Dramatically Enhanced Mechanical Properties of Nano-TiN-Dispersed n-Type Bismuth Telluride by Multi-Effect Modulation.

Bismuth telluride (Bi2Te3)-based alloys have been extensively employed in energy harvesting and refrigeration applications for decades. However, commercially produced Bi2Te3-based alloys using the zone-melting (ZM) technique often encounter challenges such as insufficient mechanical properties and susceptibility to cracking, particularly in n-type Bi2Te3-based alloys, which severely limit the application scenarios for bismuth telluride devices. In this work, we seek to enhance the mechanical properties of n-type Bi2Te2.7Se0.3 alloys while preserving their thermoelectrical performance by a mixed mechanism of grain refinement and the TiN composite phase-introduced pinning effect. These nanoscale processes, coupled with the addition of TiN, result in a reduction in grain size. The pinning effects of nano-TiN contribute to increased resistance to crack propagation. Finally, the TiN-dispersed Bi2Te2.7Se0.3 samples demonstrate increased hardness, bending strength and compressive strength, reaching 0.98 GPa, 36.3 MPa and 74 MPa. When compared to the ZM ingots, those represent increments of 181%, 60% and 67%, respectively. Moreover, the thermoelectric performance of the TiN-dispersed Bi2Te2.7Se0.3 samples is identical to the ZM ingots. The samples exhibit a peak dimensionless figure of merit (ZT) value of 0.957 at 375 K, with an average ZT value of 0.89 within the 325-450 K temperature range. This work has significantly enhanced mechanical properties, increasing the adaptability and reliability of bismuth telluride devices for various applications, and the multi-effect modulation of mechanical properties demonstrated in this study can be applied to other thermoelectric material systems.

Venetoclax plus a hypomethylating agent versus cytarabine, aclarubicin, and granulocyte colony-stimulating factor chemotherapy as a first-line therapy for newly diagnosed acute myeloid leukemia: A propensity score-matched analysis.

BACKGROUND: Both venetoclax plus a hypomethylating agent (VEN/HMA) and cytarabine, aclarubicin, and granulocyte colony-stimulating factor (CAG) are low-intensity regimens for older patients with acute myeloid leukemia (AML) that show good efficacy and safety. It is unknown how VEN/HMA compares with the CAG regimen for the treatment of newly diagnosed AML. METHODS: The outcomes of patients with newly diagnosed AML treated with VEN/HMA were compared with those of patients treated with a CAG-based regimen. Propensity score matching between these two cohorts at a 1:1 ratio was performed according to age at diagnosis, sex, Eastern Cooperative Oncology Group performance status, state of fitness, and European LeukemiaNet (ELN) 2022 risk stratification to minimize bias. RESULTS: A total of 84 of 96 patients in the VEN/HMA cohort were matched with 84 of 147 patients in the CAG cohort. VEN/HMA resulted in a better response than the CAG-based regimens, as indicated by a higher composite complete remission (CRc) rate (82.1% vs. 60.7%; p = .002) and minimal residual disease negativity rate (88.2% vs. 68.2%; p = .009). In patients with an ELN adverse risk, VEN/HMA was associated with a higher CRc rate compared to CAG (80.5% vs. 58.3%; p = .006). VEN/HMA was associated with longer event-free survival (EFS) (median EFS, not reached vs. 4.5 months; p = .0004), whereas overall survival (OS) was comparable between the two cohorts (median OS, not reached vs. 18 months; p = .078). CONCLUSIONS: The VEN/HMA regimen may result in a better response than CAG-based treatment in older patients with newly diagnosed AML.

A novel strategy for Pu determination in water samples by automated separation in combination with direct ICP-MS/MS measurement.

Methods for Pu determination in water samples has been longtime studied but they generally involved tedious manual operations. In this context, we proposed a novel strategy for accurate determination of ultra-trace Pu in water samples by the combination of fully automated separation with direct ICP-MS/MS measurement. A recently commercialized extraction resin TK200 was used for single-column separation due to its distinctive nature. Acidified waters up to 1 L were directly loaded to the resin at high flow rate (15 mL min-1) with omitting the frequently used co-precipitation process. Small volumes of dilute HNO3 were used for column washing, and Pu was efficiently eluted within only 2 mL 0.5 mol L-1 HCl-0.1 mol L-1 HF with a stable recovery (65%). This separation procedure was fully automated under the control of user program, meanwhile the final eluent was compatible for direct ICP-MS/MS measurement without extra sample treatment. In that way, both the labor intensity and reagent consumption were minimized compared with existing methods. With the high decontamination (104 to 105) of U in the chemical separation and the further elimination of uranium hydrides under oxygen reaction model during ICP-MS/MS measurement, the overall interference yields of UH+/U+ and UH2+/U+ were down to 10-15. The limits of detection (LODs) of this method reached 0.32 µBq L-1 for 239Pu and 2.00 µBq L-1 for 240Pu, which were much lower than those stipulated in the general guidelines for drinking water standards, suggesting this method was promising in routine or emergency radiation monitoring. Furthermore, the established method was successfully applied in a pilot study to determine global fallout derived Pu in surface glacier samples with extremely low concentrations of 239+240Pu, which suggested the method would also be feasible in glacial chronology studies in the future.

Highly selective extraction of uranium from wastewater using amine-bridged diacetamide-functionalized silica.

A major environmental concern related to nuclear energy is wastewater contaminated with uranium, thus necessitating the development of pollutant-reducing materials with efficiency and effectiveness. Herein, highly selective mesoporous silicas functionalized with amine-bridged diacetamide ligands SBA-15-ABDMA were prepared. Different spectroscopy techniques were used to probe the chemical environment and reactivity of the chelating ligands before and after sorption. The results showed that the functionalized SBA-15-ABDMA had a strong affinity for uranium at low pH (pH = 3) with desirable sorption capacity (68.82 mg/g) and good reusability (> 5). It showed excellent separation performance with a high distribution coefficient (Kd,U > 105 mL/g) and separation factors SFU/Ln > 1000 at a pH of 3.5 in the presence of lanthanide nuclides, alkaline earth metal and transition metal ions. In particular, SiO2spheres-ABDMA was used as a column material, which achieved excellent recovery of U(VI) (> 98%) and good reusability for samples of simulated mining and nuclear industries wastewater. XPS and crystallography studies clearly illustrated the tridentate coordination mode of U(VI)/PEABDMA and the mechanism and origin behind the high selectivity for U.

A simple method for Ce-Nd separation using nano-NaBiO3: Application in the isotopic analysis of U, Sr, Pb, Nd, and Hf in uranium ores.

U, Sr, Pb, Nd, and Hf isotope ratios can provide basic and important information of nuclear materials. We established a simple and efficient column chemistry method using nano-NaBiO3, as both oxidizer and adsorbent, to completely separate Ce from rare earth elements (REEs). This new method exhibited a high decontamination (Ce/Nd < 10-5) ability and was easy to conducted, thereby providing clear advantages compared to traditional liquid-liquid and solid phase micro-extraction techniques. Additionally, a rapid four-column separation procedure, based on Sr, TUR, Ln resins and nano-NaBiO3, was developed to isolate U, Sr, Pb, Nd, and Hf in ore samples. The entire procedure could be completed in 4-5 hrs. The robustness of the proposed method was demonstrated by analyzing the 235U/238U, 87Sr/86Sr, 206Pb/204Pb, 207Pb/204Pb, 208Pb/204Pb, 142Nd/144Nd, 143Nd/144Nd, and 176Hf/177Hf isotopic ratios of two certified reference materials (CRMs). The analytical results obtained using this method showed good agreement with previously published data. The feasibility of this method was extended to the determination of isotope ratios in uranium ores. The results obtained from the two samples with different regions indicated that they have different isotopic ratios information. These findings indicate the potential for the use of this new method in nuclear forensic science.

The role of comorbid hypertriglyceridemia and abdominal obesity in the severity of acute pancreatitis: a retrospective study.

BACKGROUND: The effect of comorbid hypertriglyceridemia (HTG) and abdominal obesity (AO) on acute pancreatitis (AP) remains unclear. The aim of this study was to explore the effect of comorbid HTG and AO and discuss which is the dominant disorder. METHODS: In this study, 1219 AP patients who presented with HTG or AO were stratified into four groups: non-HTG + non-AO, HTG + non-AO, non-HTG + AO, and HTG + AO. RESULTS: The 328 patients with comorbid HTG + AO were much younger (42.29 ± 11.77), mainly male (79.57%), and had higher TG levels, larger waist circumferences, and more past medical histories than the patients in the other three non-comorbid groups (P < 0.001). The comorbidity group developed more incidences of persistent organ failure and local complications (P < 0.05). Multivariate logistic regression analysis showed that AO (OR = 3.205, 95% CI = 1.570-6.544), mild HTG (OR = 2.746, 95% CI = 1.125-6.701), and moderate to very severe HTG (OR = 3.649, 95% CI = 1.403-9.493) were independent risk factors for persistent respiratory failure (P < 0.05). Age > 60 years (OR = 1.326, 95% CI = 1.047-1.679), AO (OR = 1.701, 95% CI = 1.308-2.212), diabetes mellitus (OR = 1.551, 95% CI = 1.063-2.261), mild HTG (OR = 1.549, 95% CI = 1.137-2.112), and moderate to very severe HTG (OR = 2.810, 95% CI = 1.926-4.100) were independent risk factors associated with local complications (P < 0.05). Moreover, HTG seemed to be more dangerous than AO. The higher the serum TG level was, the greater the likelihood of persistent respiratory failure and local complications. CONCLUSIONS: Comorbid HTG and AO will aggravate the severity and increase the incidence of local complications of AP. HTG may play a dominant role of risk in the condition of comorbidity. CHINESE CLINICAL TRIAL REGISTRY: ChiCTR2100049566 . Registered on 3rd August, 2021. Retrospectively registered, https://www.chictr.org.cn/edit.aspx?pid=127374&htm=4 .

Traditional Chinese Medicine Formulas Alleviate Acute Pancreatitis: Pharmacological Activities and Mechanisms.

ABSTRACT: Acute pancreatitis (AP) is a common clinical gastrointestinal disorder with a high mortality rate for severe AP and lacks effective clinical treatment, which leads to considerable comorbidity and financial burden. Traditional Chinese medicine (TCM) has had the unique advantage of treating AP for a long time in China. Clinically, TCM formulas such as Da-cheng-qi decoction, Chai-qin-cheng-qi decoction, Qing-yi decoction, Da-chai-hu decoction, and Da-huang-fu-zi decoction are widely administrated to AP patients. All of these TCM formulas can improve gastrointestinal function, regulate the inflammatory response, and enhance immunity, thus preventing complications, reducing the mortality rate and financial burden. This review will summarize the pharmacological activities and mechanisms of TCM formulas in alleviating AP.

Pore Size Control via Multiple-Site Alkylation to Homogenize Sub-Nanoporous Covalent Organic Frameworks for Efficient Sieving of Xenon/Krypton.

Among various fission products generated in nuclear reactors, xenon and krypton are two important fission gases with high flow, diffusivity, and radioactivity. Moreover, xenon isolated from these products is an expensive industrial resource with wide applications in medicine and lighting, which makes the development of efficient methods for separation of xenon/krypton significant. However, it is usually difficult for xenon/krypton to be adsorbed by chemical adsorbents due to their inert gas properties, and sub-nanoporous adsorbents proven to be workable for the separation of xenon/krypton are still hard to prepare and regulate the pore size. Herein, we report two novel sub-nanoporous covalent organic frameworks (COFs), which were applied to the sieving of xenon/krypton for the first time. The sub-nanoporous COFs were synthesized via aldehyde-amine polycondensation reactions and the subsequent pore size regulation and homogenization process by using a facile, operational, and efficient multiple-site alkylation strategy. Impressively, the as-prepared sub-nanoporous COFs realized the efficient adsorption and sieving of xenon/krypton owing to their slightly larger pore sizes (∼7 Å) than the dynamic diameters of xenon/krypton and their larger pore volumes. The maximum adsorption capacity for xenon is up to 85.6 cm3/g, and the xenon/krypton selectivity can reach to 9.7. Moreover, the as-prepared COFs possess good γ-ray irradiation stability, which endows them with great potentials for the sieving of radioactive xenon/krypton in the practical application. The multiple-site alkylation strategy proposed in this study provides a valuable approach for the pore construction and control of the porous materials, especially the sub-nanoporous adsorption materials.

Construction of covalent organic framework with unique double-ring pore for size-matching adsorption of uranium.

The separation and recovery of key nuclides such as uranium and plutonium from effluents related to nuclear industry is of great significance for alleviating the shortage of nuclear energy resources and protecting the environment and human health. However, the high temperature, strong acidity and radioactivity of the nuclear effluents pose a severe challenge to the separation materials used in such conditions. The diversity of structure, flexibility of design, and excellent physicochemical stability of covalent organic framework materials (COFs) provide the possibility for the directional design and preparation of adsorbents for use under harsh conditions. Herein, three COFs with similar structure, different pore sizes and connecting modules were synthesized. The ingenious structure predesign enables Dp-COF to have three carboxyl groups oriented toward the pore center and laid out in appropriate spatial positions, which builds hydrogen-bonding bridges between carboxycarbonyl and hydroxyl groups, and thus constructs for the first time a unique COF material with a double-ring pore. The inner pore size of the "double-ring" is slightly larger than the diameter of uranyl hydrate, which leads to a size-matching adsorption of uranium by Dp-COF, thus greatly reducing the effect of protonation. Even in the simulated spent fuel reprocessing liquid with pH = 1.0, the adsorption capacity of Dp-COF for uranium can reach 66.3 mg g-1, and the adsorption capacity reaches 317.3 mg g-1 at pH = 4.5, which is very rare among the reported COFs. More excitingly, the removal rate for uranium reaches up to an unprecedented 99.8% due to the size-matching effect, more than any analogous adsorbents. This study not only proposes new ideas for the design and regulation of the microscopic configuration of COF materials, but also provides an alternative approach for the preparation of efficient uranium adsorbents.

Density Functional Theory Investigations on the Mechanism of Formation of Pa(V) Ion in Hydrous Solutions.

Due to the enormous threat of protactinium to the environment and human health, its disposal and chemistry have long been important topics in nuclear science. [PaO(H2O)6]3+ is proposed as the predominant species in hydrous and acidic solutions, but little is known about its formation mechanism. In this study, density functional theory (DFT) calculations demonstrate a water coordination-proton transfer-water dissociation mechanism for the formation of PaO3+ in hydrous solutions. First, Pa(V) ion preferentially forms hydrated complexes with a coordination number of 10. Through hydrogen bonding, water molecules in the second coordination sphere easily capture two protons on the same coordinated H2O ligand to form [PaO(H2O)9]3+. Water dissociation then occurs to generate the final [PaO(H2O)6]3+, which is the thermodynamic product of Pa(V) in hydrous solutions.

Binding affinity of pyridines with AmIII/CmIII elucidated by density functional theory calculations.

In recent decades, N-heterocyclic ligands have been extensively used in the separation of lanthanides/actinides, whereas the selective extraction of amercium or curium has been very challenging. Using density functional theory calculations, this study is devoted to the investigation of the binding affinity of a series of modelling pyridine ligands with AmIII and CmIII. The structure-property correlations between the amercium and curium systems and the binding affinity were obtained, and promising strategies for efficient separation of AmIII/CmIII were proposed.

The preparation of organophosphorus ligand-modified SBA-15 for effective adsorption of Congo red and Reactive red 2.

P,P-bis (2-oxooxazolidin-3-yl)-N-(3-(triethoxysilyl)propyl)phosphinic amide (APTES-BOP)-modified SBA-15 (SBA-15-BOP) was prepared by a post-synthesis grafting method for the removal of anionic azo dyes from aqueous solutions. The properties of the prepared adsorbent were characterized by PXRD, FT-IR, SEM, TEM, nitrogen sorption, and elemental analysis. Adsorption equilibrium and adsorption kinetic studies demonstrated that the experimental data fitted well with the Langmuir isotherm model and pseudo-second-order model. According to Langmuir fitting, SBA-15-BOP showed high adsorption capacity for CR and RR2 dyes, with the maximum adsorption capacities of 518.1 mg g-1 and 253.8 mg g-1, respectively. The thermodynamic study indicated that the adsorption processes of CR and RR2 dyes on SBA-15-BOP were spontaneous and exothermal. The prepared SBA-15-BOP can be a promising adsorbent for the removal of anionic dyes from aqueous solutions.

Pd-Catalyzed Vinylation of Aryl Halides with Inexpensive Organosilicon Reagents Under Mild Conditions.

Pd-catalyzed Hiyama vinylation reaction of non-activated aryl chlorides and bromides under mild conditions was developed. The use of efficient vinyl donors and electron-rich sterically hindered phosphine ligands was critical for the success of the reaction. The products of this transformation can be used for Am/Cm separation, an important challenge in nuclear fuel reprocessing. The substituent effect on Am/Cm separating selectivity was also achieved, which could contribute to the development of new chromatographic materials for the separation of Am and Cm.

The Hydrolytic Stability and Degradation Mechanism of a Hierarchically Porous Metal Alkylphosphonate Framework.

To aid the design of a hierarchically porous unconventional metal-phosphonate framework (HP-UMPF) for practical radioanalytical separation, a systematic investigation of the hydrolytic stability of bulk phase against acidic corrosion has been carried out for an archetypical HP-UMPF. Bulk dissolution results suggest that aqueous acidity has a more paramount effect on incongruent leaching than the temperature, and the kinetic stability reaches equilibrium by way of an accumulation of a partial leached species on the corrosion conduits. A variation of particle morphology, hierarchical porosity and backbone composition upon corrosion reveals that they are hydrolytically resilient without suffering any great degradation of porous texture, although large aggregates crack into sporadic fractures while the nucleophilic attack of inorganic layers cause the leaching of tin and phosphorus. The remaining selectivity of these HP-UMPFs is dictated by a balance between the elimination of free phosphonate and the exposure of confined phosphonates, thus allowing a real-time tailor of radionuclide sequestration. Moreover, a plausible degradation mechanism has been proposed for the triple progressive dissolution of three-level hierarchical porous structures to elucidate resultant reactivity. These HP-UMPFs are compared with benchmark metal-organic frameworks (MOFs) to obtain a rough grading of hydrolytic stability and two feasible approaches are suggested for enhancing their hydrolytic stability that are intended for real-life separation protocols.

An initial demonstration of hierarchically porous niobium alkylphosphonates coordination polymers as potent radioanalytical separation materials.

Combining the merits of soft-templating and perchlorate oxidation methods, the first-case investigation of niobium alkylphosphonates has uncovered their unique morphology, backbone composition, thermal behavior and huge potentiality as radioanalytical separation materials. These hierarchically porous solids are random aggregates of densely stacked nanolayers perforated with worm-like holes or vesicular voids, manifesting the massif-, tower-like "polymer brush" elevated up to ∼150nm driven by the minimal surface free energy principle. These coordination polymers consist of distorted niobium (V) ions strongly linked with tetrahedral alkylphosphonate building units, exposing uncoordinated phosphonate moieties and defective metal sites. Despite the amorphous features, they demonstrate multimodal porosity covering continuous micropores, segregated mesopores and fractional macropores, beneficial for the sequestration by active Lewis acid-base center. Evidenced by the maximum distribution coefficients of thorium, lanthanides reaching 9.0×104, 9.5×104mLg-1 and large separation factor at pH≤1 20-element cocktail, this category of niobium alkylphosphonates are capable of harvesting thorium, lanthanides directly from the radionuclide surrogate, comparable to or even surpass the performance of the metal (IV) arylphosphonates counterparts. They also display appreciable SFEu/Sm ∼20 in 1molL-1 HNO3, shedding light on dual approaches to achieve the isolation of americium from curium. A combinatorial radioanalytical separation protocol has been proposed to enrich thorium and europium, revealing facile utilization of these highly stable, phosphonated hybrids in sustainable development of radioanalytical separation.

The coordination of amidoxime ligands with uranyl in the gas phase: a mass spectrometry and DFT study.

Sequestering uranium from the ocean is a promising solution to fulfill the demand for nuclear energy. Motivated by this purpose, a series of amidoxime ligands and their analogs have been developed with high absorption capacity and selectivity. An in-depth understanding of the structural information of the uranyl-ligand complexes is essential to improve the performance of the ligands. Herein, we have studied the coordination of three amidoxime ligands (6-methoxyl-naphtha-2-amidoxime, NAO; glutarimidedioxime, GIO; and gluardiamidoxime, GDO) with uranyl in the gas phase by mass spectrometry. The identifications of the electrospray ionization (ESI) generated species, the fragmentation pathways upon dissociation, the relative binding affinities of the ligands, and the hydration reactions have been conducted and compared to reveal their structural information in the gas phase. The binding modes for all the complexes were suggested based on the experimental results and were further studied by density functional theory (DFT) calculations.

Density functional theory investigations on the binding modes of amidoximes with uranyl ions.

Density functional theory (DFT) calculations have been carried out to examine the relative facilities of different coordination modes of aromatic amidoximes (AOs) with UO2(NO3)2. Various η(1)-, η(2)- and chelated κ(2)-coordination modes of the possible neutral AO, tautomerized neutral (TAO, with the hydroxylic hydrogen transferring to the oximic nitrogen atom) and anionic amidoxime (AAO, formed by the deprotonation of AO) were examined. The results indicate that η(1)-O of the TAO and η(1)-O/η(2)-NO of AAO are the most plausible coordination modes. Three types of uranyl complexes, i.e. UO2(NO3)2(TAO)(AAO), UO2(NO3)2(AAO)2 and UO2(EtOH)2(AAO)2 are the predominant binding structures. The good consistency between the calculation results and the experimental observations verifies the proposed conclusions.

Fluorescent recognition of uranyl ions by a phosphorylated cyclic peptide.

Fluorescent recognition of uranyl ions was achieved using a phosphorylated cyclic peptide, which can be used as a fluorescent sensor for the detection of uranyl ions with high selectivity and sensitivity.

"One-pot" synthesis of amidoxime via Pd-catalyzed cyanation and amidoximation.

A novel "one-pot" reaction was developed for the synthesis of aryl or heteroaryl-substituted amidoxime compounds containing various functional groups. Fluorescence titration experiments coupled with theoretical analysis revealed that the steric hindrance and electronic effects of substituents influence the binding ability of the amidoxime compounds to uranyl ions.

Cu-catalyzed cross-coupling reactions of epoxides with organoboron compounds.

A copper-catalyzed cross-coupling reaction of epoxides with arylboronates is described. This reaction is not limited to aromatic epoxides, because aliphatic epoxides are also suitable substrates. In addition, N-sulfonyl aziridines can be successfully converted into the products. This reaction provides convenient access to ß-phenethyl alcohols, which are valuable synthetic intermediates.