Luminescent Ln(III)-Metallopeptide Sensors for Monitoring Pseudomonas aeruginosa Elastase B Activity in Complex Biological Media.

The detection and monitoring of Pseudomonas aeruginosa and its virulence factors, such as the LasB protease, are crucial for managing bacterial infections. Traditional fluorescent sensors for this protease face limitations in bacterial cultures due to interference from pigments like pyoverdine secreted by this opportunistic pathogen. We report here a Ln(III)-metallopeptide that combines a DO3A-Ln(III) complex and a sensitizing unit via a short peptide sequence as a simple, tunable, and selective probe for detecting P. aeruginosa's LasB. The probe's luminescence switches off in the presence of P. aeruginosa's secretome due to LasB cleavage but remains stable in other bacterial environments, such as non-LasB-secreting P. aeruginosa strains or E. coli cultures. It also resists degradation by other proteases, like human leukocyte elastase and trypsin, and remains stable in the presence of bioanalytes related to P. aeruginosa infections, such as glutathione, H2O2, and pyocyanin, and in complex media like FBS. Importantly, time-gated experiments completely remove the background fluorescence of P. aeruginosa pigments, thus demonstrating the potential of the developed Ln(III)-metallopeptide for real-time monitoring of LasB activity in bacterial cultures.

Highly Selective Ratiometric Sensors for Pb2+ Based on Luminescent Zn(II)-Coordination Polymers with Thiophenedicarboxylate. Crystal Structures and Spectroscopic Studies.

The development of luminescent coordination polymers for the selective sensing of Pb2+ in water constitutes an active area of research that impacts analytical, environmental, and inorganic chemistry. Herein, two novel water-stable 2D Zn-coordination polymers {[Zn2(H2O)2(tdc)2(bpy)]·(H2O)}n 1 and [Zn(tdc)(tmb)]n 2 (tdc = thiophenedicarboxylate; bpy = 4,4'-bipyridine and tmb = 4,4'-trimethylenebipyridine) were synthesized, structurally determined by single crystal X-ray diffraction, and studied in-depth as luminescent sensors for a series of cations (Ca2+, Mg2+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Zn2+ Cd2+, Hg2+ and Pb2+) in 20% aqueous ethanol. These Zn-polymers possess photostability in 20% aqueous ethanol with a strong emission at 410 upon excitation at 330 nm and quantum yields of around Φ = 0.09. Under these conditions, Pb+2 can be efficiently sensed with polymer 2 through a fluorescent ratiometric response with selectivity over common interfering metal ions such as Cu2+, Cd2+ and Hg2+ in the micromolar concentration range (detection limit = 1.78 ± 10 µM). Such selectivity/affinity of Pb2+ over Hg2+ for luminescent chemosensors is still rare. On the basis of spectroscopic tools (1H NMR, far ATR-IR, PXRD), the X-ray crystal structure of 2, and Scanning Electron Microscopy with Energy-Dispersive X-ray Spectroscopic analysis, the ratiometric fluorescent response is proposed via an efficient metal-ion exchange driven through interactions between thiophenedicarboxylate rings and Pb2+ ions. The use of flexible luminescent Zn-coordination polymers as sensors for selective and direct detection of Pb2+ in aqueous media has been unexplored until now.

Colorimetric detection of Fe2+ and Cr2O72- in environmental water samples based on dual-emitting RhB-embedded Zr-MOFs.

Three dye-loaded tunable dual-emission colorimetric fluorescent probes RhB@UiO-66-Ph (R@U-P) were prepared by in-situ encapsulation method under solvothermal conditions. The resonance energy transfer between UiO-66-Ph and RhB made the dual emission of R@U-P easily tunable with the embedded dye content changing. The R@U-P composites achieved emission from purple light to red light, and served as probes to realize comparative detection of Fe3+, Fe2+ and Cr2O72- in water through colorimetric or quenching detection mode. Mechanism study indicates that the resonance energy transfer or electron transfer interactions between R@U-P composites and inorganic ions resulted in the relative changes of the two emission peaks and realized the selective detection of analytes. The preparation and application of R@U-P probes provide a promising strategy for the in-situ encapsulation dye to obtain two dual-emission composites for the comparative detection of Fe3+, Fe2+ and Cr2O72- in water samples.

Colloidal Quantum Dots for Explosive Detection: Trends and Perspectives.

Sensitive, accurate, and reliable detection of explosives has become one of the major needs for international security and environmental protection. Colloidal quantum dots, because of their unique chemical, optical, and electrical properties, as well as easy synthesis route and functionalization, have demonstrated high potential to meet the requirements for the development of suitable sensors, boosting the research in the field of explosive detection. Here, we critically review the most relevant research works, highlighting three different mechanisms for explosive detection based on colloidal quantum dots, namely photoluminescence, electrochemical, and chemoresistive sensing. We provide a comprehensive overview and an extensive discussion and comparison in terms of the most relevant sensor parameters. We highlight advantages, limitations, and challenges of quantum dot-based explosive sensors and outline future research directions for the advancement of knowledge in this surging research field.

Two anthracene-based zirconium metal-organic frameworks with fcu and hcp topologies as versatile fluorescent sensors for detection of inorganic ions and nitroaromatics.

Two anthracene-based zirconium metal-organic frameworks (UiO-68-AN-fcu and UiO-68-AN-hcp) with blue emission were synthesized by the solvothermal reaction of ZrCl4 with anthracene-based ligand 4,4'-(9,10-anthracenediyl)dibenzoic acid. The two MOFs inherited the luminescence properties of anthracene-based ligand and exhibited different topologies due to the change of connection mode of Zr-O clusters. The two stable anthracene-based zirconium MOFs served as luminescent sensors for selectively detecting 2-nitrophenol, Fe3+ and Cr2O72-. UiO-68-AN-hcp with flower morphology exhibited stronger quenching effect for 2-nitrophenol, Fe3+ and Cr2O72- by comparing to UiO-68-AN-fcu. Adsorption tests, fluorescence lifetime and spectroscopy studies demonstrated that the fluorescence responses of MOFs for analytes can be primarily attributed to the dynamic quenching mechanism involving energy and electron transfer. These results revealed that the combination of luminescent anthracene-based ligand and Zr-O clusters is a feasible strategy to construst MOFs-based fluorescent sensors.

Dual-functional CDs@ZIF-8/chitosan luminescent film sensors for simultaneous detection and adsorption of tetracycline.

Tetracycline (TC) residues have been noted as an important class of emerging contaminants in the environment, thus fast, straightforward, highly sensitive detection method is becoming an issue that must be addressed. Herein, a novel CDs@ZIF-8 sensing material was fabricated by encapsulating luminescent carbon dots (CDs) into the metal-organic framework (ZIF-8) to achieve highly luminescent porous composites. Furthermore, to avoid the secondary contamination caused by powders, a shapable CDs@ZIF-8/CS film sensor as a portable disposable test strip with dual-function of TC detection and adsorption was designed by crosslinking CDs@ZIF-8 with chitosan (CS). The as-prepared CDs@ZIF-8/CS hybrid film exhibited the high sensitivity and selectivity for TC fluorescence detection and rapid decontaminate capability, as well as high optical transmittance and robust mechanical property, which were essential for the practical sensing application. This paper-based dual-functional luminescent sensor exhibits promising practicability for TC detection and contaminant removal in pharmaceutical analysis, food safety and water treatment.

Chromic and Fluorescence-Responsive Metal-Organic Frameworks Afforded by N-Amination Modification.

Sensory materials that show color and/or fluorescence changes in response to specific gases or vapors have important applications in many fields. Here, we report the postsynthetic preparation of novel sensory metal-organic frameworks (MOFs) and their multiple responsive properties. Through postsynthetic N-amination, the 2,2'-bipyridyl spacers in a Zr(IV) MOF are partially transformed into N-aminobipyridinium. The new MOF (Zr-bpy-A) shows chromic behavior toward ammonia and amines because the electron-deficient pyridinium groups form charge-transfer complexes with amino moieties. It also shows a unique chromic response to formaldehyde owing to the Schiff-base condensation with the N-amino groups. Furthermore, the N-amino group can be used to graft different polycyclic aromatic hydrocarbons, which endow the MOF with strong fluorescence of variable colors and afford a high-contrast fluorescence response to ammonia/amines and formaldehyde associated with the chromic response. The presence of the unquaternized bipyridyl group also leads to a fluorescence response to HCl. The multiple responsive behaviors hold appeal for applications in sensing, switching, and antifake marking, which are illustrated with a test paper and writing ink.

Minimally Invasive Platforms in Biosensing.

The interaction of sensing components with body fluids is a basic requirement for clinical diagnostics; a variety of novel platforms have recently been developed for invasive and non-invasive sensing. In this manuscript, recent advancements related to minimally invasive platform for biosensing are reviewed. Many approaches have been utilized for generating minimally invasive platforms that require a small volume of body fluid; for example, the use of small-scale needles known as microneedles for minimally invasive detection has been demonstrated. The use of capillary action in microneedle-assisted biosensing may facilitate the detection of analytes in body fluids. This review considers recent innovations in the structure and performance of minimally invasive sensos.

Eu(III)-organic complex as recyclable dual-functional luminescent sensor for simultaneous and quantitative sensing of 2,4,6-trinitrophenol and CrO42- in aqueous solution.

A novel metal-organic complex (MOC) {[Eu2(HL)2(H2O)4]·3H2O}n (1) (H4L = 3,3',5,5'-azoxybenzenetetracarboxylic acid) has been successfully constructed, which exhibits a fascinating 2D bilayer network with the 1D open channels and has excellent water, pH and thermal stabilities. Luminescence studies reveal that 1 can detect TNP and CrO42- ions with high selectivity and sensitivity in aqueous solution, even if there are related interfering substances. And the mechanisms of luminescence recognitions are discussed on the basis of experiments and theoretical calculations. Furthermore, 1 shows excellent photostability and can be repeatedly used in the above two detection systems. Most importantly, 1 can detect TNP and CrO42- concentration with a good recovery rate in practical application. Therefore, 1 should be a potential dual-functional luminescent sensor for reliable sensing of TNP and CrO42- in the field.

Color-Based Optical Detection of Glass Transitions on Microsecond Timescales Enabled by Exciplex Dynamics.

Every measurement technique operates on a given timescale and measurements using emissive small molecule sensors are no exception. A family of luminescent sensors providing first optical characterization of dynamic phenomena in polymers at a timescale of several microseconds is described. This performance originates from the dynamics manifested in the excited state of the sensor molecules where diffusioncontrolled events select the emission color while radiative phenomena define the global operation timescale. Since the mechanism responsible for signal generation is confined to the short lived excited state of emissive probe, it is possible observe an unprecedented link between the timescale of sensory action and that of photoluminescence. An application of this new methodology is demonstrated by performing general, short timescale detection of glass transitions in a temperature ranges precluding the informative range of conventional techniques by tens of degrees.

A Highly Sensitive and Recyclable Ln-MOF Luminescent Sensor for the Efficient Detection of Fe3+ and CrVI Anions.

Two new three-dimensional (3D) LnIII metal-organic frameworks (MOFs) were designed and successfully obtained via a solvothermal reaction between lanthanide(III) nitrates and a semi-flexible carbazole tetracarboxylate acid linker as a high-performance chromophore. 1 and 2 possess porous 3D networks with channels along the a axis, and more importantly, they show a highly sensitive and selective fluorescence quenching response to Fe3+ and CrVI anions. The sensing mechanism investigation revealed that the weak interactions of Fe3+ with nitrogen atoms of carbazole and deprotonated carboxylic acids protruding into the pores of MOFs quenched the luminescence of 1 and 2 effectively. In addition, the competition absorption also played an important role in the luminescence quenching detection of Fe3+ based on 1, and CrVI anions based on 1 and 2. Therefore, 1 and 2 represent an alternative example of regenerable luminescence based sensors for the quantitative detection of Fe3+ and CrVI anions.

An Ultrastable Matryoshka [Hf13 ] Nanocluster as a Luminescent Sensor for Concentrated Alkali and Acid.

Stable metal clusters that can resist both highly concentrated acid and alkali are unknown. Herein, we present a discrete neutral cluster, Hf13 (µ4 -O)8 (OCH3 )36 (1), which features extraordinary chemical stability by preserving its crystalline state in concentrated aqueous solutions of both acid (10 m HNO3 ) and alkali (20 m boiling NaOH). Importantly, 1 can serve as a luminescent probe for detecting both concentrated alkali (20 m NaOH) and strong acid (1 m HNO3 ) with high selectivity and repeatability. DFT studies of the electronic structure and bonding revealed that 1 has an extremely large HOMO-LUMO gap due to strong d π-p π bonding that accounts for the ultrahigh stability.

One-pot doping platinum porphyrin recognition centers in Zr-based MOFs for ratiometric luminescent monitoring of nitric oxide in living cells.

A new kind of nanoscale MOFs probe for nitric oxide (NO) sensing has been successfully constructed by a one-pot strategy, in which the chemically stable UiO-66 crystal structure was achieved using platinum meso-tetra(4-carboxyphenyl)porphyrin (Pt-TCPP), 1,1,2,2-Tetra(4-carboxylphenyl)ethylene (H4TCPE) and 1,4-dicarboxybenzene (BDC) as co-linkers (Pt-TCPP/H4TCPE@UiO-66). Pt-TCPP was verified to serve as a signal reporter in NO sensing fields for the first time while H4TCPE worked as a luminescence reference to build a ratiometric sensor. The integration of luminescent dyes in nanoscale MOFs effectively avoided their aggregation-caused quenching effect and poor aqueous dispersibility to rationalize NO detection in the aqueous phase. The obtained Pt-TCPP/H4TCPE@UiO-66 nanoparticles (NPs) exhibited an excellent sensing property toward NO with an ultrahigh linear correlation of the Stern-Volmer equation and a rapid response time as short as 2 min. Moreover, the elaborated sensor could work under a wide pH window (7.4, 5.6 and 0) and the limit of detection (LOD) reached as low as 0.1420 µg mL-1. The specificity of the obtained Pt-TCPP/H4TCPE@UiO-66 NPs toward NO sensing was scarcely affected by other possibly coexistent species in biological system. The in vitro monitoring for NO in living cells was also testified with these Pt-TCPP/H4TCPE@UiO-66 NPs.

Current Advancements in Transdermal Biosensing and Targeted Drug Delivery.

In this manuscript, recent advancements in the area of minimally-invasive transdermal biosensing and drug delivery are reviewed. The administration of therapeutic entities through the skin is complicated by the stratum corneum layer, which serves as a barrier to entry and retards bioavailability. A variety of strategies have been adopted for the enhancement of transdermal permeation for drug delivery and biosensing of various substances. Physical techniques such as iontophoresis, reverse iontophoresis, electroporation, and microneedles offer (a) electrical amplification for transdermal sensing of biomolecules and (b) transport of amphiphilic drug molecules to the targeted site in a minimally invasive manner. Iontophoretic delivery involves the application of low currents to the skin as well as the migration of polarized and neutral molecules across it. Transdermal biosensing via microneedles has emerged as a novel approach to replace hypodermic needles. In addition, microneedles have facilitated minimally invasive detection of analytes in body fluids. This review considers recent innovations in the structure and performance of transdermal systems.

Tunable Light Emission and Multiresponsive Luminescent Sensitivities in Aqueous Solutions of Two Series of Lanthanide Metal-Organic Frameworks Based on Structurally Related Ligands.

Two series of lanthanide metal-organic frameworks (Ln-MOFs) from two structurally related flexible carboxylate-based ligands were solvothermally synthesized. H3L2 with additional -CH2- group provides more flexibility and different coordination modes and conformations compared with H3L1. As a result, 2-Ln MOFs are modulated from two-dimensional kgd of 1-Ln to three-dimensional rtl topological frameworks and further achieve enhanced chemical stability. The Eu- and Tb-MOFs exhibit strong fluorescent emission at the solid state because of the antenna effect of the ligands. Interestingly, the emissions can be tuned by simply doping Eu3+ and Tb3+ of different concentrations within the Eu xTb1- x MOFs. Notably, 2-Ln MOFs realize nearly white light emission by means of a trichromatic approach (red of Eu(III), green of Tb(III), and blue of the H3L2 ligand). Furthermore, 2-Ln MOFs also exhibit water stability and demonstrate high selective and sensitive sensing activities toward Fe(III) and Cr(VI) in aqueous solutions. The results further highlight the importance of the ligand flexibility on tuning MOF structures with improved structural stability and ion-sensing properties.

A Cuprous/Lanthanide-Organic Framework as the Luminescent Sensor of Hypochlorite.

A new 3D framework {[Eu2 Cu(IN)5 (CO3 )(H2 O)] ⋅3 H2 O}n  (1) was obtained and structurally characterized, containing CuI and an unusual lanthanide duplex chain. The luminescent explorations of compound 1 suggest that 1 could emit the characteristic emission of CuI , and 1 can act as the luminescent sensor of ClO- with the detection limit of 10-5  m. Notably, 1 represents the first example of MOF-based sensor for detecting ClO- .

Comparative validation of amperometric and optical analyzers of dissolved oxygen: a case study.

A comprehensive comparative validation for two different types of dissolved oxygen (DO) analyzers, amperometric and optical, is presented on two representative commercial DO analyzers. A number of performance characteristics were evaluated including drift, intermediate precision, accuracy of temperature compensation, accuracy of reading (under different measurement conditions), linearity, flow dependence of the reading, repeatability (reading stability), and matrix effects of dissolved salts. The matrix effects on readings in real samples were evaluated by analyzing the dependence of the reading on salt concentration (at saturation concentration of DO). The analyzers were also assessed in DO measurements of a number of natural waters. The uncertainty contributions of the main influencing parameters were estimated under different experimental conditions. It was found that the uncertainties of results for both analyzers are quite similar but the contributions of the uncertainty sources are different. Our results imply that the optical analyzer might not be as robust as is commonly assumed; however, it has better reading stability, lower stirring speed dependence, and typically requires less maintenance. On the other hand, the amperometric analyzer has a faster response and wider linear range. Both analyzers seem to have issues with the accuracy of temperature compensation. The approach described in this work will be useful to practitioners carrying out DO measurements for ensuring reliability of their measurements.

A luminescent Lanthanide-free MOF nanohybrid for highly sensitive ratiometric temperature sensing in physiological range.

Luminescent MOF materials with tunable emissions and energy/charge transfer processes have been extensively explored as ratiometric temperature sensors. However, most of the ratiometric MOF thermometers reported thus far are based on the MOFs containing photoactive lanthanides, which are potentially facing cost issue and serious supply shortage. Here, we present a ratiometric luminescent thermometer based on a dual-emitting lanthanide-free MOF hybrid, which is developed by encapsulation of a fluorescent dye into a robust nanocrystalline zirconium-based MOF through a one-pot synthesis approach. The structure and morphology of the hybrid product was characterized by Powder X-ray diffraction (PXRD), N2 adsorption-desorption measurement and Scanning electron microscopy (SEM). The pore confinement effect well isolates the guest dye molecules and therefore suppresses the nonradiative energy transfer process between dye molecules. The incorporated dye emission is mainly sensitized by the organic linkers within MOF through fluorescence resonance energy transfer. The ratiometric luminescence of the MOF hybrid shows a significant response to temperature due to the thermal-related back energy transfer process from dye molecules and organic linkers, thus can be exploited for self-calibrated temperature sensing. The maximum thermometric sensitivity is 1.19% °C-1 in the physiological temperature range, which is among the highest for the ratiomtric MOF thermometers that operating in 25-45°C. The temperature resolution is better than 0.1°C over the entire operative range (20-60°C). By integrating the advantages of excellent stability, nanoscale nature, and high sensitivity and precision in the physiological temperature range, this dye@MOF hybrid might have potential application in biomedical diagnosis. What' more, this work has expanded the possibility of non-lanthanide luminescent MOF materials for the development of ratiometric temperature sensors.

Optimization of Temperature Sensing with Polymer-Embedded Luminescent Ru(II) Complexes.

Temperature is a key parameter in many fields and luminescence-based temperature sensing is a solution for those applications in which traditional (mechanical, electrical, or IR-based) thermometers struggle. Amongst the indicator dyes for luminescence thermometry, Ru(II) polyazaheteroaromatic complexes are an appealing option to profit from the widespread commercial technologies for oxygen optosensing based on them. Six ruthenium dyes have been studied, engineering their structure for both photostability and highest temperature sensitivity of their luminescence. The most apt Ru(II) complex turned out to be bis(1,10-phenanthroline)(4-chloro-1,10-phenanthroline)ruthenium(II), due to the combination of two strong-field chelating ligands (phen) and a substituent with electron withdrawing effect on a conjugated position of the third ligand (4-Clphen). In order to produce functional sensors, the dye has been best embedded into poly(ethyl cyanoacrylate), due to its low permeability to O2, high temperature sensitivity of the indicator dye incorporated into this polymer, ease of fabrication, and excellent optical quality. Thermosensitive elements have been fabricated thereof as optical fiber tips for macroscopic applications (water courses monitoring) and thin spots for microscopic uses (temperature measurements in cell culture-on-a-chip). With such dye/polymer combination, temperature sensing based on luminescence lifetime measurements allows 0.05 °C resolution with linear response in the range of interest (0⁻40 °C).

Luminescent gold nanocluster-based sensing platform for accurate H2S detection in vitro and in vivo with improved anti-interference.

Gold nanoclusters (Au NCs) are promising luminescent nanomaterials due to their outstanding optical properties. However, their relatively low quantum yields and environment-dependent photoluminescence properties have limited their biological applications. To address these problems, we developed a novel strategy to prepare chitosan oligosaccharide lactate (Chi)-functionalized Au NCs (Au NCs@Chi), which exhibited emission with enhanced quantum yield and elongated emission lifetime as compared to the Au NCs, as well as exhibited environment-independent photoluminescence properties. In addition, utilizing the free amino groups of Chi onto Au NCs@Chi, we designed a FRET-based sensing platform for the detection of hydrogen sulfide (H2S). The Au NCs and the specific H2S-sensitive merocyanine compound were respectively employed as an energy donor and acceptor in the platform. The addition of H2S induced changes in the emission profile and luminescence lifetime of the platform with high sensitivity and selectivity. Utilization of the platform was demonstrated to detect exogenous and endogenous H2S in vitro and in vivo through wavelength-ratiometric and time-resolved luminescence imaging (TLI). Compared to previously reported luminescent molecules, the platform was less affected by experimental conditions and showed minimized autofluorescence interference and improved accuracy of detection.