Determination of thioguanine in pharmaceutical preparations by paper substrate room temperature phosphorimetry

A room temperature phosphorimetric (RTP) procedure was used for the determination of 6-thioguanine (6-TG). The method is based on paper substrate room temperature phosphorimetry (PS-RTP) using indium sulfate, In2(SO4)3 as a heavy atom perturber. Various factors affecting the room temperature phosphorescence of 6-TG are discussed. The linear dynamic range for 6-TG is from 3.3 to 334.3 ng per spot with a detection limit of 4.6 ng per spot and a relative standard deviation (RSD) of 2.38%. The recovery of standard 6-TG added to commercial tablets is in the range 96.39-98.44%. The method is simple, rapid and sensitive and can be applied to the analysis of commercial tablets without interference.     

Study of Six Polycyclic Aromatic Hydrocarbons by Chemical Deoxygenation Microemulsion-Stabilized Room Temperature Phosphorimetry

Six polycyclic aromatic hydrocarbons (PAHs) are studied by chemical deoxygenation microemulsion-stabilized room temperature phosphorimetry with sodium sulfite as an oxygen scavenger and thallous nitrate as a heavy atom perturber in sodium dodecyl sulfate medium. Several factors influencing room temperature phosphorescence such as the concentration of sodium dodecyl sulfate, the heavy atom concentration, the pH, and the concentration of sodium sulfite are discussed and the quenching effect of NO₂⁻on room temperature phosphorimetry of PAHs was compared in the microemulsion and micelle media.     

Determination of nafronyl in pharmaceutical preparations by means of stopped-flow micellar-stabilized room temperature phosphorescence.

The stopped-flow mixing technique was applied to micellar-stabilized room temperature phosphorimetry by measuring the fast appearance of the phosphorescent signal yielded by nafronyl in the presence of sodium dodecyl sulfate and thallium nitrate. This mixing system diminishes the time required for the deoxygenation of micellar medium by sodium sulfite, allowing a kinetic curve that levels off within only 5 s to be obtained. Phosphorescence enhancers thallium(I) nitrate, sodium dodecyl sulfate and sodium sulfite were optimized to obtain maximum sensitivity and selectivity. A pH value of 10.5 was selected as adequate for phosphorescence development. Two rapid, straightforward and automatic methods were proposed using the slope and amplitude of the kinetic curve, which are directly proportional to the nafronyl concentration, as analytical parameters. Calibration graphs were linear for the concentration range from 30 to 600 ng ml-1. Praxilene, the only commercial formulation containing nafronyl, was analysed by both proposed methodologies. Suitable recovery values were obtained.     

Pharmaceutical formulation analysis of thalidomide by solid surface room temperature phosphorimetry

A rapid and simple method of analysis for thalidomide formulations has been reported based on solid surface room temperature phosphorimetry. Thalidomide phosphorescence was enhanced by Hg(II) ions deposited on paper substrates previously treated for background reduction. A calibration curve with a linear dynamic range of three orders of magnitude was obtained (1.37 × 10^–6 M – 10^–3 M) and a 1.8 ng absolute limit of detection was estimated. The recovery of the method was tested in pharmaceutical formulations containing thalidomide as the only active ingredient. The values obtained were 96.3 ± 6.6% (employing the calibration curve procedure) and 98.0 ± 5.3% (employing the standard addition procedure), which show the potential of the technique for the analysis of thalidomide in dosage forms.     

Solid surface room temperature phosphorimetry analysis of reserpine in pharmaceutical formulations

A simple, rapid and sensitive method for reserpine analysis has been developed based on solid surface room temperature phosphorimetry. Phosphorescence emission was induced by the reserpine hydrolysis reaction in basic medium. Chromatography paper previously treated for background reduction was employed as a solid substrate. Four heavy atom salts and sodium dodecyl sulfate were tested for maximum signal intensity. A calibration curve with a linear dynamic range of three orders of magnitude (10⁻⁷-10⁻⁴M) was obtained. A 1.9 ng limit of detection was estimated and recoveries of 98.7 and 100.3% were obtained in two dosage forms with different pharmaceutical matrices.     

发光分析与中药质量控制

回顾了近年来发光(荧光，室温磷光)分析技术在中草药质量控制中的应用，总结其特点并展望了可能的应用。     

乙醇-K2HPO4-KH2PO4双水相萃取固体基质室温燐光法测定色氨酸

提出了一种基于乙醇-电解质-水体系双水相萃取、固体基质室温燐光法(SS-RTP)测定色氨酸的新方法:将适量电解质和乙醇加入试液中,离心后用SS-RTP测定上相中的色氨酸.在最佳萃取体系乙醇-K2HPO4-KH2PO4-H2O中,测定色氨酸的线性范围1.0×10-7～2.0×10-6mol/L、检出限5.4×10-9mol/L(S/N=3).用于大豆、大米、玉米和竹笋中色氨酸的测定,相对标准偏差2.2%～3.3%,与荧光法比较,相对误差-3.3%～3.2%.     

Anti-oxygen-quenching room temperature phosphorescence stabilized by deoxycholate aggregate

Oxygen is the most effective dynamic quencher in liquid room temperature phosphorimetry (LRTP). Using oxygen scavenger to achieve significant or more sensitive RTP signals may bring about kinds of trouble in many cases and is apparently not very convenient in procedures. To date a few examples on LRTP without deoxygenation have been reported. Herein, we present a new named anti-oxygen-quenching RTP system using deoxycholate as a rigid medium. It can induce both lipophilic alpha-bromonaphthalene or 1-bromo-2-methylnaphthalene (BrMeN) and strongly water-soluble meso-tetrakis-(4-trimethylaminophenyl)porphyrin palladium (Pd-TAPP) to produce strong RTP emission under sodium deoxycholate of 4 mmol l(-1) and incubation time of half an hour. The maximum excitation and emission wavelengths respectively lie at 408 and 680 nm, with phosphorescence lifetime of 0.39 ms for Pd-TAPP, and at 285 and 515 nm, with lifetime of 4.9 ms for BrMeN. It is supposed that the hydrophobic and oxyphobic sandwich structure formed by two deoxycholate molecules with a phosphor in the case of deoxycholate or the interdiction fully of oxygen molecule diffusion into the microenvironment where the phosphor exists in the case of cyclodextrin is a key factor in inducing anti-oxygen-quenching RTP.     

Catalytic solid substrate room temperature phosphorimetry for the determination of trace rhamnose based on its condensation reaction with calcein

Calcein (R) could not only emit strong and stable room temperature phosphorescence (RTP) on filter paper using I(-) as perturber, but also could be oxidized by H(2)O(2) to form a non-phosphorescence compound (R'), resulting in the quenching of RTP signal of R. Moreover, the ortho-hydrogen of phenolic hydroxyl in R took condensation reaction with rhamnose (Rha) to produce non-phosphorescence compound (R-Rha) causing the RTP signal of R to further quench, and R-Rha was oxidized by H(2)O(2) to form R' and Rha, bringing about the sharp RTP signal quenching of R. Thus, a new solid substrate room temperature phosphorimetry (SSRTP) for the determination of trace Rha based on its strong catalytic effect on H(2)O(2) oxidizing R has been established, with the detection limit (LD) of 7.8zgspot(-1) (corresponding concentration: 2.0×10(-17) gm l(-1), sample volume: 0.40 μl spot(-1)). This method has been applied to determine trace Rha in cigarettes and jujubes, with the results coinciding well with those determined by a high performance liquid chromatography (HPLC). The component of R-Rha also was analyzed by means of HPLC, mass spectrometer and nuclear magnetic resonance (NMR) measurements. The mechanism of catalytic SSRTP for the determination of trace Rha was discussed.     

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.     

The dynamic nature of incubation solution after cooling to room temperature in amyloid formation of hen egg white lysozyme: An FTIR assessment

Amyloid formation of hen egg white lysozyme (HEWL) usually requires elevated temperature, while biophysical characterizations on the incubation solution are often performed at room temperature. Whether maintaining the incubation solution at room temperature results in further structural changes is a significantly important issue that has never been explored. Herein, we use FTIR spectroscopy to assess this issue and reveal that the hot incubation solution of HEWL after cooling to room temperature is in a dynamically evolving state and forms β-sheet aggregates continuously over time. Combined with AFM, we show that these aggregates are non-fibrillar β-sheet aggregates and have vibrational signature distinct from that of fibrillar aggregates. Using FTIR difference spectroscopy, we demonstrate that these non-fibrillar aggregates are in an anti-parallel β-sheet configuration. We also provide a detailed discussion on the spectral assignments for protein aggregates in anti-parallel and parallel β-sheet configurations. With FTIR second derivative technique, we show that these non-fibrillar aggregates are in fact present along with fibrillar aggregates during incubation under elevated temperature but are less stable compared with that at room temperature. Implications from the current work are discussed.     

Studies on properties and application of non-protected room temperature phosphorescence of propranolol

A direct and simple non-protected room temperature phosphorimetry (NP-RTP) for determine propranolol, which using I- as a heavy atom perturber and sodium sulfite as a deoxygenator, has been developed. The phosphorescence peak wavelength maxima lambda(ex)/lambda(em) = 288/494, 522 nm. The analytical curve of propranolol gives a linear dynamic range of 8.0 x 10(-8)-2.0 x 10(-5) mol l(-1) and a detection limit of 3 x 10(-8) mol l(-1). The influence of I- concentration on RTP lifetime of propranolol was studied and the luminescence kinetic parameters were calculated. It is found that the relation between I- concentration (x) and RTP lifetime (tau) can be expressed as tau = 1.25e(-0.477x) and the rate constants of phosphorescence emission k(p) was 0.800 per ms. The method was applied directly to determination of propranolol in urine and drug tablets with a satisfactory result. The recoveries were 96.6-97.4% and the relative standard deviation was 2% for the 1.00 x 10(-6)-4.00 x 10(-6) mol l(-1) propranolol in spiked urine sample.     

滤纸基质室温燐光法中实验技术的研究

本文分别以苊、2,6-二氨基嘌呤和对位三联苯为模型化台物,对滤纸基质室温燐光法中的烘烤温度、烘干方式、重原子加入方式和顺序、增加样品稳定性的方法以及降低滤纸RTP背景的方法进行了较为深入的研究。     

Determination of trace calcium by solid substrate-room temperature phosphorimetry

A new method for the determination of trace calcium by solid substrate-room temperature phosphorimetry is established. It is based on the fact that chromeazurols azurol S-phenanthroline-NaCMC (CAS-phen-NaCMC) system can emit strong and stable room temperature phosphorescence (RTF) on the solid substrate in the filter paper. Ca2 and phenanthroline can form complex ion Ca(phen)32 , which will form complex [Ca(phen)3(CAS)2] with CAS. In the result, the number of CAS molecules in each spot increased, causing sharp increase of the RTP signal of the CAS-phen-NaCMC system.     

A highly sensitive coupling technique for the determination of trace quercetin based on solid substrate room temperature phosphorimetry and poly (vinyl alcohol) complex imprinting

Al³⁺ could react with quercetin (Q) to form [AlQ]³⁺ complex which could be used as a template for the preparation of poly (vinyl alcohol)–[AlQ]³⁺ complex imprinting (PVA-C-I). The [AlQ]³⁺ not only had good matching ability and selectivity with the cavity of PVA-C-I, but also could react with the fluorescein isothiocyanate anion (FITC⁻) on the outside of cavity by electrostatic interaction to form ion-association complex [AlQ]³⁺·[(FITC)⁻]₃. The ion-association complex could emit strong and stable room temperature phosphorescence (RTP) on polyamide membrane (PAM) and the ΔI_p of the system had linear relationship with the content of Q, showing the highly selective identification of PVA-C-I to Q. Thus, a new coupling technique for the determination of trace Q based on solid substrate room temperature phosphorimetry and poly (vinyl alcohol) complex imprinting (PVA-C-I-SSRTP) was established. The linear range and limit of detection (LOD) of this method were 0.010–2.0 (×10⁻¹² g mL⁻¹) and 2.0 × 10⁻¹⁴ g mL⁻¹, respectively, showing wide linear range and high sensitivity of PVA-C-I-SSRTP. This method was used to determine the content of Q in waste water, and the results are consistent with those by spectrofluorimetry. Meanwhile, the mechanism for the determination of Q using PVA-C-I-SSRTP was also discussed.     

Oriented attachment-based assembly of dendritic silver nanostructures at room temperature

How particles aggregate into an interesting dendritic structure has been the object of research for many years because of its importance in understanding physical processes involved and in designing novel materials. In this work, we for the first time describe an oriented attachment-based assembly mechanism for formation of different types of dendritic silver nanostructures at room temperature. It is found that the concentration of both AgNO(3) and p-aminoazobenzene (PA) molecules has a significant effect on the formation and growth of these novel nanostructures. Characterization by transmission electron microscopy (TEM) clearly shows that the dendritic silver nanostructures can be obtained through the preferential oriented growth along a crystallographically special direction. Interestingly, we observe that the oriented attachment at room temperature can also take place between relatively large single-crystalline silver particles with a diameter range from 20 to 60 nm, which may provide a new possibility for the design of novel metal nanostructures by using large metal nanoparticles as building blocks at room temperature. Moreover, a surface-enhanced Raman scattering (SERS) technique is used to investigate the role of PA molecules during the growth of the dendritic silver nanostructures.     

Study on using I- as heavy atom perturber in cyclodextrin-induced room temperature phosphorimetry

A cyclodextrin induced room temperature phosphorimetry (CD-RTP) for determine beta-NOA, which using I- as a heavy atom perturber (HAP) and sodium sulfite as a deoxygenator, was developed. The phosphorescence peak wavelength maxima lambda(ex)/lambda(em) = 287/496,521 nm. The analytical curve of beta-NOA gives a linear dynamic range of 2.0 x 10(-7)-6.0 x 10(-6) mol/l and a detection limit of 4 x 10(-8) mol/l. The relative standard deviation (RSD; n = 7) was 3.2% for the 4.0 x 10(-6) mol/l beta-NOA in spiked apple samples. The influence of I- concentration on RTP lifetime of beta-NOA was studied in detail, the static Stern-Volmer equation for phosphorescence was derived and the luminescence kinetic parameters were calculated. It is found that the relation between I- concentration (x) and RTP lifetime (tau) can be expressed as tau = 1.047 e(-0.354x) and the rate constants of phosphorescence emission k(p) and non-radiation process k(i) from T1 --> S0 were 0.9551 s(-1) and 0.4276 s(-1) l(-1) mol, respectively.     

Copper(0)-mediated radical polymerization of styrene at room temperature

The “living’/controlled radical polymerization (LRP) of styrene (St) at room temperature is rarely reported. In this work, copper(0) (Cu(0))-mediated radical polymerization of St at room temperature was investigated in detail. Dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF) as well as a binary solvent, tetrahydrofuran/1,1,1,3,3,3-hexafluoro-2-propanol were used as the solvents, respectively. Methyl-2-bromopropionate and ethyl 2-bromoisobutyrate were used as the initiators, respectively. The polymerization proceeded smoothly with moderate conversions at room temperature. It was found that DMF was a good solvent with the essential features of LRP, while DMSO was a poor solvent with uncontrollable molecular weights. Besides, the match among the initiator, solvent and molar ratios of reactants can modulate the livingness of the polymerization, and the proper selection of ligand was also crucial to a controlled process. This work provided a first example of Cu(0)-mediated radical polymerization of St at room temperature, which would enrich and strength the LRP technique.     

A novel method of fabrication of latex-stabilized water-core colloidosomes at room temperature

Colloidosomes have attracted great interest in recent years because of the capability of storage and delivery of useful materials in various fields. In this article, a novel technique for formation of colloidosomes at room temperature suitable for encapsulation of biomaterials was examined. We demonstrate the formation of colloidosomes of 18.0 μm in size at room temperature by adding a small amount of ethanol into the continuous phase of sunflower oil. Poly(methyl methacrylate-co-butyl acrylate) latex particles of 185 nm in size, used in this study, were found to aggregate when ethanol was added to their suspension. We suggest that the shell of the water-core emulsions was locked by the aggregation of latex particles due to the diffusion of ethanol into the aqueous latex suspension.     

Preparation of CdSe quantum dots with full color emission based on a room temperature injection technique

High quality CdSe quantum dots are synthesized through a room temperature injection technique by using CdAc2 and Na2SeSO3 as precursors. In this synthesis approach, small CdSe clusters are formed after the injection at room temperature. Thereafter, CdSe quantum dots with emissions from the green to the red region can be obtained by transferring these clusters to different temperatures (40-150 degrees C) for particle growth. Meanwhile, CdSe quantum dots with emission in the blue-violet region (500-430 nm) are gained by an oxidation etching approach using H2O2 as oxidant. The advantage of this method is the natural separation of the nucleation and the growth process, which can provide a longer time for the preparation of the nuclei in simple operations and a well controlled fluorescence of the products, as the evolution of the fluorescence is slow at this low particle growth temperature.