The first discovery of Polypedatesteraiensis (Dubois, 1987) (Rhacophoridae, Anura) in China.

Background: The genus of Polypedates Tschudi, 1838 currently comprises 25 recognised species with four of these species reported in Yunnan, China. Dubois (1987) speculated the distribution of P.teraiensis in China; however, there was no study carried out to confirm its distribution in the region. New information: We herein describe P.teraiensis as a new national record, based on a specimen collected from Yunnan border region. Phylogenetically, our sequence clustered with the sequences of recognised P.teraiensis specimens from Bangladesh, Myanmar and India. The uncorrected pairwise distances between the specimens from China and other P.teraiensis localities was small, ranging from 0.0-0.7%, based on 16S rRNA gene. Therefore, we report P.teraiensis as a new species record for China.

Design and Performance of Small-Molecule Donors with Donor-π-Acceptor Architecture Toward Vacuum-Deposited Organic Photovoltaics Having Heretofore Highest Short-Circuit Current Density.

The development of high-performance organic photovoltaic materials is of crucial importance for the commercialization of organic solar cells (OSCs). Herein, two structurally simple donor-π-conjugated linker-acceptor (D-π-A)-configured small-molecule donors with methyl-substituted triphenylamine as D unit, 1,1-dicyanomethylene-3-indanone as A unit, and thiophene or furan as π-conjugated linker, named DTICPT and DTICPF, are developed. DTICPT and DTICPF are facilely prepared via a two-step synthetic process with simple procedures. DTICPF with a furan π-conjugated linker exhibits stronger and broader optical absorption, deeper highest occupied molecular orbital (HOMO) energy levels, and better charge transport, compared to its thiophene analog DTICPT. As a result, vacuum-deposited OSCs based on DTICPF: C70 show an impressive power conversion efficiency (PCE) of 9.36% (certified 9.15%) with short-circuit current density (Jsc) up to 17.49 mA cm-2 (certified 17.56 mA cm-2), which is the highest Jsc reported so far for vacuum-deposited OSCs. Besides, devices based on DTICPT: C70 and DTICPF: C70 exhibit excellent long-term stability under different aging conditions. This work offers important insights into the rational design of D-π-A configured small-molecule donors for high efficient and stable vacuum-deposited OSCs.

Tetraspanins predict the prognosis and characterize the tumor immune microenvironment of glioblastoma.

Glioblastoma (GBM) is the most aggressive and lethal primary brain tumor. Conventional treatments have not achieved breakthroughs in improving survival. Therefore, novel molecular targets and biomarkers need to be identified. As signal transduction docks on the cell membrane, tetraspanins (TSPANs) are associated with various tumors; however, research on their role in GBM remains extremely scarce. Gene expression and clinicopathological characteristic data were obtained from GEPIA, CGGA, HPA, cBioPortal, and GSCA databases to analyze the mRNA and protein expression levels, prognostic value, clinical relevance, mutation status, and targeted drug sensitivity of TSPANs in GBM. Gene set enrichment analysis (GSEA), Gene Ontology (GO), and the Kyoto Encyclopedia of Genes and Genomes (KEGG) analysis were used for biological process enrichment. Data from TCGA and TCIA were used to construct the tumor immune microenvironment landscape of TSPANs. Different R software algorithms were used to analyze the immune score, immune cell infiltration, and immune checkpoint correlation. Univariate and multivariate analyses were performed for TSPAN4, which had the most significant predictive prognostic value, and a nomogram model was constructed to predict individual outcomes. The expression and function of TSPAN4 were verified in vitro. TSPAN3/4/6/11/12/18/23/24/25/26/27/28/29/30/31expressions were significantly upregulated in GBM, and TSPAN3/4/6/11/18/24/25/26/29/30 were strongly correlated with prognosis. The expression of multiple TSPANs significantly correlated with 1p/19q co-deletion status, IDH mutation status, recurrence, age, and tumor grade. GSEA and GO analyses revealed the potential contribution of TSPANs in cell adhesion and migration. Immune correlation analysis revealed that TSPANs are related to the formation of the GBM tumor microenvironment (TME) and may influence immunotherapy outcomes. TSPAN4 is an independent prognostic factor and TSPAN4 knockdown has been demonstrated to strongly inhibit glioma cell proliferation, invasion, and migration in vitro. We comprehensively elaborated the prognostic value and potential role of differentially expressed TSPANs in GBM, including molecules that scientists have previously overlooked. This study provides a novel and comprehensive perspective on the pathological mechanisms of GBM and the future direction of individualized tumor immunotherapy, which may be a critical link between GBM malignant progression and TME remodeling.

Two Metastable Endohedral Metallofullerenes Sc2C2@C1(39656)-C82 and Sc2C2@C1(51383)-C84: Direct-C2-Insertion Products from Their Most Stable Precursors.

Endohedral metallofullerenes (EMFs) are sub-nano carbon materials with diverse applications, yet their formation mechanism, particularly for metastable isomers, remains ambiguous. The current theoretical methods focus mainly on the most stable isomers, leading to limited predictability of metastable ones due to their low stabilities and yields. Herein, we report the successful isolation and characterization of two metastable EMFs, Sc2C2@C1(39656)-C82 and Sc2C2@C1(51383)-C84, which violate the isolated pentagon rule (IPR). These two non-IPR EMFs exhibit a rare case of planar and pennant-like Sc2C2 clusters, which can be considered hybrids of the common butterfly-shaped and linear configurations. More importantly, the theoretical results reveal that despite being metastable, these two non-IPR EMFs survived as the products from their most stable precursors, Sc2C2@C2v(5)-C80 and Sc2C2@Cs(6)-C82, via a C2 insertion during the post-formation annealing stages. We propose a systematic theoretical method for predicting metastable EMFs during the post-formation stages. The unambiguous molecular-level structural evidence, combined with the theoretical calculation results, provides valuable insights into the formation mechanisms of EMFs, shedding light on the potential of post-formation mechanisms as a promising approach for EMF synthesis.

Machine learning algorithm can provide assistance for the diagnosis of non-ST-segment elevation myocardial infarction.

INTRODUCTION: Our aim was to use the constructed machine learning (ML) models as auxiliary diagnostic tools to improve the diagnostic accuracy of non-ST-elevation myocardial infarction (NSTEMI). MATERIALS AND METHODS: A total of 2878 patients were included in this retrospective study, including 1409 patients with NSTEMI and 1469 patients with unstable angina pectoris. The clinical and biochemical characteristics of the patients were used to construct the initial attribute set. SelectKBest algorithm was used to determine the most important features. A feature engineering method was applied to create new features correlated strongly to train ML models and obtain promising results. Based on the experimental dataset, the ML models of extreme gradient boosting, support vector machine, random forest, naïve Bayesian, gradient boosting machines and logistic regression were constructed. Each model was verified by test set data, and the diagnostic performance of each model was comprehensively evaluated. RESULTS: The six ML models based on the training set all play an auxiliary role in the diagnosis of NSTEMI. Although all models taken for comparison performed differences, the extreme gradient boosting ML model performed the best in terms of accuracy rate (0.95±0.014), precision rate (0.94±0.011), recall rate (0.98±0.003) and F-1 score (0.96±0.007) in NSTEMI. CONCLUSIONS: The ML model constructed based on clinical data can be used as an auxiliary tool to improve the accuracy of NSTEMI diagnosis. According to our comprehensive evaluation, the performance of the extreme gradient boosting model was the best.

Carbene Addition Isomers of C70 formed in the Flame of Low-Pressure Combustion.

In the flames during low-pressure combustion, not only a rich variety of fullerenes but also many reactive intermediates can be produced (e.g., carbene, CH2) that are short-lived and cannot be stabilized directly under normal circumstances. These intermediates can be captured by fullerene carbon cages for stabilization. In this paper, three C71H2 isomers were synthesized in situ in low-pressure benzene-acetylene-oxygen diffusion flame combustion. The results, which were unambiguously characterized by single-crystal X-ray diffraction, show that the three isomers are carbene addition products of D5h-C70 on different sites. The relative energies and stability of different C71H2 isomers are revealed by Ultraviolet-Visible (UV-Vis) absorption spectroscopy, in combination with theoretical calculations, in this work. Both the in situ capture and theoretical study of these C71H2 isomers in low-pressure combustion will provide more information regarding carbene additions to other fullerenes or other carbon clusters at high temperatures.

Self-driven carbon atom implantation into fullerene embedding metal-carbon cluster.

Hundreds of members have been synthesized and versatile applications have been promised for endofullerenes (EFs) in the past 30 y. However, the formation mechanism of EFs is still a long-standing puzzle to chemists, especially the mechanism of embedding clusters into charged carbon cages. Here, based on synthesis and structures of two representative vanadium-scandium-carbido/carbide EFs, VSc2C@Ih (7)-C80 and VSc2C2@Ih (7)-C80, a reasonable mechanism-C1 implantation (a carbon atom is implanted into carbon cage)-is proposed to interpret the evolution from VSc2C carbido to VSc2C2 carbide cluster. Supported by theoretical calculations together with crystallographic characterization, the single electron on vanadium (V) in VSc2C@Ih (7)-C80 is proved to facilitate the C1 implantation. While the V=C double bond is identified for VSc2C@Ih (7)-C80, after C1 implantation the distance between V and C atoms in VSc2C2@Ih (7)-C80 falls into the range of single bond lengths as previously shown in typical V-based organometallic complexes. This work exemplifies in situ self-driven implantation of an outer carbon atom into a charged carbon cage, which is different from previous heterogeneous implantation of nonmetal atoms (Group-V or -VIII atoms) driven by high-energy ion bombardment or high-pressure offline, and the proposed C1 implantation mechanism represents a heretofore unknown metal-carbon cluster encapsulation mechanism and can be the fundamental basis for EF family genesis.

Capturing nonclassical C70 with double heptagons in low-pressure combustion.

A double-heptagon-containing C70H6 (dihept-C70H6) was isolated and unambiguously characterized in the soot of low-pressure combustion, which shares the identical heptagonal cage as dihept-C70Cl6 previously identified in the products of carbon arc, and thus represents the first nonclassical fullerene isolable in both carbon arc and combustion.

Surface Re-Engineering of Perovskites with Buckybowls to Boost the Inverted-Type Photovoltaics.

Despite their multifaceted advantages, inverted perovskite solar cells (PSCs) still suffer from lower power conversion efficiencies (PCEs) than their regular counterparts, which is largely due to recombination energy losses (Eloss) that arise from the chemical, physical, and energy level mismatches, especially at the interfaces between perovskites and fullerene electron transport layers (ETLs). To address this problem, we herein introduce an aminium iodide derivative of a buckybowl (aminocorannulene) that is molecularly layered at the perovskite-ETL interface. Strikingly, besides passivating the PbI2-rich perovskite surface, the aminocorannulene enforces a vertical dipole and enhances the surface n-type character that is more compatible with the ETL, thus boosting the electron extraction and transport dynamics and suppressing interfacial Eloss. As a result, the champion PSC achieves an excellent PCE of over 22%, which is superior compared to that of the control device (∼20%). Furthermore, the device stability is significantly enhanced, owing to a lock-and-key-like grip on the mobile iodides by the buckybowls and the resultant increase of the interfacial ion-migration barrier. This work highlights the potential of buckybowls for the multifunctional surface engineering of perovskite toward high-performance and stable PSCs.

Synthesis and Fluorescent Properties of Multi-Functionalized C70 Derivatives of C70(OCH3)10[C(COOEt)2] and C70(OCH3)10[C(COOEt)2]2.

Due to the partially reduced π-conjugation of the fullerene cage, multi-functionalized fullerene derivatives exhibit remarkable fluorescent properties compared to pristine fullerenes, which have high potential for application in organic light-emitting diodes (OLEDs). In this study two multi-functionalized C70 derivatives, C70(OCH3)10[C(COOEt)2] and C70(OCH3)10[C(COOEt)2]2, with excellent fluorescence properties, were designed and synthesized. Compared with C70(OCH3)10 containing a single kind of functional group, both the C70(OCH3)10[C(COOEt)2] and C70(OCH3)10[C(COOEt)2]2 exhibited enhanced fluorescence properties with blue fluorescence emission. The fluorescence quantum yields of the C70(OCH3)10[C(COOEt)2] and C70(OCH3)10[C(COOEt)2]2 were 1.94% and 2.30%, respectively, which were about ten times higher than that of C70(OCH3)10. The theoretical calculations revealed that the multi-functionalization of the C70 increased the S1-T1 energy gap, reducing the intersystem crossing efficiency, resulting in the higher fluorescence quantum yield of the C70 derivatives. The results indicate that multi-functionalization is a viable strategy to improve the fluorescence of fullerene derivatives.

Ambient-pressure synthesis of ethylene glycol catalyzed by C60-buffered Cu/SiO2.

Bulk chemicals such as ethylene glycol (EG) can be industrially synthesized from either ethylene or syngas, but the latter undergoes a bottleneck reaction and requires high hydrogen pressures. We show that fullerene (exemplified by C60) can act as an electron buffer for a copper-silica catalyst (Cu/SiO2). Hydrogenation of dimethyl oxalate over a C60-Cu/SiO2 catalyst at ambient pressure and temperatures of 180° to 190°C had an EG yield of up to 98 ± 1%. In a kilogram-scale reaction, no deactivation of the catalyst was seen after 1000 hours. This mild route for the final step toward EG can be combined with the already-industrialized ambient reaction from syngas to the intermediate of dimethyl oxalate.

EQA/PT scheme to improve the equivalence of enzymatic results between mutual recognition laboratories in Beijing.

BACKGROUND: To utilize the external quality assessment (EQA)/proficiency testing (PT) scheme to evaluate the equivalence of different clinical enzymatic measuring systems in Beijing. METHODS: The Beijing Center for Clinical Laboratory (BCCL) distributed three investigation samples to mutual recognition clinical laboratories in Beijing including alanine aminotransferase (ALT), aspartate aminotransferase (AST), γ-glutamyltransferase (GGT), creatine kinase (CK), and lactate dehydrogenase (LDH). These samples were derived from serum pools with values assigned by the International Federation of Clinical Chemistry and Laboratory Medicine (IFCC) enzymatic reference measurement procedures (RMPs). Each laboratory performed duplicate tests of the samples. Then, the samples at level 1 were used to recalibrate individual measuring systems for repeating the tests. BCCL collected data for evaluation of their analytical quality. RESULTS: Before recalibration, the biases of ALT and AST tests were not traceable to the IFCC RMPs, and the bias pass rates of GGT, CK, and LDH tests were only 51.2%, 55.7%, and 48.6% respectively. After recalibration, the pass rates of ALT, AST, GGT, CK, and LDH increased to 95.1%, 82.9%, 95.1%, 97.1%, and 70.0% respectively. The EQA/PT also showed that after recalibration, more than 95% of laboratories met the optimum level specifications of the biological variation for ALT, AST, GGT, and CK tests and the desirable for LDH tests. CONCLUSION: The enzymatic tests in Beijing need to be further standardized by category 1 or 2 EQA/PT scheme for mutual recognition between clinical laboratories. The criteria of biological variation are more relevant for determining the equivalence of clinical enzymatic tests.

Dissection of bicapped octahedral copper hydride cluster to form two chiral tetrahedral copper hydride cluster series exhibiting auto deracemization and photoluminescence.

Three series of copper hydride clusters [Cu8H6L6]2+ (1), [Cu4HX2L4]+ where X- = Cl- (2a), Br- (2b), I- (2c), N3- (2d) and SCN- (2e), and [Cu4HX3L3] where X- = Br- (3b) and I- (3c) (L = 2-(diphenylphosphino)pyridine, dppy) were synthesized and characterized by single-crystal X-Ray crystallography and standard spectroscopic techniques. The metal core of 1, Cu8, can be described as a bicapped octahedron, while those of 2 and 3 series adopt tetrahedral structures. The hydride positions were deduced from difference electron density maps and corroborated by NMR and DFT calculations. For 1, there are two µ4-H-, one each in the two tetrahedral cavities of the two capping atoms and four µ3-H- on the six triangular faces around the waist of the octahedron. For [Cu4HX2L4]+ and [Cu4HX3L3] series, the single µ4-H- resides in the center of the Cu4 tetrahedron. It was found that these three series of copper clusters are intimately connected and can convert from one to another under specific reaction conditions. Their transformation pathways were investigated in detail. Spontaneous resolution to form optically pure enantiomeric single crystals was observed for [Cu4H(SCN)2L4]+ (2e) and [Cu4HBr3L3] (3b). Photoluminescence was observed for [Cu4HX2L4]+, as well as [Cu4HX3L3] with strong emissions from green to yellow regions.

Retraction: ASIC1a involves acidic microenvironment-induced activation and autophagy of pancreatic stellate cells.

[This retracts the article DOI: 10.1039/C8RA03679A.].

Fullertubes: Cylindrical Carbon with Half-Fullerene End-Caps and Tubular Graphene Belts, Their Chemical Enrichment, Crystallography of Pristine C90-D5h(1) and C100-D5d(1) Fullertubes, and Isolation of C108, C120, C132, and C156 Cages of Unknown Structures.

We report a chemical separation method to isolate fullertubes: a new and soluble allotrope of carbon whose structure merges nanotube, graphene, and fullerene subunits. Fullertubes possess single-walled carbon nanotube belts resembling a rolled graphene midsection, but with half-fullerene end-caps. Unlike nanotubes, fullertubes are reproducible in structure, possess a defined molecular weight, and are soluble in pristine form. The high reactivity of amines with spheroidal fullerene cages enables their removal and allows a facile isolation of C96-D3d(3), C90-D5h(1), and C100-D5d(1) fullertubes. A nonchromatographic step (Stage 1) uses a selective reaction of carbon cages with aminopropanol to permit a highly enriched sample of fullertubes. Spheroidal fullerenes are reacted and removed by attaching water-soluble groups onto their cage surfaces. With this enriched (100-1000 times) fullertube mixture, Stage 2 becomes a simple HPLC collection with a single column. This two-stage separation approach permits fullertubes in scalable quantities. Characterization of purified C100-D5d(1) fullertubes is done with samples isolated in pristine and unfunctionalized form. Surprisingly, C60 and C100-D5d(1) are both purplish in solution. For X-ray crystallographic analysis, we used decapyrrylcorannulene (DPC). Isomerically purified C90 and C100 fullertubes were mixed with DPC to obtain black cocrystals of 2DPC{C90-D5h(1)}·4(toluene) and 2DPC{C100-D5d(1)}·4(toluene), respectively. A serendipitous outcome of this chemical separation approach is the enrichment and purification of several unreported larger carbon species, e.g., C120, C132, and C156. Isolation of these higher cage species represents a significant advance in the unknown experimental arena of C100-C200 structures. Our findings represent seminal experimental evidence for the existence of two mathematically predicted families of fullertubes: one family with an axial hexagon with the other series based on an axial pentagon ring. Fullertubes have been predicted theoretically, and herein is their experimental evidence, isolation, and initial characterization.

Hybrid Fullerene-Based Electron Transport Layers Improving the Thermal Stability of Perovskite Solar Cells.

The structure-dependent thermal stability of fullerene electron transport layers (ETLs) and its impact on device stability have been underrated for years. Based on cocrystallographic understanding, herein, we develop a thermally stable ETL comprising a hybrid layer of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) and [6,6]-phenyl-C61-propylbenzene (PCPB). By tuning the weight ratios of PCBM and PCPB to influence the noncovalent intermolecular interactions and packing of fullerene derivatives, we obtained a champion device based on the 20PCPB (20 wt % addition of PCPB into the mixture of PCBM/PCPB) ETL and excellent thermal stability of 500 h under 85 °C thermal aging in a N2 atmosphere in the dark. The present work exemplifies that cocrystallography can be a precise tool to probe the interaction and aggregation of fullerene derivatives in ETLs, and mixed fullerene derivatives can be sought as promising ETLs to enhance the long-term stability of perovskite solar cells under high-temperature working environments.

[Professor ZUO Chang-bo's experience in treatment of dysmenorrhea with "three-regulation and one-harmonization" therapy of acupuncture].

The clinical experience of professor ZUO Chang-bo in treatment of dysmenorrhea with "three-regulation and one-harmonization" therapy of acupuncture was introduced. Professor ZUO Chang-bo invented a needling technique for "three-regulation and one-harmonization", meaning qi regulation, blood regulation and regulation of meridian tendon region as well as the spirit (shen) harmonization. In qi regulation, the extreme fine needles are used to regulate qi movement of the whole function with the coordination of respiration and the corresponding acupoint prescriptions. In blood regulation, the special small bleeding device is selected and the bloodletting theory is improved for bloodletting at the specific stagnant site. In the regulation of meridian tendon region, a special sterile injection needle is chosen to release the cord-like mass. The spirit harmonization is exerted in combination with qi regulation. During acupuncture, the spirit of both the clinical practitioner and the patient should be in a harmonized spirit condition, coordinated with respiration regulation. In the treatment with acupuncture therapy of "three-regulation and one-harmonization" for dysmenorrhea, bloodletting therapy is used firstly to remove stasis, secondly, the "releasing cord-like mass" technique is followed to regulate meridian tendon region, finally, the fine needling technique is adopted to regulate qi and harmonize spirit. The clinical effect is definite in clinical practice.

Rational synthesis of an atomically precise carboncone under mild conditions.

Carboncones, a special family of all-carbon allotropes, are predicted to have unique properties that distinguish them from fullerenes, carbon nanotubes, and graphenes. Owing to the absence of methods to synthesize atomically well-defined carboncones, however, experimental insight into the nature of pure carboncones has been inaccessible. Herein, we describe a facile synthesis of an atomically well-defined carboncone[1,2] (C70H20) and its soluble penta-mesityl derivative. Identified by x-ray crystallography, the carbon skeleton is a carboncone with the largest possible apex angle. Much of the structural strain is overcome in the final step of converting the bowl-shaped precursor into the rigid carboncone under mild reaction conditions. This work provides a research opportunity for investigations of atomically precise single-layered carboncones having even higher cone walls and/or smaller apex angles.

General One-step Synthesis of Symmetrical or Unsymmetrical 1,4-Di(organo)fullerenes from Organo(hydro)fullerenes through Direct Oxidative Arylation.

A general one-step synthesis of symmetrical or unsymmetrical 1,4-di(organo)fullerenes from organo(hydro)fullerenes (RC60H) is realized by direct oxidative arylation. The new combination of catalytic trifluoromethanesulfonic acid (TfOH) and stoichiometric o-chloranil is the first to be used to directly generate an R-C60+ intermediate from common RC60H. Unexpectedly, the in situ generated R-C60+ intermediate is shown to be quite stable in whole 13C NMR spectroscopy characterization in the absence of cation quenching reagents. Because the direct oxidation of common RC60H to form the corresponding R-C60+ has never been realized, the present combination of TfOH and o-chloranil solves the challenges associated with the formation of stable RC60+ cations from common RC60H without any coordination of an R group.

Double Negatively Curved C70 Growth through a Heptagon-Involving Pathway.

All previously reported C70 isomers have positive curvature and contain 12 pentagons in addition to hexagons. Herein, we report a new C70 species with two negatively curved heptagon moieties and 14 pentagons. This unconventional heptafullerene[70] containing two symmetric heptagons, referred to as dihept-C70 , grows in the carbon arc by a theoretically supported pathway in which the carbon cluster of a previously reported C66 species undergoes successive C2 insertion via a known heptafullerene[68] intermediate with low energy barriers. As identified by X-ray crystallography, the occurrence of heptagons facilitates a reduction in the angle of the π-orbital axis vector in the fused pentagons to stabilize dihept-C70 . Chlorination at the intersection of a heptagon and two adjacent pentagons can greatly enlarge the HOMO-LUMO gap, which makes dihept-C70 Cl6 isolable by chromatography. The synthesis of dihept-C70 Cl6 offers precious clues with respect to the fullerene formation mechanism in the carbon-clustering process.