Triangulating Dopant-Level Mn(II) Insertion in a Cs2NaBiCl6 Double Perovskite Using Magnetic Resonance Spectroscopy.

Lead-free metal halide double perovskites are gaining increasing attention for optoelectronic applications. Specifically, doping metal halide double perovskites using transition metals enables broadband tailorability of the optical bandgap for these emerging semiconducting materials. One candidate material is Mn(II)-doped Cs2NaBiCl6, but the nature of Mn(II) insertion on chemical structure is poorly understood due to low Mn loading. It is critical to determine the atomic-level structure at the site of Mn(II) incorporation in doped perovskites to better understand the structure-property relationships in these materials and thus to advance their applicability to optoelectronic applications. Magnetic resonance spectroscopy is uniquely qualified to address this, and thus a comprehensive three-pronged strategy, involving solid-state nuclear magnetic resonance (NMR), high-field dynamic nuclear polarization (DNP), and electron paramagnetic resonance (EPR) spectroscopies, is used to identify the location of Mn(II) insertion in Cs2NaBiCl6. Multinuclear (23Na, 35Cl, 133Cs, and 209Bi) one-dimensional (1D) magnetic resonance spectra reveal a low level of Mn(II) incorporation, with select spins affected by paramagnetic relaxation enhancement (PRE) induced by Mn(II) neighbors. EPR measurements confirm the oxidation state, octahedral symmetry, and low doping levels of the Mn(II) centers. Complementary EPR and NMR measurements confirm that the cubic structure is maintained with Mn(II) incorporation at room temperature, but the structure deviates slightly from cubic symmetry at low temperatures (<30 K). HYperfine Sublevel CORrelation (HYSCORE) EPR spectroscopy explores the electron-nuclear correlations of Mn(II) with 23Na, 133Cs, and 35Cl. The absence of 209Bi correlations suggests that Bi centers are replaced by Mn(II). Endogenous DNP NMR measurements from Mn(II) → 133Cs (<30 K) reveal that the solid effect is the dominant mechanism for DNP transfer and supports that Mn(II) is homogeneously distributed within the double-perovskite structure.

A unified description for polarization-transfer mechanisms in magnetic resonance in static solids: Cross polarization and DNP.

Polarization transfers are crucial building blocks in magnetic resonance experiments, i.e., they can be used to polarize insensitive nuclei and correlate nuclear spins in multidimensional nuclear magnetic resonance (NMR) spectroscopy. The polarization can be transferred either across different nuclear spin species or from electron spins to the relatively low-polarized nuclear spins. The former route occurring in solid-state NMR can be performed via cross polarization (CP), while the latter route is known as dynamic nuclear polarization (DNP). Despite having different operating conditions, we opinionate that both mechanisms are theoretically similar processes in ideal conditions, i.e., the electron is merely another spin-1/2 particle with a much higher gyromagnetic ratio. Here, we show that the CP and DNP processes can be described using a unified theory based on average Hamiltonian theory combined with fictitious operators. The intuitive and unified approach has allowed new insights into the cross-effect DNP mechanism, leading to better design of DNP polarizing agents and extending the applications beyond just hyperpolarization. We explore the possibility of exploiting theoretically predicted DNP transients for electron-nucleus distance measurements-such as routine dipolar-recoupling experiments in solid-state NMR.

Clustering and optimising regional segregated resource allocation networks.

Policymakers and officials worldwide are making more stringent environmental norms and waste disposal policies to encourage industries to move towards cleaner production. One of the main challenges that industries face moving towards cleaner production is the adoption of different strategies for optimising their resource utilisation and waste reduction economically. This is particularly challenging for large-scale industries or a group of industrial plants located in an industrial region. This paper presents a novel approach to economic resource optimisation focussed mainly on large-scale industries, different industrial plants located in the vicinity of each other, or an industrial symbiosis network. In this work, a clustering algorithm is developed to segregate the given plants into different clusters based on the concept of load deficits and surpluses of each plant. The concept ideally allows only the plants with surpluses to send out their unused sources and plants with deficits to only receive external sources/resources. The clusters are formed based on the distances between plants, which in turn helps in saving transportation and communication costs. The clustered plants are then easy to optimise and manage for resource and cost optimality. The applicability of the proposed clustering algorithm is demonstrated using two case studies from the domain of water recycling networks containing multiple contaminants with detailed network design, highlighting the importance of clustering in an industrial symbiosis network. It is observed that directing the excess flows from one plant to other plants in the same cluster can save a considerable amount of fresh resources. It implies that in the broader aspect, the developed methodology can address the optimisation of economic resources and can aid in the better management of overall resources for a large-scale industrial symbiosis network.

P-Site Structural Diversity and Evolution in a Zeosil Catalyst.

Phosphorus-modified siliceous zeolites, or P-zeosils, catalyze the selective dehydration of biomass derivatives to platform chemicals such as p-xylene and 1,3-butadiene. Water generated during these reactions is a critical factor in catalytic activity, but the effects of hydrolysis on the structure, acidity, and distribution of the active sites are largely unknown. In this study, the P-sites in an all-silica self-pillared pentasil (P-SPP) with a low P-loading (Si/P = 27) were identified by solid-state 31P NMR using frequency-selective detection. This technique resolves overlapping signals for P-sites that are covalently bound to the solid phase, as well as oligomers confined in the zeolite but not attached to the zeolite. Dynamic Nuclear Polarization provides the sensitivity necessary to conduct 29Si-filtered 31P detection and 31P-31P correlation experiments. The aforementioned techniques allow us to distinguish sites with P-O-Si linkages from those with P-O-P linkages. The spectra reveal a previously unappreciated diversity of P-sites, including evidence for surface-bound oligomers. In the dry P-zeosil, essentially all P-sites are anchored to the solid phase, including mononuclear sites and dinuclear sites containing the [Si-O-P-O-P-O-Si] motif. The fully-condensed sites evolve rapidly when exposed to humidity, even at room temperature. Partially hydrolyzed species have a wide range of acidities, inferred from their calculated LUMO energies. Initial cleavage of some P-O-Si linkages results in an evolving mixture of surface-bound mono- and oligonuclear P-sites with increased acidity. Subsequent P-O-P cleavage leads to a decrease in acidity as the P-sites are eventually converted to H3PO4. The ability to identify acidic sites in P-zeosils and to describe their structure and stability will play an important role in controlling the activity of microporous catalysts by regulating their water content.

Surface chemical heterogeneity modulates silica surface hydration.

An in-depth knowledge of the interaction of water with amorphous silica is critical to fundamental studies of interfacial hydration water, as well as to industrial processes such as catalysis, nanofabrication, and chromatography. Silica has a tunable surface comprising hydrophilic silanol groups and moderately hydrophobic siloxane groups that can be interchanged through thermal and chemical treatments. Despite extensive studies of silica surfaces, the influence of surface hydrophilicity and chemical topology on the molecular properties of interfacial water is not well understood. In this work, we controllably altered the surface silanol density, and measured surface water diffusivity using Overhauser dynamic nuclear polarization (ODNP) and complementary silica-silica interaction forces across water using a surface forces apparatus (SFA). The results show that increased silanol density generally leads to slower water diffusivity and stronger silica-silica repulsion at short aqueous separations (less than ∼4 nm). Both techniques show sharp changes in hydration properties at intermediate silanol densities (2.0-2.9 nm-2). Molecular dynamics simulations of model silica-water interfaces corroborate the increase in water diffusivity with silanol density, and furthermore show that even on a smooth and crystalline surface at a fixed silanol density, adjusting the spatial distribution of silanols results in a range of surface water diffusivities spanning ∼10%. We speculate that a critical silanol cluster size or connectivity parameter could explain the sharp transition in our results, and can modulate wettability, colloidal interactions, and surface reactions, and thus is a phenomenon worth further investigation on silica and chemically heterogeneous surfaces.

Phosphonate-Modified UiO-66 Brønsted Acid Catalyst and Its Use in Dehydra-Decyclization of 2-Methyltetrahydrofuran to Pentadienes.

Phosphorus-modified all-silica zeolites exhibit activity and selectivity in certain Brønsted acid catalyzed reactions for biomass conversion. In an effort to achieve similar performance with catalysts having well-defined sites, we report the incorporation of Brønsted acidity to metal-organic frameworks with the UiO-66 topology, achieved by attaching phosphonic acid to the 1,4-benzenedicarboxylate ligand and using it to form UiO-66-PO3 H2 by post-synthesis modification. Characterization reveals that UiO-66-PO3 H2 retains stability similar to UiO-66, and exhibits weak Brønsted acidity, as demonstrated by titrations, alcohol dehydration, and dehydra-decyclization of 2-methyltetrahydrofuran (2-MTHF). For the later reaction, the reported catalyst exhibits site-time yields and selectivity approaching that of phosphoric acid on all-silica zeolites. Using solid-state NMR and deprotonation energy calculations, the chemical environments of P and the corresponding acidities are determined.

Computationally efficient approach for identification of fuzzy dynamic groundwater sampling network.

In the present work, uncertainty-based dynamic sampling frameworks were tested for a sampling horizon with multiple time steps. Future concentration values were assumed as fuzzy numbers. Multiple realization-based simulations were used for generation of fuzzy numbers. The first framework considers fuzzy variance reduction. The second framework considers mass estimation error reduction with maximization of spatial coverage of the dynamic sampling network. It is a multi-objective optimization problem with a large number of objectives. In Dhar and Patil (2012), uncertainty-based optimal sampling design model was suggested using Nondominated Sorting Genetic Algorithm-II (NSGA-II) as its optimization algorithm. However, NSGA-II becomes computationally expensive while handling more than three objectives. We extend the previously suggested algorithm for multi-objective sampling network design problems based on NSGA-III framework. Two design frameworks were proposed: one incorporating a simulation model and a fuzzy covariance for minimizing the total contaminant-concentration variance and the other incorporating a simulation model and a fuzzy kriging model in conjunction with an optimization model to minimize the fuzzy mass estimation error and spatial coverage of spatiotemporal sampling locations. NSGA-III was used for solving the sampling network design model. Performances of the proposed frameworks were evaluated for two hypothetical illustrative examples. The results indicate that the proposed design frameworks perform satisfactorily under uncertain system conditions.

Maximizing NMR signal per unit time by facilitating the e-e-n cross effect DNP rate.

The dynamic nuclear polarization (DNP) efficiency is critically dependent on the properties of the radical, solvent, and solute constituting the sample system. In this study, we focused on the three spin e-e-n cross effect (CE)'s influence on the nuclear longitudinal relaxation time constant T1n, the build-up time constants of nuclear magnetic resonance (NMR) signal, TDNP and DNP-enhancement of NMR signal. The dipolar interaction strength between the electron spins driving the e-e-n process was systematically modulated using mono-, di-, tri-, and dendritic-nitroxide radicals, while maintaining a constant global electron spin concentration of 10 mM. Experimental results showed that an increase in electron spin clustering led to an increased electron spin depolarization, as mapped by electron double resonance (ELDOR), and a dramatically shortened T1n and TDNP time constants under static and magic angle spinning (MAS) conditions. A theoretical analysis reveals that strong e-e interactions, caused by electron spin clustering, increase the CE rate. The three spin e-e-n CE is a hitherto little recognized mechanism for shortening T1n and TDNP in solid-state NMR experiments at cryogenic temperatures, and offers a design principle to enhance the effective CE DNP enhancement per unit time. Fast CE rates will benefit DNP at liquid helium temperatures, or at higher magnetic fields and pulsed DNP, where slow e-e-n polarization transfer rate is a key bottleneck to achieving maximal DNP performance.

Off-resonance NOVEL.

Dynamic nuclear polarization (DNP) is theoretically able to enhance the signal in nuclear magnetic resonance (NMR) experiments by a factor γe/γn, where γ's are the gyromagnetic ratios of an electron and a nuclear spin. However, DNP enhancements currently achieved in high-field, high-resolution biomolecular magic-angle spinning NMR are well below this limit because the continuous-wave DNP mechanisms employed in these experiments scale as ω0-n where n ∼ 1-2. In pulsed DNP methods, such as nuclear orientation via electron spin-locking (NOVEL), the DNP efficiency is independent of the strength of the main magnetic field. Hence, these methods represent a viable alternative approach for enhancing nuclear signals. At 0.35 T, the NOVEL scheme was demonstrated to be efficient in samples doped with stable radicals, generating 1H NMR enhancements of ∼430. However, an impediment in the implementation of NOVEL at high fields is the requirement of sufficient microwave power to fulfill the on-resonance matching condition, ω0I = ω1S, where ω0I and ω1S are the nuclear Larmor and electron Rabi frequencies, respectively. Here, we exploit a generalized matching condition, which states that the effective Rabi frequency, ω1Seff, matches ω0I. By using this generalized off-resonance matching condition, we generate 1H NMR signal enhancement factors of 266 (∼70% of the on-resonance NOVEL enhancement) with ω1S/2π = 5 MHz. We investigate experimentally the conditions for optimal transfer of polarization from electrons to 1H both for the NOVEL mechanism and the solid-effect mechanism and provide a unified theoretical description for these two historically distinct forms of DNP.

Designing dipolar recoupling and decoupling experiments for biological solid-state NMR using interleaved continuous wave and RF pulse irradiation.

Rapid developments in solid-state NMR methodology have boosted this technique into a highly versatile tool for structural biology. The invention of increasingly advanced rf pulse sequences that take advantage of better hardware and sample preparation have played an important part in these advances. In the development of these new pulse sequences, researchers have taken advantage of analytical tools, such as average Hamiltonian theory or lately numerical methods based on optimal control theory. In this Account, we focus on the interplay between these strategies in the systematic development of simple pulse sequences that combines continuous wave (CW) irradiation with short pulses to obtain improved rf pulse, recoupling, sampling, and decoupling performance. Our initial work on this problem focused on the challenges associated with the increasing use of fully or partly deuterated proteins to obtain high-resolution, liquid-state-like solid-state NMR spectra. Here we exploit the overwhelming presence of (2)H in such samples as a source of polarization and to gain structural information. The (2)H nuclei possess dominant quadrupolar couplings which complicate even the simplest operations, such as rf pulses and polarization transfer to surrounding nuclei. Using optimal control and easy analytical adaptations, we demonstrate that a series of rotor synchronized short pulses may form the basis for essentially ideal rf pulse performance. Using similar approaches, we design (2)H to (13)C polarization transfer experiments that increase the efficiency by one order of magnitude over standard cross polarization experiments. We demonstrate how we can translate advanced optimal control waveforms into simple interleaved CW and rf pulse methods that form a new cross polarization experiment. This experiment significantly improves (1)H-(15)N and (15)N-(13)C transfers, which are key elements in the vast majority of biological solid-state NMR experiments. In addition, we demonstrate how interleaved sampling of spectra exploiting polarization from (1)H and (2)H nuclei can substantially enhance the sensitivity of such experiments. Finally, we present systematic development of (1)H decoupling methods where CW irradiation of moderate amplitude is interleaved with strong rotor-synchronized refocusing pulses. We show that these sequences remove residual cross terms between dipolar coupling and chemical shielding anisotropy more effectively and improve the spectral resolution over that observed in current state-of-the-art methods.

Low-power polarization transfer between deuterons and spin-1/2 nuclei using adiabatic (RESPIRATION)CP in solid-state NMR.

Establishing high-resolution structures of biological macromolecules in heterogeneous environments by MAS solid-state NMR is an important challenge where development of advanced experimental procedures is in high demand. Promising new methods take advantage of samples with extensive (2)H, (13)C, and (15)N isotope labelling, effectively diluting (1)H spins. In many cases, a sufficient amount of (1)H at exchangeable sites cannot be re-established during the purification procedure, hence it is necessary to exploit also the potential of (2)H as a starting point in pulse sequences, capitalizing on its short T1 as compared to (13)C, and to detect carbon or proton spins as appropriate. Here we present a new method that enables the required high-efficiency (2)H to (13)C or (15)N polarization transfer to be accomplished under the limited (2)H rf power conditions using current (1)H, (2)H, (13)C and (15)N quadruple-resonance MAS NMR instrumentation.

Embedding plasmonic nanoparticles in soft crystals: an approach exploiting CTAB-I structures.

Embedding nanoparticles with different functionalities into soft substrates is a convenient tool to realize technologically significant multifunctional materials. This study focuses on incorporating bimetallic plasmonic nanoparticles into soft crystals made of cetyltrimethylammonium bromide-iodide. We observed the emergence of a novel symmetry-lowered cetrimonium crystal polymorph that enables the realization of strong interparticle plasmonic coupling in these composite materials. The observed crystal polymorph exhibits a triclinic structure with significantly reduced unit cell volume compared to standard CTAB. Solid-state nuclear magnetic resonance studies revealed an enhanced cetrimonium chain rigidity and a commensurate decrease in the mobility of the methyl groups. This is attributed to iodide incorporation. To study the influence of these interactions on solution phase dynamical properties, we employed light scattering measurements using gold nanospheres as markers, where we observed aggregation of these particles. We then develop a two step synthetic scheme that successfully enables high levels (533 particles per µm2) of incorporation of bimetallic plasmonic particles into the emergent crystal polymorph.

Dynamic Nuclear Polarization Enhanced Multiple-Quantum Spin Counting of Molecular Assemblies in Vitrified Solutions.

Crystallization pathways are essential to various industrial, geological, and biological processes. In nonclassical nucleation theory, prenucleation clusters (PNCs) form, aggregate, and crystallize to produce higher order assemblies. Microscopy and X-ray techniques have limited utility for PNC analysis due to the small size (0.5-3 nm) and time stability constraints. We present a new approach for analyzing PNC formation based on 31P nuclear magnetic resonance (NMR) spin counting of vitrified molecular assemblies. The use of glassing agents ensures that vitrification generates amorphous aqueous samples and offers conditions for performing dynamic nuclear polarization (DNP)-amplified NMR spectroscopy. We demonstrate that molecular adenosine triphosphate along with crystalline, amorphous, and clustered calcium phosphate materials formed via a nonclassical growth pathway can be differentiated from one another by the number of dipolar coupled 31P spins. We also present an innovative approach for examining spin counting data, demonstrating that a knowledge-based fitting of integer multiples of cosine wave functions, instead of the traditional Fourier transform, provides a more physically meaningful retrieval of the existing frequencies. This is the first report of multiquantum spin counting of assemblies formed in solution as captured under vitrified DNP conditions, which can be useful for future analysis of PNCs and other aqueous molecular clusters.

Design of a cryogen-free high field dual EPR and DNP probe.

We present the design and construction of a cryogen free, dual electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) probe for novel dynamic nuclear polarization (DNP) experiments and concurrent "in situ" analysis of DNP mechanisms. We focus on the probe design that meets the balance between EPR, NMR, and low temperature performance, while maintaining a high degree of versatility: allowing multi-nuclear NMR detection as well as broadband DNP/EPR excitation/detection. To accomplish high NMR/EPR performance, we implement a novel inductively coupled double resonance NMR circuit (1H-13C) in a solid state probe operating at cryogenic temperatures. The components of the circuit were custom built to provide maximum NMR performance, and the physical layout of this circuit was numerically optimized via magnetic field simulations to allow maximum microwave transmission to the sample for optimal EPR performance. Furthermore this probe is based around a cryogen free gas exchange cryostat and has been designed to allow unlimited experiment times down to 8.5 Kelvin with minimal cost. The affordability of EPR/DNP experiment is an extremely important aspect for broader impact with magnetic resonance measurements. The purpose of this article is to provide as complete information as we have available for others with interest in building a dual DNP/EPR instrument based around a cryogen-free cryostat.

In vitro conservation of twenty-three overexploited medicinal plants belonging to the Indian sub continent.

Twenty-three pharmaceutically important plants, namely, Elaeocarpus spharicus, Rheum emodi, Indigofera tinctoria, Picrorrhiza kurroa, Bergenia ciliata, Lavandula officinalis, Valeriana wallichii, Coleus forskohlii, Gentiana kurroo, Saussurea lappa, Stevia rebaudiana, Acorus calamus, Pyrethrum cinerariaefolium, Aloe vera, Bacopa monnieri, Salvia sclarea, Glycyrrhiza glabra, Swertia cordata, Psoralea corylifolia, Jurinea mollis, Ocimum sanctum, Paris polyphylla, and Papaver somniferum, which are at the verge of being endangered due to their overexploitation and collection from the wild, were successfully established in vitro. Collections were made from the different biodiversity zones of India including Western Himalaya, Northeast Himalaya, Gangetic plain, Western Ghats, Semiarid Zone, and Central Highlands. Aseptic cultures were raised at the morphogenic level of callus, suspension, axillary shoot, multiple shoot, and rooted plants. Synseeds were also produced from highly proliferating shoot cultures of Bacopa monnieri, Glycyrrhiza glabra, Stevia rebaudiana, Valeriana wallichii, Gentiana kurroo, Lavandula officinalis, and Papaver somniferum. In vitro flowering was observed in Papaver somniferum, Psoralea corylifolia, and Ocimum sanctum shoots cultures. Out of 23 plants, 18 plants were successfully hardened under glasshouse conditions.

Role of electron spin dynamics and coupling network in designing dynamic nuclear polarization.

Dynamic nuclear polarization (DNP) has emerged as a powerful sensitivity booster of nuclear magnetic resonance (NMR) spectroscopy for the characterization of biological solids, catalysts and other functional materials, but is yet to reach its full potential. DNP transfers the high polarization of electron spins to nuclear spins using microwave irradiation as a perturbation. A major focus in DNP research is to improve its efficiency at conditions germane to solid-state NMR, at high magnetic fields and fast magic-angle spinning. In this review, we highlight three key strategies towards designing DNP experiments: time-domain "smart" microwave manipulation to optimize and/or modulate electron spin polarization, EPR detection under operational DNP conditions to decipher the underlying electron spin dynamics, and quantum mechanical simulations of coupled electron spins to gain microscopic insights into the DNP mechanism. These strategies are aimed at understanding and modeling the properties of the electron spin dynamics and coupling network. The outcome of these strategies is expected to be key to developing next-generation polarizing agents and DNP methods.

Cloud Services for Patient Cohort Identification Using the Informatics for Integrating Biology and the Bedside Platform.

Despite the widespread use of the "Informatics for Integrating Biology and the Bedside" (i2b2) platform, there are substantial challenges for loading electronic health records (EHR) into i2b2 and for querying i2b2. We have previously presented a simplified framework for semantic abstraction of EHR records into i2b2. Building on our previous work, we have created a proof-of-concept implementation of cloud services on an i2b2 data store for cohort identification. Specifically, we have implemented a graphical user interface (GUI) that declares the key components for data import, transformation, and query of EHR data. The GUI integrates with Azure cloud services to create data pipelines for importing EHR data into i2b2, creation of derived facts, and querying for generating Sankey-like flow diagrams that characterize the patient cohorts. We have evaluated the implementation using the real-world MIMIC-III dataset. We discuss the key features of this implementation and direction for future work, which will advance the efforts of the research community for patient cohort identification.

Cross-Effect Dynamic Nuclear Polarization Explained: Polarization, Depolarization, and Oversaturation.

The scope of this Perspective is to analytically describe NMR hyperpolarization by the three-spin cross effect (CE) dynamic nuclear polarization (DNP) using an effective Hamiltonian concept. We apply, for the first time, the bimodal operator-based Floquet theory in the Zeeman-interaction frame for two and three coupled spins to derive the known interaction Hamiltonian for CE-DNP. With a unified understanding of CE-DNP, and supported by empirical observation of the state of electron spin polarization under the given experimental conditions, we explain diverse manifestations of CE from oversaturation, enhanced hyperpolarization by broad-band saturation, to nuclear spin depolarization under magic-angle spinning.

Design and experimental investigations on six-stroke SI engine using acetylene with water injection.

In the present study, a four-stroke cycle gasoline engine is redesigned and converted into a six-stroke cycle engine and experimental study has been conducted using gasoline and acetylene as fuel with water injection at the end of the recompression stroke. Acetylene has been used as an alternative fuel along with gasoline and performance of the six-stroke spark ignition (SI) engine with these two fuels has been studied separately and compared. Brake power and thermal efficiency are found to be 5.18 and 1.55% higher with acetylene as compared to gasoline in the six-stroke engine. However, thermal efficiency is found to be 45% higher with acetylene in the six-stroke engine as compared to four-stroke SI engine. The CO and HC emissions were found to be reduced by 13.33 and 0.67% respectively with acetylene as compared to gasoline due to better combustion of acetylene. The NOx emission was reduced by 5.65% with acetylene due to lower peak temperature by water injection. The experimental results showed better engine performance and emissions with acetylene as fuel in the six-stroke engine.

Proton-Assisted Recoupling (PAR) in Peptides and Proteins.

Proton-assisted recoupling (PAR) is examined by exploring optimal experimental conditions and magnetization transfer rates in a variety of biologically relevant nuclear spin-systems, including simple amino acids, model peptides, and two proteins-nanocrystalline protein G (GB1), and importantly amyloid beta 1-42 (M0Aß1-42) fibrils. A selective PAR protocol, SUBPAR (setting up better proton assisted recoupling), is described to observe magnetization transfer in one-dimensional spectra, which minimizes experiment time (in comparison to two-dimensional experiments) and thereby enables an efficient assessment of optimal PAR conditions for a desired magnetization transfer. In the case of the peptide spin systems, experimental and simulated PAR data sets are compared on a semiquantitative level, thereby elucidating the interactions influencing PAR magnetization transfer and their manifestations in different spin transfer networks. Using the optimum Rabi frequencies determined by SUBPAR, PAR magnetization transfer trajectories (or buildup curves) were recorded and compared to simulated results for short peptides. PAR buildup curves were also recorded for M0Aß1-42 and examined conjointly with a recent structural model. The majority of salient cross-peak intensities observed in the M0Aß1-42 PAR spectra are well-modeled with a simple biexponential equation, although the fitting parameters do not show any strong correlation to internuclear distances. Nevertheless, these parameters provide a wealth of invaluable semiquantitative structural constraints for the M0Aß1-42. The results presented here offer a complete protocol for recording PAR 13C-13C correlation spectra with high-efficiency and using the resulting information in protein structural studies.