0G-D refers to 4.0-generation dendrimers) was found. Quantitative specific affinity adsorption (AA) reaction between Triton-100X-4.0G-D-WGA and glucose (G) was carried out on the surface of nitrocellulose membrane (NCM), and the DeltaI(p) of the product of AA reaction was linear correlation to the content of G. Based on the facts above, a new method for the determination of trace G was established by WGA labeled with Triton-100X-4.0G-D affinity adsorption solid substrate room temperature phosphorimetry (Triton-100X-4.0G-D-WGA-AA-SS-RTP). This research showed that AA-SS-RTP for either direct method or sandwich method could combine very well the characteristics of both the high sensitivity of SS-RTP and the specificity of the AA reaction. Detection limits (LD) were 0.24 fg spot(-1) for direct method and 0.18 fg spot(-1) for sandwich method, indicating both of them were of high sensitivity. The method has been applied to the determination of the content of G in human serum, and the results were coincided with those obtained by glucose oxidize enzyme method. It can also be applied to forecast accurately some human diseases, such as primary hepatic carcinoma, cirrhosis, acute and chronic hepatitis, transfer hepatocellular, etc. Meanwhile, the mechanism for the determination of G with AA-SS-RTP was discussed.     

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.     

Determination of trace alpha-fetoprotein variant by affinity adsorption solid substrate-room temperature phosphorimetry and its application to the forecast of human diseases

In the presence of ion perturber LiAc, 4-generation polyamidoamine dendrimers (4G-D) could emit strong and stable room temperature phosphorescence (RTP) signal at on nitrocellulose membrane (NCM), and Triton X-100 could sharply enhance the RTP signal of 4G-D. Triton X-100-4G-D was used to label concanavalin agglutinin (Con A) to get the labeling product Triton X-100-4G-D-Con A. Quantitative specific affinity adsorption (AA) reaction between Triton X-100-4G-D-Con A and α-fetoprotein variant (AFP-V) could be carried out on the surface of NCM, whose product Triton X-100-4G-D-Con A-AFP-V could emit strong and stable RTP and its ΔI_p was proportional to the content of AFP-V. According to the facts above, a new affinity adsorption solid substrate-room temperature phosphorimetry (AA-SS-RTP) for the determination of trace AFP-V by Con A labeled with Triton X-100-4G-D was established. Detection limits of this method were 0.23 fg spot⁻¹ (direct method, corresponding concentration: 5.8 × 10⁻¹³ g mL⁻¹) and 0.13 fg spot⁻¹ (sandwich method, corresponding concentration: 3.2 × 10⁻¹³ g mL⁻¹). It has been successfully applied to determine the content of AFP-V in human serum and forecast human diseases, for its high sensitivity, long RTP lifetime, good repeatability, high accuracy and little background perturbation with at the long wavelength area. Meanwhile, the mechanism for the determination of trace AFP-V using AA-SS-RTP was also discussed.     

Determination of trace formaldehyde by solid substrate-room temperature phosphorescence quenching method based on the rose bengal-potassium bromate-Tween-80 system

A new method for the determination of trace formaldehyde by solid substrate-room temperature phosphorescence quenching method has been proposed. It is based on the facts that rose bengal (R) can emit intense and stable room temperature phosphorescence on the solid substrate of filter paper (SS-RTP). Potassium bromate (KBrO(3)) can oxidize R, which causes the quenching of RTP. In the presence of HCHO, it can react with KBrO(3) to form Br(2) and Br(2) can oxidize R, which causes smart quenching of RTP. The phosphorescence intensity (DeltaI(p)) is directly proportional to the concentration of HCHO. In the presence of Tween-80, the DeltaI(p) will be increased to 9.1 times higher than that without it. The linear range of this method is 0.016-1.6fgspot(-1) (corresponding concentration: 0.040-4.0 pgml(-1), 0.40 microlspot(-1)) with the detection limit of 4.5agspot(-1) (corresponding concentration: 1.1 x 10(-14) gml(-1)). The regression equation for working curve is DeltaI(p)=136.6+28.28m(HCHO)fgspot(-1) (r=0.9935, n=6). This method is sensitive, simple, rapid and has been applied to the determination of trace formaldehyde in real samples with satisfactory results. The mechanism of determination of trace formaldehyde by SS-RTP quenching method based on the rose bengal-KBrO(3)-Tween-80 system is also discussed.     

Multiple Luminescence Responses towards Mechanical Stimulus and Photo-Induction: The Key Role of the Stuck Packing Mode and Tunable Intermolecular Interactions

Organic luminescence with different forms continues to be one of the most active research fields in science and technology. Herein, an ultra-simple organic molecule (TPA-B), which exhibits both mechanoluminescence (ML) and photo-induced room-temperature phosphorescence (RTP) in the crystalline state, provides an opportunity to reveal the internal mechanism of ML and the dynamic process of photo-induced RTP in the same molecule. Through the detailed investigation of photophysical properties together with crystal structures, the key role of molecular packing and intermolecular interactions was highlighted in the luminescence response by mechanical and light stimulus, affording efficient strategies to design potential smart functional materials with multiple luminescence properties.     

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.     

A New 4.0-Generation Dendrimer Phosphorescence Labeling Reagent and Its Application to Determination of Trace Alkaline Phosphatase by Affinity Adsorption Solid Substrate-room Temperature Phosphorimetry

A Triton X-100-4.0G-D （4.0G-D refers to a 4.0-generation dendrimer） was brought forward as a new phosphorescence labeling reagent. Two types of specific affinity adsorption （AA） reactions （direct method and sandwich method） were carried out between the labeling product of Triton X-100-4：0G-D-Wheat germ agglutinin （WGA） and alkaline phosphatase （ALP）, the product of AA reaction preserved the good characteristics of room temperature phosphorescence （RTP） of 4.0G-D and △Ip of the product was proportional to the content of ALP. According to the fact stated above, a new method for the determination of trace ALP by affinity adsorption solid substrate-room temperature phosphorimetry （AA-SS-RTP） was established on the basis of WGA labeled with the Triton X-100-4.0G-D. The detection limits were 0.20 ag·spot^-1 （corresponding concentration： 5.0×10^-16 g·mL^-1, namely 5.0×10^-18 mol·L^-1） for a direct method and 0.14 ag·spot^-1 （corresponding concentration： 3.5×10^-16 g·mL^-1, namely 3.5×10^-18 mol·L^-1） for a sandwich method, respectively. For their high sensitivity, good repeatability and high accuracy, the direct method and sandwich method have been successfully appfied to determine the content of ALP in human serum, and the results were coincided with the clinical detection results of the enzyme-linked immunosorbent assay method by the Zhangzhou Hospital of Traditional Chinese Medicine. Meanwhile, the mechanism for the determination of trace ALP by AA-SS-RTP was discussed.     

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.     

Spectroscopy behavior of 6-Mercaptopurine, Azathiopurine, and 8-Azaguanine

A comparative study, luminescence behavior of 6-Mercaptopurine (6-MP), Azathiopurine (BAN), and 8-Azaguanine (8-Azan) have been investigated including the low temperature phosphorescence, the low temperature fluorescence, the room temperature phosphorescence (RTP) and the room temperature fluorescence (RTF). The effect of pH on the luminescence intensity is discussed. Analytical characteristics of RTF and RTP of 6-MP, BAN, and 8-Azan have been studied. The lifetime of phosphorescence and the polarity of RTF and RTP have been examined.     

Determination of photophysical rate constants for the non-protected fluid room temperature phosphorescence of several naphthalene derivatives.

The determination of kinetic parameters for luminescence processes is very important in understanding the phosphorescence process and the mechanisms of the heavy atom effect (HAE). In our previous work, we reported that room temperature phosphorescence (RTP) emission of many naphthalene derivatives can be induced directly from their aqueous solution without using any kind of protective medium, and the name Non-Protected Fluid Room Temperature Phosphorescence (NP-RTP) is suggested for this new type of RTP emission. In order to further understand this kind of luminescence phenomenon, the influence of heavy atom perturber (HAP) concentration on RTP lifetime of several naphthalene derivatives was studied in detail in this paper. The possibility of determination of photophysical parameters for emission of NP-RTP was explored based on the definition on the phosphorescence lifetime and the relation with the concentration of HAP in this paper. A static Stern-Volmer equation for phosphorescence was derived and the luminescence kinetic parameters were calculated. The results obtained by two different ways proved that photophysical parameters for RTP emission can be determined based on the changes of the RTP lifetime.     

COMPARISON OF THE SOLID-MATRIX LUMINESCENCE PROPERTIES OF BENZO(a)PYRENE-DNA ADDUCTS ON α-CYCLODEXTRIN/NaCl and TREHALOSE/NaCl MATRICES

Abstract— The solid-matrix luminescence properties of (±)- trans -7,8-dihydroxy-anti-9,10-epoxy-7,8,9,10-tetrahydrobenzo(a)pyrene-DNA ([±]-anti-BPDE-DNA) adducts were compared on α-cyclo-dextrin (CD)/NaCl and trehalose/NaCl solid matrices. Both the optimum composition for the solid matrices and the best solvent system were obtained experimentally for acquiring the maximum room-temperature fluorescence (RTF) and room-temperature phosphorescence (RTP) signals for the (±)- anti -BPDE-DNA. Most of the solid-matrix RTF and RTP data were obtained at 296 K and 93 K for (±)-anti-BPDE-DNA adducts adsorbed on 1%α-CD/NaCl and 80% trehalose/NaCl. The RTF signals were strong for (±)-BPDE-DNA adducts on both solid matrices, but RTP was only obtained on the trehalose/NaCl solid matrices with the 80% trehalose yielding the strongest RTP signal for (±)-anti-BPDE-DNA. The fluorescence lifetime data for (±)-anti-BPDE-DNA gave two components on 1 %α-CD/NaCl. For 80% trehalose/NaCl, three components were revealed, but two components were obtained with 80% trehalose/NaCl after ether extraction of the solid matrix. The third component was ascribed to the formation of the tetrols from (±)- anti -BPDE-DNA adducts during the drying step in the sample preparation of 80% trehalose/NaCl. The results give the first reported data on the solid-matrix luminescence of the (±)- anti -BPDE-DNA adducts. These results should be of considerable interest not only from an analytical viewpoint but as a new means of studying the luminescence characteristics of the adducts.     

Spectroscopy behavior of diiodofluorescein and tetrabromofluorescein

The luminescence behavior of diiodofluorescein (DIF) and tetrabromofluorescein (TBF) have been investigated including the solid surface room temperature phosphorescence (SS-RTP) and the room temperature fluorescence (RTF). The luminescence intensities of the two compounds are strongest in alkaline solution. RTP lifetime of the two compounds are in the range of 130-140 ms. The RTP and RTF polarization was in the range of 0.01-0.05. The two analytical methods--SS-RTP and RTF, of the two compounds have been established.     

Recent Advances of Pure Organic Room Temperature Phosphorescence Materials for Bioimaging Applications

Bioimaging,as a powerful and helpful tool,which allows people to investigate deeply within living organisms,has contributed a lot for both clinical theranostics and scientific research.Pure organic room temperature phosphorescence(RTP)materials with the unique features of ultralong luminescence lifetime and large Stokes shift,can efficiently avoid biological autofluorescence and scattered light through a time-resolved imaging modality,and thus are attracting increasing attention.This review classifies pure organic RTP materials into three categories,including small molecule RTP materials,polymer RTP materials and supramolecular RTP materials,and summarizes the recent advances of pure organic RTP materials for bioimaging applications.     

Room Temperature Phosphorescence of 1-Bromo-4-(bromoacetyl)naphthalene Induced by Sodium Deoxycholate

Sodium deoxycholate (NaDOC) can induce 1-bromo-4-(bromoacetyl)naphthalene (BBAN) to undergo strong room temperature phosphorescence (RTP) without the removal of dissolved oxygen from the solution. RTP spectra, phosphorescence polarization and ¹³C NMR results, along with the molecular modeling calculations, supported the conclusion that BBAN molecule was combined in a sandwich with two NaDOC molecules by a “back-to-back” hydrophobic interaction arising from the apolar faces of the NaDOC molecules, which provided BBAN with a rigid enough microenvironment to produce RTP.     

Luminescence Properties and Analytical Figures of Merits of Benzo(a)Pyrene Guanosine Adduct Adsorbed on α- β- and γ-Cyclodextrin/NaCl,and Trehalose/NaCl Solid Matrices

Abstract

Several cyclodextrin/NaCl and trehalose/NaCl mixtures were investigated as solid matrices for obtaining room-temperature luminescence from a benzo(a)pyrene (B(a)P) guanosine adduct. Room-temperature fluorescence (RTF) and room-temperature phosphorescence (RTP) intensities from the B(a)P-guanosine adduct were compared for different solid matrices. These results showed that 25% trehalose/NaCl, 1% α-cyclodextrin/NaCl, and 1% γ-cyclodextrin/NaCl solid matrices yielded strong fluorescence signals and moderately strong phosphorescence signals at room temperature from the B(a)P-guanosine adduct. In addition, the luminescence properties of pyrene, guanosine, guanosine 3′ -monophosphate free acid and guanosine 3′-monophosphate sodium salt on 1% α-, β-, and γ- cyclodextrin/NaCl solid matrices were obtained.     

Non-protected fluid room temperature phosphorescence of several naphthalene derivatives

In our previous work, we reported that with TlNO(3) as a heavy atom perturber and Na(2)SO(3) as a deoxygenator, room temperature phosphorescence (RTP) emission of dansyl chloride and its amino acid derivatives can be induced directly from their aqueous solution without a protective medium. Is this kind of fluid luminescence phenomenon unique for the dansyl chloride compounds? The present work has shown that many naphthalene derivatives can also exhibit RTP emission in their aqueous solutions under similar conditions in the absence of a protective medium. Such an RTP emission phenomenon could be denoted as nonprotected fluid room temperature phosphorescence (NP-RTP). In order to further understand this new luminescence phenomenon, the substituent group effects and the favorable chemical structure of compounds for NP-RTP emissions are discussed in detail.     

Two-Coordinate Copper(I)/NHC Complexes: Dual Emission Properties and Ultralong Room-Temperature Phosphorescence

As a kind of photoluminescent material, Cu^I complexes have many advantages such as adjustable emission, variable structures, and low cost, attracting attention in many fields. In this work, two novel two-coordinate Cu^I-N-heterocyclic carbene complexes were synthesized, and they exhibit unique dual emission properties, fluorescence and phosphorescence. The crystal structure, packing mode, and photophysical properties under different conditions were systematically studied, proving the emissive mechanism to be the locally excited state of the carbazole group. Based on this mechanism, ultralong room-temperature phosphorescence (RTP) with a lifetime of 140 ms is achieved by selective deuteration of the carbazole group. These results deepen the understanding of the luminescence mechanism and design strategy for two-coordinate Cu^I complexes, and prove their potential in applications as ultralong RTP materials.     

Organic Room‐Temperature Phosphorescence with Strong Circularly Polarized Luminescence Based on Paracyclophanes

Pure organic materials with intrinsic room‐temperature phosphorescence typically rely on heavy atoms or heteroatoms. Two different strategies towards constructing organic room‐temperature phosphorescence (RTP) species based upon the through‐space charge transfer (TSCT) unit of [2.2]paracyclophane (PCP) were demonstrated. Materials with bromine atoms, PCP‐BrCz and PPCP‐BrCz, exhibit RTP lifetime of around 100 ms. Modulating the PCP core with non‐halogen‐containing electron‐withdrawing units, PCP‐TNTCz and PCP‐PyCNCz, successfully elongate the RTP lifetime to 313.59 and 528.00 ms, respectively, the afterglow of which is visible for several seconds under ambient conditions. The PCP‐TNTCz and PCP‐PyCNCz enantiomers display excellent circular polarized luminescence with dissymmetry factors as high as ?1.2×10^?2 in toluene solutions, and decent RTP lifetime of around 300 ms for PCP‐TNTCz enantiomers in crystalline state.