Simple and green approach for photoluminescent carbon dots prepared from faba bean seeds as a luminescent probe for determination of Hg+ ions and cell imaging

In this research, for the first time, a dedicated sensor was designed to detect Hg⁺ ions using photoluminescent carbon dots (CDs). Due to the preferred green synthesis of CDs from bio-resources, carbohydrate-rich faba bean seeds as a potential carbon precursor were applied to the synthesis of CDs. The CDs were prepared from the faba bean seeds using the hydrothermal method in an aqueous solution in the absence of substances such as an acid or base and any other additives. The synthesized CDs exhibited maximum emission intensity at 387 nm when excited at 310 nm and their luminescence quantum yield was calculated to be ~5.94%. Then, the fluorescence emission of CDs was examined in the presence of different metal ions. Results revealed that the CDs had good selectivity towards the Hg⁺ ions, so the fluorescence emission was significantly changed in the presence of these ions with a limit of detection (LOD) as low as 0.35 μM. Furthermore, because of their very low cytotoxicity, these CDs can be applied for cell imaging.     

Selective detection of azelnidipine in pharmaceuticals via carbon dot mediated spectrofluorimetric method: A green approach

A spectrofluorimetric method using fluorescent carbon dots (CDs) was developed for the selective detection of azelnidipine (AZEL) pharmaceutical in the presence of other drugs. In this study, N-doped CDs (N-CDs) were synthesized through a single-step hydrothermal process, using citric acid and urea as precursor materials. The prepared N-CDs showed a highly intense blue fluorescence emission at 447 nm, with a photoluminescence quantum yield of ~21.15% and a fluorescence lifetime of 0.47 ns. The N-CDs showed selective fluorescence quenching in the presence of all three antihypertensive drugs, which was used as a successful detection platform for the analysis of AZEL. The photophysical properties, UV–vis light absorbance, fluorescence emission, and lifetime measurements support the interaction between N-CDs and AZEL, leading to fluorescence quenching of N-CDs as a result of ground-state complex formation followed by a static fluorescence quenching phenomenon. The detection platform showed linearity in the range 10–200 μg/ml (R² = 0.9837). The developed method was effectively utilized for the quantitative analysis of AZEL in commercially available pharmaceutical tablets, yielding results that closely align with those obtained from the standard method (UV spectroscopy). With a score of 0.76 on the ‘Analytical GREEnness (AGREE)’ scale, the developed analytical method, incorporating 12 distinct green analytical chemistry components, stands out as an important technique for estimating AZEL.     

Bioinspired multicolour carbon dots: comprehensive cytotoxicity,phytotoxicity, and bioimaging in animal cells and plants

During the past decades, carbon dots (CDs) as a kind of nanoparticles with interesting fluorescence properties have retained their place as one of the best bioimaging agents, although their effects on plants have been rarely studied. In this study, we synthesized two kinds of concentration-dependent multicolour CDs using two solvent approaches, phosphate-buffered saline (PBS) and ethanol 20%. We confirmed the nature of the CDs through Fourier transform infrared spectroscopy, atomic force microscopy, dynamic light scattering, zeta potential, X-ray powder diffraction, and high-resolution transmission electron microscopy. Afterwards, the cytotoxicity, phytotoxicity, and bioimaging of animal cells and plants using both synthesized CDs were examined. Eventually, PBS-based CDs were recommended during this study as an efficient bioimaging agent for animal cells and plants because of the appealing features of this CD, such as a small size range of less than 10 nm, surface charge with an average of −24 mV, a high quantum yield of 35.82%, the higher fluorescence intensity of ~400 a.u. for blue fluorescence light and 250 a.u. for green fluorescence light. Other features showing the superiority of PBS-based CDs include high photostability, low phytotoxicity (p ≤ 0.05 and p ≤ 0.01) and above all, there was no significant cytotoxicity at the concentration range of 500–7.81 μg/ml.     

Green synthesis of fluorescent carbon dots using chloroplast dispersions as precursors and application for Fe3+ ion sensing

Water‐soluble carbon dots (CDs) were synthesized using a one‐step hydrothermal treatment of chloroplast dispersions extracted from fresh leaves as a green carbon source. The CD solution showed an emission peak centred at 445 nm when excited at 300 nm. The synthesized CDs were uniform and monodispersed with an average size of 5.6 nm. When adding ferric(III) ions (Fe³⁺) to the solution of the original CDs, the fluorescence intensity decreased significantly. Based on the linear relationship between fluorescence intensity and concentration of Fe³⁺ ions, an effective method for rapid, sensitive and selective Fe³⁺ sensing in aqueous solution could be established. Under optimum conditions, the extent of the fluorescence quenching of prepared CDs strongly depended on the Fe³⁺ ions over a wide concentration range 1.0–100.0 μM with a detection limit (3σ/k) of 0.3 μM. Furthermore, the quantitative determination of Fe³⁺ ions in environmental water samples was realized.     

Carbon dots synthesized by the m‐trihydroxybenzene as the carbon source and its application on the detection of pH value

New carbon dots (CDs) were prepared by a microwave method using m‐trihydroxybenzene and dilute sulphuric acid as raw materials. The as‐prepared CDs exhibited excellent water solubility and photoluminesence properties. The optimum excitation and emission wavelengths of the new CDs were at 365 nm and 465 nm, respectively. The fluorescence of the new CDs experienced remarkable changes in the presence of Britton–Robinson (BR) buffer solution with different pH values under 4°C after reacting for 70 min. In addition, a linear relationship between the logarithm of the relative fluorescence intensity ratio [lg(I_F/I_Fo)] of CDs and the pH values of the sensing system ranging 1.81–5.72 was obtained, with a correlation coefficient of 0.9933. Thus, a sensitive and simple method to detect the pH value of solution was developed. Furthermore, the analytical application of detecting the concentration of acetic acid in vinegar was investigated. The detection values were found similar to the reference values, fully demonstrating a good linear relationship between the logarithm of the relative fluorescence intensity ratio of the CDs and the pH value of the system. Hence, the method could be used to detect the concentration of acetic acid in vinegar.     

The effect of cyclodextrins on the ethanol tolerance of microorganisms suggests potential application

Cyclodextrins (CDs) are used in food, pharmaceutical, and chemical industries, as well as agriculture and environmental engineering. Cyclodextrin glucanotransferase (CGTase) is an important industrial extracellular enzyme which is used to produce CDs and oligosaccharides. We previously developed a novel yeast-surface CGTase expression system which was used for the production of CDs from starch. In the present study, we showed that the presence of CDs may increase the ethanol tolerance of microorganisms. The cell numbers of Saccharomyces cerevisiae and Escherichia coli in the presence of β-cyclodextrin and ethanol were 1,000-fold and 10-fold higher than that without CDs. The yeast strain with the immobilized CGTase produced 13 g CDs/l and 1.8 g ethanol/l when it was incubated in yeast medium supplemented with 4% starch. The effect of CDs on microorganisms suggests a potential application for the co-production of CDs and ethanol.     

Induction of ethylene biosynthesis in tobacco leaf discs by cell wall disesting enzymes

Cellulysin induces ethylene production in tobacco leaf discs by initiating the formation of 1-aminocyclopropane-1-carboxylic acid. Induction occurred within 30 to 60 min of incubation and was inhibited by aminoethoxyvinylglycine, and the antiproteases, PMSF and soybean trypsin inhibitor. Cycloheximide (CHI) at 2.8 μg/ml and chloramphenicol (CAP) at 100 μg/ml did not inhibit this induction although incorporation of the label from (3,4-¹⁴C)methionine into the acid-insoluble fraction was inhibited by 57%. At 14 μg/ml CHI, and CAP, ethylene production was inhibited by 25% while protein synthesis was inhibited by 75%. We suggest that either the low amounts of protein synthesis that appear to be insensitive to CHI is sufficient to induce ethylene biosynthesis or that Cellulysin activates a preexisting but inactive form of ACC synthase to promote ethylene biosynthesis. Also, induction of ethylene production by microbial enzymes that digests plant cell walls may be an initial protective response of plants that serves to combat microbial infection.     

Highly fluorescent carbon dots from wheat bran as a novel drug delivery system for bacterial inhibition

In this study, we prepared carbon dots (CDs) from wheat bran via hydrothermal treatment at 180°C for 3 h. The prepared CDs showed blue‐green fluorescence under UV light. The fluorescence emission study of the CDs revealed that they showed maximum fluorescence emission at 500 nm. The prepared CDs showed a high quantum yield of 33.23%. Solvent‐dependent fluorescence emission analysis of the CDs was performed to study the variation in fluorescence emission characteristics with solvent polarity. The prepared CDs were conjugated with amoxicillin (AMX) to explore its potential for use as a drug delivery agent for AMX. The drug release profile of the CD–AMX conjugates was analyzed at different pH (5.0, 6.8 and 7.2) to study drug release kinetics. CD–AMX conjugates showed notable bacterial inhibition against Gram‐positive (S. aureus) and Gram‐negative (E. coli) strains with minimal cytotoxic effects, indicating its potential as a promising antibacterial drug delivery system.     

Dramatic red fluorescence enhancement and emission red shift of carbon dots following Zn/ZnO decoration

Metal atom doping, an easy and convenient method, can optimize and tune the physical–chemical properties and photometrics of carbon dots (CDs). However, there are few reports on the preparation of metal‐decorated CDs that give red emission and a high photoluminescence quantum yield (PLQY). Here, we demonstrate a zinc (existing in human body) ion‐doping strategy to observably enhance the PLQY and lengthen the CD emission wavelength. The prepared Zn/ZnO‐decorated CDs (Zn‐CDs) produced red fluorescence (623 nm) with a superior PLQY of 40.3%. Through a series of analyses, Zn‐CDs were confirmed to contain an oxidation state and reduction state of Zn doping into the internal defects and surface of Zn‐CDs. More valuably, the Zn‐CDs had excellent chemical stability, photo‐stability, long‐term storage stability, and high biocompatibility, and therefore could be used as a robust red fluorescence probe for high‐quality cellular imaging.     

Nitrogen‐doped carbon dots as a fluorescent probe for the highly sensitive detection of Ag+ and cell imaging

An easy hydrothermal synthesis strategy was applied to synthesize green‐yellow emitting nitrogen‐doped carbon dots (N‐CDs) using 1,2‐diaminobenzene as the carbon source, and dicyandiamide as the dopant. The nitrogen‐doped CDs resulted in improvement in the electronic characteristics and surface chemical activities. N‐CDs exhibited bright fluorescence emission and could response to Ag⁺ selectively and sensitively. Other ions produced nearly no interference. A N‐CDs based fluorescent probe was then applied to sensitively determine Ag⁺ with a detection limit of 5 × 10^?8 mol/L. The method was applied to the determination of Ag⁺ dissolved in water. Finally, negligibly cytotoxic, excellently biocompatibile, and highly fluorescent carbon dots were applied for HepG2 cell imaging and the quenched fluorescence by adding Ag⁺, which indicated its potential applications.     

Metal ion-mediated carbon dot nanoprobe for fluorescent turn-on sensing of N-acetyl-l-cysteine

In this work, carbon dots (CDs) was easily synthesized from aspartic acid through a pyrolysis method. Based on their favourable fluorescence properties, CDs were utilized to design a metal ion-mediated fluorescent probe for N-acetyl-l -cysteine (NAC) detection. The fluorescence intensity of CDs was firstly quenched by manganese ions (Mn²⁺) through static quenching effect and subsequently restored by NAC via the combination with Mn²⁺ due to the coordination effect. Therefore, the fluorescent turn-on sensing of NAC was actuated based on the fluorescence quenching stimulated by Mn²⁺ and recovery induced by coordination. The fluorescence recovery efficiencies showed a proportional range to the concentration of NAC in the range 0.04–5 mmol L⁻¹ and the detection limit was 0.03 mmol L⁻¹. Furthermore, this metal ion-mediated fluorescent nanoprobe was applied to human urine sample detection and the standard recovery rates were located in the range 97.62–102.34%. This was the first time that Mn²⁺ was used to construct a fluorescent nanoprobe for NAC. Compared with other heavy metal ions, Mn²⁺ with good biosecurity prevented the risk of application, which made the nanoprobe green and biopractical. The facile synthesis of CDs and novel metal ion-mediated sensing mode made it a promising method for pharmaceutical analysis.     

Recent progress on performances and mechanisms of carbon dots for gas sensing

Carbon dots (CDs), as an attractive zero-dimensional carbon nanomaterial with unique photoluminescent merits, have recently exhibited significant application potential in gas sensing as a result of their excellent optical/electronic characteristics, high chemical/thermal stability, and tunable surface states. CDs exhibit strong light absorption in the ultraviolet range and tunable photoluminescence characteristics in the visible range, which makes CDs an effective tool for optical sensing applications. Optical gas sensor based on CDs have been investigated, which generally responds to the target gas by corresponding changes in optical absorption or fluorescence. Moreover, electrical gas sensor and quartz crystal microbalance sensor whose sensing layer involves CDs have also been designed. Electrical gas sensor exhibits an increase or a decrease in electrical current, capacitance, or conductance once exposed to the target gas. Quartz crystal microbalance sensor responds to the target gas with a frequency shift. CDs greatly promote the absorption of the target gas and improve the sensitivity of both sensors. In this review, we aim to summarize different types of gas sensors involving CDs, and sensing performances of these sensors for monitoring diverse gases or vapors, as well as the mechanisms of CDs in different types of sensors. Moreover, this review provides the prospect of the potential development of CDs based gas sensors.     

Inhibition of NADH oxidation by chloramphenicol in the freely moving rat measured by picosecond time-resolved emission spectroscopy

Owing to the lack of methods capable to monitor the energetic processes taking place within small brain regions (i.e. nucleus raphe dorsalis, nRD), the neurotoxicity of various categories of substances, including antibiotics and psycho-active drugs, still remains difficult to evaluate. Using an in vivo picosecond optical spectroscopy imaging method, we report that chloramphenicol (CAP), besides its well-known ability to inhibit the mitochondria protein synthesis, also influences the NADH/NAD+ redox processes of the respiratory chain. At a 200-mg/kg dose, CAP indeed produces a marked increase in the fluorescent signal of the nRD which, according to clear evidence, is likely to be related to the NADH concentration. This effect also implies an efficient inhibition of complex I of the respiratory chain by CAP. It refers to the mechanism through which the adverse effects of the antibiotic may take place. It could explain why paradoxical sleep, a state needing aerobic energy to occur, is suppressed after CAP administration. The present approach constitutes the first attempt to determine by fluorescence methods the effects of substances on deep brain structures of the freely moving animal. It points out that in vivo ultrafast optical methods are innovative and adequate tools for combined neurochemical and behavioural approaches.     

Die Steigerung der durch Phytochrom bewirkten Anthocyansynthese des Senfkeimlings (Sinapis alba L.) durch Chloramphenicol

Zusammenfassung Chloramphenicol (CAP) steigert in einem gewissen Konzentrationsbereich (etwa 20–40 g/ml) die durch Dunkelrot (DR) ausgelöste Anthocyansynthese des Senfkeimlings. Die lag-Phase sowie der Zeitpunkt der Beendigung der Anthocyansynthese werden durch das Antibioticum nicht beeinflußt. Mit und ohne CAP beobachtet man bei allen untersuchten DR-Intensitäten eine konstante Akkumulationsrate an Anthocyan über einen Zeitraum von mindestens 24 Std. —Die Steigerung der Akkumulationsrate durch CAP (20 g/ml) liegt stets im Bereich von 25%, auch wenn die DR-Intensität auf die Hälfte oder ein Viertel gesenkt wird (Wirkung des CAP=25% · Wirkung des DR). Man kann daraus formal schließen, daß CAP und DR unabhängig voneinander die Anthocyansynthese beeinflussen. Molekular läßt sich der Sachverhalt folgendermaßen deuten: CAP hemmt bei einer Konzentration von 20 g/ml die Proteinsynthese der Plastiden. Dadurch wird der Phenylalanin-pool in den Kotyledonen erhöht. Da diese geringe CAP-Konzentration die cytoplasmatische Proteinsynthese noch nicht hemmt, kann die Anthocyansynthese ungestört ablaufen. Da Phenylalanin als eine Vorstufe der Flavonoidsynthese fungiert, führt das erhöhte Angebot an dieser Substanz zu einer Steigerung der Anthocyansynthese.

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The increase of phytochrome-mediated anthocyanin synthesis in the mustard seedling (Sinapis alba L.) by chloramphenicol

Summary Chloramphenicol (CAP) within a certain range of concentration (about 20–30g/ml) increases the rate of far-red mediated anthocyanin accumulation in the mustard seedling (Sinapis alba L.) (Fig. 1). The lag-phase after the onset of far-red and the time of termination of anthocyanin synthesis are not influenced by the presence of the antibiotic (Fig. 2). With and without CAP we observe a constant rate of anthocyanin accumulation over a period of at least 24 hours after the lag-phase at all far-red intensities investigated (Fig. 2). The percentage increase of the rate of anthocyanin accumulation which is due to CAP (20 g/ml) is independent of the far-red intensity applied and always amounts to about 25% (Table). Formally one can conclude that CAP and far-red seem to act as two independent factors in a multiplicative system. On the molecular level the observations can possibly be explained as follows: CAP at a concentration of 20 g/ml inhibits protein synthesis of the plastids. This inhibition leads to an increase of the pool of phenylalanine in the cotyledons. Because the small concentration of CAP does not interfere with protein synthesis (enzyme synthesis) in the cytoplasm, far-red mediated anthocyanin synthesis can proceed normally. Since phenylalanine acts as a precursor of flavonoids the increased pool of this substance will lead to an increase in the rate of anthocyanin accumulation.

     

Enzyme‐triggered fluorescence turn‐off/turn‐on of carbon dots for monitoring β‐glucosidase and its inhibitor in living cells

Energy transfer engineering based on fluorescent probes for directly sensing enzyme activities are in great demand as enzyme‐mediated transformations, which are central to all biological processes. Here, a fluorescence carbon dot (CD)‐based assay exhibiting selective responses to the quantitation of β‐glucosidase and the effect of its inhibitor was developed. The most common substrate, para‐nitrophenyl‐β‐d ‐glucopyranoside (pNPG) was hydrolyzed by β‐glucosidase to release p‐nitrophenol (pNP), which can efficiently quench fluorescence of CDs via an inner filter effect and electron transfer. However, in the presence of inhibitors of β‐glucosidase, the fluorescence intensity gradually recovered as the concentration of inhibitors increased. Therefore, the enzyme‐triggered fluorescence turn‐off/turn‐on of specific CDs successfully achieved sensitive detection of β‐glucosidase and monitored the effect of its inhibitors. This new strategy was applied to detect β‐glucosidase and monitor β‐glucosidase inhibitor in hepatoma cells using cell imaging. All results suggest that the new method is sensitive and promising for use in cancer diagnosis and treatment.     

Conformational studies of a peptide corresponding to a region of the C-terminus of ribonuclease A: implications as a potential chain-folding initiation site

Conformational properties of the OT-16 peptide, the C-terminal 20 amino acids of RNase A, were examined by nonradiative energy transfer. A modified OT-16 peptide was prepared by solid-phase synthesis with the inclusion of diaminobutyric acid (DABA) at the C-terminus. The OT-16-DABA peptide was labeled with a fluorescent 1,5-dimethylaminonaphthalene sulfonyl (dansyl, DNS) acceptor at the N-terminal amine and a fluorescent naphthoxyacetic acid (NAA) donor at the gamma-amine of the DABA located at the C-terminus of the peptide by using an orthogonal protection scheme. Energy transfer was monitored in DNS-OT-16-DABA-NAA by using both fluorescence intensity (sensitized emission) and lifetime (donor quenching) experiments. The lifetime data indicate that the peptide system is a dynamic, flexible one. A detailed analysis, based on a dynamic model that includes a skewed Gaussian function to model the equilibrium distribution of interprobe distances and a mutual diffusion coefficient between the two probes to model conformational dynamics in the peptide [Beechem & Haas (1989) Biophys. J. 55, 1225.], identified the existence of a partially ordered structure (relatively narrow distribution of interprobe distances) at temperatures greater than or equal to 20 degrees C in the absence of denaturant. The width and the position of the average of the distributions decrease with increasing temperature, in this range; this suggests that the structure is stabilized by hydrophobic interactions. In addition, the peptide undergoes cold denaturation at around 1.5 degrees C as indicated by broadening of the distance distribution. The addition of 6 M guanidine hydrochloride (Gdn-HCl) also broadens the distance distribution significantly, presumably by eliminating the hydrophobic interactions and unfolding the peptide. The results of the analysis of the distance distribution demonstrate that (1) nonradiative energy transfer can be used to study the conformational dynamics of peptides on the nanosecond time scale, (2) a partially ordered structure of OT-16-DABA exists in solution under typical refolding conditions, and (3) structural constraints (presumably hydrophobic interactions) necessary for the formation of a chain-folding initiation site in RNase A are also present in the OT-16-DABA peptide in the absence of denaturant and are disrupted by Gdn-HCl.     

A ratiometric fluorescent sensor for the detection of phosphate

Over the past few years, ratiometric fluorescent nanoprobes have garnered substantial interest because of their self-calibration characteristics. This research developed a ratiometric fluorescent sensor to detect phosphate. Through encapsulating luminescent materials, gold nanoclusters (AuNCs) and carbon dots (CDs) into a zeolitic imidazolate framework-8 (ZIF-8), the fluorescence signal of AuNCs was enhanced, while that of CDs was suppressed. After phosphate was added, it could decompose ZIF-8, and AuNCs and CDs were released, which weakened the fluorescence signal of the AuNCs while restoring that of the CDs. Thereby, this makes CDs/AuNCs@ZIF-8 a potential fluorescent sensor for phosphate determination. The ratiometric sensor had facile synthesis, good selectivity, and a low detection limit. Therefore, this sensor was an effective tool for the detection of phosphate.     

Low-Cost Plasmonic Carbon Spacer for Surface Plasmon-Coupled Emission Enhancements and Ethanol Detection: a Smartphone Approach

Surface plasmon-coupled emission (SPCE) has led to significant advancements in analytical techniques on account of its unique characteristics that include highly polarized photon-sorting ability. In this study, we report the use of a low-cost activated carbon as a plasmonic spacer in the SPCE substrate for achieving 30-fold enhancement in fluorescence emission. We extend the use of this spacer in the presence of Rhodamine B Base, a lactone dye as the sensing material for smartphone-based ethanol detection on the SPCE platform. Ethanol detection from 1 to 6% concentration highlights the potential use of this technique in monitoring fermentation processes.     

Polymer composite fluorescent hydrogel film based on nitrogen‐doped carbon dots and their application in the detection of Hg2+ ions

A simple microwave‐assisted solvothermal method was used to prepare fluorescent nitrogen‐doped carbon dots (N‐CDs) with high fluorescence quantum yield (79.63%) using citric acid and N‐(2‐hydroxyethyl)ethylenediamine as starting materials. The PVAm‐g‐N‐CDs grafted products were synthesized by amide bond formation between the carboxylic groups of N‐CDs and amine groups of polyvinylamine (PVAm). Fluorescent hydrogel films (PVAm‐g‐N‐CDs/PAM) were synthesized by interpenetration polymer network polymerization of PVAm‐g‐N‐CDs and acrylamide (AM). When used for ion detection, we found that the fluorescence of the hydrogel films was clearly quenched by addition of Hg²⁺. Repeatability tests on using the hydrogel films for Hg²⁺ detection showed that they could be applied at least three times. The PVAm‐g‐N‐CDs/PAM could serve as an effective fluorescent sensing platform for sensitive detection of Hg²⁺ ions with a detection limit of 0.089 μmol/L. This work may offer a new approach for developing recoverable and sensitive N‐CDs‐based sensors for biological and environmental applications.     

Réoxydation du quencher de fluorescence “Q” en présence de 3-(3,4-dichlorophényl)-1,1-diméthylurée

Reoxidation of the fluorescence quencher “Q” in the presence of 3-(3,4-dichlorophenyl)-1,1-dimethylurea

Reoxidation of the fluorescence quencher Q in the presence of 3-(3,4-dichlorophenyl)-1,1-dimethylurea shows the following properties:

It is sensitive to very low concentrations of hydroxylamine (a few μM).

It corresponds to a back reaction between Q⁻ and the primary oxidant Z⁺ formed in the light. A part of this back reaction gives rise to luminescence emission.

Within the range we studied the kinetic of reoxidation is second order with regards to Q⁻.