Pentacenequinone-Modulated 2D GdSn-PQ Nanosheets as a Fluorescent Probe for the Detection of Enrofloxacin in Biological and Environmental Samples.

The fate and effects of fluoroquinolone antibacterial (FQ) on the environment are important since there appears to be a surge in FQ resistance like enrofloxacin (ENR) in both environmental and clinical organisms. Numerous reports indicate that the sensing capabilities of these antibiotics need to be improved. Here, we have investigated the interaction of ENR with our synthesized pentacenequinone-modulated gadolinium-tin (GdSn-PQ) nanosheets and the formation of intermolecular interactions that caused the occurrence of aggregation-induced emission enhancement. The concept for designing hybrid metallic nanosheets comes from the unique features inherited from the parent organic precursor. Due to the distinct interaction between ENR and GdSn-PQ, the interstate conversion (ISC) between GdSn-PQ and ENR induces a significant wavelength shift in photoluminescence (PL), improving reliability, selectivity, and visibility compared to quenching- or AIEE-based methods without peak shifts, allowing for highly sensitive and visually detectable analyses. The fluorescence signal of GdSn-PQ exhibited a linear relationship (R2 = 0.9911), with the added ENR concentrations ranging from 5 to 90 nM, with a detection limit of 0.10 nM. We have demonstrated its potential and wide use in the detection of ENR in biological samples (human urine and blood serum) and environmental samples (tap water and seawater) with a recovery rate of 98- 108%. The current approach has demonstrated that the 2D GdSn-PQ nanosheet is a novel and powerful platform for future biological and environmental studies.

Crosstalk between H2O2 and Ca2+ signaling is involved in root endophyte-enhanced tanshinone biosynthesis of Salvia miltiorrhiza.

Tanshinones are bioactive ingredients derived from the herbal plant Salvia miltiorrhiza and are used for treating diseases of the heart and brain, thus ensuring quality of S. miltiorrhiza is paramount. Applying the endophytic fungus Trichoderma atroviride D16 can significantly increase the content of tanshinones in S. miltiorrhiza, but the potential mechanism remains unknown. In the present study, the colonization of D16 effectively enhanced the levels of Ca2+ and H2O2 in the roots of S. miltiorrhiza, which is positively correlated with increased tanshinones accumulation. Further experiments found that the treatment of plantlets with Ca2+ channel blocker (LaCl3) or H2O2 scavenger (DMTU) blocked D16-promoted tanshinones production. LaCl3 suppressed not only the D16-induced tanshinones accumulation but also the induced Ca2+ and H2O2 generation; nevertheless, DMTU did not significantly inhibit the induced Ca2+ biosynthesis, implying that Ca2+ acted upstream in H2O2 production. These results were confirmed by observations that S. miltiorrhiza treated with D16, CaCl2, and D16+LaCl3 exhibit H2O2 accumulation and influx in the roots. Moreover, H2O2 as a downstream signal of Ca2+ is involved in D16 enhanced tanshinones synthesis by inducing the expression of genes related to the biosynthesis of tanshinones, such as DXR, HMGR, GGPPS, CPS, KSL and CYP76AH1 genes. Transcriptomic analysis further supported that D16 activated the transcriptional responses related to Ca2+ and H2O2 production and tanshinones synthesis in S. miltiorrhiza seedlings. This is the first report that Ca2+ and H2O2 play important roles in regulating fungal-plant interactions thus improving the quality in the D16-S. miltiorrhiza system.

Two-dimensional oxygen-deficient ZnO1-x nanosheet as a highly selective and sensitive fluorescence probe for ferritin detection: the electron transfer biosensor (ETBS).

Iron proteins are of great scientific interest due to their importance as an excellent biomarker for human diseases. Ferritin (Fe3+), being an iron-rich blood protein, is related to various diseases like anemia and cancer. For the first time, we have developed a highly sensitive and selective ferritin biosensor based on fluorescent oxygen-deficient zinc oxide nanosheets through hydrothermal and probe-ultrasonication combined methods. The fluorescence study showed an intense bluish-green fluorescence at λex = 370 nm, after optimization at different excitation wavelengths. In addition, the fluorescence of ZnO1-x nanosheets can be efficiently quenched due to electron transfer reactions in order to achieve quantification analysis. The limit of detection (LOD) was calculated to be 0.015 nM (7.2 ng mL-1) with high linearity (R2 = 0.9930). In addition, the real-world application of the proposed biosensor has been performed on human blood serum samples in the presence of various interfering analytes showing high selectivity and sensitivity with a regression value R2 = 0.9980 indicating the current approach is an excellent biosensor platform.

Synthesis of 2D VO2 Nanosheets for the Dual Optical Sensor Method by Colorimetric and Fluorometric Sensing of Catecholamines.

For the first time, we report a dual optical sensor method (DOSM) using novel 2D VO2 nanosheets to act as fluorometric and colorimetric sensors to perform quantitative analysis of epinephrine (EP) and dopamine (DA). The wide color spectrum of the 2D vanadium oxidation series and specifically metastable blue 2D VO2 nanosheets were used to develop a DOSM biosensor. DA and EP are the major catecholamines in the human body that play vital roles as neurotransmitters and stress-responsive hormones of the endocrine system, respectively. Accurate and selective detection of these biomolecules can assist in the diagnosis of many neuroendocrine system-related diseases. The newly synthesized 2D VO2 nanosheet sensor showed bluish-green fluorescence as the first-ever fluorescence from 2D VO2 nanosheets. This sensor showed dual-function sensing toward EP by a dominant color change and fluorescence quenching. It is capable of individually detecting and quantifying both EP and DA with high selectivity and sensitivity by using both colorimetry and fluorometry simultaneously, with the detection limits of 1.07 and 5.54 µM for colorimetric analysis, respectively, and 48.07 and 3.98 µM for fluorescence analysis, respectively. The DOSM sensor was directly applied to real urine samples and gained satisfactory recovery above 90% by means of spiked concentrations. This study has opened a new platform using the DOSM and the vanadium oxidation spectrum in a much more effective way for biosensing. The fluorescence capabilities of this metal oxide can be further applied to many sensor applications based on both fluorescence and colorimetric detection.

SnO2-xNx based tpod nanostructure for SARS-CoV2 spike protein detection.

The worldwide spreading of severe acute respiratory syndrome SARS-CoV2 pandemic, a massive setback to every human being. In response to strategies actions against Covid-19 spreading many detection, prevention, and post-measures are being studied in large capacities. Association of SARS-CoV2 with ACE2 is well acknowledged and used for developing point-of-care detection kits. Recently, cases and studies have surfaced showing relation of ACE I/D polymorphism with spreading of SARS-CoV2 and highlighted a slip section towards detection and these studies show specificity with older males, high diabetes, and hypertension. To address the raised concern, we report synthesis of unique SnO2-xNx tpod nanostructure, showing affirmative attachment to both ACE1 and ACE2 efficiently. The attachment is examined in different ratios and studied with µ-Raman spectroscopy. The tpod nanostructure has served with its signature raman signals and used as probe for detection of SARS-CoV2 spike protein (S1). The linearity response for tpod raman signal at 630.4 cm-1 shows R2 0.9705, comparatively peak 1219.13 cm-1 show R2 0.9865 and calculated limit of detection of 35 nM.

"Synergistic effect" based novel and ultrasensitive approach for the detection of serotonin using DEM-modulated bimetallic nanosheets.

Neurotransmitters have been of immense scientific interest due to their importance as human-health biomarkers. Several reports suggest necessary improvisations in the sensing capabilities of these neurotransmitters. Herein, the authors report a novel synthesis methodology for bimetallic aluminum-tungsten (Al-W) nanosheets, with the hybrid nanostructure showing high specificity toward serotonin neurotransmitters. The inspiration to design hybrid metallic nanosheets depends on the inherited optical properties of the parent precursors. The interstate conversion (ISC) between Al-W nanosheets promoted photoluminescent behavior with serotonin. The PL study shows that serotonin drastically enhanced λem at 335 nm. The importance of emission below the visible spectrum is to modulate any possible aggregation-induced emissions, which earlier troubled analytical chemists. The understanding of the selective detection of serotonin from a group of similar neurotransmitters is discussed with nanomolar quantification. The quantified detection limit using Al-W nanosheets is 0.05 nm with high linearity (R2 = 0.9906). Furthermore, real-world quantification studies have been performed on human urine and serum samples with R2 of 0.9938 and 0.9801, respectively.

Development of Two-Dimensional Functional Nanomaterials for Biosensor Applications: Opportunities, Challenges, and Future Prospects.

New possibilities for the development of biosensors that are ready to be implemented in the field have emerged thanks to the recent progress of functional nanomaterials and the careful engineering of nanostructures. Two-dimensional (2D) nanomaterials have exceptional physical, chemical, highly anisotropic, chemically active, and mechanical capabilities due to their ultra-thin structures. The diversity of the high surface area, layered topologies, and porosity found in 2D nanomaterials makes them amenable to being engineered with surface characteristics that make it possible for targeted identification. By integrating the distinctive features of several varieties of nanostructures and employing them as scaffolds for bimolecular assemblies, biosensing platforms with improved reliability, selectivity, and sensitivity for the identification of a plethora of analytes can be developed. In this review, we compile a number of approaches to using 2D nanomaterials for biomolecule detection. Subsequently, we summarize the advantages and disadvantages of using 2D nanomaterials in biosensing. Finally, both the opportunities and the challenges that exist within this potentially fruitful subject are discussed. This review will assist readers in understanding the synthesis of 2D nanomaterials, their alteration by enzymes and composite materials, and the implementation of 2D material-based biosensors for efficient bioanalysis and disease diagnosis.

Recent advances in nanomaterials-based optical sensors for detection of various biomarkers (inorganic species, organic and biomolecules).

This review briefly emphasizes the different detection approaches (electrochemical sensors, chemiluminescence, surface-enhanced Raman scattering), functional nanostructure materials (quantum dots, metal nanoparticles, metal nanoclusters, magnetic nanomaterials, metal oxide nanoparticles, polymer-based nanomaterials, and carbonaceous nanomaterials) and detection mechanisms. Furthermore, the emphasis of this review is on the integration of functional nanomaterials with optical spectroscopic techniques for the identification of various biomarkers (nucleic acids, glucose, uric acid, oxytocin, dopamine, ascorbic acid, bilirubin, spermine, serotonin, thiocyanate, Pb2+ , Cu2+ , Hg2+ , F- , peptides), and cancer biomarkers (mucin 1, prostate specific antigen, carcinoembryonic antigen, CA15-3, human epidermal growth factor receptor 2, C-reactive protein, and interleukin-6). Analytical characteristics of nanomaterials-based optical sensors are summarized in the tables, providing the insights of nanomaterials-based optical sensors for biomarkers detection. Finally, the opportunities and challenges of nanomaterials-based optical analytical approaches for the detection of various biomarkers (inorganic, organic, biomolecules, peptides and proteins) are discussed.

A MALDI-MS-based impact assessment of ZnO nanoparticles, nanorods and quantum dots on the lipid profile of bacterial pathogens.

MALDI-MS was used for studying the impact of zinc oxide (ZnO) nanomaterials on Pseudomonas aeruginosa and Staphylococcus aureus. The growth patterns of both these bacterial pathogens in the presence of the ZnO nanomaterials and the subsequent lipidomic changes were assessed using an optimized simple, rapid MALDI-MS based methodology. All three nanostructures tested exhibited differential bactericidal activity unique to P. aeruginosa and S. aureus. The results indicated that the ZnO nanomaterials were highly inhibitory to S. aureus even at 70 mg L-1, while in the case of P. aeruginosa, the ZnO nanomaterials were compatible for up to 10 h and beyond 10 h only marginal growth inhibition was observed. The results proved that the shapes of the ZnO nanomaterials did not affect their toxicity properties. MALDI-MS was applied to study the lipidomic changes of P. aeruginosa and S. aureus after nanomaterial treatment, in order to throw light on the mechanism of growth inhibition. The results from the MALDI-MS studies showed that the ZnO nanostructures exhibited only marginal changes in the lipidomic profile both in the case of P. aeruginosa and S. aureus. These preliminary results indicate that the mechanism of growth inhibition by the ZnO nanomaterial is not through lipid-based interactions, but apparently more so via protein inhibitions.

Synthesis of Fluorescent Titanium Nanoclusters at ambient temperature for highly sensitive and selective detection of Creatine Kinase MM in myocardial infarction.

Fluorescent-based biosensing in Photoluminescence nanomaterials has emerged as a new sensing platform commonly used for disease diagnosis. However, the synthesis of Titanium nanoclusters is highly challenging since Titanium is easily oxidized into TiO2 at ambient temperature. To overcome this problem, we used an acidic medium and simple and robust protocol to synthesize the Titanium nanoclusters of 3-4 nm diameter, which could report the first fluorescent Titanium nanoclusters. New approaches for the novel synthesis of TiNCs can be used for rapid sensing of myocardial infarction (cardiac arrest). In converting creatine to phosphocreatine, CK-MM activates the reaction to convert ATP to ADP, thereby releasing the phosphate groups. Titanium nanoclusters bind strongly to the phosphate group and then quench the Fluorescence. Thus, this phenomenon can be further applied for quantification approaches. The quenching of fluorescence intensity with CK-MM concentration is linear with R² = 0.9829. The current approach can be applied for CK-MM sensing for a wide concentration range (0.625 U/L - 10 U/L). The detection limit was 0.2513 ng/ml in aqueous medium and 0.3465 ng/ml in human serum with high sensitivity when compared with the previous reported methods. Also, this is the first fluorescent-based sensing method to detect CK- MM. The fluorescent TiNCs is a novel platform to be widely applied for the phosphopeptide and phosphoprotein analysis due to the strong and covalent bondings between Ti with P atoms in the near future in medicine, biomedicine, and biological fields.

Unique Properties of Surface-Functionalized Nanoparticles for Bio-Application: Functionalization Mechanisms and Importance in Application.

This review tries to summarize the purpose of steadily developing surface-functionalized nanoparticles for various bio-applications and represents a fascinating and rapidly growing field of research. Due to their unique properties-such as novel optical, biodegradable, low-toxicity, biocompatibility, size, and highly catalytic features-these materials are considered superior, and it is thus vital to study these systems in a realistic and meaningful way. However, rapid aggregation, oxidation, and other problems are encountered with functionalized nanoparticles, inhibiting their subsequent utilization. Adequate surface modification of nanoparticles with organic and inorganic compounds results in improved physicochemical properties which can overcome these barriers. This review investigates and discusses the iron oxide nanoparticles, gold nanoparticles, platinum nanoparticles, silver nanoparticles, and silica-coated nanoparticles and how their unique properties after fabrication allow for their potential use in a wide range of bio-applications such as nano-based imaging, gene delivery, drug loading, and immunoassays. The different groups of nanoparticles and the advantages of surface functionalization and their applications are highlighted here. In recent years, surface-functionalized nanoparticles have become important materials for a broad range of bio-applications.

Introducing Tb4+ in (Ce0.09/Eu0.96)Tb0.92Mo1.1O6.93 Metal Oxide at Room Temperature and Its Use in Amyloid Defibrillation.

Tunable optical properties in nanomaterials enable a variety of applications in multidisciplinary areas. These properties are directly related to several different factors such as solvent conditions, synthesis methods, and most significantly, the oxidation states of metals participating in the absorption or emission properties. Lanthanide metals containing ABO3 perovskites are among such nanomaterials that can be tuned to a great extent by only modifying the charged states on the metals in the composition. We report a green synthesis method through sonication to synthesize ABO3 perovskites to incorporate Tb4+ into the perovskite composition at room temperature. The optical properties of the nanomaterial show emission in the entire ultraviolet-visible-near-infrared spectral regions through charge transfer between europium and terbium. The combination of cerium (C), molybdenum (M), europium (E), and terbium (T) results in a sheet-like CMET perovskite obeying hexagonal geometry. The nanomaterial is highly stable in an aqueous medium, showing finely suspended Tyndall effect due to particle size <300 nm. Owing to their wide range of emission behavior, surface charge, and aqueous stability, CMET perovskites were used to study the defibrillation of hen egg-white lysozyme (HEWL) as an amyloid model protein. The intrinsic property of the nanomaterial assists in the interaction of the fibrils with the perovskite and the emission range becomes the reporter of the defibrillation. Infrared spectroscopy shows the change in the material properties during the defibrillation. A preliminary test on the varying concentration of HEWL incubated with CMET perovskites shows linear behavior with R2 = 0.9841. The tunable emission characteristic and aqueous stability of the perovskite material make it suitable for future biological applications.

Sand bath assisted green synthesis of carbon dots from citrus fruit peels for free radical scavenging and cell imaging.

A sand bath assisted strategy for the synthesis of fluorescent carbon dots (CDs) using citrus fruit peels as a renewable green resource is reported in this work. The CDs were synthesized without any alkaline or acidic environment. The synthesized CDs were characterized by various spectroscopic and microscopy techniques. The CDs exhibited excellent water solubility and superior optical properties like excitation dependent emission, and multicolor fluorescence. In addition, the CDs have exhibited remarkable free radical scavenging activity (EC50: 4.7382 µg ml-1).The CDs were highly biocompatible and showed lower toxicity. The CDs when modified with folic acid have shown a significant potential as biological labels for cellular imaging at multiple excitations. Synthesis of CDs from natural fruit peels as an excellent carbon source for versatile applications has been demonstrated.

2D CTAB-MoSe2 Nanosheets and 0D MoSe2 Quantum Dots: Facile Top-Down Preparations and Their Peroxidase-Like Catalytic Activity for Colorimetric Detection of Hydrogen Peroxide.

We report the facile and economic preparation of two-dimensional (2D) and 0D MoSe2 nanostructures based on systematic and non-toxic top-down strategies. We demonstrate the intrinsic peroxidase-like activity of these MoSe2 nanostructures. The catalytic processes begin with facilitated decomposition of H2O2 by using MoSe2 nanostructures as peroxidase mimetics. In turn, a large amount of generated radicals oxidizes 3,3,5,5-tetramethylbenzidine (TMB) to produce a visible color reaction. The enzymatic kinetics of our MoSe2 nanostructures complies with typical Michaelis-Menten theory. Catalytic kinetics study reveals a ping-pong mechanism. Moreover, the primary radical responsible for the oxidation of TMB was identified to be È®2- by active species-trapping experiments. Based on the peroxidase mimicking property, we developed a new colorimetric method for H2O2 detection by using 2D and 0D MoSe2 nanostructures. It is shown that the colorimetric sensing capability of our MoSe2 catalysts is comparable to other 2D materials-based colorimetric platforms. For instance, the linear range of H2O2 detection is between 10 and 250 µM by using 2D functionalized MoSe2 nanosheets as an artificial enzyme. Our work develops a systematic approach to use 2D materials to construct novel enzyme-free mimetic for a visual assay of H2O2, which has promising prospects in medical diagnosis and food security monitoring.

Correction: Progress of electrospray ionization and rapid evaporative ionization mass spectrometric techniques for the broad-range identification of microorganisms.

Correction for 'Progress of electrospray ionization and rapid evaporative ionization mass spectrometric techniques for the broad-range identification of microorganisms' by Suresh Kumar Kailasa et al., Analyst, 2019, 144, 1073-1103, DOI: 10.1039/C8AN02034E.

Photoluminescent hydrophilic cyclodextrin-stabilized cysteine-protected copper nanoclusters for detecting lysozyme.

Lysozyme (LYZ) sensors have attracted increased attention because rapid and sensitive detection of LYZ is highly desirable for various diseases associated with humans. In this research, we designed L-cysteine-protected ultra small photoluminescent (PL) copper nanoclusters (CuNCs) conjugated with ß-cyclodextrin (ß-CD) for rapid detection of LYZ in human serum samples at room temperature. The proposed ß-CD-CuNCs exhibited excellent water solubility, ultrafine size, good dispersion, bright photoluminescence, and good photostability. The ß-CD-CuNCs exhibit an excitation and emission maximum at 370 nm and 492 nm, respectively, with an absolute quantum yield (QY) of 54.6%. ß-CD-CuNCs showed a fluorescence lifetime of 12.7 ns. The addition of LYZ would result in PL quenching from ß-CD-CuNCs. The lowest detectable LYZ concentration was 50 nM for the naked eye and the limit of detection (LOD) and limit of quantification (LOQ) were 0.36 nM and 1.21 nM, respectively, by emission measurement observed in the LYZ concentration range from 30 to 100 nM. It is important to note that the PL ß-CD-CuNC strategy possessed great selectivity toward LYZ relative to other biomolecules. The proposed nanosensor was efficiently applied to determine the LYZ level in human serum sample average recoveries from 96.15 to 104.05% and relative standard deviation (RSD) values lower than 3.0%. Moreover, the proposed sensing system showed many advantages, including high speed, high sensitivity, high selectivity, low cost, and simple preparation.

The emergence of red fluorescence from two-dimensional nitrogenated-stanene oxide nanosheets.

The instigation of fluorescence in 2D metal oxide nanosheets is a daunting task to achieve. In the present work, we have synthesized bright red fluorescent stanene oxide (rStNS nanosheets) using an exceptionally simple method. Tin(ii) chloride added to a complex solvent (non-aqueous solution) of acetone and acetonitrile was sonicated and incubated at ambient temperature for ∼six days. After three days (72 h), the solution turned light yellow with bright red fluorescence; this is possible due to interactions between Sn and nitrogen atoms in a nanoscale environment. The emission from rStNS nanosheets (λex = 370 nm) covered a broad range of the optical spectrum (with a prominent peak at 590 nm). Interestingly, after day five, the colour of the solution became darker, and the colour of fluorescence changed from red to green (gStNS nanosheets).

Electrocatalytic synthesis of black tin oxide nanomaterial as photothermal agent for cancer therapy.

Photothermal therapy (PTT) is among the popular approach for treating solid tumours. The rapid killing of cancer cells under the influence of infrared radiation by a rapid increase in the temperature of the remote area now demands external agents with high photothermal transduction efficiency (PTE). Despite their improved PTE, black nanomaterials such as black phosphorus and titanium oxide are unable to meet the challenges in the physiological conditions. To address this major concern, we have developed black tin oxide (bSnO) with enhanced capabilities to respond in the physiological milieu. To make the synthesis cost-effective and eco-friendly, we have used electrochemical oxidation at 5 V and 100 mA to achieve ∼15 nm nanoparticle of bSnO. The as-synthesized bSnO exhibited high NIR absorption as well as high photothermal transduction efficiency. To circumvent the low aqueous solubility and photostability, bSnO was functionalized with polyethyleneimine (PEI). Upon exposure to 808 nm laser for ∼8-10 min, the temperature of the bSnO@PEI solution reached ∼58.5 °C. PTE of bSnO@PEI was calculated to be 51.2%. Owing to its high biological compatibility, tin offers relatively better stability when exposed to cancer cells in vitro and in vivo. In comparison to other black nanomaterials, bSnO@PEI was found to exhibit better response under NIR irradiance for non-invasive photothermal therapy of cancer.

A New Binary Matrix for Specific Detection of Mercury(II) Using Matrix-Assisted Laser Desorption Ionization Mass Spectrometry.

The development of simple, low-cost, and specific detection method for mercury (Hg(II)) ions in aqueous media using matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS) is a challenge due to matrix interferences and acidity that destroy weak interactions. Herein, a new binary matrix consists of mefenamic acid, and thymine (T) is applied for simple and specific detection of Hg(II) in aqueous solution and blood sample. Mass spectra show metal-to-ligand ratio of 1:2 (Hg(II):T) in which Hg(II) ions are bound to two T molecules and two water molecules, i.e., [Hg(T)2(H2O)2]. The method is simple and fast, and requires cheap reagents. In addition, the spectra show extremely specific signals for Hg(II) ions and insignificant signals in case of other competing metal ions. The concept of our protocol can be applied for other metals. The new matrix may be used for the analysis of small molecules with minimal interferences peaks.