基于HS-GC-Orbitrap联用定性与定量测定活血止痛膏挥发性成分

目的建立活血止痛膏中挥发性成分定性、定量检测方法。方法采用顶空进样-气相色谱-静电场轨道阱质谱(HS-GC-Orbitrap)技术进行分析。样品除去背膜,以乙腈为溶剂,顶空进样;以高纯氦气为载气,TG-5SILMS色谱柱,程序升温,恒压模式,电子轰击源(EI源),全扫描监测模式测定。结果可定性活血止痛膏中5味药的12个主要成分,同时定量测定樟脑、异龙脑、龙脑、薄荷脑、水杨酸甲酯和丁香酚等6个成分。结论研究建立的方法提升了活血止痛膏质量控制水平,操作简便。

基于UPLC-Q-Orbitrap HRMS和网络药理学及分子对接分析助眠汤治疗失眠的潜在机制

目的:基于UPLC-Q-Orbitrap HRMS和网络药理学及分子对接,阐明助眠汤治疗失眠的物质基础及潜在的作用机制。方法:采用UPLC-Q-Orbitrap HRMS技术鉴定助眠汤的化学成分。流动相:0.3%甲酸水溶液(A)-乙腈(B);梯度洗脱:0~7.1 min,8%~16.7%B;7.1~7.7 min,16.7%B;7.7~8.3 min,16.7%~17%B;8.3~9.5 min,17%~18.2%B;9.5~10.1 min,18.2%B;10.1~17.3 min,18.2%~26%B;17.3~24.5 min,26%~55%B;24.5~40 min,55%B。流速:0.3 mL·min^(-1),电喷雾离子源:ESI,正、负离子模式扫描,扫描范围:m/z 50~2200。在此基础上,选择失眠的临床表现和病因作为媒介,利用在线数据库对助眠汤的促进睡眠机制潜在药效物质基础、作用靶点和作用特征进行预测分析。从煎煮后测得的活性成分的作用特点入手,运用网络药理学探究助眠汤治疗失眠的潜在机制。结果:使用UPLC-Q-Orbitrap HRMS分析并鉴定了助眠汤中391种成分,其中有43种成分能于在线数据库中找到其作用的相关靶点。使用相关数据库检索“insomnia”“sleeplessness”关键词,找到失眠相关靶点基因28182个,通过韦恩分析,预测筛选出与助眠汤失眠作用相关靶点92个,经分析,共筛选得到37个关键靶点。助眠汤通过作用于环加氧酶1(PTGS1),环加氧酶2(PTGS2),内皮型一氧化氮合酶(NOS3),DNA拓扑异构酶2(TOP2),β2肾上腺素能受体(ADRB2)等靶点和RAS、Jak-STAT等信号通路发挥对失眠症的治疗作用。结论:助眠汤呈现了多成分、多靶点、多途径治疗失眠的作用特点。

Orbital liposarcoma: a retrospective, single-center study of thirteen patients

AIM:To explore the clinical and pathological characteristics of thirteen patients with orbital liposarcoma.METHODS:The clinical history data of thirteen patients diagnosed as orbital liposarcoma at Beijing Tongren Hospital,from 2006 to 2021 were collected and analyzed.The data includes age,gender,affected orbital side,course of disease,status of disease(primary or recurrent),clinical manifestations,preoperative visual acuity,operative treatment,the relations between liposarcoma and surrounding tissue,longest diameter of liposarcoma,histological subtype,immunohistochemical indicators,follow-up treatment and prognosis.RESULTS:The initial symptoms are diverse.Proptosis is the most frequent chief complaint and the others included vision loss,epiphora,diplopia,and eyelid palpable mass.Results of imaging examination[computed tomography(CT)or magnetic resonance imaging(MRI)]showed orbital mass.In terms of treatment,10 patients received tumor resection,and the mean longest diameter of the tumor was 3.39±1.36 cm.The other 3 patients had optic nerve invaded,so they received orbital exenteration.Pathological examination results confirmed the diagnose of liposarcoma for 13 patients.Six patients displayed as myxoid type,and three patients in each type of dedifferentiated and welldifferentiated type.One patient was verified as pleomorphic,which was a rare type of liposarcoma.All of the patients showed Vimentin positive,and most showed CD34 and S-100 positive.Besides,four patients showed smooth muscle actin positive.All thirteen patients were alive.CONCLUSION:Orbital liposarcoma is a rare disease and it has no specific clinical manifestation.The diagnosis of liposarcoma should be considered when proptosis and orbital mass occurred in orbit.It is recommended to perform pathological examination to achieve early detection and early treatment.

The Contribution of the Gravitational Propagation Delay to Orbital and Center of Mass Motions

Recent measurements have shown that gravitational waves and thus the gravitational interaction propagate with the speed of light. The propagation delay of the gravitational interaction in orbiting systems couples the orbital and center of mass motions. This causes the orbits to spiral out and the center of mass to accelerate. It is one of a number of small effects modifying the Kepler orbits. The calculations show that the analytical describable expansion of the semimajor axis started at a time that is less than the age of the systems. This could be caused by a collision of a system component in the past. The effect of this propagation delay on the motion of the Earth Moon and the Brown Dwarf 569Bab binary star system is analyzed. These systems were chosen because a considerable amount of measured astronomical data is available. The calculated results are in excellent agreement with the measured data. In galaxies, too, the energy transfer from the orbit of the star cloud to the center of mass motion causes the galaxies to ac-celerate. If galaxies are considered to be molecules of the universe, then the acceleration of the galaxies will cause the molecular gas to heat and expand. Alternatively, the loss in orbital internal energy of the galaxies should be included in the mass and energy in the calculation of the expanding Universe.

Analysis of radiometer effect on proof mass in purely gravitational orbit

Spacecrafts with the pure gravity environment are of great significance in precision navigation, gravity field measurement for celestial bodies, and basic physics ex- periments. The radiometer effect is one of the important interfering factors on the proof mass in a purely gravitational orbit. For the gravity field measurement system based on the inner-formation flying, the relationship between the radiometer effect on the inner- satellite and the system parameters is studied by analytical and numerical methods. An approximate function of the radiometer effect suitable for the engineering computation and the correction factor are obtained. The analytic results show that the radiometer effect on the inner-satellite is proportional to the average pressure while inversely pro- portional to the average temperature in the outer-satellite cavity. The radiometer effect increases with the temperature difference in the cavity, and its minimum exists when the cavity radius increases. When the minimum of the radiometer effect arrives, the ratio of the cavity radius to the inner-satellite radius is 1.189 4. This constant is determined by the spherical cavity configuration and independent of the temperature and pressure distributions. When the ratio of the cavity radius to the inner-satellite radius is more than 10, it is believed that the cavity is large enough, the radiometer effect is approxi- mately proportional to the square of the inner-satellite radius, and the influence of the outer-satellite cavity radius on the radiometer effect can be ignored.

Optical coherence tomography enhanced depth imaging of chorioretinal folds in patients with orbital tumors

AIM:To characterize spectral-domain optical coherence tomography(SD-OCT)features of chorioretinal folds in orbital mass imaged using enhanced depth imaging(EDI).METHODS:Prospective observational case-control study was conducted in 20 eyes of 20 patients,the uninvolved eye served as a control.All the patients underwent clinical fundus photography,computed tomography,EDI SDOCT imaging before and after surgery.Two patients with cavernous hemangiomas underwent intratumoral injection of bleomycin A5;the remaining patients underwent tumor excision.Patients were followed 1 to 14mo following surgery(average follow up,5.8mo).RESULTS:Visual acuity prior to surgery ranged from 20/20 to 20/200.Following surgery,5 patients’visual acuity remained unchanged while the remaining 15 patients had a mean letter improvement of 10(range 4 to 26 letters).Photoreceptor inner/outer segment defects were found in 10 of 15 patients prior to surgery.Following surgical excision,photoreceptor inner/outer segment defects fully resolved in 8 of these 10 patients.CONCLUSION:Persistence of photoreceptor inner/outer segment defects caused by compression of the globe by an orbital mass can be associated with reduced visual prognosis.Our findings suggest that photoreceptor inner/outer segment defects on EDI SD-OCT could be an indicator for immediate surgical excision of an orbital mass causing choroidal compression.

清瘟护肺颗粒化学成分研究

目的研究清瘟护肺颗粒的化学成分。方法查阅中国知网、PubMed、Web of Science等数据库,检索该制剂组方药材化学成分的相关文献,结合文献报道和ChemicalBook数据库信息,建立化学成分数据库。采用超高效液相色谱-四极杆/静电场轨道阱高分辨质谱(UHPLC-Q Exactive Focus MS/MS)法分析制剂的图谱数据,并以Xcalibur 4.0软件拟合分子式,与自建数据库信息进行匹配,初步推测分子式信息,与ChemicalBook或ChemSpider数据库比对,推测化学成分结构。结果共鉴定出158个化学成分,包括苷类36个,黄酮类29个,苯丙素类28个,有机酸类18个,萜类17个,色原酮类8个,其他类22个。结论所建立的方法可系统、准确、快速地定性分析清瘟护肺颗粒中的化学成分。

超高效液相色谱-静电场轨道阱高分辨质谱法测定水产品中地西泮及丁香酚类化合物残留

目的建立基于Turboflow在线净化结合超高效液相色谱-静电场轨道阱高分辨质谱法(ultra performance liquid chromatography-electrostatic field orbital high resolution mass spectrometry,UPLC-Q Exactive MS)测定水产品中4种地西泮及代谢物和6种丁香酚类化合物的方法。方法采用Turboflow在线净化,Accucore^(TM) aQ C_(18)柱(100 mm×2.1 mm,2.6μm)分离,以水-乙腈为流动相梯度洗脱,全扫描+自动触发二级质谱的正离子扫描监测模式,外标法定量。结果地西泮及代谢物和丁香酚类化合物在1.0~100.0μg/L范围内线性良好,化合物的相关系数(r^(2))均大于0.995;在水产品中的定量限分别为0.5μg/kg、2.0μg/kg;加标回收率为75.3%~110.0%,相对标准偏差小于10%。结论该方法操作简便、灵敏度高、检出限低,适用于水产品中地西泮及丁香酚类化合物的测定。通过调查发现,运输环节中水产品中检出地西泮和丁香酚类化合物,亟需对水产品中镇静剂或麻醉剂残留情况开展风险监测,加强监管以保障水产品质量安全。

高效液相色谱-四级杆/静电场轨道阱高分辨率质谱测定大米中的四种香精

对大米中四种香精采用高效液相色谱-四极杆/静电场轨道阱高分辨率质谱建立了检测方法。大米样品经水溶液浸泡,加入酸化的乙腈提取、涡旋震荡12 min、离心后,提取液过C18固相萃取柱,流出液过0.45μm滤膜。梯度洗脱采用乙腈-0.1%(V/V)甲酸水溶液为流动相,分析色谱柱采用Agilent EclipsePlus C18(100 mm×2.1 mm,1.8μm)。质谱采用正离子模式,采用Full MS/dd-MS2扫描模式,以一级质谱提取的母离子对应峰面积进行定量,以自动触发扫描所得的二级子离子进行定性确证,外标法定量。四种香精香兰素、甲基香兰素、乙基香兰素、香豆素在所建立的色谱条件下分离度较好。该方法对四种香精的检测限可达15μg/kg,定量限可达50μg/kg,在5~500 ng/mL质量浓度范围内线性关系良好,相关系数均大于0.99。在三个浓度水平下进行加标验证,四种香精的平均回收率为79.0%~95.8%、相对标准偏差(RSD)为3.1%~7.7%。该方法样品处理过程简单,回收率高、稳定性好,可以用于大米中四种香精的筛查和确证,为规范大米中香精的使用具有重要意义。

Generalized flyby trajectories around elongated minor celestial bodies as a rotating mass dipole

The aim of this paper is to understand the common characteristics of the generalized flyby trajectory around natural elongated bodies. Such flyby trajectories provide a short-term mechanism to clear away vicinal objects or temporally capture ejecta into circling orbits. The gravitational potential of elongated bodies is described by a unified approximate model, i.e., the rotating mass dipole which is two point masses connected with a constant massless rod The energy power is used to illustrate the flyby effect in terms of the instantaneous orbital energy. The essential of the single flyby trajectory is studied analytically, and the relationship between the flyby trajectory and its Jacobi integral is also illustrated. Sample trajectories are given to show the variational trend of the energy increment with respect to differen orbital periapsides. The distribution of natural ejecting orbits is presented by varying the parameters of the approximate model.

LTQ-Orbitrap Velos双分压线性阱和静电场轨道阱组合式高分辨质谱性能及应用

Orbitrap是近20多年来质量分析器的突破性技术,由静电场轨道阱方式提供高质量分辨能力和精确质量数。本文简述Orbitrap的基本工作原理和Orbitrap质谱仪的发展,重点讲述基于用线性离子阱或双分压线性阱和Orbitrap质量分析器组合的高分辨质谱仪LTQ Orbitrap Velos的结构、性能和功能,并和其它类型的高分辨质谱作比较。LTQ OrbitrapVelos由于其性能特点的优势,在前沿研究领域如蛋白组学、代谢组学、药物代谢和高通量筛选确证常规检测被广泛使用,因而对其在几个主要领域的应用特点进行讨论。

基于UPLC-LTQ-Orbitrap-MS分析刺果番荔枝叶的化学成分

目的利用UPLC-LTQ-Orbitrap-MS技术对刺果番荔枝叶的化学成分进行定性分析。方法采用Waters Acquity UPLC HSS T 3色谱柱(2.1 mm×100 mm,1.8μm),流动相为0.1%甲酸水(A)和乙腈(B)梯度洗脱,流速为0.3 mL/min,进样量2μL,在电喷雾正负离子模式下采集数据。经Reaxys数据库检索番荔枝属类化合物信息,通过质谱信息比对各化合物的m/z值、保留时间、质谱特征碎片等,并结合文献数据对鉴定的化合物进行验证。结果根据各化合物的特征裂解规律,从刺果番荔枝叶中共鉴定出45个化合物,包括16个生物碱类,14个番荔枝内酯类,7个黄酮类和8个其他类化合物,其中以番荔枝内酯类和生物碱类成分居多,与文献报道番荔枝内酯与生物碱类化合物是发挥抗癌的主要活性成分一致。结论利用UPLC-LTQ-Orbitrap-MS技术对刺果番荔枝叶中的化学成分进行了快速、准确的定性分析,为刺果番荔枝叶的提取分离与药效物质基础的研究提供依据。

Estimating masses of selected stars in the Pulkovo program by means of astrometry methods

Stars in the Pulkovo Observatory program are observed with a 65-cm refractor during many years to study their positions and movements. We present examples of two visual binary stars, for which orbits and masses of components were determined, and two astrometric stars, for which masses of their unseen companions were estimated. The first two stars are ADS 14636 （61 Cygni） and ADS 7251, and the others are Gliese 623 and ADS 8035 （Alpha UMa）. Direct astrometric methods are used for estimation of mass-ratio and masses.

纳升液相色谱-静电场轨道阱质谱法检测鹅膏菌属毒性相关内源性前体蛋白

目的建立纳升液相色谱-静电场轨道阱质谱法测定鹅膏菌属中MSDIN毒性相关前体蛋白的方法。方法样品经纯水提取、超滤分离后,采用StageTips C18进行样品除盐;以0.1%甲酸水溶液和含0.1%甲酸的乙腈/水(4:1,V:V)溶液为流动相,采用梯度洗脱方式,经AcclaimTMPepMapTM100 C18(70 mm×75μm,3μm)预富集,AcclaimTMPepMapTM100 C18(150 mm×75μm,3μm)分离,采用电喷雾离子源正离子模式测定,Protein Discover软件对蛋白质进行鉴定;分别对蛋白提取液种类、蛋白质纯化方法和蛋白酶种类进行对比和优化。结果优化前处理条件后选择纯水作为提取溶剂,提取液经Vivaspin Turbo 4(3 kDa)分离纯化和StageTips C18除盐后,样品在非酶解状态下进行分析;将本方法用于2017—2020年四川地区食物中毒事件中收集到的23株鹅膏菌属类蘑菇,共鉴定MSDIN毒性相关内源性前体蛋白50个;与市售8种可食用蘑菇比较,差异表达前体蛋白41个,其中13条前体蛋白为全部23株鹅膏菌属类蘑菇共有,可作为鹅膏菌属潜在的特征性靶标分子。结论该方法简单快速、特异性强,可作为形态学鉴定、DNA测序和毒素检测的补充方法,初步用于鹅膏菌属的快速识别。

Terrestrial End-Triassic Mass Extinction and the Triassic/Jurassic Boundary of the Junggar Basin,NW China:A Brief Review

1 Introduction The end-Triassic mass extinction event is one of the five global mass extinctions,and destroyed both the marine and terrestrial biological worlds.Though years the marine endTriassic mass extinction(ETE)event has been widely studied and discussed,and the standard marine Triassic/Jurassic boundary(TJB)(base-Jurassic)has also been determined.However.

论太阳轨道运动不绕过太阳系质心的准2400年周期成因

K指数越大表明行星系统在某一径向方向会合的程度越大.K指数极值标定的太阳轨道运动半径的变化具有凸显的准20 a、179 a、2400 a周期嵌套关系.随时间尺度的增大,K指数极大值不但呈现出显著的准2400 a周期,而且太阳系质心在太阳本体内外持续的时间长度的变化也具有准2400 a周期.这其中隐含太阳轨道运动不绕过太阳系质心的准2400 a周期特殊规律.本文以木星和太阳连线为基准方向,创建了行星会合向量指数K.K向量指数图像清晰地呈现出由13~14个准179 a包络线周期(其中3~4个周期谷值出现K<0)构成的太阳轨道运动不绕过太阳系质心的准2400a周期.这一发现为科学辨识太阳轨道运动特征的复杂性又向前推进一步.

基于UPLC-Q-Exactive Orbitrap-MS技术分析炙淫羊藿炮制前后对细胞内源性代谢物的影响

目的基于细胞代谢组学分析炙淫羊藿炮制前后对小鼠黑色素瘤细胞(B16细胞)内源性代谢物的影响,探讨炙淫羊藿炮制前后的药性变化。方法采用超高效液相色谱串联四级杆轨道阱质谱(UHPLC-Q-Exactive Orbitrap-MS)技术,对淫羊藿、炙淫羊藿干预的B16细胞内源性小分子进行代谢组学分析,获取组间差异代谢产物,并基于MetaboAnalyst 5.0数据库分析相关代谢通路。结果经炙淫羊藿及其生品干预后,B16细胞中13个细胞内源性差异性代谢物发生变化,分别为丙氨酸、肉毒碱C3∶0、谷氨酸-1、乳酸、异亮氨酸、胆碱、磷脂酰胆碱(34∶2、36∶2)、游离脂肪酸、柠檬酸、肉毒碱C4∶0、溶血磷脂酰胆碱16∶0、苹果酸,且炮制品对差异代谢物的影响强于生品。涉及的主要通路有瓦博格效应、丙酮酸代谢、苹果酸-天冬氨酸穿梭、丙酮醛降解等。结论淫羊藿、炙淫羊藿对细胞代谢途径有一定影响,可能与淫羊藿炮制前后药效作用、寒热药性变化有关。

^(13)C示踪技术在利玛原甲藻中腹泻性贝毒合成研究的应用

选取具有显著产毒差异的利玛原甲藻(Prorocentrum lima)SHG株与2XS株为研究对象,以2-^(13)C-甘氨酸为示踪原料结合高分辨质谱方法,为腹泻性贝类毒素及其酯化态毒素合成与代谢途径的研究提供新方法和思路。结果表明,两株藻共发现16种腹泻性贝毒及其酯化态毒素成分。对照培养条件下SHG株(大田软海绵酸毒素含量为7.88 pg/cell,鳍藻毒素1含量为4.35 pg/cell)的产毒能力高于2XS株(大田软海绵酸毒素5.70pg/cell),而甘氨酸作为氮源培养条件可显著提高两株藻的产毒总量(P<0.05)。^(13)C-甘氨酸标记组与甘氨酸培养组单细胞产毒量无显著变化(P>0.05)。腹泻性贝毒被标记后其同位素异构体丰度发生变化,其中酯化态受^(13)C标记的影响程度更高,二级质谱图清晰表示出其碎片离子及脱水峰的标记情况。该方法直观阐明了甘氨酸可作为P.lima标记原料的产毒供体,并使用稳定同位素标记方法首次实现了酯化态的同步标记,有助于腹泻性贝毒生成机制的进一步研究。

一步式QuEChERS结合液相色谱-四极杆/静电场轨道阱高分辨质谱同时筛查与分析生牛乳中153种兽药残留

该文建立了液相色谱-四极杆/静电场轨道阱高分辨质谱(LC-Q Orbitrap HRMS)同时筛查与定量生牛乳基质中15类153种兽药的方法。生牛乳样品加入6 mL Na2EDTA-McIlvaine缓冲液,经10 mL 1%(体积分数)乙酸酸化乙腈提取,30 mg PSA和90 mg C_(18)净化后,以0.1%甲酸水溶液和乙腈为流动相,Agilent Eclipse plus C_(18)柱分离,分别在Full MS/dd-MS^(2)正离子和负离子模式下进行检测。在最优条件下对方法学参数进行验证,各类兽药在相应浓度范围内线性关系良好,线性系数(r^(2))在0.99以上,所有兽药的筛查限(SDL)为0.1~20µg/kg,定量下限(LOQ)为0.1~20µg/kg,在1倍LOQ、2倍LOQ和10倍LOQ 3个加标水平下进行回收率实验,目标兽药的回收率为70%~120%,且相对标准偏差(RSD)≤20%的占比分别为92.8%、94.1%和94.8%。该方法样品处理简单、耗时短且灵敏度高,适用于生牛乳中多类兽药的快速筛查与定量。

不同段式婴儿配方奶粉香气特征及主要香味物质比较

婴幼儿配方奶粉成为母乳外广泛应用的婴儿食品,其香气特征在很大程度上反映了产品的感官质量,影响了消费者的购买意愿。按照不同月龄,婴幼儿配方奶粉可以分为1段(0~6个月)、2段(6~12个月)、3段(12~24个月)等段式。本研究组合应用定量描述分析(quantitative descriptive analysis,QDA)、气相色谱-嗅闻-质谱(gas chromatography-olfactometry-mass spectrometry,GC-O-MS)技术及气相色谱静电场轨道阱高分辨质谱(gas chromatography-Orbitrap-mass spectrometry,GC-Orbitrap-MS)等技术研究了不同段式婴幼儿配方奶粉的香气特征及主要香味物质。结果表明,不同段式的奶粉的香气轮廓存在明显差异;特别是奶香味、鱼腥味、豆腥味、整体腥味等4种属性存在极显著差异(P<0.01),甜香、谷物味等2种属性存在显著差异(P<0.05);GC-OMS分析共鉴定到24种关键化合物,其中醛类化合物达到15种,酮类化合物有4种,醇类化合物4种及1种呋喃类化合物;对3个样品进行GC-Orbitrap-MS分析,共鉴定到包括18种醛类、9种酮类、6种醇类等在内的47种化合物,覆盖了GC-O-MS鉴定到的所有化合物;GC-Orbitrap-MS鉴定的化合物中有41种化合物在3个段式样品间具有显著差异。综上,不同段式婴幼儿配方奶粉的香气轮廓和主要呈香组分存在差异,本研究的开展为婴幼儿配方奶粉产品感官品质控制和提升提供了依据。