Ionic liquid electrospray(ILE) in an atmospheric environment is often accompanied by the gas discharge phenomenon. It interferes with the normal operation of the electrospray and the measurement of experimental parame...Ionic liquid electrospray(ILE) in an atmospheric environment is often accompanied by the gas discharge phenomenon. It interferes with the normal operation of the electrospray and the measurement of experimental parameters. In this study, electrospray experiments were conducted on the ionic liquid EMI-BF4. The observations revealed that the operating modes of the ionic liquid depend on the voltage polarity at high voltages. Additionally, a correspondence between the operating mode of ILE and the current signal in the circuit was established. The shape of the liquid cone formed at the needle tip bore a striking resemblance to the plume of corona discharge, suggesting that the motion trajectory of electrons influenced the curvature of the liquid cone. Steamer theory provided a clear explanation for the change in curvature as the voltage increased.展开更多
During the analysis of benziamidazole-class irreversible proton pump inhibitors,an unusual mass spectral response with the mass-to-charge ratio at[Mt10]t intrigued us,as it couldn't be assigned to any literature k...During the analysis of benziamidazole-class irreversible proton pump inhibitors,an unusual mass spectral response with the mass-to-charge ratio at[Mt10]t intrigued us,as it couldn't be assigned to any literature known relevant structure,intermediate or adduct ion.Moreover,this mysterious mass pattern of[Mt10]t has been gradually observed by series of marketed proton pump inhibitors,viz.omeprazole,pantoprazole,lansoprazole and rabeprazole.All the previous attempts to isolate the corresponding component were unsuccessful.The investigation of present work addresses this kind of signal to a pyridinium thiocyanate mass spectral intermediate(10),which is the common fragment ion of series of labile aggregates.The origin of such aggregates can be traced to the reactive intermediates formed by acid-promoted degradation.These reactive intermediates tend to react with each other and give raise series of complicated aggregates systematically in a water/acetonitrile solution by electrospray ionization.The structure of the corresponding pyridinium thiocyanate species of omeprazole(10a)has been eventually characterized with the help of synthetic specimen(10a′).Our structural proposal as well as its origin was supported by in situ nuclear magnetic resonance,chemical derivatization and colorimetric experiments.展开更多
The rapid and accurate authentication of traditional Chinese medicines(TCMs)has always been a key scientific and technical problem in the field of pharmaceutical analysis.Herein,a novel heating online extraction elect...The rapid and accurate authentication of traditional Chinese medicines(TCMs)has always been a key scientific and technical problem in the field of pharmaceutical analysis.Herein,a novel heating online extraction electrospray ionization mass spectrometry(H-oEESI-MS)was developed for the rapid and direct analysis of extremely complex substances without the requirement for any sample pretreatment or pre-separation steps.The overall molecular profile and fragment structure features of various herbal medicines could be completely captured within 10–15 s,with minimal sample(<0.5 mg)and solvent consumption(<20μL for one sample).Furthermore,a rapid differentiation and authentication strategy for TCMs based on H-oEESI-MS was proposed,including metabolic profile characterization,characteristic marker screening and identification,and multivariate statistical analysis model validation.In an analysis of 52 batches of seven types of Aconitum medicinal materials,20 and 21 key compounds were screened out as the characteristic markers of raw and processed Aconitum herbal medicines,respectively,and the possible structures of all the characteristic markers were comprehensively identified based on Compound Discoverer databases.Finally,multivariate statistical analysis showed that all the different types of herbal medicines were well differentiated and identified(R^(2)X>0.87,R^(2)Y>0.91,and Q^(2)>0.72),which further verified the feasibility and reliability of this comprehensive strategy for the rapid authentication of different TCMs based on H-oEESI-MS.In summary,this rapid authentication strategy realized the ultra-high-throughput,low-cost,and standardized detection of various complex TCMs for the first time,thereby demonstrating wide applicability and value for the development of quality standards for TCMs.展开更多
The ginkgo terpenoids including bilobalide and ginkgolides are the main pharmaceutical components in the leaves or extracts of Ginkgo biloba L. In this paper, the analysis of bilobalide and ginkgolides in leaves of Gi...The ginkgo terpenoids including bilobalide and ginkgolides are the main pharmaceutical components in the leaves or extracts of Ginkgo biloba L. In this paper, the analysis of bilobalide and ginkgolides in leaves of Ginkgo biloba L. by high performance liquid chromatography (HPLC)-electrospray ionization (ESI)-mass spectrometry (MS) was carried out. The separation was performed on Inertsil ODS3 column with methanol-water (36:64) as mobile phase, with 1 mL·min -1 of flow rate at 35℃. Then the mass spectrum analysis was conducted by ZMD micromass electrospray ionization (ESI)-mass spectrometer (MS). The HPLC total ion chromatogram and selected ion chromatogram (with 325, 407, 423, 439 of m/z) of the sample and ESI-/MS mass spectra of the peaks in the chromatograms were obtained. So bilobalide, ginkgolide A, B, C and J in Ginkgo biloba L. leaves were identified. The method is easy and rapid, with a good accuracy.展开更多
An ionic liquid(IL)electrospray thruster was developed for application in micro-nano satellites or gravitational wave detectors.The thruster employed a porous ceramic emitter with seven emitter strips located on its e...An ionic liquid(IL)electrospray thruster was developed for application in micro-nano satellites or gravitational wave detectors.The thruster employed a porous ceramic emitter with seven emitter strips located on its emission surface.Without any liquid-supply device,IL was delivered through porous media to emitter strips via capillary effect.Multiple emission sites then formed at the tip of each strip.A charged beam of up to 350μA(with a current density of 540μA cm^(-2))was stably produced in the negative mode.However,in the positive mode,a corona was observed which could prevent the thruster from emitting larger current.A time-of-flight mass spectrometer with significantly improved signal-to-noise ratio was built,which was used to obtain the mass distribution of the beam of the thruster.A retarding potential analysis was also performed.The test results showed that the thruster worked in the pure-ion regime,and delivered a maximum thrust of 67.1μN with specific impulses of 3952 s and 3117 s in the positive and negative modes,respectively.展开更多
Electrospray ionization mass spectrometry（ESI-MS） was applied simultaneously in determining norditerpenoid alkaloids from the roots of Aconitum sinomantanum Nakai （RAS） based on molecular mass information. The tan...Electrospray ionization mass spectrometry（ESI-MS） was applied simultaneously in determining norditerpenoid alkaloids from the roots of Aconitum sinomantanum Nakai （RAS） based on molecular mass information. The tandem mass spectra（ ESI-MS^n） provided the alkaloidal structural information, through which the existence of these alkaloids was further confirmed. Accordingly, six known norditerpenoid alkaloids were simultaneously determined on the basis of their ESI-MS^n spectra. Furthermore, based on the diagnostic fragmentation pathways of alkaloidal MS^n, a rapid method for direct detection and characterization of alkaloids from an ethanolic extract of RAS was described.展开更多
A study was conducted regarding the effect of concentration of poly (vinylidene fluoride) (PVDF)/N,N-dimethylformamide (DMF) and PVDF/DMF/acetone solutions on the transition between electrospray and electrospinning an...A study was conducted regarding the effect of concentration of poly (vinylidene fluoride) (PVDF)/N,N-dimethylformamide (DMF) and PVDF/DMF/acetone solutions on the transition between electrospray and electrospinning and on the formation of the ? and ? crystalline phases of PVDF. The crystalline phases present in the samples, crystallinity and morphology were determined by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM), respectively. Low concentration solutions resulted in films consisting of small droplets (electrospray) containing predominantly the ? phase. High concentration solutions resulted in a non-woven mesh of nano-to-micron diameter fibers (electrospinning) containing exclusively the ? phase. These results showed that, the formation of this phase in the electrospinning is related mainly to the solvent evaporation rate, and not to drawing experienced by the polymer during the process. Solvent type affected the amount of crystalline phase present, the boundary concentration between the two processes and the average diameter of fibers. Meshes processed by electrospinning display a degree of crystallinity higher than the films obtained by electrospray.展开更多
Hypromellose acetate succinate(HPMCAS) microparticles containing the poorly-water soluble drug celecoxib(CEL) were prepared by electrospraying intended for oral drug delivery. Various solvent mixtures with different s...Hypromellose acetate succinate(HPMCAS) microparticles containing the poorly-water soluble drug celecoxib(CEL) were prepared by electrospraying intended for oral drug delivery. Various solvent mixtures with different solubility for CEL and HPMCAS were used to induce changes in the polymer structural conformation of the microparticles. The performance of the prepared microparticles was evaluated by studying the solid state from, particle size and morphology, radial drug distribution and drug release. CEL was amorphous in all electrosprayed HPMCAS microparticles. The particle size and morphology was dependent on the solubility of HPMCAS in the solvent mixture used with poorer solvents resulting in smaller microparticles with rougher appearance. The CEL distribution on the particles surface was relatively homogeneous and similar for all microparticles. Drug release from the microparticles was observed at a higher rate depending on the solubility of HPMCAS in the solvent used for electrospraying, and in all cases an at least 4-fold higher rate was observed compared with the crystalline drug. Drug precipitation from the supersaturated solution was inhibited by HPMCAS for all microparticles based on its parachute effect while crystalline CEL did not reach supersaturation. This study demonstrated that electrospraying can be used to produce microparticles with tailored properties for pharmaceutical application by adjusting solvent selection.展开更多
Solution processible photovoltaics(PV)are poised to play an important role in scalable manufacturing of low-cost solar cells.Electrospray is uniquely suited for fabricating PVs due to its several desirable characteris...Solution processible photovoltaics(PV)are poised to play an important role in scalable manufacturing of low-cost solar cells.Electrospray is uniquely suited for fabricating PVs due to its several desirable characteristics of an ideal manufacturing process such as compatibility with roll-to-roll production processes,tunability and uniformity of droplet size,capability of operating at atmospheric pressure,and negligible material waste and nano structures.This review begins with an introduction of the fundamentals and unique properties of electrospray.We put emphasis on the evaporation time and residence time that jointly affect the deposition outcome.Then we review the efforts of electrospray printing polymer solar cells,perovskite solar cells,and dye sensitized solar cells.Collectively,these results demonstrate the advantages of electrospray for solution processed PV.Electrospray has also exhibited the capability of producing uniform films as well as nanostructured and even multiscale films.So far,the electrospray has been found to improve active layer morphology,and create devices with efficiencies comparable with that of spin-coating.Finally,we discuss challenges and research opportunities that enable electrospray to become a mainstream technique for industrial scale production.展开更多
In the present work, 2-mercaptoethanol and dithiothreitol were used to hydrogenise the internal disulfide bond in lysozyme. The experimental results indicate that the charge distribution of the proteins are different ...In the present work, 2-mercaptoethanol and dithiothreitol were used to hydrogenise the internal disulfide bond in lysozyme. The experimental results indicate that the charge distribution of the proteins are different in the reaction process. From the calculated molecular weight, the reduction process of the disulfide bond in the molecules can be described, and the number of the disulfide bonds in the molecule can also be determined.展开更多
The electrospray thruster is becoming popular in space propulsion due to its low power and high specific impulse.Before this work,an electrospray thruster based on a porous emitter was developed.In order to achieve la...The electrospray thruster is becoming popular in space propulsion due to its low power and high specific impulse.Before this work,an electrospray thruster based on a porous emitter was developed.In order to achieve larger and more stable thrust,the thruster was redesigned,and the influence of the space between strips on thrust was studied.Four types of emitter were tested,and they had 1,3,4 and 14 emitter-strips on the emission surface of the same size respectively.According to the experimental results,the maximum extraction voltage and emission current of the four thrusters are different under stable operational conditions.The measured stable emission currents and extraction voltages were-500μA/-5000 V,-1570μA/-3800 V,-1200μA/-3800 V,and-650μA/-4500 V,respectively.Increasing the number of strips may not result in the emission current increasing,but changing the stable operational range of the emission current per strip and the extraction voltage.The maximum stable operational extraction voltages of 3 and 4 emitter-strips are lower than those of 1 and 14 emitter-strips,but the emission currents are higher than those of 1 and 14 emitter-strips.Time-of-flight mass spectrometry was used to analyze the mass distribution and obtain the performance of the thruster in the case of thrusters with 1 and 3 emitter-strips.Both of their plumes were composed of very small ion cluster(the pure-ion regime),and their thrusts were 80.1μN,219.2μN with specific impulses of 5774 s,5047 s,respectively.展开更多
A modified electrospraying process is exploited to enhance the dissolution profiles of a poorly water-soluble drug. With polyvinylpyrrolidone (PVP) as a hydrophilic polymer matrix and ketoprofen (KET) as a model drug,...A modified electrospraying process is exploited to enhance the dissolution profiles of a poorly water-soluble drug. With polyvinylpyrrolidone (PVP) as a hydrophilic polymer matrix and ketoprofen (KET) as a model drug, polymer-drug composites in the form of nanoparticles were prepared and characterized. The surface morphologies, the physical status of the drug, and the drug-polymer interactions were studied using FESEM, DSC, XRD, and ATR-FTIR. FESEM observations demonstrated that the nanoparticles gradually decreased in size from 640 ± 350, to 530 ± 320, 460 ± 200 and 320 ± 160 nm as the KET content increased from 0, to 9.1%, 16.7% and 33.3% w/w, respectively. Results from DSC and XRD suggested that KET was distributed in the PVP matrix in an amorphous manner at the molecular level. This is thought to be due to their compatibility, arising through hydrogen bonding as demonstrated by ATR- FTIR spectra. In vitro dissolution tests showed that the nanoparticles released the incorporated KET within 1 min, evidencing markedly improved dissolution over pure KET and a KET-PVP physical mixture. Electrospraying can hence offer a facile route to develop new polymer composites for biomedical applications, in particular for improving dissolution rate of poorly water-soluble drugs.展开更多
Electrospraying/electrospinning of poly(γ-stearyl-L-glutamate) (PSLG) was investigated on a series solutions with different concentrations in chloroform.Field emission scanning electron microscopy (FESEM) and attenua...Electrospraying/electrospinning of poly(γ-stearyl-L-glutamate) (PSLG) was investigated on a series solutions with different concentrations in chloroform.Field emission scanning electron microscopy (FESEM) and attenuated Iotal reflectance Fourier transform infrared spectroscopy (FT-IR/ATR) were used to characterize the morphology and structure of the electrosprayed/electrospun polypeptide mats.It was found that electrospraying of PSLG with concentrations lower than 16 wt% afforded beads,while microfibers cou...展开更多
Electrospray,as a liquid source supply system,has been applied to chemical vapour deposition（CVD）.In thermal CVD,the microstructure of the obtained films changes from dense to coarse granular because of the decreasi...Electrospray,as a liquid source supply system,has been applied to chemical vapour deposition（CVD）.In thermal CVD,the microstructure of the obtained films changes from dense to coarse granular because of the decreasing surface temperature during deposition.Using the electrospray laser chemical vapour deposition method,we prepared homogenous alumina coatings.We found that laser irradiation was effective in compensating the surface temperature decrease,and an alpha-alumina coating with dense columnar microstructures was obtained at a deposition rate of 200 μm/h using 200 W Nd：YAG laser irradiation.展开更多
The unicellular green alga Chlamydomonas reinhardtii,a well-established model organism,has been widely used in dissecting glycerolipid metabolism in oxygenating photosynthetic organisms.In previous studies,it has been...The unicellular green alga Chlamydomonas reinhardtii,a well-established model organism,has been widely used in dissecting glycerolipid metabolism in oxygenating photosynthetic organisms.In previous studies,it has been found that shunting carbon precursors from the starch synthesis pathway can lead to a 10-fold increase in TAG content as compared to the wild type,but it is unknown whether inactivation of AGPase may affect membrane lipids biosynthesis.The study aims to investigate global changes in lipid metabolism and homeostasis in the starchless mutant C.reinhardtii sta6.By utilizing an electrospray ionization/mass spectrometry(ESI/MS)-based lipidomics approach,a total of 105 membrane lipid molecules of C.reinhardtii were resolved,including 16 monogalactosyldiacylglycerol(MGDG),16 digalactosyldiacylglycerol(DGDG),11 phosphatidylglycerol(PG),6 sulfoquinovosyldiacylglycerol(SQDG),49 diacylglyceryl-N,N,N-trimethylhomoserine(DGTS),2 phosphatidylethanolamine(PE),and 5 phosphatidylinositol(PI)molecules.The quantitative results indicated that the membrane lipid profiles were similar between the two C.reinhardtii strains grown under both low-and high-light conditions,but the cellular contents of a great number of lipids were altered in sta6 due to the defect in starch biosynthesis.Under low-light conditions,sta6 accumulated more PI,MGDG,DGDG but less amounts of DGTS as compared to WT.Under high light,sta6 cells contained higher content membrane lipids than cc-124,except for PG,which is more or less similar in both strains.Our results demonstrate that the cellular membrane lipid homeostasis underwent profound changes in the starchless mutant,and thereby its physiological impact remains to be explored.展开更多
Though tremendous efforts have been made to investigate electrospray,some aspects,such as the evolution of the menisci on the micropores of porous emitter tips and the transient response of the meniscus during the pol...Though tremendous efforts have been made to investigate electrospray,some aspects,such as the evolution of the menisci on the micropores of porous emitter tips and the transient response of the meniscus during the polarity alternation,need to be further understood.This paper presents a computation fluid dynamics(CFD)model to describe the meniscus formation in the ionic liquid electrospray process.The CFD model,based on the Taylor–Melcher leaky dielectric fluid theory and the volume of fluid(VOF)method,is validated by experiments.The evolution of the meniscus on the basis of a micropore is presented using two typical ionic liquids,EMI-BF_(4) and EMI-Im.The influences of the pore size,flow rate and applied voltage on the formation of the meniscus have been studied.Results show that a larger pore is more likely to start emission,and the time consumed for liquid meniscus formation decreases with increasing applied voltage and flow rate.Further,it is found that alternation of polarity does not destroy the structure of the meniscus but retards the formation process,and a faster polarity alteration leads to a shorter delay in meniscus formation time.展开更多
The silver ionic complexes of xanthone glycosides were studied by ESI-MS/MS in the positive ion mode. The fragmentation pathways of silver ionic complexes under collisioninduced dissociation （CID） were investigated ...The silver ionic complexes of xanthone glycosides were studied by ESI-MS/MS in the positive ion mode. The fragmentation pathways of silver ionic complexes under collisioninduced dissociation （CID） were investigated and the differences in MS/MS spectra of different silver ionic complexes of xanthones were correlated to the characterization of saccharide and the coordination pattern of silver ion with xanthones, including the glycosilation position and linkage type of disaccharide （1-2 and 1-6 linkages）.展开更多
Fast detection of trace lysozyme,one of the most important food allergens in white wine samples,was achieved by extractive electrospray ionization mass spectrometry without sample pretreatment in this study.The multip...Fast detection of trace lysozyme,one of the most important food allergens in white wine samples,was achieved by extractive electrospray ionization mass spectrometry without sample pretreatment in this study.The multiply-charged ions of m/z1587 were chosen for the quantitative detection of lysozyme in white wine,showing linear dynamic signal responses in a range of 5―75μg/mL with a linearity coefficient of 0.999 and an acceptable relative standard deviation（RSD） of 8.0%―15.0% for directly measuring lysozyme in the complex food samples.The limit of detection for lysozyme in white wine sample was calculated to be 5 μg/mL,which was lower than the amounts that can provoke allergic reactions（oral test with 3 mg or labial test with 1 mg/mL）.A single sample analysis was completed within 1 min.The data demonstrate that extractive electrospray ionization mass spectrometry is a useful tool for fast screening lysozyme in the complex matrix,showing promising application in the rapid detection of food allergen.展开更多
PLGA thin films were prepared onto implantable devices by the electrospray and pressurized spray method. Thin films with structural gradients were obtained by controlling four parameters consisting of solution conce...PLGA thin films were prepared onto implantable devices by the electrospray and pressurized spray method. Thin films with structural gradients were obtained by controlling four parameters consisting of solution concentration, applied voltage, air pressure , and deposition time. The surface morphologies of the deposited films were observed using scanning electron microscopy （SEM）. The image analysis revealed the control factors on the preparation of PLGA thin films. The beaded structure is ensily formed with a decrease in polymer concentration while the fibrous structure is easily formed with an increuse in polymer concentration. With the increase in applied voltage, the surface morphologies changed continnously from a small amount of fibrous shape to a large fibrous one： a small amount of.fibrous shape at 10 kV, more fibers with non-uniform diameter at 20 kV, and most fibers with uniform diameter at 30 kV. Low air pressure（0.1 MPa ） corresponded to round particles while high air pressure （0.3 MPa ） corresponded to fiat particles. The change in thickness from 5.34 to 10.1μm was a result of deposition time increasing from 5 to 10 s. From our above work, films of the bead or fiber structures can be obtained by changing electrical parameters to impropvc tbe biocompntibility of the film.展开更多
The behavior of N-methylidenemalonates of 3-arylaminoindoles and p-dimetylamino-N-phenylanyline (M = ANa) was studied during their analysis with ESI mass spectrometer operated in negative (NI) and positive (PI) ion mo...The behavior of N-methylidenemalonates of 3-arylaminoindoles and p-dimetylamino-N-phenylanyline (M = ANa) was studied during their analysis with ESI mass spectrometer operated in negative (NI) and positive (PI) ion modes. Anions [A] and both [M + H]+ and [M + Na]+ were recorded under conditions of the NI-ESI and PI-ESI, respectively. The fragmentation processes of [A] and [M + H]+ were found that probably occurred as “insource collusion induced dissociation”. The main paths for [A] proved to be elimination of CO2 and breakage of the N-methylidenemalonate bond. A route [A]- - CO2 - ROH (R = Me or Et) was less expressed and occurred for the indolyl-containing compounds with the NH bond only. Experiments employing heavy water demonstrated the isotope exchange to occur involving the hydrogen atom of this bond. This and other facts evidenced that the last fragmentation included abstraction of just this atom. Quantum-chemical calculations allowed picking out a structure for the product ion from the possible ones. The calculations also indicated that the protonation of M occurred at the anionic oxygen atom of the malonate moiety. The fragmentation of [M + H]+ ions included elimination of two water molecules that was supported by their MS2 spectra. A common feature of the NI- and PI-ESI mass spectra was the presence of oligomeric ions, up to tetramers and trimers for the NI- and PI-ESI ones, respectively. The oligomers were formed by interaction of the corresponding ions with neutral molecules. When ions contained extra hydrogen atoms, they were introduced by hydrolysis.展开更多
基金supported by the National Key Research and Development Program of China(No.2020YFC2201004)National Natural Science Foundation of China(No.12172110)。
文摘Ionic liquid electrospray(ILE) in an atmospheric environment is often accompanied by the gas discharge phenomenon. It interferes with the normal operation of the electrospray and the measurement of experimental parameters. In this study, electrospray experiments were conducted on the ionic liquid EMI-BF4. The observations revealed that the operating modes of the ionic liquid depend on the voltage polarity at high voltages. Additionally, a correspondence between the operating mode of ILE and the current signal in the circuit was established. The shape of the liquid cone formed at the needle tip bore a striking resemblance to the plume of corona discharge, suggesting that the motion trajectory of electrons influenced the curvature of the liquid cone. Steamer theory provided a clear explanation for the change in curvature as the voltage increased.
基金supported by the National Natural Science Foundation of China(Grant Nos.:82030107 and 81872831)the National Science and Technology Major Projects for significant new drugs creation of the 13th five-year plan(Grant Nos.:2017ZX09101001 and 2018ZX09721002007).
文摘During the analysis of benziamidazole-class irreversible proton pump inhibitors,an unusual mass spectral response with the mass-to-charge ratio at[Mt10]t intrigued us,as it couldn't be assigned to any literature known relevant structure,intermediate or adduct ion.Moreover,this mysterious mass pattern of[Mt10]t has been gradually observed by series of marketed proton pump inhibitors,viz.omeprazole,pantoprazole,lansoprazole and rabeprazole.All the previous attempts to isolate the corresponding component were unsuccessful.The investigation of present work addresses this kind of signal to a pyridinium thiocyanate mass spectral intermediate(10),which is the common fragment ion of series of labile aggregates.The origin of such aggregates can be traced to the reactive intermediates formed by acid-promoted degradation.These reactive intermediates tend to react with each other and give raise series of complicated aggregates systematically in a water/acetonitrile solution by electrospray ionization.The structure of the corresponding pyridinium thiocyanate species of omeprazole(10a)has been eventually characterized with the help of synthetic specimen(10a′).Our structural proposal as well as its origin was supported by in situ nuclear magnetic resonance,chemical derivatization and colorimetric experiments.
基金supported by the CACMS Innovation Fund,China(Grant Nos.:CI2021A04504 and CI2021A05206)the National Natural Science Foundation of China(Grant Nos.:82104380,81891010,81891013,and 82074012)+2 种基金the Fundamental Research Funds for the Central Public Welfare Research Institutes,China(Grant Nos.:ZZ14-YQ-047 and ZZXT202105)the Key Project at Central Government Level(Grant No.:2060302-2201-26)the Beijing Nova Program.
文摘The rapid and accurate authentication of traditional Chinese medicines(TCMs)has always been a key scientific and technical problem in the field of pharmaceutical analysis.Herein,a novel heating online extraction electrospray ionization mass spectrometry(H-oEESI-MS)was developed for the rapid and direct analysis of extremely complex substances without the requirement for any sample pretreatment or pre-separation steps.The overall molecular profile and fragment structure features of various herbal medicines could be completely captured within 10–15 s,with minimal sample(<0.5 mg)and solvent consumption(<20μL for one sample).Furthermore,a rapid differentiation and authentication strategy for TCMs based on H-oEESI-MS was proposed,including metabolic profile characterization,characteristic marker screening and identification,and multivariate statistical analysis model validation.In an analysis of 52 batches of seven types of Aconitum medicinal materials,20 and 21 key compounds were screened out as the characteristic markers of raw and processed Aconitum herbal medicines,respectively,and the possible structures of all the characteristic markers were comprehensively identified based on Compound Discoverer databases.Finally,multivariate statistical analysis showed that all the different types of herbal medicines were well differentiated and identified(R^(2)X>0.87,R^(2)Y>0.91,and Q^(2)>0.72),which further verified the feasibility and reliability of this comprehensive strategy for the rapid authentication of different TCMs based on H-oEESI-MS.In summary,this rapid authentication strategy realized the ultra-high-throughput,low-cost,and standardized detection of various complex TCMs for the first time,thereby demonstrating wide applicability and value for the development of quality standards for TCMs.
文摘The ginkgo terpenoids including bilobalide and ginkgolides are the main pharmaceutical components in the leaves or extracts of Ginkgo biloba L. In this paper, the analysis of bilobalide and ginkgolides in leaves of Ginkgo biloba L. by high performance liquid chromatography (HPLC)-electrospray ionization (ESI)-mass spectrometry (MS) was carried out. The separation was performed on Inertsil ODS3 column with methanol-water (36:64) as mobile phase, with 1 mL·min -1 of flow rate at 35℃. Then the mass spectrum analysis was conducted by ZMD micromass electrospray ionization (ESI)-mass spectrometer (MS). The HPLC total ion chromatogram and selected ion chromatogram (with 325, 407, 423, 439 of m/z) of the sample and ESI-/MS mass spectra of the peaks in the chromatograms were obtained. So bilobalide, ginkgolide A, B, C and J in Ginkgo biloba L. leaves were identified. The method is easy and rapid, with a good accuracy.
文摘An ionic liquid(IL)electrospray thruster was developed for application in micro-nano satellites or gravitational wave detectors.The thruster employed a porous ceramic emitter with seven emitter strips located on its emission surface.Without any liquid-supply device,IL was delivered through porous media to emitter strips via capillary effect.Multiple emission sites then formed at the tip of each strip.A charged beam of up to 350μA(with a current density of 540μA cm^(-2))was stably produced in the negative mode.However,in the positive mode,a corona was observed which could prevent the thruster from emitting larger current.A time-of-flight mass spectrometer with significantly improved signal-to-noise ratio was built,which was used to obtain the mass distribution of the beam of the thruster.A retarding potential analysis was also performed.The test results showed that the thruster worked in the pure-ion regime,and delivered a maximum thrust of 67.1μN with specific impulses of 3952 s and 3117 s in the positive and negative modes,respectively.
文摘Electrospray ionization mass spectrometry（ESI-MS） was applied simultaneously in determining norditerpenoid alkaloids from the roots of Aconitum sinomantanum Nakai （RAS） based on molecular mass information. The tandem mass spectra（ ESI-MS^n） provided the alkaloidal structural information, through which the existence of these alkaloids was further confirmed. Accordingly, six known norditerpenoid alkaloids were simultaneously determined on the basis of their ESI-MS^n spectra. Furthermore, based on the diagnostic fragmentation pathways of alkaloidal MS^n, a rapid method for direct detection and characterization of alkaloids from an ethanolic extract of RAS was described.
文摘A study was conducted regarding the effect of concentration of poly (vinylidene fluoride) (PVDF)/N,N-dimethylformamide (DMF) and PVDF/DMF/acetone solutions on the transition between electrospray and electrospinning and on the formation of the ? and ? crystalline phases of PVDF. The crystalline phases present in the samples, crystallinity and morphology were determined by Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC) and scanning electron microscopy (SEM), respectively. Low concentration solutions resulted in films consisting of small droplets (electrospray) containing predominantly the ? phase. High concentration solutions resulted in a non-woven mesh of nano-to-micron diameter fibers (electrospinning) containing exclusively the ? phase. These results showed that, the formation of this phase in the electrospinning is related mainly to the solvent evaporation rate, and not to drawing experienced by the polymer during the process. Solvent type affected the amount of crystalline phase present, the boundary concentration between the two processes and the average diameter of fibers. Meshes processed by electrospinning display a degree of crystallinity higher than the films obtained by electrospray.
基金the Danish Council for Inde-pendent Research(Grant No.DFF-12-131927)for financial sup-port of this project
文摘Hypromellose acetate succinate(HPMCAS) microparticles containing the poorly-water soluble drug celecoxib(CEL) were prepared by electrospraying intended for oral drug delivery. Various solvent mixtures with different solubility for CEL and HPMCAS were used to induce changes in the polymer structural conformation of the microparticles. The performance of the prepared microparticles was evaluated by studying the solid state from, particle size and morphology, radial drug distribution and drug release. CEL was amorphous in all electrosprayed HPMCAS microparticles. The particle size and morphology was dependent on the solubility of HPMCAS in the solvent mixture used with poorer solvents resulting in smaller microparticles with rougher appearance. The CEL distribution on the particles surface was relatively homogeneous and similar for all microparticles. Drug release from the microparticles was observed at a higher rate depending on the solubility of HPMCAS in the solvent used for electrospraying, and in all cases an at least 4-fold higher rate was observed compared with the crystalline drug. Drug precipitation from the supersaturated solution was inhibited by HPMCAS for all microparticles based on its parachute effect while crystalline CEL did not reach supersaturation. This study demonstrated that electrospraying can be used to produce microparticles with tailored properties for pharmaceutical application by adjusting solvent selection.
基金X.Z.acknowledges the funding support from National Science Foundation of China(NSFC)(No.61975073 and No.61605076)W.D.thanks the financial support from NSFC(No.11872199 and No.11932009).
文摘Solution processible photovoltaics(PV)are poised to play an important role in scalable manufacturing of low-cost solar cells.Electrospray is uniquely suited for fabricating PVs due to its several desirable characteristics of an ideal manufacturing process such as compatibility with roll-to-roll production processes,tunability and uniformity of droplet size,capability of operating at atmospheric pressure,and negligible material waste and nano structures.This review begins with an introduction of the fundamentals and unique properties of electrospray.We put emphasis on the evaporation time and residence time that jointly affect the deposition outcome.Then we review the efforts of electrospray printing polymer solar cells,perovskite solar cells,and dye sensitized solar cells.Collectively,these results demonstrate the advantages of electrospray for solution processed PV.Electrospray has also exhibited the capability of producing uniform films as well as nanostructured and even multiscale films.So far,the electrospray has been found to improve active layer morphology,and create devices with efficiencies comparable with that of spin-coating.Finally,we discuss challenges and research opportunities that enable electrospray to become a mainstream technique for industrial scale production.
文摘In the present work, 2-mercaptoethanol and dithiothreitol were used to hydrogenise the internal disulfide bond in lysozyme. The experimental results indicate that the charge distribution of the proteins are different in the reaction process. From the calculated molecular weight, the reduction process of the disulfide bond in the molecules can be described, and the number of the disulfide bonds in the molecule can also be determined.
文摘The electrospray thruster is becoming popular in space propulsion due to its low power and high specific impulse.Before this work,an electrospray thruster based on a porous emitter was developed.In order to achieve larger and more stable thrust,the thruster was redesigned,and the influence of the space between strips on thrust was studied.Four types of emitter were tested,and they had 1,3,4 and 14 emitter-strips on the emission surface of the same size respectively.According to the experimental results,the maximum extraction voltage and emission current of the four thrusters are different under stable operational conditions.The measured stable emission currents and extraction voltages were-500μA/-5000 V,-1570μA/-3800 V,-1200μA/-3800 V,and-650μA/-4500 V,respectively.Increasing the number of strips may not result in the emission current increasing,but changing the stable operational range of the emission current per strip and the extraction voltage.The maximum stable operational extraction voltages of 3 and 4 emitter-strips are lower than those of 1 and 14 emitter-strips,but the emission currents are higher than those of 1 and 14 emitter-strips.Time-of-flight mass spectrometry was used to analyze the mass distribution and obtain the performance of the thruster in the case of thrusters with 1 and 3 emitter-strips.Both of their plumes were composed of very small ion cluster(the pure-ion regime),and their thrusts were 80.1μN,219.2μN with specific impulses of 5774 s,5047 s,respectively.
文摘A modified electrospraying process is exploited to enhance the dissolution profiles of a poorly water-soluble drug. With polyvinylpyrrolidone (PVP) as a hydrophilic polymer matrix and ketoprofen (KET) as a model drug, polymer-drug composites in the form of nanoparticles were prepared and characterized. The surface morphologies, the physical status of the drug, and the drug-polymer interactions were studied using FESEM, DSC, XRD, and ATR-FTIR. FESEM observations demonstrated that the nanoparticles gradually decreased in size from 640 ± 350, to 530 ± 320, 460 ± 200 and 320 ± 160 nm as the KET content increased from 0, to 9.1%, 16.7% and 33.3% w/w, respectively. Results from DSC and XRD suggested that KET was distributed in the PVP matrix in an amorphous manner at the molecular level. This is thought to be due to their compatibility, arising through hydrogen bonding as demonstrated by ATR- FTIR spectra. In vitro dissolution tests showed that the nanoparticles released the incorporated KET within 1 min, evidencing markedly improved dissolution over pure KET and a KET-PVP physical mixture. Electrospraying can hence offer a facile route to develop new polymer composites for biomedical applications, in particular for improving dissolution rate of poorly water-soluble drugs.
基金supported by the National Natural Science Foundation of China (No.20434020).
文摘Electrospraying/electrospinning of poly(γ-stearyl-L-glutamate) (PSLG) was investigated on a series solutions with different concentrations in chloroform.Field emission scanning electron microscopy (FESEM) and attenuated Iotal reflectance Fourier transform infrared spectroscopy (FT-IR/ATR) were used to characterize the morphology and structure of the electrosprayed/electrospun polypeptide mats.It was found that electrospraying of PSLG with concentrations lower than 16 wt% afforded beads,while microfibers cou...
文摘Electrospray,as a liquid source supply system,has been applied to chemical vapour deposition（CVD）.In thermal CVD,the microstructure of the obtained films changes from dense to coarse granular because of the decreasing surface temperature during deposition.Using the electrospray laser chemical vapour deposition method,we prepared homogenous alumina coatings.We found that laser irradiation was effective in compensating the surface temperature decrease,and an alpha-alumina coating with dense columnar microstructures was obtained at a deposition rate of 200 μm/h using 200 W Nd：YAG laser irradiation.
基金Supported by the State Development&Investment Corporation(No.IHB/CN/2014033)the One Hundred Talents Program of Chinese Academy of Sciences(No.Y623031Z01)。
文摘The unicellular green alga Chlamydomonas reinhardtii,a well-established model organism,has been widely used in dissecting glycerolipid metabolism in oxygenating photosynthetic organisms.In previous studies,it has been found that shunting carbon precursors from the starch synthesis pathway can lead to a 10-fold increase in TAG content as compared to the wild type,but it is unknown whether inactivation of AGPase may affect membrane lipids biosynthesis.The study aims to investigate global changes in lipid metabolism and homeostasis in the starchless mutant C.reinhardtii sta6.By utilizing an electrospray ionization/mass spectrometry(ESI/MS)-based lipidomics approach,a total of 105 membrane lipid molecules of C.reinhardtii were resolved,including 16 monogalactosyldiacylglycerol(MGDG),16 digalactosyldiacylglycerol(DGDG),11 phosphatidylglycerol(PG),6 sulfoquinovosyldiacylglycerol(SQDG),49 diacylglyceryl-N,N,N-trimethylhomoserine(DGTS),2 phosphatidylethanolamine(PE),and 5 phosphatidylinositol(PI)molecules.The quantitative results indicated that the membrane lipid profiles were similar between the two C.reinhardtii strains grown under both low-and high-light conditions,but the cellular contents of a great number of lipids were altered in sta6 due to the defect in starch biosynthesis.Under low-light conditions,sta6 accumulated more PI,MGDG,DGDG but less amounts of DGTS as compared to WT.Under high light,sta6 cells contained higher content membrane lipids than cc-124,except for PG,which is more or less similar in both strains.Our results demonstrate that the cellular membrane lipid homeostasis underwent profound changes in the starchless mutant,and thereby its physiological impact remains to be explored.
基金supported by National Natural Science Foundation of China(No.52075334)。
文摘Though tremendous efforts have been made to investigate electrospray,some aspects,such as the evolution of the menisci on the micropores of porous emitter tips and the transient response of the meniscus during the polarity alternation,need to be further understood.This paper presents a computation fluid dynamics(CFD)model to describe the meniscus formation in the ionic liquid electrospray process.The CFD model,based on the Taylor–Melcher leaky dielectric fluid theory and the volume of fluid(VOF)method,is validated by experiments.The evolution of the meniscus on the basis of a micropore is presented using two typical ionic liquids,EMI-BF_(4) and EMI-Im.The influences of the pore size,flow rate and applied voltage on the formation of the meniscus have been studied.Results show that a larger pore is more likely to start emission,and the time consumed for liquid meniscus formation decreases with increasing applied voltage and flow rate.Further,it is found that alternation of polarity does not destroy the structure of the meniscus but retards the formation process,and a faster polarity alteration leads to a shorter delay in meniscus formation time.
文摘The silver ionic complexes of xanthone glycosides were studied by ESI-MS/MS in the positive ion mode. The fragmentation pathways of silver ionic complexes under collisioninduced dissociation （CID） were investigated and the differences in MS/MS spectra of different silver ionic complexes of xanthones were correlated to the characterization of saccharide and the coordination pattern of silver ion with xanthones, including the glycosilation position and linkage type of disaccharide （1-2 and 1-6 linkages）.
基金Supported by the Project of National Institute of Metrology of China(No.21-YS1046)
文摘Fast detection of trace lysozyme,one of the most important food allergens in white wine samples,was achieved by extractive electrospray ionization mass spectrometry without sample pretreatment in this study.The multiply-charged ions of m/z1587 were chosen for the quantitative detection of lysozyme in white wine,showing linear dynamic signal responses in a range of 5―75μg/mL with a linearity coefficient of 0.999 and an acceptable relative standard deviation（RSD） of 8.0%―15.0% for directly measuring lysozyme in the complex food samples.The limit of detection for lysozyme in white wine sample was calculated to be 5 μg/mL,which was lower than the amounts that can provoke allergic reactions（oral test with 3 mg or labial test with 1 mg/mL）.A single sample analysis was completed within 1 min.The data demonstrate that extractive electrospray ionization mass spectrometry is a useful tool for fast screening lysozyme in the complex matrix,showing promising application in the rapid detection of food allergen.
文摘PLGA thin films were prepared onto implantable devices by the electrospray and pressurized spray method. Thin films with structural gradients were obtained by controlling four parameters consisting of solution concentration, applied voltage, air pressure , and deposition time. The surface morphologies of the deposited films were observed using scanning electron microscopy （SEM）. The image analysis revealed the control factors on the preparation of PLGA thin films. The beaded structure is ensily formed with a decrease in polymer concentration while the fibrous structure is easily formed with an increuse in polymer concentration. With the increase in applied voltage, the surface morphologies changed continnously from a small amount of fibrous shape to a large fibrous one： a small amount of.fibrous shape at 10 kV, more fibers with non-uniform diameter at 20 kV, and most fibers with uniform diameter at 30 kV. Low air pressure（0.1 MPa ） corresponded to round particles while high air pressure （0.3 MPa ） corresponded to fiat particles. The change in thickness from 5.34 to 10.1μm was a result of deposition time increasing from 5 to 10 s. From our above work, films of the bead or fiber structures can be obtained by changing electrical parameters to impropvc tbe biocompntibility of the film.
文摘The behavior of N-methylidenemalonates of 3-arylaminoindoles and p-dimetylamino-N-phenylanyline (M = ANa) was studied during their analysis with ESI mass spectrometer operated in negative (NI) and positive (PI) ion modes. Anions [A] and both [M + H]+ and [M + Na]+ were recorded under conditions of the NI-ESI and PI-ESI, respectively. The fragmentation processes of [A] and [M + H]+ were found that probably occurred as “insource collusion induced dissociation”. The main paths for [A] proved to be elimination of CO2 and breakage of the N-methylidenemalonate bond. A route [A]- - CO2 - ROH (R = Me or Et) was less expressed and occurred for the indolyl-containing compounds with the NH bond only. Experiments employing heavy water demonstrated the isotope exchange to occur involving the hydrogen atom of this bond. This and other facts evidenced that the last fragmentation included abstraction of just this atom. Quantum-chemical calculations allowed picking out a structure for the product ion from the possible ones. The calculations also indicated that the protonation of M occurred at the anionic oxygen atom of the malonate moiety. The fragmentation of [M + H]+ ions included elimination of two water molecules that was supported by their MS2 spectra. A common feature of the NI- and PI-ESI mass spectra was the presence of oligomeric ions, up to tetramers and trimers for the NI- and PI-ESI ones, respectively. The oligomers were formed by interaction of the corresponding ions with neutral molecules. When ions contained extra hydrogen atoms, they were introduced by hydrolysis.
