Using the unsymmetrical one-range addition theorems introduced by one of the authors with the help of complete orthonormal sets of $／varPsi ^／alpha $-exponential type orbitals （$／alpha = 1,0, - 1, - 2,...）$, this...Using the unsymmetrical one-range addition theorems introduced by one of the authors with the help of complete orthonormal sets of $／varPsi ^／alpha $-exponential type orbitals （$／alpha = 1,0, - 1, - 2,...）$, this paper presents the sets of series expansion relations for multicentre nuclear attraction integrals over Slater-type orbitals arising in Hartree--Fock--Roothaan equations for molecules. The final results are expressed through multicentre charge density expansion coefficients and basic integrals. The convergence of the series is tested by calculating concrete cases for arbitrary values of parameters of orbitals.展开更多
Unraveling the essence of electronic structure effected by d-d orbital coupling of transition metal and methanol oxidation reaction(MOR)performance can fundamentally guide high efficient catalyst design.Herein,density...Unraveling the essence of electronic structure effected by d-d orbital coupling of transition metal and methanol oxidation reaction(MOR)performance can fundamentally guide high efficient catalyst design.Herein,density functional theory(DFT)calculations were performed at first to study the d–d orbital interaction of metallic Pt Pd Cu,revealing that the incorporation of Pd and Cu atoms into Pt system can enhance d-d electron interaction via capturing antibonding orbital electrons of Pt to fill the surrounding Pd and Cu atoms.Under the theoretical guidance,Pt Pd Cu medium entropy alloy aerogels(Pt Pd Cu MEAAs)catalysts have been designed and systematically screened for MOR under acid,alkaline and neutral electrolyte.Furthermore,DFT calculation and in-situ fourier transform infrared spectroscopy analysis indicate that Pt Pd Cu MEAAs follow the direct pathway via formate as the reactive intermediate to be directly oxidized to CO_(2).For practical direct methanol fuel cells(DMFCs),the Pt Pd Cu MEAAs-integrated ultra-thin catalyst layer(4–5μm thickness)as anode exhibits higher peak power density of 35 m W/cm^(2) than commercial Pt/C of 20 m W/cm^(2)(~40μm thickness)under the similar noble metal loading and an impressive stability retention at a 50-m A/cm^(2) constant current for 10 h.This work clearly proves that optimizing the intermediate adsorption capacity via d-d orbital coupling is an effective strategy to design highly efficient catalysts for DMFCs.展开更多
Surface chemistry plays a critical role in the fields of electrochemistry,heterogeneous catalysis,adsorption,etc.[1–4].The representative D-band center theory reported through Hammer and Nørskov in surface chemi...Surface chemistry plays a critical role in the fields of electrochemistry,heterogeneous catalysis,adsorption,etc.[1–4].The representative D-band center theory reported through Hammer and Nørskov in surface chemistry has been widely used in early studies to predict adsorption strength[5,6].Generally,the adsorption strength of active sites correlates inversely with the downward shift of the D-band center(εd)relative to the Fermi level,as lower-energy positioning increases anti-bonding orbital occupancy,weakening surface interactions(Fig.1(a)).展开更多
Dear Editor,Idiopathic orbital inflammation(IOI),also known as orbital inflammatory pseudotumor,is a relatively common orbital disorder[1].Its pathogenesis remains unclear,often regarded as a nonspecific immune-mediat...Dear Editor,Idiopathic orbital inflammation(IOI),also known as orbital inflammatory pseudotumor,is a relatively common orbital disorder[1].Its pathogenesis remains unclear,often regarded as a nonspecific immune-mediated response[2].IOI presents with symptoms such as pain,photophobia,proptosis,eyelid swelling,edema,conjunctival congestion,and diplopia,with possible vision loss occurring in some cases.Based on the soft tissue structures involved,IOI can be classified into subtypes such as myositis,optic neuritis,dacryoadenitis,diffuse orbital inflammation,and orbital inflammatory masses[2].展开更多
AIM:To investigate the clinical features and prognosis of patients with orbital inflammatory myofibroblastic tumor(IMT).METHODS:This retrospective study collected clinical data from 22 patients diagnosed with orbital ...AIM:To investigate the clinical features and prognosis of patients with orbital inflammatory myofibroblastic tumor(IMT).METHODS:This retrospective study collected clinical data from 22 patients diagnosed with orbital IMT based on histopathological examination.The patients were followed up to assess their prognosis.Clinical data from patients,including age,gender,course of disease,past medical history,primary symptoms,ophthalmologic examination findings,general condition,as well as imaging,laboratory,histopathological,and immunohistochemical results from digital records were collected.Orbital magnetic resonance imaging(MRI)and(or)computed tomography(CT)scans were performed to assess bone destruction of the mass,invasion of surrounding tissues,and any inflammatory changes in periorbital areas.RESULTS:The mean age of patients with orbital IMT was 28.24±3.30y,with a male-to-female ratio of 1.2:1.Main clinical manifestations were proptosis,blurred vision,palpable mass,and pain.Bone destruction and surrounding tissue invasion occurred in 72.73%and 54.55%of cases,respectively.Inflammatory changes in the periorbital site were observed in 77.27%of the patients.Hematoxylin and eosin staining showed proliferation of fibroblasts and myofibroblasts,accompanied by infiltration of lymphocytes and plasma cells.Immunohistochemical staining revealed that smooth muscle actin(SMA)and vimentin were positive in 100%of cases,while anaplastic lymphoma kinase(ALK)showed positivity in 47.37%.The recurrence rate of orbital IMT was 27.27%,and sarcomatous degeneration could occur.There were no significant correlations between recurrence and factors such as age,gender,laterality,duration of the disease,periorbital tissue invasion,bone destruction,periorbital inflammation,tumor size,fever,leukocytosis,or treatment(P>0.05).However,lymphadenopathy and a Ki-67 index of 10%or higher may be risk factors for recurrence(P=0.046;P=0.023).CONCLUSION:Orbital IMT is a locally invasive disease that may recur or lead to sarcomatoid degeneration,primarily affecting young and middle-aged patients.The presence of lymphadenopathy and a Ki-67 index of 10%or higher may signify a poor prognosis.展开更多
AIM:To define the prevalence and anatomical patterns of paranasal sinus abnormalities(PSA)in thyroid-associated ophthalmopathy(TAO)and to test the hypothesis that TAO is partially driven by contiguous orbital inflamma...AIM:To define the prevalence and anatomical patterns of paranasal sinus abnormalities(PSA)in thyroid-associated ophthalmopathy(TAO)and to test the hypothesis that TAO is partially driven by contiguous orbital inflammation rather than systemic autoimmunity or generalized orbital pressure.METHODS:Data included ophthalmic assessments and a panel of thyroid function and autoimmune biomarkers.Blinded radiological analysis of orbital computed tomography(CT)scans was performed to quantify sinus abnormalities and extraocular muscles(EOMs)involvement.Patients were categorized into two groups based on CT findings,those with no radiological evidence of sinus abnormalities(non-PSA control group)and those with identifiable PSA.Furthermore,ethmoid sinus mucosal biopsies from a subset of TAO patients and noninflammatory controls were subjected to histopathological analysis.RESULTS:Totally 121 TAO patients(mean age 42.4±12.8y,range 10-78y),male:female=42:79,were included.PSA was identified in 44.6%(n=54)of patients,with a distribution anatomically restricted to the maxillary(50.0%isolated)and ethmoid sinuses(18.5%isolated;29.6%combined).Compared to the non-PSA group(n=67),patients with PSA were significantly older(45.1±11.8 vs 40.3±13.2y;P=0.040)and were more likely to be male(55.6%vs 17.9%;P<0.001).They also had significantly higher proptosis(22.1±3.2 vs 20.7±2.9 mm;P<0.001).Medial/inferior rectus involvement was most frequent(88.4%vs 89.3%).Histopathological analysis of sinus mucosa from PSA patients provided direct evidence of pathology,revealing a dense,chronic lymphoplasmacytic infiltrate and submucosal edema,validating the radiological findings as a true inflammatory process.No significant correlation was found with systemic autoimmune markers,including thyroid-stimulating hormone(TSH)receptor antibodies(TRAb,median 4.86 vs 2.71 IU/L,P=0.104).CONCLUSION:TAO is associated with a high prevalence of PSA in a pattern consistent with the orbital anatomy.The correlation with ipsilateral muscle thickening combined with the lack of association with proptosis laterality or systemic biomarkers lend strong support to a model of contiguous inflammation over systemic autoimmunity,a hypothesis that warrants further validation through longitudinal and mechanistic studies.展开更多
The effect of plasma and charged particle interaction with spacecraft in a low Earth orbit(LEO)environment leads to ion focusing and the formation of an ion void in the downstream region as a result of charging.Simula...The effect of plasma and charged particle interaction with spacecraft in a low Earth orbit(LEO)environment leads to ion focusing and the formation of an ion void in the downstream region as a result of charging.Simulations and investigations using a fixed potential imposed on the spacecraft showed the nonsignificance of geophysical parameter changes to ion focusing.Variation of the temperature ratio(T_(r))contributed only to local ion focusing and manifested as two-ion streamers dispersed at the upper and lower edges of the spacecraft-the outermost layers of the satellite structure at the top and bottom,respectively.A simulation involving changing the ambient plasma density(N_(p))also showed the formation of local ion focusing,in which ions were more concentrated as the density increased.Furthermore,auroral electron density(N_(ae))variation had no clear impact on ion focusing,as indicated by static two-ion structures in the wake field.However,variation of the object potential(ϕ)strongly affected ion focusing formation,leading to distortion of the initial ion void region behind the spacecraft.The formation of ion focusing in this study was subject to the electric field produced by the object potential and the ambipolar electric field resulting from plasma expansion in the downstream region.展开更多
The binding energy spectrum and electron momentum distributions for the outer valence orbitals of n-propyl iodide molecule have been measured using the electron momentum spectrometer employing non-coplanar asymmetric ...The binding energy spectrum and electron momentum distributions for the outer valence orbitals of n-propyl iodide molecule have been measured using the electron momentum spectrometer employing non-coplanar asymmetric geometry at impact energy of 2.5 keV plus binding energy. The ionization bands have been assigned in detail via the high accuracy SACCI general-R method calculation and the experimental momentum profiles are compared with the theoretical ones calculated by Hartree-Fock and B3LYP/aug-cc-pVTZ（C,H）6-311G？？（I）. The spin-orbit coupling effect and intramolecular orbital interaction have been analyzed for the outermost two bands, which are assigned to the iodine 5p lone pairs, using NBO method and non-relativistic as well as relativistic calculations. It is found that both of the interactions will lead to the observed differences in electron momentum distributions. The experimental results agree with the relativistic theoretical momentum profiles, indicating that the spin-orbit coupling effect dominates in n-propyl iodide molecule.展开更多
In this paper, the extended Pade approximant is used to construct the homoclinic and the heteroclinic trajectories in nonlinear dynamical systems that are asymmetric at origin. Meanwhile, the conservative system, the ...In this paper, the extended Pade approximant is used to construct the homoclinic and the heteroclinic trajectories in nonlinear dynamical systems that are asymmetric at origin. Meanwhile, the conservative system, the autonomous system, and the nonautonomous system equations with quadratic and cubic nonlinearities are considered. The disturbance parameter ~ is not limited to being small. The ranges of the values of the linear and the nonlinear term parameters, which are variables, can be determined when the boundary values are satisfied. New conditions for the potentiality and the convergence are posed to make it possible to solve the boundary-value problems formulated for the orbitals and to evaluate the initial amplitude values.展开更多
This paper calculates the five most stable conformers of serine with Hartree-Fock theory, density functional theory （B3LYP）, Moller-Plesset perturbation theory （MP4（SDQ）） and electron propagation theory with the...This paper calculates the five most stable conformers of serine with Hartree-Fock theory, density functional theory （B3LYP）, Moller-Plesset perturbation theory （MP4（SDQ）） and electron propagation theory with the 6-311＋＋G（2d,2p） basis set. The calculated vertical ionization energies for the valence molecular orbitals of each conformer are in agreement with the experimental data, indicating that a range of molecular conformations would coexist in an equilibrium sample. Information of the five outer valence molecular orbitals for each conformer is explored in coordinate and momentum spaces using dual space analysis to investigate the conformational processes, which are generated from the global minimum conformer Serl by rotation of C2-C3 （Ser4）, C1 C2 （Ser5） and C1-O2 （Set2 and Ser3）. Orbitals 28a, 27a and 26a are identified as the fingerprint orbitals for all the conformational processes.展开更多
Basing on the DFT calculations we propose the new theoretical model which describes both the surface tension σ of the short chain n-alkanes at their normal boiling points and their reaction rate constants with hydrox...Basing on the DFT calculations we propose the new theoretical model which describes both the surface tension σ of the short chain n-alkanes at their normal boiling points and their reaction rate constants with hydroxyl radicals OH<span style="white-space:nowrap;">• (at 297 ± 2 K) on the basis of their molecular orbital electronic characteristics. It has been shown that intermolecular dispersion attraction within the surface liquid monolayer of these compounds, as well as their reaction rate constants k with OH<span style="white-space:nowrap;">• radicals are determined by the energies E<sub>orb</sub> of the specific occupied molecular orbitals which are the same in the determination of both the above physico-chemical characteristics of the studied n-alkanes. The received regression equations confirm the theoretically found dependences between the quantities of σ and k and the module |E<sub>orb</sub>|. For the compounds under study this fact indicates the key role of their electronic structure particularities in determination of both the physical (surface tension) and the chemical (reaction rate constants) properties.展开更多
Accelerating the sluggish redox kinetics of lithium polysulfides(LiPSs)by electrocatalysis is essential to achieve high performance lithium-sulfur(Li-S)batteries.However,the issue of insufficient catalytic activity re...Accelerating the sluggish redox kinetics of lithium polysulfides(LiPSs)by electrocatalysis is essential to achieve high performance lithium-sulfur(Li-S)batteries.However,the issue of insufficient catalytic activity remains to be addressed.Herein,a strategy of modulating e_(g) orbitals through ligand engineering has been proposed to boost the catalytic activity of NiSe for rapid LiPSs redox conversion.The X-ray spectroscopic measurements and theoretical calculations reveal that partial substitution of Se with N disrupts the octahedral coordination of Ni atoms in NiSe,leading to the reduced degeneracy and upward shift of e_(g) orbitals of Ni 3 d states.As a consequence,the bonding strength of N-substituted NiSe(N-NiSe)with LiPSs is enhanced,which facilitates the interfacial charge transfer kinetics and accelerates the LiPSs redox kinetics.Therefore,the Li-S batteries assembled with N-NiSe present a high capacity of 682.6 mAh g^(-1) at a high rate of 5 C and a high areal capacity of 6.5 mAh cm^(-2)at a high sulfur loading of 6 mg cm^(-2).This work provides a promising strategy to develop efficient transition-metal based electrocatalysts for Li-S batteries through e_(g) orbital modulation.展开更多
In this paper, we have declined the formalism of the method of the Modified Atomic Orbital Theory (MAOT) applied to the calculations of energies of doubly excited states 2<em>snp</em>, 3<em>snp</e...In this paper, we have declined the formalism of the method of the Modified Atomic Orbital Theory (MAOT) applied to the calculations of energies of doubly excited states 2<em>snp</em>, 3<em>snp</em>, and 4<em>snp</em> Helium-like systems. Then we also applied the variational procedure of the Modified Atomic Orbital Theory to the computations of total energies, excitation energies of doubly-excited states 2<em>snp</em>, 3<em>snp</em>, 4<em>snp</em> types of Helium-like systems. The results obtained in this work are in good agreement with the experimental and theoretical values available.展开更多
The electronic modulation characteristics of efficient metal phosphide electrocatalysts can be utilized to tune the performance of oxygen evolution reaction(OER).However,improving the overall water splitting performan...The electronic modulation characteristics of efficient metal phosphide electrocatalysts can be utilized to tune the performance of oxygen evolution reaction(OER).However,improving the overall water splitting performance remains a challenging task.By building metal organic framework(MOF)on MOF heterostructures,an efficient strategy for controlling the electrical structure of MOFs was presented in this study.ZIF-67 was in-situ synthesized on MIL-88(Fe)using a two-step self-assembly method,followed by low-temperature phosphorization to ultimately synthesize FeP-CoP_(3)bimetallic phosphides.By combining atomic orbital theory and theoretical calculations(density functional theory),the results reveal the successful modulation of electronic orbitals in FeP-CoP_(3)bimetallic phosphides,which are synthesized from MOF on MOF structure.The synergistic impact of the metal center Co species and the phase conjugation of both kinds of MOFs are responsible for this regulatory phenomenon.Therefore,the catalyst demonstrates excellent properties,demonstrating HER 81 mV(η10)in a 1.0 mol L^(−1)KOH solution and OER 239 mV(η50)low overpotentials.The FeP-CoP_(3)linked dual electrode alkaline batteries,which are bifunctional electrocatalysts,have a good electrocatalytic ability and may last for 50 h.They require just 1.49 V(η50)for total water breakdown.Through this technique,the electrical structure of electrocatalysts may be altered to increase catalytic activity.展开更多
Recently, there was a hot controversy about the concept of localized orbitals, which was triggered by Grushow＇s work titled ＂Is it time to retire the hybrid atomic orbital？＂ [J. Chem. Educ. 88, 860 （2011）]. To c...Recently, there was a hot controversy about the concept of localized orbitals, which was triggered by Grushow＇s work titled ＂Is it time to retire the hybrid atomic orbital？＂ [J. Chem. Educ. 88, 860 （2011）]. To clarify the issue, we assess the delocalized and localized molecular orbitals from an experimental view using electron momentum spectroscopy. The delocalized and localized molecular orbitals based on various theoretical models for CH4, NH3, and H20 are compared with the experimental momentum distributions. Our results show that the delocalized molecular orbitals rather than the localized ones can give a direct interpretation of the experimental （e, 2e） results.展开更多
The outer valence electron momentum distributions of benzene are reinvestigated with theoretical calculations involving the vibrational effects.The results are compared with recent experimental measurements[Phys.Rev.A...The outer valence electron momentum distributions of benzene are reinvestigated with theoretical calculations involving the vibrational effects.The results are compared with recent experimental measurements[Phys.Rev.A 98042705(2018)].The significant discrepancies between theories and experiments in previous works have now been interpreted quantitatively,indicating that the vibrational motion in benzene molecule has noticeable influence on its electron momentum distributions.展开更多
The single ionization rate of the diatomic molecular ion H2^＋ with different active orbitals in an intense field is studied by using S-matrix theory. Our results show that the orientation-dependent single ionization ...The single ionization rate of the diatomic molecular ion H2^＋ with different active orbitals in an intense field is studied by using S-matrix theory. Our results show that the orientation-dependent single ionization probability of H2^＋ is greatly dependent on the symmetry and the electron density distribution of its initial states, and it can be used to identify the excited state of the molecular ion in the dissociation process.展开更多
The present paper covers a kind of localized orbitals, namely bond-distorted or-bitals in the valence bond calculation. Test calculation on benzene is reported. The results indicate that Dewar structures are important...The present paper covers a kind of localized orbitals, namely bond-distorted or-bitals in the valence bond calculation. Test calculation on benzene is reported. The results indicate that Dewar structures are important in the description of benzene.展开更多
Rehybridization of electronic orbitals in carbon nanotubes contains tilting angles of π orbital, electrons wavefunctions of π orbital and a orbital, degrees of hybridization, etc. In this paper, we have obtained ana...Rehybridization of electronic orbitals in carbon nanotubes contains tilting angles of π orbital, electrons wavefunctions of π orbital and a orbital, degrees of hybridization, etc. In this paper, we have obtained analytical formulas of tilting angle of π orbital relative to tube surface, electrons wavefunctions of π orbital and a orbital, degrees of hybridization, separately, as well as the numerical results.展开更多
This paper studies the molecular rotational excitation and field-free spatial alignment in a nonresonant intense laser field numerically and analytically by using the time-dependent SchrSdinger equation. The broad rot...This paper studies the molecular rotational excitation and field-free spatial alignment in a nonresonant intense laser field numerically and analytically by using the time-dependent SchrSdinger equation. The broad rotational wave packets excited by the femtosecond pulse are defined in conjugate angle space, and their coefficients are obtained by solving a set of coupled linear equations. Both single molecule orientation angles and an ensemble of O2 and CO molecule angular distributions are calculated in detail. The numerical results show that, for single molecule highest occupied molecular orbital （HOMO） symmetry σ tends to have a molecular orientation along the laser polarization direction and the permanent dipole moment diminishes the mean of the orientation angles; for an ensemble of molecules, angular distributions provide more complex and additional information at times where there are no revivals in the single molecule plot. In particular, at the revival peak instant, with the increase of temperature of the molecular ensemble, the anisotropic angular distributions with respect to the laser polarization direction of the πg orbital gradually transform to the symmetrical distributions regarding the laser polarization vector and for two HOMO configurations angular distributions of all directions are confined within a smaller angle when the temperature of the molecular ensemble is higher.展开更多
文摘Using the unsymmetrical one-range addition theorems introduced by one of the authors with the help of complete orthonormal sets of $／varPsi ^／alpha $-exponential type orbitals （$／alpha = 1,0, - 1, - 2,...）$, this paper presents the sets of series expansion relations for multicentre nuclear attraction integrals over Slater-type orbitals arising in Hartree--Fock--Roothaan equations for molecules. The final results are expressed through multicentre charge density expansion coefficients and basic integrals. The convergence of the series is tested by calculating concrete cases for arbitrary values of parameters of orbitals.
基金financially supported by the National Natural Science Foundation of China(Nos.52073214 and 22075211)Guangxi Natural Science Fund for Distinguished Young Scholars(No.2024GXNSFFA010008)+5 种基金Natural Science Foundation of Shandong Province(Nos.ZR2023MB049 and ZR2021QB129)China Postdoctoral Science Foundation(No.2020M670483)Science Foundation of Weifang University(No.2023BS11)supported by the open research fund of the Laboratory of Xinjiang Native Medicinal and Edible Plant Resources Chemistry at Kashi Universitysupported by the Tianhe Qingsuo Open Research Fund of TSYS in 2022 and NSCC-TJNankai University Large-scale Instrument Experimental Technology R&D Project(No.21NKSYJS09)。
文摘Unraveling the essence of electronic structure effected by d-d orbital coupling of transition metal and methanol oxidation reaction(MOR)performance can fundamentally guide high efficient catalyst design.Herein,density functional theory(DFT)calculations were performed at first to study the d–d orbital interaction of metallic Pt Pd Cu,revealing that the incorporation of Pd and Cu atoms into Pt system can enhance d-d electron interaction via capturing antibonding orbital electrons of Pt to fill the surrounding Pd and Cu atoms.Under the theoretical guidance,Pt Pd Cu medium entropy alloy aerogels(Pt Pd Cu MEAAs)catalysts have been designed and systematically screened for MOR under acid,alkaline and neutral electrolyte.Furthermore,DFT calculation and in-situ fourier transform infrared spectroscopy analysis indicate that Pt Pd Cu MEAAs follow the direct pathway via formate as the reactive intermediate to be directly oxidized to CO_(2).For practical direct methanol fuel cells(DMFCs),the Pt Pd Cu MEAAs-integrated ultra-thin catalyst layer(4–5μm thickness)as anode exhibits higher peak power density of 35 m W/cm^(2) than commercial Pt/C of 20 m W/cm^(2)(~40μm thickness)under the similar noble metal loading and an impressive stability retention at a 50-m A/cm^(2) constant current for 10 h.This work clearly proves that optimizing the intermediate adsorption capacity via d-d orbital coupling is an effective strategy to design highly efficient catalysts for DMFCs.
文摘Surface chemistry plays a critical role in the fields of electrochemistry,heterogeneous catalysis,adsorption,etc.[1–4].The representative D-band center theory reported through Hammer and Nørskov in surface chemistry has been widely used in early studies to predict adsorption strength[5,6].Generally,the adsorption strength of active sites correlates inversely with the downward shift of the D-band center(εd)relative to the Fermi level,as lower-energy positioning increases anti-bonding orbital occupancy,weakening surface interactions(Fig.1(a)).
基金Supported by the National Natural Science Foundation of China(No.82388101,No.81930024)the Science and Technology Commission of Shanghai(No.22YS1400400,No.20DZ2270800).
文摘Dear Editor,Idiopathic orbital inflammation(IOI),also known as orbital inflammatory pseudotumor,is a relatively common orbital disorder[1].Its pathogenesis remains unclear,often regarded as a nonspecific immune-mediated response[2].IOI presents with symptoms such as pain,photophobia,proptosis,eyelid swelling,edema,conjunctival congestion,and diplopia,with possible vision loss occurring in some cases.Based on the soft tissue structures involved,IOI can be classified into subtypes such as myositis,optic neuritis,dacryoadenitis,diffuse orbital inflammation,and orbital inflammatory masses[2].
基金Supported by the National Key R&D Program of China(No.2023YFC2410203)Beijing Hospitals Authority Clinical Medicine Development of Special Funding Support(No.ZLRK202503).
文摘AIM:To investigate the clinical features and prognosis of patients with orbital inflammatory myofibroblastic tumor(IMT).METHODS:This retrospective study collected clinical data from 22 patients diagnosed with orbital IMT based on histopathological examination.The patients were followed up to assess their prognosis.Clinical data from patients,including age,gender,course of disease,past medical history,primary symptoms,ophthalmologic examination findings,general condition,as well as imaging,laboratory,histopathological,and immunohistochemical results from digital records were collected.Orbital magnetic resonance imaging(MRI)and(or)computed tomography(CT)scans were performed to assess bone destruction of the mass,invasion of surrounding tissues,and any inflammatory changes in periorbital areas.RESULTS:The mean age of patients with orbital IMT was 28.24±3.30y,with a male-to-female ratio of 1.2:1.Main clinical manifestations were proptosis,blurred vision,palpable mass,and pain.Bone destruction and surrounding tissue invasion occurred in 72.73%and 54.55%of cases,respectively.Inflammatory changes in the periorbital site were observed in 77.27%of the patients.Hematoxylin and eosin staining showed proliferation of fibroblasts and myofibroblasts,accompanied by infiltration of lymphocytes and plasma cells.Immunohistochemical staining revealed that smooth muscle actin(SMA)and vimentin were positive in 100%of cases,while anaplastic lymphoma kinase(ALK)showed positivity in 47.37%.The recurrence rate of orbital IMT was 27.27%,and sarcomatous degeneration could occur.There were no significant correlations between recurrence and factors such as age,gender,laterality,duration of the disease,periorbital tissue invasion,bone destruction,periorbital inflammation,tumor size,fever,leukocytosis,or treatment(P>0.05).However,lymphadenopathy and a Ki-67 index of 10%or higher may be risk factors for recurrence(P=0.046;P=0.023).CONCLUSION:Orbital IMT is a locally invasive disease that may recur or lead to sarcomatoid degeneration,primarily affecting young and middle-aged patients.The presence of lymphadenopathy and a Ki-67 index of 10%or higher may signify a poor prognosis.
基金Supported by The National Natural Science Foundation of China(No.82101180)the Fund for Beijing Science&Technology Development of TCM(No.BJZYYB-2023-17)the Beijing Municipal Natural Science Foundation grant(No.7252093).
文摘AIM:To define the prevalence and anatomical patterns of paranasal sinus abnormalities(PSA)in thyroid-associated ophthalmopathy(TAO)and to test the hypothesis that TAO is partially driven by contiguous orbital inflammation rather than systemic autoimmunity or generalized orbital pressure.METHODS:Data included ophthalmic assessments and a panel of thyroid function and autoimmune biomarkers.Blinded radiological analysis of orbital computed tomography(CT)scans was performed to quantify sinus abnormalities and extraocular muscles(EOMs)involvement.Patients were categorized into two groups based on CT findings,those with no radiological evidence of sinus abnormalities(non-PSA control group)and those with identifiable PSA.Furthermore,ethmoid sinus mucosal biopsies from a subset of TAO patients and noninflammatory controls were subjected to histopathological analysis.RESULTS:Totally 121 TAO patients(mean age 42.4±12.8y,range 10-78y),male:female=42:79,were included.PSA was identified in 44.6%(n=54)of patients,with a distribution anatomically restricted to the maxillary(50.0%isolated)and ethmoid sinuses(18.5%isolated;29.6%combined).Compared to the non-PSA group(n=67),patients with PSA were significantly older(45.1±11.8 vs 40.3±13.2y;P=0.040)and were more likely to be male(55.6%vs 17.9%;P<0.001).They also had significantly higher proptosis(22.1±3.2 vs 20.7±2.9 mm;P<0.001).Medial/inferior rectus involvement was most frequent(88.4%vs 89.3%).Histopathological analysis of sinus mucosa from PSA patients provided direct evidence of pathology,revealing a dense,chronic lymphoplasmacytic infiltrate and submucosal edema,validating the radiological findings as a true inflammatory process.No significant correlation was found with systemic autoimmune markers,including thyroid-stimulating hormone(TSH)receptor antibodies(TRAb,median 4.86 vs 2.71 IU/L,P=0.104).CONCLUSION:TAO is associated with a high prevalence of PSA in a pattern consistent with the orbital anatomy.The correlation with ipsilateral muscle thickening combined with the lack of association with proptosis laterality or systemic biomarkers lend strong support to a model of contiguous inflammation over systemic autoimmunity,a hypothesis that warrants further validation through longitudinal and mechanistic studies.
基金Kobe Universitythe National Research and Innovation Agency (BRIN)
文摘The effect of plasma and charged particle interaction with spacecraft in a low Earth orbit(LEO)environment leads to ion focusing and the formation of an ion void in the downstream region as a result of charging.Simulations and investigations using a fixed potential imposed on the spacecraft showed the nonsignificance of geophysical parameter changes to ion focusing.Variation of the temperature ratio(T_(r))contributed only to local ion focusing and manifested as two-ion streamers dispersed at the upper and lower edges of the spacecraft-the outermost layers of the satellite structure at the top and bottom,respectively.A simulation involving changing the ambient plasma density(N_(p))also showed the formation of local ion focusing,in which ions were more concentrated as the density increased.Furthermore,auroral electron density(N_(ae))variation had no clear impact on ion focusing,as indicated by static two-ion structures in the wake field.However,variation of the object potential(ϕ)strongly affected ion focusing formation,leading to distortion of the initial ion void region behind the spacecraft.The formation of ion focusing in this study was subject to the electric field produced by the object potential and the ambipolar electric field resulting from plasma expansion in the downstream region.
文摘The binding energy spectrum and electron momentum distributions for the outer valence orbitals of n-propyl iodide molecule have been measured using the electron momentum spectrometer employing non-coplanar asymmetric geometry at impact energy of 2.5 keV plus binding energy. The ionization bands have been assigned in detail via the high accuracy SACCI general-R method calculation and the experimental momentum profiles are compared with the theoretical ones calculated by Hartree-Fock and B3LYP/aug-cc-pVTZ（C,H）6-311G？？（I）. The spin-orbit coupling effect and intramolecular orbital interaction have been analyzed for the outermost two bands, which are assigned to the iodine 5p lone pairs, using NBO method and non-relativistic as well as relativistic calculations. It is found that both of the interactions will lead to the observed differences in electron momentum distributions. The experimental results agree with the relativistic theoretical momentum profiles, indicating that the spin-orbit coupling effect dominates in n-propyl iodide molecule.
基金Project supported by the National Natural Science Foundation of China (Grant Nos.11072168 and 10872141)
文摘In this paper, the extended Pade approximant is used to construct the homoclinic and the heteroclinic trajectories in nonlinear dynamical systems that are asymmetric at origin. Meanwhile, the conservative system, the autonomous system, and the nonautonomous system equations with quadratic and cubic nonlinearities are considered. The disturbance parameter ~ is not limited to being small. The ranges of the values of the linear and the nonlinear term parameters, which are variables, can be determined when the boundary values are satisfied. New conditions for the potentiality and the convergence are posed to make it possible to solve the boundary-value problems formulated for the orbitals and to evaluate the initial amplitude values.
基金supported by the Doctoral Research Fund of Henan Normal University,China (Grant No. 525449)
文摘This paper calculates the five most stable conformers of serine with Hartree-Fock theory, density functional theory （B3LYP）, Moller-Plesset perturbation theory （MP4（SDQ）） and electron propagation theory with the 6-311＋＋G（2d,2p） basis set. The calculated vertical ionization energies for the valence molecular orbitals of each conformer are in agreement with the experimental data, indicating that a range of molecular conformations would coexist in an equilibrium sample. Information of the five outer valence molecular orbitals for each conformer is explored in coordinate and momentum spaces using dual space analysis to investigate the conformational processes, which are generated from the global minimum conformer Serl by rotation of C2-C3 （Ser4）, C1 C2 （Ser5） and C1-O2 （Set2 and Ser3）. Orbitals 28a, 27a and 26a are identified as the fingerprint orbitals for all the conformational processes.
文摘Basing on the DFT calculations we propose the new theoretical model which describes both the surface tension σ of the short chain n-alkanes at their normal boiling points and their reaction rate constants with hydroxyl radicals OH<span style="white-space:nowrap;">• (at 297 ± 2 K) on the basis of their molecular orbital electronic characteristics. It has been shown that intermolecular dispersion attraction within the surface liquid monolayer of these compounds, as well as their reaction rate constants k with OH<span style="white-space:nowrap;">• radicals are determined by the energies E<sub>orb</sub> of the specific occupied molecular orbitals which are the same in the determination of both the above physico-chemical characteristics of the studied n-alkanes. The received regression equations confirm the theoretically found dependences between the quantities of σ and k and the module |E<sub>orb</sub>|. For the compounds under study this fact indicates the key role of their electronic structure particularities in determination of both the physical (surface tension) and the chemical (reaction rate constants) properties.
基金supported by the Natural Science Foundation of Jiangsu Province (BK20190814)the National Natural Science Foundation of China (11905154)+4 种基金the Suzhou Science and Technology Project-Prospective Application Research Program(SYG202109)the Gusu innovative and entrepreneurial talent(ZXL2019245)the Collaborative Innovation Center of Suzhou Nano Science&Technologythe 111 ProjectSuzhou Key Laboratory of Functional Nano&Soft Materials,Soochow University-Western University Centre for Synchrotron Radiation Research
文摘Accelerating the sluggish redox kinetics of lithium polysulfides(LiPSs)by electrocatalysis is essential to achieve high performance lithium-sulfur(Li-S)batteries.However,the issue of insufficient catalytic activity remains to be addressed.Herein,a strategy of modulating e_(g) orbitals through ligand engineering has been proposed to boost the catalytic activity of NiSe for rapid LiPSs redox conversion.The X-ray spectroscopic measurements and theoretical calculations reveal that partial substitution of Se with N disrupts the octahedral coordination of Ni atoms in NiSe,leading to the reduced degeneracy and upward shift of e_(g) orbitals of Ni 3 d states.As a consequence,the bonding strength of N-substituted NiSe(N-NiSe)with LiPSs is enhanced,which facilitates the interfacial charge transfer kinetics and accelerates the LiPSs redox kinetics.Therefore,the Li-S batteries assembled with N-NiSe present a high capacity of 682.6 mAh g^(-1) at a high rate of 5 C and a high areal capacity of 6.5 mAh cm^(-2)at a high sulfur loading of 6 mg cm^(-2).This work provides a promising strategy to develop efficient transition-metal based electrocatalysts for Li-S batteries through e_(g) orbital modulation.
文摘In this paper, we have declined the formalism of the method of the Modified Atomic Orbital Theory (MAOT) applied to the calculations of energies of doubly excited states 2<em>snp</em>, 3<em>snp</em>, and 4<em>snp</em> Helium-like systems. Then we also applied the variational procedure of the Modified Atomic Orbital Theory to the computations of total energies, excitation energies of doubly-excited states 2<em>snp</em>, 3<em>snp</em>, 4<em>snp</em> types of Helium-like systems. The results obtained in this work are in good agreement with the experimental and theoretical values available.
文摘The electronic modulation characteristics of efficient metal phosphide electrocatalysts can be utilized to tune the performance of oxygen evolution reaction(OER).However,improving the overall water splitting performance remains a challenging task.By building metal organic framework(MOF)on MOF heterostructures,an efficient strategy for controlling the electrical structure of MOFs was presented in this study.ZIF-67 was in-situ synthesized on MIL-88(Fe)using a two-step self-assembly method,followed by low-temperature phosphorization to ultimately synthesize FeP-CoP_(3)bimetallic phosphides.By combining atomic orbital theory and theoretical calculations(density functional theory),the results reveal the successful modulation of electronic orbitals in FeP-CoP_(3)bimetallic phosphides,which are synthesized from MOF on MOF structure.The synergistic impact of the metal center Co species and the phase conjugation of both kinds of MOFs are responsible for this regulatory phenomenon.Therefore,the catalyst demonstrates excellent properties,demonstrating HER 81 mV(η10)in a 1.0 mol L^(−1)KOH solution and OER 239 mV(η50)low overpotentials.The FeP-CoP_(3)linked dual electrode alkaline batteries,which are bifunctional electrocatalysts,have a good electrocatalytic ability and may last for 50 h.They require just 1.49 V(η50)for total water breakdown.Through this technique,the electrical structure of electrocatalysts may be altered to increase catalytic activity.
基金supported by the National Natural Science Foundation of China(Grant No.11174175)the Tsinghua University Initiative Scientific Research Program,China
文摘Recently, there was a hot controversy about the concept of localized orbitals, which was triggered by Grushow＇s work titled ＂Is it time to retire the hybrid atomic orbital？＂ [J. Chem. Educ. 88, 860 （2011）]. To clarify the issue, we assess the delocalized and localized molecular orbitals from an experimental view using electron momentum spectroscopy. The delocalized and localized molecular orbitals based on various theoretical models for CH4, NH3, and H20 are compared with the experimental momentum distributions. Our results show that the delocalized molecular orbitals rather than the localized ones can give a direct interpretation of the experimental （e, 2e） results.
基金Project supported by the National Key Research and Development Program of China(Grant No.2017YFA0402300).
文摘The outer valence electron momentum distributions of benzene are reinvestigated with theoretical calculations involving the vibrational effects.The results are compared with recent experimental measurements[Phys.Rev.A 98042705(2018)].The significant discrepancies between theories and experiments in previous works have now been interpreted quantitatively,indicating that the vibrational motion in benzene molecule has noticeable influence on its electron momentum distributions.
基金Project supported by the National Natural Science Foundation of China (Grant No.10674087)the National Basic Research Program of China (Grant No.2006CB806000)+2 种基金the Hebei Provincial Natural Science Foundation (Grant No.A2008000136)the Project of National Center for Educational Techonology of the Ministry of Education of China (Grant NCET-08-0883)the Program of TYAl of Shanxi Province and China Academy of Engineering Physics Foundation (Grant No.2008B0102007)
文摘The single ionization rate of the diatomic molecular ion H2^＋ with different active orbitals in an intense field is studied by using S-matrix theory. Our results show that the orientation-dependent single ionization probability of H2^＋ is greatly dependent on the symmetry and the electron density distribution of its initial states, and it can be used to identify the excited state of the molecular ion in the dissociation process.
基金A state major key project for basic researches supported by the National Natural Science Foundation of China
文摘The present paper covers a kind of localized orbitals, namely bond-distorted or-bitals in the valence bond calculation. Test calculation on benzene is reported. The results indicate that Dewar structures are important in the description of benzene.
基金Project supported by the Specialized Research Fund of Doctoral Program of Higher Education of China (Grant No 20030532008)
文摘Rehybridization of electronic orbitals in carbon nanotubes contains tilting angles of π orbital, electrons wavefunctions of π orbital and a orbital, degrees of hybridization, etc. In this paper, we have obtained analytical formulas of tilting angle of π orbital relative to tube surface, electrons wavefunctions of π orbital and a orbital, degrees of hybridization, separately, as well as the numerical results.
基金supported by the Program of Excellent Team in Harbin Institute of Technologythe Program for New Century Excellent Talents in University (NCET)National Natural Science Foundation of China (Grant Nos 10774033,60878018 and 10674036)
文摘This paper studies the molecular rotational excitation and field-free spatial alignment in a nonresonant intense laser field numerically and analytically by using the time-dependent SchrSdinger equation. The broad rotational wave packets excited by the femtosecond pulse are defined in conjugate angle space, and their coefficients are obtained by solving a set of coupled linear equations. Both single molecule orientation angles and an ensemble of O2 and CO molecule angular distributions are calculated in detail. The numerical results show that, for single molecule highest occupied molecular orbital （HOMO） symmetry σ tends to have a molecular orientation along the laser polarization direction and the permanent dipole moment diminishes the mean of the orientation angles; for an ensemble of molecules, angular distributions provide more complex and additional information at times where there are no revivals in the single molecule plot. In particular, at the revival peak instant, with the increase of temperature of the molecular ensemble, the anisotropic angular distributions with respect to the laser polarization direction of the πg orbital gradually transform to the symmetrical distributions regarding the laser polarization vector and for two HOMO configurations angular distributions of all directions are confined within a smaller angle when the temperature of the molecular ensemble is higher.
