Shift Correlation Research Articles

Iridium(I) homobinuclear complexes containing salen-type ligands as bridge

New binuclear iridium(I) complexes with general formula [Ir2(η4-cod)2(μ-SB)] (1–12) derived from the reactions of tetradentate Schiff bases ligands [N,N′-ethylenebis(5-R-salicylideneimine)] (5,5′-R-salenH2), [N,N′-1,3-propylenebis(5-R-salicylideneimine)] (5,5′-R-salpenH2), and [N,N′-o-phenylenebis(5-R-salicylideneimine)] (5,5′-R-salphenH2) (R = H, MeO, Cl, NO2) with [Ir(cod)(μ-Cl)]2 were synthesized. The homobinuclear nature of this iridium complexes was supported by elemental analysis, FAB-Mass and 1H NMR spectrometry. Full characterization was accomplished by IR spectroscopy, 13C NMR and bidimensional NMR experiments (COSY, HSQC, HMBC and NOESY). In addition, iridium complex [(Ir(η4-cod)2(μ-5,5′-MeO-salen)] (2) was characterized by X-ray crystallography, showing that ethylene bridge is a s-trans conformation, and that the Schiff base ligand act as a bridging N,O-bidentate ligand toward two iridium atoms, and 1,5-cyclooctadiene (cod) ligand complete the coordination sphere of metal center. The effect of the substituent groups on salicylaldiminate fragments has been studied by 13C{1H} NMR shift and Hammett sigma correlations for each series of complexes.

Determination of the Full 207Pb Chemical Shift Tensor of Anglesite, PbSO4, and Correlation of the Isotropic Shift to Lead–Oxygen Distance in Natural Minerals

The full 207 Pb chemical shift (CS) tensor of lead in the mineral anglesite, PbSO 4 , was determined from orientation-dependent nuclear magnetic resonance (NMR) spectra of a large natural single crystal, using a global fit over two rotation patterns. The resulting tensor is characterised by the reduced anisotropy Δ δ = ( − 327 ± 4 ) ppm, asymmetry η C S = 0.529 ± 0.002 , and δ i s o = ( − 3615 ± 3 ) ppm, with the isotropic chemical shift δ i s o also verified by magic-angle spinning NMR on a polycrystalline sample. The initially unknown orientation of the mounted single crystal was included in the global data fit as well, thus obtaining it from NMR data only. By use of internal crystal symmetries, the amount of data acquisition and processing for determination of the CS tensor and crystal orientation was reduced. Furthermore, a linear correlation between the 207 Pb isotropic chemical shift and the shortest Pb–O distance in the co-ordination sphere of Pb 2 + solely surrounded by oxygen has been established for a large database of lead-bearing natural minerals.

Real-Time Frequency Tracking of an Electro-Thermal Piezoresistive Cantilever Resonator with ZnO Nanorods for Chemical Sensing

The asymmetric resonance response in electro-thermal piezoresistive cantilever resonators causes a need of an optimization treatment for taking parasitic actuation-sensing effects into account. An electronic reference circuit for signal subtraction, integrated with the cantilever resonator has the capability to reduce the effect of parasitic coupling. Measurement results demonstrated that a symmetric amplitude shape (Lorentzian) and an optimized phase characteristic (i.e., monotonically decreasing) were successfully extracted from an asymmetric resonance response. With the monotonic phase response, real-time frequency tracking can be easier to implement using a phase-locked loop (PLL) system. In this work, an electro-thermal piezoresistive cantilever resonator functionalized with self-assembled monolayers of chitosan-covered ZnO nanorod arrays as sensitive layers has been investigated under different relative humidity (rH) levels. Enhancement of resonance phase response has been demonstrated by implementing the reference signal subtraction. Subsequently, a lock-in amplifier integrated with PLL system (MFLI, Zurich Instruments, Zurich, Switzerland) was then employed for continuously tracking the resonant frequency. As a result, we find a good correlation of frequency shift (∆f0) with change in rH monitored using a commercial reference sensor.

Alumina: discriminative analysis using 3D correlation of solid-state NMR parameters.

Synthetic transition aluminas (χ, κ, θ, γ, δ, η, ρ) exhibit unique adsorptive and catalytic properties leading to numerous practical applications. Generated by thermal transformation of aluminium (oxy)hydroxides, structural differences between them arise from the variability of aluminium coordination numbers and degree of dehydroxylation. Unequivocal identification of these phases using X-ray diffraction has proven to be very difficult. Quadrupolar interactions of 27Al nuclei, highly sensitive to each site symmetry, render advanced 27Al solid-state NMR a unique spectroscopic tool to fingerprint and identify the different phases. In this paper, 27Al NMR spectroscopic data on alumina reported in literature are collected in a comprehensive library. Based on this dataset, a new 3D correlative method of NMR parameters is presented, enabling fingerprinting and identification of such phases. Providing a gold standard from crystalline samples, this approach demonstrates that any sort of crystalline, ill crystallized or amorphous, mixed periodic or aperiodically ordered transition alumina can now be assessed beyond the current limitations of characterisation. Adopting the presented approach as a standard characterisation of alumina samples will readily reveal NMR parameter-structure-property relations suitable to develop new or improved applications of alumina. Methodological guidance is provided to assist consistent implementation of this characterisation throughout the fields involved.

Functional Data Analyses of Gait Data Measured Using In-Shoe Sensors

In studies of gait, continuous measurement of force exerted by the ground on a body, or ground reaction force (GRF), provides valuable insights into biomechanics, locomotion, and the possible presence of pathology. However, gold-standard measurement of GRF requires a costly in-lab observation obtained with sophisticated equipment and computer systems. Recently, in-shoe sensors have been pursued as a relatively inexpensive alternative to in-lab measurement. In this study, we explore the properties of continuous in-shoe sensor recordings using a functional data analysis approach. Our case study is based on measurements of three healthy subjects, with more than 300 stances (defined as the period between the foot striking and lifting from the ground) per subject. The sensor data show both phase and amplitude variabilities; we separate these sources via curve registration. We examine the correlation of phase shifts across sensors within a stance to evaluate the pattern of phase variability shared across sensors. Using the registered curves, we explore possible associations between in-shoe sensor recordings and GRF measurements to evaluate the in-shoe sensor recordings as a possible surrogate for in-lab GRF measurements.

NMR Quantification of Hydrogen-Bond-Activating Effects for Organocatalysts including Boronic Acids.

The hydrogen-bonding activation for 66 organocatalysts has been quantified using a 31P NMR binding experiment with triethylphosphine oxide (TEPO). Diverse structural classes, including phenols, diols, silanols, carboxylic acids, boronic acids, and phosphoric acids, were examined with a variety of steric and electronic modifications to understand how the structure and secondary effects contribute to hydrogen-bonding ability and catalysis. Hammett plots demonstrate high correlation for the Δδ 31P NMR shift to Hammett parameters, establishing the ability of TEPO binding to predict electronic trends. Upon correlation to catalytic activity in a Friedel-Crafts addition reaction, data demonstrate that 31P NMR shifts correlate to catalytic activity better than p Ka values. Boronic acids were investigated, and 31P NMR binding experiments predicted strong hydrogen-bonding ability, for which catalytic activity was confirmed, resulting in the greatest rate enhancement observed in the Friedel-Crafts addition of all organocatalysts studied. A detailed investigation supports that boronic acid activation proceeds through hydrogen-bonding interactions and not coordination with the Lewis acidic boron center. Using 31P NMR spectroscopy offers a simple and rapid tool to quantify and predict hydrogen-bonding abilities for the design and applications of new organocatalysts and supramolecular synthons.

Anatomic Anterior Cruciate Ligament Reconstruction Using Hamstring Tendons Restores Quantitative Pivot Shift.

Background:It is still uncertain how surgical reconstruction of the anterior cruciate ligament (ACL) is able to restore rotatory laxity of the involved joint. The desired amount of restraint applied by the ACL graft, as compared with the healthy knee, has not been fully clarified.Purpose:To quantify the ability of single-bundle anatomic ACL reconstruction using hamstring tendons in reducing the pivot-shift phenomenon immediately after surgery under anesthesia.Study Design:Case series; Level of evidence, 4.Methods:An inertial sensor and image analysis were used at 4 international centers to measure tibial acceleration and lateral compartment translation of the knee, respectively. The standardized pivot-shift test was quantified in terms of the side-to-side difference in laxity both preoperatively and postoperatively with the patient under anesthesia. The reduction in both tibial acceleration and lateral compartment translation after surgery and the side-to-side difference were evaluated using the Wilcoxon signed-rank test. Alpha was set at P < .05.Results:A total of 107 patients were recruited for the study, and data were available for 89 patients. There was a statistically significant reduction in quantitative rotatory knee laxity between preoperatively (inertial sensor, 2.55 ± 4.00 m/s2; image analysis, 2.04 ± 2.02 mm) and postoperatively (inertial sensor, –0.54 ± 1.25 m/s2; image analysis, –0.10 ± 1.04 mm) between the involved and healthy joints, as measured by the 2 devices (P < .001 for both). Postoperatively, both devices detected a lower rotatory laxity value in the involved joint compared with the healthy joint (inertial sensor, 2.45 ± 0.89 vs 2.99 ± 1.10 m/s2, respectively [P < .001]; image analysis, 0.99 ± 0.83 vs 1.09 ± 0.92 mm, respectively [P = .38]).Conclusion:The data from this study indicated a significant reduction in the pivot shift when compared side to side. Both the inertial sensor and image analysis used for the quantitative assessment of the pivot-shift test could successfully detect restoration of the pivot shift after anatomic single-bundle ACL reconstruction. Future research will examine how pivot-shift control is maintained over time and correlation of the pivot shift with return to full activity in patients with an ACL injury.

Correction to "Correlation of device Performance and Fermi Level Shift in the Emitting Layer of Organic Light-Emitting Diodes with Amine-Based Electron Injection Layers".

ADVERTISEMENT RETURN TO ISSUEPREVAddition/CorrectionNEXTORIGINAL ARTICLEThis notice is a correctionCorrection to “Correlation of device Performance and Fermi Level Shift in the Emitting Layer of Organic Light-Emitting Diodes with Amine-Based Electron Injection Layers”Sebastian StolzSebastian StolzLight Technology Institute, Karlsruhe Institute of Technology, Engesserstrasse 13, Karlsruhe 76131, GermanyInnovationLab, Speyerer Strasse 4, Heidelberg 69115, GermanyMore by Sebastian Stolzhttp://orcid.org/0000-0001-8804-0207, Martin PetzoldtMartin PetzoldtInnovationLab, Speyerer Strasse 4, Heidelberg 69115, GermanyOrganisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, Heidelberg 69120, GermanyMore by Martin Petzoldt, Uli LemmerUli LemmerLight Technology Institute, Karlsruhe Institute of Technology, Engesserstrasse 13, Karlsruhe 76131, GermanyInstitute of Microstructure Technology, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, Eggenstein-Leopoldshafen 76344, GermanyMore by Uli Lemmerhttp://orcid.org/0000-0001-9892-329X, Uwe H. F. BunzUwe H. F. BunzOrganisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, Heidelberg 69120, GermanyCentre for Advanced Materials, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 225, Heidelberg 69120, GermanyMore by Uwe H. F. Bunzhttp://orcid.org/0000-0002-9369-5387, Manuel HamburgerManuel HamburgerInnovationLab, Speyerer Strasse 4, Heidelberg 69115, GermanyOrganisch-Chemisches Institut, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer Feld 270, Heidelberg 69120, GermanyMore by Manuel Hamburger, Gerardo Hernandez-SosaGerardo Hernandez-SosaLight Technology Institute, Karlsruhe Institute of Technology, Engesserstrasse 13, Karlsruhe 76131, GermanyInnovationLab, Speyerer Strasse 4, Heidelberg 69115, GermanyMore by Gerardo Hernandez-Sosahttp://orcid.org/0000-0002-2871-6401, and Eric Mankel*Eric MankelInnovationLab, Speyerer Strasse 4, Heidelberg 69115, GermanyTechnische Universität Darmstadt, Materials Science Department, Surface Science Division, Otto-Berndt-Straße 3, Darmstadt 64287, GermanyMore by Eric Mankelhttp://orcid.org/0000-0001-6566-157XCite this: ACS Appl. Mater. Interfaces 2018, 10, 34, 29187Publication Date (Web):August 14, 2018Publication History Published online14 August 2018Published inissue 29 August 2018https://doi.org/10.1021/acsami.8b09792Copyright © 2018 American Chemical SocietyRIGHTS & PERMISSIONSArticle Views562Altmetric-Citations1LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (268 KB) Get e-Alerts Get e-Alerts

Investigation of the thermal shift assay and its power to predict protein and virus stabilizing conditions

Protein thermal shift assay (TSA) has been extensively used in investigation of protein stabilization (for protein biopharmaceutics stabilization, protein crystallization studies or screening of recombinant proteins) and drug discovery (screening of ligands or inhibitors). This work aimed to analyze thermal shift assay results in comparison to protein polymerization (multimerization and aggregation) propensity and test the most stabilizing formulations for their stabilization effect on enveloped viruses. Influence of protein concentration, buffer pH and molarity was tested on three proteins (immunoglobulin G, ovalbumin, and albumin) and results showed that each of these factors has an impact on determined shift in protein melting point Tm, and the impact was similar for all three proteins. In case of ovalbumin, molecular dynamics simulations were performed with the goal to understanding molecular basis of protein’s thermal stability dependence on pH. Effect of three denaturing agents in a wide concentration range on Tm showed nicely that chemical denaturation occurs only at the highest concentrations. Results showed similar effect on Tm for most formulations on different proteins. Most successful formulations were tested for enveloped virus stabilizing potential using cell culture infectivity assay (CCID50) and results showed lack of correlation with TSA results. Only weak correlation of Tm shift and protein polymerization measured by SEC-HPLC was obtained, meaning that polymerization cannot be predicted from Tm shifts.

Probing Protein-Protein Interactions Using Asymmetric Labeling and Carbonyl-Carbon Selective Heteronuclear NMR Spectroscopy.

Protein-protein interactions (PPIs) regulate a plethora of cellular processes and NMR spectroscopy has been a leading technique for characterizing them at the atomic resolution. Technically, however, PPIs characterization has been challenging due to multiple samples required to characterize the hot spots at the protein interface. In this paper, we review our recently developed methods that greatly simplify PPI studies, which minimize the number of samples required to fully characterize residues involved in the protein-protein binding interface. This original strategy combines asymmetric labeling of two binding partners and the carbonyl-carbon label selective (CCLS) pulse sequence element implemented into the heteronuclear single quantum correlation (1H-15N HSQC) spectra. The CCLS scheme removes signals of the J-coupled 15N–13C resonances and records simultaneously two individual amide fingerprints for each binding partner. We show the application to the measurements of chemical shift correlations, residual dipolar couplings (RDCs), and paramagnetic relaxation enhancements (PRE). These experiments open an avenue for further modifications of existing experiments facilitating the NMR analysis of PPIs.

Chemical shift-based identification of monosaccharide spin-systems with NMR spectroscopy to complement untargeted glycomics.

A better understanding of oligosaccharides and their wide-ranging functions in almost every aspect of biology and medicine promises to uncover hidden layers of biology and will support the development of better therapies. Elucidating the chemical structure of an unknown oligosaccharide remains a challenge. Efficient tools are required for non-targeted glycomics. Chemical shifts are a rich source of information about the topology and configuration of biomolecules, whose potential is however not fully explored for oligosaccharides. We hypothesize that the chemical shifts of each monosaccharide are unique for each saccharide type with a certain linkage pattern, so that correlated data measured by NMR spectroscopy can be used to identify the chemical nature of a carbohydrate. We present here an efficient search algorithm, GlycoNMRSearch, which matches either a subset or the entire set of chemical shifts of an unidentified monosaccharide spin system to all spin systems in an NMR database. The search output is much more precise than earlier search functions and highly similar matches suggest the chemical structure of the spin system within the oligosaccharide. Thus, searching for connected chemical shift correlations within all electronically available NMR data of oligosaccharides is a very efficient way of identifying the chemical structure of unknown oligosaccharides. With an improved database in the future, GlycoNMRSearch will be even more efficient deducing chemical structures of oligosaccharides and there is a high chance that it becomes an indispensable technique for glycomics. The search algorithm presented here, together with a graphical user interface, is available at http://glyconmrsearch.nmrhub.eu. Supplementary data are available at Bioinformatics online.

Does a flexible exchange rate regime increase inflation persistence?

A dynamic panel model with country and regime-specific smooth shifts in mean is applied to examine the impacts of exchange rate regimes on inflation persistence. We provide robust support for higher inflation persistence under floating rates than under pegged rates. However, the impacts of the exchange rate regime on relative inflation persistence is ambiguous. The neutrality of exchange rate regimes to inflation persistence tends to be observed if smooth shifts in mean are not controlled. Failure to control for contemporaneous correlation of disturbances and smooth shifts in mean overestimates inflation persistence.

Wavelength-scanning coherent OTDR for dynamic high strain resolution sensing.

Distributed vibration sensing in optical fibers opened entirely new opportunities and penetrated various sectors from security to seismic monitoring. Here, we demonstrate a most simple and robust approach for dynamic strain measurement using wavelength-scanning coherent optical time domain reflectometry (C-OTDR). Our method is based on laser current modulation and Rayleigh backscatter shift correlation. As opposed to common single-wavelength phase demodulation techniques, also the algebraic sign of the strain change is retrieved. This is crucial for the intended applications in structural health monitoring and modal analysis. A linear strain response down to 47.5 pε and strain noise of 100 pε/√Hz is demonstrated for repetition rates in the kHz range. A field application of a vibrating bridge is presented. Our approach provides a cost-effective high-resolution method for structural vibration analysis and geophysical applications.

Symptom reliability: S‐parameters evaluation of power laterally diffused‐metal–oxide–semiconductor field‐effect transistor after pulsed‐RF life tests for a radar application

This paper treats the s -parameter performance degradation by hot electron induced for N-MOSFET devices used in radar applications. This study is relevant for devices operating in the RF frequency regime. The power LD-MOSFET device (0.8 µm channel length, Gate oxide thickness 0.065 µm and 2.2 GHz) are designed and fabricated. Subsequently, life tests in pulsed RF cause, after ageing, the electrical behaviour and its relation with charge trapping at the interface are presented and discussed. Unlike all other current methods, a complete evaluation of S parameters is carried out to obtain key information concerning the defects location. The s -parameter performance degradation can be explained by the transconductance and the miller capacitance move, and by the leakage current augmentation IG, which is shown by hot-carrier event from the Si/SiO 2 interface state generation and/or in a build up of negative charge. Also, the degradation can be predicted by the experimental correlation of RF and dc performance shifts, favour by the measurement of dc performance or initial leakage current. The analysis accompanied proves that the s -parameters shift by hot electron induced and should be taken into consideration in the design. Through physical processes of ATLAS-SILVACO simulations these degradation phenomena are located and confirmed

The STAGGER-grid: A grid of 3D stellar atmosphere models

Context. The surface structures and dynamics of cool stars are characterised by the presence of convective motions and turbulent flows which shape the emergent spectrum. Aims. We used realistic three-dimensional (3D) radiative hydrodynamical simulations from the STAGGER-grid to calculate synthetic spectra with the radiative transfer code OPTIM3D for stars with different stellar parameters to predict photometric colours and convective velocity shifts. Methods. We calculated spectra from 1000 to 200 000 Å with a constant resolving power of λ∕Δλ = 20 000 and from 8470 and 8710 Å (Gaia Radial Velocity Spectrometer – RVS – spectral range) with a constant resolving power of λ∕Δλ = 300 000. Results. We used synthetic spectra to compute theoretical colours in the Johnson-Cousins UBV (RI)C, SDSS, 2MASS, Gaia, SkyMapper, Strömgren systems, and HST-WFC3. Our synthetic magnitudes are compared with those obtained using 1D hydrostatic models. We showed that 1D versus 3D differences are limited to a small percent except for the narrow filters that span the optical and UV region of the spectrum. In addition, we derived the effect of the convective velocity fields on selected Fe I lines. We found the overall convective shift for 3D simulations with respect to the reference 1D hydrostatic models, revealing line shifts of between −0.235 and +0.361 km s−1. We showed a net correlation of the convective shifts with the effective temperature: lower effective temperatures denote redshifts and higher effective temperatures denote blueshifts. We conclude that the extraction of accurate radial velocities from RVS spectra need an appropriate wavelength correction from convection shifts. Conclusions. The use of realistic 3D hydrodynamical stellar atmosphere simulations has a small but significant impact on the predicted photometry compared with classical 1D hydrostatic models for late-type stars. We make all the spectra publicly available for the community through the POLLUX database.

Correlation of Device Performance and Fermi Level Shift in the Emitting Layer of Organic Light-Emitting Diodes with Amine-Based Electron Injection Layers.

We investigate three amine-based polymers, polyethylenimine and two amino-functionalized polyfluorenes, as electron injection layers (EILs) in organic light-emitting diodes (OLEDs) and find correlations between the molecular structure of the polymers, the electronic alignment at the emitter/EIL interface, and the resulting device performance. X-ray photoelectron spectroscopy measurements of the emitter/EIL interface indicate that all three EIL polymers induce an upward shift of the Fermi level in the emitting layer close to the interface similar to n-type doping. The absolute value of this Fermi level shift, which can be explained by an electron transfer from the EIL polymers into the emitting layer, correlates with the number of nitrogen-containing groups in the side chains of the polymers. Whereas polyethylenimine (PEI) and one of the investigated polyfluorenes (PFCON-C) have six such groups per monomer unit, the second investigated polyfluorene (PFN) only possesses two. Consequently, we measure Fermi level shifts of 0.5-0.7 eV for PEI and PFCON-C and only 0.2 eV for PFN. As a result of these Fermi level shifts, the energetic barrier for electron injection is significantly lowered and OLEDs which comprise PEI or PFCON-C as an EIL exhibit a more than twofold higher luminous efficacy than OLEDs with PFN.

Pushing the Boundaries of Interfacial Sensitivity in Graphene FET Sensors: Polyelectrolyte Multilayers Strongly Increase the Debye Screening Length

Nanomaterial-based FET sensors represent an attractive platform for ultrasensitive, real-time, and label-free detection of chemical and biological species. Nevertheless, because their response is screened by mobile ions, it remains a challenge to use them to sense in physiological ionic strength solutions. In this work, it is demonstrated, both experimentally and theoretically, that polyelectrolyte multilayers are capable of increasing the sensing range of graphene-based FETs. Potential shifts at graphene surfaces and film thickness are recorded upon the construction of PDADMAC/PSS polyelectrolyte multilayer (PEM) films. By correlation of the potential shift with the film thickness, the electrostatic screening length and the concentration of mobile ion inside the films have been deduced. Across the polymer interface the Debye length is increased more than 1 order of magnitude. The fundamentals of this strategy are described by a conceptually simple thermodynamic model, which accounts for the entropy loss ...

Real-time homonuclear broadband decoupled pure shift COSY.

The present manuscript reports development and applications of real-time homonuclear broadband decoupled pure shift version of in-phase zero-quantum filtered COSY (PS-IPZF-COSY) and clean in-phase COSY (PS-CLIP-COSY) pulse schemes. In contrast to the conventional COSY schemes, these pure shift versions provide enhanced spectral resolution and simplify the chemical shift correlation analysis of scalar coupled spins in complex organic molecules, which are exemplified for erythromycin A, estradiol, and a mixture of estradiol and testosterone.

Coordinated Network Changes Across the Catalytic Cycle of Alpha Tryptophan Synthase

Networks of noncovalent interactions play important roles in the structural dynamics of globular proteins. Allosteric signals can propagate from the surface of an enzyme into its active site through these amino acid interaction networks. We used nuclear magnetic resonance chemical shift covariance analyses on a catalytically inactive variant of the alpha subunit of tryptophan synthase to map its amino acid interaction networks across its entire catalytic cycle. Each enzyme intermediate has unique sets of residues that display high chemical shift correlations across a set of alanine-to-glycine loop substitutions. Moreover, these chemical shift correlations systematically increase or decrease as a function of the catalytic cycle. These studies indicate that the enzyme intermediates have different amino acid interaction networks, and these network transitions are likely important for catalytic cycle progression. The different network interactions likely help to position catalytic machinery and coordinate function with the beta subunit.

Spin-echo based diagonal peak suppression in solid-state MAS NMR homonuclear chemical shift correlation spectra

The feasibility of using the spin-echo based diagonal peak suppression method in solid-state MAS NMR homonuclear chemical shift correlation experiments is demonstrated. A complete phase cycling is designed in such a way that in the indirect dimension only the spin diffused signals are evolved, while all signals not involved in polarization transfer are refocused for cancellation. A data processing procedure is further introduced to reconstruct this acquired spectrum into a conventional two-dimensional homonuclear chemical shift correlation spectrum. A uniformly 13C, 15N labeled Fmoc-valine sample and the transmembrane domain of a human protein, LR11 (sorLA), in native Escherichia coli membranes have been used to illustrate the capability of the proposed method in comparison with standard 13C–13C chemical shift correlation experiments.