Nuclear volume effects in kinetic isotope fractionation:A case study of mercury oxidation by chlorine species

It is well-known that the equilibrium isotope fractionation of mercury(Hg)includes classical massdependent fractionations(MDFs)and nuclear volume effect(NVE)induced mass-independent fractionations(MIFs).However,the effect of the NVE on these kinetic processes is not known.The total fractionations(MDFs+NVEinduced MIFs)of several representative Hg-incorporated substances were selected and calculated with ab initio calculations in this work for both equilibrium and kinetic processes.NVE-induced MIFs were calculated with scaled contact electron densities at the nucleus through systematic evaluations of their accuracy and errors using the Gaussian09 and DIRAC19 packages(named the electron density scaling method).Additionally,the NVE-induced kinetic isotope effect(KIE)of Hg isotopes are also calculated with this method for several representative Hg oxidation reactions by chlorine species.Total KIEs for 202 Hg/^(198)Hg ranging from−2.27‰to 0.96‰are obtained.Three anomalous^(202)Hg-enriched KIEs(δ^(202)Hg/^(198)Hg=0.83‰,0.94‰,and 0.96‰,)caused by the NVE are observed,which are quite different from the classical view(i.e.,light isotopes react faster than the heavy ones).The electron density scaling method we developed in this study can provide an easier way to calculate the NVE-induced KIEs for heavy isotopes and serve to better understand the fractionation mechanisms of mercury isotope systems.

Hemoglobin loss method calculates blood loss during pancreaticoduodenectomy and predicts bleeding-related risk factors

BACKGROUND The common clinical method to evaluate blood loss during pancreaticoduoden-ectomy(PD)is visual inspection,but most scholars believe that this method is extremely subjective and inaccurate.Currently,there is no accurate,objective me-thod to evaluate the amount of blood loss in PD patients.We retrospectively analyzed the clinical data of 341 patients who underwent PD in Shandong Provincial Hospital from March 2017 to February 2019.According to different surgical methods,they were divided into an open PD(OPD)group and a laparoscopic PD(LPD)group.The differences and correlations between the in-traoperative estimation of blood loss(IEBL)obtained by visual inspection and the intraoperative calculation of blood loss(ICBL)obtained using the Hb loss method were analyzed.ICBL,IEBL and perioperative calculation of blood loss(PCBL)were compared between the two groups,and single-factor regression analysis was performed.RESULTS There was no statistically significant difference in the preoperative general patient information between the two groups(P>0.05).PD had an ICBL of 743.2(393.0,1173.1)mL and an IEBL of 100.0(50.0,300.0)mL(P<0.001).There was also a certain correlation between the two(r=0.312,P<0.001).Single-factor analysis of ICBL showed that a history of diabetes[95%confidence interval(CI):53.82-549.62;P=0.017]was an independent risk factor for ICBL.In addition,the single-factor analysis of PCBL showed that body mass index(BMI)(95%CI:0.62-76.75;P=0.046)and preoperative total bilirubin>200μmol/L(95%CI:7.09-644.26;P=0.045)were independent risk factors for PCBL.The ICBLs of the LPD group and OPD group were 767.7(435.4,1249.0)mL and 663.8(347.7,1138.2)mL,respectively(P>0.05).The IEBL of the LPD group 200.0(50.0,200.0)mL was slightly greater than that of the OPD group 100.0(50.0,300.0)mL(P>0.05).PCBL was greater in the LPD group than the OPD group[1061.6(612.3,1632.3)mL vs 806.1(375.9,1347.6)mL](P<0.05).CONCLUSION The ICBL in patients who underwent PD was greater than the IEBL,but there is a certain correlation between the two.The Hb loss method can be used to evaluate intraoperative blood loss.A history of diabetes,preoperative bilirubin>200μmol/L and high BMI increase the patient's risk of bleeding.

外部验证CALCULATE量表预测重症监护病房老年患者压力性损伤的价值

目的通过外部验证评估CALCULATE量表预测ICU老年患者压力性损伤(PI)的价值。方法回顾性分析上海市浦东医院综合ICU内2018年1月-2018年12月收治的老年患者临床资料,根据ICU期间是否发生PI分为PI组和非PI组。从区分度,校准度和有效性等方面评估CALCULATE量表的效能。结果最终纳入研究老年患者614例,ICU期间发生PI患者70例(11.4%),大部分是1、2期(97.1%),最常见部位是骶尾部(77.3%),CALCULATE量表预测PI的AUC为0.724(95%CI:0.687~0.759),优于传统的Braden量表的AUC(0.633)(95%CI:0.594~0.672),统计值Z=6.326(P<0.001);多因素二元Logistic回归显示,CALCULATE量表评分大于3分是独立危险因素(OR=3.835,95%CI:2.522~5.832,P<0.001);Hosmer-Lemeshow检验显示,CALCULATE量表的校准度较差(χ^(2)=15.103,P=0.004),决策曲线分析显示,CALCULATE量表具有较好的临床应用效能。结论CALCULATE量表预测ICU老年患者PI有一定的价值,但仍有待进一步完善。

Health Phys.Abstracts,Volume 123,Number 5

Practical Tools for Patient-specific Characterization and Dosimetry of Radiopharmaceutical Extravasation Extravasation during radiopharmaceutical injection may occur with a frequency of more than 10%.In these cases,radioactivity remains within tissue and deposits unintended radiation dose.Characterization of extravasations is a necessary step in accurate dosimetry,but a lack of free and publicly available tools hampers routine standardized analysis.Our objective was to improve existing extravasation characterization and dosimetry methods and to create and validate tools to facilitate standardized practical dosimetric analysis in clinical settings.Using Monte Carlo simulations,we calculated dosimetric values for sixteen nuclear medicine isotopes:^(11 )C,^(64) Cu,^(18) F,^(67 )Ga,^(68) Ga,^(123) I,^(131) I,111 In,177 Lu,13 N,15 O,82 Rb,153 Sm,89 Sr,99m Tc,and 90 Y.We validated our simulation results against five logical alternative dose assessment methods.We then created three new characterization tools:a worksheet,a spreadsheet,and a web application.We assessed each tool by recalculating extravasation dosimetry results found in the literature and used each of the tools for patient cases to show clinical practicality.Average variation between our simulation results and alternative methods was 3.1%.Recalculation of published dosimetry results indicated an average error of 7.9%.Time required to use each characterization tool ranged from 1 to 5 min,and agreement between the three tools was favorable.We improved upon existing methods by creating new tools for characterization and dosimetry of radiopharmaceutical extravasation.These free and publicly available tools will enable standardized routine clinical analysis and benefit patient care,clinical follow-up,documentation,and event reporting.

Sequential Inverse Optimal Control of Discrete-Time Systems

This paper presents a novel sequential inverse optimal control(SIOC)method for discrete-time systems,which calculates the unknown weight vectors of the cost function in real time using the input and output of an optimally controlled discrete-time system.The proposed method overcomes the limitations of previous approaches by eliminating the need for the invertible Jacobian assumption.It calculates the possible-solution spaces and their intersections sequentially until the dimension of the intersection space decreases to one.The remaining one-dimensional vector of the possible-solution space’s intersection represents the SIOC solution.The paper presents clear conditions for convergence and addresses the issue of noisy data by clarifying the conditions for the singular values of the matrices that relate to the possible-solution space.The effectiveness of the proposed method is demonstrated through simulation results.

Emerging perovskite materials for supercapacitors:Structure,synthesis,modification,advanced characterization,theoretical calculation and electrochemical performance

As a new generation electrode materials for energy storage,perovskites have attracted wide attention because of their unique crystal structure,reversible active sites,rich oxygen vacancies,and good stability.In this review,the design and engineering progress of perovskite materials for supercapacitors(SCs)in recent years is summarized.Specifically,the review will focus on four types of perovskites,perovskite oxides,halide perovskites,fluoride perovskites,and multi-perovskites,within the context of their intrinsic structure and corresponding electrochemical performance.A series of experimental variables,such as synthesis,crystal structure,and electrochemical reaction mechanism,will be carefully analyzed by combining various advanced characterization techniques and theoretical calculations.The applications of these materials as electrodes are then featured for various SCs.Finally,we look forward to the prospects and challenges of perovskite-type SCs electrodes,as well as the future research direction.

From charge storage mechanism to performance:A strategy toward boosted lithium/sodium storage through heterostructure optimization

Solving the problems of low electrical conductivity and poor cycling durability in transition metal oxidesbased anode materials for lithium-ion batteries(LIBs)and sodium-ion batteries(SIBs)has already turned into an urgent requirement.In this paper,we successfully synthesized Co_(2)VO_(4)/Co compounds with Co-VMOF(metal-organic framework)as a sacrificial template and investigated their electrochemical mechanism in order to improve the electrochemical properties of LIBs and SIBs.The optimized heaping configuration and the existence of metallic Co catalyzed the formation of radical ions,thereby facilitating higher conductivity,shortening Li+and Na+transport paths,and providing more active sites.Co_(2)VO_(4)/Co constructed with 2-methylimidazole as a ligand showed a discharge capacity of 1605.1 mA h g^(-1)after 300 cycles at 0.1 A g^(-1)in LIB and 677.2 mA h g^(-1)in SIB.Density functional theory(DFT)calculation emphasizes the crucial role of Co_(2)VO_(4)/Co in enhancing electrode conductivity,decreasing the migratory energy barrier,and thereby strengthening electrochemical properties.This heterostructure building technique may pave the way for the development of high-performance LIBs and SIBs.Furthermore,the problem of the low first-loop coulombic efficiency faced by transition metal oxides is improved.

Mg/Fe site-specific dual-doping to boost the performance of cobalt-free nickle-rich layered oxide cathode for high-energy lithium-ion batteries

Layer-type LiNi0.9Mn0.1O2is promising to be the primary cathode material for lithium-ion batteries(LIBs)due to its excellent electrochemical performance.Unfortunately,the cathode with high nickel content suffers from severely detrimental structural transformation that causes rapid capacity attenuation.Herein,site-specific dual-doping with Fe and Mg ions is proposed to enhance the structural stability of LiNi0.9Mn0.1O2.The Fe3+dopants are inserted into transition metal sites(3b)and can favorably provide additional redox potential to compensate for charge and enhance the reversibility of anionic redox.The Mg ions are doped into the Li sites(3a)and serve as O_(2)^(-)-Mg^(2+)-O_(2)^(-)pillar to reinforce the electrostatic cohesion between the two adjacent transition-metal layers,which further suppress the cracking and the generation of harmful phase transitions,ultimately improving the cyclability.The theoretical calculations,including Bader charge and crystal orbital Hamilton populations(COHP)analyses,confirm that the doped Fe and Mg can form stable bonds with oxygen and the electrostatic repulsion of O_(2)^(-)-O_(2)^(-)can be effectively suppressed,which effectively mitigates oxygen anion loss at the high delithiation state.This dual-site doping strategy offers new avenues for understanding and regulating the crystalline oxygen redox and demonstrates significant potential for designing high-performance cobalt-free nickel-rich cathodes.

Efficient C-N coupling in electrocatalytic urea generation on copper carbonate hydroxide electrocatalysts

Urea generation through electrochemical CO_(2) and NO_(3)~-co-reduction reaction(CO_(2)NO_(3)RR)is still limited by either the low selectivity or yield rate of urea.Herein,we report copper carbonate hydroxide(Cu_2(OH)_2CO_(3))as an efficient CO_(2)NO_(3)RR electrocatalyst with an impressive urea Faradaic efficiency of45.2%±2.1%and a high yield rate of 1564.5±145.2μg h~(-1)mg_(cat)~(-1).More importantly,H_(2) evolution is fully inhibited on this electrocatalyst over a wide potential range between-0.3 and-0.8 V versus reversible hydrogen electrode.Our thermodynamic simulation reveals that the first C-N coupling follows a unique pathway on Cu_2(OH)_2CO_(3) by combining the two intermediates,~*COOH and~*NHO.This work demonstrates that high selectivity and yield rate of urea can be simultaneously achieved on simple Cu-based electrocatalysts in CO_(2)NO_(3)RR,and provide guidance for rational design of more advanced catalysts.

Critical Opalescence and Its Impact on the Jet Quenching Parameter q

Jet quenching parameter q is essential for characterizing the interaction strength between jet partons and nuclear matter.Based on the quark-meson model,we develop a new framework for calculating q at finite chemical potentials,in which q is related to the spectral function of the chiral order parameter.

Random Green's Function Method for Large-Scale Electronic Structure Calculation

We report a linear-scaling random Green's function(rGF) method for large-scale electronic structure calculation. In this method, the rGF is defined on a set of random states and is efficiently calculated by projecting onto Krylov subspace. With the rGF method, the Fermi–Dirac operator can be obtained directly, avoiding the polynomial expansion to Fermi–Dirac function. To demonstrate the applicability, we implement the rGF method with the density-functional tight-binding method. It is shown that the Krylov subspace can maintain at small size for materials with different gaps at zero temperature, including H_(2)O and Si clusters. We find with a simple deflation technique that the rGF self-consistent calculation of H_(2)O clusters at T = 0 K can reach an error of~ 1 me V per H_(2)O molecule in total energy, compared to deterministic calculations. The rGF method provides an effective stochastic method for large-scale electronic structure simulation.

Active MoS_(2)-based electrode for green ammonia synthesis

Nitrogen electro-reduction under mild conditions is one promising alternative approach of the energyconsuming Haber-Bosch process for the artificial ammonia synthesis.One critical aspect to unlocking this technology is to discover the catalysts with high selectivity and efficiency.In this work,the N_(2)-to-NH_(3)conversion on the functional MoS_(2)is fully investigated by density functional theory calculations since the layered MoS_(2)provides the ideal platform for the elaborating copies of the nitrogenase found in nature,wherein the functionalization is achieved via basal-adsorption,basal-substitution or edge-substitution of transition metal elements.Our results reveal that the edge-functionalization is a feasible strategy for the activity promotion;however,the basal-adsorption and basal-substitution separately suffer from the electrochemical instability and the NRR inefficiency.Specifically,MoS_(2)functionalized via edge W-substitution exhibits an exceptional activity.The energetically favored reaction pathway is through the distal pathway and a limiting potential is less than 0.20 V.Overall,this work escalates the rational design of the high-effective catalysts for nitrogen fixation and provides the explanation why the predicated catalyst have a good performance,paving the guidance for the experiments.

Structural and electrochemical stabilization enabling high-energy P3-type Cr-based layered oxide cathode for K-ion batteries

Layered-type transition metal(TM)oxides are considered as one of the most promising cathodes for K-ion batteries because of the large theoretical gravimetric capacity by low molar mass.However,they suffer from severe structural change by de/intercalation and diffusion of K^(+)ions with large ionic size,which results in not only much lower reversible capacity than the theoretical capacity but also poor power capability.Thus,it is important to enhance the structural stability of the layered-type TM oxides for outstanding electrochemical behaviors under the K-ion battery system.Herein,it is investigated that the substitution of the appropriate Ti^(4+)contents enables a highly enlarged reversible capacity of P3-type KxCrO_(2) using combined studies of first-principles calculation and various experiments.Whereas the pristine P3-type KxCrO_(2) just exhibits the reversible capacity of∼120 mAh g^(−1) in the voltage range of 1.5-4.0 V(vs.K^(+)/K),the∼0.61 mol K^(+)corresponding to∼150 mAh g^(−1) can be reversible de/intercalated at the structure of P3-type K0.71[Cr_(0.75)Ti_(0.25)]O_(2) under the same conditions.Furthermore,even at the high current density of 788 mA g^(−1),the specific capacity of P3-type K0.71[Cr_(0.75)Ti_(0.25)]O_(2) is∼120 mAh g^(−1),which is∼81 times larger than that of the pristine P3-type KxCrO_(2).It is believed that this research can provide an effective strategy to improve the electrochemical performances of the cathode materials suffered by severe structural change that occurred during charge/discharge under not only K-ion battery system but also other rechargeable battery systems.

Tuning interface mechanism of FeCo alloy embedded N,S-codoped carbon substrate for rechargeable Zn-air battery

The interface mechanism between catalyst and carbon substrate has been the focus of research.In this paper,the FeCo alloy embedded N,S co-doped carbon substrate bifunctional catalyst(FeCo/S-NC)is obtained by a simple one-step pyrolysis strategy.The experimental results and density functional theory(DFT)calculation show that the formation of FeCo alloy is conducive to promoting electron transfer,and the introduction of S atom can enhance the interaction between FeCo alloy and carbon substrate,thus inhibiting the migration and agglomeration of particles on the surface of carbon material.The FeCo/SNC catalysts show outstanding performance for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER).FeCo/S-NC shows a high half-wave potential(E_(1/2)=0.8823 V)for ORR and a low overpotential at 10 mA cm^(-2)(E_(j=10)=299 mV)for OER.In addition,compared with Pt/C+RuO_(2) assembled Zn-air battery(ZAB),the FeCo/S-NC assembled ZAB exhibits a larger power density(198.8 mW cm^(-2)),a higher specific capacity(786.1 mA h g_(zn)~(-1)),and ultra-stable cycle performance.These results confirm that the optimized composition and the interfacial interaction between catalyst and carbon substrate synergistically enhance the electrochemical performance.

Precision tuning of highly efficient Pt-based ternary alloys on nitrogen-doped multi-wall carbon nanotubes for methanol oxidation reaction

The electrochemical methanol oxidation is a crucial reaction in the conversion of renewable energy.To enable the widespread adoption of direct methanol fuel cells(DMFCs),it is essential to create and engineer catalysts that are both highly effective and robust for conducting the methanol oxidation reaction(MOR).In this work,trimetallic PtCoRu electrocatalysts on nitrogen-doped carbon and multi-wall carbon nanotubes(PtCoRu@NC/MWCNTs)were prepared through a two-pot synthetic strategy.The acceleration of CO oxidation to CO_(2) and the blocking of CO reduction on adjacent Pt active sites were attributed to the crucial role played by cobalt atoms in the as-prepared electrocatalysts.The precise control of Co atoms loading was achieved through precursor stoichiometry.Various physicochemical techniques were employed to analyze the morphology,element composition,and electronic state of the catalyst.Electrochemical investigations and theoretical calculations confirmed that the Pt_(1)Co_(3)Ru_(1)@NC/MWCNTs exhibit excellent electrocatalytic performance and durability for the process of MOR.The enhanced MOR activity can be attributed to the synergistic effect between the multiple elements resulting from precisely controlled Co loading content on surface of the electrocatalyst,which facilitates efficient charge transfer.This interaction between the multiple components also modifies the electronic structures of active sites,thereby promoting the conversion of intermediates and accelerating the MOR process.Thus,achieving precise control over Co loading in PtCoRu@NC/MWCNTs would enable the development of high-performance catalysts for DMFCs.

Determining Hubbard U of VO_(2) by the quasi-harmonic approximation

Vanadium dioxide VO_(2) is a strongly correlated material that undergoes a metal-to-insulator transition around 340 K.In order to describe the electron correlation effects in VO_(2), the DFT+U method is commonly employed in calculations.However, the choice of the Hubbard U parameter has been a subject of debate and its value has been reported over a wide range. In this paper, taking focus on the phase transition behavior of VO_(2), the Hubbard U parameter for vanadium oxide is determined by using the quasi-harmonic approximation(QHA). First-principles calculations demonstrate that the phase transition temperature can be modulated by varying the U values. The phase transition temperature can be well reproduced by the calculations using the Perdew–Burke–Ernzerhof functional combined with the U parameter of 1.5eV. Additionally,the calculated band structure, insulating or metallic properties, and phonon dispersion with this U value are in line with experimental observations. By employing the QHA to determine the Hubbard U parameter, this study provides valuable insights into the phase transition behavior of VO_(2). The findings highlight the importance of electron correlation effects in accurately describing the properties of this material. The agreement between the calculated results and experimental observations further validates the chosen U value and supports the use of the DFT+U method in studying VO_(2).

Progress in Mechanical Modeling of Implantable Flexible Neural Probes

Implanted neural probes can detect weak discharges of neurons in the brain by piercing soft brain tissue,thus as important tools for brain science research,as well as diagnosis and treatment of brain diseases.However,the rigid neural probes,such as Utah arrays,Michigan probes,and metal microfilament electrodes,are mechanically unmatched with brain tissue and are prone to rejection and glial scarring after implantation,which leads to a significant degradation in the signal quality with the implantation time.In recent years,flexible neural electrodes are rapidly developed with less damage to biological tissues,excellent biocompatibility,and mechanical compliance to alleviate scarring.Among them,the mechanical modeling is important for the optimization of the structure and the implantation process.In this review,the theoretical calculation of the flexible neural probes is firstly summarized with the processes of buckling,insertion,and relative interaction with soft brain tissue for flexible probes from outside to inside.Then,the corresponding mechanical simulation methods are organized considering multiple impact factors to realize minimally invasive implantation.Finally,the technical difficulties and future trends of mechanical modeling are discussed for the next-generation flexible neural probes,which is critical to realize low-invasiveness and long-term coexistence in vivo.

An Efficient Optimization Design Framework for Low-Resistance Shape of Bionic Amphibious Robot

To realize the low-resistance shape optimization design of amphibious robots,an efficient optimization design framework is proposed to improve the geometric deformation flexibility and optimization efficiency.In the proposed framework,the free-form deformation parametric model of the flat slender body is established and an analytical calculation method for the height constraints is derived.CFD method is introduced to carry out the high-precision resistance calculation and a constrained Kriging-based optimization method is built to improve the optimization efficiency by circularly infilling the new sample points which satisfying the constraints.Finally,the shape of an amphibious robot example is optimized to get the low-resistance shape and the results demonstrate that the presented optimization design framework has the advantages of simplicity,flexibility and high efficiency.

Rational construction of CuFe_(2)O_(4)@C/Cd_(0.9)Zn_(0.1)S S-scheme heterojunction photocatalyst for extraordinary photothermal-assisted photocatalytic H_(2) evolution

Rational design of photocatalyst to maximize the use of sunlight is one of the issues to be solved in photocatalysis technology.In this study,the CuFe_(2)O_(4)@C/Cd_(0.9)Zn_(0.1)S(CFO@C/CZS)S-scheme photocatalyst with photothermal effect was synthesized by ultrasonic self-assembly combined with calcination.The dark CFO@C absorbed visible light and partly converted into heat to promote the hydrogen evolution reaction.The presence of heterojunctions inhibited the photogenerated electron-hole recombination.The graphite-carbon layer provided a stable channel for electron transfer,and the presence of magnetic CFO made recycle easier.Under the action of photothermal assistance and heterojunction,the hydrogen evolution rate of the optimal CFO@C/CZS was 80.79 mmol g^(-1) h^(-1),which was 2.55 times and 260.61 times of that of pure CZS and CFO@C,respectively.Notably,the composite samples also exhibit excellent stability and a wide range of environmental adaptability.Through experimental tests and first-principles simulation calculation methods,the plausible mechanism of photoactivity enhancement was proposed.This work provided a feasible strategy of photothermal assistance for the development of heterojunction photocatalysts with distinctive hydrogen evolution.

Toward a comprehensive hypothesis of oxygen-evolution reaction in the presence of iron and gold

This study investigates the effects of Fe on the oxygen-evolution reaction(OER)in the presence of Au.Two distinct areas of OER were identified:the first associated with Fe sites at low overpotential(~330 mV),and the second with Au sites at high overpotential(~870 mV).Various factors such as surface Fe concentration,electrochemical method,scan rate,potential range,concentration,method of adding K_(2)Fe O_(4),nature of Fe,and temperature were varied to observe diverse behaviors during OER for Fe O_(x)H_(y)/Au.Trace amounts of Fe ions had a significant impact on OER,reaching a saturation point where the activity did not increase further.Strong electronic interaction between Fe and Au ions was indicated by X-ray photoelectron spectroscopy(XPS)and electron paramagnetic resonance(EPR)analyses.In situ visible spectroscopy confirmed the formation of Fe O_(4)^(2-)during OER.In situ Mossbauer and surfaceenhanced Raman spectroscopy(SERS)analyses suggest the involvement of Fe-based species as intermediates during the rate-determining step of OER.A lattice OER mechanism based on Fe O_(x)H_(y)was proposed for operation at low overpotentials.Density functional theory(DFT)calculations revealed that Fe oxide,Fe-oxide clusters,and Fe doping on the Au foil exhibited different activities and stabilities during OER.The study provides insights into the interplay between Fe and Au in OER,advancing the understanding of OER mechanisms and offering implications for the design of efficient electrocatalytic systems.