Fabrication of Two-Dimensional Platelets with Heat-Resistant Luminescence and Large Two-Photon Absorption Cross Sections via Cooperative Solution/Solid Self-Assembly.

The combination of solution self-assembly, which enables primary morphological control, and solid self-assembly, which enables the creation of novel properties, can lead to the formation of new functional materials that cannot be obtained using either technique alone. Herein, we report a cooperative solution/solid self-assembly strategy to fabricate novel two-dimensional (2D) platelets. Precursor 2D platelets with preorganized packing structure, shape, and size are formed via the living self-assembly of a donor-acceptor fluorophore and volatile coformer (i.e., propanol) in solution phase. After high-temperature annealing, propanol is released from the precursor platelets, and new continuous intermolecular hydrogen bonds are formed. The new 2D platelets formed retain the controllable morphologies originally defined by the solution phase living self-assembly but exhibit remarkable heat-resistant luminescence up to 200 °C and high two-photon absorption cross sections (i.e., >19,000 GM at 760 nm laser excitation).

Living Self-Assembly of Metastable and Stable Two-Dimensional Platelets from a Single Small Molecule.

This study reports the design of a donor-acceptor (D-A) molecule with two fluorene units on each side of a benzothiadiazole moiety, which allows multiple intermolecular interactions to compete with one another so as to induce the evolution of the metastable 2D platelets to the stable 2D platelets during the self-assembly of the D-A molecule. Importantly, the living seeded self-assembly of metastable and stable 2D structures with precisely controlled sizes can be conveniently achieved using an appropriate supersaturated level of a solution of the D-A molecule as the seeded growth medium that can temporarily hold the almost-proceeding spontaneous nucleation from competing with the seeded growth. The stable 2D platelets with smaller area sizes exhibit higher sensitivity to gaseous dimethyl sulfide, illustrating that the novel living self-assembly method provides more available functional structures with controlled sizes for practical applications. The key finding of this study is that the new living methodology is separated into two independent processes: the elaborate molecular design for various crystalline structures as seeds and the application of a supersaturated solution with appropriate levels as the growth medium to grow the uniform structures with controlled sizes; this would make convenient and possible the living seeded self-assembly of rich 1D, 2D, and 3D architectures.

Practical application of Pd-based bimetallic catalysts with enhanced selectivity supported by chelating resin for catalytic nitrate reduction in real water.

An innovative Pd-Me (Pd-Cu, Pd-In and Pd-Sn) bimetallic catalyst supported on porous chelating DOWEX M4195 resin (D) was established to reduce the nitrate almost entirely and achieved high selectivity to the expected harmless form of nitrogen. In this study, sodium borohydride (NaBH4) was applied in preparing bimetallic catalysts by liquid-phase reduction as the prestoring reductant. Pd-In/D and Pd-Sn/D groups performed well in N2selectivity (all above 97%). In addition, Pd-In and Pd-Sn bimetallic catalysis yields higher selectivity towards N2than the Pd-Cu pair in the presence of HCO3-, Cl-, SO42-and humic acid. Likewise, in terms of N2selectivity, Pd-In/D and Pd-Sn/D bimetallic catalysts were superior to that of Pd-Cu/D (72.16%) in the municipal wastewater treatment plant sewage. The current results provide insight into the superb reactivity, excellent stability, and most important-extremely high harmless N2selectivity of Pd-In and Pd-Sn-based bimetallic catalysts in practical application and provide new ideas for enhancing the feasibility of the catalytic reduction of nitrate by minimizing environmentally harmful by-products.

PEDOT Films Doped with Titanyl Oxalate as Chemiresistive and Colorimetric Dual-Mode Sensors for the Detection of Hydrogen Peroxide Vapor.

Hydrogen peroxide (H2O2) is commonly used as an oxidizing, bleaching, or antiseptic agent. It is also hazardous at increased concentrations. It is therefore crucial to monitor the presence and concentration of H2O2, particularly in the vapor phase. However, it remains a challenge for many state-of-the-art chemical sensors (e.g., metal oxides) to detect hydrogen peroxide vapor (HPV) because of the interference of moisture in the form of humidity. Moisture, in the form of humidity, is guaranteed to be present in HPV to some extent. To meet this challenge, herein, we report a novel composite material based on poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) doped with ammonium titanyl oxalate (ATO). This material can be fabricated as a thin film on electrode substrates for use in chemiresistive sensing of HPV. The adsorbed H2O2 will react with ATO, causing a colorimetric response in the material body. Combining colorimetric and chemiresistive responses resulted in a more reliable dual-function sensing method that improved the selectivity and sensitivity. Moreover, the composite film of PEDOT:PSS-ATO could be coated with a layer of pure PEDOT via in situ electrochemical synthesis. The pure PEDOT layer was hydrophobic, shielding the sensor material underneath from coming into contact with moisture. This was shown to mitigate the interference of humidity when detecting H2O2. A combination of these material properties makes the double-layer composite film, namely PEDOT:PSS-ATO/PEDOT, an ideal sensor platform for the detection of HPV. For example, upon a 9 min exposure to HPV at a concentration of 1.9 ppm, the electrical resistance of the film increased threefold, surpassing the bounds of the safety threshold. Meanwhile, the colorimetric response observed was 2.55 (defined as the color change ratio), a ratio at which the color change could be easily seen by the naked eye and quantified. We expect that this reported dual-mode sensor will find extensive practical applications in the fields of health and security with real-time, onsite monitoring of HPV.

[Qianliexin Capsules for carrageenin-induced chronic nonbacterial prostatitis: A metabolomics study].

OBJECTIVE: To explore the regulating mechanism of the Chinese medicinal compound Qianliexin Capsules (QLX) in the treatment of chronic nonbacterial prostatitis (CNP). METHODS: We randomly divided 18 SPF SD male rats into a normal control (n = 6), a model control (n = 6) and a QLX group (n = 6). After successful establishment of a CNP model in the latter two groups by injecting 50 µl 1% carrageenan bilaterally into the prostate, we treated the rats in the QLX group by intragastrical administration of QLX at 4 g/kg, tid, and those in the normal and model control groups with the same volume of pure water, all for 45 days. Then, we examined the possible lower urinary tract symptoms (LUTS) of CNP by detecting the prostate indexes, expression of the tissue inflammatory factor IL-1 ß, 24-hour urine volume and pain threshold reaction (PTR) time, and conducted a metabonomics analysis of the urine and plasma samples. RESULTS: Compared with the normal controls, the CNP model rats showed dramatically increased prostate coefficient (ï¼»0.75 ± 0.09ï¼½ ‰ vs ï¼»1.60 ± 0.35ï¼½ ‰, P < 0.01) and the expression of IL-1ß (ï¼»22.61 ± 2.77ï¼½ vs ï¼»55.12 ± 4.94ï¼½ ng/ml, P < 0.01), which were both decreased in the QLX group (ï¼»0.97 ± 0.10ï¼½ ‰ and ï¼»36.64 ± 7.25ï¼½ ng/ml) in comparison with those in the model controls (P < 0.01). The urine volume was remarkably reduced in the model control group compared with that in the normal controls (4 ml vs 16.38 ml, P < 0.01), and so was the PTR time (ï¼»13.83 ± 5.67ï¼½ vs ï¼»23.73 ± 2.52ï¼½ s, P < 0.01), while the levels of urea nitrogen (ï¼»23.06 ± 3.71ï¼½ vs ï¼»17.92 ± 1.41ï¼½ mg/dL, P < 0.01), creatinine (ï¼»48.08 ± 9.31ï¼½ vs ï¼»40.31 ± 3.53ï¼½ µmol/L, P < 0.01) and uric acid (ï¼»181.36 ± 64.06ï¼½ vs ï¼»84.33 ± 21.40ï¼½ µmol/L, P < 0.01) increased significantly. The animals in the QLX group exhibited significant improvement in the urine volume (ï¼»13.44 ± 2.26ï¼½ ml), PTR time (ï¼»31.45 ± 2.96ï¼½ s), urea nitrogen (ï¼»16.49 ± 1.86ï¼½ mg/dL), creatinine (ï¼»36.88 ± 7.98ï¼½ µmol/L) and uric acid (ï¼»117.47 ± 40.09ï¼½ µmol/L) in comparison with the model controls (P < 0.01). Metabonomics analysis revealed a reversing effect of QLX on the carrageenin-induced alteration in a variety of metabolites in the urine and serum, restoring the ratios of such metabolites as glycine, cysteine, ketoimine quinolinic acid, aminobutyraldehyde and triphosphate to almost normal. Pathway enrichment analysis showed that the main metabolic pathways were aspartate and glutamate pathways. The ratios of such metabolites as neuroside, adipic acid, diacylglycerol, choline lecithin and so on in the plasma sample were dramatically improved in the QLX group compared with those in the model controls (P < 0.01). CONCLUSION: QLX significantly improves the symptoms of CNP and has a definite effect on amino acids, phosphatidyl and other biomarkers through the tricarboxylic acid cycle, amino acid metabolism, lipid metabolism and other related pathways.

Unprecedented Small Molecule-Based Uniform Two-Dimensional Platelets with Tailorable Shapes and Sizes.

Fabrication of uniform two-dimensional (2D) structures from small molecules remains a formidable challenge for living self-assembly despite its great success in producing uniform one-dimensional (1D) structures. Here, we report the construction of unprecedented uniform 2D platelets with tailorable shapes and controlled sizes by creating new nuclei from a donor-acceptor (D-A) molecule and 1-hexanol to initiate 2D living self-assembly. We demonstrate that the D-A molecule undergoes 1-hexanol-induced twisting to form continuous alternative hydrogen bonds in-between under electrostatic attraction, which in turn forms a new nucleus. This connection architecture of the new nucleus allows to simultaneously regulate the growth rate of 1 in two dimensions to generate 2D platelets of distinct shapes through simply varying the amount of 1-hexanol relative to hexane. Furthermore, the living nature of the new nucleus enables seeded growth of complex concentric multiblock 2D heteroplatelets by sequential and alternative addition of different D-A molecules. Interestingly, the resulting 2D platelets obtained by such living self-assembly exhibit enhanced photostability compared to those obtained by conventional self-assembly without the involvement of 1-hexanol.

Enhancement of Dissolving Capacity and Reducing Gastric Mucosa Irritation by Complex Formation of Resibufogenin with ß-Cyclodextrin or 2-Hydroxypropyl-ß-cyclodextrin.

Resibufogenin (RBG) is a natural medicinal ingredient with promising cardiac protection and antitumor activity. However, poor solubility and severe gastric mucosa irritation restrict its application in the pharmaceutical field. In this study, the inclusion complex of RBG with ß-cyclodextrin (ß-CD) and 2-hydroxypropyl-ß-cyclodextrin (HP-ß-CD) was prepared using the co-evaporation method, and the molar ratio of RBG to CD was determined to be approximately 1:2 by continuous variation plot for both CDs. The formation of inclusion complexes between RBG and each CD (RBG/ß-CD and RBG/HP-ß-CD) was evaluated by phase solubility study, Fourier transform infrared spectroscopy, and thin-layer chromatography. Powder X-ray diffraction and differential scanning calorimetry confirmed drug amorphization and encapsulation in the molecular cage for both CDs. Moreover, the inclusion complexes' morphologies were observed using scanning electron microscopy. The dissolution rate of the inclusion complexes was markedly improved compared to that of RBG, and the complexes retained their antitumor activity, as shown in the in vitro cytotoxicity assay on a human lung adenocarcinoma cancer (A549) cell line. Moreover, less gastric mucosal irritation was observed for the inclusion complex. Thus, the inclusion complex should be considered a promising strategy for the delivery of poorly water-soluble anticancer agents, such as RBG.

Performance of Pd/Sn catalysts supported by chelating resin prestoring reductant for nitrate reduction in actual water.

Catalytic hydrogen reduction has appeared as a promising strategy for chemical denitrification with advantages of high activity and simple operation. However, the risk and low utilization of H2 is the disadvantage of catalytic hydrogen reduction. In recent years, catalytic reduction reactions in the presence of sodium borohydride (NaBH4) have been extensively studied. NaBH4 can be used as an electron source to generate electrons on the surface of the catalyst and can catalyze the reduction of pollutants. But it makes commercialization costly and causes significant environmental pollution if widely use NaBH4. In this study, we prepared supported Pd/Sn bimetallic nanoparticles which could adsorb NaBH4 during the preparation of the Pd/Sn bimetallic catalyst as the prestoring reductant. No additional reducing agent is required during nitrate reduction process. The performance and mechanism for nitrate reduction by using Pd/Sn bimetallic nanoparticles were discussed. Moreover, the catalyst D-Pd1/Sn1 reached a complete nitrate removal in the municipal wastewater treatment plant effluent water within 3 h. The results provide a prospect for denitrification in biological wastewater treatment plants.

Perylene Diimide-Based Fluorescent and Colorimetric Sensors for Environmental Detection.

Perylene tetracarboxylic diimide (PDI) and its derivatives exhibit excellent thermal, chemical and optical stability, strong electron affinity, strong visible-light absorption and unique fluorescence on/off features. The combination of these features makes PDIs ideal molecular frameworks for development in a broad range of sensors for detecting environmental pollutants such as heavy metal ions (e.g., Cu2+, Cd2+, Hg2+, Pd2+, etc.), inorganic anions (e.g., F-, ClO4-, PO4-, etc.), as well as poisonous organic compounds such as nitriles, amines, nitroaromatics, benzene homologues, etc. In this review, we provide a comprehensive overview of the recent advance in research and development of PDI-based fluorescent sensors, as well as related colorimetric and multi-mode sensor systems, for environmental detection in aqueous, organic or mixed solutions. The molecular design of PDIs and structural optimization of the sensor system (regarding both sensitivity and selectivity) in response to varying analytes are discussed in detail. At the end, a perspective summary is provided covering both the key challenges and potential solutions for the future development of PDI-based optical sensors.

Electrochemical Study of Structure Tunable Perylene Diimides and The Nanofibers Deposited on Electrodes.

The electrochemical behavior of organic conjugated semiconductors and their bulk materials is a considerable and irreplaceable parameter to maintain their diverse electronic or optoelectronic applications. In this paper, a series of n-type symmetrical perylene diimide derivatives (PTCDIs) with substituents (3,4-ethylenedioxythiophene (EDOT), cyclohexane, acetic acid, or propionic acid) at located the nitrogens imide position were synthesized, and their solubility, optical features, thermal stability, as well as solution-phase interfacial self-assembly into one-dimensional (1D) nanofibers and related morphology were discussed in detail. Moreover, a simple but effective method, in situ deposition following in situ self-assembly, was developed to construct uniform electrodes over a large area coated with networked PTCDI nanofibers. Then the electrochemical properties of the PTCDI nanofibers were researched in comparison with their molecules. The excellent variability at molecular or nanoscale morphological level will provide an interesting insight into the research of PTCDIs in a wide range applications of organic electronics.

A Ratiometric Fluorescent Sensor for Cd2+ Based on Internal Charge Transfer.

This work reports on a novel fluorescent sensor 1 for Cd2+ ion based on the fluorophore of tetramethyl substituted bis(difluoroboron)-1,2-bis[(1H-pyrrol-2-yl)methylene]hydrazine (Me4BOPHY), which is modified with an electron donor moiety of N,N-bis(pyridin-2-ylmethyl)benzenamine. Sensor 1 has absorption and emission in visible region, at 550 nm and 675 nm, respectively. The long wavelength spectral response makes it easier to fabricate the fluorescence detector. The sensor mechanism is based on the tunable internal charge transfer (ICT) transition of molecule 1. Binding of Cd2+ ion quenches the ICT transition, but turns on the π - π transition of the fluorophore, thus enabling ratiometric fluorescence sensing. The limit of detection (LOD) was projected down to 0.77 ppb, which is far below the safety value (3 ppb) set for drinking water by World Health Organization. The sensor also demonstrates a high selectivity towards Cd2+ in comparison to other interferent metal ions.

Interfacial Donor-Acceptor Engineering of Nanofiber Materials To Achieve Photoconductivity and Applications.

Self-assembly of π-conjugate molecules often leads to formation of well-defined nanofibril structures dominated by the columnar π-π stacking between the molecular planes. These nanofibril materials have drawn increasing interest in the research frontiers of nanomaterials and nanotechnology, as the nanofibers demonstrate one-dimensionally enhanced exciton and charge diffusion along the long axis, and present great potential for varying optoelectronic applications, such as sensors, optics, photovoltaics, and photocatalysis. However, poor electrical conductivity remains a technical drawback for these nanomaterials. To address this problem, we have developed a series of nanofiber structures modified with different donor-acceptor (D-A) interfaces that are tunable for maximizing the photoinduced charge separation, thus leading to increase in the electrical conductivity. The D-A interface can be constructed with covalent linker or noncovalent interaction (e.g., hydrophobic interdigitation between alkyl chains). The noncovalent method is generally more flexible for molecular design and solution processing, making it more adaptable to be applied to other fibril nanomaterials such as carbon nanotubes. In this Account, we will discuss our recent discoveries in these research fields, aiming to provide deep insight into the enabling photoconductivity of nanofibril materials, and the dependence on interface structure. The photoconductivity generated with the nanofibril material is proportional to the charge carriers density, which in turn is determined by the kinetics balance of the three competitive charge transfer processes: (1) the photoinduced electron transfer from D to A (also referred to as exciton dissociation), generating majority charge carrier located in the nanofiber; (2) the back electron transfer; and (3) the charge delocalization along the nanofiber mediated by the π-π stacking interaction. The relative rates of these charge transfer processes can be tuned by the molecular structure and nanoscale interface engineering. As a result, maximal photoconductivity can be achieved for different D-A nanofibril composites. The photoconductive nanomaterials thus obtained demonstrate unique features and functions when employed in photochemiresistor sensors, photovoltaics and photocatalysis, all taking advantages of the large, open interface of nanofibril structure. Upon deposition onto a substrate, the intertwined nanofibers form networks with porosity in nanometer scale. The porous structure enables three-dimensional diffusion of molecules (analytes in sensor or reactants in catalysis), facilitating the interfacial chemical interactions. For carbon nanotubes, the completely exposed π-conjugation facilitates the surface modification through π-π stacking in conjunction with D-A interaction. Depending on the electronic energy levels of D and A parts, appropriate band alignment can be achieved, thus producing an electric field across the interface. Presence of such an electric field enhances the charge separation, which may lead to design of new type of photovoltaic system using carbon nanotube composite.

Stimuli-Responsive Polyoxometalate/Ionic Liquid Supramolecular Spheres: Fabrication, Characterization, and Biological Applications.

We report fabrication, characterization, and potential applications of polyoxometalate (POM)/ionic liquid (IL) supramolecular spheres in water for the first time. These supramolecular spheres have highly ordered structures and show excellent reversible self-assembly and tunable photoluminescence properties, which can be manipulated by adjusting pH of the aqueous solution. Specifically, the formation of POM/IL supramolecular spheres results in quenching of fluorescence emitted by Eu-POM because hopping of the d1 electron in the POM molecule is blocked by hydrogen bond existing between the oxygen atom of POM and the carboxylic acid group of IL. However, the fluorescence can be completely recovered by gradually increasing pH of the aqueous solution due to the pH-induced deprotonation of the carboxylic acid group of IL, which results in disassembly of the fabricated supramolecular spheres. Applications of these stimuli-responsive photoluminescent POM-based supramolecular materials are demonstrated in biological media. Dual signaling responses of turbidity and fluorescence are observed simultaneously in the detection of urease and heavy metals based on pH-induced disassembly of the supramolecular spheres during the biochemical events in aqueous solution. In addition, guest molecules are encapsulated into the supramolecular spheres, and controlled release of these entrapped molecules is demonstrated in the presence of external stimuli. This study shows potential of stimuli-responsive POM/IL supramolecular materials in biological applications.

A Cu2+-Selective Probe Based on Phenanthro-Imidazole Derivative.

A novel fluorescent Probe 1, based on phenanthro-imidazole has been developed as an efficient chemosensor for the trace detection of copper ions (Cu2+). Probe 1 demonstrated sensitive fluorescence quenching upon binding with Cu2+ through 1:1 stoichiometric chelation. The detection limit for Cu2+ ions was projected through linear quenching fitting to be as low as 2.77 × 10-8 M (or 1.77 ppb). The sensing response was highly selective towards Cu2+ with minimal influence from other common metal ions, facilitating the practical application of Probe 1 in trace detection.

Factors associated with medication adherence in patients living with cirrhosis.

AIMS AND OBJECTIVES: Medication adherence in people with cirrhosis is largely unknown. This study aims to determine adherence patterns and factors associated with adherence in patients with cirrhosis. BACKGROUND: Prescribed medications are a pivotal component in the clinical management of cirrhosis with potential to retard disease progression and reduce complication risks. Medication adherence is necessary to optimise health outcomes. Understanding why medications are missed may help to develop strategies and inform nursing practice. DESIGN: Prospective cohort study. METHODS: Participants (n = 29) diagnosed with cirrhosis attending a tertiary hospital consented to complete a self-reported survey. Demographic information, adherence to medications, patient knowledge and quality of life data were collected, collated, checked and analysed using SPSS version 21. RESULTS: Less than half of the 28 patients who completed the adherence questionnaire (n = 13, 46%) reported that they had never missed medication. Being forgetful, being away from home and falling asleep contributed to nonadherence. Having less abdominal symptoms, less fatigue and increased emotional well-being were significantly associated with patients never missing medications. CONCLUSIONS: To our knowledge this is the first published study to describe adherent behaviour and the reasons medications are missed in this population. The percentage of nonadherent participants is of concern considering the potential morbidity risk that is associated with missed medications and rebound symptoms of cirrhosis. Strategies to improve and sustain adherence levels are required including enhanced adherence counselling offered to patients who are deteriorating or experience periodic exacerbation of symptoms. RELEVANCE TO CLINICAL PRACTICE: Study findings have the potential to change clinical practice especially the way nurses target motivational adherence counselling, key treatment messages, education and adherence monitoring. The results presented here provide a basis for developing adherence strategies and nursing management plans to improve adherence and health outcomes in people with cirrhosis.

Low dose detection of γ radiation via solvent assisted fluorescence quenching.

Development of low cost, easy-to-use chemical sensor systems for low dose detection of γ radiation remains highly desired for medical radiation therapy and nuclear security monitoring. We report herein on a new fluorescence sensor molecule, 4,4'-di(1H-phenanthro[9,10-d]imidazol-2-yl)biphenyl (DPI-BP), which can be dissolved into halogenated solvents (e.g., CHCl3, CH2Cl2) to enable instant detection of γ radiation down to the 0.01 Gy level. The sensing mechanism is primarily based on radiation induced fluorescence quenching of DPI-BP. Pristine DPI-BP is strongly fluorescent in halogenated solvents. When exposed to γ radiation, the halogenated solvents decompose into various radicals, including hydrogen and chlorine, which then combine to produce hydrochloric acid (HCl). This strong acid interacts with the imidazole group of DPI-BP to convert it into a DPI-BP/HCl adduct. The DPI-BP/HCl adduct possesses a more planar configuration than DPI-BP, enhancing the π-π stacking and thus molecular aggregation. The strong molecular fluorescence of DPI-BP gets quenched upon aggregation, due to the π-π stacking interaction (forming forbidden low-energy excitonic transition). Interestingly the quenched fluorescence can be recovered simply by adding base (e.g., NaOH) into the solution to dissociate the DPI-BP/HCl adduct. Such sensing mechanism was supported by systematic investigations based on HCl titration and dynamic light scattering measurements. To further confirm that the aggregation caused fluorescence quenching, a half size analogue of DPI-BP, 2-phenyl-1H-phenanthro[9,10-d]imidazole (PI-Ph), was synthesized and investigated in comparison with the observations of DPI-BP. PI-Ph shares the same imidazole conjugation structure with DPI-BP and is expected to bind the same way with HCl. However, PI-Ph did not show fluorescence quenching upon binding with HCl likely due to the smaller π-conjugation structure, which can hardly enforce the π-π stacking assembly. Combining the low detection limit, fast and reversible fluorescence quenching response, and low cost of halogenated solvent composites, the sensor system presented may lead to the development of new, simple chemical dosimetry for low dose detection of γ radiation.

Fluorescence Turn-on Detection of Perfluorooctanoic Acid (PFOA) by Perylene Diimide-Based Metal-Organic Framework.

A novel, water-stable, perylene diimide (PDI) based metal-organic framework (MOF), namely, U-1, has been synthesized for selective and sensitive detection of perfluorooctanoic acid (PFOA) in mixed aqueous solutions. The MOF shows highly selective fluorescence turn-on detection via the formation of a PFOA-MOF complex. This PFOA-MOF complex formation was confirmed by various spectroscopic techniques. The detection limit of the MOF for PFOA was found to be 1.68 µM in an aqueous suspension. Upon coating onto cellulose paper, the MOF demonstrated a significantly lower detection limit, down to 3.1 nM, which is mainly due to the concentrative effect of solid phase extraction (SPE). This detection limit is lower than the fluorescence sensors based on MOFs previously reported for PFAS detection. The MOF sensor is regenerable and capable of detecting PFOA in drinking and tap water samples. The PDI-MOF-based sensor reported herein represents a novel approach, relying on fluorescence turn-on response, that has not yet been thoroughly investigated for detecting per- and polyfluoroalkyl substances (PFAS) until now.

Concentric hollow multi-hexagonal platelets from a small molecule.

The creation of well-defined hollow two-dimensional structures from small organic molecules, particularly those with controlled widths and numbers of segments, remains a formidable challenge. Here we report the fabrication of the well-defined concentric hollow two-dimensional platelets with programmable widths and numbers of segments through constructing a concentric multiblock two-dimensional precursor followed by post-processing. The fabrication of concentric multi-hexagons two-dimensional platelets is realized by the alternative heteroepitaxial growth of two donor-acceptor molecules. Upon ultraviolet irradiation, one of the two donor-acceptor molecules can be selectively oxidized by singlet oxygen generated during the process, and the oxidized product becomes more soluble due to increased polarity. This allows for selective removal of the oxidized segments simply by solvent dissolution, yielding hollow multiblock two-dimensional structures. The hollow two-dimensional platelets can be utilized as templates to lithograph complex electrodes with precisely controlled gap sizes, thereby offering a platform for examining the optoelectronic performance of functional materials.

Morphology control of nanofibril donor-acceptor heterojunction to achieve high photoconductivity: exploration of new molecular design rule.

Donor-acceptor nanofibril composites have been fabricated, and the dependence of their photocurrent response on the structure and morphology of the donor part has been systematically investigated. The nanofibril composites were composed of template nanofibers, assembled from an electron acceptor molecule, perylene tetracarboxylic diimide (PTCDI), onto which (through drop-casting) various electron donor molecules (D1-D4) were coated. The donor molecules have the same π-conjugated core, but different side groups. Due to the different side groups, the four donor molecules showed distinctly different propensity for intermolecular aggregation, with D1-D3 forming segregated phases, while D4 prefers homogeneous molecular distribution within the film. It was found that the nanofibril composites with D4 exhibit the highest photocurrent, whereas those with aggregation-prone D1-D3 exhibited much lower photocurrent under the same illumination condition. Solvent annealing is found to further enhance the aggregation of D1-D3 but facilitate more uniform molecular distribution of D4 molecules. As a result, the photocurrent response of PTCDI fibers coated with D1-D3 decreased after vapor annealing, whereas those coated with D4 further increased. The detrimental effect of the aggregation of donor molecules on the PTCDI fiber is likely due to the enhanced local electrical field built up by the high charge density around the aggregate-nanofiber interface, which hinders the charge separation of the photogenerated electron-hole pair. The results reported in this study give further insight into the molecular structural effect on photoconductivity of hybrid materials, particularly those based on donor-acceptor composites or interfaces, and provide new molecular design rules and material processing guidelines to achieve high photoconductivity.

Physalin A induces apoptotic cell death and protective autophagy in HT1080 human fibrosarcoma cells.

Physalin A (1) is a withanolide isolated from Physalis alkekengi var. franchetii. In this study, the selective growth inhibitory effects on tumor cells induced by 1 were screened, and the mechanism was investigated on 1-induced growth inhibition, including apoptosis and autophagy, in human fibrosarcoma HT1080 cells. Apoptosis induced by 1 in HT1080 cells was associated with up-regulation of caspase-3 and caspase-8 expression. However, there were no significant changes in caspase-9, Bid, Bax, and Bcl-2 expression, indicating that 1-induced apoptosis in HT1080 cells occurs mainly through activation of the death receptor-associated extrinsic apoptotic pathways. Autophagy induced by 1 was found to antagonize apoptosis in HT1080 cells. This effect was enhanced by rapamycin and suppressed by the autophagy inhibitor 3-methyladenine (3MA). Loss of beclin 1 (as an autophagic regulator) function led to similar results to 3MA. However, 1 did not show inhibitory effects on normal human cells (human peripheral blood mononuclear cells). Taken together, these results suggest that 1 may be a promising agent for the treatment of cancer.