Photo- and Oxygen- Synergistically Controlled Selective Expression of Organic Phosphorescence Units.

Dynamic control of ultralong organic room-temperature phosphorescence (UORTP) is a charming target. Herein, we report a stimuli-responsive phosphorescence unit 7H-indolo[2,3-c]quinoline (NBCz) and its derivatives (PCBNBCz, FSO2NBCz, and N2BCzSO2NBCz) that show photo- and oxygen- synergistically induced afterglow activation and afterglow color change in the PMMA film. PCBNBCz and FSO2NBCz feature a donor-acceptor (D-A) structure, and N2BCzSO2NBCz features acceptor-bridged two different phosphorescence units (NBCz and N2BCz). The photoactivated UORTP of PCBNBCz and FSO2NBCz arises from the photoinduced consumption of oxygen in the PMMA film. It is clear that the phosphorescence unit NBCz contributes to subsequent photoinduced UORTP color change because the NBCz-doped PMMA film shows the same UORTP color change process. ESR and HRMS measurements confirmed that oxidation of NBCz occurs at the nitrogen atom of the quinoline ring via photogenerated superoxide radicals, which results in the UORTP color change. TDDFT calculations proved that after oxidation of NBCz, the T1 energy level declines significantly. Furthermore, photocontrolled selective expression of phosphorescence units is achieved in the case of N2BCzSO2NBCz. After further UV irradiation, oxidation of NBCz happened, and the oxidized form N2BCzSO2NBCz-O emitted the intrinsic orange UORTP of NBCz-O selectively and screened the intrinsic yellowish-green UORTP of N2BCz. Finally, multilevel photolithography can be demonstrated based on the photoactivated UORTP and the photoinduced UORTP color change. This work may give a deep insight into organic phosphorescence and pave a simple way for the development of stimulus-responsive smart UORTP materials.

Suppressive Photochromism and Promotive Mechanochromism of Rhodamine Mechanophore by the Strategy of Poly(methyl acrylate)/Polyurethane Interpenetrating Polymer Network.

As molecular design and the structure-property relationships of photochemical molecules established in the literature serve as a convenient reference for mechanophore exploration, many typical mechanophores suffer undesired responses to UV light or even sunlight in bulk polymers. We developed a strategy of a poly(methyl acrylate)/polyurethane (PMA/PU) interpenetrating polymer network (IPN) to suppress the photochromic property of the mechanophore and promote its mechanochromic property. A widely used rhodamine mechanophore (Rh-2OH) was first incorporated into polyurethane (P1). Then P1 was swollen in methyl acrylate and photopolymerized to prepare a PMA2.8/PU IPN (P2). Different from photo/force-responsive P1, P2 selectively responded to force because the low free volume in IPN greatly hinders photoisomerization of the rhodamine spirolactam, suggesting that a simple IPN strategy successfully resolves the giant problem of nonselective response to photo/force for photochromic mechanophores. Moreover, PMA/PU IPN enhanced the mechanical property, resulting in a higher mechanochemical activation ratio than PU, and the prestretching effect of PMA/PU IPN promoted the force sensitivity of rhodamine mechanophores significantly. We believe that the strategy can be applied to other mechanophores, promoting their application in more complicated environments.

Achieving Colorful Ultralong Organic Room-Temperature Phosphorescence by Precise Modification of Nitrogen Atoms on Phosphorescence Units.

We successfully tune ultralong organic room-temperature phosphorescence (UORTP) by a simple strategy of precisely modifying nitrogen atoms on Phosphorescence Units, and colorful ultralong phosphorescence can be achieved. We for the first time investigate the structure-function relationship between phosphorescence properties and molecular structures of Phosphorescence Units. With BCz and BCz-1 as comparison, eight new Phosphorescence Units were synthesized by introducing one or two nitrogen atoms to the naphthalene moiety. For all the 10 Phosphorescence Units, their room-temperature ultralong phosphorescence in the PMMA film should be assigned to monomer phosphorescence from intrinsic T1 decay. For Phosphorescence Units series I (BCz, NBCz-1, NBCz-2, NBCz-3, NBCz-4, NBCz-5, and NBCz-6), introducing one nitrogen atom to the naphthalene moiety can significantly affect the phosphorescence properties of Phosphorescence Units, and the effect is quite complicated. For modification on the inner ring, the T1 energy level of NBCz-1 decreases, and the red shift of UORTP occurs while the T1 energy level of NBCz-2 increases and the blue shift of UORTP happens. For modification on the outer ring, no phosphorescence color change is observed for NBCz-3 and NBCz-4, but their phosphorescence lifetimes vary notably due to different intersystem crossing efficiencies; as the modification site approaches the central five-member ring, the T1 energy levels of NBCz-5 and NBCz-6 decrease, and their UORTP red shifts dramatically. For Phosphorescence Units series II (BCz, 2NBCz, BCz-1, and 2NBCz-1), introducing two nitrogen atoms to the outer six-member ring reduces energy level of T1 excitons and leads to incredible red shift of UORTP for BCz and 2NBCz while surprisingly energy levels of T1 excitons rise and UORTP blue shifts for BCz-1 and 2NBCz-1. Under the condition of proper modification sites, it is true that the more the additional nitrogen atoms, the more red-shifted the ultralong phosphorescence. This study may expand our knowledge of organic phosphorescence and lay the foundation for its future applications.

A practical method for predicting and analyzing the consequences of ammonium nitrate explosion accidents adjacent to densely populated areas.

Several catastrophic ammonium nitrate (AN) explosion accidents have been reported during the last decades. Previous studies have been mainly focused on investigating adverse effects caused by the AN explosion, while only a few systematically analyzed the consequences and impacts of AN explosions. This study collects data from three typical AN explosions (accidental explosion of the US fertilizer plant in 2013; an accidental explosion of China's Tianjin port in 2015, and a recent explosion (2020) of the Beirut port in Lebanon). The consequences of accidental explosions were analyzed by mathematical equations that further provide scientific explanations for AN explosions. Based on the explosives' properties on-site, these accidental explosions were caused by condensed phase explosives. Comparison with the conditions at the explosion site indicated that blast overpressure was the primary factor in the loss of life and damage to the building, while ground shock was a secondary factor. The severity of loss of life and building damage from explosions decreased with increasing distance. These distances could be calculated by the scaling law, which was replaced by the equivalent TNT mass of the explosive and the damage scale's overpressure boundary value. In addition, mapping the damaged area on a map helped in the visual presentation of the consequence assessment. The long-term environmental and ecological impact due to the explosions was also an important issue that could not be ignored. Overall, this study establishes a simple and easy-to-use method to rapidly predict and assess the consequences of an explosion, and provides technical guidance for future emergency response to similar large-scale accidents.

Metal-organic frameworks for food contaminant adsorption and detection.

Metal-organic framework materials (MOFs) have been widely used in food contamination adsorption and detection due to their large specific surface area, specific pore structure and flexible post-modification. MOFs with specific pore size can be targeted for selective adsorption of some contaminants and can be used as pretreatment and pre-concentration steps to purify samples and enrich target analytes for food contamination detection to improve the detection efficiency. In addition, MOFs, as a new functional material, play an important role in developing new rapid detection methods that are simple, portable, inexpensive and with high sensitivity and accuracy. The aim of this paper is to summarize the latest and insightful research results on MOFs for the adsorption and detection of food contaminants. By summarizing Zn-based, Cu-based and Zr-based MOFs with low cost, easily available raw materials and convenient synthesis conditions, we describe their principles and discuss their applications in chemical and biological contaminant adsorption and sensing detection in terms of stability, adsorption capacity and sensitivity. Finally, we present the limitations and challenges of MOFs in food detection, hoping to provide some ideas for future development.

Procaspase-3-activating compound 1 stabilizes hypoxia-inducible factor 1α and induces DNA damage by sequestering ferrous iron.

Procaspase-3-activating compound 1 (PAC-1) induces procaspase-3 activation via zinc chelation. However, whether PAC-1 employs other mechanisms remains unknown. Here we systematically screened for potent PAC-1 targets using 29 enhanced green fluorescent protein-labeled reporter cell lines and identified hypoxia-inducible factor 1α (HIF1α) and RAD51 pathways as PAC-1 targets. These results were verified in HepG2 cells and two other cancer cell lines. Mechanistically, PAC-1 specifically blocked HIF1α hydroxylation and upregulated HIF1α target genes. In addition, DNA damage, G1/S cell cycle arrest, and the inhibition of DNA synthesis were induced following PAC-1 administration. Interestingly, by using ferrozine-iron sequestration and iron titration assays, we uncovered the iron sequestering capacity of PAC-1. Additionally, the expression levels of iron shortage-related genes were also increased in PAC-1-treated cells, and iron (II) supplementation reversed all of the observed cellular responses. Thus, our results indicate that PAC-1 induces HIF1α stabilization and DNA damage by sequestering ferrous iron.

Historically-informed nursing: A transnational case study in China.

The term 'nurse' (hushi-'caring scholar') did not enter the Chinese language until the early 20th century. Modern nursing-a fundamentally Western notion popularized by Nightingale and introduced to China in 1884-profoundly changed the way care of the sick was practiced. For 65 years, until 1949, nursing developed in China as a transnational project, with Western and Chinese influences shaping the profession of nursing in ways that linger today. Co-authored by Chinese, Canadian, and American nurses, this paper examines the early stages of nursing in one province of China as an exemplar of the transnational nature of nursing development. By identifying sociopolitical influences on the early development of nursing in Shandong, the authors aimed not only to contribute to the nascent body of knowledge on China nursing history, but also to heighten readers' sensitivity to the existence of historical echoes, residue, and resonances in their own nursing practices. Tracing current issues, values, or practices back to their roots provides context and helps us to better understand the present. Whether we are aware of the details or not, the gestalt of nursing practice in a particular place has been shaped by its history-including in Shandong province in China.

Square wave anodic stripping voltammetric determination of Cd²âº and Pb²âº at bismuth-film electrode modified with electroreduced graphene oxide-supported thiolated thionine.

Graphene oxide (GO)-thionine (TH) nanocomposite was prepared by π-π stacking. The nanocomposite was cast-coated on a glassy carbon electrode (GCE) to prepare an electroreduced GO (ERGO)-TH/GCE, then 2-mercaptoethanesulfonate (MES) was covalently tethered to ERGO-TH by potentiostatic anodization to form an ERGO-TH-MES/GCE. The thiolation reaction was monitored by electrochemical quartz crystal microbalance (EQCM). Square wave anodic stripping voltammetry (SWASV) was used to determine Cd(2+) and Pb(2+) at the ERGO-TH-MES/GCE further modified with Nafion and Bi. Under the optimal conditions, the linear calibration curves for Cd(2+) and Pb(2+) are from 1 to 40 µg L(-1), with limits of detection (S/N=3) of 0.1 µg L(-1) for Cd(2+) and 0.05 µg L(-1) for Pb(2+), respectively. The electrode was used for the simultaneous analysis of Cd(2+) and Pb(2+) in water samples with satisfactory recovery.

Filling carbon nanotubes with Prussian blue nanoparticles of high peroxidase-like catalytic activity for colorimetric chemo- and biosensing.

Facile filling of multiwalled carbon nanotubes (MWCNTs) with Prussian blue nanoparticles (PBNPs) of high peroxidase-like catalytic activity was performed to develop novel colorimetric sensing protocols for assaying H2O2 and glucose. Fine control of PBNP growth was achieved by modulating the concentration ratio of K3 [Fe(CN)6] and FeSO4 precursors in an acidic solution containing ultrasonically dispersed MWCNTs, and thus size-matched PBNPs could be robustly immobilized in the cavities of the MWCNTs (MWCNT-PBin). Unlike other reported methods involving complicated procedures and rigorous preparation/separation conditions, this mild one-pot filling method has advantages of easy isolation of final products by centrifugation, good retention of the pristine outer surface of the MWCNT shell, and satisfactory filling yield of (24±2) %. In particular, encapsulation of PBNPs of poor dispersibility and limited functionality in dispersible and multifunctional MWCNT shells creates new and valuable opportunities for quasihomogeneous-phase applications of PB in liquid solutions. The MWCNT-PBin nanocomposites were exploited as a peroxidase mimic for the colorimetric assay of H2O2 in solution by using 3,3',5,5'-tetramethylbenzidine (TMB) as reporter, and they gave a linear absorbance response from 1 µM to 1.5 mM with a limit of detection (LOD) of 100 nM. Moreover, glucose oxidase (GOx) was anchored on the outer surface of MWCNT-PBin to form GOx/MWCNT-PBin bionanocomposites. The cooperation of outer-surface biocatalysis with peroxidase-like catalysis of interior PB resulted in a novel cooperative colorimetric biosensing mode for glucose assay. The use of GOx/MWCNT-PBin for colorimetric biosensing of glucose gave a linear absorbance response from 1 µM to 1.0 mM and an LOD of 200 nM. The presented protocols may be extended to other multifunctional nanocomposite systems for broad applications in catalysis and biotechnology.

Horseradish peroxidase-catalyzed synthesis of poly(thiophene-3-boronic acid) biocomposites for mono-/bi-enzyme immobilization and amperometric biosensing.

We report here on a facile enzymatic polymerization protocol to prepare enzyme-poly(thiophene-3-boronic acid) (PTBA) polymeric biocomposites (PBCs) for high-performance mono-/bi-enzyme amperometric biosensing. Horseradish peroxidase (HRP)-catalyzed polymerization of thiophene-3-boronic acid (TBA) monomer was conducted in aqueous solution containing HRP (or plus glucose oxidase (GOx)) by either directly added or GOx-glucose generated oxidant H2O2. The mono-/bi-enzyme amperometric biosensors were prepared simply by casting the dialysis-isolated PBCs on Au-plated Au electrode (Auplate/Au), followed by coating with an outer-layer chitosan (CS) film. The boronic acid residues are capable of covalent bonding with enzyme at the glycosyl sites (boronic acid-diols interaction), which should less affect the enzymatic activity as compared with the common cases of covalent bonding at the peptide chains, and UV-vis spectrophotometric tests confirmed that the encapsulated HRP almost possesses its pristine enzymatic specific activity. The enzyme electrodes were studied by cyclic voltammetry, electrochemical impedance spectroscopy and chronoamperometry in the presence of Fe(CN)6(4-) mediator. The CS/HRP-PTBA/Auplate/Au electrode responded linearly to H2O2 concentration from 1 to 300 µM with a sensitivity of 390 µA mM(-1)cm(-2) and a limit of detection (LOD) of 0.1 µM. The bienzyme CS/GOx-HRP-PTBA(H2O2)/Auplate/Au electrode responded linearly to glucose concentration from 5 µM to 0.83 mM with a sensitivity of 75.1 µA mM(-1)cm(-2) and a LOD of 1 µM, and it is found here that the use of Fe(CN)6(4-) that can only efficiently mediate HRP favorably avoids the "unusual amperometric responses" observed when other mediators that can efficiently turn over both HRP and GOx are used.

Novel amperometric aptasensor based on analyte-induced suppression of enzyme catalysis in polymeric bionanocomposites.

We report on a novel label-free biosensing interface based on multifunctional polymeric bionanocomposites (PBNCs) and its application for sensitive detection of protein based on the analyte-induced suppression of enzymatic catalysis in PBNCs. Thrombin and its aptamer are adopted as a model system to construct an amperometric aptasensor. First, polydopamine-based PBNCs with glucose oxidase (GOx) entrapped at high load/activity and Au nanoparticles (AuNPs) dispersed in high abundance on the surface were prepared through a chemical/biochemical synthesis method, as proven by UV-vis spectrophotometry, digital imaging, and transmission electron microscopy. Then, the PBNCs were cast-coated onto an Au electrode. The PBNC-modified Au electrode presented a high chronoamperometric sensitivity of 113 ± 2 µA cm(-2) mM(-1) to glucose, as well as a high capability of immobilizing the aptamer through the surficial AuNPs to fabricate a label-free aptasensing interface. The binding of thrombin to the aptasensor surface significantly hindered the mass-transfer of the enzymatic substrates/products and thus suppressed the enzymatic catalysis efficiency, which produced obvious signal change through measuring the electrooxidation of enzymatically generated H(2)O(2). The thus-prepared aptasensor could detect thrombin with a broad detection range (1-100 nM), a detection limit down to 0.1 nM, and satisfactory specificity. The developed aptasensing method may find broad applications in the fields of clinical diagnosis, environmental protection, and food safety.

Exploiting metal-organic coordination polymers as highly efficient immobilization matrixes of enzymes for sensitive electrochemical biosensing.

We report on the exploitation of metal-organic coordination polymers (MOCPs) as new and efficient matrixes to immobilize enzymes for amperometric biosensing of glucose or phenols. A ligand, 2,5-dimercapto-1,3,4-thiadiazole (DMcT), two metallic salts, NaAuCl(4) and Na(2)PtCl(6), and two enzymes, glucose oxidase (GOx) and tyrosinase, are used to demonstrate the novel concept. Briefly, one of the metallic salts is added into an aqueous suspension containing DMcT and one of the enzymes to trigger the metal-organic coordination reaction, and the yielded MOCPs-enzyme biocomposite (MEBC) is then cast-coated on an Au electrode for biosensing. The aqueous-phase coordination polymerization reactions of the metallic ions with DMcT are studied by visual inspection as well as some spectroscopic, microscopic, and electrochemical methods. The thus-prepared glucose and phenolic biosensors perform better in analytical performance (such as sensitivity and limit of detection) than those prepared by the conventional chemical and/or electrochemical polymerization methods and most of the reported analogous biosensors, as a result of the improved enzyme load/activity and mass-transfer efficiency after using the MOCPs materials with high adsorption/encapsulation capability and unique porous structure. For instance, the detection limit for catechol is as low as 0.2 nM here, being order(s) lower than those of most of the reported analogues. The enzyme electrode was also used to determine catachol in real samples with satisfactory results. The emerging MOCPs materials and the suggested aqueous-phase preparation strategy may find wide applications in the fields of bioanalysis, biocatalysis, and environmental monitoring.

A post-labeling strategy based on dye-induced peeling of the aptamer off single-walled carbon nanotubes for electrochemical aptasensing.

A simple and efficient post-labeling strategy based on dye-induced peeling of the aptamer molecules off single-walled carbon nanotubes was developed for electrochemical aptasensing of thrombin with a detection limit down to 3 pM.

Novel polymeric bionanocomposites with catalytic Pt nanoparticles label immobilized for high performance amperometric immunoassay.

We report on the aqueous preparation of novel polymeric bionanocomposites (PBNCs) with polydopamine (PDA) as an efficient matrix to support antibody and uniformly dispersed abundant Pt nanoparticles (PtNPs) for high performance sandwich-type amperometric immunoassay. We prepare three kinds of PBNCs (PBNCs 1, 2, and 3) via chemical polymerization synthesis (1) and further adsorption (2) or glutaldehyde (GA) covalent crosslinking (3) of antibody. Transmission electron microscopy, atomic force microscopy, and quartz crystal microbalance are used to characterize the PBNCs. The results show that PDA is an excellent matrix to support antibody and PtNPs due to its high biocompatibility, adsorbability, and processibility, and the thus-prepared PBNCs are of high immuno-recognition efficiency and high catalytic activity toward H(2)O(2) reduction. Then, we examine the applicability of the prepared PBNCs for sandwich-type amperometric immunosensing using a model immuno-pair of human immunoglobulin G (hIgG) and anti-hIgG, and obtain the signal by detecting the electro-reduction of H(2)O(2) catalyzed by the PtNPs label. The constructed immunosensors using PBNCs 1, 2 and 3 exhibit detection limits of 0.068, 0.037, and 0.018 ng mL(-1), respectively, being competitive with or better than the reported analogues. Our immunosensors also present good reproducibility, stability, regeneration ability, specificity, and satisfactory feasibility for target assay in clinical human serum samples. The suggested protocol for the preparation of PBNCs with high signal-transduction ability is expected to find wide bioassay applications.