Accelerating the understanding of cancer biology through the lens of genomics.

A core mission of cancer genomics is to comprehensively chart molecular underpinnings of cancer-driving events and to provide personalized therapeutic strategies. Primarily focused on cancer cells, cancer genomics studies have successfully uncovered many drivers for major cancer types. Since the emergence of cancer immune evasion as a critical cancer hallmark, the paradigm has been elevated to the holistic tumor ecosystem, with distinct cellular components and their functional states elucidated. We highlight the milestones of cancer genomics, depict the evolving path of the field, and discuss future directions in completing the understanding of the tumor ecosystem and in advancing therapeutic strategies.

Multisignal Biosensors Based on Mn Paramagnetic Relaxation and Nanocatalysis for Norovirus Detection.

A multisignal method for the sensitive detection of norovirus based on Mn paramagnetic relaxation and nanocatalysis was developed. This dual-modality sensing platform was based on the strong relaxation generated by cracked Au@MnO2 nanoparticles (NPs) and their intrinsic enzyme-like activity. Ascorbic acid rapidly cracked the MnO2 layer of Au@MnO2 NPs to release Mn(II), resulting in the relaxation modality being in a "switch-on" state. Under the optimal conditions, the relaxation modality exhibited a wide working range (6.02 × 103-3.01 × 107 copies/µL) and a limit of detection (LOD) of 2.29 × 103 copies/µL. Using 4,4',4″,4″'-(porphine-5,10,15,20-tetrayl) tetrakis (benzenesulfonic acid) (tpps)-ß-cyclodextrin (tpps-ß-CD) as a T1 relaxation signal amplification reagent, a lower LOD was obtained. The colorimetric modality exploited the "peroxidase/oxidase-like" activity of Au@MnO2 NPs, which catalyzed the oxidation of colorless 3,3',5,5'-tetramethylbenzidine (TMB) to blue oxidized TMB, which exhibited a working range (6.02 × 104-6.02 × 106 copies/µL) and an LOD of 2.6 × 104 copies/µL. In addition, the rapid amplification reaction of recombinase polymerase enabled the detection of low norovirus levels in food samples and obtained a working range of 101-106 copies/mL and LOD of 101 copies/mL (relaxation modality). The accuracy of the sensor in the analysis of spiked samples was consistent with that of the real-time quantitative reverse transcription polymerase chain reaction, demonstrating the high accuracy and practical utility of the sensor.

Structure and Defect Engineering of V3S4-xSex Quantum Dots Confined in a Nitrogen-Doped Carbon Framework for High-Performance Sodium-Ion Storage.

Constructing quantum dot-scale metal sulfides with defects and strongly coupled with carbon is significant for advanced sodium-ion batteries (SIBs). Herein, Se substituted V3S4 quantum dots with anionic defects confined in nitrogen-doped carbon matrix (V3S4-xSex/NC) are fabricated. Introducing element Se into V3S4 crystal expands the interlayer distance of V3S4, and triggers anionic defects, which can facilitate Na+ diffusions and act as active sites for Na+ storage. Meanwhile, the quantum dots tightly encapsulated by conductive carbon framework improve the stability and conductivity of the electrode. Theoretical calculations also unveil that the presence of Se enhances the conductivity and Na+ adsorption ability of V3S4-xSex. These properties contribute to the V3S4-xSex/NC with high specific capacity of 447 mAh g-1 at 0.2 A g-1, and prominent rate and cyclic performance with 504 mAh g-1 after 1000 cycles at 10 A g-1. The sodium-ion hybrid capacitors (SIHCs) with V3S4-xSex/NC anode and activated carbon cathode can achieve high energy/power density (maximum 144 Wh kg-1/5960 W kg-1), capacity retention ratio of 71% after 4000 cycles at 2 A g-1. This work not only synthesizes V3S4-xSex/NC, but also provides a promising opportunity for designing quantum dots and utilizing defects to improve the electrochemical properties.

How the Most Neglected Residual Species in MOF-Based Catalysts Involved in Catalytic Reactions to Form Toxic Byproducts.

In recent years, multifarious new materials have been developed for environmental governance. Thereinto, metal organic framework (MOF)-based catalysts have been widely employed for heterogeneous catalysis because of their high porosity to confine noble metal particles faraway from aggregation. However, the potential reactions between residual species from the material synthesis process and target pollutants, which could form highly toxic byproducts, are often neglected. Herein, we took the widely used Zr-MOF, UiO-66, with highly thermal stability supported Pd catalysts as the example to investigate how the residual species in catalysts are involved in aromatic volatile organic compounds (VOCs) degradation reaction. The results showed that residual Cl species originated from the ZrCl4 metal precursor participated in the VOC degradation reaction, leading to the production of various chlorine-containing byproducts, even the hypertoxicity dioxin precursor, dichlorobenzene. Meanwhile, the chlorination mechanism for the formation of chlorine-containing byproducts was revealed by density functional theory calculation. Furthermore, the highly efficient residual Cl removal approaches are proposed. Importantly, the migration and transformation of residual Cl during the degradation of five benzene series VOCs are comprehensively studied and elucidated. We anticipate that these findings will raise alarm about the neglected issue of residual species in MOF-based catalysts for heterogeneous catalysis, especially environmentally friendly catalysis.

Cubic Na0.5Bi0.5TiO3 nanoperovskite significantly expands the application of sensitive immunosensor for the detection of carcinoembryonic antigen.

Nanosized sodium bismuth perovskite titanate (NBT) was synthesized and first used as the electrochemical immune sensing platform for the sensitive detection of carcinoembryonic antigen (CEA). Gold nanoparticles (Au NPs) grew on the surface of NBT through forming Au-N bond to obtain Au@NBT, and a label-free electrochemical immunosensor was proposed using Au@NBT as an immunosensing recognizer towards CEA. The well-ordered crystal structure of NBT was not changed at all after the modification of Au NPs outside, but significantly improved the conductivity, catalytic activity, and biocompatibility of the Au@NBT-modified electrode. The unique cubic crystal nanostructure of NBT offered a large active area for both Au NP modification and the subsequent immobilization of biomolecules over the electrode surface, triggering the effective generation of promising properties of the proposed Au@NBT-based electrochemical immunosensor. As expected, favorable detection performances were achieved using this immunosensor towards CEA detection, where a good linear relationship between the current response and CEA concentration was obtained in the concentration range 10 fg mL-1 to 100 ng mL-1 with a low detection limit (LOD) of 13.17 fg mL-1. Also, the significantly enhanced selectivity, and stability guaranteed the promising electrochemical properties of this immunosensor. Furthermore, the analysis of real serum samples verified the high feasibility of this new method in clinical CEA detection. This work opens a new window for the application of nanoperovskite in the early detection of CEA.

[Effects of freeze-drying bovine pericardium using a combination of polyethylene glycol and trehalose].

The freeze-drying is a technology that preserves biological samples in a dry state, which is beneficial for storage, transportation, and cost saving. In this study, the bovine pericardium was treated with a freeze-drying protectant composed of polyethylene glycol (PEG) and trehalose (Tre), and then freeze-dried. The results demonstrated that the mechanical properties of the pericardium treated with PEG + 10% w/v Tre were superior to those of the pericardium fixed with glutaraldehyde (GA). The wet state water content of the rehydrated pericardium, determined using the Karl Fischer method, was (74.81 ± 1.44)%, which was comparable to that of the GA-fixed pericardium. The dry state water content was significantly reduced to (8.64 ± 1.52)%, indicating effective dehydration during the freeze-drying process. Differential scanning calorimetry (DSC) testing revealed that the thermal shrinkage temperature of the pericardium was (84.96 ± 0.49) ℃, higher than that of the GA-fixed pericardium (83.14 ± 0.11) ℃, indicating greater thermal stability. Fourier transform infrared spectroscopy (FTIR) results showed no damage to the protein structure during freeze-drying. Hematoxylin and eosin (HE) staining demonstrated that the freeze-drying process reduced pore formation, prevented ice crystal growth, and resulted in a tighter arrangement of tissue fibers. The frozen-dried bovine pericardium was subjected to tests for cell viability and hemolysis rate. The results revealed a cell proliferation rate of (77.87 ± 0.49)%, corresponding to a toxicity grade of 1. Additionally, the hemolysis rate was (0.17 ± 0.02)%, which is below the standard of 5%. These findings indicated that the frozen-dried bovine pericardium exhibited satisfactory performance in terms of cytotoxicity and hemolysis, thus meeting the relevant standards. In summary, the performance of the bovine pericardium treated with PEG + 10% w/v Tre and subjected to freeze-drying could meet the required standards.

[Research progress of methylcellulose-based thermosensitive hydrogels applied in biomedical field].

Methylcellulose is a semi-flexible cellulose ether derivative, whose hydrogels are thermosensitive and reversible, with good biocompatibility and adjustable function, and its application has attracted much attention in the biomedical field. In this paper, the application of methylcellulose-based thermo-sensitive hydrogels in biomedical field was reviewed. Based on the mechanism of gelation and influencing factors of methylcellulose, this paper focused on the recent advances in biomedical applications of methylcellulose-based hydrogels, including drug delivery, regenerative medicine, and other related fields. The current achievements in these fields were summarized in the form of lists in this paper to provide ideas and tendencies for future research. Finally, the future development of multifunctional methylcellulose-based hydrogel materials with improved performance was also discussed.

Sulfur-Bridged Bonds Heightened Na-Storage Properties in MnS Nanocubes Encapsulated by S-Doped Carbon Matrix Synthesized via Solvent-Free Tactics for High-Performance Hybrid Sodium Ion Capacitors.

The exploitation of electrode materials with ability to balance capacity and kinetics between cathode and anode is a challenge for sodium-ion hybrid capacitors (SIHCs). Mn-based anode materials are limited by poor electrical conductivity, sluggish reaction kinetics, large volume variation, weak cycling stability, and inferior reversible capacity. Herein, MnS nanocubes encapsulated in S-doped porous carbon matrix (MSC) with strong sulfur-bridged bond interactions (CSMn) are successfully synthesized by solvent-free tactics. The CSMn bonds generated between MnS and carbon significantly inhibit the aggregation of nanostructural MnS cubes, restrict the volume expansion, and stabilize the nanostructure, which improves the Na+ storage reversibility and stability. Moreover, S-doped porous carbon enhances the electrical conductivity and electrons/ions diffusion rate, which boosts a fast kinetic reaction. As expected, MSC anode presents an outstanding reversible capacity of 600 mAh g-1 at 0.2 A g-1 and a long-term stable capacity of 357 mAh g-1 for 1000 cycles at a high current density of 10 A g-1 in sodium-ion batteries (SIBs). The as-assembled SIHCs deliver a high energy density of 109 W h kg-1 and a high power output of 98 W kg-1 , with 88% capacity retention at 2 A g-1 after 2000 cycles and practical applications (55 LEDs can be lighted for 10 min).

Revisiting the pericarp as a barrier restricting water entry/loss from cotyledons and embryonic axis of temperate desiccation-sensitive Quercus acorns.

MAIN CONCLUSIONS: Fully mature acorns of Quercus variabilis, Q. aliena, Q. mongolica, and Q. glandulifera are desiccation-sensitive. X-ray computer tomography showed that cotyledons shrink during drying, but embryos are protected. Information available on recalcitrant acorns of tropical and sub-tropical species of Quercus suggests that an impermeable pericarp, which limits the entry and loss of water only through the hilum (scar), is the underlying mechanism that prevents drying of the embryo axis following dispersal until the germination season. However, there is a lack of consensus supporting this proposition across species, and it is not well understood if such mechanisms occur in temperate Quercus species. This study investigated the significance of the acorn pericarp for temperate oak species and presents an ecological framework based on the post-dispersal climatic conditions. Using Quercus variabilis, Q. aliena, Q. mongolica, and Q. glandulifera acorns, the relationship between moisture content (MC) and germination was established, and X-ray computed tomography (X-ray CT) was used to understand the internal structural changes of cotyledons and embryonic axis occurring during desiccation. Water entry and exit routes through the scar, pericarp and apex were determined by imbibition and drying experiments. Climatic data and acorn morphological characteristics and germination were subjected to a principal component analysis (PCA). Freshly dispersed acorns of all species had a moisture content (MC) above 35% fresh weight (FW) basis, but drying to 15-10% MC resulted in complete loss of viability, implying recalcitrance behaviour. X-ray CT images suggested that the pericarp offers some protection to cotyledons and embryonic axis during desiccation, but it is contingent on MC. Extensive drying to a low MC with the scar and apex covered with vaseline resulted in internal tissues shrinkage, corresponding with viability loss. Water could enter or exit through the pericarp, albeit at a much slower rate than through the scar. A combination of factors including acorn anatomy, moisture content at the time of dispersal, microhabitat, the position of acorns in the soil prevent embryo desiccation below the critical MC and thus promotes survival of acorns on/in the soil during winter in temperate regions. Pericarp anatomy, to some extent, prevents excessive drying of the embryonic axis by slowing water movement, but prolonged drying or predatory pressure could result in pericarp cracks, favouring the absorption of water during sporadic rain. In the latter case, the survival of acorns possibly depends extensively on the continuous erratic rainfall, i.e. continuous wet-dry cycle, but in-situ experiments are yet to be performed to test this hypothesis.

A systematic review on distribution, sources and sorption of perfluoroalkyl acids (PFAAs) in soil and their plant uptake.

Perfluoroalkyl acids (PFAAs) are ubiquitous in environment, which have attracted increasing concerns in recent years. This study collected the data on PFAAs concentrations in 1042 soil samples from 15 countries and comprehensively reviewed the spatial distribution, sources, sorption mechanisms of PFAAs in soil and their plant uptake. PFAAs are widely detected in soils from many countries worldwide and their distribution is related to the emission of the fluorine-containing organic industry. Perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) are found to be the predominant PFAAs in soil. Industrial emission is the main source of PFAAs contributing 49.9% of the total concentrations of PFAAs (Æ© PFAAs) in soil, followed by activated sludge treated by wastewater treatment plants (WWTPs) (19.9%) and irrigation of effluents from WWTPs, usage of aqueous film-forming foam (AFFFs) and leaching of leachate from landfill (30.2%). The adsorption of PFAAs by soil is mainly influenced by soil pH, ionic strength, soil organic matter and minerals. The concentrations of perfluoroalkyl carboxylic acids (PFCAs) in soil are negatively correlated with the length of carbon chain, log Kow, and log Koc. The carbon chain lengths of PFAAs are negatively correlated with the root-soil concentration factors (RCFs) and shoot-soil concentration factors (SCFs). The uptake of PFAAs by plant is influenced by physicochemical properties of PFAAs, plant physiology and soil environment. Further studies should be conducted to make up the inadequacy of existing knowledge on the behavior and fate of PFAAs in soil-plant system.

Perfluorooctanoic acid disrupts thyroid-specific genes expression and regulation via the TSH-TSHR signaling pathway in thyroid cells.

Perfluorooctanoic acid (PFOA) is a highly persistent and widespread chemical in the environment with endocrine disruption effects. Although it has been reported that PFOA can affect multiple aspects of thyroid function, the exact mechanism by which it reduces thyroxine levels has not yet been elucidated. In this study, FRTL-5 rat thyroid follicular cells were used as a model to study the toxicity of PFOA to the genes related to thyroid hormone synthesis and their regulatory network. Our results reveal that PFOA interfered with the phosphorylation of the cyclic adenosine monophosphate (cAMP)-response element binding protein (CREB) induced by thyroid-stimulating hormone (TSH), as well as the transcription levels of paired box 8 (PAX8), thyroid transcription factor 1 (TTF1), sodium/iodide cotransporter (NIS), thyroglobulin (TG), and thyroid peroxidase (TPO). However, the above outcomes can be alleviated by enhancing cAMP production with forskolin treatment. Further investigations showed that PFOA reduced the mRNA level of TSH receptor (TSHR) and impaired its N-glycosylation, suggesting that PFOA has disrupting effects on both transcriptional regulation and post-translational regulation. In addition, PFOA increased endoplasmic reticulum (ER) stress and decreased ER mass in FRTL-5 cells. Based on these findings, it can be inferred that PFOA disrupts the TSH-activated cAMP signaling pathway by inhibiting TSHR expression and its N-glycosylation. We propose that this mechanism may contribute to the decrease in thyroid hormone levels caused by PFOA. Our study sheds light on the molecular mechanism by which PFOA can disrupt thyroid function and provides new insights and potential targets for interventions to counteract the disruptive effects of PFOA.

Effect of cryoprotectant-induced intracellular ice formation and crystallinity on bactria during cryopreservation.

Cryopreservation is widely used for the long-term storage of bacteria. Glycerol is one of the traditional cryoprotectants used widely to prevent cryoinjury during the cryopreservation of bacteria,although it may be toxic to the cells. To overcome these issues, synthetic antifreeze polymers are also used as cryoprotectants to inhibit ice formation. In the study, we compared the performance of various antifreeze synthetic polymers including poly(vinyl alcohol) (PVA), poly(vinylpyrrolidone), poly(ethylene glycol), and dextran with glycerol, among which PVA performed best on decreasing the ice growth rate.The impacts of glycerol, trehalose, combined with PVA on the survival of S. thermophilus were also explored. Notably,. S. thermophilus stored in 100 mg/mL trehalose and 1 mg/mL PVA +50 mg/mL trehalose combo showed significantly enhanced survival when compared with those in traditional cryoprotectant (20% [v/v] glycerol), which achieved the survival percentage of only 41.03 ± 0.09%. The effects of the freezing temperature and crystallinity on the survival of S. thermophilus were elucidated.

Ti3C2@Bi2O3 nanoaccordion for electrochemical determination of miRNA-21.

Based on a dual signal amplification strategy of novel accordion-like Bi2O3-decorated Ti3C2 (Ti3C2@Bi2O3) nanocomposites and hybridization chain reaction (HCR), an ultra-sensitive electrochemical biosensor was constructed for miRNA-21 detection. By etching Ti3AlC2 with HF, Ti3C2 with an accordion-like structure was first obtained and subsequently covered by Bi2O3 nanoparticles (NPs), forming Ti3C2@Bi2O3. A layer of Au NPs was electrodeposited on the glassy carbon electrode coated with Ti3C2@Bi2O3, which not only significantly improved the electron transport capacity of the electrode but also greatly increased its surface active area. Upon the immobilization of the thiolated capture probe (SH-CP) on the electrode, the target miRNA-21 specifically hybridized with SH-CP and thus opened its hairpin structure, triggering HCR to form a long double strand with the primers H1 and H2. A large number of the electrochemical indicator molecules were thus embedded inside the long double strands to produce the desirable electrochemical signal at a potential of - 0.19 V (vs. Ag/AgCl). Such dual signal amplification strategy successfully endowed the biosensor with ultra-high sensitivity for miRNA-21 detection in a wide linear range from 1 fM to 100 pM with a detection limit as low as 0.16 fM. The excellent detection of miRNA-21 in human blood plasma displayed a broad prospect in clinical diagnosis. An ultra-sensitive electrochemical biosensor was successfully constructed for miRNA-21 detection in human blood plasma based on the dual signal amplification strategy of novel accordion-like Bi2O3 decorated Ti3C2 (Ti3C2@Bi2O3) nanocomposites and hybridization chain reaction.

Pt Nanodot Inlaid Mesoporous NaBiOF Nanoblackberry for Remarkable Signal Amplification Toward Biomarker Detection.

A new ultrasensitive sandwich-type electrochemical immunosensor has been successfully constructed to quantitatively detect carcinoembryonic antigen (CEA) using blackberry-like mesoporous bismuth-based nanospheres NaBiOF (NBOF NSs) inlaid with Pt nanodots (NDs) (BiPt NSs) as the antibody capture and signal-amplifying probe. The growth of Pt NDs inside the holes of NBOF NSs formed the nanozyme inlay outside NBOF NSs, greatly increasing the specific surface area and exposure of the catalytic active sites by minimizing the particle size of the Pt to nanodot scale. Such a blackberry-shaped heterojunction structure of BiPt NSs was well-suited to antibody capture and improved the catalytic performance of BiPt NSs in reducing H2O2, amplifying the signal, and yielding highly sensitive detection of CEA. The use of Au nanoparticle-modified multi-walled carbon nanotubes (Au@MWCNTs) as the electrode substrates significantly enhanced the electron transfer behavior over the electrode surface, further increasing the conductivity and sensitivity of the immunosensor. Remarkably, good compatibility with human body fluid was achieved using the newly developed BiPt-based immunosensor resulting from the favorable biocompatibility and stability of both BiPt NSs and Au@MWCNTs. Benefiting from the double signal amplification strategy and the high biocompatibility, the immunosensor responded linearly to CEA in a wide range from 50 fg/mL to 100 ng/ml with an extremely low detection limit of 3.52 fg/mL (S/N = 3). The excellent detection properties of this new immunosensor were evidenced by the satisfactory selectivity, reproducibility, and stability obtained, as well as the reliable and precise determination  of CEA in actual human blood samples. This work provides a new strategy for the early clinical diagnosis of cancer. Novel blackberry-like mesoporous NaBiOF nanospheres with Pt nanodot inlay were successfully usedto construct a sandwich-type electrochemical immunosensor for the ultra-sensitive detection ofcarcinoembryonic antigen in human blood plasma based on a remarkable signal amplification strategy.

The association between COVID-19 and cognitive performance: A Mendelian randomization analysis.

INTRODUCTION: People with COVID-19 had poorer general cognitive functioning compared to people without COVID-19. The causal link between COVID-19 and cognitive impairment is still unknown. METHODS: Mendelian randomization (MR) is a statistical approach based on genome-wide association studies (GWAS) to construct instrumental variables (IVs) and can effectively bring down the confounding bias of environmental or other disease factors, because alleles are randomly assigned to offspring. RESULTS: There was consistent evidence that cognitive performance was causally associated with COVID-19; this suggests that people with better cognitive performance are less likely to be infected with COVID-19. The reverse MR analysis treating COVID-19 as the exposure and cognitive performance as the outcome demonstrated an insignificant association, indicating the unidirectionality of the relationship. DISCUSSION: Our study provided credible evidence that cognitive performance has an impact on COVID-19. Future research should focus on long-term impact of cognitive performance on COVID-19.

Recent Development of Rhenium-Based Materials in the Application of Diagnosis and Tumor Therapy.

Rhenium (Re) is widely used in the diagnosis and treatment of cancer due to its unique physical and chemical properties. Re has more valence electrons in its outer shell, allowing it to exist in a variety of oxidation states and to form different geometric configurations with many different ligands. The luminescence properties, lipophilicity, and cytotoxicity of complexes can be adjusted by changing the ligand of Re. This article mainly reviews the development of radionuclide 188Re in radiotherapy and some innovative applications of Re as well as the different therapeutic approaches and imaging techniques used in cancer therapy. In addition, the current application and future challenges and opportunities of Re are also discussed.

Heavy metals in paired samples of hair and nails in China: occurrence, sources and health risk assessment.

The occurrence of heavy metals including chromium (Cr), nickel (Ni), copper (Cu), zinc (Zn), arsenic (As), cadmium (Cd) and lead (Pb) was investigated in paired samples of hair and nails collected from 121 volunteers in 16 cities, China. Results showed that the mean concentrations of Zn, Cu, As, Pb, Cr, Ni and Cd were 205, 18.0, 7.79, 6.18, 3.54, 2.02, 0.533 µg g-1 in hair and 103, 8.09, 0.760, 7.27, 6.07, 8.81, 0.485 µg g-1 in nails, respectively. The concentrations of Zn, Ni, Cr, Cd and Pb were positively correlated in paired samples of hair and nails, whereas a negative correlation was found for Cu and As between hair and nails. Higher concentrations of heavy metals were found in northern China than southern China. The multivariate analysis of variance revealed that dwelling environment was the dominant factor influencing the levels of Cd in hair (p < 0.05), while age was the dominant factor influencing the levels of Cr in nails (p < 0.05). Moreover, industrial pollution and smoking were also the important factors leading to the accumulation of heavy metals in human body. Principal component analysis (PCA) showed that industrial pollution and decoration material immersion were the main factors for the high concentrations of Cr and Ni in hair, accounting for 62.9% of the total variation; As in hair was dominantly related to groundwater pollution. The concentrations of heavy metals were within the recommended ranges in nails from this study. However, the mean levels of Cr, Ni and As in hair exceeded their recommended reference values, indicating potential health risks from heavy metals for residents in China.

A nationwide survey of polycyclic aromatic hydrocarbons (PAHs) in household dust in China: spatial distribution, sources, and health risk assessment.

As a carrier of toxic substances, household dust has a great impact on human health. Here we collected 73 household dust samples from 27 provinces and 1 municipality in China to investigate the levels, spatial distribution, sources, and carcinogenic risk of 16 polycyclic aromatic hydrocarbons (PAHs). The total concentrations of 14 detected PAHs (∑14 PAHs) ranged from 3.72 to 60,885 ng g-1. High ∑14 PAHs were found in Northeast and Southwest China. High molecular weights (HMW) PAHs (4-6 rings) were predominant PAHs in most dust samples, accounting for 93.6% of ∑14 PAHs. Household fuel, cooking frequency, air conditioning, and smoking were the main factors influencing PAH concentrations in household dust. Principal component analysis model indicated that fossil combustion (81.5%) and biomass combustion and vehicle exhaust (8.1%) are the primary sources of PAHs. Positive matrix factorization model suggested that household cooking and heating contributed about 70% of ∑14 PAHs, and smoking contributed another 30%. The values of benzo[a]pyrene equivalent in rural dust were found to be higher than those in urban dust. The sum of toxic equivalents (TEQs) of 14 PAHs were in range of 0.372-7241 ng g-1, in which 7 HMW PAHs accounted for 98.0 ± 1.98% of the total TEQs. Monte Carlo Simulation showed a low to moderate potential carcinogenic risk of PAHs in household dusts. This study documents comprehensive information on human exposure to PAHs in household dust at a national-scale.

Magnetic Relaxation Switch Sensor Based on Magnetophoresis and "T-Hg(II)-T" Signal Amplification.

In this study, we designed a magnetic relaxation switch (MRS) sensor combined with magnetophoresis technology (MS-MRS), which helps solve the problems of traditional MRS sensors. The sensor is based on a new combined magnet and is composed of small magnetic blocks and iron sheets that can rapidly separate magnetic nanoparticles of different sizes within 5 min. The MS-MRS sensor consists of aptamer-functionalized magnetic nanoparticles (diameter: 200 nm) (MNP200-Apt), complementary DNA-functionalized magnetic nanoparticles (diameter: 20 nm) (MNP20-cDNA), and a combined magnet ("M2" magnet). The MNP200-Apt probe could be separated by an "M2" magnet but the MNP20-cDNA probe could not. To further improve the sensitivity of the sensor, we successfully constructed an MS-MRS-Hg sensor based on the "T-Hg(II)-T" specific recognition that aggregated MNP20-cDNA probes to amplify the relaxation signal. The detection working range of the MS-MRS sensor is 0.5-100 ng/mL and that of the MS-MRS-Hg sensor is 0.05-100 ng/mL. Their limit of detection (LOD) values are 0.15 and 0.01 ng/mL, respectively. The relative recoveries of the MS-MRS and MS-MRS-Hg sensors are 95.2-119.5% and 93.1-113.1%, respectively. These results indicate that the proposed sensors have a high accuracy level.

Switchable C2/C3 positional selectivity of thioisatins in a three-component domino reaction: combined computational and experimental studies.

The nucleophile-induced domino reaction is a featured reactivity mode of thioisatin, but the C2/C3 positional selectivity towards a nucleophile has not been understood in-depth. In this work, a domino reaction of thioisatin with bromoacetophenone and tryptamine hydrochloride to produce a benzothiophene-fused eight-membered N-heterocycle was described, showing that the Brønsted acid-base form of the amine partner was crucial for the selectivity, because using tryptamine instead of tryptamine hydrochloride gave a different product. Control experiments and density functional calculations revealed that the domino reaction using tryptamine or tryptamine hydrochloride was triggered by a condensation reaction at the C2 or C3 position of thioisatin, respectively. A delicate balance between local electrophilicity and polarization effect may be responsible for the observed selectivity.