Poly(ionic liquid)s-Based Thermal-Responsive Microgel for Use as SERS Substrates with "ON-OFF" Switchable Effect.

A temperature-responsive surface-enhanced Raman scattering (SERS) substrate with "ON-OFF" switching based on poly(ionic liquid)s (PILs) block copolymer microgels have been designed and synthesized. The PIL units act as a joint component to anchor the gold nanoparticles (AuNPs) and analytes onto poly(N-isopropylacrylamide) (PNIPAm). This anchor allows the analytes to be fixed at the formed hot spots under temperature stimulus. Owing to the regulation of the PNIPAm segment, the SERS substrates exhibit excellent thermally responsive SERS activity with a reversible "ON-OFF" effect. Additionally, because of the anion exchange of PILs, microgels can introduce new analytes, which offers more flexibility for the system. The substrate shows excellent reversibility, controllability, and flexibility of SERS activity, which is expected to have a broad application in the field of practical SERS sensors.

Surface-enhanced Raman scattering spectroscopy monitoring and degradation of organic pollutants using a novel nanowire.

A multifunctional Ag/AlOOH nanowires (ANW) composite substrate was constructed, which not only accomplishes highly sensitive detection of organic dye molecules, but also has excellent performance in the degradation of pollutants. The ANW in the Ag/ANW substrate possesses a high aspect ratio, which extends the distribution area of Ag and enables a large number of hot spots on the active substrate. Additionally, due to the abundant OH groups on the ANW, there is an increased number of anchor sites for adsorbed metal ions in the Ag/ANW compound, thus contributing to the enhancement and degradation of molecules. Moreover, the constructed multifunctional Ag/ANW nanocomplexes also show great promise for practical applications, providing a reference for the detection and degradation of contaminants.

ExoBCD: a comprehensive database for exosomal biomarker discovery in breast cancer.

Effective and safe implementation of precision oncology for breast cancer is a vital strategy to improve patient outcomes, which relies on the application of reliable biomarkers. As 'liquid biopsy' and novel resource for biomarkers, exosomes provide a promising avenue for the diagnosis and treatment of breast cancer. Although several exosome-related databases have been developed, there is still lacking of an integrated database for exosome-based biomarker discovery. To this end, a comprehensive database ExoBCD (https://exobcd.liumwei.org) was constructed with the combination of robust analysis of four high-throughput datasets, transcriptome validation of 1191 TCGA cases and manual mining of 950 studies. In ExoBCD, approximately 20 900 annotation entries were integrated from 25 external sources and 306 exosomal molecules (49 potential biomarkers and 257 biologically interesting molecules). The latter could be divided into 3 molecule types, including 121 mRNAs, 172 miRNAs and 13 lncRNAs. Thus, the well-linked information about molecular characters, experimental biology, gene expression patterns, overall survival, functional evidence, tumour stage and clinical use were fully integrated. As a data-driven and literature-based paradigm proposed of biomarker discovery, this study also demonstrated the corroborative analysis and identified 36 promising molecules, as well as the most promising prognostic biomarkers, IGF1R and FRS2. Taken together, ExoBCD is the first well-corroborated knowledge base for exosomal studies of breast cancer. It not only lays a foundation for subsequent studies but also strengthens the studies of probing molecular mechanisms, discovering biomarkers and developing meaningful clinical use.

Surface plasmon-assisted catalytic reduction of p-nitrothiophenol for the detection of Fe2+ by surface-enhanced Raman spectroscopy.

Herein, we developed a concise, time-efficient, and high selective assay for detecting Fe2+ through its triggered surface plasmon-assisted reduction reaction of p-nitrothiophenol (PNTP) to p,p'-dimercaptoazobenzene (DMAB) on the surface of gold nanoparticles (AuNPs) based on surface-enhanced Raman scattering (SERS) spectroscopy. When Fe2+ was added to the PNTP-AuNPs system, the appearance of three characteristic peaks at 1142, 1392, and 1440 cm-1 attributed to DMAB demonstrated that Fe2+ induced the catalytic coupling reaction of PNTP. The Raman intensity ratio of the peak at 1142 cm-1 to the peak at 1336 cm-1 and the concentration of Fe2+ presented a good linear response from 10 to 100 µM with a limit of detection (LOD) of 0.35 µM. More importantly, the entire detection process can be completed within 2 min and further successfully used for the detection of Fe2+ in river water.

Fully-Exposed Pd Cluster Catalyst: An Excellent Catalytic Antibacterial Nanomaterial.

Exploring antibacterial nanomaterials with excellent catalytic antibacterial properties has always been a hot research topic. However, the construction of nanomaterials with robust antibacterial activity at the atomic level remains a great challenge. Here a fully-exposed Pd cluster atomically-dispersed on nanodiamond-graphene (Pdn /ND@G) with excellent catalytic antibacterial properties is reported. The fully-exposed Pd cluster nanozyme provides atomically-dispersed Pd cluster sites that facilitate the activation of oxygen. Notably, the oxidase-like catalytic performance of the fully-exposed Pd cluster nanozyme is much higher than that of Pd single-atom oxidase mimic, Pd nanoparticles oxidase mimic and even the previously reported palladium-based oxidase mimics. Under the density functional theory (DFT) calculations, the Pd cluster sites can efficiently catalyze the decomposition of oxygen to generate reactive oxygen species, resulting in strong antibacterial properties. This research provides a valuable insight to the design of novel oxidase mimic and antibacterial nanomaterial.

Highly stable acetylcholinesterase electrochemical biosensor based on polymerized ionic liquids microgel for pesticides detection.

A highly stable electrochemical biosensor for pesticide detection was developed. For the first time polymeric ionic liquids (PILs) were introduced to construct an acetylcholinesterase (AChE) biosensor . AChE was entrapped in PILs microspheres through an emulsion polymerization reaction, where negatively charged Au nanoparticles (Au NPs) can be immobilized by the positively charged PILs, leading to improved catalytic performance. The results suggest that the positively charged PILs not only provide a biocompatible microenvironment around the enzyme molecule, stabilizing its biological activity and preventing its leakage, but also act as a modifiable interface allowing other components with electron transport properties to be loaded onto the polymer substrate, thus providing an efficient electron transport channel for the entrapped enzyme. More notably, when AChE was immobilized in a positively charged environment, the active site is closer to the electrode, promoting faster electron transfer. The detection limits of the constructed electrochemical biosensor AChE@PILs@Au NPs/GCE toward carbaryl and dichlorvos (DDVP) were 5.0 × 10-2 ng ml-1 and 3.9 × 10-2 ng ml-1, in a wide linear range of 6.3 × 10-2-8.8 × 102 ng ml-1 and 1.3 × 10-1-1.4 × 103 ng ml-1, respectively. More importantly, the biosensor has high thermal and storage stability, which facilitates rapid field analysis of fruits and vegetables in a variety of climates. In addition, the biosensor reported has good repeatability and selectivity and has high accuracy in the analysis of peaches, tap water, and other types of samples.

Integrating a Luminescent Porous Aromatic Framework into Indicator Papers for Facile, Rapid, and Selective Detection of Nitro Compounds.

Porous aromatic framework materials with high stability, sensitivity, and selectivity have great potential to provide new sensors for optoelectronic/fluorescent probe devices. In this work, a luminescent porous aromatic framework material (LNU-23) was synthesized via the palladium-catalyzed Suzuki cross-coupling reaction of tetrabromopyrene and 1,2-bisphenyldiborate pinacol ester. The resulting PAF solid exhibited strong fluorescence emission with a quantum yield of 18.31%, showing excellent light and heat stability. Because the lowest unoccupied molecular orbital (LUMO) of LNU-23 was higher than that of the nitro compounds, there was an energy transfer from the excited LNU-23 to the analyte, leading to the selective fluorescence quenching with a limit of detection (LOD) ≈ 1.47 × 10-5 M. After integrating the luminescent PAF powder on the paper by a simple dipping method, the indicator papers revealed a fast fluorescence response to gaseous nitrobenzene within 10 s, which shows great potential in outdoor fluorescence detection of nitro compounds.

An Azo-Group-Functionalized Porous Aromatic Framework for Achieving Highly Efficient Capture of Iodine.

The strong radioactivity of iodine compounds derived from nuclear power plant wastes has motivated the development of highly efficient adsorbents. Porous aromatic frameworks (PAFs) have attracted much attention due to their low density and diverse structure. In this work, an azo group containing PAF solid, denoted as LNU-58, was prepared through Suzuki polymerization of tris-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-phenyl)-amine and 3,5-dibromoazobenzene building monomers. Based on the specific polarity properities of the azo groups, the electron-rich aromatic fragments in the hierarchical architecture efficiently capture iodine molecules with an adsorption capacity of 3533.11 mg g-1 (353 wt%) for gaseous iodine and 903.6 mg g-1 (90 wt%) for dissolved iodine. The iodine uptake per specific surface area up to 8.55 wt% m-2 g-1 achieves the highest level among all porous adsorbents. This work illustrates the successful preparation of a new type of porous adsorbent that is expected to be applied in the field of practical iodine adsorption.

Nerve Regeneration Effect of a Composite Bioactive Carboxymethyl Chitosan-Based Nerve Conduit with a Radial Texture.

Chitosan (CTS) has been used as a nerve guidance conduit (NGC) material for bridging peripheral nerve defects due to its biocompatible, biodegradable, and non-toxic properties. However, the nerve regeneration effect of chitosan alone is restricted due to its inadequate biological activity. Herein, a composite, bioactive chitosan based nerve conduit, consisting of outer warp-knitted tube scaffold made from medical-grade chitosan fiber, and inner porous cross linked carboxymethyl chitosan (C-CM-CTS) sponge with radial texture was developed. The inner wall of the scaffold was coated with C-CM-CTS solution. CM-CTS provided favorable bioactivities in the composite chitosan-based nerve conduit. An in vitro study of CM-CTS revealed its satisfying biocompatibility with fibroblast and its inhibition of oxidative damage to Schwann cells. As the internal filler of the NGC, the lyophilized sponge of C-CM-CTS showed a longitudinal guidance effect for nerve reconstruction. After 10 mm defect in rat sciatic nerve was bridged with the composite bioactive chitosan-based nerve conduit, the nerve conduit was able to effectively promote axonal regeneration and played a positive role in inducing nerve regeneration and functional recovery. In addition to the functional advantages, which are equal to those of an autograft; the technology for the preparation of this conduit can be put into mass production.

Introducing Polar Groups in Porous Aromatic Framework for Achieving High Capacity of Organic Molecules and Enhanced Self-Cleaning Applications.

Due to the frequent oil/organic solvent leakage, efficient oil/water separation has attracted extensive concern. However, conventional porous materials possess nonpolar building units, which reveal relatively weak affinity for polar organic molecules. Here, two different polarities of superhydrophobic porous aromatic frameworks (PAFs) were synthesized with respective orthoposition and paraposition C=O groups in the PAF linkers. The conjugated structure formed by a large number of alkynyl and benzene ring structures enabled porous and superhydrophobic quality of PAFs. After the successful preparation of the PAF solids, PAF powders were coated on polyester fabrics by a simple dip-coating method, which endowed the resulting polyester fabrics with superhydrophobicity, porosity, and excellent stability. Based on the unique structure, the oil/water separation efficiency of two superhydrophobic flexible fabrics was more than 90% for various organic solvents. Polar LNU-26 PAF showed better separation performance for the polar oils. This work takes the lead in adopting the polar groups as building units for the preparation of porous networks, which has great guiding significance for the construction of advanced oil/water separation materials.

Sources of ambient non-methane hydrocarbon compounds and their impacts on O3 formation during autumn, Beijing.

The field observation of 54 non-methane hydrocarbon compounds (NMHCs) was conducted from September 1 to October 20 in 2020 during autumn in Haidian District, Beijing. The mean concentration of total NMHCs was 29.81 ± 11.39 ppbv during this period, and alkanes were the major components. There were typical festival effects of NMHCs with lower concentration during the National Day. Alkenes and aromatics were the dominant groups in ozone formation potential (OFP) and OH radical loss rate (LOH). The positive matrix factorization (PMF) running results revealed that vehicular exhaust became the biggest source in urban areas, followed by liquefied petroleum gas (LPG) usage, solvent usage, and fuel evaporation. The box model coupled with master chemical mechanism (MCM) was applied to study the impacts of different NMHCs sources on ozone (O3) formation in an O3 episode. The simulation results indicated that reducing NMHCs concentration could effectively suppress O3 formation. Moreover, reducing traffic-related emissions of NMHCs was an effective way to control O3 pollution at an urban site in Beijing.

Integrative analysis of miRNAs and mRNAs revealed regulation of lipid metabolism in dairy cattle.

Lipid metabolism in bovine mammary epithelial cells has been the primary focus of the research of milk fat percentage of dairy cattle. Functional microRNAs can affect lipid metabolism by regulating the expression of candidate genes. The purpose of the study was to screen and identify differentially expressed miRNAs, candidate genes, and co-regulatory pathways related to the metabolism of milk fat. To achieve this aim, we used miRNA and transcriptome data from the mammary epithelial cells of dairy cattle with high (H, 4.85%) and low milk fat percentages (L, 3.41%) during mid-lactation. One hundred ninety differentially expressed genes and 33 differentially expressed miRNAs were significantly enriched in related regulatory networks, of which 27 candidate genes regulated by 18 differentially expressed miRNAs significantly enriched in pathways related to lipid metabolism (p < 0.05). Target relationships between PDE4D and bta-miR-148a, PEG10 and bta-miR-877, SOD3 and bta-miR-2382-5p, and ADAMTS1 and bta-miR-2425-5p were verified using luciferase reporter assays and quantitative RT-PCR. The detection of triglyceride production in BMECs showed that bta-miR-21-3p and bta-miR-148a promote triglyceride synthesis, whereas bta-miR-124a, bta-miR-877, bta-miR-2382-5p, and bta-miR-2425-5p inhibit triglyceride synthesis. The conjoint analysis could identify functional miRNAs and regulatory candidate genes involved in lipid metabolism within the co-expression networks of the dairy cattle mammary system, which contributes to the understanding of potential regulatory mechanisms of genetic element and gene signaling networks involved in milk fat metabolism.

Dimensionality Control of 1D Coupling Reaction for the Facile Preparation of Porous Carbon Nanofibers.

Porous carbon nanofibers with unique hierarchical structures have great potential in many fields, including heterogeneous catalysis, optoelectronics, and sensing. However, several preparation issues, such as additional templates, complicated processes, and harsh conditions, seriously hamper their widespread use. Here, we control the Sonogashira coupling reaction of linear building monomers─1,4-dibromaphthalene and 1,4-ethylbenzene─at the molecular level. Due to the occurrence of branching chain reaction (side reaction), 1D oligomer expands the growth orientation in the plane direction, forming a curled 1D fiber polymer. After thermal-driven skeleton engineering, porous carbon nanofibers were obtained with hierarchical channels of macro- (150 nm), meso- (5.2 nm), and microcavities (0.5 and 1.3 nm). The integration of macro-/meso-/microporous structure reveals a fast and sufficient interaction with electrolyte molecules, facilitating the construction of high-performance electrical devices. Our strategy, using a side reaction to achieve the dimensionality control of 1D copolymerization, paves a new way for the facile preparation of porous carbon nanofibers.

A Carbazole-Functionalized Porous Aromatic Framework for Enhancing Volatile Iodine Capture via Lewis Electron Pairing.

Nitrogen-rich porous networks with additional polarity and basicity may serve as effective adsorbents for the Lewis electron pairing of iodine molecules. Herein a carbazole-functionalized porous aromatic framework (PAF) was synthesized through a Sonogashira-Hagihara cross-coupling polymerization of 1,3,5-triethynylbenzene and 2,7-dibromocarbazole building monomers. The resulting solid with a high nitrogen content incorporated the Lewis electron pairing effect into a π-conjugated nano-cavity, leading to an ultrahigh binding capability for iodine molecules. The iodine uptake per specific surface area was ~8 mg m-2 which achieved the highest level among all reported I2 adsorbents, surpassing that of the pure biphenyl-based PAF sample by ca. 30 times. Our study illustrated a new possibility for introducing electron-rich building units into the design and synthesis of porous adsorbents for effective capture and removal of volatile iodine from nuclear waste and leakage.

Pyrene-Based Fluorescent Porous Organic Polymers for Recognition and Detection of Pesticides.

Eating vegetables with pesticide residues over a long period of time causes serious adverse effects on the human body, such as acute poisoning, chronic poisoning, and endocrine system interference. To achieve the goal of a healthy society, it is an urgent issue to find a simple and effective method to detect organic pesticides. In this work, two fluorescent porous organic polymers, LNU-45 and LNU-47 (abbreviation for Liaoning University), were prepared using π-conjugated dibromopyrene monomer and boronic acid compounds as building units through a Suzuki coupling reaction. Due to the large π-electron delocalization effect, the resulting polymers revealed enhanced fluorescence performance. Significantly, in sharp contrast with the planar π-conjugated polymer framework (LNU-47), the distorted conjugated structure (LNU-45) shows a higher specific surface area and provides a broad interface for analyte interaction, which is helpful to achieve rapid response and detection sensitivity. LNU-45 exhibits strong fluorescence emission at 469 nm after excitation at 365 nm in THF solution, providing strong evidence for its suitability as a luminescent chemosensor for organic pesticides. The fluorescence quenching coefficients of LNU-45 for trifluralin and dicloran were 5710 and 12,000 (LNU-47 sample by ca. 1.98 and 3.38 times), respectively. Therefore, LNU-45 serves as an effective "real-time" sensor for the detection of trifluralin and dicloran with high sensitivity and selectivity.

Mushroom extracts and compounds with suppressive action on breast cancer: evidence from studies using cultured cancer cells, tumor-bearing animals, and clinical trials.

This article reviews mushrooms with anti-breast cancer activity. The mushrooms covered which are better known include the following: button mushroom Agaricus bisporus, Brazilian mushroom Agaricus blazei, Amauroderma rugosum, stout camphor fungus Antrodia camphorata, Jew's ear (black) fungus or black wood ear fungus Auricularia auricula-judae, reishi mushroom or Lingzhi Ganoderma lucidum, Ganoderma sinense, maitake mushroom or sheep's head mushroom Grifola frondosa, lion's mane mushroom or monkey head mushroom Hericium erinaceum, brown beech mushroom Hypsizigus marmoreus, sulfur polypore mushroom Laetiporus sulphureus, Lentinula edodes (shiitake mushroom), Phellinus linteus (Japanese "meshimakobu," Chinese "song gen," Korean "sanghwang," American "black hoof mushroom"), abalone mushroom Pleurotus abalonus, king oyster mushroom Pleurotus eryngii, oyster mushroom Pleurotus ostreatus, tuckahoe or Fu Ling Poria cocos, and split gill mushroom Schizophyllum commune. Antineoplastic effectiveness in human clinical trials and mechanism of anticancer action have been reported for Antrodia camphorata, Cordyceps sinensis, Coriolus versicolor, Ganoderma lucidum, Grifola frondosa, and Lentinula edodes.

New ribosome-inactivating proteins and other proteins with protein synthesis-inhibiting activities.

Ribosome-inactivating proteins (RIPs) consist of three varieties. Type 1 RIPs are single-chained and approximately 30-kDa in molecular weight. Type 2 RIPs are double-chained and composed of a type 1 RIP chain and a lectin chain. Type III RIPs, such as maize b-32 barley and JIP60 which are produced as single-domain proenzymes, possess an N-terminal domain corresponding to the A domain of RIPs and fused to a C-terminal domain. In addition to the aforementioned three types of RIPs originating from flowering plants, there are recently discovered proteins and peptides with ribosome-inactivating and protein synthesis inhibitory activities but which are endowed with characteristics such as molecular weights distinctive from those of the regular RIPs. These new/unusual RIPs discussed in the present review encompass metazoan RIPs from Anopheles and Culex mosquitos, antimicrobial peptides derived from RIP of the pokeweed Phytolacca dioica, maize RIP (a type III RIP derived from a precursor form), RIPs from the garden pea and the kelp. In addition, RIPs with a molecular weight smaller than those of regular type 1 RIPs are produced by plants in the Cucurbitaceae family including the bitter gourd, bottle gourd, sponge gourd, ridge gourd, wax gourd, hairy gourd, pumpkin, and Chinese cucumber. A small type II RIP from camphor tree (Cinnamomum camphora) seeds and a snake gourd type II RIP with its catalytic chain cleaved into two have been reported. RIPs produced from mushrooms including the golden needle mushroom, king tuber mushroom, straw mushroom, and puffball mushroom are also discussed in addition to a type II RIP from the mushroom Polyporus umbellatus. Bacterial (Spiroplasma) RIPs associated with the fruitfly, Shiga toxin, and Streptomyces coelicolor RIP are also dealt with. The aforementioned proteins display a diversity of molecular weights, amino acid sequences, and mechanisms of action. Some of them are endowed with exploitable antipathogenic activities.

New function of the CD44 gene: Lipid metabolism regulation in bovine mammary epithelial cells.

The CD44 gene encodes a cell-surface glycoprotein that participates in a variety of biological processes such as cell interactions, adhesion, hematopoiesis, and tumor metastasis. We compared the transcriptome in bovine mammary epithelial cells (bMEC) of Chinese Holstein dairy cows producing milk of high and low fat contents. Our results suggest that CD44 might be a candidate gene affecting milk fat synthesis. In the present study, the overexpression of the CD44 gene increased the contents of intracellular triglycerides (TG) and cholesterol (CHOL), whereas knockdown of the CD44 gene decreased bMEC CHOL and TG contents. Gas chromatography analysis of fatty acid composition showed that the contents of α-linolenic acid, palmitic acid, and cis-8,11,14-eicosatrienoic acid were altered due to changes in the level of expression of the CD44 gene. Additionally, elaidic acid, palmitoleic acid, tridecanoic acid, and oleic acid were markedly reduced in the CD44 gene overexpression group compared with the control group. On the contrary, cis-5,8,11,14-eicosatetraenoic acid and stearic acid were markedly increased in the CD44 knockdown group compared with the control group. And RT2 Profiler PCR array (Qiagen, CLAB24070A Frankfurt, Germany) further suggested that overexpression or knockdown of the CD44 gene altered expression levels of functional genes associated with lipid metabolism. The present data indicate that CD44 plays a key regulatory role in lipid metabolism in bMEC.

Surface plasmon-catalyzed oxidation of 4-aminodiphenyl disulfide for determination of Ag+ ion in aqueous samples.

A new sensor for determination of Ag+ ion (Ag+) by surface-enhanced Raman scattering (SERS) is reported. Gold nanoparticles (AuNPs) and 4-aminodiphenyl disulfide (APDS) were chosen as the SERS substrate and probe molecule, respectively. With the addition of Ag+, three new peaks (1141, 1392, and 1435 cm-1) appeared in the SERS spectrum, indicating that the conversion of APDS to p,p'-dimercaptoazobenzene (DMAB) was achieved. As the concentration of Ag+ increased, the conversion of APDS to DMAB also increased and showed a good linear relationship (R2 = 0.9746) in the range of 10 to 100 µM of Ag+. The limit of detection (LOD) was 7 µM. Compared with the traditional determination method, the SERS method is convenient and fast and requires no complicated preprocessing. Graphical abstract.

Temperature-Responsive Electrocatalysis Based on Poly(N-Isopropylacrylamide)-Modified Graphene Oxide (PNIPAm-GO).

Poly(N-isopropylacrylamide)-modified graphene oxide (PNIPAm-GO), which is a type of thermally responsive GO, was designed and synthesized through a covalent "grafting-from" strategy. The as-prepared modified nanosheets integrated the individual advantages of two components, such as the thermal sensitivity of the PNIPAm terminal as well as the conductivity and the open 2D structure of the GO substrate. PNIPAm-GO was able to perform the reversible regulation of hydrophilicity/hydrophobicity in aqueous solution upon variations in the temperature. Such a unique property might also lead to the utilization of PNIPAm-GO as an intelligent electrode material to achieve a switchable electrochemical response toward a [Fe(CN)6 ]3-/4- probe. The PNIPAm-GO modified glassy carbon electrode (PNIPAm-GO/GC electrode) was able to exhibit better electrochemical performance in an ON/OFF switching effect than the PNIPAm-modified glassy carbon electrode (PNIPAm/GC electrode) without GO owing to the intrinsic properties and large surface area of the introduced GO. Moreover, it was found that the PNIPAm-GO/GC electrode also displayed excellent thermally responsive electrocatalysis toward the detection of 1,4-dihydro-ß-nicotinamide adenine dinucleotide (NADH) and dopamine (DA), which resulted in two different catalytic statuses on the same electrode. This kind of switchable catalytic performance of the PNIPAm-GO/GC electrode might greatly enhance the flexibility of its application, and thus it is expected to have wide potential for applications in the fields of biosensors and biocatalysis.