Richard H Perry

Stanford University, Stanford, CA, United States

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Publications (17)103.77 Total impact

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    ABSTRACT: Ruthenium transfer hydrogenation catalysts physisorbed onto edge-plane graphite electrodes are active electrocatalysts for the oxidation of alcohols. Electrooxidation of CH3OH (1.23 M) in a buffered aqueous solution at pH 11.5 with [(η(6)-p-cymene)(η(2)-N,O-(1R,2S)-cis-1-amino-2-indanol)]Ru(II)Cl (2) on edge-plane graphite exhibits an onset current at 560 mV vs NHE. Koutecky-Levich analysis at 750 mV reveals a four-electron oxidation of methanol with a rate of 1.35 M(-1) s(-1). Mechanistic investigations by (1)H NMR, cyclic voltammetry, and desorption electrospray ionization mass spectrometry indicate that the electroxidation of methanol to generate formate is mediated by surface-supported Ru-oxo complexes.
    Journal of the American Chemical Society 09/2013; · 10.68 Impact Factor
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    ABSTRACT: We apply desorption electrospray ionization mass spectrometry imaging (DESI-MSI) to provide an in situ lipidomic profile of genetically modified tissues from a conditional transgenic mouse model of MYC-induced hepatocellular carcinoma (HCC). This unique, label-free approach of combining DESI-MSI with the ability to turn specific genes on and off has led to the discovery of highly specific lipid molecules associated with MYC-induced tumor onset. We are able to distinguish normal from MYC-induced malignant cells. Our approach provides a strategy to define a precise molecular picture at a resolution of about 200 microns that may be useful in identifying lipid molecules that define how the MYC oncogene initiates and maintains tumorigenesis.
    Analytical Chemistry 04/2013; · 5.82 Impact Factor
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    ABSTRACT: We have applied an ambient ionization technique, desorption electrospray ionization MS, to identify transient reactive species of an archetypal C-H amination reaction catalyzed by a dirhodium tetracarboxylate complex. Using this analytical method, we have detected previously proposed short-lived reaction intermediates, including two nitrenoid complexes that differ in oxidation state. Our findings suggest that an Rh-nitrene oxidant can react with hydrocarbon substrates through a hydrogen atom abstraction pathway and raise the intriguing possibility that two catalytic C-H amination pathways may be operative in a typical bulk solution reaction. As highlighted by these results, desorption electrospray ionization MS should have broad applicability for the mechanistic study of catalytic processes.
    Proceedings of the National Academy of Sciences 10/2012; · 9.81 Impact Factor
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    ABSTRACT: Desorption electrospray ionization (DESI) coupled to high-resolution Orbitrap mass spectrometry (MS) was used to study the reactivity of a (β-amino alcohol)(arene)RuCl transfer hydrogenation catalytic precursor in methanol (CH(3)OH). By placing [(p-cymene)RuCl(2)](2) on a surface and spraying a solution of β-amino alcohol in methanol, two unique transient intermediates having lifetimes in the submillisecond to millisecond range were detected. These intermediates were identified as Ru (II) and Ru (IV) complexes incorporating methyl formate (HCOOCH(3)). The Ru (IV) intermediate is not observed when the DESI spray solution is sparged with Ar gas, indicating that O(2) dissolved in the solvent is necessary for oxidizing Ru (II) to Ru (IV). These proposed intermediates are supported by high-resolution and high mass accuracy measurements and by comparing experimental to calculated isotope profiles. Additionally, analyzing the bulk reaction mixture using gas chromatography-MS and nuclear magnetic resonance spectroscopy confirms the formation of HCOOCH(3). These results represent an example that species generated from the (β-amino alcohol)(arene)RuCl (II) catalytic precursor can selectively oxidize CH(3)OH to HCOOCH(3). This observation leads us to propose a pathway that can compete with the hydrogen transfer catalytic cycle. Although bifunctional hydrogen transfer with Ru catalysts has been well-studied, the ability of DESI to intercept intermediates formed in the first few milliseconds of a chemical reaction allowed identification of previously unrecognized intermediates and reaction pathways in this catalytic system.
    Proceedings of the National Academy of Sciences 02/2012; 109(7):2246-50. · 9.81 Impact Factor
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    Angewandte Chemie International Edition 07/2011; 50(37):8634-7. · 11.34 Impact Factor
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    ABSTRACT: The powerful hybrid analysis method of capillary-based separations followed by mass spectrometric analysis gives substantial chemical identity and structural information. It is usually carried out using electrospray ionization. However, the salts and detergents used in the mobile phase for electrokinetic separations suppress ionization efficiencies and contaminate the inlet of the mass spectrometer. This report describes a new method that uses desorption electrospray ionization (DESI) to overcome these limitations. Effluent from capillary columns is deposited on a rotating Teflon disk that is covered with paper. As the surface rotates, the temporal separation of the eluting analytes (i.e., the electropherogram) is spatially encoded on the surface. Then, using DESI, surface-deposited analytes are preferentially ionized, reducing the effects of ion suppression and inlet contamination on signal. With the use of this novel approach, two capillary-based separations were performed: a mixture of the rhodamine dyes at milligram/milliliter levels in a 10 mM sodium borate solution was separated by capillary electrophoresis, and a mixture of three cardiac drugs at milligram/milliliter levels in a 12.5 mM sodium borate and 12.5 mM sodium dodecyl sulfate solution was separated by micellar electrokinetic chromatography. In both experiments, the negative effects of detergents and salts on the MS analyses were minimized.
    Analytical Chemistry 02/2011; 83(6):1955-9. · 5.82 Impact Factor
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    Angewandte Chemie International Edition 01/2011; 50(1):250-4. · 11.34 Impact Factor
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    ABSTRACT: Ambient ionization methods such as desorption electrospray ionization (DESI) allow the analysis of chemicals adsorbed at surfaces without the need for sample (or surface) pretreatment. A limitation of current implementations of these ionization sources is the small size of the area that can be sampled. This makes examination of surfaces of large areas time-consuming because of the need to raster across the surface. This paper describes a DESI source that produces a spray plume with an effective desorption/ionization area of 3.6 cm(2), some 200 times larger than given by conventional DESI sources. Rhodamine 6G and several drugs of abuse (codeine, heroin and diazepam) were used to demonstrate the ability to use large-area DESI MS to perform rapid (a few seconds) representative sampling of areas of the order of several square centimetres without scanning the probe across the surface. The large area ion source displayed high sensitivity (limits of detection in the high nanogram range) and high reproducibility (approximately 20 to 35% relative standard deviation). The rapid analysis of even larger surfaces (hundreds of cm(2)) for traces of explosives is possible using a sorbent surface wipe followed by large-area DESI interrogation performed directly on the wipe material. The performance of this mass transfer dry wipe method was examined by determination of the limits of detection of several explosives. Surfaces with different topographies and compositions were also tested. Using this method, absolute limits of detection observed for HMX and RDX from plastic surfaces and skin were found to be as low as 10 ng cm(-2). The concentration of residue from large surface areas in this technique allowed the detection of 100 ng of explosives from surfaces with areas ranging from 1.00 x 10(3) cm(2) to 1.40 x 10(4) cm(2).
    The Analyst 08/2010; 135(8):1953-60. · 4.23 Impact Factor
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    ABSTRACT: A recently developed hand-held, rectilinear ion trap mass spectrometer, capable of performing in situ analysis, has been evaluated for a variety of environmentally relevant analytes. Different sampling and ionization methods were implemented, demonstrating the considerable versatility of this instrument. A discontinuous (viz. pulsed) atmospheric pressure inlet (DAPI) was used to introduce externally-generated analyte ions. Nitro compounds were ionized by electrosonic spray ionization (ESSI) yielding the protonated and sodiated forms of the molecular ion, as well as fragment ions. The amines 2,2,6,6-tetramethylpiperidine, triethylamine and 2,6-diphenylpyridine showed low parts per billion (ppb) detection limits. Vapor phase external ionization was used to examine the chemical warfare simulant dimethyl methylphosphonate and the insect repellant N,N-diethyl-m-toluamide. Membrane introduction mass spectrometry (MIMS) was used as the introduction system for hydrophobic analytes using a selectively permeable (polydimethylsiloxane) membrane placed within the vacuum manifold with subsequent ionization of the thermally desorbed neutral compounds inside the ion trap. MIMS allowed the quantitation of trace levels (a few ppb) of fluorinated compounds in the vapor phase. MIMS was also applied to the quantitation of aqueous polycyclic aromatic hydrocarbons (PAH's) with limits of detection again in the low ppb range for naphthalene, acenaphthene, anthracene and phenanthrene.
    European Journal of Mass Spectrometry 01/2010; 16(1):11-20. · 1.26 Impact Factor
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    ABSTRACT: The analysis of Stevia leaves has been demonstrated without any sample preparation using desorption electrospray ionization (DESI) mass spectrometry. Direct rapid analysis was achieved using minimal amounts of sample ( approximately 0.15 cm x 0.15 cm leaf fragment). Characteristic constituents of the Stevia plant are observed in both the positive and negative ion modes including a series of diterpene 'sweet' glycosides. The presence of the glycosides was confirmed via tandem mass spectrometry analysis using collision-induced dissociation and further supported by exact mass measurements using an LTQ-Orbitrap. The analysis of both untreated and hexane-extracted dry leaves proved that DESI can be successfully used to analyze untreated leaf fragments as identical profiles were obtained from both types of samples. Characterization and semi-quantitative determination of the glycosides was achieved based on the glycoside profile within the full mass spectrum. In addition, the presence of characteristic glycosides in an all-natural commercial Stevia dietary supplement was confirmed. This study provides an example of the application of DESI to direct screening of plant materials, in this case diterpene glycosides.
    The Analyst 06/2009; 134(5):867-74. · 4.23 Impact Factor
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    ABSTRACT: A method is described to improve resolution and peak shape in the Orbitrap under certain experimental conditions. In these experiments, an asymmetric anharmonic axial potential was first produced in the Orbitrap by detuning the voltage on the compensator electrode, which results in broad and multiply split mass spectral peaks. An AC waveform applied to the outer electrode, 180 degrees out of phase with ion axial motion and resonant with the frequency of ion axial motion, caused ions of a given m/z to be de-excited to the equator (z = 0) and then immediately re-excited. This process, termed "rephasing," leaves the ion packet with a narrower axial spatial extent and frequency distribution. For example, when the Orbitrap axial potential is thus anharmonically de-tuned, a resolution of 124,000 to 171,000 is obtained, a 2- to 3-fold improvement over the resolution of 40,000 to 60,000 without rephasing, at 10 ng/microL reserpine concentration. Such a rephasing capability may ultimately prove useful in implementing tandem mass spectrometry (MS/MS) in the Orbitrap, bringing the Orbitrap's high mass accuracy and resolution to bear on both the precursor and product ions in the same MS/MS scan and making available the collision energy regime of the Orbitrap, approximately 1500 eV.
    Journal of the American Society for Mass Spectrometry 03/2009; 20(8):1397-404. · 3.59 Impact Factor
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    ABSTRACT: Desorption electrospray ionization (DESI) is a droplet-based ionization method that is applied to samples in the ambient environment with little or no sample preparation. Its utility for industrial applications is explored here for the case of pharmaceutical cleaning validation. A non-proximate large-area DESI system was built to examine representative areas of the surfaces of reaction vessels used in active product ingredient (API) manufacturing. A large-area sprayer capable of sampling an area of approximately 2.5 cm(2) was coupled with a transport tube to allow sensitive, representative sampling of APIs from a stainless steel surface 1 m away from the mass spectrometer. The system was used to detect the APIs neostigmine, acebutolol, amiloride, amiodarone, ibuprofen, montelukast, potassium clavulanate, and beta-estradiol, at levels as low as 30-10 ng/cm(2), easily satisfying the general acceptable limits set by the pharmaceutical industry. These levels were achieved from surfaces resembling the equipment used in API manufacturing processes at a rate of 30 s per analysis.
    Rapid Communications in Mass Spectrometry 12/2008; 23(1):131-7. · 2.51 Impact Factor
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    Richard H Perry, R Graham Cooks, Robert J Noll
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    ABSTRACT: Since its introduction, the orbitrap has proven to be a robust mass analyzer that can routinely deliver high resolving power and mass accuracy. Unlike conventional ion traps such as the Paul and Penning traps, the orbitrap uses only electrostatic fields to confine and to analyze injected ion populations. In addition, its relatively low cost, simple design and high space-charge capacity make it suitable for tackling complex scientific problems in which high performance is required. This review begins with a brief account of the set of inventions that led to the orbitrap, followed by a qualitative description of ion capture, ion motion in the trap and modes of detection. Various orbitrap instruments, including the commercially available linear ion trap-orbitrap hybrid mass spectrometers, are also discussed with emphasis on the different methods used to inject ions into the trap. Figures of merit such as resolving power, mass accuracy, dynamic range and sensitivity of each type of instrument are compared. In addition, experimental techniques that allow mass-selective manipulation of the motion of confined ions and their potential application in tandem mass spectrometry in the orbitrap are described. Finally, some specific applications are reviewed to illustrate the performance and versatility of the orbitrap mass spectrometers.
    Mass Spectrometry Reviews 09/2008; 27(6):661-99. · 7.74 Impact Factor
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    Wm Craig Byrdwell, Richard H Perry
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    ABSTRACT: Liquid chromatography coupled to atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI) mass spectrometry (MS), in parallel, was used for simultaneous detection of bovine milk sphingolipids (BMS). APCI-MS mass spectra exhibited mostly ceramide-like fragment ions, [Cer-H(2)O+H](+) and [Cer-2H(2)O+H](+), which were used to identify individual molecular species of BMS according to fatty acyl chain length:degree of unsaturation and long-chain base (LCB). ESI-MS was used to confirm the molecular weights of BMS species. Both sphingomyelin (SM) and dihydrosphingomyelin (DSM) molecular species were identified, with DSM species constituting 20% of BMS. Approximately 56 to 58% of DSM species contained a d16:0 LCB, while 34 to 37% contained a d18:0 LCB. Approximately 26 to 30% of SM species contained a d16:1 LCB, while 57 to 60% contained a d18:1 LCB. BMS species contained both odd and even carbon chain lengths. The most abundant DSM species contained a d16:0 LCB with a 22:0, 23:0 or 24:0 fatty acyl chain, while the most abundant SM species contained a d18:1 LCB with a 16:0 or 23:0 fatty acyl chain. (31)P NMR spectroscopy was used to conclusively confirm that DSM is a dietary component in BMS.
    Journal of Chromatography A 05/2007; 1146(2):164-85. · 4.61 Impact Factor
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    ABSTRACT: Sublimation of near-racemic samples of serine yields a sublimate which is highly enriched in the major enantiomer; this simple one-step process occurs under relatively mild conditions, and represents a possible mechanism for the chiral amplification step in homochirogenesis.
    Chemical Communications 04/2007; · 6.38 Impact Factor
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    William Craig Byrdwell, Richard H Perry
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    ABSTRACT: Liquid chromatography coupled to atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI) mass spectrometry (MS), in parallel, was used for detection of bovine brain and chicken egg sphingolipids (SLs). APCI-MS mass spectra exhibited mostly ceramide-like fragment ions, [Cer-H(2)O+H](+) and [Cer-2H(2)O+H](+), whereas ESI-MS produced mostly intact protonated molecules, [M+H](+). APCI-MS/MS and MS(3) were used to differentiate between isobaric SLs. APCI-MS/MS mass spectra exhibited long-chain base related fragments, [LCB](+) and [LCB-H(2)O](+), that allowed the sphinganine backbone to be differentiated from the sphingenine backbone. Fragments formed from the fatty amide chain, [FA(long)](+) and [FA(short)](+), allowed an overall fatty acid composition to be determined. The presence of both dihydrosphingomyelin (DSM) and sphingomyelin (SM) sphingolipid classes was confirmed using (31)P NMR spectroscopy.
    Journal of Chromatography A 12/2006; 1133(1-2):149-71. · 4.61 Impact Factor
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    ABSTRACT: The newly developed version of the multi-particle ion trajectory simulation program, ITSIM 6.0, was applied to simulate ac dipolar excitation of ion axial motion in the Orbitrap. The Orbitrap inner and outer electrodes were generated in AutoCAD, a 3D drawing program. The electrode geometry was imported into the 3D field solver COMSOL; the field array was then imported into ITSIM 6.0. Ion trajectories were calculated by solving Newton's equations using Runge–Kutta integration methods. Compared to the analytical solution, calculated radial components of the field at the device's “equator” (z = 0) were within 0.5% and calculated axial components midway between the inner and outer electrodes were within 0.2%.The experiments simulated here involved the control of axial motion of ions in the Orbitrap by the application of dipolar ac signals to the split outer electrodes, as described in a recently published paper from this laboratory [Hu et al., J. Phys. Chem. A 110 (2006) 2682]. In these experiments, ac signal was applied at the axial resonant frequency of a selected ion. Axial excitation and eventual ion ejection resulted when the ac was in phase with, i.e., had 0° phase relative to ion axial motion. De-excitation of ion axial motion until the ions were at z = 0 and at rest with respect to the z-axis resulted if the applied ac was out of phase with ion motion, with re-excitation of ion axial motion occurring if the dipolar ac was continued beyond this point. Both de-excitation and re-excitation could be achieved mass-selectively and depended on the amplitude and duration (number of cycles) of the applied ac. The effects of ac amplitude, frequency, phase relative to ion motion, and bandwidth of applied waveform were simulated. All simulation results were compared directly with the experimental data and good agreement was observed. Such ion motion control experiments and their simulation provide the possibility to improve Orbitrap performance and to develop tandem mass spectrometry (MS/MS) capabilities inside the Orbitrap.
    International Journal of Mass Spectrometry. 01/2006; 254:53-62.

Publication Stats

242 Citations
103.77 Total Impact Points

Institutions

  • 2011–2012
    • Stanford University
      • Department of Chemistry
      Stanford, CA, United States
  • 2006–2010
    • Purdue University
      • Department of Chemistry
      West Lafayette, IN, United States
  • 2006–2007
    • Agricultural Research Service
      Kerrville, Texas, United States