Molecular imprinting resonance light scattering nanoprobes based on pH-responsive metal-organic framework for determination of hepatitis A virus.

Molecularly imprinted polymer (HM@MIP) nanoprobes were designed form the pH-responsive polymer (dimethylaminoethyl methacrylate (DMA)) and MIL-101. This probe was applied to the selective determination of hepatitis A virus (HAV) through Resonance light scattering (RLS) technique. DMA adjusts pH of the system to facilitate the capture and release of virus by HM@MIPs as anticipated. And it results in the enhancement or weaken of RLS intensity. According to RLS intensity at 470 nm, a linear concentration of 0.02-2.0 nmol·L-1 and a limit of detection of 0.1 pmol·L-1 were obtained within 20 min. The excellent recoveries ranges from 88% to 107%, and it indicates the prominent ability of the HM@MIPs to determination HAV in human serum and their potential ability to determination virus in real applications. Graphical abstractPrinciple of preparation of the HM@MIPs and detection of virus.

Fluctuation correlation spectroscopy and its applications in homogeneous analysis.

Fluctuation correlation spectroscopy (FCS) is a single-molecule/particle detection technique based on measuring signal fluctuations in a highly focused detection volume. Multiple-parameter information can be obtained from the FCS measurement including the amplitude, characteristic diffusion time of correlation curve, and brightness of the adopted probes. The multiple-parameter change is related with physical or chemical change occurring in the probes. Meanwhile, the detection method has advantages such as short sample time in seconds, sample volume with low limit in femtoliters, and mixing to detection without any separations. These advantages make the FCS technique suitable for homogeneous analysis. In this review, we summarized recent novel applications of FCS and its variants in homogeneous analysis including nucleic acid analysis, protein analysis, enzyme activity assay, direct characterization of nanoparticles in solution, and others. Graphical abstract.

Highly sensitive and selective determination of hydrogen sulfide by resonance light scattering technique based on silver nanoparticles.

We have developed a green approach to prepare DNA-templated silver nanoparticles (Ag-NPs) from the direct reaction between Ag+ and ascorbic acid in the presence of DNA and sodium hydroxide. The Ag-NPs showed strong resonance light scattering (RLS) intensity property. Then, the interaction between hydrogen sulfide (H2S) and Ag-NPs was studied by measuring their RLS spectra. The results showed that there is a strong interaction between Ag-NPs and H2S, which resulted in a decrease in the size of Ag-NPs and a decrease in the RLS intensity of the Ag-NPs solution at the wavelength of 467 nm. The results demonstrated that the RLS technique offers a sensitive and simple tool for investigating the interaction between Ag-NPs and H2S, which can be applied to detect H2S with high sensitivity and selectivity without complex readout equipment. The linear range for H2S determination was found to be the range from 5.0 × 10-9 to 1.0 × 10-7 mol L-1, and the detection limit (3σ/k) was 2.8 × 10-9 mol L-1. Moreover, the proposed method was applied for the determination of H2S in natural water samples with satisfactory results. Graphical abstract The application of Ag-NPs in H2S detection.

Resonance light scattering method for detecting kanamycin in milk with enhanced sensitivity.

In this paper, a resonance light scattering (RLS) method was developed for detecting kanamycin with high sensitivity and selectivity. Here, aptamer specific to kanamycin was utilized for recognizing and competitively binding with kanamycin, and gold nanoparticles (GNPs) were used as probes. After adding kanamycin into solutions containing aptamer and GNPs, the GNPs would aggregate in the presence of NaCl, which resulted in the RLS signal intensities enhanced dramatically. Based on this phenomenon, kanamycin can be detected in the range of 10 to 600 nM with a limit of detection as 1 nM, which is more sensitive than many other instrumental methods, especially the commonly used UV-visible spectroscopic method. Furthermore, we demonstrated that this method can be used for detecting kanamycin in milk samples with satisfactory results, which is meaningful for solving food safety problems.

Spectroscopic investigation of water-soluble alloyed QDs with bovine serum albumin.

We present here a systematic investigation on the interaction between a water-soluble alloyed semiconductor quantum dot and bovine serum albumin using various spectroscopic techniques i.e. fluorescence quenching, resonance light scattering and synchronous fluorescence spectroscopy. The analysis of fluorescence spectrum and fluorescence intensity indicates that the intrinsic fluorescence of bovine serum albumin (BSA) gets quenched by both static and dynamic quenching mechanism. The Stern-Volmer quenching constants, energy transfer efficiency parameters, binding parameters and corresponding thermodynamic parameters (ΔH0 , ΔS0 and ΔG0 ) have been evaluated by using van 't Hoff equation at different temperatures. A positive entropy change with a positive enthalpy change was observed suggesting that the binding process was an entropy-driven, endothermic process associated with the hydrophobic effect. The intermolecular distance (r) between donor (BSA) and acceptor (CdSeS/ZnS quantum dots) was estimated according to Förster's theory of non-radiative energy transfer. The synchronous fluorescence spectra revealed a blue shift in the emission maxima of tryptophan which is indicative of increasing hydrophobicity. Negative ΔG0 values implied that the binding process was spontaneous. It was found that hydrophobic forces played a role in the quenching process. Copyright © 2016 John Wiley & Sons, Ltd.

Study on the interaction between three benzimidazole anthelmintics and eosin Y by high performance liquid chromatography associating with resonance light scattering and its application.

A novel, highly selective, and sensitive resonance light scattering (RLS) detection approach coupled with high performance liquid chromatography (HPLC) was researched and developed for the synchronous analysis of three kinds of benzimidazole anthelmintics, including mebendazole (MBZ), albendazole (ABZ), and fenbendazole (FBZ) for the first time. In the pH range of 3.5-3.7 Britton-Robinson buffer medium, three kinds of anthelmintics, which were separated by HPLC, reacted with eosin Y (EY) to form 1:1 ion-association complexes, resulting in significantly enhanced RLS signals and the maximum peak located at 335 nm. The enhanced RLS intensity was in proportion to the MBZ, ABZ, and FBZ concentration in the range 0.2-25, 0.2-23, and 0.15-20 µg/mL, respectively. The limit of detection was in the range of 0.064-0.16 µg/mL. In addition, human urine was determined to validate the proposed method by spiked samples and real urine samples. Satisfactory results were obtained by HPLC-RLS method. Graphical Abstract The diagram mechanism of generating resonance between emitted light and scattered light.

Using resonance light scattering and UV/vis absorption spectroscopy to study the interaction between gliclazide and bovine serum albumin.

At different temperatures (298, 310 and 318 K), the interaction between gliclazide and bovine serum albumin (BSA) was investigated using fluorescence quenching spectroscopy, resonance light scattering spectroscopy and UV/vis absorption spectroscopy. The first method studied changes in the fluorescence of BSA on addition of gliclazide, and the latter two methods studied the spectral change in gliclazide while BSA was being added. The results indicated that the quenching mechanism between BSA and gliclazide was static. The binding constant (Ka ), number of binding sites (n), thermodynamic parameters, binding forces and Hill's coefficient were calculated at three temperatures. Values for the binding constant obtained using resonance light scattering and UV/vis absorption spectroscopy were much greater than those obtained from fluorescence quenching spectroscopy, indicating that methods monitoring gliclazide were more accurate and reasonable. In addition, the results suggest that other residues are involved in the reaction and the mode 'point to surface' existed in the interaction between BSA and gliclazide. Copyright © 2015 John Wiley & Sons, Ltd.

Resonance light scattering detection of fructose bisphosphates using uranyl-salophen complex-modified gold nanoparticles as optical probe.

In this paper, we report a resonance light scattering (RLS) method for the determination of fructose bisphosphates (FBPs) in water solution using fructose 1,6-bisphosphate (F-1,6-BP) as a model analyte without the procedure of extracting target analyte. The method used a type of modified gold nanoparticles (GNPs) as optical probe. The modified GNPs are uranyl-salophen-cysteamine-GNPs (U-Sal-Cy-GNPs) which are obtained through the acylation reaction of carboxylated salophen with cysteamine-capped GNPs (Cy-GNPs) to form Sal-Cy-GNPs and then the chelation reaction of uranyl with tetradentate ligand salophen in the Sal-Cy-GNPs. A FBP molecule is used easily to connect two U-Sal-Cy-GNPs to cause the aggregation of the GNPs by utilizing the specific affinity of uranyl-salophen complex to phosphate group, resulting in the production of strong RLS signal from the system. The amount of FBPs can be determined through detecting the RLS intensity change of the system. A linear range was found to be 2.5 to 75 nmol/L with a detection limit of 0.91 nmol/L under optimal conditions. The method has been successfully used to determine FBPs in real samples with the recoveries of 96.5-103.5 %.

Resonance light scattering determination of trace bisphenol A with signal amplification by aptamer-nanogold catalysis.

HAuCl4 was reduced by sodium citrate to prepare 10 nm gold nanoparticles (AuNPs) that were modified by the bisphenol A aptamer (Apt) to obtain an aptamer-nanogold probe (Apt-AuNP) for bisphenol A (BPA). The probes were aggregated nonspecifically to form large clusters, which showed a strong resonance light scattering (RLS) peak at 520 nm, under preparation conditions (pH 7.6 Na2HPO4-NaH2PO4 buffer and ultrasonication). Upon addition of BPA, the probe reacted specifically to form dispersed BPA-Apt-AuNP conjugates that exhibited strong catalysis of the two particle reactions of glucose-Cu(II) and hydrazine hydrochloride-Cu(II) with a strong RLS peak at 360 nm and 510 nm respectively. When the BPA concentration increased, the RLS intensity at 360 nm and 510 nm increased respectively. Accordingly, two new and highly-sensitive RLS methods were established for the detection of BPA, using the Apt-AuNP catalytic amplification.

Interactions of ferulic acid and ferulic acid methyl ester with endogenous proteins: Determination using the multi-methods.

Ferulic acid (FA) and ferulic acid methyl ester (FAM) are important phenolic compounds in Baijiu. In this study, the interaction of FA and FAM with human serum albumin (HSA) and lysozyme (LZM) was investigated using multispectral methods and molecular dynamics simulation. FA and FAM could interact with HSA and LZM, changing the conformation and hydrophilicity of the protein. The quenching mechanisms of FA-HSA, FA-LZM, FAM-HSA, and FAM-LZM were all static-quenching. In the FA-HSA, FAM-HSA, and FA-LZM systems, the interaction forces were mainly hydrophobic interactions and hydrogen bonding. In the FAM-LZM system, the interaction forces were mainly hydrophobic interactions, hydrogen bonding, and van der Waals force. Common metal ions such as K+, Ca2+, Cu2+, Mg2+, and Mn2+ could affect the binding ability of FA and FAM to HSA and LZM. Moreover, FA and FAM could increase the stability of HSA and LZM, and the protein bound to FA/FAM was more stable than the free protein. FA and FAM had varying degrees of impact on the physiological activities of HSA and LZM. This study provides relevant information on the interactions and metabolic mechanisms of FA and its derivatives with endogenous proteins.

A dual-mode method for detection of miRNA based on the photoluminescence and resonance light scattering.

MicroRNAs (miRNAs) hold potential as useful biomarkers for early diagnosis and evaluation of diverse cancers, but their low abundance and short length make the detection of miRNAs face low sensitivity and accuracy. Herein, a photoluminescence (PL)-resonance light scattering (RLS) dual-mode method was developed for the sensitive and accurate detection of miRNA-141 using CdTe quantum dots (QDs) and Au nanoparticles. The presence of miRNA-141 induced PL quenching and RLS increasing. The limit of detection (LOD) was as low as 3.7 fM, and the miRNA-141 was detected linearly in a range from 10 fM to 10 nM. The dual signals generated no mutual interference and were detected using the same spectrophotometer, allowing for mutual validation to ensure the accuracy and reliability of the detection results. This study proposes valuable references for constructing dual-mode detection methods.

Optimization of aflatoxin B1 removal efficiency of DNA by resonance light scattering spectroscopy.

In this paper, firstly, the resonance light scattering spectra of aflatoxin B1 (AFB1) and DNA were measured by resonance light scattering spectroscopy (RLS), and the DNA binding saturation value (DBSV) of AFB1 was calculated from their spectral results. Then the interaction intensity between DNA and AFB1 and the effects of some external factors on the interaction between DNA and AFB1 were evaluated by corresponding DBSVs, so as to establish and optimize a way for removing AFB1 by DNA. DBSV of AFB1 was 2.04 at 30℃ and pH 7.40. However, after adding sodium ion, calcium ion, vitamin E, vitamin C and D-glucose, DBSV of AFB1 was changed to 2.72, 3.17, 2.67, 1.68 and 1.33 respectively. Correspondingly, the removal efficiency of AFB1 by DNA was changed from 90.05% to 93.25%, 95.48%, 93.08%, 82.36% and 78.90% respectively. These results indicated that the external factors had a significant impact on the interaction between DNA and AFB1. Among them, some factors enhanced the interaction between DNA and AFB1, while some factors weakened the interaction between DNA and AFB1. The change of these external factors led to the corresponding changes in DBSV and the removal efficiency of AFB1. DBSV of AFB1 could really be used as an index to evaluate the intensity of the interaction between DNA and AFB1, and to optimize the removal efficiency of AFB1 by DNA. The experimental data also showed that the adsorption of AFB1 to DNA was consistent with the pseudo-second-order kinetic model and the Freundlich isothermal model, was an exothermic and spontaneous process. All these results will give good references for establishing and optimizing a way of AFB1 removal via DNA intercalation.

A highly sensitive dual-readout assay for perfluorinated compounds based CdTe quantum dots.

Perfluorooctanoic acid (PFOA) and Perfluorooctane sulfonate (PFOS) are two typical perfluorinated compounds (PFCs) that poss potential ecological toxicity. In this work, a fluorescence and resonance light scattering (RLS) dual-readout strategy for the detection of PFCs at picomole level based on the water-soluble CdTe quantum dots (CdTe QDs) has been proposed. It is found that the CdTe QDs exhibit a quenching in the presence of PFCs and thus serve as useful probes for PFCs. The linear ranges are 0.032-10.0 nM with a limit of detection(LOD) of 32.02 pM for PFOA and 0.044-15.0 nM with a LOD of 43.96 pM for PFOS, respectively. Meanwhile, PFCs can form complexes with CdTe QDs in acid medium, resulting in remarkable RLS signals. The enhanced RLS intensities are in proportion to the concentrations of PFOA and PFOS, respectively. And the linear ranges are 0.048-5.0 nM with a LOD of 47.78 pM for PFOA, and 0.057-5.0 nM with a LOD of 56.72 pM for PFOS, respectively. This dual-mode detection increases the reliability of the measurement. The proposed method is simple, sensitive and cost-effective, with potential applications in environmental monitoring and assessment.

Resonance light scattering technique for sensitive detection of heparin using plasmonic Cu2-xSe nanoparticles.

Heparin (Hep) is a mucopolysaccharide sulfate anticoagulant drug widely used in clinic and thus the quantification of Hep concentration is of great significance. In this work, a simple resonance light scattering (RLS) method for the determination of Hep concentration using plasmonic copper selenide nanoparticles (Cu2-xSe NPs) was developed. The positively-charged Cu2-xSe NPs capped by cetyltrimethyl ammonium bromide (CTAB) were aggregated by negatively-charged Hep, consequently inducing a significant enhancement in the RLS signals of plasmonic Cu2-xSe NPs. Under the optimal reaction conditions, the increased RLS intensity is linearly correlated with the concentrations of Hep in the range of 0.01-0.60 µg mL-1 (R2 = 0.999), with a low detection limit (LOD) of 4.0 ng mL-1 (3σ). This method offered a simple, sensitive and selective strategy for determining Hep, which can be further successfully applied to quantify Hep in the heparin sodium injection.

Ratiometric bioassay and visualization of dopamine ß-hydroxylase in brain cells utilizing a nanohybrid fluorescence probe.

Dopamine ß-hydroxylase (DBH) is involved in various neuronal transmission processes in the brain. Due to the severe diseases caused by abnormity levels of such important enzyme in human serum, sensitive and rapid detection of DBH at early stages is crucial, particularly for clinical analysis. Herein, we developed optical sensors for DBH that include the following: (i) a ratiometric fluorescence sensor that hybridizes the bovine serum albumin (BSA)-gold nanoclusters (BSA-AuNCs) and nitrogen doped carbon dots (N-CDs). The sensor proved to be highly selective and sensitive, achieving a linear range of 0.02-0.16 µg mL-1 and a limit of detection of 4.0 ng mL-1. In the presence of DBH, the fluorescence intensity of BSA-AuNCs (λem = 615 nm) was remarkably quenched by DBH serving as a reporter signal, whereas the N-CDs fluorescence intensity at 440 nm was almost kept unchanged serving as a reference signal. The developed ratiometric sensor is capable of demonstrating a color change from pink to violet and blue with a gradual increase in DBH concentration, which is discernible by the naked-eye. A test strip is prepared for semi-quantitative assay and convenient use. Intriguingly, by taking advantage of the inter-AuNCs aggregation in the presence of DBH, (ii) a resonance light scattering (RLS) sensor was also developed based on the nanohybrid probe (detection limit 95 ng mL-1). Fluorescence imaging in PC12 cell lines demonstrated that the BSA-AuNCs could be utilized in visualization assay towards intracellular DBH. Additionally, the sensors were tested in a real matrix by spiking serum samples with satisfactory recoveries.

Ni0.5Zn0.5Fe2O4 nanoparticles-decorated poly (vinyl alcohol) nanofiber as resonance light scattering probe for determination of sunitinib in serum samples.

Nickel zinc ferrite (Ni0.5Zn0.5Fe2O4) nanoparticles decorated poly (vinyl alcohol) was constructed by the electrospinning method and used for determining the sunitinib amount in real sample. In this study, resonance light scattering (RLS) technique was used for studying the interaction of nanofibers with sunitinib. Similar Ni0.5Zn0.5Fe2O4 nanoparticles-decorated nanofibers with average diameter of 200 nm and length up to several millimeters were prepared. The morphology and microstructure of the as prepared Ni 0.5Zn 0.5Fe2O4 nanoparticles-decorated nanofibers were studied in details. The nanofibers were characterized by energy dispersive X-ray spectroscopy, scanning electron microscopy, and transmission electron microscopy techniques. The nanofibers are formed through assembling magnetic nanoparticles with poly (vinyl alcohol) as the structure-directing template. Under the optimal conditions, the linear dynamic range and RSD were 5.0 × 10-3-10.0 mg L-1 and 1.62% (n = 3), respectively. A limit of detection of 1.0 × 10-3 mg L-1 sunitinib was obtained from this method. The obtained results showed successful application of the method for the analysis of sunitinib in real samples.

Resonance light scattering sensor of the metal complex nanoparticles using diethyl dithiocarbamate doped graphene quantum dots for highly Pb(II)-sensitive detection in water sample.

This study was aimed to detect Pb2+ using diethyl dithiocarbamate-doped graphene quantum dots (DDTC-GQDs) based pyrolysis of citric acid. The excitation maximum wavelength (λmax, ex = 337 nm) of the DDTC-GQDs solution was blue shift from bare GQDs (λmax, ex = 365 nm), with the same emission maximum wavelength (λmax, em = 459 nm) indicating differences in the desired N, S matrices decorating in the nanoparticles. Their resonance light scattering intensities were peaked at the same λmax, ex/em = 551/553 nm without any background effect of both ionic strength and masking agent. Under optimal conditions, the linear range was 1.0-10.0 µg L-1 (R2 = 0.9899), limit of detection was 0.8 µg L-1 and limit of quantification was 1.5 µg L-1. The precision, expressed as the relative standard deviations, for intra-day and inter-day analyses was 0.87% and 4.47%, respectively. The recovery study of Pb2+ for real water samples was ranged between 80.8% and 109.5%. The proposed method was also proved with certified water sample containing 60 µg L-1 Pb2+ giving an excellent accuracy and was then implied satisfactorily for ultra-trace determination of Pb2+ in drinking water and tap water samples.

Membrane fouling by the aggregations formed from oppositely charged organic foulants.

Due to the lack of robust ways to quantify aggregations, fouling of two-foulant aggregations is poorly understood. This work systematically reports the ultrafiltration membrane fouling by aggregations formed from two oppositely charged organic foulants (i.e., humic acid (HA) and lysozyme (LYS)) with the aid of resonance light scattering (RLS) technique. RLS provides an effective approach to detecting the aggregation concentration and reveals that the HA-LYS aggregations were formed at a mass ratio of m(LYS)/m(HA) = 2.77. During the filtration of the mixture of HA and LYS, aggregations over individual foulants were identified to be the main substances deposited on the membrane surface, where the mass of deposition had a good linear relationship with the feed concentration of the aggregations. The HA-LYS aggregations might decrease the total fouling due to their large size, but reduce the fouling reversibility. In the pH range of 5.5-9.2, the pH value had limiting effects on the concentration of HA-LYS aggregations, as well as the consequent fouling. At low ionic strength, the membrane fouling by HA-LYS aggregations decreased as the ionic strength increased due to the reduction of the aggregation concentration. Oppositely, at high ionic strength, this tendency was reversed due to the electrical double layer compression effect. These results suggest that RLS is a simple and effective way to quantify the aggregations of foulants, and the aggregations of foulants have distinct fouling behaviors compared with the individual foulants.

Fast and sensitive detection of Japanese encephalitis virus based on a magnetic molecular imprinted polymer-resonance light scattering sensor.

A magnetic surface molecularly imprinted-resonance light scattering sensor was developed for rapid and highly sensitive detection of Japanese encephalitis virus (JEV). To prepare the surface imprinted polymer, Fe3O4 microspheres were selected as imprinting substrates which coated by silicon. Aminopropyl-triethoxysilane (APTES) as functional monomers for fixing template molecules JEV through a polymerization process of tetraethyl-orthosilicate (TEOS). The target virus JEV could be captured by the imprinted particles fastly and selectively, resulting in an increase of the RLS intensity. The results of RLS analysis proved that the obtained imprinted nanoparticles exhibited excellent specific recognition ability and high selectivity for the template virus (JEV). Furthermore, the response time of the sensor is within 20 min, which is much shorter than the previous works. The sensor with convenient separation and the limit of detection was 1.3 pM. These experimental results show that the proposed strategy is expected to achieve rapid and sensitive detection of JEV in practical applications.

Determination of diclofenac sodium by resonance light scattering method using silver nanoparticles as probe.

A sensitive, simple and novel method was developed to determine diclofenac sodium (DS) using silver nanoparticles (AgNPs) as probe by resonance light scattering (RLS) technique. It was found that DS could quench the RLS intensity of AgNPs. Moreover, the decrease in RLS intensity was linearly correlated to the concentration of DS over the range of 0.01-2.0µgmL-1. DS can be measured in a short time (5min) without any complicated or time-consuming sample pretreatment process. Parameters that affect the RLS intensities such as pH, concentration of AgNPs, reaction time, electrolyte concentration, and coexisting substances were systematically investigated and optimized. The results showed that the method had a very good selectivity and could be used conveniently for the determination of DS. The limit of detection (LOD) was 2.85ngmL-1 (3σ), and the relative standard deviation (RSD) was less than 3.6% (n=6). Possible mechanism for the RLS changes of AgNPs in the presence of DS was discussed and the method was successfully applied for the analysis of tablets and urine samples.