Manipulating Radiation-Sensitive Z-DNA Conformation for Enhanced Radiotherapy.

DNA double-strand breaks (DSBs) yield highly determines radiotherapy efficacy. However, improving the inherent radiosensitivity of tumor DNA to promote radiation-induced DSBs remains a challenge. Using theoretical and experimental models, the underexplored impact of Z-DNA conformations on radiosensitivity, yielding higher DSBs than other DNA conformations, is discovered. Thereout, a radiosensitization strategy focused on inducing Z-DNA conformation, utilizing CBL@HfO2 nanocapsules loaded with a Z-DNA inducer CBL0137, is proposed. A hollow mesoporous HfO2 (HM-HfO2) acts as a delivery and an energy depositor to promote Z-DNA breakage. The nanocapsule permits the smart DSBs accelerator that triggers its radiosensitization with irradiation stimulation. Impressively, the CBL@HfO2 facilitates the B-Z DNA conformational transition, augmenting DSBs about threefold stronger than irradiation alone, generating significant tumor suppression with a 30% cure rate. The approach enables DSBs augmentation by improving the inherent radiosensitivity of DNA. As such, it opens up an era of Z-DNA conformation manipulation in radiotherapy.

In Situ Growth 3D GDY-NCNTs Nanocomposites for High-Performance Supercapacitors.

New binary carbon composites (GDY-NCNTs and GDY-CNTs) with a three-dimensional porous structure, which are synthesized by an in situ growth method, are adopted in this article. The GDY-NCNTs composites exhibit excellent specific capacitance performance (679 F g-1, 2 mV s-1, 139% increase compared to GDY-CNTs) and good cycling stability (with a capacity retention rate of up to 116% after 10000 cycles). The three-dimensional porous structure not only promotes ion transfer and increases the effective specific surface area to improve its specific capacitance performance but also adapts to the volume expansion and contraction during the charging and discharging process to improve its cycling stability. The presence of nitrogen doping in the carbon nanotubes of GDY-NCNTs increases the surface defects of the composites, provides more electrochemical points, and improves the surface wettability of the composites, further improving the electrochemical performance of the composites.

Tuning Hole Transport Properties and Perovskite Crystallization via Pyridine-Based Molecules for Quasi-2D Perovskite Solar Cells.

Quasi-2D perovskites show great potential as photovoltaic devices with superior stability, but the power conversion efficiency (PCE) is limited by poor carrier transport. Here, it is simultaneously affected the hole transport layer (HTL) and the perovskite layer by incorporating pyridine-based materials into poly(3,4-ethylenedioxythiophene): polystyrene sulfonate (PEDOT:PSS) to address the key problem above in 2D perovskites. With this approach, the enhanced optoelectronic performance of the novel PEDOT:PSS is due to electron transfer between the additives and PEDOT or PSS, as well as a dissociation between PEDOT and PSS based on experimental and theoretical studies, which facilitates the charge extraction and transfer. Concurrently, in-situ X-ray scattering studies reveal that the introduction of pyridine-based molecules alters the transformation process of the perovskite intermediate phase, which leads to a preferred orientation and ordered distribution caused by the Pb─N chemical bridge, achieving efficient charge transport. As a result, the pyridine-treated devices achieve an increased short-circuit current density (Jsc) and PCE of over 17%.

In Situ Formed Z-Scheme Graphdiyne Heterojunction Realizes NIR-Photocatalytic Oxygen Evolution and Selective Radiosensitization for Hypoxic Tumors.

Photon radiotherapy is a common tool in the armory against tumors, but it is limited by hypoxia-related radioresistance of tumors and radiotoxicity to normal tissues. Here, we constructed a spatiotemporally controlled synergistic therapy platform based on the heterostructured CuO@Graphdiyne (CuO@GDY) nanocatalyst for simultaneously addressing the two key problems above in radiotherapy. First, the in situ formed Z-scheme CuO@GDY heterojunction performs highly efficient and controlled photocatalytic O2 evolution upon near-infrared (NIR) laser stimulation for tumor hypoxia alleviation. Subsequently, the CuO@GDY nanocatalyst with X-ray-stimulated Cu+ active sites can accelerate Fenton-like catalysis of ·OH production by responding to endogenous H2O2 for the selective killing of tumor cells rather than normal cells. In this way, the sequential combination of NIR-triggered photocatalytic O2 production and X-ray-accelerated Fenton-like reaction can lead to a comprehensive radiosensitization. Overall, this synergism underscores a controllable and precise therapy modality for simultaneously unlocking the hypoxia and non-selectivity in radiotherapy.

Graphdiyne Oxide Quantum Dots: The Enhancement of Peroxidase-like Activity and Their Applications in Sensing H2O2 and Cysteine.

As one of the typical carbon nanomaterials, graphdiyne (GDY) with unique chemical, physical, and electronic properties has a great potential in various fields. Although it is an important member of carbon nanozymes, the research on its intrinsic enzyme mimetic properties and applications is still limited. Herein, graphdiyne oxide quantum dots (GDYO QDs) have been synthesized through oxidative cleavage, which exhibit enhanced peroxidase-like activity with lower Km and higher Vmax than those of most carbon-based nanozymes. The catalytic mechanism is explored, showing that the enhanced catalytic performance is attributed to the good conjugated structure, large number of oxygen-containing groups, and small-sized nanosheets with few layers. As a kind of peroxidase mimetic, the GDY-based nanozyme has excellent potential in sensing H2O2 and biological antioxidants through the colorimetric assay, with a linear range from 5 to 500 µM and detection limit of 1.5 µM for H2O2 and a linear range from 0 to 90 µM and detection limit of 0.48 µM for l-cysteine. Our work will be beneficial to develop high-performance artificial enzymes and to understand their mechanism for better applications.

Long noncoding RNA ANRIL up-regulates CCND1 via sponging miR-98-5p to promote TGF-ß1-induced human airway smooth muscle cell proliferation, migration, and extracellular matrix deposition.

Excessive proliferation and migration of airway smooth muscle cell (ASMC) contribute to asthma pathogenesis. Long noncoding RNAs (lncRNAs) are reported to take part in asthma pathogenesis. This study is targeted at deciphering the role of the lncRNA antisense noncoding RNA in the INK4 locus (ANRIL) in ASMC proliferation, migration and extracellular matrix (ECM) deposition. qRT-PCR was performed to determine ANRIL, miR-98-5p, and cyclin D1 (CCND1) mRNA expression levels in transforming growth factor-ß1 (TGF-ß1)-treated ASMCs. CCK-8 and Transwell assays were employed to examine ASMC proliferation and migration, respectively. Dual-luciferase reporter gene assay and RNA immunoprecipitation assay were carried out for analyzing the targeted relationship of miR-98-5p with ANRIL or CCND1 mRNA 3'-UTR. The levels of CCND1 and ECM proteins (such as fibronectin, COL3A1, and COL1A2) in ASMCs were detected through Western blot. In this work, we found that ANRIL and CCND1 were up-regulated in TGF-ß1-treated ASMCs, whereas miR-98-5p was down-regulated. ANRIL overexpression facilitated the proliferation, ECM deposition and migration of TGF-ß1-induced ASMCs, while knocking down ANRIL had the opposite effect. Furthermore, ANRIL targeted miR-98-5p directly, and CCND1 was miR-98-5p's downstream target. ANRIL indirectly increased CCND1 expression in ASMCs via competitively binding to miR-98-5p. MiR-98-5p inhibition or CCND1 overexpression counteracted the inhibiting effect that ANRIL knockdown had on TGF-ß1-stimulated ASMC proliferation, migration and ECM deposition. In conclusion, ANRIL indirectly up-regulates CCND1 expression by targeting miR-98-5p to promote ASMC proliferation, migration and ECM deposition, thus facilitating the pathogenesis of asthma.

A Freestanding Chitin-Derived Hierarchical Nanocomposite for Developing Electrodes in Future Supercapacitor Industry.

Crustacean cuticles are receiving extensive attention for its potential in developing environmentally friendly and high energy density electrodes for supercapacitor applications. In the current work, the demineralized tergite cuticle of mantis shrimp was employed as a precursor for the fabrication porous biochar. The structural benefits of the cuticle, including the hierarchical nanofiber networks, and the interpenetrating pore systems were maximumly retained, providing a high carbon content and specific surface area scaffold. Graphene oxide sheets were deposited across the biochar through the pore canal systems to further increase the conductivity of the biochar, forming a novel freestanding carbon composite. Throughout the modification process, the material products were examined by a range of methods, which showed desired structural, chemical and functional properties. Our work demonstrates that high performance carbon materials can be manufactured using a simple and green process to realize the great potential in energy storage applications.

CYP2C19, PON1, and ABCB1 gene polymorphisms in Han and Uygur populations with coronary artery disease in Northwestern Xinjiang, China, From 2014 Through 2019.

The morbidity of coronary artery disease (CAD) in the Uygur population of Xinjiang was much higher than the national average. Clopidogrel is the most commonly used medication worldwide in dual antiplatelet therapy for CAD, and the response of clopidogrel is affected by CYP2C19, PON1, and ABCB1 genetic polymorphisms. The distribution of CYP2C19*17, ABCB1, and PON1 genetic polymorphisms in Han and Uygur populations with CAD of Xinjiang has not been investigated.This study aimed to investigate the frequencies of CYP2C19, PON1, and ABCB1 genetic polymorphisms, and to identify the metabolizer phenotype of CYP2C19 in Han and Uygur populations with CAD in Northwestern Xinjiang, China. We identified 602 Han and 527 Uygur patients from 2014 through 2019 and studied genotypes for selected allele polymorphisms using sequencing by hybridization.There were significantly different allele frequencies and genotype frequencies between the 2 ethnic groups in terms of CYP2C19*2, *3, *17, ABCB1 and PON1, (P < .05). For CYP2C19*17, the frequency of TT genotype was 2.5% in Uygur patients, but it was undetectable in Han patients. In both the intermediate and poor metabolizer groups, the genotypes polymorphisms CYP2C19*2, *3, *17 were significantly less common in Uygur patients than in Han patients (P < .001). By contrast, the proportion of ultra-metabolizers as defined by CYP2C19*2, *3, *17 polymorphisms significantly higher in Uygur patients (18.6%) than in Han patients (1.7%, P < .001). The CYP2C19*2 frequency was significantly different between Han patients and Han healthy groups (P < .001), while the CYP2C19*3 frequency was significantly different between Uygur patients and Uygur healthy groups (P < .001).Our study supports the notion of interethnic differences in terms of CYP2C19, PON1, and ABCB1 polymorphisms and CYP2C19 genotype-defined clopidogrel metabolic groups. These finding could provide valuable data and insights into personalized CAD treatment for the Uygur and Han populations in Xinjiang.

High performance determination of Pb2+ in water by 2,4-dithiobiuret-Reduced graphene oxide composite with wide linear range and low detection limit.

In this work, a novel chelating adsorbent, 2, 4-dithiobiuret-reduced graphene oxide composite (DTB-RGO), was synthesized and worked as an electrochemical sensor for the determination of Pb2+. X-ray photoemission spectroscopy, Raman spectroscopy and Fourier transform-infrared spectroscopy were used to confirm the successful doping of the aminothiourea groups into the GO nanosheets through amide bond. The electrode modified with DTB-RGO shows two wide linear range 0.1-200 ng mL-1, 200-1000 ng mL-1 and relatively low detection limit 0.08 ng mL-1 for Pb2+, far below the level of 10 ng mL-1 proposed by WHO. This DTB-RGO modified electrode also presents satisfying selectivity, reproducibility, stability, and applicability for detection of Pb2+, providing a simple and promising platform to develop novel electrochemical sensor for detecting Pb2+ with higher performance.

Preparing dangling bonds by nanoholes on graphene oxide nanosheets and their enhanced magnetism.

The effects of dangling bonds on the magnetic properties of graphene oxide (GO) were studied experimentally by creating nanoholes on GO nanosheets. GO with more nanoholes (MHGO) and less nanoholes (LHGO) on graphene oxide nanosheets were synthesized. Results showed that nanoholes brought new dangling bonds for GO and the increase of the dangling bonds on GO could be adjusted by the amounts of the nanoholes on GO. The magnetism of GO was enhanced with increased density of nanoholes on GO (MHGO > LHGO > GO). Furthermore, the increased dangling bonds induced magnetic coupling between the spin units and so converted paramagnetism GO to ferromagnetism (MHGO, LHGO). The easy generation and adjustment of GO dangling bonds by nanoholes on GO nanosheets will promote the applications of GO.

Fluorescent activatable gadofullerene nanoprobes as NIR-MR dual-modal in vivo imaging contrast agent.

Dual mode imaging technology is widely developed to achieve the early-stage precision cancer diagnosis. Here we designed a dual-modal magnetic resonance/near infrared fluorescence optical imaging contrast agent (GdF-SS-NIR783) with the fluorescence activatable and safer gadofullerene. The nanoprobes were fabricated by conjugating the gadofullerene derivatives with a NIR fluorescence imaging agent (NIR783) via the disulfide bond. The obtained nanoprobes showed no fluorescence (OFF), but the fluorescence turned on when incubated within reduction environment such as GSH solution. The clear fluorescence signal in tumor site was observed obviously after their intratumor injection. The nanoprobes also revealed efficient MRI contrast enhancement both in vitro and in vivo. And they showed good biocompatibility and did not demonstrate any tissue toxicity in vivo. This work gave the new possibility in designing more efficient and safer nanoprobes for future medical diagnoses.

Study on the antigenicity of metallofullerenol: antibody production, characterization, and its enzyme immunoassay application.

With their intriguing structures and properties, metallofullerenols have attracted considerable attention in biological and medical applications. Due to the increasing biomedical interest, effective detection methods are important to monitor and control metallofullerenols. However, the detection of metallofullerenols becomes very difficult after polyhydroxylated modification due to the lack of detectable features. Antibody-based immunoassay methods have been important tools for detection and will better meet the needs of analysis of metallofullerenols. Thus, the antigenicity of metallofullerenol has been studied for the first time. In this study, no immune response was detected when metallofullerenol Gd@C82(OH)x was used as immunogen. However, the polyclonal antibody against metallofullerenol was produced using metallofullerenol-KLH (keyhole limpet hemocyanin) as immunogen, indicating that metallofullerenol can act as hapten. The specificity of the obtained antibody was investigated. It has been found that the hydroxyl groups on the surface of the carbon cage, the encapsulated metal, and the size and shape of the carbon cage did not affect the recognition specificity of the antibody. Based on the obtained antibody, an indirect competitive enzyme immunoassay was developed for the determination of metallofullerenol with detection limits of 18 ng/mL in PBS. This enzyme immunoassay method was successfully used to detect metallofullerenol in serum. This work can provide an innovative way to determine metallofullerenols. Graphical abstract The polyclonal antibody against metallofullerenol was produced using metallofullerenol-KLH (keyhole limpet hemocyanin) as immunogen. Based on the obtained antibody, a competitive enzyme immunoassay was developed for the determination of metallofullerenol.

Isomers of IC70BA and Their Photovoltaic Performance in Polymer Solar Cells.

Indene-C70 derivatives were synthesized, including indene-C70 mono-adduct (IC70MA), indene-C70 bis-adduct (IC70BA) and indene-C70 tris-adduct (IC70TA). All as-prepared fullerene adducts are in fact a mixture of isomers. The IC70BA mixture was further separated by high-performance liquid chromatography (HPLC) and two different IC70BA isomers were obtained. With the addition of the increased number of indene, the lowest unoccupied molecular orbital (LUMO) energy level of the C70 derivatives is also increased. IC70BA and its isomers have a slight difference in LUMO energy level, but show great differences in the absorption spectra. Polymer solar cells (PSCs) devices were fabricated under the same conditions with P3HT as donor, IC70BA and its isomer as acceptor, to examine the influence of the regioisomers on photovoltaic performance. The two IC70BA isomers exhibited varying power conversion efficiency (PCE) values of 2.80 and 3.18%, respectively, suggesting the molecular structure of the fullerene derivatives have an effect on polymer solar cells properties.

Synthesis and characterization of C70-corrole--a new electron transfer dyad.

A new electron transfer dyad, covalently linked C70-corrole, was prepared via C70 and 10-(4-Formylaryl)-5,15-bis(pentafluorophenyl). The structures and the properties of the new material were investigated by HPLC, MALDI-TOF-MS, UV-Vis-NIR spectroscopy, NMR, fluorescence analysis and CV/DPV. The free-energy of C70-corrole calculated by employing the redox potentials and singlet excited-state energy suggested the possibility of electron transfer from the excited singlet state of corrole to the fullerene entity, which agreed with the results of the theoretical calculation.

Enhanced performance of inverted organic photovoltaic cells using CNTs-TiO(X) nanocomposites as electron injection layer.

In this study, we fabricated inverted organic photovoltaic cells with the structure ITO/carbon nanotubes (CNTs)-TiO(X)/P3HT:PCBM/MoO3/Al by spin casting CNTs-TiO(X) nanocomposite (CNTs-TiO(X)) as the electron injection layer onto ITO/glass substrates. The power conversion efficiency (PCE) of the 0.1 wt% single-walled nanotubes (SWNTs)-TiO(X) nanocomposite device was almost doubled compared with the TiO(X) device, but with increasing concentration of the incorporated SWNTs in the TiO(X) film, the performance of the devices appeared to decrease rapidly. Devices with multi-walled NTs in the TiO(X) film have a similar trend. This phenomenon mainly depends on the inherent physical and chemical characteristics of CNTs such as their high surface area, their electron-accepting properties and their excellent carrier mobility. However, with increasing concentration of CNTs, CNTs-TiO(X) current leakage pathways emerged and also a recombination of charges at the interfaces. In addition, there was a significant discovery. The incorporated CNTs were highly conducive to enhancing the degree of crystallinity and the ordered arrangement of the P3HT in the active layers, due to the intermolecular π-π stacking interactions between CNTs and P3HT.

Gene interaction networks based on kernel correlation metrics.

In this paper, a Kernel correlation coefficient (KCC) method is proposed to elucidate the gene nonlinear relationships as a distance metric. To evaluate the performance of this nonlinear distance measure, a biological network of the Gaussian Kernel on a public dataset of yeast genes is constructed by using a graph theory. Specifically, the distribution and properties of this new measure are analysed and compared with the classical Pearson correlation method. The reliability and advantages of our proposed Kernel correlation metric is verified and shown formally on ten showcases of the DREAM (Dialogue for Reverse Engineering Assessments and Methods) project. Test experiment results demonstrate that the proposed Kernel correlation coefficient measure has a strong capability in identifying interaction genes, and that the proposed method can detect accurately the key genes and functional interactions (also known as the cliques) as compared to the commonly used Pearson correlation and Mutual Information measures.

Synthesis and characterization of Gd@C82-PVK and C60-PVK--a kind of fullerene-grafted polymer.

Different fullerene-grafted poly(N-vinylcarbazole) was synthesized by free radical polymerization and the influence of the amount of initiator, the reaction time and the reaction temperature on the polymerization was studied. Metallofullerene-grafted polymer (Gd@C82-PVK) was firstly synthesized and characterized by GPC, UV-vis, FTIR, DSC, XPS. The results demonstrated that the fullerenes had chemically combined with PVK. Fluorescence spectra suggested that the grafted fullerenes had certain influence on the fluorescence properties of the polymer. This is due to the better electron-attractive ability of fullerenes, which contributed a lot to form the electron donor-acceptor systems in fullerene-grafted poly(N-vinylcarbazole). Potential applications of this kind of materials in optical and memory devices were expected.

Long Distance Electron Transfer Across >100 nm Thick Au Nanoparticle/Polyion Films to a Surface Redox Protein.

Glutathione-decorated 5 nm gold nanoparticles (AuNPs) and oppositely charged poly(allylamine hydrochloride) (PAH) were assembled into {PAH/AuNP} n films fabricated layer-by-layer (LbL) on pyrolytic graphite (PG) electrodes. These AuNP/polyion films utilized the AuNPs as electron hopping relays to achieve direct electron transfer between underlying electrodes and redox proteins on the outer film surface across unprecedented distances >100 nm for the first time. As film thickness increased, voltammetric peak currents for surface myoglobin (Mb) on these films decreased but the electron transfer rate was relatively constant, consistent with a AuNP-mediated electron hopping mechanism.

Interaction between fullerenes and single-wall carbon nanotubes: the influence of fullerene size and electronic structure.

A series of fullerenes and endohedral metallofullerenes peapods have been synthesized by supercritical method in high filling rate. The interaction between SWNTs and various kinds of fullerenes (C60, C70, C78, C84) and metallofullerenes (Gd@C82, Er@C82, Ho@C82, Y@C82) has been further investigated. The slight blue shift of G-band in Raman spectra with respect to pristine SWNTs was attributed to the charge transfer from SWNTs to fullerenes cage. The obvious RBM shift strongly depended on the distance between the inner wall of the SWNTs and the fullerene cage and also partly associated with the electronic structure of the fullerene. These results indicated that the interaction between fullerenes and SWNTs, which was considered to be the van de walls interaction, can be influenced by the cage size and the kind of fullerenes.

Structural change of metallofullerene: an easier thermal decomposition.

We have studied for the first time the structural change of high-purity metallofullerene (Gd@C(82)) upon heat treatment in an ultra-high vacuum system (10(-10) Torr) and examined the decomposition product through successive analysis with MS, IR, Raman, TEM, EDS and XPS. It was found that metallofullerene (Gd@C(82)) had fully collapsed at 580 °C which was lower than that for the complete destruction of C(60). The easier decomposition should be ascribed to the encapsulated metal in the carbon cage which could induce the deformation of the C-C bond. The analysis indicated that the broken metallofullerene (Gd@C(82)) became a kind of graphite-like material with a lot of defects. The Gd atoms leaked out from the carbon cage and aggregated together to form a regular arrangement.