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Abstract The efficient purification of cyclohexane is critical, serving as an essential feedstock to produce resins, nylon fibers and pharmaceutical intermediates. However, efficient purification remains a challenging task due to the similarity of cyclohexane and benzene molecules in terms of size and boiling point. In this work, we reported on the synergy of pore size and silanols inside an -SVR-type zeolite for the efficient production of ultrapure cyclohexane (benzene

Abstract Morchella spongiola is a highly prized mushroom for its delicious flavor and medical value and is one of the most flourishing, representative, and dominant macrofungi in the Qilian Mountains of the Qinghai-Tibet Plateau subkingdoms (QTPs). However, the understanding of M. spongiola remains largely unknown, and its taxonomy is ambiguous. In this study, we redescribed a unique species of M. spongiola, i.e., micromorphology, molecular data, genomics, and comparative genomics, and the historical biogeography of M. spongiola were estimated for 182 single-copy homologous genes. A high-quality chromosome-level reference genome of M. spongiola M12-10 was obtained by combining PacBio HiFi data and Illumina sequencing technologies; it was approximately 57.1 Mb (contig N50 of 18.14 Mb) and contained 9775 protein-coding genes. Comparative genome analysis revealed considerable conservation and unique characteristics between M. spongiola M12-10 and 32 other Morchella species. Molecular phylogenetic analysis indicated that M. spongiola M12-10 is similar to the M. prava/Mes-7 present in sandy soil near rivers, differentiating from black morels ~ 43.06 Mya (million years ago), and diverged from M. parva/Mes-7 at approximately 12.85 Mya (in the Miocene epoch), which is closely related to the geological activities in the QTPs (in the Neogene). Therefore, M. spongiola is a unique species rather than a synonym of M. vulgaris/Mes-5, which has a distinctive grey-brown sponge-like ascomata. This genome of M. spongiola M12-10 is the first published genome sequence of the species in the genus Morchella from the QTPs, which could aid future studies on functional gene identification, germplasm resource management, and molecular breeding efforts, as well as evolutionary studies on the Morchella taxon in the QTPs.

Abstract Spin-orbit coupling in noncentrosymmetric crystals leads to spin-momentum locking – a directional relationship between an electron’s spin angular momentum and its linear momentum. Isotropic orthogonal Rashba spin-momentum locking has been studied for decades, while its counterpart, isotropic parallel Weyl spin-momentum locking has remained elusive in experiments. Theory predicts that Weyl spin-momentum locking can only be realized in structurally chiral cubic crystals in the vicinity of Kramers-Weyl or multifold fermions. Here, we use spin- and angle-resolved photoemission spectroscopy to evidence Weyl spin-momentum locking of multifold fermions in the chiral topological semimetal PtGa. We find that the electron spin of the Fermi arc surface states is orthogonal to their Fermi surface contour for momenta close to the projection of the bulk multifold fermion at the Γ point, which is consistent with Weyl spin-momentum locking of the latter. The direct measurement of the bulk spin texture of the multifold fermion at the R point also displays Weyl spin-momentum locking. The discovery of Weyl spin-momentum locking may lead to energy-efficient memory devices and Josephson diodes based on chiral topological semimetals.

Abstract In the realm of photovoltaics, organometallic hybridized perovskite solar cells (PSCs) stand out as promising contenders for achieving high‐efficiency photoelectric conversion, owing to their remarkable performance attributes. Nevertheless, defects within the perovskite layer, especially at the perovskite grain boundaries and surface, have a substantial impact on both the overall photoelectric performance and long‐term operational stability of PSCs. To mitigate this challenge, we propose a method for water‐induced condensation polymerization of small molecules involving the incorporation of 1,3‐phenylene diisocyanate (1,3‐PDI) into the perovskite film using an antisolvent technique. Subsequent to this step, the introduction of water triggers the polymerization of [P(1,3‐PDI)], thereby facilitating the in situ passivation of uncoordinated lead defects inherent in the perovskite film. This passivation process demonstrates a notable enhancement in both the efficiency and stability of PSCs. This approach has led to the attainment of a noteworthy power conversion efficiency (PCE) of 24.66% in inverted PSCs. Furthermore, based on the P(1,3‐PDI) modification, these devices maintain 90.15% of their initial efficiency after 5000 h of storage under ambient conditions of 25°C and 50 ± 5% relative humidity. Additionally, even after maximum power point tracking for 1000 h, the PSCs modified with P(1,3‐PDI) sustain 82.05% of the initial PCE. Small molecules can rationally manipulate water and turn harm into benefit, providing new directions and methods for improving the efficiency and stability of PSCs.

Objective: The prognosis of malignant tumors with peritoneal metastases and cancerous ascites has generally been poor, with limited treatment options. The PRaG regimen, which comprised of hypofractionated radiotherapy, programmed cell death-1 (PD-1) inhibitor, and granulocyte-macrophage colony-stimulating factor (GM-CSF), showed a survival advantage in patients with advanced solid tumors who failed at least the first line of standard systemic treatment. Intraperitoneal infusion of PD-1 inhibitors may be a novel therapeutic strategy for managing malignant ascites. Integrating the PRaG regimen with intraperitoneal perfusion of a PD-1 inhibitor might control malignant ascites and provide further survival benefits in these patients. This proposed study aims to investigate the safety and efficacy of intraperitoneal infusion of serplulimab in combination with the PRaG regimen in patients with simultaneous advanced solid tumors and cancerous ascites who fail at least the first-line treatment. Methods: This proposed study is a prospective, single-arm, open-label, multicenter clinical trial. All eligible patients will receive 2 cycles of intensive treatment, a combination of PRaG regimen with an intraperitoneal infusion of PD-1 inhibitor. The patients who are beneficially treated with intensive treatment will receive consolidation treatment every 2 weeks until ascites disappear, disease progression occurs, intolerable toxicity occurs, or for up to 1 year. Phase I of this study will be conducted using a modified 3 + 3 design. The dose of intraperitoneal infusion of PD-1 inhibitor for phase II will be determined according to dose-limiting toxicity evaluation in the phase I study. Conclusion: This prospective, open-label, multicenter study will potentially lead to intraperitoneal perfusion of a PD-1 inhibitor being a new strategy for malignant ascites patients and provide a meaningful efficacy and safety of the combination of PRaG regimen with an intraperitoneal infusion of PD-1 inhibitor for these patients.

Kobresia humilis is a major species in the alpine meadow communities of the Qinghai-Tibet Plateau (QTP); it plays a crucial role in maintaining the ecological balance of these meadows. Nevertheless, little is known about the rhizosphere fungi associated with K. humilis on the Qinghai Tibet Plateau. In this study, we used Illumina Miseq to investigate the fungal diversity, community structure, and ecological types in the root and rhizosphere soil of K. humilis across eight areas on the QTP and analyzed the correlation between rhizosphere fungi of K. humilis and environmental factors. A total of 19,423 and 25,101 operational taxonomic units (OTUs) were obtained from the roots and rhizosphere soil of K. humilis. These were classified into seven phyla, 25 classes, 68 orders, 138 families, and 316 genera in the roots, and nine phyla, 31 classes, 76 orders, 152 families, and 407 genera in the rhizosphere soil. There were 435 and 415 core OTUs identified in root and rhizosphere soil, respectively, which were categorized into 68 and 59 genera, respectively, with 25 shared genera. Among them, the genera with a relative abundance >1% included Mortierella, Microscypha, Floccularia, Cistella, Gibberella, and Pilidium. Compared with the rhizosphere soil, the roots showed five differing fungal community characteristics, as well as differences in ecological type, and in the main influencing environmental factors. First, the diversity, abundance, and total number of OTUs in the rhizosphere soil of K. humilis were higher than for the endophytic fungi in the roots by 11.85%, 9.85%, and 22.62%, respectively. The composition and diversity of fungal communities also differed between the eight areas. Second, although saprotroph-symbiotrophs were the main ecological types in both roots and rhizosphere soil; there were 62.62% fewer pathotrophs in roots compared to the rhizosphere soil. Thirdly, at the higher altitude sites (3,900–4,410 m), the proportion of pathotroph fungi in K. humilis was found to be lower than at the lower altitude sites (3,200–3,690 m). Fourthly, metacommunity-scale network analysis showed that during the long-term evolutionary process, ZK (EICZK = 1) and HY (EICHY = 1) were critical sites for development of the fungal community structure in the roots and rhizosphere soil of K. humilis, respectively. Fifthly, canonical correspondence analysis (CCA) showed that key driving factors in relation to the fungal community were longitude (R2 = 0.5410) for the root community and pH (R2 = 0.5226) for the rhizosphere soil community. In summary, these results show that K. humilis fungal communities are significantly different in the root and rhizosphere soil and at the eight areas investigated, indicating that roots select for specific microorganisms in the soil. This is the first time that the fungal distribution of K. humilis on the QTP in relation to long-term evolutionary processes has been investigated. These findings are critical for determining the effects of environmental variables on K. humilis fungal communities and could be valuable when developing guidance for ecological restoration and sustainable utilization of the biological resources of the QTP.

Encapsulation engineering is an effective strategy to improve the stability of perovskite solar cells. Here, authors design and synthesize self-crosslinked fluorosilicone polymer gel for nondestructive encapsulation at room temperature, and maintain 98% of efficiency after 1000 h in damp heat test.

Small-molecule ionic liquids (ILs) are frequently employed as efficient bulk phase modifiers for perovskite materials. However, their inherent characteristics, such as high volatility and ion migration properties, pose challenges in addressing the stability issues associated with perovskite solar cells (PSCs). In this study, we design a poly(IL) with multiple active sites, named poly[4-styrenesulfonyl(trifluoromethylsulfonyl)imide]pyridine (P[STFSI][PPyri]), as an efficient additive of perovskite materials. The S=O in the sulfonyl group chelates with uncoordinated Pb2+ and forms hydrogen bonds with the organic cations in the perovskite, suppressing the volatilization of the organic cations. The N+ in pyridine can fix halide ions through electrostatic interaction with I− and Br− ions to prevent halide ion migration. P[STFSI][PPyri] demonstrates the ability to passivate defects and suppress nonradiative recombination in PSCs. Additionally, it facilitates the fixation of organic and halide ions, thereby enhancing the device’s stability and photoelectric performance. Consequently, the introduction of P[STFSI][PPyri] as a dopant in the devices resulted in an excellent efficiency of 24.62%, demonstrating outstanding long-term operational stability, with the encapsulated device maintaining 87.6% of its initial efficiency even after 1500 h of continuous maximum power point tracking. This strategy highlights the promising potential of poly(IL) as an effective additive for PSCs, providing a combination of high performance and stability.

Patients with chemo-refractory metastatic colorectal cancer (mCRC) have poor prognoses. The application of programmed cell death protein 1 (PD-1)/programmed cell death ligand 1 (PD-L1) inhibitors encouragingly improved the survival of mCRC patients with microsatellite instability-high (MSI-H)/mismatch repair-deficient (dMMR). Unfortunately, it was ineffective for mCRC with microsatellite-stable (MSS)/proficient mismatch repair (pMMR), which accounted for 95% of mCRC. Radiotherapy can promote local control by directly killing tumor cells and inducing positive immune activities, which might help synergistically with immunotherapy. We present the report of an advanced MSS/pMMR mCRC patient who had progressive disease (PD) after first-line chemotherapy, palliative surgery and second-line chemotherapy combined with targeted therapy. Then the patient received the therapy of PD-1 inhibitor combined with radiotherapy and granulocyte-macrophage colony-stimulating factor (GM-CSF). According to Response Evaluation Criteria in Solid Tumors version 1.1 (RECIST1.1), the patient showed a complete response (CR) after triple-combined therapy with progression-free survival (PFS) for more than 2 years so far. The patient had no other significant adverse reactions except for fatigue (Grade 1). The triple-combination therapy provided a promising strategy for metastatic chemo-refractory MSS/pMMR mCRC patients.

IntroductionMorchella has become a research hotspot because of its wide distribution, delicious taste, and phenotypic plasticity. The Qinghai-Tibet Plateau subkingdoms (QTPs) are known as the cradle of Ice age biodiversity. However, the diversity of Morchella in the QTPs has been poorly investigated, especially in phylogenetic diversity, origin, and biogeography.MethodsThe genealogical concordance phylogenetic species recognition (GCPSR, based on Bayesian evolutionary analysis using sequences from the internal transcribed spacer (ITS), nuclear large subunit rDNA (nrLSU), translation elongation factor 1-α (EF1-α), and the largest and second largest subunits of RNA polymerase II (RPB1 and RPB2)), differentiation time estimation, and ancestral region reconstruction were used to infer Morchella’s phylogenetic relationships and historical biogeography in the QTPs.ResultsFirstly, a total of 18 Morchella phylogenetic species are recognized in the QTPs, including 10 Elata clades and 8 Esculenta clades of 216 individuals Secondly, the divergences of the 18 phylogenetic species were 50.24–4.20 Mya (Eocene-Pliocene), which was closely related to the geological activities in the QTPs. Furthermore, the ancestor of Morchella probably originated in the Northern regions (Qilian Shan, Elata cade) and southwestern regions (Shangri-La, Esculenta clade) of QTPs and might have migrated from North America (Rufobrunnea clade) via Beringian Land Bridge (BLB) and Long-Distance Dispersal (LDD) expansions during the Late Cretaceous. Moreover, as the cradle of species origin and diversity, the fungi species in the QTPs have spread out and diffused to Eurasia and South Africa starting in the Paleogene Period.ConclusionThis is the first report that Esculenta and Elata clade of Morchella originated from the QTPs because of orogenic, and rapid differentiation of fungi is strongly linked to geological uplift movement and refuge in marginal areas of the QTPs. Our findings contribute to increasing the diversity of Morchella and offer more evidence for the origin theory of the QTPs.

The presence of numerous trap states on the perovskite surface severely affects the performance of inorganic CsPbI2Br perovskite solar cells. Surface modification has been proven to be an effective strategy to passivate the surface trap states of CsPbI2Br perovskite. However, most modifiers behave high volatility and insulation, not enough to further develop the CsPbI2Br solar cells. Herein, an ionic liquid of 1-viny-3-propionate ethyl imidazolium chloride ([PEVIM]Cl) is applied to modify the CsPbI2Br film surface, yielding a compact film with enhanced crystallinity. The surface trap states of CsPbI2Br film are effectively passivated via the interaction between carbonyl group of [PEVIM]Cl and uncoordinated metal cations of CsPbI2Br perovskite, leading to charge recombination suppression and charge transport enhancement. Consequently, the power conversion efficiency (PCE) of [PEVIM]Cl modified CsPbI2Br device is obviously enhanced from 12.49% to 14.19% with an improved open-circuit voltage of 1.160 V. Moreover, the non-encapsulated device presents excellent thermal stability, still maintaining 91% PCE when heated at 85 °C in nitrogen atmosphere for 360 h. Meanwhile, the non-encapsulated device degrades only 11% PCE after stored at 50% relative humidity for 960 h. This simple and efficient approach provides a promising direction to fabricate high-efficiency and stable inorganic perovskite devices.

The wax esters are important cuticular wax composition that cover the outer surface of plant organs and play a critical role in protection and energy metabolism. Wax ester synthesis in plant is catalyzed by a bifunctional wax ester synthase/acyl-CoA: diacylglycerol acyltransferase (WSD). Sunflower (Helianthus annuus L.) is an important oil crop in the world; however, little is known about WSD in sunflower. In this study, we identified and performed a functional analysis of twelve HaWSD genes from sunflower genome. Tissue-specific expression revealed that 12 HaWSD genes were differentially expressed in various organs and tissues of sunflower, except seeds. HaWSD genes were highly induced by salinity, drought, cold, and abscisic acid (ABA) in sunflower. To ascertain their function, HaWSD9, with highly expressed levels in stems and leaves, was cloned and expressed in a yeast mutant defective in triacylglycerol (TAG) biosynthesis. HaWSD9 complemented the phenotype by producing wax ester but not TAG in vivo, indicating that it functions as a wax ester synthase. Subcellular localization analysis indicated that HaWSD9 was located in the endoplasmic reticulum (ER). Heterologous introduction of HaWSD9 into Arabidopsis wsd1 mutant exhibited increased epicuticular wax crystals and cuticular wax contents on the stems. As compared with the wsd1 mutant, HaWSD9 overexpressing transgenic Arabidopsis showed less cuticle permeability, chlorophyll leaching and water loss rate. Further analysis showed that the HaWSD9 transgenics enhanced tolerance to ABA, mannitol, drought and salinity, and maintained higher leaf relative water content (RWC) than the wsd1 mutant under drought stress, suggesting that HaWSD9 play an important physiological role in stress response as well as wax synthase. These results contribute to understanding the function of HaWSD genes in wax ester synthesis and stress tolerance in sunflower.

Patients with metastatic cancer refractory to standard systemic therapies have a poor prognosis and few therapeutic options. Radiotherapy can shape the tumor microenvironment (TME) by inducing immunogenic cell death and promoting tumor recognition by natural killer cells and T lymphocytes. Granulocyte macrophage-colony stimulating factor (GM-CSF) was known to promote dendric cell maturation and function, and might also induce the macrophage polarization with anti-tumor capabilities. A phase II trial (ChiCTR1900026175) was conducted to assess the clinical efficacy and safety of radiotherapy, PD-1 inhibitor and GM-CSF (PRaG regimen). This trial was registered at http://www.chictr.org.cn/index.aspx. A PRaG cycle consisted of 3 fractions of 5 or 8 Gy delivered for one metastatic lesion from day 1, followed by 200 μg subcutaneous injection of GM-CSF once daily for 2 weeks, and intravenous infusion of PD-1 inhibitor once within one week after completion of radiotherapy. The PRaG regimen was repeated every 21 days for at least two cycles. Once the PRaG therapy was completed, the patient continued PD-1 inhibitor monotherapy until confirmed disease progression or unacceptable toxicity. The primary endpoint was objective response rate (ORR). A total of 54 patients were enrolled with a median follow-up time of 16.4 months. The ORR was 16.7%, and the disease control rate was 46.3% in intent-to-treat patients. Median progression-free survival was 4.0 months (95% confidence interval [CI], 3.3 to 4.8), and median overall survival was 10.5 months (95% CI, 8.7 to 12.2). Grade 3 treatment-related adverse events occurred in five patients (10.0%) and grade 4 in one patient (2.0%). Therefore, the PRaG regimen was well tolerated with acceptable toxicity and may represent a promising salvage treatment for patients with chemotherapy-refractory solid tumors. It is likely that PRaG acts via heating upthe TME with radiotherapy and GM-CSF, which was further boosted by PD-1 inhibitors.

In order to study the hysteretic behavior and restoring force model of cold-formed thin-walled steel (CFTWS) lipped channel beam-column, a finite element analysis (FEA) model considering the material and geometric nonlinearity and the influence of the initial geometric imperfection under cyclic loading was established by ABAQUS software. Based on the verified FEA model, the hysteretic behavior of CFTWS lipped channel beam-column members with different influencing factors was analyzed by parameterization. The effects of width-to-thickness ratio, axial compression ratio and slenderness ratio on ductility, energy dissipation capacity and stiffness degradation were studied. Based on the results of parameter analysis and the theoretical and regression analysis, the calculation formula of each characteristic point of the trilinear skeleton curve of beam-column member was proposed. Based on the hysteresis curve analysis of beam-column member, the simplified restoring force model (SRFM) of CFTWS lipped channel beam-column was established according to different hysteresis rules for the different buckling modes. The results showed that the SRFM under different buckling modes was in good agreement with the hysteretic curve of FEA, which can better indicate the hysteretic behavior of the member. The proposed SRFM was accurate and applicable, and can provide a fundament for the seismic analysis of the CFTWS lipped channel beam-column.

Total flavonoids of Rhizoma drynariae (TFRD), a Chinese medicine, is widely used in the treatment of fracture, bone defect, osteoporosis and other orthopedic diseases, and has achieved good effects. Purpose of this trial was to explore efficacy of TFRD on bone graft’s mineralization and osteoblasts’ differentiation in Masquelet induced membrane technique in rats. Forty male Sprague-Dawley rats were randomly divided into high dose group (H-TFRD), middle dose group (M-TFRD), low dose group (L-TFRD) and control group (control). The critical size bone defect model of rats was established with 10 rats in each group. Polymethyl methacrylate (PMMA) spacer was implanted into the defect of right femur in rats. After the formation of the induced membrane, autogenous bone was implanted into the induced membrane. After 12 weeks of bone graft, bone tissues in the area of bone graft were examined by X-ray, Micro-CT, hematoxylin-eosin (HE) and Masson trichrome staining to evaluate the growth of the bone graft. The β-catenin, c-myc, COL1A1, BMP-2 and OPN in bone graft were quantitatively analyzed by Western blot and Immunohistostaining. Osteoblasts were cultured in the medium containing TFRD. Cell Counting Kit-8 (CCK-8) method, Alkaline phosphatase (ALP) and Alizarin Red S (ARS) staining, Western blot, RT-PCR and other methods were used to detect the effects of TFRD on the proliferation of osteoblasts and the regulation of Wnt/β-catenin signaling pathway. In vivo experiments showed that the growth and mineralization of bone graft in TFRD group was better. Moreover, the expression of Wnt/β-catenin and osteogenesis-related proteins in bone tissue of TFRD group was more than that in other groups. In vitro experiments indicated that osteoblasts proliferated faster, activity of ALP was higher, number of mineralized nodules and proteins related to osteogenesis were more in TFRD group. But blocking Wnt/β-catenin signaling pathway could limit these effects. Therefore, TFRD could promote mineralization of bone graft and differentiation of osteoblasts in a dose-dependent manner during growing period of the bone graft of induced membrane technique, which is partly related to the activation of Wnt/β-catenin signaling pathway.

A kind of Y-bearing ferritic/martensitic fuel cladding tube with qualified dimensions, acceptable mechanical properties as well as good flattening and flaring performance was manufactured recently by our group. In this paper, to improve and further evaluate its oxidation resistance, the cladding tube was aluminized firstly and then subjected to high temperature steam oxidation at 1200 °C for 8 h. The results indicated that aluminizing coating with gradient content of Al was prepared on the tube successfully. And the matrix microstructure was transformed from tempered martensite into ferrite during aluminizing. Weight gains after high temperature steam oxidation were 72.7 and 1.48 mg cm ^−2 for the bare and aluminized tubes, respectively. The latter one exhibited better oxidation resistance due to the generated dense aluminum oxide film. Meanwhile, Kirkendall pores were formed near oxidation surface and should be eliminated for the real application of the aluminized tube in the future.