Harnessing Catalytic RNA Circuits for Construction of Artificial Signaling Pathways in Mammalian Cells.

Engineering of genetic networks with artificial signaling pathways (ASPs) can reprogram cellular responses and phenotypes under different circumstances for a variety of diagnostic and therapeutic purposes. However, construction of ASPs between originally independent endogenous genes in mammalian cells is highly challenging. Here we report an amplifiable RNA circuit that can theoretically build regulatory connections between any endogenous genes in mammalian cells. We harness the system of catalytic hairpin assembly with combination of controllable CRISPR-Cas9 function to transduce the signals from distinct messenger RNA expression of trigger genes into manipulation of target genes. Through introduction of these RNA-based genetic circuits, mammalian cells are endowed with autonomous capabilities to sense the changes of RNA expression either induced by ligand stimuli or from various cell types and control the cellular responses and fates via apoptosis-related ASPs. Our design provides a generalized platform for construction of ASPs inside the genetic networks of mammalian cells based on differentiated RNA expression.

Enhancement of the Peroxidase Activity of g-C3N4 with Different Morphologies for Simultaneous Detection of Multiple Antibiotics.

The classes and forms of antibiotics directly determine their ecotoxicity and environmental chemical behavior, and developing a sensor array for simultaneous and in situ detection of antibiotics is highly anticipated. In this study, different morphologies of g-C3N4 with different fluorescence properties and peroxidase activity were prepared by regulating the degree of interlayer stacking and planar connectivity. Subsequently, in order to enhance its enzyme activity and amplify the differences in response signals to different antibiotics, three morphologies of g-C3N4/MIL-101(Fe) were prepared by in situ growth of equivalent amounts of MIL-101(Fe) on g-C3N4, respectively. The sensor array constructed based on the cross-response signals between g-C3N4/MIL-101(Fe) and antibiotics not only realized the simultaneous detection of quinolones, furans, tetracyclines, and lincomamides but also could efficiently identify their seven different forms. In the range of 0.2-0.8 ppm, the minimum detection limit for antibiotics was 12 ppb. In addition, the recovery experiments of multicomponent-mixed antibiotics in environmental samples show that the recovery rate remained at 91.42-107.59%, confirming the reliability and practicality of the sensor array. This study not only revealed the influence of crystal morphology regulation on the optical properties and enzyme activities of nanozymes, but also provided support for tracing, ecological remediation, and in situ environmental chemical behavior research of antibiotics.

Simultaneous visual detection of multiple heavy metal ions by a high-throughput fluorescent probe.

To develop simultaneous and in-situ detection techniques towards Cr(VI) and Mn(II), Eu/Tb@CDs with white fluorescence were prepared by a one-step hydrothermal method. With the increase of Cr(VI), all fluorescence channels of Eu/Tb@CDs exhibited obvious quenching, and the detection limit (LOD) was 0.10 µM. In the presence of Mn(II), only the fluorescence from Tb and Eu was quenched, while the fluorescence of CDs was not effected. The LOD for Mn(II) was 0.16 µM. More importantly, in the actual water samples where Cr(VI) and Mn(II) coexist, Eu/Tb@CDs can realize their rapid and simultaneous detection by simple spectral calculation. The selective and competitive experiments have also confirmed that the detection of Cr(VI) and Mn(II) was not interfered by common pollutants in groundwater. It is undeniable that the simultaneous detection of multiple targets by one probe not only greatly improves the detection efficiency, but also has important significance for the field monitoring of water quality parameters.

Surface Facet of CuFeO2 Nanocatalyst: A Key Parameter for H2O2 Activation in Fenton-Like Reaction and Organic Pollutant Degradation.

The development of efficient heterogeneous Fenton catalysts is mainly by "trial-and-error" concept and the factor determining H2O2 activation remains elusive. In this work, we demonstrate that suitable facet exposure to elongate O-O bond in H2O2 is the key parameter determining the Fenton catalyst's activity. CuFeO2 nanocubes and nanoplates with different surface facets of {110} and {012} are used to compare the effect of exposed facets on Fenton activity. The results indicate that ofloxacin (OFX) degradation rate by CuFeO2 {012} is four times faster than that of CuFeO2 {110} (0.0408 vs 0.0101 min-1). In CuFeO2 {012}-H2O2 system, OFX is completely removed at a pH range 3.2-10.1. The experimental results and theoretical simulations show that •OH is preferentially formed from the reduction of absorbed H2O2 by electron from CuFeO2 {012} due to suitable elongation of O-O (1.472 Å) bond length in H2O2. By contrast, the O-O bond length is elongated from 1.468 to 3.290 Å by CuFeO2 {110} facet, H2O2 tends to be dissociated into -OH group and passivates {110} facet. Besides, the new formed ≡Fe2+* on CuFeO2 {012} facet can accelerate the redox cycle of Cu and Fe species, leading to excellent long-term stability of CuFeO2 nanoplates.

[A preliminary study on the disappearance time of influenza virus antigen].

OBJECTIVE: To investigate the antigen clearance time, time to symptom disappearance, and the association between them using immunofluorescence assay for dynamic monitoring of influenza virus antigen in children with influenza. METHODS: A total of 1 063 children suspected of influenza who visited the Hunan People's Hospital from March to April, 2016 were enrolled. The influenza A/B virus antigen detection kit (immunofluorescence assay) was used for influenza virus antigen detection. The children with positive results were given oseltamivir as the antiviral therapy and were asked to re-examine influenza virus antigen at 5, 5-7, and 7 days after onset. RESULTS: Of all children suspected of influenza, 560 (52.68%) had an influenza virus infection. A total of 215 children with influenza virus infection were followed up. The clearance rate of influenza virus antigen was 9.8% (21 cases) within 5 days after onset. The cumulative clearance rate of influenza virus antigen was 32.1% (69 cases) within 5-7 days, and 98.1% (211 cases) within 7-10 days after onset. Among these children, 6 children (2.8%) achieved the improvement in clinical symptoms within 3 days after onset. The cumulative rate of symptom improvement was 84.7% (182 cases) within 3-5 days after onset, and 100% achieved the improvement after 5 days of onset. CONCLUSIONS: The time to improvement in symptoms after treatment is earlier than antigen clearance time. Almost all of the children achieve influenza virus antigen clearance 7-10 days after onset. Therefore, it is relatively safe for children to go back to school within 7-10 days after onset when symptoms disappear.

The addition of radiation to chemotherapy does not improve outcome when compared to chemotherapy in the treatment of resected pancreas cancer: the results of a single-institution experience.

BACKGROUND: Pancreas cancer is highly lethal even at early stages. Adjuvant therapy with chemotherapy (CT) or chemoradiation (CRT) is standard following surgery to delay recurrence and improve survival. There is no consensus on the added value of radiotherapy (RT). We conducted a retrospective analysis of clinical outcomes in pancreas cancer patients treated with CT or CRT following surgery. METHODS: Patients with resected pancreas adenocarcinoma were identified in our institutional database. Relevant clinicopathologic and demographic data were collected. Patients were grouped according to adjuvant treatment: group A: no treatment; group B: CT; group C: CRT. The primary endpoint of overall survival was compared between groups B vs. C. Univariate and multivariate analyses of potential prognostic factors were conducted including all patients. RESULTS: A total of 146 evaluable patients were included (group A: n = 33; group B: n = 45; group C: n = 68). Demographics and pathologic characteristics were comparable. There was no significant survival benefit for CRT compared with CT (mOS 16.8 months vs. 21.5 months, respectively, p = 0.76). Local recurrence rates were similar in all three groups. Univariate analyses identified absence of lymph node involvement (hazards ratio [HR] 1.43, p = 0.0082) and administration of adjuvant therapy (HR 0.496, p = 0.0008) as significant predictors for improved survival. Multivariate analyses suggested that patients without nodal involvement derived the most benefit from adjuvant treatment. CONCLUSIONS: The addition of RT to CT did not improve survival over CT. Lymph node involvement predicts inferior clinical outcome.

Self-acclimation mechanism of pyrite to sulfamethoxazole concentration in terms of degradation behavior and toxicity effects caused by reactive oxygen species.

Pyrite has been extensively tested for oxidizing contaminants via the activation of water molecule or dissolved oxygen, while the changing of oxidation species induced by contaminant's concentration has been largely underestimated. In this study, we revealed a self-acclimation mechanism of pyrite in terms of •OH conversion to 1O2 during the sulfamethoxazole (SMX) degradation process under oxic conditions. Two reaction stages of SMX degradation by pyrite were observed. The SMX concentration decreased by 70% rapidly in the first 12 h after the reaction was initiated, then, the removal rate began to decrease as the SMX concentration decreased. Importantly, •OH and O2•- were the dominant oxidizing species in stage one, while 1O2 was responsible for the further degradation of SMX in stage two. The self-acclimated mechanism of pyrite was proven to be caused by the conversion of oxidative species at the surface of pyrite. This process can overcome the shortages of •OH such as ultrashort lifetime and limited effective diffusion in the decontamination of micropollutant. Moreover, different reactive oxygen species will lead to different degradation pathways and environmental toxicity while degrading pollutants. This finding of oxidizing species' self-acclimation mechanism should be of concern when using pyrite for water treatment.

Ball milling synthesis of Fe3O4 nanoparticles-functionalized porous boron nitride with enhanced cationic dye removal performance.

Enhancement of the adsorption performance and recyclability of adsorbents is a crucial aspect of water treatment. Herein, we used one-dimensional porous boron nitride (PBN) as a carrier to load Fe3O4 nanoparticles for the preparation of Fe3O4 nanoparticles-functionalized porous boron nitride (Fe3O4/PBN) via a ball milling method. The high-energy ball milling promoted the creation of a negatively charged PBN surface and facilitated the uniform distribution of Fe3O4 nanoparticles on the surface of PBN. The adsorption performance of Fe3O4/PBN toward cationic dyes could be significantly improved while no enhancement was observed for anionic dyes. The great adsorption performance of Fe3O4/PBN is due to its surface functional groups and surface defects formed in the ball milling process. Moreover, the strong interaction force between Fe3O4/PBN and cationic dyes promotes rapid initial adsorption due to their negatively charged surface. Magnetic measurements demonstrated that Fe3O4/PBN is superparamagnetic. The composites with low loadings of Fe3O4 nanoparticles could be quickly separated from the aqueous solution under a low applied magnetic field, improving their recyclability. This work highlights the role of ball milling in improving the adsorption performance of Fe3O4/PBN and greatly promotes the practical application of Fe3O4/PBN in the field of environmental purification.

Chalcogen Elements in Regulating the Local Electron Density of Cu2X for an Efficient Heterogeneous Fenton-like Process.

In this work, a novel strategy for Fenton activity improvement of Cu2X was reported, in which the local electron density of Cu sites was regulated via manipulation of simple chalcogen elements (O, S, and Se). Among them, Cu2Se catalysts show excellent catalytic activity to activate H2O2 for the complete removal of ofloxacin (10 mg/L) at an initial pH of 6.5 within 120 min. Radical scavenger experiments and electron spin resonance spectroscopy confirm that •OH radicals are the primary oxygen reactive species to drive ofloxacin degradation. In addition, density functional theory calculations further proved that electrons would migrate from X and accumulate on Cu active sites in the order Se > S > O. Compared with Cu2O and Cu2S, the highly concentrated electron density of Cu atoms in Cu2Se not only decreased the activation energy of the Fenton-like reaction but also boosted the Cu2+/Cu+ cycle with the generation of more •OH radicals (18-66 µm) and the maintenance of high stability of catalysts, leading to excellent catalytic activity and application potential. We believe this work will lay the foundation for designing excellent Fenton catalysts for practical applications since developing a heterogeneous Fenton system with the highest oxidation efficiency has always been the long-term goal in this field.

Colloidal iron species driven enhanced H2O2 decomposition into hydroxyl radicals for efficient removal of methylene blue from water.

Colloids are wide-spread in natural waters and colloid-facilitated transport via adsorption was established as the most important mechanism for the mobilization of aqueous contaminants. This study reports another possible, but reasonable, role of colloids for the contaminants driven by redox reactions. Under the same conditions (pH 6.0, 0.3 ml 30% H2O2, and 25 °C), the degradation efficiencies of methylene blue (MB) at 240 min over Fe colloid, Fe ion, Fe oxide and Fe(OH)3 were 95.38%, 42.66%, 4.42% and 9.40%. We suggested that, Fe colloid can promote the H2O2 based in-situ chemical oxidation process (ISCO) compared with other iron species such as Fe(Ⅲ) ion, Fe oxide and Fe(OH)3 in natural water. Furthermore, the MB removal via adsorption by Fe colloid was only 1.74% at 240 min. Hence, the occurrence, behavior and fate of MB in Fe colloid containing natural water system mainly depends on the reduction-oxidation rather than adsorption-desorption process. Based on the mass balance of colloidal iron species and characterization of iron configurations distribution, Fe oligomers were the active and dominant components for Fe colloid-driven enhanced H2O2 activation among three types of Fe species. The quick and steady conversion of Fe(III) to Fe(II) was proven to be reason why Fe colloid can efficiently react with H2O2 to produce hydroxyl radicals.

A portable and intelligent logic detector for simultaneous and in-situ detection of Al3+ and fluoride in groundwater.

To develop a convenient and intelligent detector for simultaneous and in-situ detection of Al3+ and F- in groundwater, a novel organic probe called RBP has been prepared. With the increase of Al3+, RBP showed a significant fluorescence enhancement at 588 nm, and the detection limit was 0.130 mg/L. After combining with fluorescent internal standard CDs, the fluorescence of RBP-Al-CDs at 588 nm was quenched due to the replace of F- for Al3+, while the CDs at 460 nm remained unchanged, and the detection limit was 0.0186 mg/L. For convenient and intelligent detection, an RBP-based logic detector has been developed for simultaneous detection of Al3+ and F-. Within the ultra-trace, low concentration, and high concentration range of Al3+ and F-, the logic detector can achieve rapid feedback on their concentration levels ("U", "L" and "H") through different output modes of the signal lamps. The development of logical detector is of great significance for studying the in-situ chemical behavior of Al3+ and F- and for daily household detection.

Insight into enhanced Fenton-like degradation of antibiotics over CuFeO2 based nanocomposite: To improve the utilization efficiency of OH/O2- via minimizing its migration distance.

In Fenton or Fenton-like processes, the key step is to catalyze H2O2 and produce highly reactive OH radicals. More efforts are then focus on designing efficient heterogeneous Fenton catalysts by activating H2O2 to generate OH at the highest possible steady state concentration. In this study, using the antibiotic ofloxacin as target organic pollutant, we firstly demonstrate a point of view for improving OH utilization efficiency by regulating surface chemical reactions to minimizing its migration distance to the target pollutant. C doped g-C3N4 incorporated CuFeO2 (CCN/CuFeO2) exhibited almost ten times higher ofloxacin degradation rate constant than our previously reported CuFeO2 {012} catalyst (0.1634 vs 0.0179 min-1). Since similar amount of OH was generated, the different inhibition effect of tert-butyl alcohol and nitrobenzene on the ofloxacin degradation confirmed that the much-enhanced ofloxacin degradation was attributed to the surface Fenton reaction process. According to XPS and EXAFS characterization, the C-O-Cu bond between g-C3N4 and CuFeO2 established a closed-circuit surface Fenton reaction mechanism. H2O2 was adsorbed and decomposed into OH/O2- over ≡Cu + site in CuFeO2. The successful construction of CCN/CuFeO2 creates a negative surface potential and benefits the enrichment of target antibiotics from water, which greatly reduces the migration distance of OH/O2•- to adjacent pollutant and then increases the OH/O2- utilization efficiency by avoiding the unwanted quenching. Hence, CCN/CuFeO2 possesses superior Fenton catalytic activity and long-term stability.

Natural alumina/silica suspended particles in water to enhance ofloxacin degradation with UVA-H2O2 driven by surface chemistry.

UV-H2O2 is the most widely used oxidizing system with established effectiveness and a high level of technical development for practical application. However, little attention was paid on the effect of suspended particles in natural water on organic contaminants removal via UV-H2O2 technique. In this study, this effect of suspended particles to enhance the contaminant degradation was explored using silica/alumina-based oxides (MCM-41 and Al@MCM-41) as the representative. The results showed that MCM-41 had no effect on OFX degradation compared with UV-H2O2. While the degradation efficiency and reaction rate were greatly enhanced at a pH range of 3.0-9.0 especially at acidic pH values (3.0-5.0) in the presence of Al@MCM-41. The probe experiments proved that OFX adsorption followed by surface reaction process played an important role to enhance the performance of UV-H2O2. Based on the characterization results, the positive effect of suspended particles was not related to their surface area and pore size distribution, but dependent on the chemical composition and surface acid-base property. The suspended particles can provide an active surface composed of acid and base sites. The base site can create a local basic micro-environment by producing more •OH et al. While the dissociated acid sites in Al@MCM-41 with a negative charged surface favor OFX adsorption and then reaction with produced ROS. Our findings suggest that the enhanced performance of UVA-H2O2 induced by suspended particles should be concerned.

Surface acidity and basicity of Mg/Al hydrotalcite for 2, 4-dichlorophenoxyacetic acid degradation with ozone: Mineralization, mechanism, and implications to practical water treatment.

The Mg/Al hydrotalcite (Mg/Al HT) was firstly used as a heterogeneous ozonation catalyst and 2,4-dichlorophenoxyacetic acid (2,4-D) was efficiently degraded by Mg3/Al HT with a COD removal of 68 %. It was higher than that of α-FeOOH with a COD removal of 50 %. The effects of Mg/Al atomic ratio, phosphate and pyrrole on the ozonation performance of Mg/Al HTs were also investigated. The X-ray photoelectron spectroscopy (XPS), nitrogen adsorption-desorption experiment and temperature programmed desorption of adsorbed CO2 or NH3 were used to characterize the surface properties of Mg/Al HT. The surface acidity and basity was proven to be responsible to the excellent ozonation activity of Mg/Al HT. The results of electron spin resonance (ESR) analysis and probe experiments confirmed that OH, O2- and 1O2 were involved in the 2,4-D degradation process and their contributions are as followed: OH > O2- > 1O2. The synergistic effect of surface acid (ozone adsorption center) and base sites (catalytic center) determines Mg/Al HT in the enhanced catalytic ozone decomposition into reactive species. More important, the transition metal free based Mg/Al HTs is steady, non-toxic, naturally abundant and environment friendly, which provided a promising alternative in practical water treatment by catalytic ozonation.

Entecavir-Associated Thrombocytopenia: A Case Report and Review of the Pathophysiology, Diagnosis, and Treatment of a Rare but Reversible Cause of Thrombocytopenia.

Drug-associated thrombocytopenia is often unrecognized. We report a 76-year-old female with lymphoma who presented with easy bruising and oral bleeding. She had undergone screening for hepatitis B virus (HBV) prior to starting rituximab and was found to have hepatitis B core serum antibody (IgG anti-HBc). She was therefore treated with prophylactic entecavir 0.5 mg daily to prevent reactivation of HBV. Her initial platelet count was 136,000/mm3. Five days after starting entecavir, she presented with bruising and oral bleeding and was found to have a platelet count of 7,000/mm3. A coagulation profile and the rest of the blood parameters (RBC and WBC counts) were normal. Entecavir was stopped, and she was given 3 units of apheresed platelets followed by intravenous immunoglobulin (1 g/kg) for 5 consecutive days. Her platelet counts improved and normalized in one week. She was diagnosed with entecavir-induced thrombocytopenia based on the temporal relationship and after carefully excluding alternate causes of thrombocytopenia. This case highlights the importance of recognizing drug-induced thrombocytopenia (DITP) as a reversible cause of thrombocytopenia.

Carbon doped molybdenum disulfide nanosheets stabilized on graphene for the hydrogen evolution reaction with high electrocatalytic ability.

Fabricating a cost effective hydrogen evolution reaction catalyst without using precious metal elements is in crucial demand for environmentally-benign energy production. In this work, the thin and edge-rich molybdenum disulfide nanosheets, with carbon doped in the interlayers and decorated on graphene, were developed by a facile solvothermal process. The as-synthesized nanohybrids exhibited high catalytic ability for the hydrogen evolution electrochemical reaction with an onset overpotential of 0.165 mV and a Tafel slope of 46 mV dec(-1). Furthermore, the prepared nanohybrids also showed better durability and stability. Our work may lead to a potential method for in situ production of metal carbide-sulphur hybrid nanomaterials with promising applications for the hydrogen evolution reaction.

Novel MoSe2 hierarchical microspheres for applications in visible-light-driven advanced oxidation processes.

Advanced oxidation processes as a green technology have been adopted by combining the semiconductor catalyst MoSe2 with H2O2 under visible radiation. And novel three-dimensional self-assembled molybdenum diselenide (MoSe2) hierarchical microspheres from nanosheets were produced by using organic, selenium cyanoacetic acid sodium (NCSeCH2COONa) as the source of Se. The obtained products possess good crystallinity and present hierarchical structures with the average diameter of 1 µm. The band gap of MoSe2 microspheres is 1.68 eV and they present excellent photocatalytic activity under visible light irradiation in the MoSe2-H2O2 system. This effective photocatalytic mechanism was investigated in this study and can be attributed to visible-light-driven advanced oxidation processes.