Spatial Confinement of Co Nanoparticles in N-Doped Carbon Nanorods for Wastewater Purification via CaSO3 Activation.

Spatial confinement of organic pollutants and reactive oxygen species (e.g., SO4•- and •OH) with ultrashort lifetime inside the scale of chemical theoretical diffusion could provide a greatly promising strategy to overcome the limitation of mass transfer in the heterogeneous Fenton-like oxidation process. Herein, we first reported spatial confinement of cobalt nanoparticles in N-doped carbon nanorods (Co-NCNRs), by encapsulating Co nanoparticles into N-doped carbon nanorods, in activating CaSO3 for antibiotic degradation. Compared to Na2SO3 and NaHSO3, CaSO3 could slowly and persistently discharge SO32- due to its low solubility, thus avoiding the depletion of the generated SO3•- and •OH under the high concentration of sulfite ions. Fully physical characterizations confirmed that the 3D hydrogel was mostly transformed into the nanorod structure of Co-NCNRs at 550 °C. Co atoms were successfully nanoconfined into N-doped carbon nanorods, which contributes to mass transfer and prevents the agglomeration of Co nanoparticles, thus enhancing its catalytic activity and stability in activating CaSO3 for water decontamination. The catalytic performance, kinetic research, influences of inorganic anions, pH, and degradation mechanism of chlortetracycline degradation catalyzed by the Co-NCNRs/CaSO3 system have been studied in detail. This work not only proposed a facile method for synthesis of nanoconfined catalyst but also provided an excellent Co-NCNRs/CaSO3 system for wastewater treatment.

Facile synthesis of S, N-co-doped carbon dots for bio-imaging, Fe3+ detection and DFT calculation.

Turning waste into wealth, herein, two highly fluorescent N and S co-doped carbon dots (N, S-CDs-A and N, S-CDs-B) were synthesized by the hydrothermal reaction of contaminant reactive red 2 (RR2) and L-cysteine or L-methionine, respectively. The detailed morphology and structure of N, S-CDs were characterized by XRD, Raman spectrum, FTIR spectra, TEM, HRTEM, AFM and XPS. The maximum fluorescent of N, S-CDs-A and N, S-CDs-B are 565 and 615 nm under different excitation wavelengths with moderate fluorescence intensity of 14.0 % and 6.3 %, respectively. The microstructure models of N, S-CDs-A and N, S-CDs-B, which were induced by FT-IR, XPS and element analysis, had been applied in DFT calculation. The result indicated that the doping of S and N is beneficial to obtain the red-shift of fluorescent spectra. Both N, S-CDs-A and N, S-CDs-B showed highly sensitive and selective to Fe3+. N, S-CDs-A can also detect Al3+ ion with high sensitivity and selectivity. Finally, N, S-CDs-B was successfully applied in cell imaging.

Facile Synthesis of Tetraphenylethene (TPE)-Based Fluorophores Derived by π-Extended Systems: Opposite Mechanofluorochromism, Anti-Counterfeiting and Bioimaging.

Although remarkable progresses are achieved in the design and development of the mono-shift in photoluminescence for mechanofluorochromic materials, it is still a severe challenge to explore the opposite mechanofluorochromic materials with both blue- and red-shifted photoluminescence. Herein, two unprecedented 4,5-bis(TPE)-1H-imidazole fused pyridine or quinoline-based fluorophores X-1 and X-2 were designed and synthesized, and X-1 and X-2, exhibit completely opposite mechanofluorochromic behavior. Under UV lamp, the color of pristine X-1 changed from blue to green with reversible redshifted 27 nm in fluorescence emission spectra after ground, while the color of pristine X-2 changed from red to yellow with reversible blue-shifted 74 nm after ground. The detailed characterizations (including PXRD, SEM and DSC) confirmed that this opposite mechanofluorochromism was attributed to the transformation of order-crystalline and amorphous states. The crystal structure analysis and theoretical calculation further explain that opposite mechanofluorochromic behavior take into account different π-π stacking mode by induced π-extended systems. In addition, these TPE-based fluorophores (X-1 and X-2) exhibited excellent bio-compatibility and fluorescence properties for bio-imaging, writable data storage and anti-counterfeiting materials.

Oat ß-glucan ameliorates diabetes in high fat diet and streptozotocin-induced mice by regulating metabolites.

Oats are widely distributed worldwide and oat ß-glucan has positive effects on human health. Particularly, oat ß-glucan is reported to be beneficial in the management of type 2 diabetes. The aim of the present study is to investigate the effects of oat ß-glucan and its possible underlying mechanisms on diabetes in type 2 diabetic mice that was induced by streptozotocin/high-fat diet (STZ/HFD). The data indicated that oat ß-glucan significantly reduced the fasting blood glucose, improved glucose tolerance, and insulin sensitivity. The results further showed that oat ß-glucan remarkably decreased the levels of total cholesterol (TCHO), total triglyceride (TG), low-density lipoprotein cholesterol (LDL-C) and free fatty acids. Moreover, oat ß-glucan remarkably increased the hepatic glycogen content, but largely decreased the levels of aspartate aminotransferase (AST) and alanine aminotransferase (ALT) in STZ/HFD-induced diabetic mice. Histological analysis showed that oat ß-glucan alleviated visceral lesions. Finally, the metabolomic analysis indicated that the metabolic profile was remarkably changed after oat ß-glucan intervention in diabetic mice. There were 88 and 106 differential metabolites screened as biomarkers in negative ion mode (NEG) and positive ion mode (POS) after oat ß-glucan treatment, respectively. In addition, oat ß-glucan significantly affected the serum metabolites of amino acids, organic acids and bile acids. Collectively, the current study elucidates oat ß-glucan displays an effective nutritional intervention in diabetes.

Asymmetric Core-Expanded BOPYOs: Facile Synthesis and Optical Properties.

N,O-bidentate BF2 complexes with five- and six-membered core rings have been thoroughly investigated. However, the development of seven-membered N,O-boron complexes is still an area to be explored. We have developed BF3 ⋅ OEt2 -induced self-condensation and coordination reactions based on a single starting material, which had been elucidated by experiment and calculation. This parent asymmetric core-expanded borondifluoride-(Z)-1,3-di(1H-pyrrol-2-yl)but-2-en-1-one (BOPYO) showed reactivity with a wide range of aldehydes, thus providing a series of conjugation BOPYOs. Moreover, a BOPYO derivative with a dimethylamino group was developed as a new NIR dye that responds to acid with favorable photophysical properties based on intramolecular charge transfer effect.

A Novel Strategy to Design and Construct AIE-active Mechanofluorochromic Materials via Regulation of Molecular Structure.

In this work, we first designed and synthesized tetraphenylene-fused aryl-imidazole derivatives TM-1-4 via regulation of molecular structure, which were consisted of 1H-imidazo[4,5-f][1,10]phenanthroline, 1H-phenanthro[9,10-d]imidazole, 4,5-diphenyl-1H-imidazole, 3,3'-(1H-imidazole-4,5-diyl)dipyridine moieties and AIE-active tetraphenylethene units, respectively. The results illustrated that TM-1-4 exhibited clear AIE characteristics. Meanwhile, TM-2 and TM-3 show excellent solid emission properties (ΦTM-2 =13.73 % and ΦTM-3 =36.21 %), whereas TM-1 and TM-4 exhibit the opposite properties (ΦTM-1 =1.48 % and ΦTM-4 =4.83 %). The multiple rotors (pyridine and benzene ring) causes twisted conformations of the molecule that prevents π-π stacking and enhances solid emission(ΦTM-2<ΦTM-3, ΦTM-1<ΦTM-4). Significantly, TM-2 and TM-3 also exhibited reversible mechanochromic behavior (Emission red shifts: ΔλTM-2 =43 nm and ΔλTM-3 =41 nm) with color changes between blue and green emissions. The powder X-ray diffraction (PXRD) suggested the disordered state of ground sample could be readily returned to an ordered crystalline. Therefore, the mechanochromisms of TM-2 and TM-3 are ascribable to the phase transformation between crystal and amorphous structure. The single crystal X-ray analysis of TM-2 reveals a twisted conformation for TPE moiety and the absence of π-π intermolecular stacking. These excellent optical properties of TM-2 and TM-3 make them potentially applications in mechanochromic materials and imaging agents.

Simple and eco-friendly synthesis of crude orange-peel-derived carbon nanoparticles for detection of Fe3+ and ascorbic acid.

Although fluorescence sensors based on carbon dots (CDs) have been developed widely, multicomponent detection using CDs without extra and tedious surface modification remains a challenge. Here, the crude carbon nanoparticles (CPs) as a fluorescence sensor were prepared through one-pot hydrothermal process using orange peel as the precursor. The method was simple, rapid, economical, and eco-friendly given that such extra steps as dialysis and lyophilization were not required. By adding ethanol into the reaction solvent, the fluorescence properties of orange-peel-derived CPs as well as their sensitivity of detecting Fe3+ with a limit of detection of 0.25 µM were improved. Additionally, orange-peel-derived CPs could be used as a fluorescence sensor for detection of ascorbic acid (AA) with a LOD of 5 µM. More importantly, the proposed fluorescence methods were successfully used to qualitatively and quantitatively analyze Fe3+ and AA in real samples. Recovery of Fe3+ from tap water was within the range 97.2-105.4%. Conversely, recovery of AA from vitamin C tablets and orange juices laid within the ranges 97.7-99.3% and 93.2-97.6%, respectively.

Substituent effects on opticalproperties of pyrrolizine-fused BOPYIN.

Three new pyrrolizine-fused BOPYINs (DAB-H, DAB-OMe, DAB-ester) have been reported in 26-35% yield. The relationship between structures and optical spectra was investigated, which all the compounds show large Stokes Shift (3146-3884 cm-1) and high quantum yield (up to 99%) in solvents. Among these dyes, the decoration of electron donating/withdrawing groups on indole, pyrrole and pyrrolizine units has a significant impact on optical properties, especially emission spectra. The results suggested that electron withdrawing group on pyrrole and pyrrolizine units has hypsochromic shift on emission spectra (DAB-H, DAB-OMe, DAB-ester versus DAB-1,4,5). The optimized structure, electron distribution on frontier molecular orbital, energy gap and simulated stick spectra of DABs are discussed by Density Functional Theory (DFT) calculation. We claim the agreement between the experimental and theoretical absorption spectra.

Tuning the excited-state intramolecular proton transfer (ESIPT) process of indole-pyrrole systems by π-conjugation and substitution effects: experimental and computational studies.

A series of amino (NH)-type hydrogen-bonding (H-bonding) compounds, BNDAB-1-4, containing π-enlarged indole and ß-ethoxycarbonyl-substituted pyrrole units were designed and synthesized. BNDAB-1 and BNDAB-3 exhibited dual emission and BNDAB-2 and BNDAB-4 exhibited a single emission with a large Stokes shift in dichloromethane, methanol, DMSO and toluene except for a dual emission for BNDAB-4 in toluene. Inspired by their photophysical properties, the ESIPT process was speculated and further investigated by theoretical calculations including geometry and thermodynamic analyses. The results showed that the ester substitution on the proton donor unit and π-conjugation on the proton acceptor unit by structural modification can regulate the ESIPT behaviors of these compounds. First, a strong electron-withdrawing group promoted the ESIPT process according to the comparison of the ESIPT processes of NDAB-H and NDAB-6, BNDAB-1 and BNDAB-2, and BNDAB-3 and BNDAB-4. Second, π-conjugation in different positions ([g]- and [e]-position) of the indole unit decreased the speed of the ESIPT process irrespective of whether ethoxycarbonyl was substituted on the pyrrole ring based on the ESIPT process of Series 1 and 2. Finally, this work elucidated that the ESIPT process can be rationally tuned by π-conjugation and substitution, which is in good agreement with the experimental results.

One-pot synthesis of N-confused porphyrin-dipyrrin conjugates and their optical properties.

A conjugated N-confused porphyrin-dipyrrin system NCP-IN-X (X = H, Br, Cl, OMe, COOEt) has been reported via N-Confused tetraphenylporphyrin (NCTPP) as a π-enlarged pyrrole and substituted trimethylindole subunits in 75-82% yields by one pot. All the NCP-INs show red-shifted absorption and emission in the NIR range compared with NCTPP in a series nonpolar and polar solvents. Interesting, relative higher emission in DMF can be observed. The structures of dipyrrin-NCP conjugates are characterized by 1H-NMR and high resolution mass spectrum (HR-MS). Four frontier molecular orbital and simulated stick absorption spectra are calculated by DFT and TD-DFT calculation which is in good agreement with the experiments.

A stable AIEgen cis-diarylethene-based 'ESIPT' benchmark.

The one-flask synthesis of seven-membered free-base BOPYINs (NBs) using benzo indole and ß-substituted pyrrole moieties has been reported. This stable cis-configuration of diarylethenes with Aggregation Induced Emission (AIE) properties was locked by the seven-membered ring hydrogen bond (HB) and steric hindrance, which made 'Excited-State Intramolecular Proton Transfer (ESIPT)' phenomena take place in this benchmark.

A Simple Central Seven-Membered BOPYIN: Synthesis, Structural, Spectroscopic Properties, and Cellular Imaging Application.

A two-step, one-flask synthesis of central seven-membered borondifluoride-3,3-dimethyl-2-[2-(2-pyrrolyl)ethenyl] indole (BOPYIN) ligands has been developed by using the unexplored 3,3-dimethyl-2-[2-(2-pyrrolyl)ethenyl] indole. The simple synthetic approach has enabled modification of the electronic structure by changing the substituents on the indole unit. X-ray analysis indicated that conformations of the seven-membered BF2 complex including BOPYIN and diazaborepin differ from that of the five- and six-membered organoboron complexes. Interestingly, the bond angle of the N⋅⋅⋅B-N bond increases with the number of atoms in the core ring, based on Baeyer strain theory. These unsymmetric BOPYIN derivatives have excellent photophysical properties, including high fluorescence quantum yields, except for BOPYIN-4 in the solution state, large Stokes shifts, and good molar absorptivity. The dipole moment of BOPYIN-3 in the first excited singlet state and ground state was demonstrated by a linear Lippert-Mataga plot. The absorption and emission spectra were not mirror images for BOPYIN-1-3 and 5, in contradiction to Kasha's rule, as determined by TDDFT. The synthesized BOPYINs have been shown to be biocompatible fluorophores in cell bioimaging.

A novel 2,5-bis(benzo[d]thiazol-2-yl)phenol scaffold-based ratiometric fluorescent probe for sensing cysteine in aqueous solution and serum.

An efficient and novel 2,5-bis(benzo[d]thiazol-2-yl)phenol scaffold-based ratiometric fluorescent probe BTP-Cys for the sensing of cysteine has been developed. The probe BTP-Cys with acrylates moiety, as recognition site, has been successfully constructed on account of the excited state intramolecular proton transfer (ESIPT) mechanism. Upon the treatment with Cys (0-250 µM), this probe BTP-Cys exhibits a dramatic fluorescent intensity ratios enhancement (from 0.03 to 18.3) and a large emission shift (113 nm). The detection limit of this probe is as low as 3.8 × 10-7 M. Importantly, the concentration and time dependent of Cys in bovine serum albumin (BSA) has also been measured, indicating that BTP-Cys could be a biocompatible and rapid probe for Cys in vitro.

Synthesis of graphene quantum dot-stabilized gold nanoparticles and their application.

Herein, we report an in situ synthesis of graphene quantum dots (GQDs), which have been synthesized from only starch and water and stabilize AuNPs in water. The construction of six gold nanocomposites, i.e. AuNPs 1-6, with sizes ranging from 13.4 nm to 32.6 nm, was accomplished by only mixing the GQDs and chloroauric acid in different amounts without any additional reductants and surfactants. HRTEM has confirmed that the AuNPs have been stabilized by the GQDs, and a core/shell AuNPs@GQD structure has formed. In addition, the as-synthesized AuNPs show excellent catalytic performance in the reduction of 4-nitrophenol, a pertinacious pollutant occurring in industrial wastewater.

A detailed experimental and theoretical investigation of the role of cyano groups in the π-bridged acceptor of sensitizers for use in dye-sensitized solar cells (DSCs).

Three donor-π conjugated unit-acceptor (D-π-A) type zinc porphyrin sensitizers LX1, LX2 and LX3 bearing meso acrylic acid, α-cyanoacrylic acid, and α-cyanopentadienoic acid, respectively, as the π-bridged acceptors were designed and synthesized for use in dye-sensitized solar cells (DSCs). The interesting role of the cyano group attached to the α position of the acrylic and pentadienoic acid acceptor was investigated. It was shown that even though the introduction of the cyano group and the elongation of the π-bridge can both increase the light-harvesting as indicated by the UV-vis absorption spectra, the relevant cell performance dropped significantly. The photo to power conversion efficiencies (PCEs) of the devices increase in the order of LX1 > LX2 > LX3, with the highest PCE of 6.04% achieved for the LX1-based cell, which bears acrylic acid as the π-bridged acceptor. To further explore the effect of -CN and -CH[double bond, length as m-dash]CH- on the interaction between the absorbed dye and TiO2 substrates, their density of states (DOS) and partial density of states (PDOS), as well as electronic properties were investigated in detail using theoretical calculations. The results suggest that introducing the -CN group into the acceptor and extending the conjugation of the π-bridge have decreased the LUMO levels of the dyes, leading to weak interfacial coupling, low electron injection driving force, low Jsc, and thus poor cell performance.

A Water-Soluble Fluorescent Probe for SO2 Derivatives in Aqueous Solution and Serum Based on Phenanthroimidazole Dye.

A water-soluble fluorescent SO2 derivatives probe PI-SO 2 based on a phenanthroimidazole dye, and a sensitive SO2 recognition site, aldehyde was constructed. The probe PI-SO 2 exhibits desirable properties such as high sensitivity, high selectivity and good water-solubility. Significantly, we have demonstrated that the probe PI-SO 2 is suitable for rapidly fluorescence detecting of SO2 derivatives in aqueous solution and serum. The application of the novel probe PI-SO 2 proved that it was not only a useful tool for the detection of SO2 derivatives in vitro, but also a potential assay for investigating the effects of SO2 derivatives, and demonstrating its value in practical applicationin of complex biological samples.

Bioconjugatable, PEGylated Hydroporphyrins for Photochemistry and Photomedicine. Narrow-Band, Near-Infrared-Emitting Bacteriochlorins.

Synthetic bacteriochlorins absorb in the near-infrared (NIR) region and are versatile analogues of natural bacteriochlorophylls. The utilization of these chromophores in energy sciences and photomedicine requires the ability to tailor their physicochemical properties, including the incorporation of units to impart water solubility. Herein, we report the synthesis, from two common bacteriochlorin building blocks, of five wavelength-tunable, bioconjugatable and water-soluble bacteriochlorins along with two non-bioconjugatable benchmarks. Each bacteriochlorin bears short polyethylene glycol (PEG) units as the water-solubilizing motif. The PEG groups are located at the 3,5-positions of aryl groups at the pyrrolic ß-positions to suppress aggregation in aqueous media. A handle containing a single carboxylic acid is incorporated to allow bioconjugation. The seven water-soluble bacteriochlorins in water display Qy absorption into the NIR range (679-819 nm), sharp emission (21-36 nm full-width-at-half-maximum) and modest fluorescence quantum yield (0.017-0.13). Each bacteriochlorin is neutral (non-ionic) yet soluble in organic (e.g., CH2Cl2, DMF) and aqueous solutions. Water solubility was assessed using absorption spectroscopy by changing the concentration ∼1000-fold (190-690 µM to 0.19-0.69 µM) with a reciprocal change in pathlength (0.1-10 cm). All bacteriochlorins showed excellent solubility in water, except for a bacteriochlorin-imide that gave slight aggregation at higher concentrations. One bacteriochlorin was conjugated to a mouse polyclonal IgG antibody for use in flow cytometry with compensation beads for proof-of-principle. The antibody conjugate of B2-NHS displayed a sharp signal upon ultraviolet laser excitation (355 nm) with NIR emission measured with a 730/45 nm bandpass filter. Overall, the study gives access to a set of water-soluble bacteriochlorins with desirable photophysical properties for use in multiple fields.

Integration of Cyanine, Merocyanine and Styryl Dye Motifs with Synthetic Bacteriochlorins.

Understanding the effects of substituents on spectral properties is essential for the rational design of tailored bacteriochlorins for light-harvesting and other applications. Toward this goal, three new bacteriochlorins containing previously unexplored conjugating substituents have been prepared and characterized. The conjugating substituents include two positively charged species, 2-(N-ethyl 2-quinolinium)vinyl- (B-1) and 2-(N-ethyl 4-pyridinium)vinyl- (B-2), and a neutral group, acroleinyl- (B-3); the charged species resemble cyanine (or styryl) dye motifs whereas the neutral unit resembles a merocyanine dye motif. The three bacteriochlorins are examined by static and time-resolved absorption and emission spectroscopy and density functional theoretical calculations. B-1 and B-2 have Qy absorption bathochromically shifted well into the NIR region (822 and 852 nm), farther than B-3 (793 nm) and other 3,13-disubstituted bacteriochlorins studied previously. B-1 and B-2 have broad Qy absorption and fluorescence features with large peak separation (Stokes shift), low fluorescence yields, and shortened S1 (Qy ) excited-state lifetimes (~700 ps and ~100 ps). More typical spectra and S1 lifetime (~2.3 ns) are found for B-3. The combined photophysical and molecular-orbital characteristics suggest the altered spectra and enhanced nonradiative S1 decay of B-1 and B-2 derive from excited-state configurations in which electron density is shifted between the macrocycle and the substituents.