Nitrogen, boron-doped Ti3C2 MXene quantum dot-based ratiometric fluorescence sensing platform for point-of-care testing of tetracycline using an enhanced antenna effect by Eu3.

The Ti3C2 MXene quantum dots (Ti3C2 MQDs) derived from Ti3C2 MXene have received much attention because of their remarkable advantages in biosensing. Nevertheless, the functionalization of Ti3C2 MQDs to improve their properties is just in its infant stage. Herein, we firstly synthesized nitrogen and boron co-doped Ti3C2 MQDs (N, B-Ti3C2 MQDs) with good water solubility, strong stability, and high optical characteristics. The N, B-Ti3C2 MQDs exhibit excitation wavelength-dependent blue photoluminescence with optimal excitation/emission peaks at 335/439 nm. Nowadays, the development of fast and real-time detection of tetracycline (TC) in animal derived food is very essential. In this work, a novel point-of-care testing (POCT) platform was established based on ratiometric fluorescence method using N, B-Ti3C2 MQDs coupled with Eu3+. Upon addition of TC in the Eu3+/N, B-MQDs system, blue fluorescence emission of N, B-Ti3C2 MQDs was quenched and red fluorescence emission of Eu3+ was enhanced gradually, which was ascribed to the synergistic inner filter effect and antenna effect. Moreover, we prepared test papers with N, B-Ti3C2 MQDs and Eu3+ for TC detection based on the change of fluorescence color, which could be recognized by color recognizer app installed in the smartphone. Therefore, great promise for POCT of TC is given with the merits of simplicity and visible detection possibility. The proposed method demonstrated a low detection limit of 20 nM. Application of the platform for TC quantification in milk samples opened a novel means for the potential use of N, B-Ti3C2 MQDs in food safety.

Carbon Dots with Absorption Red-Shifting for Two-Photon Fluorescence Imaging of Tumor Tissue pH and Synergistic Phototherapy.

Phototherapy exhibits significant potential as a novel tumor treatment method, and the development of highly active photosensitizers and photothermal agents has drawn considerable attention. In this work, S and N atom co-doped carbon dots (S,N-CDs) with an absorption redshift effect were prepared by hydrothermal synthesis with lysine, o-phenylenediamine, and sulfuric acid as raw materials. The near-infrared (NIR) absorption features of the S,N-CDs resulted in two-photon (TP) emission, which has been used in TP fluorescence imaging of lysosomes and tumor tissue pH and real-time monitoring of apoptosis during tumor phototherapy, respectively. The obtained heteroatom co-doped CDs can be used not only as an NIR imaging probe but also as an effective photodynamic therapy/photothermal therapy (PDT/PTT) therapeutic agent. The efficiencies of different heteroatom-doped CDs in tumor treatment were compared. It was found that the S,N-CDs showed higher therapeutic efficiency than N-doped CDs, the efficiency of producing 1O2 was 27%, and the photothermal conversion efficiency reached 34.4%. The study provides new insight into the synthesis of carbon-based nanodrugs for synergistic phototherapy and accurate diagnosis of tumors.

Zn and N Codoped TiO2 Thin Films: Photocatalytic and Bactericidal Activity.

We explore a series of Zn and N codoped TiO2 thin films grown using chemical vapor deposition. Films were prepared with various concentrations of Zn (0.4-2.9 at. % Zn vs Ti), and their impact on superoxide formation, photocatalytic activity, and bactericidal properties were determined. Superoxide (O2•-) formation was assessed using a 2,3-bis(2-methoxy-4-nitro-5-sulfophenyl)-5-[(phenylamino)carbonyl]-2H-tetrazolium sodium salt (XTT) as an indicator, photocatalytic activity was determined from the degradation of stearic acid under UVA light, and bactericidal activity was assessed using a Gram-negative bacterium E. coli under both UVA and fluorescent light (similar to what is found in a clinical environment). The 0.4% Zn,N:TiO2 thin film demonstrated the highest formal quantum efficiency in degrading stearic acid (3.3 × 10-5 molecules·photon-1), while the 1.0% Zn,N:TiO2 film showed the highest bactericidal activity under both UVA and fluorescent light conditions (>3 log kill). The enhanced efficiency of the films was correlated with increased charge carrier lifetime, supported by transient absorption spectroscopy (TAS) measurements.

One Stone, Two Birds: pH- and Temperature-Sensitive Nitrogen-Doped Carbon Dots for Multiple Anticounterfeiting and Multiple Cell Imaging.

Carbon dots (CDs) as new fluorescent materials with excellent fluorescence properties have shown enormous potential applications, especially in anticounterfeiting and cell imaging. Herein, nitrogen-doped CDs (NCDs) with excellent biocompatibility were prepared by a simple thermal sintering method. An extremely large red shift (∼130 nm) of the emission peak was observed when the excitation wavelength changes from 355 to 550 nm, indicating that NCDs are excellent fluorescent labeling materials for multiple cell imaging. On the other hand, NCDs showed obvious changes of emission intensity and peak position when the temperature increased from 223 to 323 K and the pH values changed from 1 to 13, respectively, which has been demonstrated by the "horse" pattern printed with NCD water-soluble fluorescent inks. The nontoxic NCDs dispersed in a multiple matrix are highly sensitive to excitation wavelength, temperature, and pH, indicating their great potential application in multiple anticounterfeiting and multiple cell imaging.

A trade-off between adsorption and photocatalysis over ZIF-derived composite.

The adsorption with highly porous adsorbents is an efficient technique to trap the uncontrolled release of antibiotics in the environment, however, mere adsorption does not mineralize the discharged antibiotics. On the contrary, the regular photocatalysts completely mineralize the antibiotics, however suffers from high efficiency due to comparatively low surface area and porosity. In this work, a balance has been made between efficient adsorption followed by complete degradation of the adsorbed antibiotic over ZIF-8 derived ZnO/N-doped carbon composite. The nitrogen-doped carbon produced at 1000 °C showed a very high adsorption capacity of SMX, due to higher surface area, porosity and better surface interaction between adsorbate and adsorbent. The ZnO formed at 600 °C produced sufficient OH· that were responsible to show a very high rate of complete photocatalytic mineralization of SMX over the material. The ZnO/N-doped carbon composite showed a very high rate of photodegradation with a corresponding rate constant of 4.36 × 10-2 min-1. The complete degradation mechanism was proposed and rates were compared with existing literature.

Photo splitting of bio-polyols and sugars to methanol and syngas.

Methanol is a clean liquid energy carrier of sunshine and a key platform chemical for the synthesis of olefins and aromatics. Herein, we report the conversion of biomass-derived polyols and sugars into methanol and syngas (CO+H2) via UV light irradiation under room temperature, and the bio-syngas can be further used for the synthesis of methanol. The cellulose and even raw wood sawdust could be converted into methanol or syngas after hydrogenolysis or hydrolysis pretreatment. We find Cu dispersed on titanium oxide nanorod (TNR) rich in defects is effective for the selective C-C bond cleavage to methanol. Methanol is obtained from glycerol with a co-production of H2. A syngas with CO selectivity up to 90% in the gas phase is obtained via controlling the energy band structure of Cu/TNR.

Visible-light driven degradation of tetracycline hydrochloride and 2,4-dichlorophenol by film-like N-carbon@N-ZnO catalyst with three-dimensional interconnected nanofibrous structure.

The emergence of more and more persistent organic molecules as contaminants in water simulates research towards the development of more advanced technologies, among which photocatalysis is a feasible choice. However, it is still challenging to design a photocatalyst that fulfills all the requirements for industrial application, i.e., active under visible-light irradiation, shape with handy convenience, highly uniform distribution of active sites, substrate with excellent electronic properties, etc. In this study, we report an attempt to solve these issues at once by designing a film-like photocatalyst with uniform distribution of nitrogen-doped ZnO nanoparticles along nitrogen-doped carbon ultrafine nanofibers with three-dimensional interconnected structure. Under visible-light irradiation, the product exhibited remarkable reactivity for the degradation of two model pollutants tetracycline hydrochloride and 2,4-dichlorophenol within 100 min. The cyclic experiments demonstrated only a slight loss (ca. 5 %) of reactivity after five consecutive photocatalytic reactions. We also investigated the detailed relationship between the structural features and the superior properties of this product, as well as the degradation mechanisms. The convenient shape of the product with excellent performances for the treatment of real polluted water increases its suitability for larger scale application. Our work provides a rational design of photocatalysts for environmental remediation.

N-Doped Carbon Quantum Dot (NCQD)-Deposited Carbon Capsules for Synergistic Fluorescence Imaging and Photothermal Therapy of Oral Cancer.

Use of nanomaterials blessed with both therapeutic and diagnostic properties is a proficient strategy in the treatment of cancer in its early stage. In this context, our paper reports the synthesis of uniform size N-rich mesoporous carbon nanospheres of size 65-70 nm from pyrrole and aniline precursors using Triton-X as a structure-directing agent. Transmission electron microscopy reveals that these carbons spheres contain void spaces in which ultrasmall nitrogen-doped quantum dots (NCQD) are captured within the matrix. These mesoporous hollow NCQD captured carbon spheres (NCQD-HCS) show fluorescence quantum yield up to 14.6% under λex = 340 nm. Interestingly, samples calcined at >800 °C clearly absorb in the wavelength range 700-1000 nm and shows light-to-heat conversion efficiency up to 52%. In vitro experiments in human oral cancer cells (FaDu) show that NCQD-HCS are internalized by the cells and induce a substantial thermal ablation effect in FaDu cells when exposed under a 980 nm near-infrared laser.

Ingenious Dual-Photoelectrode Internal-Driven Self-Powered Sensing Platform for the Power Generation and Simultaneous Microcystin Monitoring Based on the Membrane/Mediator-Free Photofuel Cell.

To further heighten solar-energy utilization efficiency could be significantly meaningful for developing useful photoelectric devices. Here, by integrating the nitrogen-doped graphene-BiOBr (NG-BiOBr) nanocomposites as a photocathode with titanium dioxide (TiO2) nanoparticles as a photoanode synchronously, a dual-photoelectrode internally driven self-powered sensing platform was fabricated, which can work without an external energy input except for light illumination. In this design, the microcystin-LR (MC-LR) molecules function as the fuel and model analyte as well. Avoiding the use of the costly cathode, this is the first example of the integration of a dual photoresponsive electrode into a photofuel cell for self-powered sensing and paves a luciferous way for efficient multidimension energy conversion. Besides, in order to investigate the detailed sensing process of the self-powered system, the Nyquist curves of the interface are studied between the dual-photoelectrode before and after adding the target MC-LR. The results demonstrated that the photoanode TiO2 contributed to the oxidation of MC-LR under photoirradiation rather than the photocathode. This work not only provides an appealing idea to construct the sensitive and easy-to-use assays of microcystins but also exhibits a successful prototype of a portable and on-site sensor.

Highly selective transformation of ammonia nitrogen to N2 based on a novel solar-driven photoelectrocatalytic-chlorine radical reactions system.

A highly selective method for transforming ammonia nitrogen to N2 was proposed, based on a novel solar-driven photoelectrocatalytic-chlorine radical reactions (PEC-chlorine) system. The PEC-chlorine system was facilitated by a visible light response WO3 nanoplate array (NPA) electrode in an ammonia solution containing chloride ions (Cl-). Under illumination, photoholes from WO3 promote the oxidation of Cl- to chlorine radical (Cl). This radical can selectively transform ammonia nitrogen to N2 (79.9%) and NO3- (19.2%), similar to the breakpoint chlorination reaction. The ammonia nitrogen removal efficiency increased from 10.6% (PEC without Cl-) to 99.9% with the PEC-chlorine system within 90 min operation, which can be attributed to the cyclic reactions between Cl-/Cl and the reaction intermediates (NH2, NHCl, etc.) that expand the degradation reactions from the surface of the electrodes to the whole solution system. Moreover, Cl is the main radical species contributing to the transformation of ammonia nitrogen to N2, which is confirmed by the tBuOH capture experiment. Compared to conventional breakpoint chlorination, the PEC-chlorine system is a more economical and efficient means for ammonia nitrogen degradation because of the fast removal rate, no additional chlorine cost, and its use of clean energy (since it is solar-driven).

One-pot green synthesis of oxygen-rich nitrogen-doped graphene quantum dots and their potential application in pH-sensitive photoluminescence and detection of mercury(II) ions.

Nitrogen doping has been a powerful method to modulate the properties of carbon materials for various applications, and N-doped graphene quantum dots (GQDs) have gained remarkable interest because of their unique chemical, electronic, and optical properties. Herein, we introduce a facile one-pot solid-phase synthesis strategy for N-doped GQDs using citric acid (CA) as the carbon source and 3,4-dihydroxy-L-phenylalanine (L-DOPA) as the N source. The as-prepared N-GQDs with oxygen-rich functional groups are uniform with an average diameter of 12.5 nm. Because of the introduction of nitrogen atoms, N-GQDs exhibit excitation-wavelength-independent fluorescence with the maximum emission at 445 nm, and a high quantum yield of 18% is achieved at an excitation wavelength of 346 nm. Furthermore, a highly efficient fluorosensor based on the as-prepared N-GQDs was developed for the detection of Hg(2+) because of the effective quenching effect of metal ions via nonradiative electron transfer. This fluorosensor exhibits high sensitivity toward Hg(2+) with a detection limit of 8.6 nM. The selectivity experiments reveal that the fluorescent sensor is specific for Hg(2+). Most importantly, the practical use of the sensor based on N-GQDs for Hg(2+) detection was successfully demonstrated in river-water samples.

Water disinfection through photoactive modified titania.

TiO(2), N-TiO(2) and S-TiO(2) samples have been prepared by various chemical methods. These samples were characterized by X-ray diffractometer (XRD), X-ray photoelectron spectroscopy (XPS), Laser Raman spectrometer, UV-Visible spectrophotometer, field emission scanning electron microscope (FE-SEM) and transmission electron microscope (TEM). X-ray powder diffraction study reveals that all three samples are single anatase phase of titania and the crystallinity of titania decreases with sulphur doping whereas nitrogen doping does not affect it. UV-Visible (diffuse) reflectance spectra shows that doping of titania with nitrogen and sulphur shift the absorption edge of titania from ultraviolet to visible region. XPS study confirms that both nitrogen and sulphur are well doped in the titania lattice. It is observed that nitrogen occupies at both substitutional and interstitial position in the lattice of titania. FE-SEM and TEM studies demonstrate that the particles are below 50nm range. It is found that S and N doping of titania increased its water disinfection property in the order TiO(2)

Mechanistic modeling of destratification in cryogenic storage tanks using ultrasonics.

Stratification is one of the main causes for vaporization of cryogens and increase of tank pressure during cryogenic storage. This leads subsequent problems such as cavitation in cryo-pumps, reduced length of storage time. Hence, it is vital to prevent stratification to improve the cost efficiency of storage systems. If stratified layers exist inside the tank, they have to be removed by suitable methods without venting the vapor. Sonication is one such method capable of keeping fluid layers mixed. In the present work, a mechanistic model for ultrasonic destratification is proposed and validated with destratification experiments done in water. Then, the same model is used to predict the destratification characteristics of cryogenic liquids such as liquid nitrogen (LN2), liquid hydrogen (LH2) and liquid ammonia (LNH3). The destratification parameters are analysed for different frequencies of ultrasound and storage pressures by considering continuous and pulsed modes of ultrasonic operation. From the results, it is determined that use of high frequency ultrasound (low-power/continuous; high-power/pulsing) or low frequency ultrasound (continuous operation with moderate power) can both be effective in removing stratification.

Fabrication of nitrogen vacancy color centers by femtosecond pulse laser illumination.

We report on a novel method to fabricate single, multiple and large-area high-density ensembles of nitrogen vacancy (NV) color centers in synthetic type Ib bulk diamond by femtosecond laser illumination. Electron beams generated in propagation of intense infrared laser pulses in air sputtered on a diamond sample under high temperature aroused by the laser illumination, creating NV color centers. Typical photoluminescence (PL) spectra of NV centers could be observed on the illuminated spots. Photon streams from individual photoluminescent points exhibited anti-bunching effect by the second-order correlation measurement, evidencing single and multiple photon-emitters around the laser illuminated spots.

Overlapping photodegradable and biodegradable organic nitrogen in wastewater effluents.

Photochemical degradation of dissolved organic nitrogen (DON) in final effluent of trickling filter and activated sludge wastewater treatment plants (WWTPs) was studied. Inorganic N, mostly nitrite, was produced from the photodegradation of DON for samples from both WWTPs. Photodegradable DON (PDON), biodegradable DON (BDON), and overlapping photodegradable-biodegradable DON (OPBDON) were determined. BDON was associated with PDON as well as non-PDON. BDON and PDON concentrations in the final effluent samples were 4.71 and 4.62 mg N/L for the trickling filter plant and 3.95 and 3.73 mg N/L for the activated sludge plant, indicating that photodegradation is as important as biodegradation in the mineralization of effluent DON in receiving waters. OPBDON, which is more problematic in the water environment because it can be mineralized by light or bacteria or both, was 3.68 and 2.64 mg N/L (57% and 43% of total DON) in the final effluent samples from the trickling filter and activated sludge plants, respectively. The DON fraction that is resistant to biodegradation and photodegradation was 10% to 20% of total DON.

Strain- and electric field-induced band gap modulation in nitride nanomembranes.

The hexagonal nanomembranes of the group III-nitrides are a subject of interest due to their novel technological applications. In this paper, we investigate the strain- and electric field-induced modulation of their band gaps in the framework of density functional theory. For AlN, the field-dependent modulation of the bandgap is found to be significant whereas the strain-induced semiconductor-metal transition is predicted for GaN. A relatively flat conduction band in AlN and GaN nanomembranes leads to an enhancement of their electronic mobility compared to that of their bulk counterparts.

Enhanced stability of nitrogen-sealed carbon nanotube saturable absorbers under high-intensity irradiation.

Due to their broadband saturable absorption and fast response, carbon nanotubes have proven to be an excellent material for the modelocking of fiber lasers and have become a promising device for the implementation of novel laser configurations. However, it is imperative to address the issue of their long-term reliability under intense optical pulses before they can be exploited in widespread commercial applications. In this work, we study how carbon nanotubes degrade due to oxidation when exposed to high-intensity continuous-wave light and we demonstrate that by sealing the carbon nanotubes in a nitrogen gas, the damage threshold can be increased by over one order of magnitude. We then monitor over 24 hours the performance of the carbon nanotube saturable absorbers as the passive modelocking device of an erbium-doped fiber laser with intracavity powers ranging from 5 mW to 316 mW. We observe that when the carbon nanotubes are sealed in nitrogen environment, oxidation can be efficiently prevented and the laser can operate without any deterioration at intracavity powers higher than 300 mW. However, in the case where carbon nanotubes are unprotected (i.e. those directly exposed to the air in the environment), the nanotubes start to deteriorate at intracavity powers lower than 50 mW.

Earth's magnetic field enabled scalar coupling relaxation of 13C nuclei bound to fast-relaxing quadrupolar 14N in amide groups.

Scalar coupling relaxation, which is usually only associated with closely resonant nuclei (e.g., (79)Br-(13)C), can be a very effective relaxation mechanism. While working on hyperpolarized [5-(13)C]glutamine, fast liquid-state polarization decay during transfer to the MRI scanner was observed. This behavior could hypothetically be explained by substantial T(1) shortening due to a scalar coupling contribution (type II) to the relaxation caused by the fast-relaxing quadrupolar (14)N adjacent to the (13)C nucleus in the amide group. This contribution is only effective in low magnetic fields (i.e., less than 800 µT) and prevents the use of molecules bearing the (13)C-amide group as hyperpolarized MRS/MRI probes. In the present work, this hypothesis is explored both theoretically and experimentally. The results show that high hyperpolarization levels can be retained using either a (15)N-labeled amide or by applying a magnetic field during transfer of the sample from the polarizer to the MRI scanner.

Low-temperature hydrothermal synthesis of N-doped TiO2 from small-molecule amine systems and their photocatalytic activity.

Nitrogen-doped TiO2 nanopowders have been successfully synthesized by a one-step hydrothennal route under soft-chemistry conditions (150 degrees, 8 h) without high-temperature calcination using seven different types of nitrogen dopants: methylamine, ethylamine, diethylamine, ethylenediamine, triethylamine, triethanolamine and ammonia. X-ray diffraction, transmission electron microscopy, ultraviolet-visible spectroscopy, X-ray photoelectron spectroscopy, N2 adsorption-desorption isothenns and Fourier transform infrared spectroscopy were used to analyse the as-synthesized TiO2 powders. The results indicated that nitrogen was doped effectively and the structure and morphology of the titania samples were strongly influenced by the nitrogen sources. Among the investigated nitrogen sources, the diethylamine system was clearly superior to the other small-molecule amine or ammonia systems due to the broad-spectrum response (between 400 and 700 nm) of the interstitial nitrogen-doped TiO2 nanopowders. The diethylamine N-doped TiO2 had the largest pore volume (0.39 ml x g(-1)) and showed a well-aligned anatase phase. The visible-light photocatalytic degradation of liquid X-3B used as a probe reaction demonstrated that the removal rate over the diethylamine material reached 99.7% in 90 min.

Atomistic description of electron beam damage in nitrogen-doped graphene and single-walled carbon nanotubes.

By combining ab initio simulations with state-of-the-art electron microscopy and electron energy loss spectroscopy, we study the mechanism of electron beam damage in nitrogen-doped graphene and carbon nanotubes. Our results show that the incorporation of nitrogen atoms results in noticeable knock-on damage in these structures already at an acceleration voltage of 80 kV, at which essentially no damage is created in pristine structures at corresponding doses. Contrary to an early estimate predicting rapid destruction via sputtering of the nitrogen atoms, in the case of substitutional doping, damage is initiated by displacement of carbon atoms neighboring the nitrogen dopant, leading to the conversion of substitutional dopant sites into pyridinic ones. Although such events are relatively rare at 80 kV, they become significant at higher voltages typically used in electron energy loss spectroscopy studies. Correspondingly, we measured an energy loss spectrum time series at 100 kV that provides direct evidence for such conversions in nitrogen-doped single-walled carbon nanotubes, in excellent agreement with our theoretical prediction. Besides providing an improved understanding of the irradiation stability of these structures, we show that structural changes cannot be neglected in their characterization employing high-energy electrons.