Fluorimetric determination of histidine by exploiting its inhibitory effect on the oxidation of thiamine by cobalt-containing Prussian Blue nanocubes.

A fluorometric assay for histidine (His) is described. It is based on the inhibitory effect of His on nanocubes consisting of cobalt-containing Prussian Blue analog (CoFe NCbs), which have a strong oxidation effect on thiamine (THI) in the presence of NaOH. THI is nonfluorescent but the oxidized form (thiochrome; ThC) has a strong blue fluorescence, with excitation/emission maxima at 370/445 nm. His inhibits the oxidation effect of the CoFe NCbs due to the strong interaction between its imidazole side chain and the amino groups of the CoFe NCbs. This method is fast and has good sensitivity and selectivity. The lower detection limit is 14.3 nM of His, the linear range extends from 0.05 to 2.5 µM, and the relative standard deviation is calculated to be 1.5%. The method was successfully employed to quantify His in spiked serum samples. Graphical abstractSchematic representation of cobalt-containing Prussian Blue nanocubes (CoFe NCbs)-thiamine (THI)-based fluorometric assay for Histine (His). His inhibits the generation of thiochrome (ThC; the oxidized form of THI). The detection limit is 14.3 nM with the linear range of 0.05-2.5 µM.

[Effects of 24 Years Different Straw Return on Soil Carbon, Nitrogen, Phosphorus, and Extracellular Enzymatic Stoichiometry in Dryland of the Loess Plateau, China].

Exploring the biogeochemical cycle characteristics of soil carbon, nitrogen, and phosphorus in farmland in the dryland of the loess plateau can provide scientific basis and technical support for efficient crop production and sustainable land use. Here, based on a long-term (24 year) straw return field experiment in Shouyang, Shanxi province, the effects of different straw return regimes, i.e., straw mulching (SM), direct straw return (DS), animal-digested straw return (AS), and non-straw return (CK), on the stoichiometric ratio of soil elements and extracellular enzyme activities were studied. The vector angle and length were calculated to indicate the resource constraints faced by microorganisms. The vector angle was greater than 45° and less than 45°, indicating that microorganisms were limited by phosphorus and nitrogen, respectively. The greater the deviation from 45°, the greater the degree of limitation, and the longer the vector length, the more severely limited by carbon. The results showed that ① the soil C/N and C/P of long-term straw returning ranged from 9.81 to 14.28 and from 14.58 to 21.92, with the mean values of 12.36 and 17.51, respectively, which were 6.0% and 4.2% lower than that at the initial stage of the experiment. The soil N/P was distributed between 1.27 and 1.57, with an average of 1.42, which was 2.2% higher than that in the initial stage. The soil C/N and C/P ratios showed a trend of first decreasing and then increasing, the soil N/P ratio basically showed a flat trend, and there was no significant difference in soil element metering ratios between different straw returning treatments. ② Compared with the 24-year long-term non-straw return treatment, the activities of ß-1,4-glucosidase (BG) and ß-1,4-N-acetylglucosaminidase (NAG) in the soil of the long-term straw mulching treatment increased by 134.4% and 107.5% (P<0.05), the activities of BG and alkaline phosphatase (AP) in the soil of the long-term straw mulching treatment decreased by 59.3% and 59.5% (P<0.05), respectively, and the activities of NAG in the soil of the long-term straw mulching treatment increased by 102.8% (P<0.05). Under the long-term straw returning treatment, soil microorganisms were faced with carbon and phosphorus limitation as a whole. Long-term straw mulching aggravated microbial carbon limitation, and animal-digested straw return could alleviate the degree of carbon limitation. Compared with that in the 24-year long-term non-straw return treatment, soil EEAC/N could be significantly reduced by the animal-digested straw return treatment, and soil EEAC/P could be increased by the direct straw return treatment. The three straw returning methods had no significant indigenous effect on soil EEAN/P. The overall vector angle was greater than 45°, and the vector length increased by 3.8%-20.1% compared with that in the initial stage. ③ Correlation analysis showed that C and N inputs were significantly negatively correlated with BG activity; available nitrogen was significantly correlated with NAG activity, AP activity, and EEAC/N; C/P was significantly positively correlated with EEAC/N; there were significant correlations between N/P and NAG activity, AP activity, EEAC/N, and EEAC/P; and there was no significant correlation between EEAN/P and any environmental factors. In conclusion, the availability of soil nitrogen and phosphorus elements and N/P ratio had significant effects on soil extracellular enzyme activity and stoichiometric characteristics under different long-term straw returning treatments. In the future, more attention should be paid to the improvement of organic carbon and the promotion of nitrogen and phosphorus availability in farmland soil in soil-efficient cultivation and agricultural production activities.

Fluorometry detection for trypsin via inner filter effect between cytochrome C and in-situ formed fluorescent thiochrome.

A fluorometry assay for trypsin sensitive determination has been presented. The fluorescence of the system at 370/445 nm is derived from thiochrome obtained by in-situ oxidation of thiamine. Based on the inner filter effect, cytochrome C (Cyt C) can quench the fluorescence at 445 nm effectively. Cyt C is specifically hydrolyzed by trypsin through an enzymatic reaction, giving rise to the enhancement of the fluorescence intensity. The change value of fluorescence intensity is proportional to trypsin concentration, which is successfully used for trypsin quantitative detection. This method exhibits good repeatability and selectivity with a detection limit of 0.15 µg mL-1 and a quantification limit of 0.50 µg mL-1 for trypsin sensing. Moreover, it is applied to detect trypsin in practical serum and urine samples with accurate results. The proposed assay is not only a promising candidate for trypsin determination in practical application but also a potentially valuable tool in urine comprehensive analysis and disease diagnosis.

FRET-based fluorometry assay for curcumin detecting using PVP-templated Cu NCs.

A novel fluorometric strategy is proposed for detecting curcumin by polyvinyl pyrrolidone-templated Cu NCs (PVP-Cu NCs) as a fluorescent probe which exhibits excitation/emission peaks at 380/510 nm. The fluorescent excitation and emission spectra of PVP-Cu NCs have a striking overlap with the UV-vis spectrum of curcumin, and the fluorescence lifetime of PVP-Cu NCs decreases after the addition of curcumin. Curcumin leads to fluorescence quenching based on fluorescence resonance energy transfer. This method allows for the determination of curcumin in the range of 0.1-10 µg mL-1 and the detection limit is 21 ng mL-1. Furthermore, this method displays good selectivity and is successfully applied for real sample analysis.

In situ synthesis of nitrogen site activated cobalt sulfide@N, S dual-doped carbon composite for a high-performance asymmetric supercapacitor.

Cobalt sulfides with high theoretical capacity are considered as potential electrodes for supercapacitors (SCs). However, the insufficient reactive sites and low electrical conductivity of bulky cobalt sulfides restrict their applications. Here, we proposed an efficient approach for in situ formation of nitrogen site activated cobalt sulfide@N, S dual-doped carbon composite (CS@NSC) by vulcanizing the cobalt-glutamine complex (CG) precursor in a tube furnace. The effects of the molecular structure and calcination temperature of CG precursors on the morphology, structure and electrochemical performance of CS@NSC were studied. The designed CS@NSC-2 exhibited a specific capacity of 593 C g-1 at the current density of 1 A g-1 and good cyclic stability with 88.7% retention after 2000 cycles. Moreover, an asymmetric supercapacitor (ASC) was fabricated by CS@NSC-2 (positive electrode) and activated carbon (AC) (negative electrode), which delivered ultra-high energy density of 67.8 Wh kg-1 at a power density of 400 W kg-1 and possessed 83.1% capacitance retention after 5000 cycles. The eco-friendly method was also suitable for synthesizing nickel sulfide. This work may provide an innovative horizon for the in situ formation of active sites in electrode materials.

Tri-(Fe/F/N)-doped porous carbons as electrocatalysts for the oxygen reduction reaction in both alkaline and acidic media.

Developing a low cost, sustainable and high-performance precious-metal free catalyst to replace platinum (Pt)-based catalysts for the oxygen reduction reaction (ORR) in fuel cells has recently attracted significant attention. It is crucial to produce more abundant and more uniformly dispersed ORR active sites for improving the ORR performance of the catalyst. Herein, we synthesized tri-(Fe/F/N)-doped porous carbons as high-efficiency electrocatalysts for the ORR by using Fe-zeolitic imidazolate framework-8 (Fe-ZIF-8) and ammonium fluoride as precursors. The results indicate that the as-prepared FeFNC-5 catalysts exhibit superior ORR activity, methanol tolerance, and long-term stability compared to commercial 20 wt% Pt/C in both alkaline and acidic media because of the abundant and dispersed Fe-Nx and pyridinic-N active sites, high specific surface area, and hierarchical porous structure. This work provides a new method and insights into the synthesis of Fe, F, and N triple-doped porous carbons as high-efficiency ORR electrocatalysts.

Designed MnS/Co9S8 micro-flowers composites with serrate edges as high-performance electrodes for asymmetric supercapacitor.

The three-dimensional (3D) MnS/Co9S8 (MCS) micro-flowers composites with serrate edges on Ni foam were successfully prepared by a facile hydrothermal method. The time-dependent experiments showed that the structure was assembled by two-dimensional (2D) nanobelts. The serrate edges structures of MCS can enrich electroactive sites and enhance the specific capacity (1070 C/g at 1 A/g). In addition, MCS exhibited good cycling stability of 86% after 1000 cycles. Further, an asymmetric supercapacitor device was constructed by using MCS as the positive electrode and activated carbon (AC) as the negative electrode, which exhibited high energy density of 34.1 Wh/kg at power density of 400 W/kg with good cycling stability. The superior electrochemical performances demonstrated that the micro-flowers composites with serrate edges could offer a new opportunity in developing energy storage devices.

DNA-assisted synthesis of nickel cobalt sulfide nanosheets as high-performance battery-type electrode materials.

Nickel-cobalt sulfide (NiCo2S4) nanosheets were successfully fabricated by an environment-friendly hydrothermal method with the assistance of DNA molecules. Different morphological samples were prepared by adjusting the concentrations of DNA. The NiCo2S4 nanosheets derived from 0.2 µg/mL DNA (denoted as DS2) exhibited a desirable mesoporous feature with superior electrochemical performance compared with other samples. As a battery-type electrode material, it exhibited a high specific capacity of 644C g-1 at the current density of 1 A/g, superior rate capability of 74.3% retention at 15 A/g and remarkable cycling stability of 90.5% after 1500 cycles. Thus, the electrode material of NiCo2S4 nanosheets assisted by DNA molecule offered great potential in eco-friendly energy storage device applications.