Fragmentation Of Molecular Ions Research Articles

In situ measurement of electron emission yield at Si and SiO2 surfaces exposed to Ar/CF4 plasmas

Abstract Plasma simulations require accurate yield data to predict the electron flux that is emitted when plasma-exposed surfaces are bombarded by energetic particles. One can measure yields directly using particle beams, but it is impractical to create a separate beam of each particle produced by typical plasmas. In contrast, measurements made in situ, during plasma exposure, provide useful values for the total emitted flux and effective yield produced by all incident particles. Here, in situ measurements were made at thermally oxidized and bare silicon wafers placed on the radio-frequency (rf) biased electrode of an inductively coupled plasma system. The rf current and voltage across the sheath at the wafer were measured, along with Langmuir probe measurements of ion current density and electron temperature. The measurements are input into a numerical sheath model, which allows the emitted electron current to be distinguished from other currents. The effective yield, i.e. the ratio of the total emitted electron flux to the incident ion flux, was determined at incident ion energies from 40 eV to 1.4 keV, for Si and SiO2 surfaces in Ar, CF4, and Ar/CF4 mixtures at 1.33 Pa (10 mTorr). Yields for Ar plasmas are compared with previous work. For SiO2 surfaces in Ar/CF4 mixtures and pure CF4, the yield is dominated by ion kinetic emission, which is the same for all mixtures, and, presumably, for all ions. For Si surfaces in Ar/CF4 and CF4, the yield at high energies can be explained in part by fragmentation of molecular ions, and the yield from Ar+ can be distinguished from the other ionic species. Analytic fits of the yields are provided for use in plasma simulations.

Qualitative analysis of licorice and strychnine decoction before and after combination using UPLC-QE-Orbitrap-MS.

Glycyrrhiza glabra L. (GG) and Strychnos nux-vomica L. (NV) are traditional Chinese medicines (TCMs). Changes in the chemical composition may occur before and after the GG-NV compatibility. Ultra-performance liquid chromatography Q-exactive Orbitrap mass spectrometry (UPLC-QE-Orbitrap-MS) was applied here to study the difference in the components of the GG and NV decoctions before and after they were combined. The changes in the chemical composition of GG and NV before and after the combination were determined. The precise molecular weight, retention time, and fragment ion peak of the different components of the decoctions before and after compatibility were obtained through UPLC-QE-Orbitrap-MS. Differential analysis methods, such as principal component analysis, were used for comparison. In the positive ion mode, 200 new components were added, whereas six components were lost. In the negative ion mode, 144 new compounds were identified, whereas three components were missing. The compatibility difference between GG and NV was studied through UPLC-QE-Orbitrap-MS. The chemical composition of GG and NV changed before and after compatibility, and a class of compounds different from GG and NV was identified in the co-decoction. This study provides an experimental basis for subsequent research into detoxification mechanisms of the GG-NV combination and offers a new analytical method for investigating the compatibility of various other TCM pairs.

Direct detection of monoterpenes in evacuated air atmospheres by glow discharge plasma source for mass spectrometry

Some compounds, including the monoterpenes, are difficult to be analyzed by chemical ionization mass spectrometry (CI-MS) mass spectrometry because of having distinct chemical features of unsaturated bonds in relatively large molecule, which is responsible for occurring fragmentation of molecular ions. A direct detection of monoterpenes, including monocyclic, bicyclic and oxygenated (acyclic), was carried out using a soft plasma ionization (SPI) source combined with a q-mass spectrometer (q-MS). Detectable signals for monoterpenes were examined in an ambient air discharge plasma when varying the discharge parameters, such as discharge pressure (0.4–3.0 kPa) and sample/carrier pressure ratio (R = 5–100%). Furthermore, to consider the ionization reactions in detail, nitrogen gas was also used as the discharge gas (carrier gas). Monoterpenes, including cross-linked bicyclic (α-pinene and β-pinene) and oxygenated (linalool, geraniol, nerol and eucalyptol), in which their simple spectrum patterns can be obtained with little or no fragmentation at an ambient air pressure of several kPa, has successfully conducted by the pulsed dc SPI-MS. To our knowledge, this is the first report demonstrating that the spectrum pattern of monoterpenes could be directly detected without any complicated fragmentation of analyte ions in the SPI source.

UPLC-LTQ-Orbitrap Study on Rat Urinary Metabolites of 5-Methoxy-Alpha-Methyltryptamine.

5-Methoxy-α-Methyltryptamine (5-MeO-AMT) is a new psychoactive substance which is abused due to its hallucinogenic and euphoric effects. This study aimed to study the metabolic characteristics of 5-MeO-AMT. Five rats were given intraperitoneal injection at a dose of 50 mg/kg of 5-MeO-AMT, and their urine was subsequently collected at different times within 7 days. Ultra-high performance liquid chromatographytandem high-resolution mass spectrometry (UPLC-LTQ-Orbitrap) was used to detect the precise molecular weight and fragment ions of 5-MeO-AMT and its possible metabolites in the urine sample extracted with benzene-ethyl acetate. Three metabolites, including OH-5-MeO-AMT, α-Me-5-HT, and N-Acetyl-5-MeO-AMT were identified in rats' urine. The major metabolic pathways involved O-demethylation, hydroxylation of indole ring, and Acetylation on aliphatic amines. The results of this study are an important reference for the identification and screening of toxicants of 5-MeO-AMT.

Tracing Photoinduced Hydrogen Migration in Alcohol Dications from Time-Resolved Molecular-Frame Photoelectron Angular Distributions.

The recent implementation of attosecond and few-femtosecond X-ray pump/X-ray probe schemes in large-scale free-electron laser facilities has opened the way to visualize fast nuclear dynamics in molecules with unprecedented temporal and spatial resolution. Here, we present the results of theoretical calculations showing how polarization-averaged molecular-frame photoelectron angular distributions (PA-MFPADs) can be used to visualize the dynamics of hydrogen migration in methanol, ethanol, propanol, and isopropyl alcohol dications generated by X-ray irradiation of the corresponding neutral species. We show that changes in the PA-MFPADs with the pump-probe delay as a result of intramolecular photoelectron diffraction carry information on the dynamics of hydrogen migration in real space. Although visualization of this dynamics is more straightforward in the smaller systems, methanol and ethanol, one can still recognize the signature of that motion in propanol and isopropyl alcohol and assign a tentative path to it. A possible pathway for a corresponding experiment requires an angularly resolved detection of photoelectrons in coincidence with molecular fragment ions used to define a molecular frame of reference. Such studies have become, in principle, possible since the first XFELs with sufficiently high repetition rates have emerged. To further support our findings, we provide experimental evidence of H migration in ethanol-OD from ion-ion coincidence measurements performed with synchrotron radiation.

Синтез новых S-производных 4-амино-1,3,5-триазин-2-тиона и их исследование методами ЯМР 1Н, 13С и хромато-масс-спектрометрии

4-Amino-1,3,5-triazine-2-thione 1 interacts with allyl bromide, 2-methyl-3-chloro-1-propene, 2,3-dibromopropene-1, prenyl bromide in DMFA/K2CO3 and with cinnamyl chloride, butenyl bromide in DMFA/NaOH to form 4-allylsulfanyl- 2, 4-(2-methylpropene-2-yl)sulfanyl- 3, 4-(2-bromopropene-2-yl)sulfanyl- 4, 4-(2-methylbutene-2-yl)sulfanyl- 5, 4-cinnamylsulfanyl- 6 and 4-(butene-1-yl)sulfanyl-1,3,5-triazine-2-amines 7, respectively. The structure of compounds 2–7 was studied by 1H NMR, as well as of compounds 5 and 7, in their case including 13C NMR; allyl sulfide 2, prenyl sulfide 5 and butenyl sulfide 7 were also studied using chromatography mass spectrometry. In the 1H NMR spectra of compounds 2–7, the weakest field signal in the range of 8.22–8.30 p.p.m. is the signal of the aromatic proton of the triazine cycle, manifested as a singlet. The signals of protons of the S-CH2 group are observed in a strong field – at 3.10–4.19 p.p.m. – depending on the presence of electron donor or electron acceptor groups in the alkenyl fragment. The protons of the =CH2 group are present only in the structure of sulfides 2–4 and 7; they form two signals in the 1H NMR spectra: one signal at 4.85–5.58 p.p.m., the second at 5.03–6.10 p.p.m. In the 13C NMR spectra of prenyl sulfide 5 and butenyl sulfide 7, the carbon atoms of the S-alkenyl groups resonate in the region of strong fields. In the region of weak fields, the signals of aromatic carbon atoms of the 1,3,5-triazine cycle are observed: 182.32–157.95 p.p.m. In the mass spectra of compounds 2, 5 and 7, the characteristic peaks are [M 15]+ and [M-33]+ peaks, the formation of which is associated with the fragmentation of molecular ions undergoing cleavage of the methyl radical and the •SH radical, respectively. The haloalkyl derivative of the heterocyclic series – 2-chloro-1-(2,2,4-trimethyl-4-phenyl-3,4-dihydroquinoline-1(2H)-yl) ethanoate – in reaction with compound 1 has led to the introduction of a new pharmacophore fragment into the simm-triazine molecule, which contributes to the expansion of the spectrum of potential biological activity of its derivatives.

Probing fragment ion reactivity towards functional groups on coordination polymer surfaces.

Functionalization of surface-grown coordination polymer layers by ion soft-landing of highly reactive molecular fragment ions is demonstrated. The ions form covalent bonds to terminal functional groups of the polymer at the vacuum interface, opening new perspectives for controlled bond formation using reactive ions.

Application of Uplc/Ms/Ms Method for Dertermination of Sudan I in Chili Sauces

This study was carried out to verify and evaluate a method to quantify the relative Sudan I color product using ultra-high performance liquid chromatography coupled with tandem massspectrometry (UPLC/MS/MS). Sudan I was extracted through an Oasis HLB 3cc Vac Cartridge solid phase extraction column 60 mg, after that quantified by UPLC/MS/MS. The program uses a C18 column (2.1 x 100 mm, 1.7 µm), the mobile phase is acetonitrile and water containing 0.1% formic acid, the flow rate is 0.4 ml/min. Running conditions of MRM (Multiple Reaction Monitoring) mode, select molecular ion fragment 249 amu. The verification results have good linearity, the limit of detection (LOD) and the limit of quantification (LOQ) of the analytical procedure are 1.17 and 3.72 ng/g, respectively. The Sudan I recovery efficiency ranged from 82.00-107.33% with the relative standard deviation (RSD) between 4.35-9.04%. Highly sensitive sample extraction procedure is suitable for the determination of Sudan I in food based on 4 ionic fragments characteristics, meeting the requirements of the decision 2002/657/EC of the common European community. The verified analytical procedure was applied to quantitatively identify Sudan I in 21 chili samples. The results showed that Sudan I was not detected in all analyzed samples. The analytical procedure of Sudan I in this study could be used for food safety testing.
 
 

A Mechanism Study on the (+)-ESI-TOF/HRMS Fragmentation of Some PPI Prazoles and Their Related Substances.

Fragmentation mechanisms of some prazoles and their related substances were newly investigated in this paper via positive mode ESI-TOF HRMS1 and HRMS2. Some novel fragmentation rules or ions were found or detected in the research. The pyridine and the benzoimidazole ring remained in most cases during the ionization, and heterolytic fragmentations often occurred near the -S(O)nCH2- linker to give the [1,3]-H migration ion or [1,7]-H migration ion rearranging across the benzoimdazole ring. Smiles rearrangement ionizations also frequently occurred, initiated by the attack of the lone pair electrons from the pyridine ring, and the sulfones gave special N-(2-benzoimdazolyl) pyridine ions (11b and 12c) by a direct extraction from SO2, and the thioethers gave similar framework ions (8c, 9c and 10c) via the rearrangement and a further homolytic cleavage of SH radicals. However, the sulfoxides were seldom detected in the corresponding Smiles rearrangement ions during our measurement, and the N'-oxides of the pyridines did not undergo the Smiles rearrangement ionization due to the absence of the lone pair electrons. The 5/6-membered chelating ions with Na+ or K+ were frequently detected as the molecular and further fragment ions. Some novel and interesting fragment ions containing bivalent (8b and 9b), tetravalent (4b, 5c and 6c) or hexavalent (15b and 16b) sulfurs were first reported here.

Resonance Electron Capture by 5-Methyluridine and 3'-Deoxythymidine Molecules

Negative ion mass spectrometry is used to study processes of resonant electron attachment by 5‑methyluridine and 3'-deoxythymidine nucleoside molecules in the electron 0–14 eV range of energies. It is established that they are similar to those in nucleosides studied earlier (uridine, deoxyuridine, thymidine). The main channels of the fragmentation of molecular ions are revealed, and the absolute cross sections for the formation of fragment ions are determined. It is found that the intensity of the breaking the glycosidic bond in 3'-deoxythymidine in the region of low energies is two and a half orders of magnitude below the one in stavudine, testifying to the prospect of replacing the antiretroviral drug stavudine with 3'-deoxythymidine if radiation therapy is required for oncological diseases contracted as complications of HIV.

Investigation of the chemical components of Ciwujia injection using ultra-high performance liquid chromatography-quadrupole-electrostatic field orbitrap high-resolution mass spectrometry

Ciwujia injection is commonly used to treat cerebrovascular and central nervous system diseases in clinical practice. It can significantly improve blood lipid levels and endothelial cell function in patients with acute cerebral infarction and promote the proliferation of neural stem cells in cerebral ischemic brain tissues. The injection has also been reported to have good curative effects on cerebrovascular diseases, such as hypertension and cerebral infarction. At present, the material basis of Ciwujia injection remains incompletely understood, and only two studies have reported dozens of components, which were determined using high performance liquid chromatography-quadrupole time-of-flight mass spectrometry (HPLC-Q-TOF MS). Unfortunately, the lack of research on this injection restricts the in-depth study of its therapeutic mechanism.In the present study, a qualitative method based on ultra-high performance liquid chromatography-quadrupole-electrostatic field orbitrap high-resolution mass spectrometry (UHPLC-Q/Orbitrap HRMS) was developed to analyze the chemical components of Ciwujia injection. Separation was performed on a BEH Shield RP18 column (100 mm×2.1 mm, 1.7 μm) using 0.1% formic acid aqueous solution (A) and acetonitrile (B) as the mobile phases, and gradient elution was performed as follows: 0-2 min, 0%B; 2-4 min, 0%B-5%B; 4-15 min, 5%B-20%B; 15-15.1 min, 20%B-90%B; 15.1-17 min, 90%B. The flow rate and column temperature were set to 0.4 mL/min and 30 ℃ respectively. MS1 and MS2 data were acquired in both positive- and negative-ion modes using a mass spectrometer equipped with an HESI source. For data post-processing, a self-built library including component names, molecular formulas, and chemical structures was established by collecting information on the isolated chemical compounds of Acanthopanax senticosus. The chemical components of the injection were identified by comparison with standard compounds or MS2 data in commercial databases or literature based on precise relative molecular mass and fragment ion information. The fragmentation patterns were also considered. For example, the MS2 data of 3-caffeoylquinic acid (chlorogenic acid), 4-caffeoylquinic acid (cryptochlorogenic acid), and 5-caffeoylquinic acid (neochlorogenic acid) were first analyzed. The results indicated that these compounds possessed similar fragmentation behaviors, yielding product ions at m/z 173 and m/z 179 simultaneously. However, the abundance of the product ion at m/z 173 was much higher in 4-caffeoylquinic acid than in 5-caffeoylquinic acid or 3-caffeoylquinic acid, and the fragment signal at m/z 179 was much stronger for 5-caffeoylquinic acid than for 3-caffeoylquinic acid. Four caffeoylquinic acids were identified using a combination of abundance information and retention times. MS2 data in commercial database and literature were also used to identify unknown constituents. For example, compound 88 was successfully identified as possessing a relative molecular mass and neutral losses similar to those of sinapaldehyde using the database, and compound 80 was identified as salvadoraside because its molecular and fragmentation behaviors were consistent with those reported in the literature. A total of 102 constituents, including 62 phenylpropanoids, 23 organic acids, 7 nucleosides, 1 iridoid, and 9 other compounds, were identified. The phenylpropanoids can be further classified as phenylpropionic acids, phenylpropanols, benzenepropanals, coumarins, and lignans. Among the detected compounds, 16 compounds were confirmed using reference compounds and 65 compounds were identified in Ciwujia injection for the first time. This study is the first to report the feasibility of using the UHPLC-Q/Orbitrap HRMS method to quickly and comprehensively analyze the chemical components of Ciwujia injection. The 27 newly discovered phenylpropanoids provide further material basis for the clinical treatment of neurological diseases and new research targets for the in-depth elucidation of the pharmacodynamic mechanism of Ciwujia injection and its related preparations.

Analysis and evaluation on Paeoniae Radix Alba from different cultivars by UPLC-Q-TOF-MS and HPLC

In this study, an established ultra-high performance liquid chromatography coupled with quadrupole-time-of-flight mass spectrometry(UPLC-Q-TOF-MS) method was combined with multivariate statistical analysis to investigate the commonality and difference of main chemical components in the medicinal parts of Paeonia lactiflora from different cultivars; in addition, a high performance liquid chromatography(HPLC) method was established to simultaneously determine the content of eight active components in Paeoniae Radix Alba. Non-targeted analysis was carried out by UPLC-Q-TOF-MS on a Waters ACQUITY UPLC BEH C_(18)(2.1 mm×100 mm, 1.7 μm) column with a gradient elution of 0.1% aqueous formic acid(A)-acetonitrile(B) as the mobile phase at a flow rate of 0.2 mL·min~(-1). The column temperature was 30 ℃, and an electrospray ionization source was used to acquire mass spectrometry data in positive and negative ion modes. According to the accurate molecular weight and fragment ion information provided by multi-stage mass spectrometry and by comparison with reference substances and literature reports, thirty-six identical components were identified in Paeoniae Radix Alba from different cultivars with positive and negative ion modes. In the negative ion mode, two groups of samples were well separated; specifically, seventeen components with significant differences in content were screened and identified, and one component unique in "Bobaishao" was obtained. Quantitative analysis was conducted by high-performance liquid chromatography(HPLC) on an Agilent HC-C_(18)(4.6 mm×250 mm, 5 μm) column with a gradient elution of 0.1% aqueous phosphoric acid(A)-acetonitrile(B) as the mobile phase at a flow rate of 1.0 mL·min~(-1). The column temperature was 30 ℃ and the detection wavelength was at 230 nm. An HPLC method was developed for the simultaneous determination of eight active components(gallic acid, oxypaeoniflorin, catechin, albiflorin, paeoniflorin, galloylpaeoniflorin, 1,2,3,4,6-O-pentagalloylglucose, benzoyl-paeoniflorin) in Paeoniae Radix Albaa from different cultivars. Satisfactory linearity was achieved within the investigated linear ranges and with fine coefficients(r>0.999 0), and the methodological investigation showed that the method had good precision, repeatability and stability. The mean recoveries were 90.61% to 101.7% with RSD of 0.12% to 3.6%(n=6). UPLC-Q-OF-MS provided a rapid and efficient qualitative analytical method for the identification of the chemical components in Paeoniae Radix Alba, and the developed HPLC method was simple, rapid and accurate, which could provide a scientific basis for the evaluation of the germplasm resources and herbal quality of Paeoniae Radix Alba from different cultivars.

Use of mass spectrometry as a tool for the search or identification of flavonoids in Urticaceae

Abstract The Urticaceae family, circumscribed within the Rosales, was investigated in this study with an overview of the current literature about phytochemical studies using the Liquid Chromatography coupled to Mass Spectrometry (LC-MS) technique. The aim of this study was to review the secondary metabolites identified in the Urticaeae using LC-MS analysis. A systematic review was performed using Scifinder and ScienceDirect databases. Phenolic substances are the most abundant in the Urticaceae family, especially flavones, phenolic acids, and flavonols. We have shown that flavonoids are important chemotaxonomic markers of the chemical composition of the Urticaeae. Following chemical attributes, the C-glycosylated and O-glycosylated flavones stand out as the main skeletons. Our results revealed the chemical profile and structural variability of micromolecules from each genus of Urticaceae. This approach demonstrates a greater use of reversed-phase and liquid chromatography coupled to a mass spectrometer with a negative mode electrospray ionization (ESI) source. In addition, the mobile phase is usually composed of binary systems and eluted by gradient systems. Finally, this paper presents the identification of molecular ion patterns and fragmentation of chemical markers in Urticaceae, identified and isolated using LC-MS, which has been proven to be a valuable tool in several areas, such as phytochemistry, chemosystematics, and chemophenetics. In conclusion, this review is expected to help identify and separate phenolic compounds from the Urticaceae family.

Effect of processing method on chemical constituents of Rehmanniae Radix: based on UHPLC-LTQ-Orbitrap MS

This study aims to explore the chemical composition of Rehmanniae Radix braised with mild fire and compare the effect of processing method on the chemical composition of Rehmanniae Radix. To be specific, ultra-high performance liquid chromatography with linear ion trap-orbitrap mass spectrometry(UHPLC-LTQ-Orbitrap MS) was used to screen the chemical constituents of Rehmanniae Radix. The chemical constituents were identified based on the relative molecular weight and fragment ions, literature information, and Human Metabolome Database(HMDB). The ion peak area ratio of each component before and after processing was used as the index for the variation. SIMCA was employed to establish principal component analysis(PCA) and orthogonal partial least squares discriminant analysis(OPLS-DA) models of different processed products. According to the PCA plot, OPLS-DA plot, and VIP value, the differential components before and after the processing were screened out. The changes of the content of differential components with the processing method were analyzed. A total of 66 chemical components were identified: 57 of raw Rehmanniae Radix, 55 of steamed Rehmanniae Radix, 55 of wine-stewed Rehmanniae Radix, 51 of repeatedly steamed and sundried Rehmanniae Radix Praeparata, 62 of traditional bran-braised Rehmanniae Radix, and 63 of electric pot-braised Rehmanniae Radix. Among them, the 9 flavonoids of braised Rehmanniae Radix were from Citri Reticulatae Pericarpium. PCA suggested significant differences in the chemical composition of Rehmanniae Radix Praeparata prepared with different processing methods. OPLS-DA screened out 32 chemical components with VIP value >1 as the main differential components. Among the differential components, 9 were unique to braised Rehmanniae Radix(traditional bran-braised, electric pot-braised) and the degradation rate of the rest in braised(traditional bran-braised, electric pot-braised) or repeatedly steamed and sundried Rehmanniae Radix was higher than that in the steamed or wine-stewed products. The results indicated the chemical species and component content of Rehmanniae Radix changed significantly after the processing. The 32 components, such as rehmapicrogenin, martynoside, jionoside D, aeginetic acid, hesperidin, and naringin, were the most important compounds to distinguish different processed products of Rehmanniae Radix. The flavonoids introduced by Citri Reticulatae Pericarpium as excipient may be the important material basis for the effectiveness of braised Rehmanniae Radix compared with other processed products.

Determination of Barbiturates by Femtosecond Ionization Mass Spectrometry.

Barbiturates are highly susceptible to dissociation in mass spectrometry (MS) because of their long side chains combined with a nonaromatic ring consisting of several carbonyl and amine groups. As a result, they exhibit extensive α-cleavage and subsequent rearrangement, making the identification of these compounds difficult. Although a library of electron ionization MS (EIMS) is available, most barbiturates have very similar fragment patterns. Accordingly, it would be desirable to develop a technique for soft ionization, providing a molecular ion and large fragment ions as well. In this study, a molecular ion was clearly observed, in addition to large fragment ions, for a variety of barbiturates based on multiphoton ionization MS (MPIMS) using a tunable ultraviolet femtosecond laser as the ionization source (fs-LIMS). This favorable result was achieved when the optimal laser wavelength for minimizing the excess energy remaining in the ionic state was used. An examination of the photofragmentation pathways suggested that an H atom in the side chain was abstracted by an oxygen atom in the carbonyl group in the ring structure thus initiating fragmentation and subsequent rearrangement. Barbiturates that are substituted with alkyl groups (amobarbital and pentobarbital) had narrower spectral regions for optimal ionization than the other barbiturates with alkyl and alkenyl groups (butalbital and secobarbital) and more with alkyl and phenyl groups (phenobarbital). All of the barbiturates studied provided unique mass spectral patterns in fs-LIMS, which was useful for the reliable identification of these compounds in practical trace analysis.

Fragmenting nanoPutians: Capturing admiration to the rationality, predictability, and beauty of ion chemistry in mass spectrometry.

The fragmentation chemistry of the protonated and ionized nanoPutian 1 has been studied in the gas phase via electrospray ionization and tandem mass spectrometry. A direct analogy was observed between the fragmentation chemistry of this fascinating "humanoid molecule" and "cleavages" at certain parts of the human body. We argue that such direct analogy and illustrative schemes for the fragmentation of molecular ions of 1 offer a ludic and efficient tool to teach and capture attention to ion chemistry in mass spectrometry. Using the changes in mass for the two heavier nanoPutians with different head styles but the same body design, the analogy has also been used to predict mass spectra. The concepts of isotopic labelling and dissociation thresholds have also been illustrated. For many years, the approach has been successfully used by one of us in classes and lectures, mainly when presenting ion chemistry to students and audiences from fields other than Chemistry, most particularly from Biology, Medicine, and Forensic Chemistry.

Identification and quality control strategy of impurities in Zhengqing Fengtongning injection

Zhengqing Fengtongning injection is the sterile aqueous solution of Sinomenine Hydrochloride extracted from the root and stem of Sinomenium acutum, and is widely used to treat rheumatoid arthritis. Due to the processes of extraction, separation, purification, preparation and storage, some related impurities might be formed, which may cause side effects on patients. It is important to rapidly separate and identify the related impurities to ensure the safe use of Zhengqing Fengtongning injection. However, there are few literatures about the impurity in Zhengqing Fengtongning injection. In this work, ultra-high performance liquid chromatography- quadrupole time-of-flight mass spectrometry (UPLC-QTOF/MS) was developed to analyze impurities in both Zhengqing Fengtongning injection and its drug substance, with Sinomenine Hydrochloride as its active pharmaceutical ingredient (API). Six impurities of the Zhengqing Fengtongning injection were found. Structures of impurities 1 and 6 were confirmed by NMR and other impurities were identified from the fragmentation pattern of Sinomenine, the similarity of molecular weight and fragment ions in references. Finally, the HPLC analytical technique was developed to achieve the quantification of impurities 1 and 6. In addition, some reasonable suggestions are put forward on the quality control of Zhengqing Fengtongning injection and its drug substance based on the processes and structural characteristics of the related substances. The technical system established in this paper is helpful to strengthen the quality control of Zhengqing Fengtongning injection and improve production, and can also provide references for the production and quality control of similar drugs.

A multidimensional strategy to rapidly identify the chemical constituents in Shengxian Decoction by using ultra-performance liquid chromatography coupled with ion mobility spectrometry quadrupole time-of-flight mass spectrometry.

As a well-known traditional Chinese medicine formula, the chemical constituents of Shengxian Decoction still remain unclear due to its complexity. In this study, a multidimensional strategy based on ultra-performance liquid chromatography coupled with ion mobility spectrometry quadrupole time-of-flight mass spectrometry and informatics UNIFI platform was applied to achieve rapid and comprehensive identification of the complex composition of Shengxian Decoction. Data-independent acquisition, fast data-directed analysis, and high-definition MSE were used to obtain more and cleaner mass spectrum information. As a result, a total of 120 compounds including 74 saponins, 17 flavonoids, 7 cinnamic acid derivatives, 8 triterpenoids, and 14 others were identified or tentatively characterized by high-resolution molecular mass, fragment ions, and collision cross-section values. Furthermore, high-definition MSE was used to identify six pairs of co-eluting isomers that could not be detected from conventional data-independent acquisition and fast data-directed analysis. This research strategy has a certain potential for the analysis of other compound formulae and lays the foundation for the study of traditional Chinese medicine efficacy.

Decreased S Phase and G2/M Phase Cells by a Bioactive Fraction from the Hexane Extract of Rhododendron aroboreum Leading to the Apoptosis of HeLa Cells In-Vitro

Search for novel anticancer compounds from natural sources is a priority goal of cancer biologists. Rhododendron arboreum is one of the most stately and impressive Rhododendron species. In hilly areas, the flowers of R. arboreum are used for the treatment of chronic diseases. The current study was aimed to evaluate the anti-proliferative property of R. arboreum on HeLa cells. Crude extract of the flower was prepared using serial extraction procedure with different solvents. Cytotoxicity of the extracts on HeLa, CHO and human lymphocytes were assessed using MTT assay and trypan blue dye exclusion methods. The extract was further purified by TLC and characterized by LC-MS method. The hexane extract showed significant cytotoxicity to HeLa cells. This extract was fractionated using thin layer chromatography, 6 fractions were isolated, out of which fraction 3 showed the maximum cytotoxic activity with an IC50 of 15 μg/mL. The mechanism of action was observed as apoptosis induction as indicated by elevated caspase activity and inhibition of cell cycle with reduced cell population in the S and G2/M phases. LC-MS analysis of this promising bioactive fraction resulted in a molecular ion fragment with an m/z value of 437.48 which is corresponding to that of brefeldin A, an anticancer compound. It can be concluded that R. arboreum flower has cytotoxic activity which could be due to the presence of brefeldin A, that warrants further studies on purification and characterization towards the development of highly efficient therapeutics for cancer.
 HIGHLIGHTS
 
 Anti-cancer drug discovery from natural sources like medicinal herbs having diverse metabolites of therapeutic significance provide lead molecules towards cancer drug development
 The anti-proliferative/apoptotic potential of a bioactive fraction from Rhododendron aroboreum, was analysed on cancer cell lines by MTT, Lactate dehydrogenase, Caspase and cell cycle studies. The bioactive compound was characterized through preparative TLC and LC-MS methods
 The potent apoptotic potential of Rhododendron aroboreum flower extract was demonstrated through reduced S-phase and G2/M phase cells, increased caspase, LDH activities in our study results
 The presence of Brefeldin A, previously reported as an anticancer compound in a microbe, was observed for the 1st time in Rhododendron aroboreum through our study in LC-MS analysis
 
 GRAPHICAL ABSTRACT

Analyses of Physical and Chemical Compositions of Different Medicinal Specifications of CRPV by Use of Multiple Instrumental Techniques Combined with Multivariate Statistical Analysis.

Citri Reticulatae Pericarpium Viride (CRPV) is the processed product of Citrus reticulata Blanco. We systematically analyzed two CRPV types, Geqingpi (GQP) and Sihuaqingpi (SHQP), based on powder color, microscopic characteristics, and chemical composition. In addition, we characterized their constituents via ultra-high-performance liquid chromatography with hybrid quadrupole-orbitrap mass spectrometry (UHPLC-Q-Exactive Orbitrap-MS). Both showed significant differences in their powder color and microscopic characteristics. Fourier-transform infrared (FT-IR) spectroscopic analysis results showed that the C=O peak absorption of carboxylic acids and their carbonyl esters in SHQP was higher than that of GQP, while the C-OH and C-H plane bending peaks of polysaccharides were lower than those of GQP. We analyzed these data via similarity analysis, PCA, and OPLS-DA. GQP and SHQP had large distinct differences. Based on the mass measurements for molecular and characteristic fragment ions, we identified 44 main constituents from CRPV, including different flavonoid glycosides and flavonoid aglycones in SHQP and GQP, respectively. We found luteolin-6-C-glucoside, orientin, rhoifolin, and pilloin solely in SHQP, and naringenin and hesperetin only in GQP. The peak area measurements showed GQP having a higher flavonoid glycoside (narirutin, hesperidin, etc.) content, whereas SHQP had a higher polymethoxyflavone (nobiletin, tangeretin, etc.) content. Since we holistically analyzed two CRPV types, the results can not only support future pharmacological research, but also provide a scientific basis for formulating more reasonable CRPV quality standards and guide its clinical potential as a precision medicine.