Influence of Interlayer Cation Ordering on Na Transport in P2-Type Na0.67-xLiy Ni0.33-zMn0.67+zO2 for Sodium-Ion Batteries.

P2-type Na2/3Ni1/3Mn2/3O2 (PNNMO) has been extensively studied because of its desirable electrochemical properties as a positive electrode for sodium-ion batteries. PNNMO exhibits intralayer transition-metal ordering of Ni and Mn and intralayer Na+/vacancy ordering. The Na+/vacancy ordering is often considered a major impediment to fast Na+ transport and can be affected by transition-metal ordering. We show by neutron/X-ray diffraction and density functional theory (DFT) calculations that Li doping (Na2/3Li0.05Ni1/3Mn2/3O2, LFN5) promotes ABC-type interplanar Ni/Mn ordering without disrupting the Na+/vacancy ordering and creates low-energy Li-Mn-coordinated diffusion pathways. A structure model is developed to quantitatively identify both the intralayer cation mixing and interlayer cationic stacking fault densities. Quasielastic neutron scattering reveals that the Na+ diffusivity in LFN5 is enhanced by an order of magnitude over PNNMO, increasing its capacity at a high current. Na2/3Ni1/4Mn3/4O2 (NM13) lacks Na+/vacancy ordering but has diffusivity comparable to that of LFN5. However, NM13 has the smallest capacity at a high current. The high site energy of Mn-Mn-coordinated Na compared to that of Ni-Mn and higher density of Mn-Mn-coordinated Na+ sites in NM13 disrupts the connectivity of low-energy Ni-Mn-coordinated diffusion pathways. These results suggest that the interlayer ordering can be tuned through the control of composition, which has an equal or greater impact on Na+ diffusion than the Na+/vacancy ordering.

Breaking barriers: Stereotactic ablative proton and photon radiation therapy for renal cell carcinoma with extensive metastases: A case report.

Patients with advanced renal cancer (RCC) often have limited success with systemic therapy due to tumor heterogeneity. However, stereotactic ablative radiotherapy (SABR) has been shown to have a beneficial therapeutic effect for oligometastatic disease when used early. Despite this, current guidelines recommend the use of tyrosine kinase inhibitors (TKIs) as the first-line therapeutic agent for patients with recurrent or metastatic kidney cancer. Additionally, there is limited data on the combination of systemic treatment and SABR for extensive metastatic RCC due to concerns about high toxicity. Proton therapy offers a promising treatment option as it emits energy at a specific depth, generating high target doses while minimizing damage to normal tissue. This allows for precise treatment of various tumor lesions. In this case report, we describe a high-risk 65-year-old male with extensive pleural and thoracic lymph node metastases and 2 bone metastases of clear cell renal cancer. While the targeted therapy and immunotherapy effectively treated the bone metastases, it was not effective in treating the chest metastases, including the pleural and lymph node metastases. Thus, the patient received full-coverage radiotherapy with photon for primary renal tumor and intensity-modulated proton therapy (IMPT) for thoracic metastases. The patient showed no evidence of disease for 1 year after the initial radiotherapy, and no severe SABR-related adverse effects were observed until now. The combination of targeted therapy and immunotherapy with full-coverage radiotherapy may be a promising treatment option for selected patients with extensive metastatic renal cancer, especially as proton therapy allows for more precise control of the beam and minimal damage to normal tissue. This case has motivated us to investigate the potential advantages of administering proton therapy concurrently with systemic therapy in the management of metastatic renal cell carcinoma patients.

Coexistence of ferromagnetism and charge density waves in monolayer LaBr2.

Charge density waves (CDWs), a common phenomenon of periodic lattice distortions, often suppress ferromagnetism in two-dimensional (2D) materials, hindering their magnetic applications. Here, we report a novel CDW that generates 2D ferromagnetism instead of suppressing it, through the formation of interstitial anionic electrons as the charge modulation mechanism. Via first-principles calculations and a low-energy effective model, we find that the highly symmetrical monolayer LaBr2 undergoes a 2 × 1 CDW transition to a magnetic semiconducting T' phase. Concurrently, the delocalized 5d1 electrons of La in LaBr2 redistribute and accumulate within the interstitial space in the T' phase, forming anionic electrons, also known as 2D electride or electrene. The strongly localized nature of anionic electrons promotes a Mott insulating state and full spin-polarization, while the overlap of their extended tails yields ferromagnetic direct exchange between them. Such transition introduces a new magnetic form of CDWs, offering promising opportunities for exploring novel fundamental physics and advanced spintronics applications.

Interplay of the charge density wave transition with topological and superconducting properties.

Exotic phenomena due to the interplay of different quantum orders have been observed and the study of these phenomena has emerged as a new frontier in condensed matter research, especially in the two-dimensional limit. Here, we report the coexistence of charge density waves (CDWs), superconductivity, and nontrivial topology in monolayer 1H-MSe2 (M = Nb, Ta) triggered by momentum-dependent electron-phonon coupling through electron doping. At a critical electron doping concentration, new 2 × 2 CDW phases emerge with nontrivial topology, Dirac cones, and van Hove singularities. Interestingly, these 2 × 2 CDW phases are also superconducting. Our findings not only reveal a route towards realizing nontrivial electronic characters by CDW engineering, but also provide an exciting platform to modulate different quantum states at the confluence of CDWs, superconductivity, nontrivial topology, and electron-phonon coupling.

Unexpectedly high thermoelectric performance of anisotropic Zr2Cl4monolayer.

Recently, the Hf2Cl4-type materials as functional materials have attracted broad interest because of their enormous potential in thermoelectric (TE) applications. However, relevant investigations are still scarce up to now. To explore the Hf2Cl4-type materials with excellent TE properties, we focus on the TE properties of Zr2Cl4monolayer and calculate the TE parameters based on first-principles calculations and Boltzmann transport equation. Although, as compared to some typical TE materials, it exhibits better heat transport and thus higher lattice thermal conductivity, the figure of merits (ZT) of both p-type and n-type Zr2Cl4reach an unexpectedly high value of 3.90 and 3.60, respectively, owing to the larger electrical conductivity and higher power factor. Additionally, owing to the prominent difference in electrical conductivity between thex- andy-direction, strong anisotropy inZTvalues is observed. Our study reveals that both n-type and p-type Zr2Cl4monolayers have the potential for future TE applications.

Probing the Origin of Chiral Charge Density Waves in the Two-Dimensional Limits.

Chirality generates spontaneous symmetry breaking and profoundly influences the topology, charge, and spin orders of materials. The chiral charge density wave (CDW) exhibits macroscopic chirality in the achiral crystal during the spontaneous electronic phase transitions. However, the mechanism of chiral CDW formation is shrouded in controversy. In this work, we report that two-dimensional H-phase TaS2 synthesized by molecular-beam epitaxy (MBE) shows a predominantly chiral CDW phase. Scanning tunneling microscopy (STM) imaging of the CDW reconstruction spots reveals a clockwise or anticlockwise intensity variation along the STM-imaged spots. First-principles calculations further show that the rotational symmetry of the momentum-dependent electron-phonon coupling is broken, giving rise to chirality. Our work provides new insights into the physical origin of the chiral charge-ordered states, shedding light on a general ordering rule in chiral CDWs.

Giant g-factor in Self-Intercalated 2D TaS2.

Central to the application of spintronic devices is the ability to manipulate spins by electric and magnetic fields, which relies on a large Landé g-factor. The self-intercalation of layered transitional metal dichalcogenides with native metal atoms can serve as a new strategy to enhance the g-factor by inducing ferromagnetic instability in the system via interlayer charge transfer. Here, scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS) are performed to extract the g-factor and characterize the electronic structure of the self-intercalated phase of 2H-TaS2 . In Ta7 S12 , a sharp density of states (DOS) peak due to the Ta intercalant appears at the Fermi level, which satisfies the Stoner criteria for spontaneous ferromagnetism, leading to spin split states. The DOS peak shows sensitivity to magnetic field up to 1.85 mV T-1 , equivalent to an effective g-factor of ≈77. This work establishes self-intercalation as an approach for tuning the g-factor.

Redefine the Role of Proton Beam Therapy for the Locally-Advanced Non-Small Cell Lung Cancer Assisting the Reduction of Acute Hematologic Toxicity.

Purpose: To investigate the potential clinical benefit of utilizing intensity-modulated proton therapy (IMPT) to reduce acute hematologic toxicity for locally advanced non-small cell lung cancer (LA-NSCLC) patients and explore the feasibility of a model-based patient selection approach via the normal tissue complication probability (NTCP). Methods: Twenty patients with LA-NSCLC were retrospectively selected. Volumetric modulated arc photon therapy (VMAT) and IMPT plans were generated with a prescription dose of 60 Gy in 30 fractions. A wide range of cases with varied tumor size, location, stations of metastatic lymph nodes were selected to represent the general cancer group. Contouring and treatment planning followed RTOG-1308 protocol. Doses to thoracic vertebral bodies (TVB) and other organ at risks were compared. Risk of grade ≥ 3 acute hematologic toxicity (HT3+) were calculated based on the NTCP model, and patients with a reduction on NTCP of HT3+ from VMAT to IMPT (△NTCP_HT3+) ≥ 10% were considered to 'significantly benefit from proton therapy.' Results: Compared to VMAT, IMPT significantly reduced the dose to the TVB, the lung, the heart, the esophagus and the spinal cord. Tumor distance to TVB was significantly associated with △NTCP _HT3+ ≥ 10%. For the patients with tumor distance ≤ 0.7 cm to TVB, the absolute reduction of dose (mean, V30 and V40) to TVB was significantly lower than that in patients with tumor distance > 0.7 cm. Conclusion: IMPT decreased the probability of HT3+ compared to VMAT by reducing the dose to the TVB in LA-NSCLC patients. Patients with tumor distance to TVB less than 0.7 cm are likely to benefit most from proton over photon therapy.

Real-Space Investigation of the Multiple Halogen Bonds by Ultrahigh-Resolution Scanning Probe Microscopy.

The chemical bond is of central interest in chemistry, and it is of significance to study the nature of intermolecular bonds in real-space. Herein, non-contact atomic force microscopy (nc-AFM) and low-temperature scanning tunneling microscopy (LT-STM) are employed to acquire real-space atomic information of molecular clusters, i.e., monomer, dimer, trimer, tetramer, formed on Au(111). The formation of the various molecular clusters is due to the diversity of halogen bonds. DFT calculation also suggests the formation of three distinct halogen bonds among the molecular clusters, which originates from the noncovalent interactions of Br-atoms with the positive potential H-atoms, neutral potential Br-atoms, and negative potential N-atoms, respectively. This work demonstrates the real-space investigation of the multiple halogen bonds by nc-AFM/LT-STM, indicating the potential use of this technique to study other intermolecular bonds and to understand complex supramolecular assemblies at the atomic/sub-molecular level.

Realizing Two-Dimensional Supramolecular Arrays of a Spin Molecule via Halogen Bonding.

Well-ordered spin arrays are desirable for next-generation molecule-based magnetic devices, yet their synthetic method remains a challenging task. Herein, we demonstrate the realization of two-dimensional supramolecular spin arrays on surfaces via halogen-bonding molecular self-assembly. A bromine-terminated perchlorotriphenylmethyl radical with net carbon spin was synthesized and deposited on Au(111) to achieve two-dimensional supramolecular spin arrays. By taking advantage of the diversity of halogen bonds, five supramolecular spin arrays form and are probed by low-temperature scanning tunneling microscopy at the single-molecule level. First-principles calculations verify that the formation of three distinct types of halogen bonds can be used to tailor supramolecular spin arrays via molecular coverage and annealing temperature. Our work suggests that supramolecular self-assembly can be a promising method to engineer two-dimensional molecular spin arrays.

Investigate the Dosimetric and Potential Clinical Benefits Utilizing Stereotactic Body Radiation Therapy With Simultaneous Integrated Boost Technique for Locally Advanced Pancreatic Cancer: A Comparison Between Photon and Proton Beam Therapy.

PURPOSE: To investigate the potential clinical benefits of using stereotactic body radiation therapy (SBRT) with simultaneous integrated boost (SIB) technique for locally advanced pancreatic cancer (LAPC) among different treatment modalities and planning strategies, including photon and proton. METHOD: A total of 19 patients were retrospectively selected in this study: 13 cases with the tumor located in the head of the pancreas and 6 cases with the tumor in the body of the pancreas. SBRT-SIB plans were generated using volumetric modulated arc therapy (VMAT), two-field Intensity Modulated Proton Therapy (IMPT), and three-field IMPT. The IMPT used the robust optimization parameters of ± 3.5% range and 5-mm setup uncertainties. Root-mean-square deviation dose (RMSD) volume histograms were used to evaluate the target coverage robustness quantitatively. Dosimetric metrics based on the dose-volume histogram (DVH), homogeneity index (HI), and normal tissue complication probability (NTCP) were analyzed to evaluate the potential clinical benefits among different planning groups. RESULTS: With a similar CTV and SIB coverage, two-field IMPT provided a lower maximum dose for the stomach (median: 18.6GyE, p<0.05) and duodenum (median: 32.62GyE, p<0.05) when the target was located in the head of the pancreas compared to VMAT and three-field IMPT. The risks of gastric bleed (3.42%) and grade ≥ 3 GI toxicity (4.55%) were also decreased. However, for the target in the body of the pancreas, VMAT showed a lower maximum dose for the stomach (median 30.93GyE, p<0.05) and toxicity of gastric bleed (median: 8.67%, p<0.05) compared to two-field IMPT and three-field IMPT, while other maximum doses and NTCPs were similar. The RMSD volume histogram (RVH) analysis shows that three-field IMPT provided better robustness for targets but not for OARs. Instead, three-field IMPT increased the Dmean of organs such as the stomach, duodenum, and intestine. CONCLUSION: The results indicated that the tumor locations could play a critical role in determining clinical benefits among different treatment modalities. Two-field IMPT could be a better option for LAPC patients whose tumors are located in the head of the pancreas. It provides lower severe toxicity for the stomach and duodenum. Nevertheless, VMAT is preferred for the body with better protection for the possibility of gastric bleed.

A systematic study of independently-tuned room-specific PBS beam model in a beam-matched multiroom proton therapy system.

BACKGROUND: In the existing application of beam-matched multiroom proton therapy system, the model based on the commissioning data from the leading treatment room was used as the shared model. The purpose of this study is to investigate the ability of independently-tuned room-specific beam models of beam-matched gantries to reproduce the agreement between gantries' performance when considering the errors introduced by the modeling process. METHODS: Raw measurements of two gantries' dosimetric characteristics were quantitatively compared to ensure their agreement after initially beam-matched. Two gantries' beam model parameters, as well as the model-based computed dosimetric characteristics, were analyzed to study the introduced errors and gantries' post-modeling consistency. We forced two gantries to share the same beam model. The model-sharing patient-specific quality assurance (QA) tasks were retrospectively performed with 36 cancer patients to study the clinical impact of beam model discrepancies. RESULTS: Intra-gantry comparisons demonstrate that the modeling process introduced the errors to a certain extent indeed, which made the model-based reproduced results deviate from the raw measurements. Among them, the deviation introduced to the IDD curves was generally larger than that to the beam spots during modeling. Cross-gantry comparisons show that, from the beam model perspective, the introduced deviations deteriorated the high agreement of the dosimetric characteristics originally shown between two beam-matched gantries, but the cross-gantry discrepancy was still within the clinically acceptable tolerance. In model-sharing patient-specific QA, for the particular gantry, the beam model usage for intensity-modulated proton therapy (IMPT) QA plan generation had no significant effect on the actual delivering performance. All reached a high level of 95.0% passing rate with a 3 mm/3% criterion. CONCLUSIONS: It was preliminary recognized that among beam-matched gantries, the independently-tuned room-specific beam model from any gantry is reasonable to be chosen as the shared beam model without affecting the treatment efficacy.

Ag2S monolayer: an ultrasoft inorganic Lieb lattice.

Lieb lattice, a two-dimensional edge-centered square lattice, has attracted considerable interest due to its exotic electronic and topological properties. Although various optical and photonic Lieb lattices have been experimentally demonstrated, it remains challenging for an electronic Lieb lattice to be realized in real material systems. Here, based on first-principles calculations and tight-binding modeling, a silver sulfide (Ag2S) monolayer is reported as a long-sought-after inorganic electronic Lieb lattice. This Lieb-lattice Ag2S is further found to be ultrasoft, which enables its electronic properties and topological states near the Fermi level to be finely tuned, as evidenced by the strain-induced topologically non-trivial edge states near the valence band edge. These results not only provide an ideal platform to further explore and harvest interesting quantum properties but also pave a way to pursue other inorganic electronic Lieb lattices in a broader material domain.

Shunt products of aminoansamycins from aas1 overexpressed mutant strain of Streptomyces sp. S35.

Constitutively expression of the pathway-specific activators is an effective method to activate silent gene clusters and improve natural product production. In this study, nine shunt products of aminoansamycins (1-9) were identified from a recombinant mutant strain S35-LAL by overexpressed the large-ATP-binding regulator of the LuxR family (LAL) gene aas1 in Streptomyces sp. S35. All the compounds showed no anti-microbial, anti-T3SS and cytotoxic activities.

Atomic-Level Electronic Properties of Carbon Nitride Monolayers.

Heteroatom-doped carbon-based materials are of significance for clean energy conversion and storage because of their fascinating electronic properties, low cost, high durability, and environmental friendliness. Atomically precise fabrication of carbon-based materials with well-defined heteroatom-dopant positions and atomic-scale understanding of their atomic-level electronic properties is a challenge. Herein, we demonstrate the bottom-up on-surface synthesis of 1D and 2D monolayer carbon nitride nanostructures with precise control of the nitrogen-atom doping sites and pore sizes. We also observe an electronic band offset at the C-N heterojunction. Using high-resolution scanning tunneling microscopy, the atomic structure of the as-prepared carbon nitride nanoporous monolayers are revealed, indicating successful and precise control of the structures and N atom doping sites. Furthermore, corroborated by theoretical calculations, scanning tunneling spectroscopy measurements reveal a valence band shift of 140 meV that results in an electric field of 2.9 × 108 V m-1 at the C-N heterojunction, indicating efficient separation of the electron-hole pair at the N doping site. Our finding offers direct atomic-level insights into the local electronic structure of the heteroatom-doped carbon-based materials.

Targeted Discovery of Pentaketide Ansamycin Aminoansamycins A-G.

Ansamycins are a class of macrolactams with diverse bioactivities, characterized by the unique 3-amino-5-hydroxybenzoic acid moiety. In this study, the ansamycin gene cluster aas in Streptomyces sp. S35 was activated by the constitutive coexpression of two pathway-specific regulator genes aas1 and aas10, and seven novel pentaketide ansamycin aminoansamycins A-G (1-7) were identified. Compound 4 with better antiproliferative activity indicated that the anthranilate analogues are probably promising building blocks for the production of unnatural ansamycins with improved activity.

Chemically Exfoliated VSe2 Monolayers with Room-Temperature Ferromagnetism.

Among van der Waals layered ferromagnets, monolayer vanadium diselenide (VSe2 ) stands out due to its robust ferromagnetism. However, the exfoliation of monolayer VSe2 is challenging, not least because the monolayer flake is extremely unstable in air. Using an electrochemical exfoliation approach with organic cations as the intercalants, monolayer 1T-VSe2 flakes are successfully obtained from the bulk crystal at high yield. Thiol molecules are further introduced onto the VSe2 surface to passivate the exfoliated flakes, which improves the air stability of the flakes for subsequent characterizations. Room-temperature ferromagnetism is confirmed on the exfoliated 2D VSe2 flakes using a superconducting quantum interference device (SQUID), X-ray magnetic circular dichroism (XMCD), and magnetic force microscopy (MFM), where the monolayer flake displays the strongest ferromagnetic properties. Se vacancies, which can be ubiquitous in such materials, also contribute to the ferromagnetism of VSe2 , although density functional theory (DFT) calculations show that such effect can be minimized by physisorbed oxygen molecules or covalently bound thiol molecules.

Three-Dimensional Printing of Polyaniline/Reduced Graphene Oxide Composite for High-Performance Planar Supercapacitor.

We apply direct ink writing for the three-dimensional (3D) printing of polyaniline/reduced graphene oxide (PANI/RGO) composites with PANI/graphene oxide (PANI/GO) gel as printable inks. The PANI/GO gel inks for 3D printing are prepared via self-assembly of PANI and GO in a blend solvent of N-methyl-2-pyrrolidinone and water, and offer both shaping capability, self-sustainability, and electrical conductivity after reduction of GO. PANI/RGO interdigital electrodes are fabricated with 3D printing, and based on these electrodes, a planar solid-state supercapacitor is constructed, which exhibits high performance with an areal specific capacitance of 1329 mF cm-2. The approach developed in this work provides a simple, economic, and effective way to fabricate PANI-based 3D architectures, which leads to promising application in future energy and electric devices at micro-nano scale.

Effects of different anesthesia methods on cognitive dysfunction after hip replacement operation in elder patients.

There are many risk factors for the cause of postoperative cognitive dysfunction (POCD), however, the anesthesia selection always trigger controversy for the POCD occurrence. This study aims to explore the relationship between the anesthesia and the occurrence of POCD in elder patients, and also investigate the mechanism of the POCD. One hundred elder patients with hip replacement were included in this study, which were divided into general anesthesia (GA) and epidural analgesia (EA) group. Minimum mental state examination (MMSE) method was employed to assess the nervous and mental function (POCD) in both analgesia group patients. Aß and tau protein levels in blood were detected by using the ELISA assay. The correlation between MMSE in POCD patients and Aß or tau was analyzed by employing the Spearman rank correlation method. The results indicated that epidural analgesia decreases the MMSE scoring compared to general analgesia (P < 0.05). General analgesia enhanced the Aß and tau level compared to epidural analgesia (P < 0.05). Aß and tau level were increased in the patients with POCD. The POCD occurrence rate in GA group was significantly higher compared to EA group (P < 0.05). MMSE scores of POCD patients positively correlated with Aß or tau level (P < 0.05). In conclusion, the epidural analgesia method was better than general analgesia method for the hip replacement in elder patients. The mechanism of the POCD may be caused by the enhancement of Aß and Tau protein.

Comparison of immune response of Pacific white shrimp, Litopenaeus vannamei, after multiple and single infections with WSSV and Vibrio anguillarum.

Our previous study demonstrated that Pacific white shrimp (Litopenaeus vannamei) infected by multiple pathogens showed higher mortality and death occurred more quickly than those infected by a single pathogen (Jang et al., 2014). For better understanding the defense mechanism against white spot syndrome virus (WSSV) and Vibrio anguillarum, immune responses of shrimp were evaluated in this study. The mRNA expression levels of five immune-related genes were analyzed by quantitative reverse real-time PCR, which included proPO-activating enzyme 1 (PPAE1), PPAE2, proPO activating factor (PPAF), masquerade-like serine proteinase (Mas) and ras-related nuclear gene (Ran). Results demonstrated that the transcription was suppressed more intensively in the multiple infection group than those in single infection groups. The transcriptional suppression was directly related to the higher mortality. The hypoimmunity could benefit pathogen invasion, replication and release of toxin in vivo. Results in this study will help to understand immune defense mechanism after shrimp were infected by multiple pathogens in aquaculture.