1D Spectroscopy Research Articles

Fourier and Laplace-like low-field NMR spectroscopy: The perspectives of multivariate and artificial neural networks analyses

Low field Nuclear Magnetic Resonance (LF-NMR) is a rich source of information for a wide range of samples types. These can be hard or soft solids, such as plastics or elastomers; bulk liquids or liquids absorbed in porous materials, and can come from biomaterials, biological tissues, archaeological artifacts, cultural heritage objects. LF-NMR instruments present a significant advance especially for in situ, ex situ and in vivo measurement of relaxation and diffusion. Moreover, high resolution 1D and 2D spectroscopy, as well as magnetic resonance (MR) imaging are available in these fields. In this work we discuss the advanced analysis of the data measured in LF-NMR from the perspectives of tertiary level that implies the analysis on principal components (PCA), and on the quaternary analysis that uses an artificial neural network (ANN). The principles of PCA and ANN are largely discussed. For the PCA analysis, a series of 52 spectra were analyzed, having been recorded in vivo by LF-NMR. Of these spectra, 38 were generated from normal uterus, 7 by uterus tissue with endometrial cancer, and another 7 were obtained from tissues of women with uterine cervical cancer. The PC1 vs PC2 plot was further analyzed using an artificial neural network, and the results are presented as 2D maps of probability. Furthermore, the perspectives of applying an ANN to solve the problem of Laplace-like inversion are discussed. An example of such ANN was presented and the performance was discussed. Finally, a model of complex ANN, capable to sequentially solve this kind of problems specific to LF-NMR is proposed and discussed.

Spectroscopic Investigation of Increased Fluorescent Intensity of Fluorescent Dyes When Adsorbed onto Polystyrene Microparticles.

Microplastics as environmental pollutants are increasingly a source of alarm. The characterization of microplastics will be necessary to discriminate microplastics from other types of particles. To discriminate specific microplastics, plastic-adsorbable fluorescent dyes are used, the stained microplastics are separated from the dye-microplastic mixture by filtration, and the type of fluorescent staining of the microplastics is analyzed by fluorescent microscopy. In this study, to realize the in situ analysis of fluorescent staining, i.e., to discriminate microplastics without any separation or filtration processes, we studied the change in the fluorescent properties after adsorption of the fluorescent dyes to the microplastic particle surfaces using a 3D excitation emission matrix fluorescence spectroscopy (the excitation wavelength-dependent emission spectrum). We used three fluorescent dyes: Fluorescein, Rhodamine 6G, and Methylene Blue, and polystyrene microparticles as our model microplastic. Fluorescein and Methylene Blue showed increases in the fluorescent intensity, while Rhodamine 6G showed negligible intensity changes. This is likely due to the degree of affinity of the dyes to the polystyrene particle surface, the structural stability of the dyes on the surface, and the changes in the environment around the dyes after the adsorption of each dye to the surface. We conclude that we have demonstrated the potential to look for appropriate fluorescent dyes using the method studied here to identify and estimate individual plastic materials.

Observing Multiexciton Correlations in Colloidal Semiconductor Quantum Dots via Multiple-Quantum Two-Dimensional Fluorescence Spectroscopy.

Correlations between excitons, that is, electron-hole pairs, have a great impact on the optoelectronic properties of semiconductor quantum dots and thus are relevant for applications such as lasers and photovoltaics. Upon multiphoton excitation, these correlations lead to the formation of multiexciton states. It is challenging to observe these states spectroscopically, especially higher multiexciton states, because of their short lifetimes and nonradiative decay. Moreover, solvent contributions in experiments with coherent signal detection may complicate the analysis. Here we employ multiple-quantum two-dimensional (2D) fluorescence spectroscopy on colloidal CdSe1-xSx/ZnS alloyed core/shell quantum dots. We selectively map the electronic structure of multiexcitons and their correlations by using two- and three-quantum 2D spectroscopy, conducted in a simultaneous measurement. Our experiments reveal the characteristics of biexcitons and triexcitons such as transition dipole moments, binding energies, and correlated transition energy fluctuations. We determine the binding energies of the first six biexciton states by simulating the two-quantum 2D spectrum. By analyzing the line shape of the three-quantum 2D spectrum, we find strong correlations between biexciton and triexciton states. Our method contributes to a more comprehensive understanding of multiexcitonic species in quantum dots and other semiconductor nanostructures.

Evolution of galaxy scaling relations in clusters at 0.5 < z < 1.5

Aims. We present new gas kinematic observations with the OSIRIS instrument at the GTC for galaxies in the Cl1604 cluster system at z ∼ 0.9. These observations together with a collection of other cluster samples at different epochs analyzed by our group are used to study the evolution of the Tully-Fisher, velocity-size, and specific angular momentum-stellar mass relations in dense environments over cosmic time. Methods. We used 2D and 3D spectroscopy to analyze the kinematics of our cluster galaxies and extract their maximum rotation velocities (Vmax), which were used as the common parameter in all scaling relations under scrutiny. We determined the structural parameters of our objects by fitting surface brightness profiles to the images of our objects, while stellar-mass values were computed by fitting the spectral energy distribution by making use of extensive archival optical to near-IR photometry. Our methods were consistently applied to all our cluster samples. This makes them ideal for an evolutionary comparison. Results. Up to redshift one, our cluster samples show evolutionary trends compatible with previous observational results in the field and in accordance with semianalytical models and hydrodynamical simulations concerning the Tully-Fisher and velocity-size relations. However, we find a drop of a factor ∼3 in disk sizes and an average B-band luminosity enhancement ⟨ΔMB⟩∼2 mag by z ∼ 1.5. We discuss the role that different cluster-specific interactions may play in producing this observational result. In addition, we find that our intermediate-to-high redshift cluster galaxies follow parallel sequences with respect to the local specific angular momentum to stellar mass relation, although they display lower specific angular momentum values than field samples at similar redshifts. This may be explained by the stronger interacting nature of dense environments in comparison with the field.

Development of interface-/surface-specific two-dimensional electronic spectroscopy.

Structures, kinetics, and chemical reactivities at interfaces and surfaces are key to understanding many of the fundamental scientific problems related to chemical, material, biological, and physical systems. These steady-state and dynamical properties at interfaces and surfaces require even-order techniques with time-resolution and spectral-resolution. Here, we develop fourth-order interface-/surface-specific two-dimensional electronic spectroscopy, including both two-dimensional electronic sum frequency generation (2D-ESFG) spectroscopy and two-dimensional electronic second harmonic generation (2D-ESHG) spectroscopy, for structural and dynamics studies of interfaces and surfaces. The 2D-ESFG and 2D-ESHG techniques were based on a unique laser source of broadband short-wave IR from 1200 nm to 2200 nm from a home-built optical parametric amplifier. With the broadband short-wave IR source, surface spectra cover most of the visible light region from 480 nm to 760 nm. A translating wedge-based identical pulses encoding system (TWINs) was introduced to generate a phase-locked pulse pair for coherent excitation in the 2D-ESFG and 2D-ESHG. As an example, we demonstrated surface dark states and their interactions of the surface states at p-type GaAs (001) surfaces with the 2D-ESFG and 2D-ESHG techniques. These newly developed time-resolved and interface-/surface-specific 2D spectroscopies would bring new information for structure and dynamics at interfaces and surfaces in the fields of the environment, materials, catalysis, and biology.

Automatic Feynman diagram generation for nonlinear optical spectroscopies and application to fifth-order spectroscopy with pulse overlaps.

Perturbative nonlinear optical spectroscopies are powerful methods to understand the dynamics of excitonic and other condensed phase systems. Feynman diagrams have long provided the essential tool to understand and interpret experimental spectra and to organize the calculation of spectra for model systems. When optical pulses are strictly time ordered, only a small number of diagrams contribute, but in many experiments, pulse-overlap effects are important for interpreting results. When pulses overlap, the number of contributing diagrams can increase rapidly, especially with higher order spectroscopies, and human error is especially likely when attempting to write down all the diagrams. We present an automated Diagram Generator (DG) that generates all the Feynman diagrams needed to calculate any nth-order spectroscopic signal. We characterize all perturbative nonlinear spectroscopies by their associated phase-discrimination condition as well as the time intervals where pulse amplitudes are nonzero. Although the DG can be used to automate impulsive calculations, its greatest strength lies in automating finite pulse calculations where pulse overlaps are important. We consider third-order transient absorption spectroscopy and fifth-order exciton-exciton interaction 2D (EEI2D) spectroscopy, which are described by six or seven diagrams in the impulsive limit, respectively, but 16 or 240 diagrams, respectively, when pulses overlap. The DG allows users to automatically include all relevant diagrams at a relatively low computational cost, since the extra diagrams are only generated for the inter-pulse delays where they are relevant. For EEI2D spectroscopy, we show the important effects of including the overlap diagrams.

Confronting FCP structure with ultrafast spectroscopy data: evidence for structural variations

Diatoms are a major group of algae, responsible for a quarter of the global primary production on our planet. Their adaptation to marine environments is ensured by their light-harvesting antenna - the fucoxanthin-chlorophyll protein (FCP) complex, which absorbs strongly in the blue-green spectral region. Although these essential proteins have been the subject of many studies, for a long time their comprehensive description was not possible in the absence of structural data. Last year, the 3D structures of several FCP complexes were revealed. The structure of an FCP dimer was resolved by crystallography for the pennate diatom Phaeodactylum tricornutum [W. Wang et al., Science, 2019, 363, 6427] and the structure of the PSII supercomplex from the centric diatom Chaetoceros gracilis, containing several FCPs, was obtained by electron microscopy [X. Pi et al., Science, 2019, 365, 6452; R. Nagao et al., Nat. Plants, 2019, 5, 890]. In this Perspective article, we evaluate how precisely these structures may account for previously published ultrafast spectroscopy results, describing the excitation energy transfer in the FCP from another centric diatom Cyclotella meneghiniana. Surprisingly, we find that the published FCP structures cannot explain several observations obtained from ultrafast spectroscopy. Using the available structures, and results from electron microscopy, we construct a trimer-based FCP model for Cyclotella meneghiniana, consistent with ultrafast experimental data. As a whole, our observations suggest that the structures from the proteins belonging to the FCP family display larger variations than the equivalent LHC proteins in plants, which may reflect species-specific adaptations or original strategies for adapting to rapidly changing marine environments.

Study of the Fluorescence based Applications of Water Soluble (N, P) Doped Carbon Dots Synthesized via Microwave Assisted Green Pyrolysis

Background: Water soluble nitrogen and phosphorus doped carbon dots (CD) have been synthesized using citric acid, tris(2-aminoethyl)amine and orthophosphoric acid via one step microwave assisted pyrolytic method. Methods: The CD synthesized has been characterized using FTIR, UV-Vis, fluorescence spectroscopy and EDAX coupled with SEM techniques. Results: SEM study has shown the formation of nanosized CD with an average size of ~18 nm. Elemental analysis via EDAX has confirmed successful incorporation of nitrogen (30.8% wt) and phosphorus (5.7% wt) atoms in it. The steady state and 3D fluorescence spectroscopic studies have shown its efficient fluorescence emission with emission maxima in the region of ~450 nm. It has shown efficient “turn off” fluorescence behaviour towards transition metal ions like Fe2+ and Co2+ ions and toxic nitrophenolic compounds like p-nitrophenol and picric acid. Its efficient interaction with BSA has been revealed in terms of fluorescence quenching of BSA by steady state, synchronous and 3D fluorescence spectroscopy. It has shown very good in vitro biocompatibility and enhanced cell adhesion properties towards NIH 3T3 fibroblast cells. Moreover, fluorescence microscopy has shown significant uptake of CD by the tested cell line. Conclusion: Such bio-compatible nitrogen and phosphorous doped CD can be potentially useful to estimate metal ions, p-nitrophenol and picric acid using fluorescence spectroscopy and for fluorescence based bio-imaging.

Coarse Raman and optical diffraction tomographic imaging enable label-free phenotyping of isogenic breast cancer cells of varying metastatic potential

Identification of the metastatic potential represents one of the most important tasks for molecular imaging of cancer. While molecular imaging of metastases has witnessed substantial progress as an area of clinical inquiry, determining precisely what differentiates the metastatic phenotype has proven to be more elusive. In this study, we utilize both the morphological and molecular information provided by 3D optical diffraction tomography and Raman spectroscopy, respectively, to propose a label-free route for optical phenotyping of cancer cells at single-cell resolution. By using an isogenic panel of cell lines derived from MDA-MB-231 breast cancer cells that vary in their metastatic potential, we show that 3D refractive index tomograms can capture subtle morphological differences among the parental, circulating tumor cells, and lung metastatic cells. By leveraging its molecular specificity, we demonstrate that coarse Raman microscopy is capable of rapidly mapping a sufficient number of cells for training a random forest classifier that can accurately predict the metastatic potential of cells at a single-cell level. We also perform multivariate curve resolution alternating least squares decomposition of the spectral dataset to demarcate spectra from cytoplasm and nucleus, and test the feasibility of identifying metastatic phenotypes using the spectra only from the cytoplasmic and nuclear regions. Overall, our study provides a rationale for employing coarse Raman mapping to substantially reduce measurement time thereby enabling the acquisition of reasonably large training datasets that hold the key for label-free single-cell analysis and, consequently, for differentiation of indolent from aggressive phenotypes.

(Invited) Understanding the Corrosion of SS316L in Molten LiCl-Li2O-Li Using 3D Transmission X-Ray Microscopy and 3D XANES

Pyrochemical reprocessing (pyroprocessing) of used nuclear fuel (UNF) is a promising pathway towards closing the nuclear fuel cycle and providing the means to generate durable wasteforms for portions of the UNF that are not able to be recycled. To incorporate commercial UNF (UO2) into the pyroprocessing scheme, the ceramic UNF must be converted to a metallic form at the head end of the process, which can be accomplished via electrolytic reduction of the UNF in LiCl-Li2O molten salt electrolyte. During the electrolytic reduction of UO2 at the cathode, metallic Li is inevitably co-reduced from the electrolyte due to the proximity of the reduction potential of the U4+ in UO2 and Li+ in the electrolyte. Metallic Li disperses into the LiCl electrolyte and can then interact with the process vessel and other apparatus in contact with the electrolyte, altering the rate and mechanism of the degradation of those materials.Our group has previously shown that the presence of metallic Li in the electrolyte creates a reducing condition where the surface oxide layer of SS316 is removed, and extensive intergranular corrosion takes place. To further the understanding of the mechanism and morphology of the intergranular corrosion, transmission X-ray microscopy (TXM) at Brookhaven National Laboratory’s National Synchrotron Light Source II (NSLSII) beamline 18-ID was used to examine ~20 μm diameter focused-ion beam (FIB) milled pillars of the cross-section of SS316L exposed to LiCl-Li2O-Li with 0 wt.%, 0.3 wt.%, 0.6 wt.% and 1 wt.% Li. Computed Tomographic (CT) images were obtained at X-ray energies above and below the absorption edges of alloying elements of interest, providing insight into the distribution of alloying elements after exposure to the molten salt. 3D X-ray absorption near edge spectroscopy (XANES) tomography at the Cr K-edge was also attempted. This analysis provided additional evidence of the formation of Cr-rich intermetallic phases and 3D CT images of the void structure of the exposed samples, strengthening the evidence that the sensitization of SS316L at process temperatures and the subsequent dissolution of the Cr carbide precipitates into the electrolyte is the primary driver of the deep intergranular corrosion of SS316L in LiCl-Li2O-Li. To our knowledge, this is the first application of this FIB milling technique and TXM imaging of the FIB-milled pillars to corrosion samples and lessons learned regarding the sample preparation and analysis will be presented.Acknowledgements: The authors thank Zachary Karmiol, research scientist at Materials Characterization Nevada, for technical assistance with the FIB sample preparation. This work was performed under the auspices of the Department of Energy (DOE) under contracts DE- NE0008236, and the US Nuclear Regulatory Commission (USNRC) under contract NRC-HQ-13-G-38-0027. Dr. Kenny Osborne and Ms. Nancy Hebron-Isreal serve as the program managers for the DOE and NRC awards, respectively. This research used beamline 18-ID of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704. This work was supported as part of the Molten Salts in Extreme Environments Energy Frontier Research Center, funded by the U.S. Department of Energy (US-DOE), Office of Science, Basic Energy Sciences, at Idaho National Laboratory under contract DE-AC07-05ID14517. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship under Grant No. DGE-1447692. One of the authors, JM, acknowledges the Graduate Research Fellowship from the US National Science Foundation.

Ionized Gas in the NGC 3077 Galaxy

The nearby dwarf galaxy NGC 3077 is known for its peculiar morphology, which includes numerous dust lanes and emission-line regions. The interstellar medium in this galaxy is subject to several perturbing factors. These are primarily the central starburst and tidal structures in the M 81 group. We present a comprehensive study of the state of ionization, kinematics, and chemical composition of ionized gas in NGC 3077, including both star-forming regions and diffuse ionized gas (DIG) at the periphery. We study gas motions in the H$\alpha$ line via high-resolution ($R\approx15\,000$) 3D spectroscopy with the scanning Fabry-Perot interferometer installed into SCORPIO-2 instrument attached to the 6-m telescope of the SAO RAS. Images in the main optical emission lines were acquired with MaNGaL photometer with a tunable filter at the 2.5-m telescope of the Caucasian Mountain Observatory of SAI MSU. We also used SCORPIO-2 to perform long-slit spectroscopy of the galaxy with a resolution of $R\approx1\,000$. Our estimate of the gas metallicity, $Z=0.6Z_\odot$, is significantly lower than the earlier determination, but agrees with the "luminosity--metallicity" dependence. Spatially resolved diagnostic diagrams of the emission-line ratios do not show correlations between the gas ionization state and its velocity dispersion, and this is most likely due to strong ionization by young stars, whereas the contribution of shocks to the excitation of emission lines is less important. We also studied the locations of multicomponent H$\alpha$ profiles and provide arguments suggesting that they are mostly associated with individual kinematic components along the line of sight and not with expanding shells as it was believed earlier. We also observe there a combination of wind outflow from star-forming regions and accretion from interstellar gas clouds in the M 81 group.

Detrimental effects of sand ingression in jet engine ceramic coatings captured with Raman-based 3D rendering

The infiltration of molten calcium, magnesium, and alumino-silicates (CMAS) into jet engine thermal barrier coatings (TBCs) causes an increased stiffness and a destructive phase destabilization eventually leading to thermomechanical failure. Using 3D confocal Raman spectroscopy, the extent of thermochemical degradation was identified by mapping the monoclinic phase volume fraction (mPVF) throughout a standard EB-PVD 7YSZ TBC coating. The mPVF is characterized as a function of depth and infiltration time with microscale resolution. Results show that phase destabilization was most intense along the column's perimeter whereas the core of the column retained most of its original phase. The greatest amount of phase destabilization occurs within the first hour of the interaction after which the average minimum mPVF is 32 %. This value increases to 42 % after a ten-fold increase in interaction time. This ability to quantitatively and non-destructively characterize degradation of CMAS infiltrated TBCs will accelerate development of degradation resistant coatings.

Tribological performance of silicon nitride and carbon black Ionanofluids based on 1-ethyl-3-methylimidazolium methanesulfonate

Development of nano-lubricants by the dispersion of nano-particles in current lubricants has contributed to improving energy efficiency reducing wear and friction. During the last two decades, ionic liquids have evolved as novel lubricants or lubricant additives, especially for high vacuum and high temperature. Nevertheless, the number of experimental studies regarding the tribological properties of Ionanofluids, defined as dispersions of nano-particles in ionic liquids, is limited. 1-Ethyl-3-methylimidazolium methanesulfonate, [EMIM][MS], is a promising candidate for lubrication applications due to its wide liquid range, high thermal conductivity, low friction coefficients and low compressibility in comparison with commercial mineral and synthetic hydrocarbon based lubricants. In this work, Ionanofluid lubricants based on dispersions of nano-additives (silicon nitride and carbon black) at mass concentration between 0.10 and 1.0 wt% in [EMIM][MS] were designed. The nearly spherical morphology of the nano-additives, silicon nitride and carbon black, was described by using scanning electron microscopy. The stabilities of the resulting nano-particle dispersions in the ionic liquid were analyzed by dynamic light scattering measurements of size for one month. Tribological characterization was performed by a rotational rheometer coupled with a tribology cell with ball-on-three-pins configuration (100Cr6 steel) in sliding conditions at 298.15 and 353.15 K. Afterwards, the wear track morphology of the worn pins was analyzed by a 3D optical profiler and Raman spectroscopy. The dispersions at the optimal nano-additive concentrations for lubrication reached friction coefficient decreases of up to 16% and wear tracks with a volume 28 times lower. Additionally, the density and dynamic viscosity of [EMIM][MS] and the optimal Ionanofluids for lubrication applications measured with a rotational Stabinger visco-densimeter in the 278.15 to 373.15 K temperature range showed small increases with almost no dependence on temperature.

Lower Lactate Levels and Lower Intracellular pH in Patients with IDH-Mutant versus Wild-Type Gliomas.

Preclinical evidence points toward a metabolic reprogramming in isocitrate dehydrogenase (IDH) mutated tumor cells with down-regulation of the expression of genes that encode for glycolytic metabolism. We noninvasively investigated lactate and Cr concentrations, as well as intracellular pH using 1H/phosphorus 31 (31P) MR spectroscopy in a cohort of patients with gliomas. Thirty prospectively enrolled, mostly untreated patients with gliomas met the spectral quality criteria (World Health Organization II [n = 7], III [n = 16], IV [n = 7]; IDH-mutant [n = 23]; IDH wild-type [n = 7]; 1p/19q codeletion [n = 9]). MR imaging protocol included 3D 31P chemical shift imaging and 1H single-voxel spectroscopy (point-resolved spectroscopy sequence at TE = 30 ms and TE = 97 ms with optimized echo spacing for detection of 2-hydroxyglutarate) from the tumor area. Values for absolute metabolite concentrations were calculated (phantom replacement method). Intracellular pH was determined from 31P chemical shift imaging. At TE = 97 ms, lactate peaks can be fitted with little impact of lipid/macromolecule contamination. We found a significant difference in lactate concentrations, lactate/Cr ratios, and intracellular pH when comparing tumor voxels of patients with IDH-mutant with those of patients with IDH wild-type gliomas, with reduced lactate levels and near-normal intracellular pH in patients with IDH-mutant gliomas. We additionally found evidence for codependent effects of 1p/19q codeletion and IDH mutations with regard to lactate concentrations for World Health Organization tumor grades II and III, with lower lactate levels in patients exhibiting the codeletion. There was no statistical significance when comparing lactate concentrations between IDH-mutant World Health Organization II and III gliomas. We found indirect evidence for metabolic reprogramming in IDH-mutant tumors with significantly lower lactate concentrations compared with IDH wild-type tumors and a near-normal intracellular pH.

Effect of ionic liquids’ chemistry on their lubrication behaviour under various contact pressures

The promising properties of Ionic Liquids (ILs) such as their low vapour pressure, high thermal stability and high thermal conductivity make them strong candidates to be used as either neat lubricants or additives. The effect of ionic liquids' chemistry on their lubrication behaviour is examined in this study by comparing the performance of five neat ILs, i.e. Ethyl Methyl Imidazolium Ethyl Sulfate (EMIM ESU), Ethyl Methyl Imidazolium Octyl Sulfate (EMIM OSU), Butyl Methyl Imidazolium Octyl Sulfate (BMIM OSU), Ethyl Methyl Imidazolium Ethyl Phosphate (EMIM EP) and Butyl Methyl Phosphonium Methyl Sulfate (PSU). The first three are used to reveal the effects of both anion and cation chain length, while the other two are used to reveal the effect of anion and cation types. Tribological experiments are performed using a nanotribometer with a borosilicate ball rubbing against a silicon plate. 3D optical microscopy and X-ray Photoelectron Spectroscopy (XPS) are used to examine surface morphology and surface chemistry, respectively. The results showed that all parameters related to ILs’ chemistry have a strong influence on the tribological behaviour of the lubricated surfaces. The increase of anion/cation chain length leads to a significant decrease in wear and friction coefficients. The influence of anion and cation types appeared to vary depending on the contact pressure.

Two-dimensional spectroscopy of Rydberg gases

Two-dimensional (2D) spectroscopy uses multiple electromagnetic pulses to infer the properties of a complex system. A paradigmatic class of target systems are molecular aggregates, for which one can obtain information on the eigenstates, various types of static and dynamic disorder and on relaxation processes. However, two-dimensional spectra can be difficult to interpret without precise knowledge of how the signal components relate to microscopic Hamiltonian parameters and system-bath interactions. Here we show that two-dimensional spectroscopy can be mapped in the microwave domain to highly controllable Rydberg quantum simulators. By porting 2D spectroscopy to Rydberg atoms, we firstly open the possibility of its experimental quantum simulation, in a case where parameters and interactions are very well known. Secondly, the technique may provide additional handles for experimental access to coherences between system states and the ability to discriminate different types of decoherence mechanisms in Rydberg gases. We investigate the requirements for a specific implementation utilizing multiple phase coherent microwave pulses and a phase cycling technique to isolate signal components.

A Proposed Method to Obtain Surface Specificity with Pump-Probe and 2D Spectroscopies.

Surfaces and interfaces are ubiquitous in nature. From cell membranes, to photovoltaic thin films, surfaces have important function in both biological and materials systems. Spectroscopic techniques have been developed to probe systems like these, such as sum frequency generation (SFG) spectroscopies. The advantage of SFG spectroscopy, a second-order spectroscopy, is that it can distinguish between signals produced from molecules in the bulk versus on the surface. We propose a polarization scheme for third-order spectroscopy experiments, such as pump-probe and 2D spectroscopy, to select for surface signals and not bulk signals. This proposed polarization condition uses one pulse perpendicular compared to the other three to isolate cross-peaks arising from molecules with polar and uniaxial (i.e., biaxial) order at a surface, while removing the signal from bulk isotropic molecules. In this work, we focus on two of these cases: XXXY and YYYX, which differ by the sign of the cross-peak they create. We compare this technique to SFG spectroscopy and vibrational circular dichroism to provide insight to the behavior of the cross-peak signal. We propose that these singularly cross-polarized schemes provide odd-ordered spectroscopies the surface-specificity typically associated with even-ordered techniques.

Persistent coherence of quantum superpositions in an optimally doped cuprate revealed by 2D spectroscopy.

Quantum materials displaying intriguing magnetic and electronic properties could be key to the development of future technologies. However, it is poorly understood how the macroscopic behavior emerges in complex materials with strong electronic correlations. While measurements of the dynamics of excited electronic populations have been able to give some insight, they have largely neglected the intricate dynamics of quantum coherence. Here, we apply multidimensional coherent spectroscopy to a prototypical cuprate and report unprecedented coherent dynamics persisting for ~500 fs, originating directly from the quantum superposition of optically excited states separated by 20 to 60 meV. These results reveal that the states in this energy range are correlated with the optically excited states at ~1.5 eV and point to nontrivial interactions between quantum many-body states on the different energy scales. In revealing these dynamics and correlations, we demonstrate that multidimensional coherent spectroscopy can interrogate complex quantum materials in unprecedented ways.

Purification and characterization of seven bioactive compounds from the newly isolated Streptomyces cavourensis TN638 strain via solid-state fermentation

The strain TN638 was isolated from Tunisian soil contaminated with industrial wastewater and selected for its potent antimicrobial activity against the tested Gram positive bacteria: Staphylococcus aureus (S. aureus) ATCC 6538 and Listeria monocytogenes (L. monocytogenes) ATCCC 19117, and Gram negative bacteria: Agrobacterium tumefaciens (A. tumefaciens) ATCC 23308 and Salmonella typhimurium (S. typhimurium) ATCC 14028 and fungi: Candida albicans (C. albicans) ATCC 10231, Rhizoctonia solani (R. solani) ATCC 58938 and Fusarium sp. Solide-state fermentation (SSF) dry crude extract of the TN638 strain presents a strong inhibitory activity notably against the phytopathogenic microorganism A. tumefaciens ATCC 23308 and the two pathogenic bacteria S. aureus ATCC 6538 and L. monocytogenes ATCCC 19117 with a zone of inhibition of 48, 34 and 34 mm respectively. According to the morphological characteristic, the complete 16S rRNA gene nucleotide sequence determination [1492 bp deposited in National Center of Biotechnology Information (NCBI) database under the accession no. LN854629.1; https://www.ncbi.nlm.nih.gov/nuccore/LN854629.1/], and the phylogenetic analysis, we can deduce that our isolate is an actinomycete bacterium belonging to the genus Streptomyces and the most closely related strain was Streptomyces cavourensis (S. cavourensis) NRRL 2740T (99.9%). We propose the assignment of our strain as Streptomyces cavourensis (S. cavourensis) TN638 strain. Work-up and purification of the strain extract using different chromatographic techniques afforded seven bio-compounds namely: Cyclo-(Leu-Pro) (1), Cyclo-(Val-Pro) (2), Cyclo-(Phe-Pro) (3), nonactin (4), monactin (5), dinactin (6) and trinactin (7). The chemical structures of compounds 1–7 were confirmed by nuclear magnetic resonance (NMR) 1D and 2D spectroscopy, mass spectrometry, and comparison with literature data. The three purified diketopiperazine (DKP) derivatives (1–3), demonstrated significant antibacterial activity against A. tumefaciens ATCC 23308 and S. typhimurium ATCC 14028. The four pure macrotetrolides (4–7), exhibited strong inhibitory effect against all tested Gram positive and Gram negative bacteria notably against A. tumefaciens ATCC 23308 and S. typhimurium ATCC 14028 with a minimum inhibitory concentration (MIC) around 8 μg/mL quite similar to that of ampicillin. Thus, we propose the use of the (SSF) active extract of the S. cavourensis TN638 strain as safe biological product to control disease caused by plant pathogen A. tumefaciens. Also, the purified active molecules produced by this strain could be used in pharmaceutical field.

Compressed Sensing for Reconstructing Coherent Multidimensional Spectra.

We apply two sparse reconstruction techniques, the least absolute shrinkage and selection operator (LASSO) and the sparse exponential mode analysis (SEMA), to two-dimensional (2D) spectroscopy. The algorithms are first tested on model data, showing that both are able to reconstruct the spectra using only a fraction of the data required by the traditional Fourier-based estimator. Through the analysis of the sparsely sampled experimental fluorescence-detected 2D spectra of LH2 complexes, we conclude that both SEMA and LASSO can be used to significantly reduce the required data, still allowing one to reconstruct the multidimensional spectra. Of the two techniques, it is shown that SEMA offers preferable performance, providing more accurate estimation of the spectral line widths and their positions. Furthermore, SEMA allows for off-grid components, enabling the use of a much smaller dictionary than that of the LASSO, thereby improving both the performance and the lowering of the computational complexity for reconstructing coherent multidimensional spectra.