Plasmonic surface-enhanced Raman scattering nano-substrates for detection of anionic environmental contaminants: Current progress and future perspectives.

Surface-enhanced Raman scattering spectroscopy (SERS) is a powerful technique of vibrational spectroscopy based on the inelastic scattering of incident photons by molecular species. It has unique properties such as ultra-sensitivity, selectivity, non-destructivity, speed, and fingerprinting properties for analytical and sensing applications. This enables SERS to be widely used in real-world sample analysis and basic plasmonic mechanistic studies. However, the desirable properties of SERS are compromised by the high cost and low reproducibility of the signals. The development of multifunctional, stable and reusable nano-engineered SERS substrates is a viable solution to circumvent these drawbacks. Recently, plasmonic SERS active nano-substrates with various morphologies have attracted the attention of researchers due to promising properties such as the formation of dense hot spots, additional stability, tunable and controlled morphology, and surface functionalization. This comprehensive review focused on the current advances in the field of SERS active nanosubstrates suitable for the detection and quantification of anionic environmental pollutants. The common fabrication methods, including the techniques for morphological adjustments and surface modification, substrate categories, and the design of nanotechnologically fabricated plasmonic SERS substrates for anion detection are systematically presented. Here, the need for the design, synthesis, and functionalization of SERS nano-substrates for anions of great environmental importance is explained in detail. In addition, the broad categories of SERS nano-substrates, namely colloid-based SERS substrates and solid-support SERS substrates are discussed. Moreover, a brief discussion of SERS detection of certain anionic pollutants in the environment is presented. Finally, the prospects in the fabrication and commercialization of pilot-scale handheld SERS sensors and the construction of smart nanosubstrates integrated with novel amplifying materials for the detection of anions of environmental and health concern are proposed.

Supramolecularly Engineered Reporters with Superoxide Anion-Triggered Chemiluminescence for Early Diagnosis and Efficient Amelioration of Acute Kidney Injury.

We report the "water-in-oil-in-water" preparation of kidney injury molecule-1-targeting supramolecular chemiluminescence (CL) reporters (PCCS), consisting of L-serine-modified poly(lactic-co-glycolic) acid (PLGA)-encapsulated peroxyoxalate (CPPO), chlorin e6 (Ce6) and superoxide dismutase (SOD), for early diagnosis and amelioration of acute kidney injury (AKI). In this system, O2 ⋅- , a biomarker of AKI, triggers the oxidation of CPPO to 1,2-dioxetanedione and subsequent CL emission via CL resonance energy transfer to Ce6. The L-serine-modified PLGA stabilizes CPPO and Ce6 via noncovalent interactions, promoting long-lived CL (half-lives: ≈1000 s). Transcriptomics analysis shows that PCCS reporters reduce the inflammatory response through glutathione metabolism and inhibition of the tumor necrosis factor signaling pathway. The reporters are able to non-invasively detect AKI at least 12 h earlier than current assays, and their antioxidant properties allow simultaneous treatment of AKI.

A luminescent Zn(II)-Containing Complex: Selective Sensing of Cr(VI) Anion and Application Values on Tuberculosis Care Through Increasing the Antibacterial Response of Macrophages.

A new Zn(II)-bearing metal-organic framework (MOF), namely, {[Zn2(L)2(H2O)]·8H2O·DMF}n (1) has been generated via applying 4,4'-([2,3'-bipyridine]-4,6-diyl) dibenzoic acid (H2L), a pyridine-carboxylic acid ligand under the solvothermal reaction conditions. In the aqueous solution, complex 1 could be utilized as the fluorescent sensor for the simultaneous detection of Cr2O72- ion and CrO42- ion with low limits of detection and high sensitivity. It is important that this luminescent material can be regenerated quickly and the sensing ability of this luminescent material can be reused for three times. Furthermore, the assessment of the compound's application values against the Tuberculosis care was carried out and simultaneously its relevant mechanism was investigated. First of all, the bacterial burden in the lung macrophages was measured with plate micro-dilution method. Besides, the signaling pathway of JAK/STAT activation was evaluated with real time RT-PCR. Molecular docking simulation reveals that the polar oxygens are the active sites that could form binding interactions the protein.

Exploring the Effects of Various Polymeric Backbones on the Performance of a Hydroxyaromatic 1,2,3-Triazole Anion Sensor.

Polymeric chemosensors are vital sensing tools because of higher sensitivity compared to their monomeric counterparts and tunable mechanical properties. This study focuses on the incorporation of a hydroxyaromatic 1,2,3-triazole sensor, 2-(4-phenyl 1H-1,2,3-triazol-1-yl)phenol (PTP), into polymers. By itself, the triazole has a selective, fluorometric response to the fluoride, acetate, and dihydrogen phosphate anions, and is most responsive to fluoride. Current investigations probe the suitability of various polymeric backbones for the retention and enhancement of the triazole's sensing capabilities. Backbones derived from acrylic acid, methyl methacrylate, divinylbenzene, and styrene were explored. UV-illumination, Nuclear Magnetic Resonance (NMR) titration, and ultraviolet-visible (UV-Vis) absorption and fluorescence spectroscopy studies are used to investigate the performance of newly synthesized polymers and the derivatives of PTP that serve as the polymers' precursors. Among the polymers investigated, copolymers with styrene proved best; these systems retained the sensing capabilities and were amenable to tuning for sensitivity.

Selective and sensitive detection of cyanate using 3-amino-2-naphthoic acid-based turn-on fluorescence probe.

The cyanate anion (CNO-), formed spontaneously within cells from urea and carbamoyl phosphate, usually functions as a biomarker of some diseases such as chronic kidney disease. Therefore, accurate determination of CNO- is highly demanded. Herein, a 3-amino-2-naphthoic acid-based "turn-on" fluorescence probe was developed for specific detection of CNO-. Upon the addition of sodium cyanate, the weak-fluorescent 3-amino-2-naphthoic acid could react with CNO-, which triggered intense emission of green fluorescence. And up to 9-fold fluorescence enhancement was observed. The fluorescence enhancement ratios displayed a good linear relationship with the concentrations of CNO- in the range of 0.5-200 µM. The high selectivity and sensitivity for CNO- detection were investigated with the detection limit as low as 260 nM. The probe was further successfully applied to determine CNO- in real samples such as tap water, human urine and serum samples, which offered a promising approach in practical applications. Graphical abstract.

A highly selective colorimetric sulfide assay based on the inhibition of the peroxidase-like activity of copper nanoclusters.

The authors report that sulfide ions are capable of inhibiting the peroxidase-like activity of copper nanoclusters (CuNCs). The catalytic activity of CuNCs toward the oxidation of the chromogenic substrate 3,3',5,5'-tetramethylbenzidine by H2O2 is remarkably decreased in the presence of sulfide. Based on this finding, a colorimetric assay was developed for the rapid determination of sulfide. Best operated at a wavelength of 652 nm, it has a 0.5 µM detection limit. The method is highly selective and has been successfully applied to the quantification of sulfide in environmental water samples. Graphical abstract The catalytic activity of CuNCs toward the oxidation of 3,3',5,5'-tetramethylbenzidine by H2O2 is remarkably decreased in the presence of sulfide ions. This finding has been applied to design a method for colorimetric quantification of sulfide ions in environmental samples.

Water-soluble MoS2 quantum dots are a viable fluorescent probe for hypochlorite.

A method is described for the fluorometric determination of hypochlorite. It is making use of molybdenum disulfide quantum dots (MoS2 QDs) as a fluorescent probe. The QDs are prepared by hydrothermal reaction of sodium molybdate with glutathione. They possess diameters typically ranging from 1.4 to 3.8 nm, excellent stability in water, and blue photoluminescence (with excitation/emission peaks located at 315/412 nm and a quantum yield of 3.7%). The fluorescence of the QDs is statically quenched by hypochlorite, and the Stern-Volmer plot is linear. Hypochlorite can be detected in the 5-500 µM concentration range with a 0.5 µM detection limit. The method has been successfully applied to the determination of hypochlorite in spiked samples of tap water, lake water, and commercial disinfectants. Graphical abstract Schematic of a method for the fluorometric determination of hypochlorite using MoS2 quantum dots as a fluorescent probe. It has been applied to hypochlorite assay in spiked samples of tap water, lake water, and commercial disinfectants.

Fluorometric determination of sulfide ions via its inhibitory effect on the oxidation of thiamine by Cu(II) ions.

A fluorometric assay is described for sulfide ions determination. It is based on the finding that the oxidation of the non-fluorescent substrate thiamine (TH) by Cu(II) in basic solution to form fluorescent thiochrome is inhibited by sulfide ions. This results in a decrease in fluorescence intensity which is proportional to the concentration of sulfide ions. Under the optimized conditions, the decrease in fluorescence, best measured at excitation/emission wavelengths of 370/440 nm, decreases linearly in the 0.03 to 2.5 µM sulfide ions concentration range. The detection limit is 20 nM. The method shows excellent selectivity over many potentially interfering ions and has been successfully applied to the determination of sulfide ions in spiked tap water, lake water and the synthetic wastewater samples. The method is time-saving and environmentally friendly, and in our perception shows a great potential in water quality inspection and environmental monitoring. Graphical abstract A fluorescent assay for sulfide ions detection is proposed based on its inhibitory effect on the oxidation of thiamine by Cu(II) ions.

Mass spectrometric detection of trace anions: The evolution of paired-ion electrospray ionization (PIESI).

The negative-ion mode of electrospray ionization mass spectrometry (ESI-MS) is intrinsically less sensitive than the positive-ion mode. The detection and quantitation of anions can be performed in positive-ion mode by forming specific ion-pairs during the electrospray process. The paired-ion electrospray ionization (PIESI) method uses specially synthesized multifunctional cations to form positively charged adducts with the anions to be analyzed. The adducts are detected in the positive-ion mode and at higher m/z ratios to produce excellent signal-to-noise ratios and limits of detection that often are orders of magnitude better than those obtained with native anions in the negative-ion mode. This review briefly summarizes the different analytical approaches to detect and separate anions. It focuses on the recently introduced PIESI method to present the most effective dicationic, tricationic, and tetracationic reagents for the detection of singly and multiply charged anions and some zwitterions. The mechanism by which specific structural molecular architectures can have profound effects on signal intensities is also addressed.

Evaluation of visible light and natural photosensitizers against Staphylococcus epidermidis and Staphylococcus saprophyticus planktonic cells and biofilm.

Antimicrobial photoinactivation (API) has shown some promise in potentially treating different nosocomial bacterial infections, however, its application on staphylococci, especially other than Staphylococcus aureus or methicillin-resistant S. aureus (MRSA) species is still limited. Although S. aureus is a well-known and important nosocomial pathogen, several other species of the genus, particularly coagulase-negative Staphylococcus (CNS) species such as Staphylococcus epidermidis and Staphylococcus saprophyticus, can also cause healthcare-associated infections and foodborne intoxications. CNS are often involved in resilient biofilm formation on medical devices and can cause infections in patients with compromised immune systems or those undergoing invasive procedures. In this study, the effects of chlorophyllin and riboflavin-mediated API on S. epidermidis and S. saprophyticus planktonic cells and biofilm are demonstrated for the first time. Based on the residual growth determination and metabolic reduction ability changes, higher inactivating efficiency of chlorophyllin-mediated API was determined against the planktonic cells of both tested species of bacteria and against S. saprophyticus biofilm. Some insights on whether aqueous solutions of riboflavin and chlorophyllin, when illuminated with optimal exciting wavelength (440 nm and 402 nm, respectively) generate O2-•, are also provided in this work.

Differentiation of Functional Groups and Biologically Relevant Anions Using AT-PAMAM Dendrimers.

Biological anions have often proven to be difficult analytes to differentiate in solution. Many of the anions bear similar structural characteristics and similar charge states. Using a commercially available indicator and AT-PAMAM dendrimers, a sensing ensemble for a number of biological anions was constructed. The system was able to identify each of the different analytes as well as the regioisomers of three different tricarboxylates. The system shows responsiveness to not only functional group identity but also the charge state and identity of the anionic species.

Mechanosynthesis of Polyureas and Studies of Their Responses to Anions.

Polyureas (PUs) have already found wide practical applications, and various methods of their synthesis have been reported. In this manuscript, we wished to report the very first mechanochemical approach towards aromatic PUs via reactions between isomeric 2,2'-, 3,3'-, and 4,4'-diaminobiphenyls and triphosgene under solvent-free conditions following ball-milling. By using this synthetic approach, both PUs and azomethine-capped Pus were obtained. The fluorescence response of the above-mentioned PUs towards various anions in solutions were studied and selective fluorescence responses towards the hydroxyl and fluoride anions were observed.

Hypochlorite Detection by Fluorescent Sensors Bearing Long Alkyl Chains: The Role of Chain Length in Sensing Properties.

Three pyridinium derivatives bearing alkyl chains of different lengths (C1, C8, and C18) that show aggregation-enhanced emission were synthesized. These compounds can be used to detect ClO- ion as the reaction releases the fluorescent core with an increase in emission intensity and change in absorption wavelength. The lowest detection limit of TPA-Pyr-18C was 6.04 µM. The length of the alkyl chain and resulting lipophilicity allowed the targeting of different subcellular structures. TPA-Pyr-18C could be used for staining yolk lipids in zebrafish.

Knoevenagel condensation triggered synthesis of dual-channel oxene based chemosensor: Discriminative spectrophotometric recognition of F-, CN- and HSO4- with breast cancer cell imaging, real sample analysis and molecular keypad lock applications.

A novel oxene based unusual sensory receptor (HyMa) has been synthesized via.Knoevenagel condensation triggered carbon-heteroatom (oxygen) intramolecular bond formation reaction at room temperature for discriminative detection of multi-analytes like HSO4-, CN- & F- by spectro-photometric alterations with profound selectivity with the detection limit of 38 ppb, 18 ppb & 94 ppb respectively. Examination of the sensing mechanism was exhaustively investigated through several spectroscopic means like 1H NMR, FT-IR, absorption and fluorescence spectra etc. In addition, quantum mechanical calculations like DFT and Loewdin spin population analyses also validated the rationality of the host-guest interaction. Apart from these, the reversible spectroscopic responses of HyMa towards F- and Al3+ can imitate several complex logic functions that in turn help in preparing molecular keypad lock. This molecular keypad lock has the potential to protect the confidential information at the molecular scale. Additionally, the MTT assay of HyMa showed low cytotoxicity and membrane permeability indicating its attractive capability for bio-imaging towards triple negative breast cancer. HyMa-coated test strips could also be employed towards on-site detection of these deadly contaminants via "Dip Stick" approach without help of any instrumentation. In addition, HyMa has also been exploited for quantitative determination of HSO4- from various real water samples. In a nutshell, detection of lethal contaminants like CN-, F- & HSO4- at ppb level with in vitro live cell imaging has been explored with proper photophysical characterisation and theoretical calculations with real field applications.

Eco-friendly chitosan Schiff base as an efficient sensor for trace anion detection.

Herein, a chitosan Schiff base sample (CSAN) was strategically designed and prepared via a two-step process. In the first step, an azo derivative of 1- naphthylamine namely, [2-hydroxy-5-(naphthalene-1-yldiazenyl) benzaldehyde] (HNDB) was synthesized as an aldehyde moiety. Then the condensation reaction of HNDB with chitosan afforded CSAN as the target product. Structural analyses of synthesized material were accomplished through FT-IR, 1H NMR, UV-Vis, XRD, TGA, and SEM spectral methods. Meanwhile, the heterogeneous CSAN was able to detect the presence of hydrogen carbonate (HCO3-), acetate (AcO-), and cyanide (CN-) anions in semi-aqueous media (H2O/DMSO; 10:90%, v/v). Moreover, the selectivity of CSAN towards CN- anion was increased through variation in solvent mixture ratios. Thereupon, CSAN was explored as a promising sensor towards CN- anion in an aqueous media through considerable color variation from colorless to pale yellow as well as quantitative chemical analysis. Overall, reliable CSAN chemosensor with high sensitivity for mentioned anions has a pivotal role in practical applications owing to it's reversibility ability.

Recent advances on ionic liquid uses in separation techniques.

The molten organic salts with melting point below 100°C, commonly called ionic liquids (ILs) have found numerous uses in separation sciences due to their exceptional properties as non molecular solvents, namely, a negligible vapor pressure, a high thermal stability, and unique solvating properties due to polarity and their ionic character of molten salts. Other properties, such as viscosity, boiling point, water solubility, and electrochemical window, are adjustable playing with which anion is associated with which cation. This review focuses on recent development of the uses of ILs in separation techniques actualizing our 2008 article (same authors, J. Chromatogr. A, 1184 (2008) 6-18) focusing on alkyl methylimidazolium salts. These developments include the use of ILs in nuclear waste reprocessing, highly thermally stable ILs that allowed for the introduction of polar gas chromatography capillary columns able to work at temperature never seen before (passing 300°C), the use of ILs in liquid chromatography and capillary electrophoresis, and the introduction of tailor-made ILs for mass spectrometry detection of trace anions at the few femtogram level. The recently introduced deep eutectic solvents are not exactly ILs, they are related enough so that their properties and uses in countercurrent chromatography are presented.

Fabrication of novel superoxide anion biosensor based on 3D interface of mussel-inspired Fe3O4-Mn3(PO3)2@Ni foam.

Preparation of high performance electrochemical biosensing interface for the sensitive and rapid detection of human metabolites is of great interest for health care and biomedical science. In this paper, based on the adhesion technique of marine mussels, we designed and prepared a novel biosensor with a micro/nano-biointerface of Fe3O4-Mn3(PO3)2@Ni foam, which offered a three dimensional (3D) living environment for real cell. The constructed biosensor with a 3D micro/nano-biointerface of Fe3O4-Mn3(PO3)2@Ni foam was characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and elemental mapping. Furthermore, the electrochemical experiments by electrochemical method for detection of superoxide anion (O2•-) in situ released by cells were carried out by this biosensor we proposed. Results indicated that the 3D interface of mussel-inspired Fe3O4-Mn3(PO3)2@Ni foam offered an amicable platform for promoting cell adhesion, which was beneficial for enhancing biosensing activity. This proposed sensing platform provided high electroactivity and excellent electron transport with a lower detection limit (0.0170µM), wider linear range 0.04-2.44µM) and short diffusion distance to reaction sites. The case achieved the accurate detection of O2•- (in situ released by cells) based on the combination of mussel-inspired biomimetic adhesion technique, 3D micro/nano-biointerface construction and electrochemical biosensing technique.

Ultrasensitive detection of superoxide anion released from living cells using a porous Pt-Pd decorated enzymatic sensor.

Considering the critical roles of superoxide anion (O2(∙-)) in pathological conditions, it is of great urgency to establish a reliable and durable approach for real-time determination of O2(∙-). In this study, we propose a porous Pt-Pd decorated superoxide dismutase (SOD) sensor for qualitative and quantitative detection O2(∙-). The developed biosensor exhibits a fast, selective and linear amperometric response upon O2(∙-) in the concentration scope of 16 to 1,536 µM (R(2)=0.9941), with a detection limit of 0.13 µM (S/N=3) and a low Michaelis-Menten constant of 1.37 µM which indicating a high enzymatic activity and affinity to O2(∙-). Inspiringly, the proposed sensor possesses an ultrahigh sensitivity of 1270 µA mM(-1)cm(-2). In addition, SOD/porous Pt-Pd sensor exhibits excellent anti-interference property, reproducibility and long-term storage stability. Beyond our expectation, the trace level of O2(∙-) released from living cells has also been successfully captured. These satisfactory results are mainly ascribed to (1) the porous interface with larger surface area and more active sites to provide a biocompatible environment for SOD (2) the specific biocatalysis of SOD towards O2(∙-) and (3) porous Pt-Pd nanomaterials fastening the electron transfer. The superior electrochemical performance makes SOD/porous Pt-Pd sensor a promising candidate for monitoring the dynamic changes of O2(∙-)in vivo.

A new diketopyrrolopyrrole-based probe for sensitive and selective detection of sulfite in aqueous solution.

A new probe was synthesized by incorporating an α,ß-unsaturated ketone to a diketopyrrolopyrrole fluorophore. The probe had exhibited a selective and sensitive response to the sulfite against other thirteen anions and biothiols (Cys, Hcy and GSH), through the nucleophilic addition of sulfite to the alkene of probe with the detection limit of 0.1 µM in HEPES (10 mM, pH 7.4) THF/H2O (1:1, v/v). Meanwhile, it could be easily observed that the probe for sulfite changed from pink to colorless by the naked eye, and from pink to blue under UV lamp after the sulfite was added for 20 min. The NMR and Mass spectral analysis demonstrated the expected addition of sulfite to the C=C bonds.

Immobilization of superoxide dismutase on Pt-Pd/MWCNTs hybrid modified electrode surface for superoxide anion detection.

Monitoring of reactive oxygen species like superoxide anion (O2(∙-)) turns to be of increasing significance considering their potential damages to organism. In the present work, we fabricated a novel O2(∙-) electrochemical sensor through immobilizing superoxide dismutase (SOD) onto a Pt-Pd/MWCNTs hybrid modified electrode surface. The Pt-Pd/MWCNTs hybrid was synthesized via a facile one-step alcohol-reduction process, and well characterized by transmission electron microscopy, X-ray photoelectron spectroscopy and X-ray diffraction. The immobilization of SOD was accomplished using a simple drop-casting method, and the performance of the assembled enzyme-based sensor for O2(∙-) detection was systematically investigated by several electrochemcial techniques. Thanks to the specific biocatalysis of SOD towards O2(∙-) and the Pt-Pd/MWCNTs - promoted fast electron transfer at the fabricated interface, the developed biosensor exhibits a fast, selective and linear amperometric response upon O2(∙-) in the concentration scope of 40-1550 µM (R(2)=0.9941), with a sensitivity of 0.601 mA cm(-2) mM(-1) and a detection limit of 0.71 µM (S/N=3). In addition, the favorable biocompatibility of this electrode interface endows the prepared biosensor with excellent long-term stability (a sensitivity loss of only 3% over a period of 30 days). It is promising that the proposed sensor will be utilized as an effective tool to quantitatively monitor the dynamic changes of O2(∙-) in biological systems.