Nitrogen-doped graphene quantum dot-based portable fluorescent sensors for the sensitive detection of Fe3+ and ATP with logic gate operation.

Adenosine triphosphate (ATP) and Fe3+ are important "signaling molecules" in living organisms, and their abnormal concentrations can be used for the early diagnosis of degenerative diseases. Therefore, the development of a sensitive and accurate fluorescent sensor is essential for detecting these signaling molecules in biological matrices. Herein, nitrogen-doped graphene quantum dots (N-GQDs) with cyan fluorescence emission were prepared by thermal cleavage of graphene oxide (GO) with N,N-dimethylformamide (DMF) as a solvent. The synergistic effect of static quenching and internal filtration enabled the selective quenching of N-GQD fluorescence by Fe3+. With the introduction of ATP, Fe3+ in the N-GQDs-Fe3+ system formed a more stable complex with ATP via the Fe-O-P bond, thus restoring the fluorescence of the N-GQDs. Fe3+ and ATP were detected in the linear ranges of 0-34 µM and 0-10 µM with the limits of detection (LOD) of 2.38 nM and 1.16 nM, respectively. In addition to monitoring Fe3+ and ATP in mouse serum and urine, the proposed method was also successfully applied for cytoplasmic imaging of 4T1 cells and in vivo imaging of freshwater shrimps. Moreover, the fluorescence and solution color change-based "AND" logic gate was successfully demonstrated in the biological matrix. Importantly, a complete sensing system was constructed by combining the N-GQDs with hydrogel kits and fluorescent flexible films. Thus, the prepared N-GQDs can be expected to serve as a valuable analytical tool for monitoring Fe3+ and ATP concentrations in biological matrices.

Facile synthesis of nitrogen-doped carbon dots as sensitive fluorescence probes for selective recognition of cinnamaldehyde and l-Arginine/l-Lysine in living cells.

The disorder of amino acid metabolism and the abuse of small molecule drugs pose serious threats to public health. However, due to the limitations of existing detection technologies in sensing cinnamaldehyde (CAL) and l-Arginine/l-Lysine (l-Arg/l-Lys), there is an urgent need to develop new sensing strategies to meet the severe challenges currently facing. Herein, nitrogen-doped carbon dots (N-CDs) were developed using a simple one-pot hydrothermal carbonization method. These N-CDs exhibited numerous distinctive characteristics such as excellent photoluminescence, high water dispersibility, favorable biocompatibility, and superior chemical inertness. Strikingly, the as-prepared CDs as a highly efficient fluorescent probe possessed significant sensitivity and selectivity toward CAL and l-Arg/l-Lys over other analytes with a low detection limit of 58 nM and 16 nM/18 nM, respectively. The fluorescence of N-CDs could be quenched by CAL through an electron transfer process. Then, the strong electrostatic interaction between l-Arg/l-Lys and N-CDs induced the efficient fluorescence recovery. More importantly, the outstanding biosafety and excellent analyte-responsive fluorescence characteristics of N-CDs have also been verified in living cells as well as in serum and urine. Overall, the N-CDs had a wide application prospect in the diagnosis of amino acid metabolic diseases and small molecule drug sensing.

Surface state dominated and carbon core coordinated red-emitting carbon dots for the detection of Cr2O72- and cell imaging.

Cr(VI) as a toxic heavy metal ion can easily enter into the body through drinking or eating and cause liver and kidney diseases as well as cancer. Considering its high biological toxicity and adverse effects on human body, it is desirable to develop a probe to monitor its level in the environment. Herein, a high-efficiency fluorescent nanoprobe based on red emissive carbon dots (R-CDs) was established through a convenient solvothermal strategy. The as-prepared CDs with excitation-independency had the fixed emission wavelength at 627 nm when the excitation wavelength was 560 nm. Further study manifested that the new surface state formed by nitrogen and sulfur doping and the increased conjugated system established through dehydration and carbonization were the main reasons for the fluorescence redshift. In this system, these R-CDs as a fluorescent probe exhibited high specificity and sensitivity to Cr2O72- with the linear range of 4-40 µΜ and the limit of detection could reach 80.00 nM. The quenching of these CDs by Cr2O72- was efficiently induced through a static quenching process. Meanwhile, the obtained CDs could enter into HeLa cells through endocytosis and exhibit bright red fluorescence in cells under a confocal laser scanning microscope. Thus, this work provided a promising probe not only for detecting Cr(VI) in natural environment but also for imaging in cells.

An "on-off-on" selective fluorescent probe based on nitrogen and sulfur co-doped carbon dots for detecting Cu2+ and GSH in living cells.

The abnormal level of Cu2+ or GSH can cause variety of neurodegenerative diseases in humans. Thus, the selective and sensitive detection of Cu2+ and GSH has inspired intensive research efforts in biological sample analysis fields. Herein, an "on-off-on" fluorescent probe based on nitrogen and sulfur co-doped carbon dots (N,S-CDs) has been successfully prepared for the detection of Cu2+ and GSH. The "turn-off" process of fluorescence in the presence of Cu2+ ions was induced by forming a non-luminescent ground state complex due to the interaction between surface groups of the probe and Cu2+ ions. Moreover, the strong coordination between GSH and Cu2+ could destroy the structure of the complex and restore the fluorescence to "turn-on". This fluorescent probe had excellent selectivity and high sensitivity toward Cu2+ and GSH with the limits of detection (LODs) of 38 nM and 41 nM. More importantly, the as-prepared N,S-CDs served as an efficient fluorescent probe for not only detecting Cu2+ ions in lake water and tap water, and GSH in BSA solution, but also sensing Cu2+ and GSH in living cells. Therefore, these N,S-CDs could be considered as a promising fluorescence probe candidate for environmental monitoring and biological imaging.

Tumor microenvironment-responsive polydopamine-based core/shell nanoplatform for synergetic theranostics.

Theranostic agents that integrate diagnostic and therapeutic modalities have drawn extensive attention due to their ability to deliver real-time imaging-guided tumor treatment. Herein, a novel core-shell polydopamine (PDA)-based theranostic agent (PDA@TA-Fe) was fabricated via a two-step strategy. Upon 808 nm and 1064 nm laser irradiation, this agent exhibited high photothermal conversion efficiencies of 29% and 41%, respectively. After endocytosis into tumor cells, the TA-Fe shell of PDA@TA-Fe gradually disintegrated in the weakly acidic tumor microenvironment (TME), and released the TA as an acidity-activated reductant that could reduce Fe3+ to Fe2+. Subsequently, the generated Fe2+ reacted with H2O2 to generate toxic hydroxyl radicals (˙OH) via the Fenton reaction, which induced the apoptosis of tumor cells and achieved the chemodynamic therapy (CDT). The heat produced by photothermal therapy (PTT) accelerated the ˙OH generation to achieve a synergetic effect of CDT/PTT. In vivo tumor-xenograft imaging and therapeutic assays demonstrated obvious contrast enhancement at the tumor site in the T1/T2-weighted MR imaging and efficient tumor suppression achieved after the intravenous injection of this agent because of the enhanced permeation and retention (EPR) effect. This study offered a new strategy to design an "all-in-one" nanoplatform for T1/T2 MR imaging-guided synergistic cancer treatment of CDT/PTT.

A sensitive "ON-OFF" fluorescent probe based on carbon dots for Fe2+ detection and cell imaging.

Fe2+ is a trace metal ion required by the human body, and its abnormal metabolism can cause serious diseases. Herein, we report the development of a highly efficient "ON-OFF" fluorescent probe based on carbon dots (CDs), prepared by a simple one-step hydrothermal method. The CDs exhibited exceptional water dispersibility and stability, superior luminescence performance and low cytotoxicity. The fluorescence could be efficiently quenched by Fe2+ through an electronic transfer process. And under the optimized experimental conditions, this probe shows excellent selectivity and high sensitivity towards Fe2+ with a detection limit of 51 nmol. More interestingly, this probe could realize the visual detection of Fe2+ when Fe3+ and Cu2+ ions were efficiently shielded by tartaric acid in the presence of ascorbic acid. Furthermore, the developed fluorescent probe has been successfully applied for the detection of Fe2+ in tap water and BSA solution as well as for the biosensing of Fe2+ in living cells.

Polypyrrole-based double rare earth hybrid nanoparticles for multimodal imaging and photothermal therapy.

Nanotheranostic agents that can simultaneously provide real-time tracking and accurate treatment at tumor sites are playing an increasingly important role in medicine. Herein, a novel polypyrrole (PPy)-based theranostic agent containing double rare-earth elements (PPy@BSA-Gd/Dy NPs) was successfully synthesized via an integrated strategy combining biomineralization and oxidation polymerization. The obtained PPy@BSA-Gd/Dy NPs with a diameter of approximately 59.48 ± 6.12 nm exhibited excellent solubility, long-term stability, superior biocompatibility, and negligible toxicity. Importantly, due to its intrinsic paramagnetic and strong X-ray attenuation ability, this agent demonstrated brilliant imaging performance in both T1/T2-weighted magnetic resonance imaging (MRI) and X-ray computed tomography (CT) imaging in vitro and vivo. Additionally, with an excellent photothermal conversion efficiency (26.61%) upon irradiation by an 808 nm laser, this theranostic agent showed significant photothermal cytotoxicity against HeLa cells and 4T1 cells in vitro and antitumor efficacy through intravenous injection in vivo. Meanwhile, biodistribution and blood circulation were also used to explore its fate in vivo. In summary, this study highlighted the versatility and practicability of PPy@BSA-Gd/Dy NPs and also suggested that the agent may be a promising candidate for T1/T2-weighted MRI/CT tri-modal imaging guided photothermal cancer therapy.

"ON-OFF-ON" fluorescent probes based on nitrogen-doped carbon dots for hypochlorite and bisulfite detection in living cells.

Although hypochlorite (ClO-) and bisulfite (HSO3-) play important roles in the biological immune system and the aging process of living organisms, they are also classified as a third type of carcinogens. Hence, a convenient and efficient method to monitor ClO- and HSO3- in ecological environments is highly desired. In this article, an "ON-OFF-ON" fluorescent probe based on nitrogen-doped carbon dots (N-CDs) for the detection of ClO- and HSO3- has been demonstrated successfully. Because of the destruction of the surface passivation layer, the fluorescence of the N-CDs was quenched by ClO-. Furthermore, the quenched fluorescence of the N-CDs was restored efficiently through the increase in conjugation from the attached sulfo groups, indicating the feasibility of ClO- and HSO3- detection. This fluorescent probe exhibited excellent sensitivity and selectivity to ClO- and HSO3- detection with the limits of detection (LODs) of 3.4 µM and 0.27 µM in aqueous solution, respectively. In addition, the as-prepared N-CDs were successfully applied to detect both ClO- and HSO3- in living cells due to their low toxicity and fast response speed.

Matrix solid-phase dispersion coupled with homogeneous ionic liquid microextraction for the determination of sulfonamides in animal tissues using high-performance liquid chromatography.

Matrix solid-phase dispersion coupled with homogeneous ionic liquid microextraction was developed and applied to the extraction of some sulfonamides, including sulfamerazine, sulfamethazine, sulfathiazole, sulfachloropyridazine, sulfadoxine, sulfisoxazole, and sulfaphenazole, in animal tissues. High-performance liquid chromatography was applied to the separation and determination of the target analytes. The solid sample was directly treated by matrix solid-phase dispersion and the eluate obtained was treated by homogeneous ionic liquid microextraction. The ionic liquid was used as the extraction solvent in this method, which may result in the improvement of the recoveries of the target analytes. To avoid using organic solvent and reduce environmental pollution, water was used as the elution solvent of matrix solid-phase dispersion. The effects of the experimental parameters on recoveries, including the type and volume of ionic liquid, type of dispersant, ratio of sample to dispersant, pH value of elution solvent, volume of elution solvent, amount of salt in eluate, amount of ion-pairing agent (NH4 PF6 ), and centrifuging time, were evaluated. When the present method was applied to the analysis of animal tissues, the recoveries of the analytes ranged from 85.4 to 118.0%, and the relative standard deviations were lower than 9.30%. The detection limits for the analytes were 4.3-13.4 µg/kg.

Application of C18-functional magnetic nanoparticles for extraction of aromatic amines from human urine.

In this paper, a novel method using C18-functional ultrafine magnetic silica nanoparticles (C18-UMS NPs) as adsorbents was developed for rapid extraction and enrichment of aromatic amines from urine. C18-UMS NPs were prepared by chemical coprecipitation, silanization and alkylation. The aromatic amines can be adsorbed on C18-UMS NPs and isolated easily from the matrix with an external magnetic field. After desorption with acetonitrile, the aromatic amines were determined by ultra fast liquid chromatography. The experimental parameters, such as pH value of sample solution, amount of C18-UMS NPs, extraction time, type and volume of desorption solvent, and desorption time were optimized. The analytical performances of the present method were also evaluated. The limits of detection for 1-aminonaphthalene, 4-aminobiphenyl, 4,4'-diaminodiphenylmethane and 4-aminophenylthioether were 1.3, 0.88, 1.1 and 1.1 ng mL(-1), respectively. The results showed that the present method was simple, highly efficient and rapid for the extraction and enrichment of aromatic amines from urine.

Liquid-solid extraction coupled with magnetic solid-phase extraction for determination of pyrethroid residues in vegetable samples by ultra fast liquid chromatography.

In this study, liquid-solid extraction coupled with magnetic solid-phase extraction was successfully developed for the extraction of pyrethroid residues in vegetable samples. The analytes were determined by ultra fast liquid chromatography. The pyrethroids were extracted by liquid-solid extraction and then adsorbed onto magnetic adsorbent. Magnetic adsorbent, C18-functionalized ultrafine magnetic silica nanoparticles, was synthesized by chemical coprecipitation, silanization and alkylation. The analytes adsorbed onto the magnetic adsorbent can be simply and rapidly isolated from sample solution with a strong magnet on the bottom of the extraction vessel. The extraction parameters, such as liquid-solid extraction solvent, liquid-solid extraction time, the amount of magnetic adsorbent, magnetic solid-phase extraction time and magnetic solid-phase extraction desorption solvent, were optimized to improve the extraction efficiency. The analytical performances of this method, including linear range, detection limit, precision, and recovery were evaluated. The limits of detection for pyrethroid were between 0.63 and 1.2 ng g(-1). Recoveries obtained by analyzing the four spiked vegetable samples were between 76.0% and 99.5%. The results showed that the present method was a simple, accurate and high efficient approach for the determination of pyrethroids in the vegetable samples.

Fast determination of pyrethroid pesticides in tobacco by GC-MS-SIM coupled with modified QuEChERS sample preparation procedure.

An analytical method was developed for the extraction and determination of pyrethroid pesticide residues in tobacco. The modified QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method was applied for preparing samples. In this study, methyl cyanide (MeCN)-saturated salt aqueous was used as the two-phase extraction solvent for the first time, and a vortex shaker was used for the simultaneous shaking and concentration of the analytes. The effects of experimental parameters on extraction and clean-up efficiency were investigated and optimized. The analytes were determined by gas chromatography-mass spectrometry-selected ion monitoring (GC-MS-SIM). The obtained recoveries of the analytes at three different fortification levels were 76.85-114.1% and relative standard deviations (RSDs) were lower than 15.7%. The limits of quantification (LOQs) were from 1.28 to 26.6 µg kg(-1). This method was also applied to the analysis of actual commercial tobacco products and the analytical results were satisfactory.

Magnetic solid-phase extraction and ultrafast liquid chromatographic detection of Sudan dyes in red wines, juices, and mature vinegars.

A nanocomposite of polystyrene-coated magnetic nanoparticles was successfully synthesized and employed as adsorbent for magnetic solid-phase extraction of four Sudan dyes (I, II III, and IV) in red wines, juices, and mature vinegars. The prepared magnetic nanoparticles with highly hydrophobic properties have excellent adsorption capacity for these lipophilic Sudan dyes. Extraction conditions were optimized. Experimental results showed that the recoveries of the four Sudan dyes were very satisfactory when 70 mg of polystyrene-coated magnetic nanoparticles were used and the extraction could be completed within 20 min. It was proved that these magnetic nanoparticles can be reused after an easy washing process. By coupling the magnetic solid-phase extraction with ultrafast liquid chromatography-ultraviolet spectrometry, a rapid, green, effective, and sensitive method for the determination of Sudan dyes was developed. The LOD for Sudan I, Sudan II, Sudan III, and Sudan IV were 0.0039, 0.0063, 0.0057, and 0.017 ng/mL, respectively. Recoveries obtained by analyzing spiked water samples at three concentration levels (0.1, 1.0, and 10.0 ng/mL) were between 76.3 and 96.6%. The intra- and interday RSDs for the analytes were lower than 9.6%.

Magnetic solid-phase extraction of five pyrethroids from environmental water samples followed by ultrafast liquid chromatography analysis.

In this study, the polystyrene-coated magnetic nanoparticles (MNPs/PSt) were successfully prepared and characterized by Fourier transform infrared spectroscopy, transmission electron microscopy and vibrating sample magnetometry. The as-prepared MNPs/PSt were used as the adsorbent in magnetic solid phase extraction of five pyrethroids, including lambda-cyhalothrin, deltamethrin, esfenvalerate, permethrin, bifenthrin, in environmental water samples. The five pyrethroids were determined by ultra fast liquid chromatography-ultraviolet spectrometry. The influencing factors, including amount of MNPs/Pst, extraction time, pH value, type and volume of desorption solvent and desorption time, were examined and optimized. The extraction recoveries obtained with merely 50mg of MNPs/Pst were very satisfactory. The whole extraction process could be completed within 0.5h. The MNPs/PSt can be reused after an easy washing process. Thus, a simple, green, economical, time saving and effective method for pyrethroids analysis in environmental water samples was established. A high enrichment factor of 500 was achieved and the limits of detection for lambda-cyhalothrin, deltamethrin, esfenvalerate, permethrin, bifenthrin were 0.015±0.001 ng mL(-1), 0.012±0.001 ng mL(-1), 0.026±0.001 ng mL(-1), 0.020±0.001 ng mL(-1), 0.013±0.001 ng mL(-1), respectively. Recoveries obtained by analyzing spiked water samples at three concentration levels (0.100±0.001 ng mL(-1), 1.000±0.001 ng mL(-1), 10.000±0.001 ng mL(-1)) were between 78.97±8.38% and 96.05±8.38%. The standard curves for the five pyrethroids showed good linearity with the correlation coefficients in the range of 0.9994-0.9999. The intra-day and inter-day precision were satisfactory with the RSDs in the range of 2.05-5.52% and 2.73-8.38%, respectively.

Removal of sudan dyes from water with C18-functional ultrafine magnetic silica nanoparticles.

In this study, the new C(18)-functionalized ultrafine magnetic silica nanoparticles (C(18)-UMS NPs) were successfully synthesized and applied for extraction of sudan dyes in water samples based on the magnetic solid-phase extraction (MSPE). The extraction and concentration were carried out in one step by blending C(18)-UMS NPs and water samples. The sudan dyes adsorbed C(18)-UMS NPs were isolated from the matrix easily with an external magnetic field. After desorption the quantitation of sudan dyes was done by ultra fast liquid chromatography (UFLC). Satisfactory extraction recovery can be obtained with only 50 mg C(18)-UMS NPs. The effects of experimental parameters, including the amount of the nanoparticles, extraction time, pH value, desorption solvent, volume of desorption solvent and desorption time were investigated. The limits of detection for sudan I, II, III and IV were 0.066, 0.070, 0.12 and 0.12 ng mL(-1), respectively. Recoveries obtained by analyzing the six spiked water samples were between 68% and 103%.

[Effect of technological parameters of sputtering on the microstructure of silicon film investigated by Raman analysis].

In order to facilitate optical polishing of silicon carbide space telescope, in the present paper, silicon film, which has similar coefficient of thermal expansion with silicon carbide, was fabricated on SiC substrate by radio frequency magnetron sputtering. The effect of substrate temperature, radio frequency power, and substrate bias voltage was investigated by Raman scattering. The results indicate that at lower substrate temperature, the crystalline volume fraction of Si films increases with the increase in deposition temperature. Exceeding a certain temperature, the crystalline volume fraction decreases with further increasing deposition temperature; the increase in substrate bias voltage is bad for forming crystalline structure; the effect of radio power on microstructure of silicon film is comparatively complicated. As the rf power increases, the cluster size and crystallite volume fraction decrease, and both of them increase with further increasing the rf power. But when the rf power is too high, the crystallite volume fraction of the silicon film will decrease slightly.

Solvent-free microwave extraction coupled with headspace single-drop microextraction of essential oils from flower of Eugenia caryophyllata Thunb.

Solvent-free microwave extraction coupled with headspace single-drop microextraction was developed for extracting the essential oils from Eugenia caryophyllata Thunb. Carbonyl iron powders were mixed with the sample to extract essential oils from the dried plant materials and single-drop solvent was used to simultaneously extract essential oils from the headspace. The single-drop of decane was suspended from the tip of a microsyringe and exposed to the headspace above the sample. After the extraction was finished, the single-drop was injected into gas chromatographic system and analyzed by GC-MS. The effects of the experimental parameters, including microwave power, microwave irradiation time, the ratio of carbonyl iron powder to sample, extraction solvent, single-drop volume and extraction time, were investigated. Sixteen compounds in the essential oils of E. caryophyllata T. were obtained and identified. The constituents of essential oils obtained by hydro-distillation and solvent-free microwave extraction-headspace single-drop microextraction were not obviously different. Compared with hydro-distillation, the proposed method required shorter extraction time and less amount of the sample.

[Spectroscopic ellipsometry investigations of amorphous diamond films deposited with filtered arc].

In order to investigate thoroughly the optical properties of amorphous diamond (alpha-D) films deposited by the filtered vacuum arc technology, the optical constants of the films were measured by spectroscopic ellipsometry. Moreover, the dispersion relations of the optical constants, and the correlations among refractive index, extinction coefficient, optical gap and the substrate bias were also analyzed. It has been shown that the refractive index of alpha-D films is higher than that of diamond crystal, and the absorption edge corresponding to the interband transformation can be described with the parabolic line shape. With increasing the wavelength, the extinction coefficient gradually declines and approaches nearly to zero in the infrared band. In addition, the adjustable amplitudes of the optical constants owing to the changing bias also reduce strikingly with the extension of the wavelength. With raising the bias, the refractive index and the optical gap firstly augment, then minish, and there is a maximal value when the substrate bias is -80 V. However, the extinction coefficient firstly minishes, then augments, and there is a minimal value when the bias is -80 V.