Simple and efficient stereo-selective synthesis of exo-5-norbornene-2-carboxylic acid (NBCA) is reported. Preliminary studies on base promoted isomerization of methyl 5-norbornene-2-carboxylate (MNBC) revealed that ra...Simple and efficient stereo-selective synthesis of exo-5-norbornene-2-carboxylic acid (NBCA) is reported. Preliminary studies on base promoted isomerization of methyl 5-norbornene-2-carboxylate (MNBC) revealed that rapid isomerization was accomplished with sodium tert-butoxide (tBuONa), and the exo-content at the equilibrium was ca. 60%. The hydrolyses of endo-rich MNBC (endo/exo = 80/20) under various conditions were carried out. The exo selectivity for resulting NBCA was improved when the hydrolysis was conducted with equimolar water at room temperature in the presence of the stronger base (tBuONa) (endo/exo: 18/82). Whereas the use of excess amount of water led to rapid and non-selective hydrolysis affording high endo content of the product. The plausible reaction mechanism involving rapid equilibrium of thermodynamic isomerization and kinetically preferred hydrolysis of exo ester is proposed.展开更多
We were interested, along this work, in the phenomena of the quintessence and the inflation due to the F-harmonic maps, in other words, in the functions of the scalar field such as the exponential and trigo-harmonic m...We were interested, along this work, in the phenomena of the quintessence and the inflation due to the F-harmonic maps, in other words, in the functions of the scalar field such as the exponential and trigo-harmonic maps. We showed that some F-harmonic map such as the trigonometric functions instead of the scalar field in the lagrangian, allow, in the absence of term of potential, reproduce the inflation. However, there are other F-harmonic maps such as exponential maps which can’t produce the inflation;the pressure and the density of this exponential harmonic field being both of the same sign. On the other hand, these exponential harmonic fields redraw well the phenomenon of the quintessence when the variation of these fields remains weak. The problem of coincidence, however remains.展开更多
Recently, enzymatic peptide synthesis has drawn increasing attention due to its eco-friendly reagents and mild conditions, as compared to traditional chemical peptide synthesis. In this study, we successfully produced...Recently, enzymatic peptide synthesis has drawn increasing attention due to its eco-friendly reagents and mild conditions, as compared to traditional chemical peptide synthesis. In this study, we successfully produced an important antioxidant dipeptide precursor, BOC-Tyr-Ala, via a kinetically controlled enzymatic peptide synthesis reaction, catalyzed by the recombinant car- boxypeptidase Y （CPY） expressed in P. pastoris GS 115. In this reaction, the enzyme activity was 95.043 U/mL, and we used t-butyloxycarbonyl-L-tyrosine-methyl ester （BOC-Tyr-OMe） as the acyl donor and L-alanine （L-Ala） was the amino donor. We optimized the reaction conditions to be： 30 ℃, pH 9.5, organic phase （methanol）/aqueous phase = 1：20, BOC-Tyr-OMe 0.05 mol/L, Ala 0.5 mol/L, and a reaction time of 12 h. Under these conditions, the dipeptide yield reached 49.84%. Then, we established the kinetic model of the synthesis reaction in the form of Michaelis-Menten equation according to the con-centration-time curve during the process and the transpeptidation mechanism. We calculated the apparent Michaelis constant K^（app）mand the apparent maximum reaction rate r^（app）max to be 2.9946 x 10^-2 mol/L and 2.0406 x 10.2 mmol/（mL h）, respectively.展开更多
Up to now,the DNA molecule adsorbed on a surface was believed to always preserve its native structure.This belief implies a negligible contribution of lateral surface forces during and after DNA adsorption although th...Up to now,the DNA molecule adsorbed on a surface was believed to always preserve its native structure.This belief implies a negligible contribution of lateral surface forces during and after DNA adsorption although their impact has never been elucidated.High-resolution atomic force microscopy was used to observe that stiff DNA molecules kinetically trapped on monomolecular films comprising one-dimensional periodically charged lamellar templates as a single layer or as a sublayer are oversaturated by sharp discontinuous kinks and can also be locally melted and supercoiled.We argue that kink/anti-kink pairs are induced by an overcritical lateral bending stress(>30 pNnm)inevitable for the highly anisotropic 1D-1D electrostatic interaction of DNA and underlying rows of positive surface charges.In addition,the unexpected kink-inducing mechanical instability in the shape of the template-directed DNA confined between the positively charged lamellar sides is observed indicating the strong impact of helicity.The previously reported anomalously low values of the persistence length of the surface-adsorbed DNA are explained by the impact of the surface-induced low-scale bending.The sites of the local melting and supercoiling are convincingly introduced as other lateral stress-induced structural DNA anomalies by establishing a link with DNA high-force mechanics.The results open up the study in the completely unexplored area of the principally anomalous kinetically trapped DNA surface conformations in which the DNA local mechanical response to the surface-induced spatially modulated lateral electrostatic stress is essentially nonlinear.The underlying rich and complex in-plane nonlinear physics acts at the nanoscale beyond the scope of applicability of the worm-like chain approximation.展开更多
Restricting molecular motion of fluorophores is the most direct and effective approach to creating highly emissive fluorescent materials.However,attempts to limit molecular motion of conventional fluorophores in aqueo...Restricting molecular motion of fluorophores is the most direct and effective approach to creating highly emissive fluorescent materials.However,attempts to limit molecular motion of conventional fluorophores in aqueous environments often encounter undesired aggregation-caused quenching(ACQ).To address this challenge,this study presents an innovative design of a water-soluble supramolecular scaffold with a rigidmicrodomain,achieved by assembling a cyclic peptide-diblock copolymer conjugate into cylindrical nanoparticles,where the rigid microdomain is provided by the hydrophobic polymer segment with a high glass transition temperature.Supramolecular fluorophores(termed as Supra-fluorophores)are constructed by noncovalently dispersing fluorophores within the rigid microenvironment of the scaffold through a simple coassembly approach,effectively mitigating molecular motion and ACQ.This strategy accommodates a wide range of fluorophores,resulting in Supra-fluorophores with fluorescence quantum yields up to 71.6%and volume-normalized brightness reaching 19,910 M−1 cm−1 nm−3.Furthermore,increased rigidity significantly reduces dynamic exchange among assemblies by three orders of magnitude,thereby generating kinetically trapped Supra-fluorophores that exhibit minimal dye crosstalk upon mixing.This approach demonstrates substantial potential for advanced bioimaging applications,such as multicolor cell labeling,real-time tracking,and high-resolution cellular imaging.展开更多
The sulfation and decomposition process has proven effective in selectively extracting lithium from lepidolite.It is essential to clarify the thermochemical behavior and kinetic parameters of decomposition reactions.A...The sulfation and decomposition process has proven effective in selectively extracting lithium from lepidolite.It is essential to clarify the thermochemical behavior and kinetic parameters of decomposition reactions.Accordingly,comprehensive kinetic study by employing thermalgravimetric analysis at various heating rates was presented in this paper.Two main weight loss regions were observed during heating.The initial region corresponded to the dehydration of crystal water,whereas the subsequent region with overlapping peaks involved complex decomposition reactions.The overlapping peaks were separated into two individual reaction peaks and the activation energy of each peak was calculated using isoconversional kinetics methods.The activation energy of peak 1 exhibited a continual increase as the reaction conversion progressed,while that of peak 2 steadily decreased.The optimal kinetic models,identified as belonging to the random nucleation and subsequent growth category,provided valuable insights into the mechanism of the decomposition reactions.Furthermore,the adjustment factor was introduced to reconstruct the kinetic mechanism models,and the reconstructed models described the kinetic mechanism model more accurately for the decomposition reactions.This study enhanced the understanding of the thermochemical behavior and kinetic parameters of the lepidolite sulfation product decomposition reactions,further providing theoretical basis for promoting the selective extraction of lithium.展开更多
The localization and differential diagnosis of the sentinel lymph nodes(SLNs)are particularly important for tumor staging,surgical planning and prognosis.In this work,kinetically inert manganese(II)-based hybrid micel...The localization and differential diagnosis of the sentinel lymph nodes(SLNs)are particularly important for tumor staging,surgical planning and prognosis.In this work,kinetically inert manganese(II)-based hybrid micellar complexes(MnCs)for magnetic resonance imaging(MRI)were developed using an amphiphilic manganese-based chelate(C18-PhDTA-Mn)with reliable kinetic stability and self-assembled with a series of amphiphilic PEG-C18 polymers of different molecular weights(C18En,n=10,20,50).Among them,the probes composed by 1:10 mass ratio of manganese chelate/C18En had slightly different hydrodynamic particle sizes with similar surface charges as well as considerable relaxivities(∼13 mM^(−1)s^(−1)at 1.5 T).In vivo lymph node imaging in mice revealed that the MnC MnC-20 formed by C18E20 with C18-PhDTA-Mn at a hydrodynamic particle size of 5.5 nm had significant signal intensity brightening effect and shortened T1 relaxation time.At an imaging probe dosage of 125μg Mn/kg,lymph nodes still had significant signal enhancement in 2 h,while there is no obvious signal intensity alteration in non-lymphoid regions.In 4T1 tumor metastatic mice model,SLNs showed less signal enhancement and smaller T1 relaxation time variation at 30 min post-injection,when compared with normal lymph nodes.This was favorable to differentiate normal lymph nodes from SLN under a 3.0-T clinical MRI scanner.In conclusion,the strategy of developing manganese-based MR nanoprobes was useful in lymph node imaging.展开更多
In this article, we present a facile, direct, synthetic approach of preparing monodisperse [Au2s（SePh）ls]- nanoclusters in high yield. In this synthetic approach, two-phase Brust-Schiffrin method is used. Both PhSeH...In this article, we present a facile, direct, synthetic approach of preparing monodisperse [Au2s（SePh）ls]- nanoclusters in high yield. In this synthetic approach, two-phase Brust-Schiffrin method is used. Both PhSeH and NaBH4 should be added drop-wise to the solution of Au （III） at the same time. The formula and molecular purity of [Au25（SePh）ls] TOA＋ clusters are characterized by MALDI-TOF mass spectrometry, NMR and TGA analysis. Furthermore, some critical parameters to obtain pure [Au25（SePh）18]-TOA＋ are identified, including the NaBH4-to-Au ratio, the selenolate-to-Au ratio and the temperature. The facile, direct, high yield synthetic method can be widely applied in the theoretical research of Au clusters protected by selenol.展开更多
Kinetic impact is the most practical planetary-defense technique,with momentum-transfer efficiency central to deflection design.We present a Monte Carlo photometric framework that couples ejecta sampling,dynamical evo...Kinetic impact is the most practical planetary-defense technique,with momentum-transfer efficiency central to deflection design.We present a Monte Carlo photometric framework that couples ejecta sampling,dynamical evolution,and image synthesis to compare directly with HST,LICIACube,ground-based and Lucy observations of the DART impact.Decomposing ejecta into(1)a highvelocity(~1600 m/s)plume exhibiting Na/K resonance,(2)a low-velocity(~1 m/s)conical component shaped by binary gravity and solar radiation pressure,and(3)meter-scale boulders,we quantify each component’s mass and momentum.Fitting photometric decay curves and morphological evolution yields size-velocity distributions and,via scaling laws,estimates of Dimorphos’bulk density,cratering parameters,and cohesive strength that agree with dynamical constraints.Photometric ejecta modeling therefore provides a robust route to constrain momentum enhancement and target properties,improving predictive capability for kinetic-deflection missions.展开更多
This study explores the thin-layer convective solar drying of Marrubium vulgare L.leaves under conditions typical of sun-rich semi-arid climates.Drying experiments were conducted at three inlet-air temperatures(40℃,5...This study explores the thin-layer convective solar drying of Marrubium vulgare L.leaves under conditions typical of sun-rich semi-arid climates.Drying experiments were conducted at three inlet-air temperatures(40℃,50℃,60℃)and two air velocities(1.5 and 2.5 m·s^(-1))using an indirect solar dryer with auxiliary temperature control.Moisture-ratio data were fitted with eight widely used thin-layer models and evaluated using correlation coefficient(r),root-mean-square error(RMSE),and Akaike information criterion(AIC).A complementary heattransfer analysis based on Reynolds and Prandtl numbers with appropriate Nusselt correlations was used to relate flow regime to drying performance,and an energy balance quantified the relative contributions of solar and auxiliary heat.The logarithmic model consistently achieved the lowest RMSE/AIC with r>0.99 across all conditions.Higher temperature and air velocity significantly reduced drying time during the decreasing-rate period,with no constantrate stage observed.On average,solar input supplied the large majority of the thermal demand,while the auxiliary heater compensated short irradiance drops to maintain setpoints.These findings provide a reproducible dataset and a modelling benchmark for M.vulgare leaves,and they support energy-aware design of hybrid solar dryers formedicinal plants in sun-rich regions.展开更多
Wide-temperature applications of sodium-ion batteries(SIBs)are severely limited by the sluggish ion insertion/diffusion kinetics of conversion-type anodes.Quantum-sized transition metal dichalcogenides possess unique ...Wide-temperature applications of sodium-ion batteries(SIBs)are severely limited by the sluggish ion insertion/diffusion kinetics of conversion-type anodes.Quantum-sized transition metal dichalcogenides possess unique advantages of charge delocalization and enrich uncoordinated electrons and short-range transfer kinetics,which are crucial to achieve rapid low-temperature charge transfer and high-temperature interface stability.Herein,a quantum-scale FeS_(2) loaded on three-dimensional Ti_(3)C_(2) MXene skeletons(FeS_(2) QD/MXene)fabricated as SIBs anode,demonstrating impressive performance under wide-temperature conditions(−35 to 65).The theoretical calculations combined with experimental characterization interprets that the unsaturated coordination edges of FeS_(2) QD can induce delocalized electronic regions,which reduces electrostatic potential and significantly facilitates efficient Na+diffusion across a broad temperature range.Moreover,the Ti_(3)C_(2) skeleton reinforces structural integrity via Fe-O-Ti bonding,while enabling excellent dispersion of FeS_(2) QD.As expected,FeS_(2) QD/MXene anode harvests capacities of 255.2 and 424.9 mAh g^(−1) at 0.1 A g^(−1) under−35 and 65,and the energy density of FeS_(2) QD/MXene//NVP full cell can reach to 162.4 Wh kg^(−1) at−35,highlighting its practical potential for wide-temperatures conditions.This work extends the uncoordinated regions induced by quantum-size effects for exceptional Na^(+)ion storage and diffusion performance at wide-temperatures environment.展开更多
A green pregelatinized glutinous rice flour biological admixture was developed in this paper.The cement hydration process,hydration products,pore structure,and strength of mortar with different quantities of glutinous...A green pregelatinized glutinous rice flour biological admixture was developed in this paper.The cement hydration process,hydration products,pore structure,and strength of mortar with different quantities of glutinous rice flour(GRF),and the macroscopic changes in concrete cracking resistance testing were investigated.Simultaneously,a fast cracking resistance evaluation method based on graphic recognition was proposed.The results indicated that pregelatinized glutinous rice flour(T-GRF)delayed the dissolution rate of anhydrous cement during the induction period,shifting the main exothermic peak of hydration backward.The compressive strength developed slowly in 7-28 d age and returned to normal in 28-56 d.The compressive strength of T-GRF-0.6% modified mortar at 56 d age is less than 10% different from that of control group.The 3.0%T-GRF decreased the total porosity by 3%,and the average pore size decreased from 31.2 to 21.3 nm measured by MIP,indicating that T-GRF could inhibit harmful pores and densify concrete.The crack resistance coefficient of T-GRF modified concrete was obtained by image recognition method,and the GRF could decrease the length,width,and damaged area of cracks in the early age of concrete.展开更多
The increasing production and release of synthetic organic chemicals,including pharmaceuticals,into our envi-ronment has allowed these substances to accumulate in our surface water systems.Current purification technol...The increasing production and release of synthetic organic chemicals,including pharmaceuticals,into our envi-ronment has allowed these substances to accumulate in our surface water systems.Current purification technolo-gies have been unable to eliminate these pollutants,resulting in their ongoing release into aquatic ecosystems.This study focuses on cloperastine(CPS),a cough suppressant and antihistamine medication.The environmental impact of CPS usage has become a concern,mainly due to its increased detection during the COVID-19 pandemic.CPS has been found in wastewater treatment facilities,effluents from senior living residences,river waters,and sewage sludge.However,the photosensitivity of CPS and its photodegradation profile remain largely unknown.This study investigates the photodegradation process of CPS under simulated tertiary treatment conditions using UV photolysis,a method commonly applied in some wastewater treatment plants.Several transformation prod-ucts were identified,evaluating their kinetic profiles using chemometric approaches(i.e.,curve fitting and the hard-soft multivariate curve resolution-alternating least squares(HS-MCR-ALS)algorithm)and calculating the reaction quantum yield.As a result,three different transformation products have been detected and correctly identified.In addition,a comprehensive description of the kinetic pathway involved in the photodegradation process of the CPS drug has been provided,including observed kinetic rate constants.展开更多
Ion migration capability and interfacial chemistry of solid polymer electrolytes(SPEs)in all-solid-state sodium metal batteries(ASSMBs)are closely related to the Na^(+)coordination environment.Herein,an electrostatic ...Ion migration capability and interfacial chemistry of solid polymer electrolytes(SPEs)in all-solid-state sodium metal batteries(ASSMBs)are closely related to the Na^(+)coordination environment.Herein,an electrostatic engineering strategy is proposed to regulate the Na^(+)coordinated structure by employing a fluorinated metal–organic framework as an electron-rich model.Theoretical and experimental results revealed that the abundant electron-rich F sites can accelerate the disassociation of Na-salt through electrostatic attraction to release free Na^(+),while forcing anions into a Na^(+)coordination structure though electrostatic repulsion to weaken the Na^(+)coordination with polymer,thus promoting rapid Na^(+)transport.The optimized anion-rich weak solvation structure fosters a stable inorganic-dominated solid–electrolyte interphase,significantly enhancing the interfacial stability toward Na anode.Consequently,the Na/Na symmetric cell delivered stable Na plating/stripping over 2500 h at 0.1 mA cm^(−2).Impressively,the assembled ASSMBs demonstrated stable performance of over 2000 cycles even under high rate of 2 C with capacity retention nearly 100%,surpassing most reported ASSMBs using various solid-state electrolytes.This work provides a new avenue for regulating the Na^(+)coordination structure of SPEs by exploration of electrostatic effect engineering to achieve high-performance all-solid-state alkali metal batteries.展开更多
The water-quenched(WQ)2195 Al−Li alloy was subjected to stretching at different temperatures,from room temperature(RT)to−196℃(CT),to investigate the effect of cryogenic deformation on the aging precipitation behavior...The water-quenched(WQ)2195 Al−Li alloy was subjected to stretching at different temperatures,from room temperature(RT)to−196℃(CT),to investigate the effect of cryogenic deformation on the aging precipitation behaviors and mechanical properties.The precipitation kinetics of the T1 phase and the microstructures in peak aging state were investigated through the differential scanning calorimetric(DSC)tests and electron microscopy observation.The results show that−196℃deformation produces a high dislocation density,which promotes the precipitation of the T1 phase and refines its sizes significantly.In addition,the grain boundary precipitates(GBPs)of−196℃-stretched samples are suppressed considerably due to the high dislocation density in the grain interiors,which increases the ductility.In comparison,the strength remains nearly constant.Thus,it is indicated that cryogenic forming has the potential to provide the shape and property control for the manufacture of critical components of aluminum alloys.展开更多
NH_(4)V_(4)O_(10)(NVO)is considered a promising cathode material for aqueous zinc-ion batteries due to its high theoretical capacity.However,its practical application is limited by irreversible deamination,structural ...NH_(4)V_(4)O_(10)(NVO)is considered a promising cathode material for aqueous zinc-ion batteries due to its high theoretical capacity.However,its practical application is limited by irreversible deamination,structural collapse,and sluggish reaction kinetics during cycling.Herein,K+and C_(3)N_(4)co-intercalated NVO(KNVO-C_(3)N_(4))nanosheets with expanded interlayer spacing are synthesized for the first time to achieve high-rate,stable,and wide-temperature cathodes.Molecular dynamics and experimental results confirm that there is an optimal C_(3)N_(4)content to achieve higher reaction kinetics.The synergistic effect of K^(+)and C_(3)N_(4)co-intercalation significantly reduces the electrostatic interaction between Zn^(2+)and the[VOn]layer,improves the specific capacity and cycling stability.Consequently,the KNVO-C_(3)N_(4)electrode displays outstanding electrochemical performance at room temperature and under extreme environments.It exhibits excellent rate performance(228.4 m Ah g^(-1)at 20 A g^(-1)),long-term cycling stability(174.2 m Ah g^(-1) after 10,000 cycles at 20 A g^(-1)),and power/energy density(210.0 Wh kg^(-1)at 14,200 W kg^(-1))at room temperature.Notably,it shows remarkable storage performance at-20℃(111.3 m Ah g^(-1)at 20 A g^(-1))and 60℃(208.6 m Ah g^(-1)at 20 A g^(-1)).This strategy offers a novel approach to developing high-performance cathodes capable of operating under extreme temperatures.展开更多
We proposed and demonstrated a kinetically interlocking multiple-units supramolecular polymer-ization strategy.Through rationally designed multi-ple-units monomers,the degree of polymerization(X w)detected was more th...We proposed and demonstrated a kinetically interlocking multiple-units supramolecular polymer-ization strategy.Through rationally designed multi-ple-units monomers,the degree of polymerization(X w)detected was more than 50 with a polydispersi-ty index of∼1.4.The prepared polymers were stable when diluted to 20μM or lower concentrations.展开更多
Various silicon crystal structures with different atomic arrangements from that of diamond have been observed in chemically synthesized nanowires.The structures are typified by mixed stacking mismatches of closely pac...Various silicon crystal structures with different atomic arrangements from that of diamond have been observed in chemically synthesized nanowires.The structures are typified by mixed stacking mismatches of closely packed Si dimers.Instead of viewing them as defects,we define the concept of hexagonality and describe these structures as Si polymorphs.The small transverse dimensions of a nanowire make this approach meaningful.Unique among the polymorphs are cubic symmetry diamond and hexagonal symmetry wurtzite structures.Electron diffraction studies conducted with Au as an internal reference unambiguously confirm the existence of the hexagonal symmetry Si nanowires.Cohesive energy calculations suggest that the wurtzite polymorph is the least stable and the diamond polymorph is the most stable.Cohesive energies of intermediate polymorphs follow a linear trend with respect to their structural hexagonality.We identify the driving force in the polymorph formations as the growth kinetics.Fast longitudinal elongation during the growth freezes stacking mismatches and thus leads to a variety of Si polymorphs.The results are expected to shed new light on the importance of growth kinetics in nanomaterial syntheses and may open up ways to produce structures that are uncommon in bulk materials.展开更多
It remains a great challenge to balance the kinetic stability and intrinsic healing ability of polymer materials.Here,we present an efficient strategy of using a synthetic reaction cycle to regulate the intrinsic heal...It remains a great challenge to balance the kinetic stability and intrinsic healing ability of polymer materials.Here,we present an efficient strategy of using a synthetic reaction cycle to regulate the intrinsic healing ability of thermodynamically stable and kinetically inert multifunctional organohydrogels.By combining a double decomposition reaction with spontaneous energy dissipation,we can construct the simplest synthetic reaction cycle that can induce a transient out-of-equilibrium state for achieving the healing of organohydrogels with kinetically locked acylhydrazone bonds.In addition to balancing kinetic stability and healing ability,the synthetic reaction cycle also enables the polymer materials to have high tolerance to organic solvents,high ionic strength,high and low temperatures,and other harsh conditions.Therefore,the kinetically stable and healable organohydrogels remain mechanically flexible and electrically conductive even down to−40°C and are readily recyclable.The integration of chemical networks into healable polymers may provide novel,versatile materials for building next-generation electronic devices.展开更多
Starting with the stoichiometric and highly homogeneous gel-precursor,single-phase metastable melilite La_(2)Ga_(3)O_(7.5),as the end-member of solid solution La_(1+x)Sr_(1−x)Ga_(3)O_(7+x/2)(0≤x≤1),has been synthesi...Starting with the stoichiometric and highly homogeneous gel-precursor,single-phase metastable melilite La_(2)Ga_(3)O_(7.5),as the end-member of solid solution La_(1+x)Sr_(1−x)Ga_(3)O_(7+x/2)(0≤x≤1),has been synthesized by solid-state reaction at 700℃for 2 h via a kinetically favorable mechanism and characterized by X-ray diffraction(XRD),Raman,X-ray photoelectron spectroscopy(XPS),field emission scanning electron microscopy(FESEM),transmission electron microscopy(TEM),AC impedance spectroscopy,etc.It has been revealed that the as-synthesized melilite La_(2)Ga_(3)O_(7.5)shows an orthorhombic symmetry with crystal cell parameters a=11.4690(1)A,b=11.2825(4)A,and c=10.3735(4)A,while has more Raman active modes than LaSrGa_(3)O_(7)with a tetragonal structure,which was also synthesized under the same conditions for comparison,but tends to slowly decompose into perovskite LaGaO_(3)and Ga2O_(3)when annealed at 700℃for over 20 h driven by its meta-stability.Moreover,the metastable La2Ga3O7.5 shows a higher XPS binding energy for the excess oxide ions in the crystal structure than those at normal lattice sites.Its intrinsic grain oxide ion conductivity can reach as high as 0.04 and 0.51 mS·cm^(-1)at 550 and 700℃,respectively,characterized by a simple Arrhenius relationship ln(σT)-1/T with invariable activation energy,E_(a)=1.22 eV,over the temperature range from 300 to 700℃,along with an apparent grain boundary conductivity that is about double that from the grains thanks to the clean grain boundaries.This paper provides a new strategic approach to the synthesis of complex oxides that may be of high performance but are difficultly achieved by the conventional ceramic method at high temperatures.展开更多
文摘Simple and efficient stereo-selective synthesis of exo-5-norbornene-2-carboxylic acid (NBCA) is reported. Preliminary studies on base promoted isomerization of methyl 5-norbornene-2-carboxylate (MNBC) revealed that rapid isomerization was accomplished with sodium tert-butoxide (tBuONa), and the exo-content at the equilibrium was ca. 60%. The hydrolyses of endo-rich MNBC (endo/exo = 80/20) under various conditions were carried out. The exo selectivity for resulting NBCA was improved when the hydrolysis was conducted with equimolar water at room temperature in the presence of the stronger base (tBuONa) (endo/exo: 18/82). Whereas the use of excess amount of water led to rapid and non-selective hydrolysis affording high endo content of the product. The plausible reaction mechanism involving rapid equilibrium of thermodynamic isomerization and kinetically preferred hydrolysis of exo ester is proposed.
文摘We were interested, along this work, in the phenomena of the quintessence and the inflation due to the F-harmonic maps, in other words, in the functions of the scalar field such as the exponential and trigo-harmonic maps. We showed that some F-harmonic map such as the trigonometric functions instead of the scalar field in the lagrangian, allow, in the absence of term of potential, reproduce the inflation. However, there are other F-harmonic maps such as exponential maps which can’t produce the inflation;the pressure and the density of this exponential harmonic field being both of the same sign. On the other hand, these exponential harmonic fields redraw well the phenomenon of the quintessence when the variation of these fields remains weak. The problem of coincidence, however remains.
基金supported by Ministry of Science and Technology of China(No.2012YQ090194 and No.2013AA102204)the National Natural Science Foundation of China(No.21676191,No.21476165,and No.21621004)
文摘Recently, enzymatic peptide synthesis has drawn increasing attention due to its eco-friendly reagents and mild conditions, as compared to traditional chemical peptide synthesis. In this study, we successfully produced an important antioxidant dipeptide precursor, BOC-Tyr-Ala, via a kinetically controlled enzymatic peptide synthesis reaction, catalyzed by the recombinant car- boxypeptidase Y （CPY） expressed in P. pastoris GS 115. In this reaction, the enzyme activity was 95.043 U/mL, and we used t-butyloxycarbonyl-L-tyrosine-methyl ester （BOC-Tyr-OMe） as the acyl donor and L-alanine （L-Ala） was the amino donor. We optimized the reaction conditions to be： 30 ℃, pH 9.5, organic phase （methanol）/aqueous phase = 1：20, BOC-Tyr-OMe 0.05 mol/L, Ala 0.5 mol/L, and a reaction time of 12 h. Under these conditions, the dipeptide yield reached 49.84%. Then, we established the kinetic model of the synthesis reaction in the form of Michaelis-Menten equation according to the con-centration-time curve during the process and the transpeptidation mechanism. We calculated the apparent Michaelis constant K^（app）mand the apparent maximum reaction rate r^（app）max to be 2.9946 x 10^-2 mol/L and 2.0406 x 10.2 mmol/（mL h）, respectively.
基金This work was supported in part by a grant from Russian Scientific Foundation(Project No.17-75-30064).
文摘Up to now,the DNA molecule adsorbed on a surface was believed to always preserve its native structure.This belief implies a negligible contribution of lateral surface forces during and after DNA adsorption although their impact has never been elucidated.High-resolution atomic force microscopy was used to observe that stiff DNA molecules kinetically trapped on monomolecular films comprising one-dimensional periodically charged lamellar templates as a single layer or as a sublayer are oversaturated by sharp discontinuous kinks and can also be locally melted and supercoiled.We argue that kink/anti-kink pairs are induced by an overcritical lateral bending stress(>30 pNnm)inevitable for the highly anisotropic 1D-1D electrostatic interaction of DNA and underlying rows of positive surface charges.In addition,the unexpected kink-inducing mechanical instability in the shape of the template-directed DNA confined between the positively charged lamellar sides is observed indicating the strong impact of helicity.The previously reported anomalously low values of the persistence length of the surface-adsorbed DNA are explained by the impact of the surface-induced low-scale bending.The sites of the local melting and supercoiling are convincingly introduced as other lateral stress-induced structural DNA anomalies by establishing a link with DNA high-force mechanics.The results open up the study in the completely unexplored area of the principally anomalous kinetically trapped DNA surface conformations in which the DNA local mechanical response to the surface-induced spatially modulated lateral electrostatic stress is essentially nonlinear.The underlying rich and complex in-plane nonlinear physics acts at the nanoscale beyond the scope of applicability of the worm-like chain approximation.
基金the assistance of SUSTech Core Research Facilities,and CSNS for the allocation of beam time(grant nos.P0121122200005 and P0124052700001).
文摘Restricting molecular motion of fluorophores is the most direct and effective approach to creating highly emissive fluorescent materials.However,attempts to limit molecular motion of conventional fluorophores in aqueous environments often encounter undesired aggregation-caused quenching(ACQ).To address this challenge,this study presents an innovative design of a water-soluble supramolecular scaffold with a rigidmicrodomain,achieved by assembling a cyclic peptide-diblock copolymer conjugate into cylindrical nanoparticles,where the rigid microdomain is provided by the hydrophobic polymer segment with a high glass transition temperature.Supramolecular fluorophores(termed as Supra-fluorophores)are constructed by noncovalently dispersing fluorophores within the rigid microenvironment of the scaffold through a simple coassembly approach,effectively mitigating molecular motion and ACQ.This strategy accommodates a wide range of fluorophores,resulting in Supra-fluorophores with fluorescence quantum yields up to 71.6%and volume-normalized brightness reaching 19,910 M−1 cm−1 nm−3.Furthermore,increased rigidity significantly reduces dynamic exchange among assemblies by three orders of magnitude,thereby generating kinetically trapped Supra-fluorophores that exhibit minimal dye crosstalk upon mixing.This approach demonstrates substantial potential for advanced bioimaging applications,such as multicolor cell labeling,real-time tracking,and high-resolution cellular imaging.
基金financially supported by the National Natural Science Foundation of China(Nos.52034002 and U2202254)the Fundamental Research Funds for the Central Universities,China(No.FRF-TT-19-001)。
文摘The sulfation and decomposition process has proven effective in selectively extracting lithium from lepidolite.It is essential to clarify the thermochemical behavior and kinetic parameters of decomposition reactions.Accordingly,comprehensive kinetic study by employing thermalgravimetric analysis at various heating rates was presented in this paper.Two main weight loss regions were observed during heating.The initial region corresponded to the dehydration of crystal water,whereas the subsequent region with overlapping peaks involved complex decomposition reactions.The overlapping peaks were separated into two individual reaction peaks and the activation energy of each peak was calculated using isoconversional kinetics methods.The activation energy of peak 1 exhibited a continual increase as the reaction conversion progressed,while that of peak 2 steadily decreased.The optimal kinetic models,identified as belonging to the random nucleation and subsequent growth category,provided valuable insights into the mechanism of the decomposition reactions.Furthermore,the adjustment factor was introduced to reconstruct the kinetic mechanism models,and the reconstructed models described the kinetic mechanism model more accurately for the decomposition reactions.This study enhanced the understanding of the thermochemical behavior and kinetic parameters of the lepidolite sulfation product decomposition reactions,further providing theoretical basis for promoting the selective extraction of lithium.
基金supported by the National Natural Science Foundation of China(NSFC,52073192)the Innovative Research Groups of the National Natural Science Foundation of China(81621003).
文摘The localization and differential diagnosis of the sentinel lymph nodes(SLNs)are particularly important for tumor staging,surgical planning and prognosis.In this work,kinetically inert manganese(II)-based hybrid micellar complexes(MnCs)for magnetic resonance imaging(MRI)were developed using an amphiphilic manganese-based chelate(C18-PhDTA-Mn)with reliable kinetic stability and self-assembled with a series of amphiphilic PEG-C18 polymers of different molecular weights(C18En,n=10,20,50).Among them,the probes composed by 1:10 mass ratio of manganese chelate/C18En had slightly different hydrodynamic particle sizes with similar surface charges as well as considerable relaxivities(∼13 mM^(−1)s^(−1)at 1.5 T).In vivo lymph node imaging in mice revealed that the MnC MnC-20 formed by C18E20 with C18-PhDTA-Mn at a hydrodynamic particle size of 5.5 nm had significant signal intensity brightening effect and shortened T1 relaxation time.At an imaging probe dosage of 125μg Mn/kg,lymph nodes still had significant signal enhancement in 2 h,while there is no obvious signal intensity alteration in non-lymphoid regions.In 4T1 tumor metastatic mice model,SLNs showed less signal enhancement and smaller T1 relaxation time variation at 30 min post-injection,when compared with normal lymph nodes.This was favorable to differentiate normal lymph nodes from SLN under a 3.0-T clinical MRI scanner.In conclusion,the strategy of developing manganese-based MR nanoprobes was useful in lymph node imaging.
基金the financial support by the National Natural Science Foundation of China (20871112, 21072001, 21372006)Changjiang Scholars Program+1 种基金the Scientific Research Foundation for Returning Overseas Chinese Scholars, State Education Ministry, Ministry of Human Resources and Social Security, Anhui Province International Scientific and Technological Cooperation Project211 Project of Anhui University
文摘In this article, we present a facile, direct, synthetic approach of preparing monodisperse [Au2s（SePh）ls]- nanoclusters in high yield. In this synthetic approach, two-phase Brust-Schiffrin method is used. Both PhSeH and NaBH4 should be added drop-wise to the solution of Au （III） at the same time. The formula and molecular purity of [Au25（SePh）ls] TOA＋ clusters are characterized by MALDI-TOF mass spectrometry, NMR and TGA analysis. Furthermore, some critical parameters to obtain pure [Au25（SePh）18]-TOA＋ are identified, including the NaBH4-to-Au ratio, the selenolate-to-Au ratio and the temperature. The facile, direct, high yield synthetic method can be widely applied in the theoretical research of Au clusters protected by selenol.
基金supported by the National Natural Science Foundation of China(Grant No.12272018)the National Key Basic Research Project(2022JCJQZD20600).
文摘Kinetic impact is the most practical planetary-defense technique,with momentum-transfer efficiency central to deflection design.We present a Monte Carlo photometric framework that couples ejecta sampling,dynamical evolution,and image synthesis to compare directly with HST,LICIACube,ground-based and Lucy observations of the DART impact.Decomposing ejecta into(1)a highvelocity(~1600 m/s)plume exhibiting Na/K resonance,(2)a low-velocity(~1 m/s)conical component shaped by binary gravity and solar radiation pressure,and(3)meter-scale boulders,we quantify each component’s mass and momentum.Fitting photometric decay curves and morphological evolution yields size-velocity distributions and,via scaling laws,estimates of Dimorphos’bulk density,cratering parameters,and cohesive strength that agree with dynamical constraints.Photometric ejecta modeling therefore provides a robust route to constrain momentum enhancement and target properties,improving predictive capability for kinetic-deflection missions.
文摘This study explores the thin-layer convective solar drying of Marrubium vulgare L.leaves under conditions typical of sun-rich semi-arid climates.Drying experiments were conducted at three inlet-air temperatures(40℃,50℃,60℃)and two air velocities(1.5 and 2.5 m·s^(-1))using an indirect solar dryer with auxiliary temperature control.Moisture-ratio data were fitted with eight widely used thin-layer models and evaluated using correlation coefficient(r),root-mean-square error(RMSE),and Akaike information criterion(AIC).A complementary heattransfer analysis based on Reynolds and Prandtl numbers with appropriate Nusselt correlations was used to relate flow regime to drying performance,and an energy balance quantified the relative contributions of solar and auxiliary heat.The logarithmic model consistently achieved the lowest RMSE/AIC with r>0.99 across all conditions.Higher temperature and air velocity significantly reduced drying time during the decreasing-rate period,with no constantrate stage observed.On average,solar input supplied the large majority of the thermal demand,while the auxiliary heater compensated short irradiance drops to maintain setpoints.These findings provide a reproducible dataset and a modelling benchmark for M.vulgare leaves,and they support energy-aware design of hybrid solar dryers formedicinal plants in sun-rich regions.
基金supported by the National Nature Science Foundation of China(Nos.52202335 and 52171227)Natural Science Foundation of Jiangsu Province(No.BK20221137)National Key R&D Program of China(2024YFE0108500).
文摘Wide-temperature applications of sodium-ion batteries(SIBs)are severely limited by the sluggish ion insertion/diffusion kinetics of conversion-type anodes.Quantum-sized transition metal dichalcogenides possess unique advantages of charge delocalization and enrich uncoordinated electrons and short-range transfer kinetics,which are crucial to achieve rapid low-temperature charge transfer and high-temperature interface stability.Herein,a quantum-scale FeS_(2) loaded on three-dimensional Ti_(3)C_(2) MXene skeletons(FeS_(2) QD/MXene)fabricated as SIBs anode,demonstrating impressive performance under wide-temperature conditions(−35 to 65).The theoretical calculations combined with experimental characterization interprets that the unsaturated coordination edges of FeS_(2) QD can induce delocalized electronic regions,which reduces electrostatic potential and significantly facilitates efficient Na+diffusion across a broad temperature range.Moreover,the Ti_(3)C_(2) skeleton reinforces structural integrity via Fe-O-Ti bonding,while enabling excellent dispersion of FeS_(2) QD.As expected,FeS_(2) QD/MXene anode harvests capacities of 255.2 and 424.9 mAh g^(−1) at 0.1 A g^(−1) under−35 and 65,and the energy density of FeS_(2) QD/MXene//NVP full cell can reach to 162.4 Wh kg^(−1) at−35,highlighting its practical potential for wide-temperatures conditions.This work extends the uncoordinated regions induced by quantum-size effects for exceptional Na^(+)ion storage and diffusion performance at wide-temperatures environment.
基金Funded by Hainan Provincial Natural Science Foundation(No.522QN279)State Key Laboratory of High Performance Civil Engineering Materials(No.2023CEM004)。
文摘A green pregelatinized glutinous rice flour biological admixture was developed in this paper.The cement hydration process,hydration products,pore structure,and strength of mortar with different quantities of glutinous rice flour(GRF),and the macroscopic changes in concrete cracking resistance testing were investigated.Simultaneously,a fast cracking resistance evaluation method based on graphic recognition was proposed.The results indicated that pregelatinized glutinous rice flour(T-GRF)delayed the dissolution rate of anhydrous cement during the induction period,shifting the main exothermic peak of hydration backward.The compressive strength developed slowly in 7-28 d age and returned to normal in 28-56 d.The compressive strength of T-GRF-0.6% modified mortar at 56 d age is less than 10% different from that of control group.The 3.0%T-GRF decreased the total porosity by 3%,and the average pore size decreased from 31.2 to 21.3 nm measured by MIP,indicating that T-GRF could inhibit harmful pores and densify concrete.The crack resistance coefficient of T-GRF modified concrete was obtained by image recognition method,and the GRF could decrease the length,width,and damaged area of cracks in the early age of concrete.
基金supported by the grants PID2020-113371RA-C22 and TED2021-130845A-C32,funded by MCIN/AEI/10.13039/501100011033.M.Marín-García,R.González-OlmosC.Gómez-Canela are members of the GESPA group(Grup d’Enginyeria i Simulacióde Processos Ambientals)at IQS-URL,which has been acknowledged as a Consolidated Research Group by the Government of Catalonia(No.2021-SGR-00321)+1 种基金In addition,M.Marín-García has been awarded a public grant for the Investigo Programme,aimed at hiring young job seekers to undertake research and innovation projects under the Recovery,Transformation,and Resilience Plan(PRTR),European Union Next Generation,for the year 2022,through the Government of Catalonia and the Spanish Ministry for Work and Social Economy(No.100045ID16)Ana Belén Cuenca for her support and expertise,which helped to confirm the proposed reaction mechanism involved in the UV photolysis of cloperastine.
文摘The increasing production and release of synthetic organic chemicals,including pharmaceuticals,into our envi-ronment has allowed these substances to accumulate in our surface water systems.Current purification technolo-gies have been unable to eliminate these pollutants,resulting in their ongoing release into aquatic ecosystems.This study focuses on cloperastine(CPS),a cough suppressant and antihistamine medication.The environmental impact of CPS usage has become a concern,mainly due to its increased detection during the COVID-19 pandemic.CPS has been found in wastewater treatment facilities,effluents from senior living residences,river waters,and sewage sludge.However,the photosensitivity of CPS and its photodegradation profile remain largely unknown.This study investigates the photodegradation process of CPS under simulated tertiary treatment conditions using UV photolysis,a method commonly applied in some wastewater treatment plants.Several transformation prod-ucts were identified,evaluating their kinetic profiles using chemometric approaches(i.e.,curve fitting and the hard-soft multivariate curve resolution-alternating least squares(HS-MCR-ALS)algorithm)and calculating the reaction quantum yield.As a result,three different transformation products have been detected and correctly identified.In addition,a comprehensive description of the kinetic pathway involved in the photodegradation process of the CPS drug has been provided,including observed kinetic rate constants.
基金supported by the National Natural Science Foundation of China(No.52473213 and No.52203261)。
文摘Ion migration capability and interfacial chemistry of solid polymer electrolytes(SPEs)in all-solid-state sodium metal batteries(ASSMBs)are closely related to the Na^(+)coordination environment.Herein,an electrostatic engineering strategy is proposed to regulate the Na^(+)coordinated structure by employing a fluorinated metal–organic framework as an electron-rich model.Theoretical and experimental results revealed that the abundant electron-rich F sites can accelerate the disassociation of Na-salt through electrostatic attraction to release free Na^(+),while forcing anions into a Na^(+)coordination structure though electrostatic repulsion to weaken the Na^(+)coordination with polymer,thus promoting rapid Na^(+)transport.The optimized anion-rich weak solvation structure fosters a stable inorganic-dominated solid–electrolyte interphase,significantly enhancing the interfacial stability toward Na anode.Consequently,the Na/Na symmetric cell delivered stable Na plating/stripping over 2500 h at 0.1 mA cm^(−2).Impressively,the assembled ASSMBs demonstrated stable performance of over 2000 cycles even under high rate of 2 C with capacity retention nearly 100%,surpassing most reported ASSMBs using various solid-state electrolytes.This work provides a new avenue for regulating the Na^(+)coordination structure of SPEs by exploration of electrostatic effect engineering to achieve high-performance all-solid-state alkali metal batteries.
基金financially supported by the National Key Research and Development Program of China (No. 2019YFA0708801)the National Natural Science Foundation of China (No. 51875125)。
文摘The water-quenched(WQ)2195 Al−Li alloy was subjected to stretching at different temperatures,from room temperature(RT)to−196℃(CT),to investigate the effect of cryogenic deformation on the aging precipitation behaviors and mechanical properties.The precipitation kinetics of the T1 phase and the microstructures in peak aging state were investigated through the differential scanning calorimetric(DSC)tests and electron microscopy observation.The results show that−196℃deformation produces a high dislocation density,which promotes the precipitation of the T1 phase and refines its sizes significantly.In addition,the grain boundary precipitates(GBPs)of−196℃-stretched samples are suppressed considerably due to the high dislocation density in the grain interiors,which increases the ductility.In comparison,the strength remains nearly constant.Thus,it is indicated that cryogenic forming has the potential to provide the shape and property control for the manufacture of critical components of aluminum alloys.
基金the financial support provided by the PolyU Postdoc Matching Fund 1-W34P,ITF project ITP/023/22TP,PolyU RCRE fund 1-BBCB,IWEAR fund 1-CD8E,MTR Research Funding Scheme(PTU24019)the Hong Kong Polytechnic University(P0043508 and P0044761)。
文摘NH_(4)V_(4)O_(10)(NVO)is considered a promising cathode material for aqueous zinc-ion batteries due to its high theoretical capacity.However,its practical application is limited by irreversible deamination,structural collapse,and sluggish reaction kinetics during cycling.Herein,K+and C_(3)N_(4)co-intercalated NVO(KNVO-C_(3)N_(4))nanosheets with expanded interlayer spacing are synthesized for the first time to achieve high-rate,stable,and wide-temperature cathodes.Molecular dynamics and experimental results confirm that there is an optimal C_(3)N_(4)content to achieve higher reaction kinetics.The synergistic effect of K^(+)and C_(3)N_(4)co-intercalation significantly reduces the electrostatic interaction between Zn^(2+)and the[VOn]layer,improves the specific capacity and cycling stability.Consequently,the KNVO-C_(3)N_(4)electrode displays outstanding electrochemical performance at room temperature and under extreme environments.It exhibits excellent rate performance(228.4 m Ah g^(-1)at 20 A g^(-1)),long-term cycling stability(174.2 m Ah g^(-1) after 10,000 cycles at 20 A g^(-1)),and power/energy density(210.0 Wh kg^(-1)at 14,200 W kg^(-1))at room temperature.Notably,it shows remarkable storage performance at-20℃(111.3 m Ah g^(-1)at 20 A g^(-1))and 60℃(208.6 m Ah g^(-1)at 20 A g^(-1)).This strategy offers a novel approach to developing high-performance cathodes capable of operating under extreme temperatures.
基金This work was supported by the National Natural Science Foundation of China(No.21890731 and 21821001).
文摘We proposed and demonstrated a kinetically interlocking multiple-units supramolecular polymer-ization strategy.Through rationally designed multi-ple-units monomers,the degree of polymerization(X w)detected was more than 50 with a polydispersi-ty index of∼1.4.The prepared polymers were stable when diluted to 20μM or lower concentrations.
基金by a Department of Defense subcontract from Agiltron.Technical assistance from Y.Lin,Dr.D.Wang,Dr.J.Kong,and Y.-P.Hsieh is gratefully acknowledged.
文摘Various silicon crystal structures with different atomic arrangements from that of diamond have been observed in chemically synthesized nanowires.The structures are typified by mixed stacking mismatches of closely packed Si dimers.Instead of viewing them as defects,we define the concept of hexagonality and describe these structures as Si polymorphs.The small transverse dimensions of a nanowire make this approach meaningful.Unique among the polymorphs are cubic symmetry diamond and hexagonal symmetry wurtzite structures.Electron diffraction studies conducted with Au as an internal reference unambiguously confirm the existence of the hexagonal symmetry Si nanowires.Cohesive energy calculations suggest that the wurtzite polymorph is the least stable and the diamond polymorph is the most stable.Cohesive energies of intermediate polymorphs follow a linear trend with respect to their structural hexagonality.We identify the driving force in the polymorph formations as the growth kinetics.Fast longitudinal elongation during the growth freezes stacking mismatches and thus leads to a variety of Si polymorphs.The results are expected to shed new light on the importance of growth kinetics in nanomaterial syntheses and may open up ways to produce structures that are uncommon in bulk materials.
基金supported by the National Natural Science Foundation of China(grant no.21975145).Prof.Junqi Sun at Jilin University is thanked for the helpful discussions.
文摘It remains a great challenge to balance the kinetic stability and intrinsic healing ability of polymer materials.Here,we present an efficient strategy of using a synthetic reaction cycle to regulate the intrinsic healing ability of thermodynamically stable and kinetically inert multifunctional organohydrogels.By combining a double decomposition reaction with spontaneous energy dissipation,we can construct the simplest synthetic reaction cycle that can induce a transient out-of-equilibrium state for achieving the healing of organohydrogels with kinetically locked acylhydrazone bonds.In addition to balancing kinetic stability and healing ability,the synthetic reaction cycle also enables the polymer materials to have high tolerance to organic solvents,high ionic strength,high and low temperatures,and other harsh conditions.Therefore,the kinetically stable and healable organohydrogels remain mechanically flexible and electrically conductive even down to−40°C and are readily recyclable.The integration of chemical networks into healable polymers may provide novel,versatile materials for building next-generation electronic devices.
基金supported by the Priority Academic Program Development(PAPD)of Jiangsu Higher Education Institutions,China.
文摘Starting with the stoichiometric and highly homogeneous gel-precursor,single-phase metastable melilite La_(2)Ga_(3)O_(7.5),as the end-member of solid solution La_(1+x)Sr_(1−x)Ga_(3)O_(7+x/2)(0≤x≤1),has been synthesized by solid-state reaction at 700℃for 2 h via a kinetically favorable mechanism and characterized by X-ray diffraction(XRD),Raman,X-ray photoelectron spectroscopy(XPS),field emission scanning electron microscopy(FESEM),transmission electron microscopy(TEM),AC impedance spectroscopy,etc.It has been revealed that the as-synthesized melilite La_(2)Ga_(3)O_(7.5)shows an orthorhombic symmetry with crystal cell parameters a=11.4690(1)A,b=11.2825(4)A,and c=10.3735(4)A,while has more Raman active modes than LaSrGa_(3)O_(7)with a tetragonal structure,which was also synthesized under the same conditions for comparison,but tends to slowly decompose into perovskite LaGaO_(3)and Ga2O_(3)when annealed at 700℃for over 20 h driven by its meta-stability.Moreover,the metastable La2Ga3O7.5 shows a higher XPS binding energy for the excess oxide ions in the crystal structure than those at normal lattice sites.Its intrinsic grain oxide ion conductivity can reach as high as 0.04 and 0.51 mS·cm^(-1)at 550 and 700℃,respectively,characterized by a simple Arrhenius relationship ln(σT)-1/T with invariable activation energy,E_(a)=1.22 eV,over the temperature range from 300 to 700℃,along with an apparent grain boundary conductivity that is about double that from the grains thanks to the clean grain boundaries.This paper provides a new strategic approach to the synthesis of complex oxides that may be of high performance but are difficultly achieved by the conventional ceramic method at high temperatures.
