Molecule Engineering Metal-Organic Framework-Based Organic Photoelectrochemical Transistor Sensor for Ultrasensitive Bilirubin Detection.

The functionalization of metal-organic frameworks (MOFs) with organic small molecules by in situ postsynthetic modification has garnered considerable attention. However, the precise engineering of recognition sites using this method remains rarely explored in optically controlled bioelectronics. Herein, employing the Schiff base reaction to embed the small molecule (THBA) into a Zr-MOF, we fabricated a hydroxyl-rich MOF on the surface of titanium dioxide nanorod arrays (U6H@TiO2 NRs) to develop light-sensitive gate electrodes with tailored recognition capabilities. The U6H@TiO2 NR gate electrodes were integrated into organic photoelectrochemical transistor (OPECT) sensing systems to tailor a sensitive device for bilirubin (I-Bil) detection. In the presence of I-Bil, coordination effects, hydrogen bonding, and π-π interactions facilitated strong binding between U6H@TiO2 NRs and the target I-Bil. The electron-donating property of I-Bil influenced the gate voltage, enabling precise control of the channel status and modulation of the channel current. The OPECT device exhibited exceptional analytical performance toward I-Bil with wide linearity ranging from 1 × 10-16 to 1 × 10-9 M and a low limit detection of 0.022 fM. Leveraging the versatility of small molecules for boosting the functionalization of materials, this work demonstrates the great potential of the small molecule family for OPECT bioanalysis and holds promise for the advancement of OPECT sensors.

Activatable NIR Fluorescence Probe for Epinephrine Detection and Bioimaging Based on Anionic Heptamethine Cyanine.

Epinephrine (EP) is an essential catecholamine in the human body. Currently, most EP detection methods are not suitable for in vivo detection due to material limitations. An organic small molecule fluorescent probe based on a chemical cascade reaction for the detection of EP was designed. Anionic heptamethine cyanine dye was selected as a fluorescent dye because of its NIR fluorescence emission with excellent biocompatibility. The secondary amine of EP nucleophilically attacks the carbonate of the probe with its stronger nucleophilicity and further undergoes intramolecular nucleophilic cyclization to release the fluorophore. Other substances containing only primary amines or no ß-OH lack reaction competitiveness due to their weaker nucleophilicity or inability to undergo further cyclization. The fluorescence recovery of the probe was linearly related to the EP concentration of 2-75 µmol/L. The detection limit was 0.4 µmol/L. The recovery rate was 94.78-111.32%. Finally, we successfully achieved bioimaging of EP in living cells and EP analogue in nematodes.

A Photoelectrochemical Sensor Based on DNA Bio-Dots-Induced Aggregation of AuNPs for Methionine Detection.

Based on DNA bio-dots-induced aggregation of gold nanoparticles (AuNPs), a methionine (Met) photoelectrochemical (PEC) sensor with CS-GSH-CuNCs/TiO2 NPs as the photoelectric conversion element and AuNPs as the specific recognition element was constructed. First, a TiO2 NPs/ITO electrode and CS-GSH-CuNCs were prepared, and then the CS-GSH-CuNCs/TiO2 NPs/ITO photosensitive electrode was obtained by self-assembly. Next, DNA bio-dots were modified to the upper surface of the electrode using a coupling reaction to assemble the DNA bio-dots/CS-GSH-CuNCs/TiO2 NPs electrode. Amino-rich DNA bio-dots were used to induce the aggregation of AuNPs on the electrode surface via Au-N interactions and prepare the AuNPs/DNA bio-dots/CS-GSH-CuNCs/TiO2 NPs electrode. Due to the fluorescence resonance energy transfer (FRET) between CS-GSH-CuNCs and AuNPs, the complexation chance of electron-hole (e--h+) pair in CS-GSH-CuNCs increased, which, in turn, led to a decrease in photocurrent intensity. When Met was present, AuNPs aggregated on the electrode surface were shed and bound to Met since the Au-S interaction is stronger than the Au-N interaction, resulting in the recovery of the photocurrent signal. Under optimal conditions, the photocurrent intensity of the PEC sensor showed good linearity with the logarithm of Met concentration in the range of 25.0 nmol/L-10.0 µmol/L with the limit of detection (LOD) of 5.1 nmol/L (S/N = 3, n = 10).

An off-on fluorescence aptasensor for trace thrombin detection based on FRET between CdS QDs and AuNPs.

An off-on fluorescence aptasensor was developed for trace thrombin detection based on fluorescence resonance energy transfer (FRET) between CdS QDs and gold nanoparticles (AuNPs). Using DNA pairwise hybridization of the aptamer to the complementary DNA (cDNA), the CdS QDs (energy donor) were tightly coupled to the AuNPs (energy acceptor), resulting in the occurrence of FRET and there was a dramatic fluorescence quenching of CdS QDs (turn off). When the thrombin was added to the fluorescence aptasensor, the specific binding of the aptamer to the target formed a G-quadruplex that caused the AuNPs receptor to detach and the DNA duplex to be disassembled. The process would inhibit the FRET which contribute to the recovery of fluorescence (turn on) and an "off-on" fluorescence aptasensor for thrombin detection was constructed accordingly. Under optimal conditions, the fluorescence recovery showed good linearity with the concentration of thrombin in the range of 1.35-54.0 nmol L-1, and the detection limit was 0.38 nmol L-1 (S/N = 3, n = 9). Importantly, the fluorescence aptasensor presented excellent specificity for thrombin, and was successfully applied to the quantitative determination of thrombin in real serum with satisfactory recoveries of 98.60-102.2%.

Ascorbic Acid Sensor Based on CdS QDs@PDA Fluorescence Resonance Energy Transfer.

An ascorbic acid (AA) sensor was constructed based on the fluorescence resonance energy transfer (FRET) between CdS quantum dots (CdS QDs) and polydopamine (PDA) to detect trace AA sensitively. FRET occurred due to the broad absorption spectrum of PDA completely overlapped with the narrow emission spectrum of CdS QDs. The fluorescence of CdS QDs was quenched and in the "off" state. When AA was present, the conversion of DA to PDA was hindered and the FRET disappeared, resulting in the fluorescence of CdS QDs in an "on" state. Importantly, the degree of fluorescence recovery of CdS QDs displayed a desirable linear correlation with the concentration of AA in the range of 5.0-100.0 µmol/L, the linear equation is y=0.0119cAA+0.3113, and the detection limit is 1.16 µmol/L (S/N = 3, n = 9). There was almost no interference with common amino acid, glucose and biological sulfhydryl small molecules to AA. Trace amount of AA in vitamin C tablets were determined and satisfactory results were obtained; the recoveries were observed to be 98.01-100.7%.

Turn-on signal fluorescence sensor based on DNA derived bio-dots/polydopamine nanoparticles for the detection of glutathione.

A convenient, fast, sensitive and highly selective fluorescence sensor for the detection of glutathione (GSH) based on DNA derived bio-dots (DNA bio-dots)/polydopamine (PDA) nanoparticles was constructed. The fluorescent switch of DNA bio-dots was induced to turn off because of fluorescence resonance energy transfer (FRET) reactions between DNA bio-dots and PDA. The presence of GSH blocked the spontaneous oxidative polymerization of dopamine (DA) to PDA, leading the fluorescent switch of DNA bio-dots to be "turned on". The degree of fluorescence recovery of DNA bio-dots is linearly correlated with the concentration of GSH within the range of 1.00-100 µmol L-1, and the limit of detection (LOD) is 0.31 µmol L-1 (S/N = 3, n = 9). Furthermore, the fluorescence sensor was successfully used to quantify GSH in human urine and glutathione whitening power, indicating the fluorescence sensor has potential in the detection of human body fluids and pharmaceutical preparations.

Molecularly Imprinted Silica-Coated CdTe Quantum Dots for Fluorometric Determination of Trace Chloramphenicol.

A dual recognition system with a fluorescence quenching of quantum dots (QDs) and specific recognition of molecularly imprinted polymer (MIP) for the detection of chloramphenicol (CAP) was constructed. MIP@SiO2@QDs was prepared by reverse microemulsion method with 3-aminopropyltriethoxysilane (APTS), tetraethyl orthosilicate (TEOS) and QDs being used as the functional monomer, cross-linker and signal sources, respectively. MIP can specifically recognize CAP, and the fluorescence of QDs can be quenched by CAP due to the photo-induced electron transfer reaction between CAP and QDs. Thus, a method for the trace detection of CAP based on MIP@SiO2@QDs fluorescence quenching was established. The fluorescence quenching efficiency of MIP@SiO2@QDs displayed a desirable linear response to the concentration of CAP in the range of 1.00~4.00 × 102 µmol × L-1, and the limit of detection was 0.35 µmol × L-1 (3σ, n = 9). Importantly, MIP@SiO2@QDs presented good detection selectivity owing to specific recognition for CAP, and was successfully applied to quantify CAP in lake water with the recovery ranging 102.0~104.0%, suggesting this method has the promising potential for the on-site detection of CAP in environmental waters.

Photoelectrochemical Aptasensors Constructed with Photosensitive PbS Quantum Dots/TiO2 Nanoparticles for Detection of Kanamycin.

Kanamycin (Kana) is widely used as a veterinary medicine and its abuse causes a serious threat to human health, raising the urgent demand for detection of residual Kana in animal-derived food with high specificity and sensitivity. Here, we developed a photoelectrochemical (PEC) biosensor for rapid quantification of Kana, with lead sulfide quantum dots/titanium dioxide nanoparticles (PbS QDs/TiO2 NPs) as a photosensitive composite, a Kana-specific DNA aptamer as a functional sensor, and ruthenium(III) hexaammine (Ru(NH3)63+) as a signal booster. To prepare the PEC aptasensor, TiO2 NPs, PbS QDs, and polyethyleneimine (PEI) were respectively used to modify the indium tin oxide electrode, and then the amine-terminated aptamer probe was connected to the PEI via glutaraldehyde. Finally, Ru(NH3)63+ was attached on the surface of the aptamer to increase the photocurrent intensity. When Kana binds competitively with Ru(NH3)63+ to the aptamer immobilized on the surface of the aptasensor, Ru(NH3)63+ will be released from the aptamer, resulting in a decrease of the photocurrent signal. This PEC aptasensor exhibits a good linear relationship between the photocurrent shift and the logarithm of Kana concentration within the range of 1.0-300.0 nmol L-1, and the detection limit is 0.161 nmol L-1. Importantly, the PEC aptasensor presented good detection selectivity owing to specific interaction with Kana and was successfully implemented to quantify Kana in honey and milk, suggesting that the PEC aptasensor has the potential of rapid detection of residual Kana in animal-derived foods.

Ratiometric pH Sensing and Imaging in Living Cells with Dual-Emission Semiconductor Polymer Dots.

Polymer dots (Pdots) represent newly developed semiconductor polymer nanoparticles and exhibit excellent characteristics as fluorescent probes. To improve the sensitivity and biocompatibility of Pdots ratiometric pH biosensors, we synthesized 3 types of water-soluble Pdots: Pdots-PF, Pdots-PP, and Pdots-PPF by different combinations of fluorescent dyes poly(9,9-dioctylfluorenyl-2,7-diyl) (PFO), poly[(9,9-dioctyl-fluorenyl-2,7-diyl)-co-(1,4-benzo-{2,1',3}-thiadazole)] (PFBT), and fluorescein isothiocyanate (FITC). We found that Pdots-PPF exhibits optimal performance on pH sensing. PFO and FITC in Pdots-PPF produce pH-insensitive (λ = 439 nm) and pH-sensitive (λ = 517 nm) fluorescence respectively upon a single excitation at 380 nm wavelength, which enables Pdots-PPF ratiometric pH sensing ability. Förster resonance energy transfer (FRET) together with the use of PFBT amplify the FITC signal, which enables Pdots-PPF robust sensitivity to pH. The emission intensity ratio (I517/I439) of Pdots-PPF changes linearly as a function of pH within the range of pH 3.0 to 8.0. Pdots-PPF also possesses desirable reversibility and stability in pH measurement. More importantly, Pdots-PPF was successfully used for cell imaging in Hela cells, exhibiting effective cellular uptake and low cytotoxicity. Our study suggests the promising potential of Pdots-PPF as an in vivo biomarker.

Novel fluorescent sensor using molecularly imprinted silica microsphere-coated CdSe@CdS quantum dots and its application in the detection of 2,4,6-trichlorophenol from environmental water samples.

In this study, a high fluorescence sensitivity and selectivity, molecularly imprinted nanofluorescent polymer sensor (MIP@SiO2 @QDs) was prepared using a reverse microemulsion method. 2,4,6-Trichlorophenol (2,4,6-TCP) was detected using fluorescence quenching. Tetraethyl orthosilicate (TEOS), quantum dots (QDs) and 3-aminopropyltriethoxysilane (APTS) were used as cross-linker, signal sources and functional monomer respectively. The sensor (MIP@SiO2 @QDs) and the non-imprinted polymer sensor (NIP@SiO2 @QDs) were characterized using infra-red (IR) analysis, X-ray diffraction (XRD), transmission electron microscopy (TEM) and scanning electron microscopy (SEM). The selectivity of MIP@SiO2 @QDs was examined by comparing 2,4,6-TCP with other similar functional substances including 2,4-dichlorophenol (2,4-DCP), 2,6-dichlorophenol (2,6-DCP) and 4-chlorophenol (4-CP). Results showed that MIP@SiO2 @QDs had better selectivity for 2,4,6-TCP than the other compounds. Fluorescence quenching efficiency displayed a good linear response at the 2,4,6-TCP concentration range 5-1000 µmol/L. The limit of detection (LOD) was 0.9 µmol/L (3σ, n = 9). This method was equally applicable for testing actual samples with a recovery rate of 98.0-105.8%. The sensor had advantages of simple pretreatment, good sensitivity and selectivity, and wide linear range and could be applied for the rapid detection of 2,4,6-TCP in actual samples.

A Cu2+-doped two-dimensional material-based heterojunction photoelectrode: application for highly sensitive photoelectrochemical detection of hydrogen sulfide.

In this work, on the basis of a Cu2+-doped two-dimensional material-based heterojunction photoelectrode, a novel anodic photoelectrochemical (PEC) sensing platform was constructed for highly sensitive detection of endogenous H2S. Briefly, with g-C3N4 and TiO2 as representative materials, the sensor was fabricated by modifying g-C3N4/TiO2 nanorod arrays (NAs) onto the surface of fluorine-doped tin oxide (FTO) and then doping Cu2+ as a Cu x S (x = 1, 2) precursor. After the binding of S2- with surface-attached Cu2+, the signal was quenched owing to the in situ generation of Cu x S which offers trapping sites to hinder generation of photocurrent signals. Since the photocurrent inhibition was intimately associated with the concentration of S2-, a highly sensitive PEC biosensor was fabricated for H2S detection. More importantly, the proposed sensing platform showed the enormous potential of g-C3N4/TiO2 NAs for further development of PEC bioanalysis, which may serve as a common basis for other semiconductor applications and stimulates the exploration of numerous high-performance nanocomposites.

Special Effect of Ionic Liquids on the Extraction of Flavonoid Glycosides from Chrysanthemum morifolium Ramat by Microwave Assistance.

A microwave-assisted extraction approach based on ionic liquids of different chain lengths was successfully applied to the extraction of ten flavonoid glycosides from the flowering heads of Chrysanthemum morifolium Ramat. The pretreated sample was quantified by HPLC-ESI-MSn. The main components were identified as flavonoid glycosides, including three luteolin glycosides, three apigenin glycosides, three kaempferide glycosides, and one acacetin glycoside according to the characteristics of the corresponding CID mass spectrometric patterns. Eight ionic liquids from the imidazolium family with different chain lengths, namely, 1-alkyl-3-methylimidazolium bromide, [Cnmim]Br, (n=2-16) were studied as extraction medium in water. Results indicated that alkyl chain length had an irregular impact on the extraction efficiency. Moreover, the best extraction efficiency was achieved by 1-dodecyl-3-methylimidazolium bromide aqueous solution ([C12mim]Br). Besides the alkyl chain length of the cations, other factors influencing extraction efficiency were systematically investigated, including concentration of the IL solutions, extraction time, matrix-to-solvent ratio and irradiation power.

Formation of fluorescent carbon nanodots from kitchen wastes and their application for detection of Fe(3.).

This work reports a scalable synthesis of water-dispersible fluorescent carbon nanodots based on the simple hydrothermal method (180 °C for 6 h) of kitchen wastes (grape peel for example). We discuss the feasibility of synthesis from kitchen wastes both experimentally and theoretically, and the as-prepared nanodots have high selectivity for Fe(3+) ions based on fluorescence quenching which is due to the complexes between nanodots and metal ions.

Carbon dots as a luminescence sensor for ultrasensitive detection of phosphate and their bioimaging properties.

Highly blue fluorescence carbon dots were synthesized by one-step hydrothermal treatment of potatoes. The as-obtained C-dots have been applied to bioimaging of HeLa cells, which shows their excellent biocompatibility and low cytotoxicity. The results reveal that C-dots are promising for real cell imaging applications. In addition, the carbon dots can be utilized as a probe for sensing phosphate.

'Imperfect' conjugated polymer nanoparticles from MEH-PPV for bioimaging and Fe(III) sensing.

A simple and effective method was reported for the preparation from MEH-PPV of conjugated polymer nanoparticles (Pdots) that are water-soluble and well dispersed. The as-prepared Pdots show bright orange fluorescence at a quantum yield up to 32.37%. The fluorescence intensity of Pdots can be quenched with good selectively by the successive addition of Fe(3+) . In addition, the as-obtained Pdots were applied to the imaging of HeLa cells, and exhibited low cytotoxicity and excellent biocompatibility.

Synthesis of highly luminescent mercaptosuccinic acid-coated CdSe nanocrystals under atmospheric conditions.

Here we report a facile one-pot method for the preparation of high-quality CdSe nanocrystals (NCs) in aqueous solution under an air atmosphere. Compared with the traditional use of NaHSe or H2 Se, the more stable sodium selenite is utilized as the Se source for preparing highly luminescent CdSe nanocrystals. By using mercaptosuccinic acid (MSA) as the capping agent and borate-citrate acid as the buffering solution, CdSe nanocrystals with high quantum yield (up to 70%) have been synthesized conveniently. The influence of different experimental parameters, such as the pH of the precursor solution, the molar ratio of Cd(2+) to Na2 SeO3 and Cd(2+) to MSA on the CdSe nanocrystals, has been systematically investigated. The prepared CdSe NCs were spherical with a size of ~ 5 nm.

Molecular rotor-based fluorescent probe for selective recognition of hybrid G-quadruplex and as a K+ sensor.

This work demonstrates the significant fluorescence enhancement of thioflavin T (ThT) when binding to G-quadruplexes possessing hybrid structures by using UV-vis absorption spectra, fluorescence spectra, and Tm experiments to confirm the binding events. ThT binding does not disturb native G-quadruplex structures preformed in Na(+) and K(+) solutions. The fluorescence enhancement is caused by the rotation restriction of benzothiazole (BZT) and dimethylaminobenzene (DMAB) rings in the ThT excited state upon its G-quadruplex binding. This molecular rotor mechanism as a means of fluorescence enhancement is confirmed using a nonrotor analogue of ThT. Hydroxylation and electrolyte experiments demonstrate that ThT stacks on the tetrad of the hybrid G-quadruplexes, whereas electrostatic forces contribute more to ThT binding for other G-quadruplex structures. By stacking on the tetrad, the ThT binding favors selective identification of DNA hybrid G-quadruplex structures with enhanced fluorescence and can serve as a conformation probe to monitor G-quadruplex structure conversion between hybrid and other structures. Using these properties, we developed a selective and label-free fluorescent K(+) sensor with a detection limit of 1 mM for K(+) in the presence of 100 mM Na(+). The coexistence of other metal ions produces a fluorescence response comparable to K(+) alone. We believe that ThT can potentially provide structure identification of hybrid G-quadruplexes and aid in the construction of G-quadruplex-based sensors.

Aqueous synthesis and characterization of TGA-capped CdSe quantum dots at freezing temperature.

CdSe quantum dots (QDs) have traditionally been synthesized in organic phase and then transferred to aqueous solution by functionalizing their surface with silica, polymers, short-chain thiol ligands, or phospholipid micelles. However, a drastic increase in the hydrodynamic size and biotoxicity of QDs may hinder their biomedical applications. In this paper, the TGA-capped CdSe QDs are directly synthesized in aqueous phase at freezing temperature, and they prove to possess high QY (up to 14%).

Fluorescent core-shell silica nanoparticles as tunable precursors: towards encoding and multifunctional nano-probes.

Core-shell silica nanoparticles comprised of a RuBpy doped silica core and a Pas-DTPA doped silica shell were synthesized and post-functionalized with an encoding fluorescence combination and multiplex imaging function.