A dual-channel ratiometric fluorescent probe for determination of the activity of tyrosinase using nitrogen-doped graphene quantum dots and dopamine-modified CdTe quantum dots.

A dual-channel ratiometric fluorometric assay is described for the determination of the activity of the enzyme tyrosinase (TYR). It is making use of blue-emitting nitrogen-doped graphene quantum dots (bQDs) and of red-emitting dopamine-modified CdTe quantum dots (DA-rQDs). A mixture of the two kinds of quantum dots was prepared, with the ratiometric fluorescence intensity of red to blue adjusted to 5:1. The dopamine on the rQDs is catalytically oxidized by TYR to form dopamine quinone, and this leads to a reduction of the intensity of red fluorescence (peaking at 644 nm). The emission of the bQDs (peaking at 440 nm) represents a stable reference signal. After adding different activities of TYR, the color of the fluorescence of the system continuously changes from red to blue. This can also be visually observed. The ratio of luminescence intensities (at 644/440 nm) can be used to quantify the activity of TYR, and the detection limit is 4.5 mU mL-1. In addition, a test strip is described based on the above method. Graphical abstract Schematic representation of the ratiometric fluorometric method for determination of the activity of tyrosinase (TYR). (The full name of the abbreviation in the Scheme: 1-ethyl-3-[3-(dimethylamino)-propyl] carbodiimide hydrochloride (EDC), dopamine (DA), N-hydroxysuccinimide (NHS), nitrogen-doped graphene quantum dots (bQDs), CdTe quantum dots (rQDs)).

Efficient adaptive feature aggregation network for low-light image enhancement.

Existing learning-based methods for low-light image enhancement contain a large number of redundant features, the enhanced images lack detail and have strong noises. Some methods try to combine the pyramid structure to learn features from coarse to fine, but the inconsistency of the pyramid structure leads to luminance, color and texture deviations in the enhanced images. In addition, these methods are usually computationally complex and require high computational resource requirements. In this paper, we propose an efficient adaptive feature aggregation network (EAANet) for low-light image enhancement. Our model adopts a pyramid structure and includes multiple multi-scale feature aggregation block (MFAB) and one adaptive feature aggregation block (AFAB). MFAB is proposed to be embedded into each layer of the pyramid structure to fully extract features and reduce redundant features, while the AFAB is proposed for overcome the inconsistency of the pyramid structure. EAANet is very lightweight, with low device requirements and a quick running time. We conducted an extensive comparison with some state-of-the-art methods in terms of PSNR, SSIM, parameters, computations and running time on LOL and MIT5K datasets, and the experiments show that the proposed method has significant advantages in terms of comprehensive performance. The proposed method reconstructs images with richer color and texture, and the noises is effectively suppressed.

A low-light image enhancement method with brightness balance and detail preservation.

This paper proposes a new method for low-light image enhancement with balancing image brightness and preserving image details, this method can improve the brightness and contrast of low-light images while maintaining image details. Traditional histogram equalization methods often lead to excessive enhancement and loss of details, thereby resulting in an unclear and unnatural appearance. In this method, the image is processed bidirectionally. On the one hand, the image is processed by double histogram equalization with double automatic platform method based on improved cuckoo search (CS) algorithm, where the image histogram is segmented firstly, and the platform limit is selected according to the histogram statistics and improved CS technology. Then, the sub-histograms are clipped by two platforms and carried out the histogram equalization respectively. Finally, an image with balanced brightness and good contrast can be obtained. On the other hand, the main structure of the image is extracted based on the total variation model, and the image mask with all the texture details is made by removing the main structure of the image. Eventually, the final enhanced image is obtained by adding the mask with texture details to the image with balanced brightness and good contrast. Compared with the existing methods, the proposed algorithm significantly enhances the visual effect of the low-light images, based on human subjective evaluation and objective evaluation indices. Experimental results show that the proposed method in this paper is better than the existing methods.

Hierarchical self-assembly of surfactant-encapsulated and organically grafted polyoxometalate complexes.

A series of surfactant-encapsulated and organically grafted polyoxometalates (SEOPs) were prepared through a co-precipitation procedure. Through a rational selection of the molecular components in the structure of the complex, SEOP complexes self-assemble into ordered aggregates with two different hierarchical self-assembled structures in an organic solvent mixture of dichloromethane and methanol in different volume ratios. FTIR, (1)H NMR, and X-ray photoelectron spectroscopy were used to characterize the self-assembly process and the involved driving forces. In a weakly polar solvent, SEOPs aggregated into fibers with a lamellar structure. When the solvent polarity was increased, SEOPs formed ribbonlike aggregates with a tetragonal structure. The change of the hierarchical self-assembled structure was deduced in regard to the arrangement of alkyl chains, electrostatic interactions, and hydrogen bonding between the pyridyl groups and terminal oxygen atoms of the polyoxometalates. The ribbonlike aggregates exhibit birefringence due to the ordered arrangement of SEOPs in the microstructure.

Determination of butyrylcholinesterase activity based on thiamine luminescence modulated by MnO2 nanosheets.

In this paper, a novel strategy for biosensing butyrylcholinesterase (BChE) activity is developed based on manganese dioxide (MnO2) nanosheets to modulate the photoluminescence of thiamine (TH). The oxidase-like activity of MnO2 nanosheets enables them to catalyze the oxidation of non-fluorescent substrate TH to generate strong fluorescent thiochrome (TC). When the target BChE is introduced to form thiocholine in the presence of S-butyrylthiocholine iodide (BTCh), MnO2 nanosheets are reduced by thiocholine to Mn2+, resulting in the loss of their oxidase-like activity and the reduction of TC fluorescence. Based on this, a BChE activity fluorescence biosensor is constructed utilizing the luminescence behavior variation of TH and the oxidase-like activity of MnO2 nanosheets. The fluorescence biosensor shows a sensitive response to BChE, and the detection limit reaches 0.036 U L-1. In addition, the feasibility of the biosensor in real samples analysis is studied with satisfactory results.

Incorporation of polyoxotungstate complexes in silica spheres and in situ formation of tungsten trioxide nanoparticles.

In this paper, we demonstrated a new convenient route for in situ fabrication of well separated small sized WO(3) nanoparticles in silica spheres, through a predeposition of surfactant encapsulated polyoxotungates as tungsten source, and followed by a calcination process. In a typical procedure, selected polyoxotungates with different charges were enwrapped with dioctadecyldimethylammonium cations through electrostatic interaction. Elemental analysis, thermogravimetric analysis, and spectral characterization confirmed the formation of prepared complexes with the anticipated chemical structure. The complexes were then phase-transferred into aqueous solution that predissolved surfactant cetyltrimethylammonium bromide, and finally incorporated into silica spheres through a joint sol-gel reaction with tetraethyl orthosilicate in a well dispersed state under the protection of organic layer for polyoxotungates from the alkaline reaction condition. Transmission electron microscopic images illustrated the well dispersed WO(3) nanoparticles in the size range of ca. 2.2 nm in the silica spheres after the calcination at 465 °C. The sizes of both the silica spheres and WO(3) nanoparticles could be adjusted independently through changing the doping content to a large extent. Meanwhile, the doped polyoxotungate complexes acted as the template for the mesoporous structure in silica spheres after the calcination. Along with the increase of doping content and surfactant, the mesopore size changed little (2.0-2.9 nm), but the specific surface areas increased quite a lot. Importantly, the WO(3)-nanoparticle-doped silica spheres displayed an interesting photovoltaic property, which is favorable for the funtionalization of these nanomaterials.

Reaction controlled assemblies of polyoxotungstates (-molybdates) and coordination polymers.

To investigate the influence of reaction conditions on the compound structures, five polyoxometalate (POM)-supported inorganic-organic hybrid compounds, [Cu(I)(3)(L(1))(4)][PW(12)O(40)] (1), [Cu(I)(3)(L(1))(4)][PMo(12)O(40)] (2), [Cu(I)(3)(L(1))(4)][PW(12)O(40)] (3), [Cu(I)(3)(L(1))(3)][PW(12)O(40)] (4), and [Cu(I)(3)(L(2))(3)][PMo(12)O(40)] (5) [L(1) = 1,4-bis(pyrazol-1-ylmethyl)benzene, L(2) = 4,4'-bis(pyrazol-1-ylmethyl)biphenyl], were hydrothermally synthesized by tuning the reactant species and molar ratio and reaction temperature and were characterized by elemental analysis, IR spectroscopy, PXRD, XPS, electrochemistry, SPS, and X-ray crystallography. Compounds 1 and 2 were synthesized in the isostructural state at 150 degrees C, in which L(1) ligands link Cu(I) ions, generating a cationic 2D 6(3) (hcb) skeleton {[Cu(3)(L(1))(4)](3+)}(n)-like sheet that further connects with POM anions, forming a neutral 2D (3,4)-connected network with a Schlafli symbol of (5(3))(2)(5(4);8(2)). In contrast, compound 3 was synthesized at a relatively lower reaction temperature (130 degrees C) than that for the synthesis of 1 and 2, which exhibits a similar 2D sheet-like cationic skeleton with 1 and 2. Interestingly, the POM anions do not coordinate with the cationic moieties in 3. Compounds 4 and 5 were synthesized with a relatively lower reactant molar ratio in comparison with that for the synthesis of 1-3, in which the cationic coordination moieties all present 1D chain-like structures. Compound 4 exhibits a 3D (3,4)-connected sqc74 framework with a Schlafli symbol of (6;8(2))(6(4);8;10) formed by the POM anions linking {[Cu(3)(L(1))(3)](3+)}(n) cationic chains. In comparison to 4, compound 5 shows a 3D supramolecular framework, which is formed by POM anions and {[Cu(3)(L(2))(3)](3+)}(n) cationic chains via hydrogen bonds. The structural difference of compounds 1-5 indicates that the reaction conditions perform a crucial influence on the structures of this series. The electrochemical properties of 2 and 5 and the SPS responses of 3-5 suggest that these compounds can be used as potential electrocatalytic or photocatalytic framework materials. In addition, EFISPS curves indicate that 3-5 possess the n-type semiconductor characteristic.

Preparation and characterization of Langmuir-Blodgett films of wheel-shaped Cu-20 tungstophosphate and DODA by two different strategies.

A novel surfactant-encapsulated organic-inorganic hybrid compound (DODA)(24)Li[Cu(20)Cl(OH)(24)(P(8)W(48)O(184))] x 18 H(2)O (DODA-Cu20) has been prepared from the wheel-shaped tungstophosphate salt K(12)Li(13)[Cu(20)Cl(OH)(24)(H(2)O)(12)(P(8)W(48)O(184))] x 22 H(2)O (Cu20) and dimethyldioctadecylammonium bromide (DODA), and it has been characterized by elemental analysis (EA), thermogravimetric analysis (TGA), (1)H NMR, Fourier transform infrared spectroscopy (FT-IR), and X-ray diffraction (XRD) measurements. Monolayer and multilayer films of DODA-Cu20 were fabricated on different substrates by the Langmuir-Blodgett (LB) technique using H(2)O as the subphase. Another type of organic-inorganic hybrid film, DODA/Cu20, was also deposited on the same substrates as used for the film containing DODA-Cu20 under the same conditions by the LB technique using a Cu20 aqueous solution as the subphase and DODA as the cationic amphiphile for comparison. Both thus-prepared organic-inorganic hybrid films were characterized by UV-vis spectroscopy, XRD, transmission and polarized FT-IR spectroscopy, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). The results indicate that stable monolayers at the air-water interface for DODA-Cu20 and at the air-Cu20 solution interface for DODA can be formed and that two LB films containing DODA-Cu20 and DODA/Cu20 constructed by two different methods both exhibit well-ordered lamellar structures. It is proposed that Cu20 exhibits different packing modes in the two LB films depending on the deposition strategy used.

Organo-ruthenium supported heteropolytungstates: synthesis, structure, electrochemistry, and oxidation catalysis.

The reaction of [Ru(arene)Cl(2)](2) (arene = benzene, p-cymene) with [X(2)W(22)O(74)(OH)(2)](12-) (X = Sb(III), Bi(III)) in buffer medium resulted in four organo-ruthenium supported heteropolytungstates, [Sb(2)W(20)O(70)(RuC(6)H(6))(2)](10-) (1), [Bi(2)W(20)O(70)(RuC(6)H(6))(2)](10-) (2), [Sb(2)W(20)O(70)(RuC(10)H(14))(2)](10-) (3), and [Bi(2)W(20)O(70)(RuC(10)H(14))(2)](10-) (4), which have been characterized in solution by multinuclear ((183)W, (13)C, (1)H) NMR, UV-vis spectroscopy, electrochemistry, and in the solid state by single-crystal X-ray diffraction, IR spectroscopy, thermogravimetric analysis, and elemental analysis. Polyanions 1, 2, and 4 crystallize in the triclinic system, space group P1 with the following unit cell parameters: K(5)Na(5)[Sb(2)W(20)O(70)(RuC(6)H(6))(2)] x 22 H(2)O (KNa-1), a = 12.1625(2) A, b = 13.1677(2) A, c = 16.0141(3) A, alpha = 78.9201(7) degrees, beta = 74.4442(8) degrees, gamma = 78.9019(8) degrees, and Z = 1; Cs(2)Na(8)[Bi(2)W(20)O(70)(RuC(6)H(6))(2)] x 30 H(2)O (CsNa-2), a = 11.6353(7) A, b = 13.3638(7) A, c = 16.7067(8) A, alpha = 79.568(2) degrees, beta = 71.103(2) degrees, gamma = 80.331(2) degrees, and Z = 1; Na(10)[Bi(2)W(20)O(70)(RuC(10)H(14))(2)].35H(2)O (Na-4), a = 15.7376(12) A, b = 15.9806(13) A, c = 24.2909(19) A, alpha = 92.109(4) degrees, beta = 101.354(4) degrees, gamma = 97.365(3) degrees, and Z = 2. Polyanions 1-4 consist of two (L)Ru(2+) (L = benzene or p-cymene) units linked to a [X(2)W(20)O(70)](14-) (X = Sb(III), Bi(III)) fragment via Ru-O(W) bonds resulting in an assembly with idealized C(2h) symmetry. Polyanions 1-4 are stable in solution as indicated by the expected (183)W, (13)C, and (1)H NMR spectra. The electrochemistry of 1-4 is described by considering the reduction and the oxidation processes. The nature of the arene in Ru(arene) has practically no influence on the formal potentials of the W-centers, which are more sensitive to the Sb or Bi hetero atoms. The results suggest that the respective Sb- and Bi derivatives have very different pK(a) values, with the reduced form of 1 being the most basic, thus permitting the observation of two well-developed voltammetric waves at pH 6. In contrast, the identity of the arene influences the oxidation processes, thus permitting to distinguish them. A strong electrocatalytic water oxidation peak is observed that is more positive than the one corresponding to the Ru(arene) oxidation process. Also a stepwise oxidation of the Ru(benzene) group could be observed at pH 3. The catalytic efficiency, on the other hand, of 1-4 toward the oxidation of n-hexadecane and p-xylene illustrated the effect of ruthenium substitution on the polyanion catalytic performance.

Study of Bi-directional detection for ascorbic acid and sodium nitrite based on Eu-containing luminescent polyoxometalate.

Eu-containing polyoxometalate K13Eu(SiMoW10O39)2·28H2O (Eu-SiMoW) owns the stimu-chromic and photoluminescence properties. An ingenious test of ascorbic acid (AA) and sodium nitrite (NaNO2) was carried out based on the dual properties of Eu-SiMoW in solutions. First, the redox reaction of Eu-SiMoW and AA generated the blue reduced Eu-SiMoW, accompanied by fluorescence quenching; then the redox reaction of the reduced Eu-SiMoW and NaNO2 made Eu-SiMoW back to its original pale yellow state with red luminescence. Accordingly, the content of AA and NaNO2 could be measured by the reversible change of color and luminescence of Eu-SiMoW. This bi-directional detection method is first discovered and proven to be a simple and effective method for the detection of AA and NaNO2. The proposed method exhibited a linear response range (LRR) from 0.1 to 0.9 mmol L-1 with a limit of detection (LOD) of 0.53 µmol L-1 in UV-vis spectra and 4.67 µmol L-1 in luminescence spectra for AA as well as a LRR from 0.05 to 0.4 mmol L-1 with a LOD of 1.16 µmol L-1 in UV-vis spectra and 5.39 µmol L-1 in luminescence spectra for NaNO2. Moreover, the fluorescence switching of Eu-SiMoW could be realized by reacting with reductant and oxidant through the redox reaction. The detection mechanism is considered as a fluorescence resonance energy transfer process between discolor component SiMoW and luminescence component Eu in Eu-SiMoW.

A multilayer assembly of two mixed-valence Mn16-containing polyanions and study of their electrocatalytic activities towards water oxidation.

Herein, two mixed-valence Mn16-containing polyanions, (Mn16) [MnIII10MnII6O6(OH)6(PO4)4(A-a-SiW9O34)4]28- (Mn16-Cs) and [MnIII4MnII12(OH)12(PO4)4(A-a-SiW9O34)4]28- (Mn16-Rb), were successfully fabricated on an indium tin oxide (ITO)-coated glass electrode and a glass carbon electrode (GCE) by a layer-by-layer assembly method. Moreover, four composite films, i.e. [PDDA/Mn16-Cs]n, [PDDA/Mn16-Rb]n, [Mn16-Cs/Rubpy]n, and [Mn16-Rb/Rubpy]n (PDDA: poly(diallyldimethylammonium chloride); Rubpy: tris(2,2'-bipyridyl)ruthenium(ii) chloride; n = 1-10), were constructed for comparison and characterized by UV-visible spectroscopy, cyclic voltammetry (CV), and X-ray photoelectron spectroscopy (XPS). Their electrocatalytic activities towards water oxidation were studied under the same experimental conditions. The results of the controlled experiments indicate that (1) all the four films exhibit expected electrocatalytic activities towards water oxidation; (2) the electrocatalytic activity of Mn16-Cs is better than that of Mn16-Rb in solution and composite films; and (3) the electrocatalytic activities of the composite film [Mn16/Rubpy]n are better than those of the composite film [PDDA/Mn16]n.

Highly Efficient, Near-Infrared and Visible Light Modulated Electrochromic Devices Based on Polyoxometalates and W18O49 Nanowires.

Over the past years the performance of electrochromic smart windows with the promising potential for significant energy savings has been progressively improved; however, the electrochromic windows have not yet to come into use at scale mainly because the electrochromic materials suffer from some significant drawbacks such as low coloration efficiency, slow switching time, bad durability and poor functionality. Herein, we fabricate the optically modulated electrochromic smart devices through sequential deposition of the crown-type polyoxometalates, K28Li5H7P8W48O184·92H2O (P8W48), and W18O49 nanowires. Unlike most reported electrochromic smart devices, the resulting P8W48 and W18O49 nanocomposites allow active and selective manipulation of the transmittance of near-infrared (750-1360 nm) and visible light (400-750 nm) by varying the applied potential. Furthermore, thanks to the stable nature of both P8W48 and W18O49 and precise structural control over the nanocomposites, the prepared electrochromic smart devices exhibit high efficiency, quick response and excellent stability.

Simple and efficient polyoxomolybdate-mediated synthesis of novel graphene and metal nanohybrids for versatile applications.

The application of nanohybrids based on polyoxomolybdates, reduced graphene oxide (rGO) and/or metal nanoparticles (NPs) high-performance electrode materials in electrocatalysis and energy storage devices is promising but still limited due to the complexity and the cost of the synthesis. Here we introduce a simple polyoxomolybdate, [MoV4O8(OH)2(H2O)2(C4O4)2]2- (MoS), as reducing and stabilizing agent for the facile and one-pot syntheses of large quantity of highly stable MoS/rGO and MoS/Au NPs nanohybrids in aqueous solution without any catalyst or toxic co-solvent. They were characterized by various physical techniques and electrochemistry which confirm strong interaction between MoS and rGO sheets. We also used DFT calculations to investigate the affinity between MoS or its neutral form with graphene. The adsorption energy for the most stable configuration is -1.97 eV, indicating a strong adsorption process of MoS, which can also be confirmed by the distance (3.04 Å) and the charge transfer (0.86 e) between MoS and graphene. These observations are also consistent with the electrochemical results which underscore the excellent redox properties and high stability of MoS/rGO. Importantly, the MoS/rGO nanohybrids are excellent noble metal-free electrocatalysts for hydrogen peroxide reduction with high sensitivity, large detection range and low detection limit. Finally, the preliminary tests reveal that the electrode materials based on MoS/rGO and a low-cost carbon cloth (CC) composite MoS/rGO/CC may have a potential for an application in energy storage as performant and flexible supercapacitor, showing specific capacitance as high as 870 F g-1 at 10 mV s-1 and excellent stability after 5000 cycles.

Fetal echocardiographic screening in twins for congenital heart diseases.

BACKGROUND: Congenital heart disease (CHD) is the most common congenital disorder at birth. Yagel and colleagues's method of heart examination has been proved valuable in finding CHD prenatally in single pregnancies. The aim of this study was to analyze the frequency of CHD in twin pregnancies and the sensitivity of the method. METHODS: A total of 1103 pregnant women with twins were enrolled in this study, including 127 cases with high-risk for CHD. Five transverse ultrasound measurements were used for fetal heart examination, including the upper abdomen view, four-chamber view, five-chamber view, pulmonary artery bifurcation view, and three-vessel view. In the fetuses who were diagnosed with CHD and whose parents requested termination of the pregnancy, autopsy of the fetal heart was performed after an abortion, and a blood sample was collected from the heart for chromosome evaluation. In the other fetuses, a close follow-up was conducted by echocardiography within one year after birth. RESULTS: Antenatally, CHD was found in 12 twins, of which 4 were from the high-risk group (3.15%), and 8 from the low-risk group (0.82%). In 2 pairs of the twins, the two fetuses had a same kind of CHD (one pair had tetralogy of Fallot (TOF), another pair had rhabdomyoma). Another pair had different types of anomaly (one fetus had TOF, and the other duodenal atresia with a normal heart). Termination of pregnancy was performed in these three pairs and the autopsy of the fetal heart confirmed the ultrasound findings. In the other 9 pairs, CHD was detected in one fetus, and a normal heart in the others. In the cases who received chromosome evaluation, 2 had abnormal chromosomes. During the follow-up after birth, heart examinations confirmed the prenatal diagnosis in 7 of the 9. The diagnosis of CHD was missed antenatally in 2 pairs of twins. In both the cases, one fetus was normal, and the other was confirmed as having CHD after birth (small ventricle septum defect in one, and persistent open ductus arteriosus in the other). Thus, the total frequency of CHD was 16 (7.3/1000), which was similar to that in single pregnancies. The sensitivity of fetal echocardiography was 87.5% and the specificity was 100%. CONCLUSIONS: The frequency of CHD is the same in twin as in single pregnancies. Systemic ultrasound scanning with five transverse views is effective in diagnosing fetal CHD in twin pregnancies.

[Prenatal diagnosis of congenital fetal heart abnormalities in twins by Yagel's heart examination method].

OBJECTIVE: To investigate the value and clinical significance of congenital heart diseases (CHD) detection in twins. METHODS: A total of 1103 twins were included in this study (127 twins were at high risk for CHD). The fetal hearts were scanned by ultrasound using Yagel's heart examination method. Autopsies were done when the pregnancy was terminated. And blood samples from fetal hearts or umbilical veins were used to evaluate fetal chromosomes. A close follow-up was conducted for normal heart cases and another heart examination was done within three months after birth. RESULTS: (1) 12 twins (1.09%, 12/1103) had CHD. Among them, 4 cases were from the high risk for CHD group (33.3%, 4/12), and 8 cases (66.7%, 8/12) were from the low risk pregnancy group. (2) Two twins suffered from the same CHD (one pair were both TOF, and the other pair were both rhabdomyoma). One pair of twins had different abnormalities (one baby was TOF, and the other was duodenal atresia with a normal heart). All three pairs of twins chose termination and autopsies were conducted. Unanimous conclusions between prenatal ultrasound and autopsy were obtained. Nine twins were CHD in one baby and a normal heart in the other baby. Seven of them had the same conclusion after delivery. (3) Two twins with CHD were found with fetal abnormal chromosome. (4) 1091 cases were not found having any abnormality, however, one fetus from one twin pair was diagnosed with ventricular septal defect (VSD) with abnormal chromosome after birth, and one fetus from another twin pair had patency of ductus arteriosus after birth. (5) The sensitivity of Yagel's heart examination was 82.4% and specificity was 100% in twins. CONCLUSION: Yagel's heart examination is an effective and time-saving method to scan fetal hearts in twins.

Fabrication of white luminescence composite films containing Dy-polyoxometalate and the study of their luminescence switching behaviors.

White luminescence composite films containing Dy-polyoxometalate (Dy-POM) were firstly constructed by a layer-by-layer assembly method for the realization of electrically controlled luminescence switching. Additionally, blue-white luminescence could be switched by the choice of POM structural types and control of the concentration ratio of POM/Dy-POM in solution and composite films.

First Orange Fluorescence Composite Film Based on Sm-Substituted Tungstophosphate and Its Electrofluorochromic Performance.

We chose a Sm-containing sandwich-type tungstophosphate K3Cs8[Sm(PW11O39)2]·10H2O (SmPW11) as a molecular dyad, which contains photoluminescence and electrochromism components in a skeletal structure, and investigated its electrofluorochromic performance both in solution and in composite films. First, the electrochemical activity and luminescence property of SmPW11 were studied in different pH solutions to determine the optimal pH solution medium; and then, the electrofluorochromic performance of SmPW11 was investigated under the optimized pH solution medium. Subsequently, the composite films containing SmPW11 were prepared on quartz substrates and conductive ITO substrates through a layer-by-layer (LbL) assembly method, using PDDA and PEI as molecular linkers. Characterization methods of the composite films include UV-vis spectra, fluorescence spectroscopy, cyclic voltammetry (CV), bulk electrolysis with coulometry, chronoamperometry, X-ray photoelectron spectroscopy (XPS), and atomic force microscopy (AFM). Finally, in situ UV-vis and fluorescence spectroelectrochemical systems were used to research electrofluorochromic properties for the composite films under electrochemical modulation. The results indicate that the composite films display not only orange luminescence emission but also reversible orange luminescence switching behaviors manipulated by the redox process of tungstophosphate species PW11 via the energy transfer between the orange luminescence component Sm and electroreduced species of tungstophosphate PW11.

Reference Intervals of Thyroid Function During Pregnancy: Self-Sequential Longitudinal Study Versus Cross-Sectional Study.

BACKGROUND: A self-sequential longitudinal reference interval may be expected to minimize the inter-individual variation of thyroid function. Comparison between the self-sequential longitudinal reference interval (SLRI) and cross-sectional reference interval (CSRI) in pregnancy has not been well investigated. The objectives of this study were to establish a stringent SLRI of thyroid function in pregnant women and to compare it with the conventional CSRI. METHODS: Three cohorts were enrolled: group 1, pregnant women for an SLRI (n = 99); group 2, pregnant women for a CSRI (n = 1318); group 3, non-pregnant control women (NC) as a control group (n = 301) according to the criteria of the National Academy of Clinical Biochemistry. Thyrotropin (TSH), total thyroxine (TT4), free thyroxine (fT4), total triiodothyronine (TT3), free triiodothyronine (fT3), serum ferritin (SF), and urine iodine concentration (UIC) were measured in the three groups. RESULTS: Compared with CSRI, the reference interval of the SLRI group had narrower reference intervals of fT4 in the first and second trimesters (p < 0.05). The median of TSH was at a low level during the first trimester, and then gradually elevated in the second and third trimesters. The median of fT4 persistently decreased from 12 weeks, and did not return to the level of the NC group until 12 months postpartum. The TT4 increased to 131.4 nmol/L at gestational week 8, and reached a peak (170.0 nmol/L) at gestational week 12. In the first trimester, the prevalence of hypothyroxinemia was 9.1%, 4.0%, and 2.0% with a fT4 value below the 10th, 5th, and 2.5th percentile, respectively. In contrast, 29.3% of TT4 values were below the lower non-pregnancy reference limit multiplied by 1.5. CONCLUSIONS: No significant difference was found between a SLRI and a CSRI, even in a stringent self-sequential longitudinal reference interval of thyroid function in pregnant women. In addition, the limit of TT4 below the non-pregnant level multiplied by a factor 1.5 is not appropriate for diagnosing hypothyroxinemia in the first trimester.

The Ru(II)-supported heptatungstates [HXW7O28Ru(dmso)3]6-(X=P, As).

The ruthenium(II)-supported heteropolyanions [HXW7O28Ru(dmso)3]6-(X=P, 1; As, 2) are composed of a Ru(dmso)3 group attached to an unprecedented heptatungstate fragment via two Ru-O-W bonds and one Ru-O-X bond, which represents a fundamentally novel mode of Ru-coordination to a polyoxoanion framework. Multinuclear 183W, 31P, 13C, and 1H NMR studies indicate high stability of 1 and 2 in solution.

An effective combination of electrodeposition and layer-by-layer assembly to construct composite films with luminescence switching behavior.

This article presents a combination strategy of electrodeposition and a layer-by-layer assembly to fabricate functional composite films with luminescence switching behavior. Firstly, a novel green luminescence film consisting of 8-hydroxypyrene-1,3,6-trisulfonic acid trisodium salt (HOPTS) was first obtained on ITO by a facile electrodeposition method. Then, the multilayer films containing different layers of tungstophosphate K12.5Na1.5[NaP5W30O110]·15H2O (P5W30) were further fabricated on the green luminescence film to form the composite films [(HOPTS)50/(PDDA/P5W30)n] (n = 10, film 1; n = 27, film 2; n = 57, film 3). Cyclic voltammetry and fluorescence spectroscopy were used to characterize the electrochemical activity of P5W30 and the luminescence property of HOPTS in the composite films, respectively. Lastly, in situ UV-Vis spectroelectrochemical and fluorescence spectroelectrochemical measurements were applied to investigate the luminescence switching behaviors of the composite films controlled by the electrochromism component of P5W30 upon electrochemical modulation. In summary, the investigation results revealed that the electrodeposition method is convenient and rapid, and thus-prepared composite films showed improved luminescence switching performance in terms of switching process, activation cycles, coloration efficiency, and bleached-state transparency as well as good stability, wide voltage range and good reversibility. Therefore, the present study offers a new fabrication route for the multifunctional composite films through an effective combination of electrodeposition and layer-by-layer assembly technique.