Oligosaccharides in human milk represent a group of bioactive molecules that have evolved to be an abundant and diverse component milk, even though they no direct nutritive value the infant. A recent hypothesis proposes could substrates for development intestinal microflora mucosal immune system. The inability determine exact composition these oligosaccharides limits research ability understand their biological functions. isolated from lipids proteins individual samples were analyzed by...

This report demonstrates the use of bioinformatic and chemometric tools on liquid chromatography-mass spectrometry (LC-MS) data for discovery trace forensic signatures sample matching ten stocks nerve-agent precursor known as methylphosphonic dichloride (dichlor). XCMS, a software tool primarily used in bioinformatics, was to comprehensively search find candidate LC-MS peaks set dichlor samples. These were down selected group 34 impurity peaks. Hierarchal cluster analysis factor demonstrated...

This article introduces the concept of chiral ion mobility spectrometry (CIMS) and presents examples demonstrating gas-phase separation enantiomers a wide range racemates including pharmaceuticals, amino acids, carbohydrates. CIMS is similar to traditional spectrometry, where ions, when subjected potential gradient, are separated at atmospheric pressure due differences in their shapes sizes. In addition size shape, separates ions based on stereospecific interaction with gas. order achieve...

For the first time, a traditional radioactive nickel (63Ni) beta emission ionization source for ion mobility spectrometry was employed with an atmospheric pressure orthogonal reflector time-of-flight mass spectrometer (IM(tof)MS) to detect chemical warfare agent (CWA) simulant from aerosol samples. Aerosol-phase sampling quartz cyclonic chamber sample introduction. The reference material, which closely mimicked characteristic structure of CWAs as defined and described by Schedule 1, 2, or 3...

Because the glycosylation of proteins is known to change in tumor cells during development breast cancer, a glycomics approach used here find relevant biomarkers cancer. These changes are correlate with increasing burden and poor prognosis. Current antibody-based immunochemical tests for cancer ovarian (CA125), (CA27.29 or CA15-3), pancreatic, gastric, colonic, carcinoma (CA19-9) target highly glycosylated mucin proteins. However, these lack specificity sensitivity use early detection. This...

A series of isobaric disaccharide-alditols, four derived from O-linked glycoproteins, and select trisaccharides were rapidly resolved using tandem high resolution atmospheric pressure ion-mobility time-of-flight mass spectrometry. Electrospray ionization was used to create the gas-phase sodium adducts each carbohydrate. Using this technique it possible separate up three disaccharide alditols in gas phase. Reduced mobility values experimentally determined ion-neutral cross sections are...

Carbohydrates are an extremely complex group of isomeric molecules that have been difficult to analyze in the gas phase by mass spectrometry because (1) precursor ions and product successive stages MSn frequently mixtures isomers, (2) detailed information about anomeric configuration location specific stereochemical variants monosaccharides within larger has not possible obtain a general way. Herein, it is demonstrated gas-phase analyses direct combination electrospray ionization, ambient...

Protein glycosylation involves the addition of monosaccharides in a stepwise process requiring no glycan template. Therefore, identifying numerous glycoforms, including isomers, can help elucidate biological function(s) particular glycans. A method to assess diversity N-linked oligosaccharides released from human serum without derivatization has been developed using on-line nanoLC and high resolution TOF MS. The were analyzed with MALDI FT-ICR MS microchip LC (HPLC-Chip/TOF MS). Two...

Recent trends in cannabis legalization have increased the necessity to better understand effects of use. Animal models involving traditional cannabinoid self-administration approaches been notoriously difficult establish and differences drug used its route administration limited translational value preclinical studies. To address this challenge field, we developed a novel method using response-contingent delivery vaporized Δ9-tetrahydrocannabinol-rich (CANTHC) or cannabidiol-rich (CANCBD)...

The ability of ion mobility spectrometry coupled with mass (IMS-MS) to characterize biological mixtures has been illustrated over the past eight years. However, challenges posed by extreme complexity many samples have demonstrated need for higher resolution IMS-MS measurements. We developed a ESI-IMS-TOF MS utilizing high-pressure electrodynamic funnels at both ends IMS drift cell and operating an elevated pressure compared that conventionally used. instrument consists ESI source, hourglass...

Conventional ion mobility spectrometers that sample packets from continuous sources have traditionally been constrained by an inherently low duty cycle. As such, utilization efficiencies limited to <1% in order maintain instrumental resolving power. Using a modified electrodynamic funnel, we demonstrated the ability accumulate, store, and eject ions conjunction with spectrometry (IMS), which elevated charge density of ejected funnel trap (IFT) provided considerable increase overall...

A new instrument configuration for native ion mobility-mass spectrometry (IM-MS) is described. Macromolecule ions are generated by using a static ESI source coupled to an RF funnel, and these then mobility mass analyzed periodic focusing drift tube IM analyzer Orbitrap spectrometer. The design retains the capabilities first-principles determination of rotationally averaged ion-neutral collision cross sections high-resolution measurements in both analysis modes intact protein complexes....

Graphical abstractAbstractWhen operated as a stand-alone device, an ion mobility spectrometer (IMS) routinely offers low limits of detection (pptv-range) for gas-phase analytes even measurement times less than second. Mass analyzers further enhance the analytical power IMS separations, however, high performance drift-cell instruments are often highly customized, relatively large, and require extensive expertise to operate. In this work we present optimized, cost system that leverages...

For the first time, use of a traditional ionization source for ion mobility spectrometry (radioactive nickel ((63)Ni) beta emission ionization) and three alternative sources (electrospray (ESI), secondary electrospray (SESI), electrical discharge (corona) (CI)) were employed with an atmospheric pressure orthogonal reflector time-of-flight mass spectrometer (IM(tof)MS) to detect chemical warfare agent (CWA) simulants from both aqueous- gas-phase samples. liquid-phase samples, ESI was used as...

The use of electrospray ionization ambient pressure ion mobility spectrometry with an orthogonal reflector time-of-flight mass spectrometer to analyze chemical warfare (CW) degradation products from aqueous environmental samples has been demonstrated. Certified reference materials analytical standards for the detection Schedule 1, 2, or 3 toxic chemicals their precursors as defined by convention treaty verification were used in this study. A combination six G/V-type nerve and four S-type...

The investigation of site-specific glycosylation is essential for further understanding the many biological roles that glycoproteins play; however, existing methods characterizing either are slow or yield incomplete information. Mass spectrometry (MS) being applied to investigate with bottom-up proteomic type strategies. When using these approaches, tandem mass techniques often verify glycopeptide composition, minimize false positives, and structure. fragmentation behavior ions has...

A fully developed understanding of protein glycosylation requires characterization the modifying oligosaccharides, elucidation their covalent attachment sites, and determination glycan heterogeneity at specific sites. Considering complexity inherent to glycosylation, establishing these features for even a single can present an imposing challenge. To meet demands glycoproteomics, capability screen far more complex systems glycosylated proteins must be developed. Although proteome wide...

Ion mobility spectrometry-time-of-flight mass spectrometry (IMS-TOFMS) has been increasingly used in analysis of complex biological samples. A major challenge is to transform IMS-TOFMS a high-sensitivity, high-throughput platform, for example, proteomics applications. In this work, we have developed and integrated three advanced technologies, including efficient ion accumulation an funnel trap prior IMS separation, multiplexing (MP) packet introduction into the drift tube, signal detection...

The results in this manuscript represent a demonstration of RDX vapor detection real time at ambient temperature without sample preconcentration. vapors from the low volatility explosive compound was achieved through selective atmospheric pressure chemical ionization using nitrate reactant ions (NO(3)(-)) and NO(3)(-)·HNO(3) adducts generated an electrical discharge source. were ionized reaction region, which provided variable (up to several seconds) time. times controlled either by flow...

Historically, high pressure ion mobility drift tubes have suffered from low duty cycles and this problem is magnified when such instrumentation coupled with trap mass spectrometers. To significantly alleviate these issues, we outline the result coupling an atmospheric pressure, dual-gate tube spectrometer (IMS) to a linear (LIT-MS) via modulation of beam frequency chirp. The time-domain current, once Fourier transformed, reveals standard spectrum that corresponds mode analysis. By...

Phased structures for lossless ion manipulation offer significant improvements over the scanning second gate method coupling with trap mass analyzers. With an experimental run time of under 1 min select conditions and average less than 4 min, this approach significantly reduces while enhancing temporal duty cycle. The outlined SLIM system connects to analyzer via a PCB stacked ring guide, which replaces commercial optics capillary inlet. By applying discrete repeating injection pulse solving...