Robert E. Santini

Coherent broad-band decoupling—An alternative to proton noise decoupling in carbon-13 nuclear magnetic resonance spectroscopy

Abstract Phase modulation of the decoupler carrier frequency with a 50% duty cycle square wave is shown to be an efficient method for broad-band decoupling. Experimental and theoretical studies show that this coherent broad-band decoupling is more effective than random noise decoupling for many applications. In the particular case of proton decoupled carbon-13 NMR spectroscopy, coherent broad-band decoupling is the method of choice because it is more efficient and is simpler to apply than random noise decoupling. Signal/noise improvements by a factor of 2 or more are observed because of the better decoupling even when the resolution is limited by computer criteria.

An Airborne and Wind Tunnel Evaluation of a Wind Turbulence Measurement System for Aircraft-Based Flux Measurements*

Abstract Although the ability to measure vertical eddy fluxes of gases from aircraft platforms represents an important capability to obtain spatially resolved data, accurate and reliable determination of the turbulent vertical velocity presents a great challenge. A nine-hole hemispherical probe known as the “Best Air Turbulence Probe” (often abbreviated as the “BAT Probe”) is frequently used in aircraft-based flux studies to sense the airflow angles and velocity relative to the aircraft. Instruments such as inertial navigation and global positioning systems allow the measured airflow to be converted into the three-dimensional wind velocity relative to the earth’s surface by taking into account the aircraft’s velocity and orientation. Calibration of the aircraft system has previously been performed primarily through in-flight experiments, where calibration coefficients were determined by performing various flight maneuvers. However, a rigorous test of the BAT Probe in a wind tunnel has not been previously ...

Broad-Band Fourier Transform Quadrupole Ion Trap Mass Spectrometry

Broad-band nondestructive ion detection is achieved in a quadrupole ion trap mass spectrometer by impulsive excitation of a collection of trapped ions of different masses and recording of ion image currents induced on a small detector electrode embedded in but isolated from the adjacent end cap electrode. The image currents are directly measured using a simple differential preamplifier, filter, and amplifier combination and then Fourier analyzed to obtain broad-band frequency domain spectra characteristic of the sample ions. The use of the detector electrode provides a significant reduction in capacitive coupling with the ring electrode. This minimizes coupling of the rf drive signal, which can saturate the front-end stage of the detection circuit and prevent measurement of the relatively weaker ion image currents. Although impulsive excitation is preferred due to its broad-band characteristics and simplicity of use, results are also given for narrow-band ac and broad-band SWIFT (stored wave-form inverse Fourier transform) excitation. Data using argon, acetophenone, and n-butylbenzene show that a resolution of better than 1000 is obtained with a detection bandwidth of 400 kHz. An advantage of nondestructive ion detection is the ability to measure a single-ion population multiple times. This is demonstrated using argon as the sample gas with an average remeasurement efficiency of >90%. Tandem mass spectrometry experiments using a population of acetophenone ions are also shown.

Adaptation of a 3-D Quadrupole Ion Trap for Dipolar DC Collisional Activation

Means to allow for the application of a dipolar DC pulse to the end-cap electrodes of a three-dimensional (3-D) quadrupole ion trap for as short as a millisecond to as long as hundreds of milliseconds are described. The implementation of dipolar DC does not compromise the ability to apply AC waveforms to the end-cap electrodes at other times in the experiment. Dipolar DC provides a nonresonant means for ion acceleration by displacing ions from the center of the ion trap where they experience stronger rf electric fields, which increases the extent of micro-motion. The evolution of the product ion spectrum to higher generation products with time, as shown using protonated leucine enkephalin as a model protonated peptide, illustrates the broad-band nature of the activation. Dipolar DC activation is also shown to be effective as an ion heating approach in mimicking high amplitude short time excitation (HASTE)/pulsed Q dissociation (PQD) resonance excitation experiments that are intended to enhance the likelihood for observing low m/z products in ion trap tandem mass spectrometry.

A versatile computer-controlled pulsed nuclear quadrupole resonance spectrometer

A new, pulsed nuclear quadrupole resonance (NQR) spectrometer capable of performing a variety of pulsed and swept experiments is described. The spectrometer features phase locked, superheterodyne detection using a commercial spectrum analyzer and a fully automatic, computer-controlled tuning and matching network. The tuning and matching network employs stepper motors which turn high power air gap capacitors in a “moving grid” optimization strategy to minimize the reflected power from a directional coupler. In the duplexer circuit, digitally controlled relays are used to switch different lengths of coax cable appropriate for the different radio frequencies. A home-built pulse programmer card controls the timing of radio frequency pulses sent to the probe, while data acquisition and control software is written in Microsoft Quick Basic. Spin-echo acquisition experiments are typically used to acquire the data, although a variety of pulse sequences can be employed. Scan times range from one to several hours de...

Differential non-destructive image current detection in a fourier transform quadrupole ion trap

Dual-detector differential non-destructive Fourier transform detection in a quadrupole ion trap is shown to improve signal intensity and reduce noise compared with spectra recorded using a single detector. A larger area detector in each end-cap electrode is machined to fit its hyperbolic shape and so minimize field imperfections on the z-axis. Argon, acetophenone and bromobenzene spectra were recorded to allow a comparison between single- and dual-detector (differential) modes of detection and to demonstrate the improvement achieved with differential detection. Copyright 1999 John Wiley & Sons, Ltd.

R: A quantitative measure of NMR signal receiving efficiency.

Recognizing that the sensitivity of NMR is influenced by factors such as conductance and dielectric constant of the sample, we propose the receiving efficiency R to characterize how efficiently the NMR signal can be observed from a unit transverse magnetization in a sample under optimal probe tuning and matching conditions. Conveniently, the relative receiving efficiency can be defined as the ratio of the NMR signal induced by a unit transverse magnetization in a sample of interest and a reference solution. Based on the reciprocal relationship between excitation and observation in NMR, the relative receiving efficiency can be correlated with the 90 degrees pulse length (tau(90)). In the special case of perfect probe tuning (impedance matched to 50 Omega), R is inversely proportional to tau(90). Application of the NMR receiving efficiency in quantitative analysis potentially enables a single external concentration reference for almost any sample, eliminating the need to know its exact chemical composition or detailed electromagnetic properties.

Absorption mode Fourier transform electrostatic linear ion trap mass spectrometry.

In Fourier transform mass spectrometry, it is well-known that plotting the spectrum in absorption mode rather than magnitude mode has several advantages. However, magnitude spectra remain commonplace due to difficulties associated with determining the phase of each frequency at the onset of data acquisition, which is required for generating absorption spectra. The phasing problem for electrostatic traps is much simpler than for Fourier transform ion cyclotron resonance (FTICR) instruments, which greatly simplifies the generation of absorption spectra. Here, we present a simple method for generating absorption spectra from a Fourier transform electrostatic linear ion trap mass spectrometer. The method involves time shifting the data prior to Fourier transformation in order to synchronize the onset of data acquisition with the moment of ion acceleration into the electrostatic trap. Under these conditions, the initial phase of each frequency at the onset of data acquisition is zero. We demonstrate that absorption mode provides a 1.7-fold increase in resolution (full width at half maximum, fwhm) as well as reduced peak tailing. We also discuss methodology that may be applied to unsynchronized data in order to determine the time shift required to generate an absorption spectrum.

Nondestructive Tandem Mass Spectrometry Using a Linear Quadrupole Ion Trap Coupled to a Linear Electrostatic Ion Trap

A novel hybrid tandem mass spectrometer is presented that combines a linear quadrupole ion trap (QLIT) with a linear electrostatic ion trap (ELIT), which is composed of opposing ion mirrors. The QLIT is used both as an accumulation device for the pulsed injection of ions into the ELIT and as a collision cell for ions released from the ELIT and back into the QLIT. Ions are subjected to mass analysis in the ELIT via Fourier transformation of the time-domain signal obtained from an image current measurement using a pick-up electrode in the field-free region of the ELIT. The nondestructive nature of ion detection and the relatively straightforward axial entrance and exit of ions into and from the ELIT allow for the execution of nondestructive tandem mass spectrometry experiments whereby both the initial mass spectrum and the product ion spectrum are obtained on the same initial ion population. The timed pulsing of a deflection electrode, in conjunction with the release of ions from the ELIT, allows for the selection of precursor ions for recapture by the QLIT. The transfer of ions back and forth between the QLIT and ELIT is illustrated with Cs ions, the selection of precursor ions is demonstrated with isotopes of tetraoctylammonium cations, and complete nondestructive tandem mass spectrometry experiments are demonstrated with a mixture of angiotensin II and bradykinin cations. With the current apparatus, the efficiency for the process of recapturing ions and then reinjecting them into the ELIT is 35%-40%. The instrument is capable of isolating an ion from a neighbor with a mass as close as 1 part in 500, with negligible loss of the desired species.

Saturation transfer double-difference NMR spectroscopy using a dual solenoid microcoil difference probe

An experiment designed to collect a saturation transfer double difference (STDD) NMR spectrum using a solenoid microcoil NMR difference probe is reported. STDD‐NMR allows the investigation of ligand‐biomolecule binding, with moderate concentration requirements for unlabeled molecular targets and the ability to discern binding events in the presence of non‐binding ligands. The NMR difference probe acquires the signals from two different samples at once, and cancels common signals automatically through a mechanism of switching between parallel excitation and serial acquisition of the sample signals. STDD spectra were acquired on a system consisting of human serum albumin and two ligands, octanoic acid and glucose. The non‐binding ligand, glucose, was cancelled internally through phase cycling, while the protein signal was subtracted automatically by the difference probe. The proton NMR resonance signal from octanoic acid remained in the double difference spectrum. This work demonstrates that the double difference can be performed both internally and automatically through the utilization of the solenoid microcoil NMR difference probe and STDD‐NMR pulse sequence, resulting in a clean signal from the binding ligand with good protein background subtraction and an overall favorable result when compared to the conventional approach. Copyright