SVEN_5003 is a Major Developmental Regulator in Streptomyces venezuelae.

Many regulatory genes that affect cellular development in Streptomyces, such as the canonical bld genes, have already been identified. However, in this study, we identified sven_5003 in Streptomyces venezuelae as a major new developmental regulatory gene, the deletion of which leads to a bald phenotype, typical of bld mutants, under multiple growth conditions. Our data indicated that disruption of sven_5003 also has a differential impact on the production of the two antibiotics jadomycin and chloramphenicol. Enhanced production of jadomycin but reduced production of chloramphenicol were detected in our sven_5003 mutant strain (S. venezuelae D5003). RNA-Seq analysis indicated that SVEN_5003 impacts expression of hundreds of genes, including genes involved in development, primary and secondary metabolism, and genes of unknown function, a finding confirmed by real-time PCR analysis. Transcriptional analysis indicated that sven_5003 is an auto-regulatory gene, repressing its own expression. Despite the evidence indicating that SVEN_5003 is a regulatory factor, a putative DNA-binding domain was not predicted from its primary amino acid sequence, implying an unknown regulatory mechanism by SVEN_5003. Our findings revealed that SVEN_5003 is a pleiotropic regulator with a critical role in morphological development in S. venezuelae.

Improving Oxygen Reduction Performance of Surface-Layer-Controlled Pt-Ni Nano-Octahedra via Gaseous Etching.

This study demonstrates an atomic composition manipulation on Pt-Ni nano-octahedra to enhance their electrocatalytic performance. By selectively extracting Ni atoms from the {111} facets of the Pt-Ni nano-octahedra using gaseous carbon monoxide at an elevated temperature, a Pt-rich shell is formed, resulting in an ∼2 atomic layer Pt-skin. The surface-engineered octahedral nanocatalyst exhibits a significant enhancement in both mass activity (∼1.8-fold) and specific activity (∼2.2-fold) toward the oxygen reduction reaction compared with its unmodified counterpart. After 20,000 potential cycles of durability tests, the surface-etched Pt-Ni nano-octahedral sample shows a mass activity of 1.50 A/mgPt, exceeding the initial mass activity of the unetched counterpart (1.40 A/mgPt) and outperforming the benchmark Pt/C (0.18 A/mgPt) by a factor of 8. DFT calculations predict this improvement with the Pt surface layers and support these experimental observations. This surface-engineering protocol provides a promising strategy for developing novel electrocatalysts with improved catalytic features.

Characteristics of mass-forming autoimmune pancreatitis commonly misdiagnosed as a malignant tumor.

Objective: This study aimed to explore the clinical characteristics and differential diagnosis of patients with autoimmune pancreatitis (AIP) and pancreatic cancer to prevent misdiagnosis and mistreatment. Methods: The clinical data of patients with AIP with suspected pancreatic or bile duct malignancy and pancreatic cancer were retrospectively analyzed. The risk factors and the diagnostic value of IgG4 and Tbil levels before treatment for AIP was investigated. Moreover, the imaging features and response to hormone therapy were analyzed. Results: AIP was commonly observed in men. Compared to patients with pancreatic cancer, the incidence of poor appetite and weight loss and carbohydrate antigen 19-9 (CA19-9) level was lower in patients with AIP, while the immunoglobulin G4 (IgG4) level was higher (p < 0.05). After treatment, the IgG4 and CA19-9 levels in patients with AIP were decreased (p < 0.001). IgG4 level before treatment (OR = 2.452, 95%CI: 1.180-5.096, P = 0.016) and total bilirubin (Tbil) level before treatment (OR = 0.992, 95%CI: 0.985-0.998, P = 0.013) were independent risk factors of AIP. Furthermore, the diagnostic value of IgG4 level before treatment, Tbil level before treatment, IgG4/Tbil before treatment, and a combination of these indicators was high. Moreover, 15 (68.18%) patients with AIP had space-occupying lesions of the pancreas, and 16 (72.73%) had autoimmune cholangitis. Most patients with AIP were sensitive to hormone therapy. Conclusions: The Tbil and IgG4 levels, imaging findings, and hormone therapy reactivity could differentiate AIP from pancreatic cancer. A combination of IgG4, Tbil, and IgG4/Tbil before treatment might be a promising diagnostic biomarker for AIP.

Oxygen-Loss-Induced Structural Degradation in ε-LiVOPO4.

The ε-LiVOPO4 cathode for Li-ion batteries has attracted wide attention with its multivalent electronic states and improved discharge capacity of over 300 mAh/g. Oxygen loss stands as a potential cause for structural degradations of the ε-LiVOPO4 cathode and its derivatives but has been barely studied. Through in situ environmental transmission electron microscopy, we probe lattice oxygen loss and the associated structural degradations by spatially and temporally resolving the atomic-scale structural dynamics and phase transformation pathways in ε-LiVOPO4. We demonstrate that the mild oxygen loss at 400 °C induces a topotactic phase transformation of ε-LiVOPO4 → α-Li3V2(PO4)3 in the particle surface via a nucleation and growth mechanism, leading to the formation of a core-shell configuration. The phase transformation can be reversed by switching to an oxidizing environment, in which the α-Li3V2(PO4)3 is reoxidized to ε-LiVOPO4. By contrast, oxygen loss at higher temperatures of 500 and 600 °C results in a high concentration of oxygen vacancies that subsequently induces irreversible structural damages including lattice amorphization and formation of nanocavities. This work illustrates the fundamental mechanisms governing the structural failure of oxide cathodes and underlines possible strategies to overcome such issues by exploiting environmental constraints.

Ultrahigh-temperature melt printing of multi-principal element alloys.

Multi-principal element alloys (MPEA) demonstrate superior synergetic properties compared to single-element predominated traditional alloys. However, the rapid melting and uniform mixing of multi-elements for the fabrication of MPEA structural materials by metallic 3D printing is challenging as it is difficult to achieve both a high temperature and uniform temperature distribution in a sufficient heating source simultaneously. Herein, we report an ultrahigh-temperature melt printing method that can achieve rapid multi-elemental melting and uniform mixing for MPEA fabrication. In a typical fabrication process, multi-elemental metal powders are loaded into a high-temperature column zone that can be heated up to 3000 K via Joule heating, followed by melting on the order of milliseconds and mixing into homogenous alloys, which we attribute to the sufficiently uniform high-temperature heating zone. As proof-of-concept, we successfully fabricated single-phase bulk NiFeCrCo MPEA with uniform grain size. This ultrahigh-temperature rapid melt printing process provides excellent potential toward MPEA 3D printing.

Design metastability in high-entropy alloys by tailoring unstable fault energies.

Metastable alloys with transformation-/twinning-induced plasticity (TRIP/TWIP) can overcome the strength-ductility trade-off in structural materials. Originated from the development of traditional alloys, the intrinsic stacking fault energy (ISFE) has been applied to tailor TRIP/TWIP in high-entropy alloys (HEAs) but with limited quantitative success. Here, we demonstrate a strategy for designing metastable HEAs and validate its effectiveness by discovering seven alloys with experimentally observed metastability for TRIP/TWIP. We propose unstable fault energies as the more effective design metric and attribute the deformation mechanism of metastable face-centered cubic alloys to unstable martensite fault energy (UMFE)/unstable twin fault energy (UTFE) rather than ISFE. Among the studied HEAs and steels, the traditional ISFE criterion fails in more than half of the cases, while the UMFE/UTFE criterion accurately predicts the deformation mechanisms in all cases. The UMFE/UTFE criterion provides an effective paradigm for developing metastable alloys with TRIP/TWIP for an enhanced strength-ductility synergy.

Oxygen Loss in Layered Oxide Cathodes for Li-Ion Batteries: Mechanisms, Effects, and Mitigation.

Layered lithium transition metal oxides derived from LiMO2 (M = Co, Ni, Mn, etc.) have been widely adopted as the cathodes of Li-ion batteries for portable electronics, electric vehicles, and energy storage. Oxygen loss in the layered oxides is one of the major factors leading to cycling-induced structural degradation and its associated fade in electrochemical performance. Herein, we review recent progress in understanding the phenomena of oxygen loss and the resulting structural degradation in layered oxide cathodes. We first present the major driving forces leading to the oxygen loss and then describe the associated structural degradation resulting from the oxygen loss. We follow this analysis with a discussion of the kinetic pathways that enable oxygen loss, and then we address the resulting electrochemical fade. Finally, we review the possible approaches toward mitigating oxygen loss and the associated electrochemical fade as well as detail novel analytical methods for probing the oxygen loss.

Nanometal Thermocatalysts: Transformations, Deactivation, and Mitigation.

Nanometals have been proven to be efficient thermocatalysts in the last decades. Their enhanced catalytic activity and tunable functionalities make them intriguing candidates for a wide range of catalytic applications, such as gaseous reactions and compound synthesis/decomposition. On the other hand, the enhanced specific surface energy and reactivity of nanometals can lead to configuration transformation and thus catalytic deactivation during the synthesis and catalysis, which largely undermines the activity and service time, thereby calling for urgent research effort to understand the deactivating mechanisms and develop efficient mitigating methods. Herein, the recent progress in understanding the configuration transformation-induced catalytic deactivation within nanometals is reviewed. The major pathways of configuration transformations, and their kinetics controlled by the environmental factors are presented. The approaches toward mitigating the transformation-induced deactivation are also presented. Finally, a perspective on the future academic approaches toward in-depth understanding of the kinetics of the deactivation of nanometals is proposed.

Microbial community responses to soil parameters and their effects on petroleum degradation during bio-electrokinetic remediation.

This study evaluated the interactions among total petroleum hydrocarbons (TPH), soil parameters, and microbial communities during the bio-electrokinetic (BIO-EK) remediation process. The study was conducted on a petroleum-contaminated saline-alkali soil inoculated with petroleum-degrading bacteria with a high saline-alkali resistance. The results showed that the degradation of TPH was better explained by second-order kinetics, and the efficacy and sustainability of the BIO-EK were closely related to soil micro-environmental factors and microbial community structures. During a 98-d remediation process, the removal rate of TPH was highest in the first 35 d, and then decreased gradually in the later period, which was concurrent with changes in the soil physicochemical properties (conductivity, inorganic ions, pH, moisture, and temperature) and subsequent shifts in the microbial community structures. According to the redundancy analysis (RDA), TPH, soil temperature, and electric conductivity, as well as SO42-, Cl-, and K+ played a better role in explaining the changes in the microbial community at 0-21 d. However, pH and NO3- better explained the changes in the microbial community at 63-98 d. In particular, the dominant genera, Marinobacter and Bacillus, showed a positive correlation with TPH, conductivity, and SO42-, Cl-, and K+, but a negative relationship with pH and NO3. Rhodococcus was positively correlated with soil temperature. The efficacy and sustainability of the BIO-EK remediation process is likely to be improved by controlling these properties.

Ultra-Microtome for the Preparation of TEM Specimens from Battery Cathodes.

With the wide application of ultra-microtome sectioning in the preparation of transmission electron microscopy (TEM) specimens with bio- and organic materials, here, we report an ultra-microtome-based method for the preparation of TEM specimens from cathodes of Li-ion batteries. The ultra-microtome sectioning reduces the sample thickness to tens of nanometers and yields atomic resolution from the core region of particles of hundreds of nanometers. Analysis indicates that the mechanical cross-sectioning introduces no observable microstructural artifacts or structural damage, such as microcracking and nanoporosity. These results demonstrate the high efficiency of the ultra-microtome approach in preparing well-thinned specimens of particulate materials that allow for atomic-scale TEM imaging of a large number of sectioned particles in one single TEM specimen, thereby providing statistically significant results of the TEM analysis.

Sulfur-Grafted Hollow Carbon Spheres for Potassium-Ion Battery Anodes.

Sulfur-rich carbons are minimally explored for potassium-ion batteries (KIBs). Here, a large amount of S (38 wt%) is chemically incorporated into a carbon host, creating sulfur-grafted hollow carbon spheres (SHCS) for KIB anodes. The SHCS architecture provides a combination of nanoscale (≈40 nm) diffusion distances and CS chemical bonding to minimize cycling capacity decay and Coulombic efficiency (CE) loss. The SHCS exhibit a reversible capacity of 581 mAh g-1 (at 0.025 A g-1 ), which is the highest reversible capacity reported for any carbon-based KIB anode. Electrochemical analysis of S-free carbon spheres baseline demonstrates that both the carbon matrix and the sulfur species are highly electrochemically active. SHCS also show excellent rate capability, achieving 202, 160, and 110 mAh g-1 at 1.5, 3, and 5 A g-1 , respectively. The electrode maintains 93% of the capacity from the 5th to 1000th cycle at 3 A g-1 , with steady-state CE being near 100%. Raman analysis indicates reversible breakage of CS and SS bonds upon potassiation to 0.01 V versus K/K+ . The galvanostatic intermittent titration technique (GITT) analysis provides voltage-dependent K+ diffusion coefficients that range from 10-10 to 10-12 cm2 s-1 upon potassiation and depotassiation, with approximately five times higher coefficient for the former.

A study on the relationship between waist phenotype, hypertriglyceridemia, coronary artery lesions and serum free fatty acids in adult and elderly patients with coronary diseases.

BACKGROUND: Abdominal obesity is an independent risk factor for coronary heart disease (CHD) and high serum triglyceride (TG) and free fatty acid levels may precipitate or aggravate CHD. METHODS: We enrolled patients with coronary heart disease in our hospital from October 2008 to July 2009. Patients with high TG and increased WC, i.e. waist phenotype WP were included in group A. In group B, were included patients with high TG but not WP. Group C consisted of patients with WP but not high TG. Finally, Group D was composed of patients without high TG or WP. Serum FFA levels for all patients were measured by ELISA. The relationship between TG levels, WC, FFA levels, and coronary artery score was analysed by a single variable regression. RESULTS: Group A had a significantly higher FFA level than the other groups. Regression analysis showed that FFA, TG, WC, hip circumference, waist-to-height ratio, systolic blood pressure, pulse pressure index, and low-density lipoprotein cholesterol all positively correlated with CAS (r = 0.160 ~ 0.415, P = 0.000 ~ 0.032). After we controlled for traditional risk factors for cardiovascular disease, FFA levels remained positively correlated to the CAS (r = 0.365, P < 0.001). CONCLUSION: The serum FFA level for patients with complications of both increased WC and high TG levels was significantly higher than that of patients without either of these complications. The close correlation between the CAS and FFA levels showed by regression analysis suggested that inflammation in these patients was more serious. Increased WC and high TG levels as well as FFA level are valuable for the prediction of cardiovascular disease and can be applied as a clinical guidance for early intervention in the treatment of coronary heart diseases.

Enabling multi-electron reaction of ε-VOPO4 to reach theoretical capacity for lithium-ion batteries.

By controlling the morphology and particle size of the epsilon polymorph of vanadyl phosphate, ε-VOPO4, it can fully reversibly intercalate two Li-ions and reach the theoretical capacity of 305 mA h g-1 over two voltage plateaus at about 4.0 and 2.5 V.

In situ atomic-scale observation of inhomogeneous oxide reduction.

We report in situ atomic-scale transmission electron microscopy observations of the surface dynamics during Cu2O reduction. We show inhomogeneous oxide reduction caused by the preferential adsorption of hydrogen at step edges that induces oxygen loss and destabilizes Cu atoms within the step edge, thereby resulting in the retraction motion of atomic steps at the oxide surface.

A Fe5C2 nanocatalyst for the preferential synthesis of ethanol via dimethyl oxalate hydrogenation.

A Fe-based catalyst exhibits extremely high selectivity (89.6%) besides excellent catalytic activity in gas-phase dimethyl oxalate hydrogenation. The ethanol formation occurs via hydrogenation of methyl acetate instead of ethylene glycol over the active species Fe5C2.