Spontaneous aggregation-enhanced electrochemiluminescence via galvanic strategy.

Researchers unremittingly strive to develop innovative luminophores to enhance intrinsic electrochemiluminescence (ECL) performance. However, the potential to harness facile strategies, such as manipulating the physical properties of luminophores while retaining functional chemical properties to fabricate cost-effective ECL complexes, remains underexplored. Herein, we reported a novel and efficient one-step galvanic technique to actualize aggregation-enhanced ECL (AEECL) of ruthenium complexes. It marked the first instance of the galvanic process being employed to synthesize aggregate luminophores through electrostatic attraction. The ECL intensity and efficiency of the prepared ruthenium complexes with AEECL properties surpassed traditional ruthenium complexes by 8.9 and 13.6 times, respectively, outperforming most reported luminophores. Remarkably, the target luminophore exhibited high stability across varied scan rates and temperatures. Furthermore, a binder-free and carbon paper-based AEECL analytical device for lidocaine detection was fabricated, achieving a satisfactory detection limit (0.34 nM) and selectivity. The convenient modulation strategy of aggregate structure, along with the transformative leap from insufficient ECL to AEECL, bring forth a new revenue in aggregate science. This research also promises a universally applicable and versatile protocol for future biological analysis and bioimaging applications.

Cu/Au nanoclusters with peroxidase-like activity for chemiluminescence detection of α-amylase.

Herein, a novel chemiluminescence method was developed for efficient and sensitive detection of α-amylase activity. α-Amylase is closely related to our life, and α-amylase concentration is a marker for the diagnosis of acute pancreatitis. In this paper, Cu/Au nanoclusters with peroxidase-like activity were prepared using starch as a stabilizer. Cu/Au nanoclusters can catalyze H2O2 to generate reactive oxygen species and increase the CL signal. The addition of α-amylase makes the starch decompose and causes the nanoclusters to aggregate. The aggregation of the nanoclusters caused them to increase in size and decrease in the peroxidase-like activity, resulting in a decrease in the CL signal. α-Amylase was detected by the CL method of signal changes caused by dispersion-aggregation in the range of 0.05-8 U mL-1 with a low detection limit of 0.006 U mL-1. The chemiluminescence scheme based on the luminol-H2O2-Cu/Au NC system is of great significance for the sensitive and selective determination of α-amylase in real samples, and the detection time is short. This work provides new ideas for the detection of α-amylase based on the chemiluminescence method and the signal lasts for a long time, which can realize timely detection.

Colorimetric determination of cysteine based on Au@Pt nanoparticles as oxidase mimetics with enhanced selectivity.

A H2O2-free colorimetric protocol based on urchin-like Au@Pt nanoparticles (Au@Pt NPs) has been developed for the sensitive and selective determination of cysteine (Cys). We verified the intrinsic oxidase-like activity of the Au@Pt NPs. They can act as artificial mimic oxidases to catalyse the oxidization of 3,3',5,5'-tetramethylbenzidine (TMB) with the assistance of dissolved oxygen, avoiding the use of H2O2 in the colorimetric determination of Cys. In addition, the discrimination of Cys from the other two biothiol analogues, homocysteine and glutathione, can be easily realized through a simple ageing process. HNO3 is added to this colorimetric system to terminate the reaction by oxidizing ox-TMB (oxidized form of TMB) to diphenoquinone (DPQ), thus generating a characteristic absorption peak of DPQ at 450 nm. By recording the absorbance at 450 nm, interference from the aggregated Au@Pt NPs (absorption peak at 670 nm) when 650 nm (the characteristic absorption peak of ox-TMB) is used as the absorption wavelength can be eliminated. We investigated this H2O2-free colorimetric protocol and obtained high sensitivity, with a detection limit of 1.5 nM and relatively high selectivity. The analytical performance for real samples was further explored. The Au@Pt NP-based H2O2-free colorimetric protocol is of great significance for the sensitive and selective determination of Cys in practical samples in different scenarios.

A Fast Dual-responsive OFF-ON Fluorescent Probe for Cysteine and Glutathione without Interference from Homocysteine.

Abnormal levels of biothiols, such as cysteine (Cys), homocystine (Hcy), and glutathione (GSH), are generally known to result in various diseases. A fast dual-responsive OFF-ON fluorescent probe HBO-AC was synthesized and developed. Non-fluorescent HBO-AC can sense Cys by regaining fluorescence at 444 nm within 10 min and a response to GSH by restoring fluorescence at 349 nm within 20 min. There is no mutual interference with Δλ ca. 100 nm. A novel method was developed by utilizing a low reaction rate between HBO-AC and Hcy to eliminate common interference from Hcy. A successful determination of Cys and GSH in fetal bovine serum (FBS) indicated that the probe had potential application for clinical diagnosis. Moreover, it was confirmed that HBO-AC can resist interference from protein to some extent, since FBS was not pretreated before use.

A colorimetric sensor for detecting thiourea based on inhibiting peroxidase-like activity of gold-platinum nanoparticles.

In this study, gold-platinum nanoparticles (Au@PtNPs) with peroxidase-like activity were synthesized. In the absence of thiourea (TU), the Au@PtNPs can catalyze the decomposition of hydrogen peroxide, and oxidize 3,3',5,5'-tetramethylbenzidine dihydrochloride (TMB, colorless) into oxidized 3,3',5,5'-tetramethylbenzidine dihydrochloride (oxTMB, blue). The peroxidase-like activity of the Au@PtNPs is inhibited in the presence of TU, and TMB cannot be oxidized to oxTMB effectively, and no blue color could be observed. Based on this finding, a novel colorimetric sensor for detecting TU is proposed. The absorbance response curve showed a good linearity for the concentration of TU in the range of 10 nmol L-1 to 10 µmol L-1 with a correlation coefficient of R2 = 0.999, and the limit of detection is 9.57 nmol L-1. The colorimetric sensor possesses excellent selectivity, anti-interference ability, and application value in actual samples.

New Insights into the Operating Voltage of Aqueous Supercapacitors.

The main limitation of aqueous supercapacitors (SCs) lies in their narrow operating voltages, especially when compared with organic SCs. Fundamental understanding of factors relevant to the operating voltage helps providing guidance for the assembly of high-voltage aqueous SCs. In this regard, this concept analyzes the deciding factors for the operating voltage of aqueous SCs. Strategies applied to expand the operating voltage are summarized and discussed from the aspects of electrolyte, electrode, and asymmetric structure. Dynamic factors associated with water electrolysis and maximally using the available potential ranges of electrodes are particularly emphasized. Finally, other promising approaches that have not been explored and their challenges are also elaborated, hoping to provide more insights for the design of high-voltage aqueous SCs.

Isolation, characterization, and in rats plasma pharmacokinetic study of a new triterpenoid saponin from Dianthus superbus.

One new oleanolic acid triterpenoid saponin, 3-O-ß-D-glucopyranosyl olean-11, 13(18)-diene-23,28-dioic acid, (hereafter referred to as DS-1) was isolated from the traditional Chinese medicinal plant Dianthus superbus (D. superbus). DS-1 plays an important role in the bioactivity of D. superbus. Thus, a sensitive, reliable and accurate reversed-phased liquid chromatography with tandem mass spectrometry (LC-MS/MS) in negative ion mode was developed and validated for the quantification and pharmacokinetic study of DS-1 in rats plasma. The pharmacokinetic profile showed that DS-1 was rapidly absorbed and eliminated in plasma, indicating that significant accumulation of the compound in biological specimen is unlikely. In addition, poor absorption into systemic circulation was observed after oral administration of DS-1, resulting in low absolute bioavailability (0.92 %).

Identification of candidate synovial membrane biomarkers after Achyranthes aspera treatment for rheumatoid arthritis.

Rheumatoid arthritis (RA) is a systemic autoimmune disease whose main symptom is a heightened inflammatory response in synovial tissues. To verify the anti-arthritic activities of Achyranthes aspera and its possible therapy-related factors on the pathogenesis of RA, the saponins in A. aspera root were isolated and identified to treat the collagen-induced arthritis (CIA) rats. Phytochemical analysis isolated and identified methyl caffeate, 25-S-inokosterone, 25-S-inokosterone ß-D-glucopyranosyl 3-(O-ß-D-glucopyranosyloxy)-oleanolate, and ß-D-glucopyranosyl 3-(O-ß-D-galactopyranosyl (1→2)(O-ß-D-glucopyranosyloxy)-oleanolate as main compounds in the root of A. aspera. Proteomics was performed to determine the differentially expressed proteins in either inflamed or drug-treated synovium of CIA rats. Treatment resulted in dramatically decreased paw swelling, proliferation of inflammatory cells, and bone degradation. Fibrinogen, procollagen, protein disulfide-isomerase A3, and apolipoprotein A-I were all increased in inflamed synovial tissues and were found to decrease when administered drug therapy. Furthermore, Alpha-1-antiproteinase and manganese superoxide dismutase were both increased in drug-treated synovial tissues. The inhibition of RA progression shows that A. aspera is a promising candidate for future treatment of human arthritis. Importantly, the total saponins found within A. aspera are the active component. Finally, autoantigens such as fibrinogen and collagen could act as inducers of RA due to their aggravation of inflammation. Given this, it is possible that the vimentin and PDIA3 could be the candidate biomarkers specific to Achyranthes saponin therapy for rheumatoid arthritis in synovial membrane.