Ultrasensitive Fluorescence Detection of Ascorbic Acid Using Silver Ion-Modulated High-Quality CdSe/CdS/ZnS Quantum Dots.

Improving the sensitivity of the fluorescence method for the detection of bioactive molecules is crucial in biochemical analysis. In this work, an ultrasensitive sensing strategy was constructed for the detection of ascorbic acid (AA) using high-quality 3-mercaptopropionic acid-capped CdSe/CdS/ZnS quantum dots (MPA-CdSe/CdS/ZnS QDs) as the fluorescent probe. The prepared water-soluble QDs exhibited a high photoluminescence quantum yield (PL QY) of up to 96%. Further, the fluorescence intensity of the QDs was intensively quenched through the dynamic quenching of Ag+ ions due to an efficient photoinduced electron transfer progress. While the existence of AA before adding Ag+ ions, Ag+ ions were reduced. Thus, the interaction of the QDs and Ag+ ions was destroyed, which led to the fluorescence distinct recovery. The detection limit of AA could be as low as 0.2 nM using this sensing system. Additionally, most relevant small molecules and physiological ions had no influence on the analysis of AA. Satisfactory results were obtained in orange beverages, showing its great potential as a meaningful platform for highly sensitive and selective AA sensing for clinical analysis.

DNA tetrahedron-based dual-signal fluorescence detection of apoE4 gene sites on a microplate reader.

As a neurodegenerative disorder, Alzheimer's disease (AD) is characterized by cognitive dysfunction and behavioral impairment. Among the various genetic risk factors for AD, apoE4 gene plays a pivotal role in the onset and progression of AD, and detection of apoE4 gene holds significance for prevention and early diagnosis of AD. Herein, dual-signal fluorescence detection of fragments associated with apoE ε4 allele near codon 112 (Tc1) and codon 158 (Tc2) was achieved using DNA tetrahedron nanostructure (DTN). The Förster resonance energy transfer (FRET) process in the DTN was initiated in which the nucleic acid intercalating dye thiazole orange (TO) served as the donor and the cyanine dyes of cyanine3 (Cy3) and cyanine5 (Cy5) at the two vertices of DTN served as the acceptors. In the presence of Tc1 and Tc2, the FRET process between TO and the cyanine dyes was hindered by the enzymatic cleavage reaction, which ensures the dual-signal fluorescence assay of apoE4 gene sites. The limit of detection for Tc1 and Tc2 was estimated to be 0.82 nM and 0.77 nM, respectively, and the whole assay was accomplished within 1 h on a microplate reader. The proposed method thus possesses the advantages of easy operation, short detection time, and high-throughput capability.

Conversion of Photoluminescence Blinking Types in Single Colloidal Quantum Dots.

Almost all colloidal quantum dots (QDs) exhibit undesired photoluminescence (PL) blinking, which poses a significant obstacle to their use in numerous luminescence applications. An in-depth study of the blinking behavior, along with the associated mechanisms, can provide critical opportunities for fabricating high-quality QDs for diverse applications. Here the blinking of a large series of colloidal QDs is investigated with different surface ligands, particle sizes, shell thicknesses, and compositions. It is found that the blinking behavior of single alloyed CdSe/ZnS QDs with a shell thickness of up to 2 nm undergoes an irreversible conversion from Auger-blinking to band-edge carrier blinking (BC-blinking). Contrastingly, single perovskite QDs with particle sizes smaller than their Bohr diameters exhibit reversible conversion between BC-blinking and more pronounced Auger-blinking. Changes in the effective trapping sites under different excitation conditions are found to be responsible for the blinking type conversions. Additionally, changes in shell thickness and particle size of QDs have a significant effect on the blinking type conversions due to altered wavefunction overlap between excitons and effective trapping sites. This study elucidates the discrepancies in the blinking behavior of various QD samples observed in previous reports and provides deeper understanding of the mechanisms underlying diverse types of blinking.

A High-Quality CdSe/CdS/ZnS Quantum-Dot-Based FRET Aptasensor for the Simultaneous Detection of Two Different Alzheimer's Disease Core Biomarkers.

The simultaneous detection of two different biomarkers for the point-of-care diagnosis of major diseases, such as Alzheimer's disease (AD), is greatly challenging. Due to the outstanding photoluminescence (PL) properties of quantum dots (QDs), a high-quality CdSe/CdS/ZnS QD-based fluorescence resonance energy transfer (FRET) aptasensor for simultaneously monitoring the amyloid-ß oligomers (AßO) and tau protein was proposed. By engineering the interior inorganic structure and inorganic−organic interface, water-soluble dual-color CdSe/CdS/ZnS QDs with a near-unity PL quantum yield (>90%) and mono-exponential PL decay dynamics were generated. The π−π stacking and hydrogen bond interaction between the aptamer-functionalized dual-color QDs and gold nanorods@polydopamine (Au NRs@PDA) nanoparticles resulted in significant fluorescence quenching of the QDs through FRET. Upon the incorporation of the AßO and tau protein, the fluorescence recovery of the QDs-DNA/Au NRs@PDA assembly was attained, providing the possibility of simultaneously assaying the two types of AD core biomarkers. The lower detection limits of 50 pM for AßO and 20 pM for the tau protein could be ascribed to the distinguishable and robust fluorescence of QDs and broad spectral absorption of Au NRs@PDA. The sensing strategy serves as a viable platform for the simultaneously monitoring of the core biomarkers for AD and other major diseases.

Phylogenomics, plastome structure and species identification in Mahonia (Berberidaceae).

BACKGROUND: Elucidating the phylogenetic relationships within species-rich genera is essential but challenging, especially when lineages are assumed to have been going through radiation events. Mahonia Nutt. (Berberidaceae) is a genus with cosmopolitan distribution, comprising approximately 100 species, two of which are known as Caulis Mahoniae (M. bealei and M. fortunei) with crucial pharmacological significance in Chinese herbal medicine. Mahonia is a taxonomically challenging genus, and intrageneric phylogenetic relationships still need to be explored using genome data. Universal DNA barcodes and floral morphological attributes have limited discriminatory power in Mahonia. RESULTS: We sequenced 17 representative plastomes and integrated three published plastome data together to conduct comparative and phylogenetic analyses. We found that Mahonia and Berberis share a large IR expansion (~ 12 kb), which is recognized as a typical character of Berberideae. Repeated sequences are revealed in the species of Mahonia, which are valuable for further population genetic studies. Using a comparative plastome analysis, we determined eight hypervariable regions whose discriminative power is comparable to that of the whole plastid genomes. The incongruence of the ITS and the plastome tree topologies may be ascribed to ancestral hybridization events and/or to incomplete lineage sorting. In addition, we suggest that leaf epidermal characters could help to distinguish closely related species in Mahonia. CONCLUSIONS: We propose an integrative approach combining special barcodes and micromorphological traits to circumscribe Mahonia species. The results cast a new light on the development of an integrative method for accurate species circumscription and provide abundant genetic resources for further research on Mahonia.

Effect of 580 °C (20 h) Heat Treatment on Mechanical Properties of 25Cr2NiMo1V Rotor-Welded Joints of Oscillating Arc (MAG) Narrow Gap Thick Steel.

The thick plate narrow gap welding of 25Cr2NiMo1V rotor steel is achieved by metal active gas arc welding, in which the weld gap was 18.04-19.9 mm. After welding, the weldment was heat treated at 580 °C (20 h). The impact and tensile properties in the as-welded and heat-treated were studied. The results show that after heat treatment, the coarse carbides in the center of the weld were transformed into fine granular carbides distributed along the grain boundaries, and the quantity of carbide precipitates in the weld near the fusion line was reduced. The tensile fracture mode changed from a ductile fracture to a combination of brittle and ductile fractures, and the tensile strength of the weld metal changed from 605 MPa to 543 MPa. After heat-treated, the radiation zone of the weld center changed from a brittle fracture to a combination of brittle and ductile fractures, and the impact energy changed from 141 J to 183 J; the characteristics of the brittle fracture in the radial zone of the fusion line were more obvious, and the impact energy changed from 113 J to 95 J. Therefore, after heat treatment, the toughness of the welded metal was improved, without reducing the strength and hardness of the welded metal to a large extent.

Clinical effect of warm needle penetration in treating knee osteoarthritis.

OBJECTIVE: Our aim was to explore the clinical effect of warm needle penetration in treating knee osteoarthritis. METHODS: We randomly divided 118 patients with knee osteoarthritis into the observation group (n=59) and the control group (n=59). The observation group was treated with warm needle penetration combined with western medicine therapy, and the control group was only given western medicine therapy. The clinical effective rate, Visual analogue scale pain score, knee joint score, Western Ontario and McMaster Universities osteoarthritis index and subjective satisfaction were observed and compared between the two groups. RESULTS: The clinical effective rate, knee joint score and subjective satisfaction rate were higher (all P<0.05), while the Visual analogue scale pain score and Western Ontario and McMaster Universities osteoarthritis indices score were lower in the observation group than in the control group (both P<0.05). CONCLUSION: Warm needle penetration can ameliorate the efficiency of treatment, reduce pain, and improve the range of knee joint motion and subjective satisfaction of patients with knee osteoarthritis.

Evaluation of the effect of a three-color ladder management model for knee osteoarthritis in the community.

OBJECTIVE: To explore the application effect of a three-color ladder management system for knee osteoarthritis in the community. METHODS: Eighty-six patients with knee osteoarthritis in our community were obtained for study and randomly grouped. The control group received routine management, while the research group received three-color ladder management for 12 months. The knee joint function (WOMAC score), pain degree (VAS score), joint flexibility, health-related behavior score, self-care ability scale (exercise of self-care agency scale (ESCA) score), quality of life (knee osteoarthritis quality of life scale (AIMS2-SF) score) and knee replacement rate were compared between the two groups before and after management, and the changes of patients' visits and treatment costs before and after management were observed. RESULTS: After 12 months, the scores of WOMAC and VAS in the research group were significantly lower than those of the control group (P<0.05), while the scores of joint flexibility and extension, cognition, behavior and condition of Omaha System health-related behaviors, ESCA and AIMS2-SF were significantly higher than those of the control group (P<0.05). After 12 months, the monthly visits and expenses of green cards, yellow cards and red cards in the research group were significantly lower than those before entering the group (P<0.05). After 12 months, the knee replacement rate was 20.93% (9/43) in the research group, while it was 27.91% (12/43) in the control group, with no significant difference between the two groups (P>0.05). CONCLUSION: The three-color ladder management system for knee osteoarthritis patients in the community can reduce the number of doctor visits and overall expenses, improve knee joint function, reduce pain, improve self-management ability and quality of life, and it has high community popularization.

Enhancing Dielectric Screening for Auger Suppression in CdSe/CdS Quantum Dots by Epitaxial Growth of ZnS Shell.

Auger recombination is the main nonradiative process in multicarrier states of high-quality quantum dots (QDs). For the most-studied CdSe/CdS core/shell QDs, we effectively reduce the biexciton Auger rate by enhancing dielectric screening of band-edge carriers via epitaxial growth of additional ZnS shells. Super volume scaling of negative-trion Auger lifetime for CdSe/CdS core/shell QDs is achieved with the outermost ZnS shells. The volume of CdSe/CdS/ZnS QDs can be less than half that of CdSe/CdS QDs with the same negative-trion Auger lifetime. Auger suppression by the ZnS shells is more pronounced for QDs with wave functions of band-edge carriers spreading close to the inorganic-organic interface, such as CdSe/CdS QDs with small cores. A maximum drop of biexciton Auger rate of ∼50% and a maximum enhancement of biexciton emission quantum yield of 75% are achieved. Auger engineering by dielectric screening opens up new opportunities to improve the emission properties of multicarrier states in QDs.

Effects of interface-potential smoothness and wavefunction delocalization on Auger recombination in colloidal CdSe-based core/shell quantum dots.

Auger nonradiative recombination dominates decay of multicarrier states in high quality colloidal quantum dots (QDs) and thus is critical for many of their optical and optoelectronic applications. Controlling interface-potential smoothness and wavefunction delocalization are proposed as two main strategies for Auger engineering in core/shell QDs. Here, a series of CdSe-based core/shell QDs with nearly ideal optical quality of their single-exciton states are developed and applied for studying biexciton quantum yields and Auger nonradiative recombination rates. Comparative experiments find that the interface-potential smoothness has little influence on biexciton quantum yield and Auger rates of these core/shell QDs with the same CdS outer shells. In contrast, with a fixed total size of the series of QDs, the decreasing hole wavefunction delocalization can increase the Auger rates of positive trions by ∼400%. A mild decrease in electron wavefunction delocalization among the series of QDs results in a small increase in the Auger rates of negative trions (∼50%). Smoothing the core/shell interface can indeed affect the Auger rates, but this is by the way of altering wavefunction delocalization. These findings highlight the importance of control of wavefunction delocalization among the strategies of Auger engineering and provide guidelines for rational design QDs for applications.

Author Correction: Engineering Auger recombination in colloidal quantum dots via dielectric screening.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Engineering Auger recombination in colloidal quantum dots via dielectric screening.

Auger recombination is the main non-radiative decay pathway for multi-carrier states of colloidal quantum dots, which affects performance of most of their optical and optoelectronic applications. Outstanding single-exciton properties of CdSe/CdS core/shell quantum dots enable us to simultaneously study the two basic types of Auger recombination channels-negative trion and positive trion channels. Though Auger rates of positive trion are regarded to be much faster than that of negative trion for II-VI quantum dots in literature, our experiments find the two rates can be inverted for certain core/shell geometries. This is confirmed by theoretical calculations as a result of geometry-dependent dielectric screening. By varying the core/shell geometry, both types of Auger rates can be independently tuned for ~ 1 order of magnitude. Experimental and theoretical findings shed new light on designing quantum dots with necessary Auger recombination characteristics for high-power light-emitting-diodes, lasers, single-molecular tracking, super-resolution microscope, and advanced quantum light sources.

Stoichiometry-Controlled InP-Based Quantum Dots: Synthesis, Photoluminescence, and Electroluminescence.

We introduce stoichiometry control within both core and shell regions of InP/ZnSe/ZnS core/shell/shell quantum dots (QDs) to advance their properties drastically, approaching those of state-of-the-art CdSe-based QDs. The resulting QDs possess near-unity photoluminescence quantum yield, monoexponential decay dynamics, narrow line width, and nonblinking at a single-dot level. Quantum-dot light-emitting diodes (QLEDs) with the InP/ZnSe/ZnS core/shell/shell QDs as emitters exhibit a peak external quantum efficiency of 12.2% and a maximum brightness of >10 000 cd m-2, greatly exceeding those of the Cd/Pb-free QLEDs reported in literature. These results pave the way toward Cd/Pb-free QDs as outstanding optical and optoelectronic materials.

[Analysis of medicinal resources diversity of 33 pilots (districts) in Guizhou province].

This study is based on the data analysis of medicinal plant resources and diversity collected from the fourth Chinese traditional medicine resource survey( pilot). Through the analysis of relevant data from 33 census pioneer plots in Guizhou province( area),a total of 265 families,1 432 genera and 5 296 species of medicinal resources were reported,including algae,fungi,lichens,mosses,a total of 43 genera and 35 families,57,48 families,120 genera and 453 species of ferns,gymnosperms 11 families,22 genera and 61 species,167 families,1 243 genera and 4 721 species of angiosperms,4 genera and 4 families four medicinal animals.Compared with the data related to the third survey of traditional Chinese medicine resources,the number of ferns,gymnosperms and angiosperms in the fourth survey has increased far more than that of the third survey. From the regional distribution of medicinal resources,the composition of the genus,the type of life,and the location of the medicine,the richness of the medicinal plant resources in Guizhou province is not only reflected in many types,but also in the variety of medicinal resources. These studies provide a scientific basis for vigorously developing the Chinese herbal medicine industry and the sustainably using medicinal plant resources in Guizhou province.

Genetic and chemical differentiation characterizes top-geoherb and non-top-geoherb areas in the TCM herb rhubarb.

Medicinal herbs of high quality and with significant clinical effects have been designated as top-geoherbs in traditional Chinese medicine (TCM). However, the validity of this concept using genetic markers has not been widely tested. In this study, we investigated the genetic variation within the Rheum palmatum complex (rhubarb), an important herbal remedy in TCM, using a phylogeographic (six chloroplast DNA regions, five nuclear DNA regions, and 14 nuclear microsatellite loci) and a chemical approach (anthraquinone content). Genetic and chemical data identified two distinct groups in the 38 analysed populations from the R. palmatum complex which geographically coincide with the traditional top-geoherb and non-top-geoherb areas of rhubarb. Molecular dating suggests that the two groups diverged in the Quaternary c. 2.0 million years ago, a time of repeated climate changes and uplift of the Qinghai-Tibetan Plateau. Our results show that the ancient TCM concept of top-geoherb and non-top-geoherb areas corresponds to genetically and chemically differentiated groups in rhubarb.

Deciphering Charging Status, Absolute Quantum Efficiency, and Absorption Cross Section of Multicarrier States in Single Colloidal Quantum Dots.

Upon photo- or electrical-excitation, colloidal quantum dots (QDs) are often found in multicarrier states due to multiphoton absorption, photocharging, or imbalanced carrier injection of the QDs. While many of these multicarrier states are observed in single-dot spectroscopy, their properties are not well studied due to random charging/discharging, emission intensity intermittency, and uncontrolled surface defects of single QDs. Here we report in situ deciphering of the charging status, precisely assessing the absorption cross section, and determining the absolute emission quantum yield of monoexciton and biexciton states for neutral, positively charged, and negatively charged single core/shell CdSe/CdS QDs. We uncover very different photon statistics of the three charge states in single QDs and unambiguously identify their charge signs together with the information on their photoluminescence decay dynamics. We then show their distinct photoluminescence saturation behaviors and evaluate the absolute values of absorption cross sections and quantum efficiencies of monoexcitons and biexcitons. We demonstrate that the addition of an extra hole or electron in a QD not only changes its emission properties but also varies its absorption cross section.

A Two-Step Synthetic Strategy toward Monodisperse Colloidal CdSe and CdSe/CdS Core/Shell Nanocrystals.

CdSe magic-size clusters with close-shell surface and fixed molecular formula are well-known in the size range between ∼1 and 3 nm. By applying high concentration of cadmium alkanoates as ligands, a conventional synthetic system for CdSe nanocrystals was tuned to discriminate completion from initiation of atomic flat facets. This resulted in ∼4-13 nm CdSe nanocrystals with hexahedral shape terminated with low-index facets, namely three (100), one (110), and two (111) facets. These low-symmetry (Cs group with single mirror plane) yet monodisperse hexahedra were found to be persistent not only in a broad size range but also under typical synthetic temperatures for growth of both CdSe and CdS. Atomic motion on the surface of the nanocrystals under enhanced ligand dynamics initiated intraparticle ripening without activating interparticle ripening, which converted the hexahedral nanocrystals to monodisperse spherical ones. This new synthetic strategy rendered optimal color purity of photoluminescence (PL) of the CdSe and CdSe/CdS core/shell nanocrystals, with the ensemble PL peak width comparable with that of a corresponding single dot.

Morphological variation in leaf dissection of Rheum palmatum complex (Polygonaceae).

AIMS: Rheum palmatum complex comprises all taxa within section Palmata in the genus Rheum, including R. officinale, R. palmatum, R. tanguticum, R. tanguticum var. liupanshanense and R. laciniatum. The identification of the taxa in section Palmata is based primarily on the degree of leaf blade dissection and the shape of the lobes; however, difficulties in species identification may arise from their significant variation. The aim of this study is to analyze the patterns of variation in leaf blade characteristics within and among populations through population-based sampling covering the entire distribution range of R. palmatum complex. METHODS: Samples were taken from 2340 leaves from 780 individuals and 44 populations representing the four species, and the degree of leaf blade dissection and the shape of the lobe were measured to yield a set of quantitative data. Furthermore, those data were statistically analyzed. IMPORTANT FINDINGS: The statistical analysis showed that the degree of leaf blade dissection is continuous from lobed to parted, and the shape of the lobe is also continuous from broadly triangular to lanceolate both within and between populations. We suggested that taxa in section Palmata should be considered as one species. Based on the research on the R. palmatum complex, we considered that the quantitative characteristics were greatly influenced by the environment. Therefore, it is not reliable to delimitate the species according to the continuously quantitative vegetative characteristics.

Genetic diversity of the endemic and medicinally important plant Rheum officinale as revealed by Inter-Simpe Sequence Repeat (ISSR) Markers.

Rheum officinale Baill., an important but endangered medicinal herb, is endemic to China. Inter-simple sequence repeat (ISSR) markers were employed to investigate the genetic diversity and differentiation of 12 populations of R. officinale. Thirteen selected primers yielded 189 bright and discernible bands, with an average of 14.54 per primer. The genetic diversity was low at the population level, but pretty high at the species level (H = 0.1008, I = 0.1505, PPB = 28.95% vs. H = 0.3341, I = 0.5000, PPB = 95.24%, respectively) by POPGENE analysis. Analysis of molecular variance (AMOVA) showed that the genetic variation was found mainly among populations (74.38%), in line with the limited gene flow (N(m) = 0.2766) among populations. Mantel test revealed a significant correlation between genetic and geographic distances (r = 0.5381, P = 0.002), indicating the role of geographic isolation in shaping the present population genetic structure. Both Bayesian analysis and UPGMA cluster analysis demonstrated the similar results. Our results imply that the conservation efforts should aim to preserve all the extant populations of this endangered species, and cultivation is proposed in this study.

Genetic variation in Rheum palmatum and Rheum tanguticum (Polygonaceae), two medicinally and endemic species in China using ISSR markers.

AIMS: Both Rheum palmatum and R. tanguticum are important but endangered medicinal plants endemic to China. In this study, we aimed to (i) investigate the level and pattern of genetic variability within/among populations of those species; (ii) evaluate genetic differentiation between both species and its relationships and ascertain whether both species are consistent with their current taxonomical treatment as separate species; and (iii) discuss the implications for the effective conservation of two species. METHODS: Total 574 individuals from 30 populations of R. palmatum and R. tanguticum were collected, covering the entire distribution range of two species in China. The genetic variation within and among 30 populations was evaluated using inter-simple sequence repeat (ISSR) markers. IMPORTANT FINDINGS: Twelve selected ISSR primers generated a total of 175 fragments, 173 (98.86%) of which were polymorphic. The Nei's gene diversity (H) and Shannon's index (I) of both species were high at species level (H = 0.3107, I = 0.4677 for R. palmatum; H = 0.2848, I = 0.4333 for R. tanguticum). But for both species, the genetic diversity was low at population level, and average within-population diversity of R. palmatum was H = 0.1438, I = 0.2151, and that of R. tanguticum was H = 0.1415, I = 0.2126. The hierarchical AMOVA revealed high levels of among-population genetic differentiation in both species, in line with the gene differentiation coefficient and the limited among-population gene flow (R. palmatum: Φ(st) = 0.592, G(st) = 0.537, N(m) = 0.432; R. tanguticum: Φ(st) = 0.567, G(st) = 0.497, N(m) = 0.507). By contrast, only 6.52% of the total genetic variance was partitioned between R. palmatum and R. tanguticum. Bayesian analysis, UPGMA cluster analysis, and PCoA analysis all demonstrated the similar results. A significant isolation-by-distance pattern was revealed in R. palmatum (r = 0.547, P = 0.010), but not in R. tanguticum (r = 0.241, P = 0.100). Based on these results, effective conservation strategies were proposed for these two species. The small molecular variance between R. palmatum and R. tanguticum revealed that they had a common ancestor, and we considered that these two species might not be good species.