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Creative use of 3D printing to create analytical standards greatly increased the sample homogeneity and the accuracy of the desired concentration.

RATIONALE An absolute method that does not require calibration is very important in several areas of isotope analysis due to the shortage of suitable certified reference materials (CRMs). As total evaporation thermal ionization mass spectrometry (TE-TIMS) theoretically overcomes mass fractionation through integrating the ion currents till the sample on the filament is completely exhausted, it could be an absolute method that does not require the use of CRMs for calibration. However, the lack of reliable method verification and reasonable uncertainty evaluation restricts its extensive application, and these effects need to be quantitatively evaluated. METHODS A series of different amounts of strontium reference material SRM987 was deposited on both single and triple tantalum filament sources, and analyzed by TE-TIMS. The work function of the tantalum filament loaded with the sample was measured by ultraviolet photoelectron spectroscopy. In order to evaluate the change in ion transmission efficiency, we terminated the total evaporation process manually after running for a certain period of time, and recorded the ion beam intensity before and after this operation. RESULTS The TE results obtained with the triple filament source agreed well with the reference values of SRM987, while the TE results obtained with the single filament source changed significantly with the amount of sample loading. The crucial effect factors on TE-TIMS, including ionization temperature fluctuation, variation of ion transmission efficiency and ion loss before data acquisition, were quantitatively assessed. These factors were used to correct the single filament TE results and the measurement uncertainty was quantitatively evaluated. CONCLUSIONS The reliability of strontium isotopic ratio measurement with triple filament TE-TIMS was verified. The mathematical model for correction of each crucial effect factor was successfully established, thus providing a feasible way for the correction of single filament TE-TIMS results.

Modern advances in multi-collector inductively coupled plasma mass spectrometry (MC-ICPMS) have greatly promoted the investigation of copper isotopes in various research fields. To meet the demand, an improved calibrated mass spectrometry for the absolute determination of copper isotopic composition was developed in this study. The method has made progress in the investigation of instrumental mass bias correction factor for copper isotopic analysis using MC-ICPMS through employing two independent strategies. One is the conventional mathematical iterative method based on the MC-ICPMS measurement data; the other one is direct calculation using the absolute copper isotopic compositions in isotopically enriched

Liver plays a major role in metabolism and acts as a source of energy for the body by storing glycogen. With the growing interest and investigation in the biological effects in recent years, it is important and necessary to develop accurate and comparable analytical methods for elements in bio-samples. It has, however, been 10 years since the tissue sample (bovine liver) of CCQM-K49 key comparison. The purpose of CCQM-K145 is to ensure the comparable and traceable measurement results for essential and toxic elements such as P, S, Zn, Mn, Ni, Mo, Sr, Cr, Co, Pb, As and Hg in bovine liver among NMIs and other designated measurement bodies worldwide. The comparison was agreed by IAWG as 6th IAWG Benchmarking Exercise with Zn and Ni as exemplary elements at the meeting in Korea in the early October 2016. The results of CCQM-K145 are expected to cover the measurement capability and support CMCs claiming for inorganic elements in the similar biological tissue materials and food samples. 30 NMIs and DIs registered in CCQM-K145. With respect to the methodology, a variety of techniques such as IDMS, ICP-OES, ICP-MS(non-ID), AAS and NAA were adopted by the participants. For Zn, Ni, Sr, Pb and Hg measurements, most participants chose ID-ICP-MS method, which showed the better performance in terms of consistency and reliability of the measurement results. In aspect of the traceability for the measurement results in CCQM-K145, most participants used their own (in house) CRMs or other NMI's CRMs to guarantee trace to SI unit. Most participants used similar matrix CRMs for quality control or method validation. Base on different statistic way to calculate the reference mass fraction values and associated uncertainties for each measurand, removal of the suspected extreme values, and discussion at the IAWG meetings, the median values are proposed as the KCRV for Zn, Ni, Mn, Mo, Cr, Pb and Hg; the arithmetic mean values are proposed as the KCRV for P, S, Sr, Co and As. In general, the performances of the majority of CCQM-K145 participants are very good, illustrating their measurement capabilities for Zn, Ni, P, S, Mn, Mo, Sr, Cr, As, Co, Pb and Hg in a complex biological tissue matrix. Bovine liver contains many kinds of nutrients and microelements, it can be regarded as a typical representative material of biological tissue and food. In CCQM-K145, the analytes involved alkali metals and transition elements, metalloids / semi-metals and non metals with a range of mass fraction from mg/g to μg/kg. CCQM-K145 also tested the ability of NMIs/DIs to determine elements that were easy to be lost and polluted, and interfered significantly. The chemical pretreatment methods of samples used in the comparison is suitable for general food and biological matrix samples. A variety of measurement methods used in the comparison represent the main instrumental technology for elemental analysis. Therefore, for supporting CMC claim, CCQM-K145 is readily applicable to measurement of more elements in a wide range of biological materials (including liquids and solids) and meat products. Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

Artificial enzyme mimics based on nanomaterials have attracted sustained attention owing to their multiple advantages compared with natural enzymes. However, there are a few enzyme self-cascade systems for the highly sensitive detection of analytical targets. Herein, we have described a self-cascade catalytic system based on single-component cupric oxide nanoparticles (CuO NPs) for an ultrasensitive fluorescent detection toward glutathione (GSH) and Ag+ ions. The limit of detection is lower for nanomolar (nM) and picomolar (pM) levels for GSH and Ag+, respectively. To the best of our knowledge, for the first time, we find that CuO NPs possess the intrinsic GSH-oxidase and peroxidase-like activity as a dual-functional nanozyme, coupling with terephthalic acid (TA) and GSH to construct a self-cascade fluorescent system. The turn-on fluorescence signal of oxidation hydroxyterephthalate (TAOH) is generated in the presence of GSH. Then, the fluorescence of a reaction mixture is quenched after the addition of A...

Mercury is a common heavy metal element in natural systems and is highly toxic to the human body. Herein, a novel colorimetric detection of Hg2+ ions is proposed based on the aggregation of gold nanoparticles (AuNPs) induced by carbon quantum dots (CDs) with the assistance of glutathione (GSH). In this sensing system, the AuNP/CDs composite forms through Au–N bonds. Simultaneously, the color of the solution turns from wine red to blue. The well-dispersed AuNPs can be restored after the addition of GSH, because GSH competes with CDs to bind onto the surface of AuNPs and protect AuNPs from aggregation. In the presence of Hg2+ ions, GSH can chelate with Hg2+ to form a complex, which subsequently enables CDs to facilitate the aggregation of the AuNPs again. Therefore, according to the red-to-blue color change, a colorimetric sensor is established for the sensitive and selective detection of Hg2+ with a detection limit of 7.5 nM. Moreover, this sensor is successfully used to detect Hg2+ spiked in environmental water. This very simple and cost-effective strategy will promote the development of a colorimetric sensor for the determination of other metal ions in biological and environmental fields.

A selective phosphorescent on-off-on probe with long decay lifetime has been designed for the detection of pyrophosphate ions (PPi). The detection scheme is based on the use of europium(III)-modulated Mn(II)-doped ZnS quantum dots capped with N-acetyl-L-cysteine. Both the aggregation of quantum dots and electron transfer induced by Eu(III) ions cause phosphorescence to be quenched ("off" state). Phosphorescence is, however, restored on addition of PPi to the system ("on" state). The effect is attributed to the removal of Eu(III) from the carboxy groups on the surface of the quantum dots owing to the stronger interaction between PPi and Eu(III). A linear relationship exists between phosphorescence intensity (best measured at excitation/emission wavelengths of 316/594 nm) and PPi concentration in the 400 nM to 6000 nM with a detection limit of 145 nM. An additional attractive feature is provided by the long-lived phosphorescence (1920 μs) of the quantum dots. It can be used to eliminate interference by short-lived fluorescence in biological samples by performing time resolved measurements. The probe was applied to the determination of PPi in spiked in urine samples and gave recoveries in the range from 98 to 105% with RSDs of2.0%. Graphical abstract Schematic of a long-lived phosphorescent on-off-on probe for the sensitive and selective detection of pyrophosphate ions (PPi). It is based on the use of Eu(III)-modulated Mn(II)-doped ZnS quantum dots (QDs). Phosphorescence is quenched of QDs after the addition of Eu

A fully calibrated strategy has been investigated for the first time for the accurate determination of absolute isotopic composition and atomic weight of molybdenum using multiple-collector inductively coupled plasma mass spectrometry. The correction for instrumental mass bias was performed using synthetic isotope mixtures, which were gravimetrically prepared with all of the seven high-purity and isotopically enriched molybdenum isotope materials together. Six natural molybdenum materials, including molybdenum standard solution NIST SRM 3134, were accurately measured and yielded the absolute isotopic composition (in atom %, k = 1) of 92Mo-14.690(18), 94Mo-9.173(6), 95Mo-15.865(5), 96Mo-16.666(3), 97Mo-9.588(4), 98Mo-24.307(16), and 100Mo-9.711(13). These isotopic data enable an atomic weight Ar(Mo) of 95.9466(34) (k = 2) to be calculated, which is slightly lower than the current standard atomic weight 95.95(1) and with a much improved uncertainty. The associated uncertainties were evaluated according to t...

A fluorescent chemosensor for Cu2+ has been developed based on the aggregation-induced emission (AIE) characteristics of bis(pyridin-2-ylmethylene) terephthalohydrazide (1). The dye molecule 1 exhibits a large Stokes shift of ~182 nm and shows highly sensitive and selective response to Cu2+ over other metal ions by forming a 1:2 metal-to-ligand complex in aqueous solution. Cu2+-induced fluorescence quenching at 516 nm was proportional to the concentration of Cu2+ in the range of 0.2–8.0 μM, with a detection limit as low as 160 nM. In addition, by taking advantage of its AIE characteristics, compound 1 can also enable the fabrication of test papers for in-field detections, which is challenging for many other fluorescent Cu2+ sensors due to their strong self-quenching effect in solid state.

A turn-on fluorescent probe DNBS-CSA is reported here with selective detection of thiols over other amino acids. Probe DNBS-CSA possesses the widely-used thiol-selective 2,4-dinitrobenzenesulfonyl (DNBS) group to react with thiols and release the fluorescent salicylaldehyde azine with aggregation-induced emission (AIE) characteristics. The use of AIE dye prevented the sensor from aggregation-induced fluorescence quenching which is challenging for other thiols sensors. Upon the addition of cysteine (Cys) to DNBS-CSA in aqueous solution (10 mM PBS buffer at pH 7.4 containing 30% DMSO), an intense fluorescence enhancement was observed at 558 nm with a large stokes shift of ∼170 nm. Under the optimal condition, the fluorescence intensity linearly increased with the concentration of Cys in the range of 8–18 μM with a correlation coefficient of R2 = 0.991. The fluorescence enhancement of DNBS-CSA upon addition of Cys on test paper was also observed, enabling DNBS-CSA function as solid materials (such as test papers) for thiols detection. The detection of thiols in serum samples was successfully performed. With good cell permeability, the probe was applied to the imaging of thiols in HEK 293T cells.

A facile, rapidly responsive fluorescence turn-on probe for heparin with high selectivity and sensitivity was reported in this paper. The probe could aggregate on the negatively charged heparin template through electrostatic interactions and then display intense fluorescence due to its aggregation-induced emission (AIE) characteristics. Under optimal condition, the probe showed high selectivity to heparin over chondroitin sulfate(ChS), hyaluronic acid (HA), dextran (DeX) and other substances, with a linear range of 0.2–14 μg/mL, and a detection limit of 57.6 ng/mL. In diluted serum, it also showed good performance.

In this work, (2-hydroxy-4-methoxyphenyl)(phenyl)methanone azine (1) was found to exhibit aggregation-induced emission (AIE) and tunable solid fluorescence upon alternate annealing/melting treatments. According to the characterizations by X-ray crystallography, X-ray powder diffraction, and differential scanning calorimetry, the switching between the two different polymorphs was responsible for the tunable solid fluorescence as a consequence of polymorph-dependent excited-state intramolecular proton transfer (ESIPT) fluorescence, while the thermochromism was contributed by the conformational flexibility of rotary phenyl rings. The change in the tightness of packing upon annealing or melting thermal treatments resulted in the emission at different wavelengths. Therefore, polymorph-dependent ESIPT fluorescence could be utilized as a new strategy to develop efficient AIE-active materials in response to external stimuli.

In this work, two methods with complementary features, catalytic and molecular beacon (CAMB) and label-free fluorescent sensors using an abasic site, have been combined into new label-free CAMB sensors that possess advantages of each method. The label-free method using a dSpacer-containing molecular beacon makes CAMB more cost-effective and less interfering with the catalytic activity, while CAMB allows the label-free method to use true catalytic turnovers for signal amplifications, resulting in a new label-free CAMB sensor for Pb(2+) ion, with a detection limit of 3.8 nM while maintaining the same selectivity. Furthermore, by using CAMB to overcome the label-free method's limitation of requiring excess enzyme strands, a new label-free CAMB sensor using aptazyme is also designed to detect adenosine down to 1.4 μM, with excellent selectivity over other nucleosides.

A salicylaldehyde azine-based derivative, which exhibited switchable solid-state fluorescence in response to external thermal and mechanical grinding stimulus, was reported in this study. Diffuse reflectance solid-state spectroscopy, fluorescence spectroscopy, solid-state 13C and 1H NMR spectroscopy, single crystal XRD analyses, powder X-ray diffractometry, and differential scanning calorimetry were used for investigating the changes of molecular packing modes. The multistimuli fluorescence originated from two distinctive crystalline lattices via different π–π interactions. The local dipole coupling among molecules with donor–planar–acceptor structure was evidenced to be the essential factor for the effective solid luminescence-switching properties.

In this study, p-carboxyl-N-salicylideneaniline (pCSA) derivatives were simply synthesized by condensing salicylaldehyde and primary amine. With two planar π-conjugated moieties linked by rotatable C–N single bond in the molecular structure, pCSA derivatives were characteristic of aggregation-induced emission enhancement (AIEE) properties, exhibiting strong fluorescence in solid state. Facilely recrystallized from organic solvent, one-dimensional (1D) microrods of pCSA were prepared with green, yellow and orange AIEE colors depending on substituents on salicylaldimine moiety. The obtained 1D microrods could be utilized as potential optical waveguides for propagating and manipulating light in miniaturized devices.

Conventional fluorophores usually undergo aggregation-caused quenching (ACQ), which limits the loading amount of these fluorophores in nanoparticles for bright fluorescence imaging. On the contrary, fluorophores with aggregation-induced emission (AIE) characteristics are strongly fluorescent in their aggregate states and have been an ideal platform for developing highly fluorescent nanomaterials, such as fluorescent silica nanoparticles (FSNPs). In this work, AIE luminogens based on salicylaldehyde hydrazones were embedded in silica nanoparticles through a facile noncovalent approach, which afforded AIE-FSNPs emitting much brighter fluorescence than that of some commercial fluorescein-doped silica and polystyrene nanoparticles. These AIE-FSNPs displaying multiple fluorescence colors were fabricated by a general method, and they underwent much less fluorescence variation due to environmental pH changes compared with fluorescein-hybridized FSNPs. In addition, a DNA aptamer specific to nucleolin was functionalized on the surface of AIE-FSNPs for targeted cell imaging. Fluorescent microscopy and flow cytometry studies both revealed highly selective fluorescence staining of MCF-7 (a cancer cell line with nucleolin overexpression) over MCF-10A (normal) cells by the aptamer-functionalized AIE-FSNPs. The fluorescence imaging in different color channels was achieved using AIE-FSNPs containing each of the AIE luminogens, as well as photoactivatable fluorescent imaging of target cells by the caged AIE fluorophore.

The activity of uracil-DNA glycosylase (UDG), an enzyme in the base excision repair, is detected at a high sensitivity by a DNA substrate containing only one uracil through a label-free fluorescent approach, which is also successfully applied for the measurement of UDG inhibitors.

A novel fluorescent probe 1 is reported here with ratiometric response to hydrophobic proteins (casein) or proteins with hydrophobic pockets (BSA, HSA) through hydrophobic interaction. Probe 1 underwent deprotonation in aqueous solution at pH 7.4 and emitted blue fluorescence at 436 nm. Upon the addition of BSA, HSA or casein, the aggregation-induced emission fluorescence of 1 at 518 nm was turned on. The fluorescence intensity ratio, I518/I436 was linearly related to the concentrations of these proteins. The detection limits for BSA, HSA and casein based on IUPAC (CDL = 3Sb m(-1)) were 16.2 μg mL(-1), 10.5 μg mL(-1) and 5.7 μg mL(-1), respectively.

A ratiometric fluorescent pH probe, 4-carboxylaniline-5-chlorosalicylaldehyde Schiff base (1) was synthesized via a facile reaction and used for pH sensing in live cells. While exhibiting weak fluorescence when dispersed in solution, 1 displayed aggregation-induced emission enhancement (AIEE) characteristics in its aggregate/solid state, as a result of the restriction of free intramolecular rotation of a C–N bond and the non-planar configuration in the aggregate/solid state. The integration of hydroxyl and carboxyl groups provided 1 with a ratiometric fluorescent response to pH based on AIEE and the pH-dependent spectral characteristics of compound 1, with proton dissociation constants pKa1 and pKa2 of 4.8 ± 0.1 and 7.4 ± 0.1, respectively. The probe exhibited a significant fluorescence color change from orange to green with an intensity ratio (I516 nm/ I559 nm) enhanced when the pH increased from 5.0 to 7.0 in aqueous solution. Confocal fluorescence imaging of intracellular pH through ratiometric response was successfully achieved in live HepG2 cells. The results demonstrate that probe 1 is a good candidate for monitoring pH fluctuations in live cells with good selectivity, stability, and excellent membrane permeability.

A novel fluorescence turn-on method for sensitive and selective detection of protamine was developed based on aggregation-induced emission enhancement (AIEE) characteristics of 4-(6'-carboxyl)hexyloxysalicylaldehyde azine (CHSA) induced by electrostatic interaction between protamine and CHSA(-). Under optimal conditions described, a large Stokes shift of approximately 198 nm could be observed, and the fluorescence enhancement at 538 nm was linearly related to the concentration of protamine in the range of 0.6-18 microg mL(-1) with the relative correlation coefficient of R(2) = 0.9996 (n = 11) and a detection limit as low as 43 ng mL(-1). The relative standard deviation (R.S.D.) was 2.0% (n = 5). The proposed method was successfully utilized in quantifying protamine in diluted horse serum. In addition, due to the special electrostatic association between protamine and heparin, CHSA could also be employed as a probe to study the interaction between them.