Low-frequency Spectral Density Research Articles

An efficient protocol for excited states of large biochromophores.

Efficient energy transport in photosynthetic antenna is a long-standing source of inspiration for artificial light harvesting materials. However, characterizing the excited states of the constituent chromophores poses a considerable challenge to mainstream quantum chemical and semiempirical excited state methods due to their size and complexity and the accuracy required to describe small but functionally important changes in their properties. In this paper, we explore an alternative approach to calculating the excited states of large biochromophores, exemplified by a specific method for calculating the Qy transition of bacteriochlorophyll a, which we name Chl-xTB. Using a diagonally dominant approximation to the Casida equation and a bespoke parameterization scheme, Chl-xTB can match time-dependent density functional theory's accuracy and semiempirical speed for calculating the potential energy surfaces and absorption spectra of chlorophylls. We demonstrate that Chl-xTB (and other prospective realizations of our protocol) can be integrated into multiscale models, including concurrent excitonic and point-charge embedding frameworks, enabling the analysis of biochromophore networks in a native environment. We exploit this capability to probe the low-frequency spectral densities of excitonic energies and interchromophore interactions in the light harvesting antenna protein LH2 (light harvesting complex 2). The impact of low-frequency protein motion on interchromophore coupling and exciton transport has routinely been ignored due to the prohibitive costs of including it in simulations. Our results provide a more rigorous basis for continued use of this approximation by demonstrating that exciton transition energies are unaffected by low-frequency vibrational coupling to exciton interaction energies.

A fuzzy-oscillatory model of medial prefrontal cortex control function in spatial memory retrieval in human navigation function.

Navigation can be broadly defined as the process of moving from an origin to a destination through path-planning. Previous research has shown that navigation is mainly related to the function of the medial temporal lobe (MTL), including the hippocampus (HPC), and medial prefrontal cortex (mPFC), which controls retrieval of the spatial memories from this region. In this study, we suggested a cognitive and computational model of human navigation with a focus on mutual interactions between the hippocampus (HPC) and the mPFC using the concept of synchrony. The Van-der-pol oscillator was used to model the synchronous process of receiving and processing "what stream" information. A fuzzy lookup table system was applied for modeling the controlling function of the mPFC in retrieving spatial information from the HPC. The effect of attention level was also included and simulated. The performance of the model was evaluated using information reported in previous experimental research. Due to the inherent stability of the proposed fuzzy-oscillatory model, it is less sensitive to the exact values of the initial conditions, and therefore, it is shown that it is consistent with the actual human performance in real environments. Analyzing the proposed cognitive and fuzzy-oscillatory computational model demonstrates that the model is able to reproduce certain cognitive and functional disturbances in navigation in related diseases such as Alzheimer's disease (AD). We have shown that an increase in the bifurcation parameter of the Van-der-pol equation represents an increase in the low-frequency spectral power density and a decrease in the high-frequency spectral power as occurs in AD due to an increase in the amyloid plaques in the brain. These changes in the frequency characteristics of neuronal activity, in turn, lead to impaired recall and retrieval of landmarks information and learned routes upon encountering them. As a result, and because of the wrong frequency code being transmitted, the relevant set of rules in the mPFC is not activated, or another unrelated set will be activated, which leads to forgetfulness and erroneous decisions in routing and eventually losing the route in Alzheimer's patients.

Rehabilitation program combining physical exercise and heart rate variability biofeedback in hematologic patients: a feasibility study

PurposeHematologic patients have a poorer health-related quality of life due to the disease and its treatments. Non-pharmacological interventions represent an opportunity in tertiary cancer prevention to manage persistent symptoms and support patients in their return to active daily living. This interventional study aimed to evaluate the feasibility of a program combining physical exercise (PE) and heart rate variability biofeedback (HRVB) in hematologic patients.MethodHematologic patients in remission within 6 months participated in a 12-week rehabilitation program including 24 supervised sessions of PE associated with 10 supervised sessions of HRVB and daily home-based practice of paced breathing. We assessed patient adherence, fatigue, physical function, and heart rate variability.ResultsTwenty patients were included, 17 completed the protocol and 3 dropped out due to disease progression or time constraints; no adverse events or incidents were reported. Participation rates were 85% for PE and 98% for HRVB-supervised sessions. Significant improvements of physical capacity (6-min walk test, p < 0.001; 50-foot walk test, p < 0.001), muscle strength (grip force test, p < 0.01), and flexibility (toe-touch test, p < 0.001; back scratch test, p < 0.05) were measured. Coherence ratio (p < 0.001) and low-frequency spectral density of HRV signal (p < 0.003) increased significantly, suggesting improved autonomic function. Fatigue, static balance, and other time and frequency indicators of HRV were not improved (all p > 0.05).ConclusionA rehabilitation program combining PE and HRVB is feasible in hematologic patients and effective on physical function. Further research with a larger sample size is needed to investigate effectiveness on patients’ autonomic functions and their impacts on symptomatology.

Ultrafast vibrational dynamics of a solute correlates with dynamics of the solvent.

Two-dimensional infrared (2D-IR) spectroscopy is used to measure the spectral dynamics of the metal carbonyl complex cyclopentadienyl manganese tricarbonyl (CMT) in a series of linear alkyl nitriles. 2D-IR spectroscopy provides direct readout of solvation dynamics through spectral diffusion, probing the decay of frequency correlation induced by fluctuations of the solvent environment. 2D-IR simultaneously monitors intramolecular vibrational energy redistribution (IVR) among excited vibrations, which can also be influenced by the solvent through the spectral density rather than the dynamical friction underlying solvation. Here, we report that the CMT vibrational probe reveals solvent dependences in both the spectral diffusion and the IVR time scales, where each slows with increased alkyl chain length. In order to assess the degree to which solute-solvent interactions can be correlated with bulk solvent properties, we compared our results with low-frequency dynamics obtained from optical Kerr effect (OKE) spectroscopy-performed by others-on the same nitrile solvent series. We find excellent correlation between our spectral diffusion results and the orientational dynamics time scales from OKE. We also find a correlation between our IVR time scales and the amplitudes of the low-frequency spectral densities evaluated at the 90-cm-1 energy difference, corresponding to the gap between the two strong vibrational modes of the carbonyl probe. 2D-IR and OKE provide complementary perspectives on condensed phase dynamics, and these findings provide experimental evidence that at least at the level of dynamical correlations, some aspects of a solute vibrational dynamics can be inferred from properties of the solvent.

Tethering role of the autonomic nervous system on cardioventilatory coupling

Hypovolemia and intermittent positive pressure ventilation are conditions that frequently characterize the state of critical illness, but their interaction and resulting cardioventilatory coupling is poorly understood even in healthy humans.We explored heart rate variability, baroreflex activity, and their interaction in an experimental protocol involving twelve mildly hypovolemic healthy subjects during spontaneous breathing and noninvasive positive-pressure ventilation. In seven subjects, an echocardiographic assessment was also performed.Correction of hypovolemia, raising cardiac preload, produced an increase in high-frequency spectral power density of heart rate, left low-frequency spectral power density unchanged but enhanced baroreflex sensitivity. Cardioventilatory coupling was affected by both central blood volume and ventilatory mode and was mainly entrained by the respiratory oscillation.In conclusion, the autonomic nervous system and baroreflex have a significant role in compensating the hemodynamic perturbation due to changes of volemia and ventilatory-induced fluctuations of venous return. They exert an integrative function on the adaptive pattern of cardioventilatory coupling.

Cerebral Aβ40 and systemic hypertension

Mid-life hypertension and cerebral hypoperfusion may be preclinical abnormalities in people who later develop Alzheimer’s disease. Although accumulation of amyloid-beta (Aβ) is characteristic of Alzheimer’s disease and is associated with upregulation of the vasoconstrictor peptide endothelin-1 within the brain, it is unclear how this affects systemic arterial pressure. We have investigated whether infusion of Aβ40 into ventricular cerebrospinal fluid modulates blood pressure in the Dahl salt-sensitive rat. The Dahl salt-sensitive rat develops hypertension if given a high-salt diet. Intracerebroventricular infusion of Aβ induced a progressive rise in blood pressure in rats with pre-existing hypertension produced by a high-salt diet (p < 0.0001), but no change in blood pressure in normotensive rats. The elevation in arterial pressure in high-salt rats was associated with an increase in low frequency spectral density in systolic blood pressure, suggesting autonomic imbalance, and reduced cardiac baroreflex gain. Our results demonstrate the potential for intracerebral Aβ to exacerbate hypertension, through modulation of autonomic activity. Present findings raise the possibility that mid-life hypertension in people who subsequently develop Alzheimer’s disease may in some cases be a physiological response to reduced cerebral perfusion complicating the accumulation of Aβ within the brain.

Critical exponent of quantum phase transitions driven by colored noise

We demonstrate that criticality in a driven-dissipative system is strongly influenced by the spectral properties of the reservoir. We study the open-system realization of the Dicke model, where a bosonic cavity mode couples to a large spin formed by two motional modes of an atomic Bose-Einstein condensate. The cavity mode is driven by a high frequency laser and it decays to a Markovian bath, while the atomic mode interacts with a colored reservoir. We reveal that the soft mode fails to describe the characteristics of the criticality. We calculate the critical exponent of the superradiant phase transition and identify an inherent relation to the low-frequency spectral density function of the colored bath. We show that a finite temperature of the colored reservoir does not modify qualitatively this dependence on the spectral density function.

The Role of Quantum Interference Effects in Normal-State Transport Properties of Electron-Doped Cuprates

The normal-state resistivity of thin films of the infinite-layer electron-doped cuprate Sr 1−x La x CuO 2±δ has been investigated. Under-doped samples, which clearly show a metal-to-insulator transition (MIT) at low temperatures, have allowed the determination of the fundamental physical mechanism behind the upturn of the resistivity, namely the quantum interference effects (QIEs) in three-dimensional systems. The occurrence of weak localization effects has been unambiguously proven by low-frequency voltage spectral density measurements, which show a linear dependence of the 1/f noise on the applied bias current at low temperatures. The identification of the QIEs at low temperatures has therefore allowed the determination of the high-temperature non-Fermi liquid metallic phase, which is dominated by a linear temperature dependence of the resistivity for all of the samples investigated.

High temperature spin dynamics in linear magnetic chains, molecular rings, and segments by nuclear magnetic resonance

We present the room temperature proton nuclear magnetic resonance (NMR) nuclear spin-lattice relaxation rate (NSLR) results in two 1D spin chains: the Heisenberg antiferromagnetic (AFM) Eu(hfac)3NITEt and the magnetically frustrated Gd(hfac)3NITEt. The NSLR as a function of external magnetic field can be interpreted very well in terms of high temperature spin dynamics dominated by a long time persistence of the decay of the two-spin correlation function due to the conservation of the total spin value for isotropic Heisenberg chains. The high temperature spin dynamics are also investigated in Heisenberg AFM molecular rings. In both Cr8 closed ring and in Cr7Cd and Cr8Zn open rings, i.e., model systems for a finite spin segment, an enhancement of the low frequency spectral density is found consistent with spin diffusion but the high cut-off frequency due to intermolecular anisotropic interactions prevents a detailed analysis of the spin diffusion regime.

Hot-electron noise properties of graphene-like systems

We study the hot-electron noise properties of two-dimensional materials with a graphene-like energy dispersion under a strong applied electric field which drives the system far from equilibrium. Calculations are based on a Boltzmann--Green-function method within a two-relaxation-time approximation that allows for both inelastic scattering coming from electron-phonon scattering and elastic scattering coming from electron-impurity scattering. The steady-state distribution function is used to calculate the average current and the low-frequency spectral density for current fluctuations (noise) in the nonequilibrium steady-state. We find that as the electric field strength increases, the noise decreases from its equilibrium thermal noise value. This is in contrast with semiconductors with a quadratic energy--wave-vector dispersion where the noise increases in a constant-relaxation-time model with the square of the electric field due to the Joule heating of the electron gas by the electric field. We have also studied these properties for an electronic dispersion with a gap introduced into the Dirac spectrum. The inclusion of the gap in the electronic dispersion causes an initial increase in the noise as a function of external electric field due to the heating of the electron gas for large gap values. At high electric fields, the noise decreases with increasing electric field as in the case of gapless dispersion at higher fields.

Laser Doppler measurement and CFD validation in 3 × 3 bundle flow

The five-beam three-component laser Doppler system is operated in the three-beam two-component mode to measure the 3×3 bundle flow with simple grid spacer. Experiment has been conducted at Re=15,200 and 29,900. According to the experiment result, the root mean square (RMS) of axial velocity fluctuation shows large value in the gap and the near-wall region of the edge sub-channel which is induced by the axial velocity gradient. Significant intensity of lateral velocity fluctuation is observed which indicates the strong lateral mixing in a 3×3 rod bundle. Through the correlation analysis coherent structures have been observed in the gap region. The spectral analysis shows that the LDV measurement complies to the Komogorov spectrum law, f−5/3, well. The low-frequency peak spectral density of the axial velocity fluctuation has been observed in the gap region connecting sub-channels with velocity difference. The performance of the SSG model and the baseline Reynolds stress model are investigated based on the experiment result. The models predict higher axial velocity in the interior sub-channel and lower in the edge and corner ones than the experiment result. Large discrepancy between the calculated and measured axial flow velocity is resulted from failure in calculating the strong negative u′w′¯ in the gap region connecting different sub-channels.

Investigations of the Low-Frequency Spectral Density of Cytochrome c upon Equilibrium Unfolding

The equilibrium unfolding process of ferric horse heart cytochrome c (cyt c), induced by guanidinium hydrochloride (GdHCl), was studied using UV-vis absorption spectroscopy, resonance Raman spectroscopy, and vibrational coherence spectroscopy (VCS). The unfolding process was successfully fit using a three-state model which included the fully folded (N) and unfolded (U) states, along with an intermediate (I) assigned to a Lys bound heme. The VCS spectra revealed for the first time several low-frequency heme modes that are sensitive to cyt c unfolding: γ(a) (~50 cm(-1)), γ(b) (~80 cm(-1)), γ(c) (~100 cm(-1)), and ν(s)(His-Fe-His) at 205 cm(-1). These out-of-plane modes have potential functional relevance and are activated by protein-induced heme distortions. The free energies for the N-I and the I-U transitions at pH 7.0 and 20 °C were found to be 4.6 kcal/M and 11.6 kcal/M, respectively. Imidazole was also introduced to replace the methionine ligand so the unfolding can be modeled as a two-state system. The intensity of the mode γ(b)~80 cm(-1) remains nearly constant during the unfolding process, while the amplitudes of the other low frequency modes track with spectral changes observed at higher frequency. This confirms that the heme deformation changes are coupled to the protein tertiary structural changes that take place upon unfolding. These studies also reveal that damping of the coherent oscillations depends sensitively on the coupling between heme and the surrounding water solvent.

Conduction Mechanism and Low Frequency Noise Analysis in Al/Pr0.7Ca0.3MnO3 for Bipolar Resistive Switching

The low-frequency noise (LFN) Characteristics of bipolar switching devices consisting of Pt (top)/Al/Pr0.7Ca0.3MnO3 (PCMO)/Pt (bottom) were investigated. The noise spectral density in a low frequency range showed a classical 1/f dependence in both high-resistance state (HRS) and low-resistance state (LRS). The random telegraph noise (RTN) were observed in both HRS and LRS which is due to the AlOx layer acting as traps at the interface between Al and PCMO or traps in PCMO bulk layer. The voltage dependence of the normalized low-frequency spectral density of current fluctuations (Si/I2) presents that the noise properties can be useful indicators to explain the switching mechanism of Al/PCMO device but new noise models should be suggested for the clear approach to analysis of the conduction characteristics in the devices.

Optimized, unequal pulse spacing in multiple echo sequences improves refocusing in magnetic resonance.

A recent quantum computing paper (G. S. Uhrig, Phys. Rev. Lett. 98, 100504 (2007)) analytically derived optimal pulse spacings for a multiple spin echo sequence designed to remove decoherence in a two-level system coupled to a bath. The spacings in what has been called a "Uhrig dynamic decoupling (UDD) sequence" differ dramatically from the conventional, equal pulse spacing of a Carr-Purcell-Meiboom-Gill (CPMG) multiple spin echo sequence. The UDD sequence was derived for a model that is unrelated to magnetic resonance, but was recently shown theoretically to be more general. Here we show that the UDD sequence has theoretical advantages for magnetic resonance imaging of structured materials such as tissue, where diffusion in compartmentalized and microstructured environments leads to fluctuating fields on a range of different time scales. We also show experimentally, both in excised tissue and in a live mouse tumor model, that optimal UDD sequences produce different T(2)-weighted contrast than do CPMG sequences with the same number of pulses and total delay, with substantial enhancements in most regions. This permits improved characterization of low-frequency spectral density functions in a wide range of applications.

The power of spectral density analysis for mapping endogenous BOLD signal fluctuations

FMRI has revealed the presence of correlated low-frequency cerebro-vascular oscillations within functional brain systems, which are thought to reflect an intrinsic feature of large-scale neural activity. The spatial correlations shown by these fluctuations has been their identifying feature, distinguishing them from fluctuations associated with other processes. Major analysis methods characterize these correlations, identifying networks and their interactions with various factors. However, other analysis approaches are required to fully characterize the regional signal dynamics contributing to these correlations between regions. In this study we show that analysis of the power spectral density (PSD) of regional signals can identify changes in oscillatory dynamics across conditions, and is able to characterize the nature and spatial extent of signal changes underlying changes in measures of connectivity. We analyzed spectral density changes in sessions consisting of both resting-state scans and scans recording 2 min blocks of continuous unilateral finger tapping and rest. We assessed the relationship of PSD and connectivity measures by additionally tracking correlations between selected motor regions. Spectral density gradually increased in gray and white matter during the experiment. Finger tapping produced widespread decreases in low-frequency spectral density. This change was symmetric across the cortex, and extended beyond both the lateralized task-related signal increases, and the established "resting-state" motor network. Correlations between motor regions also reduced with task performance. In conclusion, analysis of PSD is a sensitive method for detecting and characterizing BOLD signal oscillations that can enhance the analysis of network connectivity.

Low Frequency Spectral Density of Ferrous Heme: Perturbations Induced by Axial Ligation and Protein Insertion

Femtosecond coherence spectroscopy is used to probe low frequency (20–400 cm −1) modes of the ferrous heme group in solution, with and without 2-methyl imidazole (2MeIm) as an axial ligand. The results are compared to heme proteins (CPO, P450 cam, HRP, Mb) where insertion of the heme into the protein results in redistribution of the low frequency spectral density and in (∼60%) longer damping times for the coherent signals. The major effect of imidazole ligation to the ferrous heme is the “softening” of the low frequency force constants by a factor of ∼0.6 ± 0.1. The functional consequences of imidazole ligation are assessed and it is found that the enthalpic CO rebinding barrier is increased significantly when imidazole is bound. The force constant softening analysis, combined with the kinetics results, indicates that the iron is displaced by only ∼0.2 Å from the heme plane in the absence of the imidazole ligand, whereas it is displaced by ∼0.4 Å when imidazole (histidine) is present. This suggests that binding of imidazole (histidine) as an axial ligand, and the concomitant softening of the force constants, leads to an anharmonic distortion of the heme group that has significant functional consequences.

Field Verification of ADCP Surface Gravity Wave Elevation Spectra

Abstract Acoustic Doppler current profilers (ADCPs) can measure orbital velocities induced by surface gravity waves, yet the ADCP estimates of these velocities are subject to a relatively high noise level. The present paper introduces a linear filtration technique to significantly reduce the influence of noise and turbulence from energy spectra of combined orbital velocity measurements. Data were collected in 13-m-deep water with a 1.2-MHz ADCP sampling in mode 12, where a collocated wave buoy was used for verification. The surface elevation spectra derived from the filtrated and nonfiltrated measurements were compared with corresponding wave buoy spectra. In the frequency range between 0.12 and 0.5 Hz, ADCP- and wave-buoy-derived spectral estimates matched very well, even without applying the filtration technique. At frequencies below 0.12 Hz, the ADCP-derived surface elevation spectra are biased, caused by a depth-varying excess of spectral energy density in the measured orbital velocities, peaking at middepth. Internal waves may provide an explanation for the energy excess, as the experiment was conducted in the region of influence of the Rhine freshwater plume. Alternatively, infragravity waves may be the cause of the depth variation of low-frequency spectral energy density.

Autonomic Function Is Impaired in Elderly Stroke Survivors

Impaired autonomic function is common in the acute poststroke phase but little is known about the longer term effects, particularly in older people. We sought to determine if autonomic function is impaired after stroke recovery in older patients. A cross-sectional case-control study comparing autonomic function in 76 nondemented stroke patients with 70 community-living controls aged older than 75 years. Cases were assessed on average 9 months after stroke. From power spectral analysis of heart rate variability, stroke patients had lower total (P=0.032) and low-frequency (P=0.014) spectral densities and impaired baroreflex sensitivity (alpha low-frequency baroreflex sensitivity, P=0.006). From a series of cardiovascular autonomic reflex tests, heart rate variation during forced respiration, Valsalva ratio, and blood pressure overshoot during Valsalva maneuver were significantly lower in stroke patients (P=0.003, <0.001, and 0.027, respectively). Blood pressure response to isometric exercise was significantly exaggerated in stroke patients (P=0.007). Cardiovascular autonomic function is impaired long after the index event in stroke survivors. Impaired autonomic function may increase the risk of all-cause mortality and cardiovascular mortality in older stroke survivors.

Measurements of low-frequency noise spectral densities for a small-sized stack of intrinsic Josephson junctions of Bi2Sr2CaCu2Oy single crystal

We measured the low-frequency-voltage noise properties of a small-sized stack of intrinsic Josephson junctions formed on the surface of a cleaved Bi2Sr2CaCu2Oy (Bi-2212) single crystal, containing a few intrinsic Josephson junctions. A stack with an area of 2×2μm was fabricated by electron-beam lithography and argon-ion-milling. The current–voltage (I–V) characteristics along the c-axis direction of the stack were measured by a three-terminal method. The stack showed (I–V) and dV∕dI-V curves without backbending due to heating effects. Five discrete resistive branches with hysteresis were observed in the low-voltage region of these curves. The measured noise-voltage spectral density SV(f) had a 1∕f dependence on frequency. We estimated the magnitude of the 1∕f noise parameter η from SV(f) in a Bi-2212 stack and found that above the sum-gap voltage in a small-sized stack η was almost the same as that for low-Tc Nb∕Al+AlOx∕Nb high-quality tunnel junctions.

Orientational and interaction induced dynamics in the isotropic phase of a liquid crystal: polarization resolved ultrafast optical Kerr effect spectroscopy.

The ultrafast dynamics of the isotropic phase of a liquid crystal 4'-pentyl-4-p-biphenylcarbonitrile (5CB) have been investigated using polarization resolved optical Kerr effect spectroscopy. Measurements were made as a function of both temperature and dilution in nonpolar solvents. To separate single molecule and interaction induced components to the relaxation of the induced birefringence, measurements of both the anisotropic and isotropic response were made. The isotropic response was found to be dominated by a damped low-frequency mode of intramolecular origin. There is a minor additional component assigned to an interaction induced contribution. There is at most an extremely weak isotropic signal beyond 1 ps, showing that the picosecond time scale dynamics of 5CB are dominated by orientational relaxation. The isotropic response is independent of temperature in the range studied (0.2-50 K above the nematic to isotropic phase-transition temperature). The anisotropic response exhibits relaxation dynamics on time scales spanning subpicosecond to several hundred picoseconds and beyond. The fastest components are dominated by a librational response, but there are smaller contributions from three low-frequency intramolecular modes, and a contribution from interaction induced effects. The low-frequency spectral density extracted from these data are independent of temperature in the range studied, 0.2-30 K above the phase-transition temperature, but shift to lower frequency on dilution in alkane solvents. In neat 5CB the picosecond time scale orientational dynamics are dominated by temperature-independent reorientation within the pseudonematic domains, while in solution these are disrupted, and the orientational response becomes faster and temperature dependent.