Magnetism in a 2D Hybrid Ruddlesden-Popper Perovskite through Charge Redistribution Driven by an Organic Functional Spacer.

Two-dimensional Ruddlesden-Popper (RP) perovskites are emerging materials offering great synthetic versatility and remarkable features due to the tunability of their crystal structure. We present a novel strategy to provide magnetism in a 2D RP perovskite using histidine molecules as a spacer, which could induce charge rebalancing at the interface of the inorganic layer. We observe that the amide and imidazole groups are close to Pb ions. The interaction with the imidazole indicates that this functional group, possibly assisted by the carboxyl close to the vicinity of the amine terminal, is inducing charge rearrangement from Pb2+ to paramagnetic Pb3+ ions, resulting in a positive magnetic moment. This magnetized 2D hybrid perovskites can be classified as a novel class of promising materials showing a magnetic moment at their interface, which may result in intriguing physical properties due to a delicate balance between magnetism and a quantum well confinement effect in the inorganic layer.

The effects of crocetin supplementation on the blastocyst outcome, transcriptomic and metabolic profile of in vitro produced bovine embryos.

The earliest stages of embryo development are deeply influenced by reactive oxygen species (ROS), byproducts of the mitochondrial oxygen metabolism that play a key role as messengers in normal cell signal transduction and cell cycling. Despite its positive roles, the imbalance caused by the excess of ROS and an inefficient antioxidant system leads to oxidative stress, with negative consequences to the cell such as DNA damage, metabolic changes, mitochondrial stress and cell death. In the present work, crocetin - a natural antioxidant - was added to the culture media of bovine embryos to evaluate the efficiency of its antioxidant capability during embryo culture. Oocytes were in vitro matured (IVM) and fertilized according to standard protocols. Embryos were cultured at 38.5 °C under humidified air with 5% CO2, 7% O2, and 90% N2 in Synthetic Oviduct Fluid (SOF) medium supplemented with amino acids and either 5% of FBS (SOFaa) (control group) or SOFaa supplemented with 1  µM crocetin (crocetin group). After 5 days from the beginning of in vitro culture (IVC) (day 5 - D5), embryos were transferred to individual drops of culture media. At day 7 (D7), embryos were assessed by means of blastocyst rates, morphophysiological analyzes (total cell number, ROS and mitochondrial activity levels), transcript quantitation of 47 genes and metabolomic evaluation of the culture media by Raman spectroscopy. In the crocetin group blastocyst rates were higher and embryos had increased total cell number and decreased intracellular levels of ROS. These embryos also had upregulation of genes related with response to stress and lipid metabolism (ATF4, BAX, FOXO3, GADD45A, GPX1, GPX4, HSF1, SOD2, ACACA, SREBF1 and SREBF2). Raman spectroscopy corroborated these results indicating more active lipid and amino acid production in this group. The absence of crocetin in the culture media resulted in higher ROS level, as well as up regulation of genes related to DNA damage, stress response and energy metabolism (MORF4L2, SOD1, TXN, PFKP, PGK1 and PPARGC1A). In conclusion, crocetin supplementation during culture protects embryos from oxidative stress and influences the adaptive response to stress conditions, leading to an increase in both blastocyst yield and quality, as well as changes in transcriptomic and metabolic profile of in vitro produced bovine embryos.

First-principles calculations of Raman vibrational modes in the fingerprint region for connective tissue.

Vibrational spectroscopy has been widely employed to unravel the physical-chemical properties of biological systems. Due to its high sensitivity to monitoring real time "in situ" changes, Raman spectroscopy has been successfully employed, e.g., in biomedicine, metabolomics, and biomedical engineering. The interpretation of Raman spectra in these cases is based on the isolated macromolecules constituent vibrational assignment. Due to this, probing the anharmonic or the mutual interactions among specific moieties/side chains is a challenge. We present a complete vibrational modes calculation for connective tissue in the fingerprint region (800 - 1800 cm-1) using first-principles density functional theory. Our calculations accounted for the inherent complexity of the spectral features of this region and useful spectral markers for biological processes were unambiguously identified. Our results indicated that important spectral features correlated to molecular characteristics have been ignored in the current tissue spectral bands assignments. In particular, we found that the presence of confined water is mainly responsible for the observed spectral complexity.

Two-step kinetic model of the self-assembly mechanism for diphenylalanine micro/nanotube formation.

Peptide nanostructures compose a new class of materials that have gained attention due to their interesting properties. Among them, nanotubes of diphenylalanine (FF) and its analogues have been one of the most studied structures in the last few years. Their importance originates from the need to better understand the formation of ß-amyloid fibrils which are associated with Alzheimer's disease. In this work, the FF self-assembly process was probed using time-resolved Raman microscopy. The changes in the Raman spectra are followed over time after injecting water into a FF-film until micro/nanotubes (MNTs) are formed. Specific features of the Raman spectra clearly suggest that FF-molecules after water injection form an intermediate species before forming FF-MNTs. The broad Raman bands observed for the intermediate species suggest the presence of very heterogeneous structures based on FF. The FF-MNTs appear almost instantaneously (detected via the rise of the typical Raman bands of FF-MNTs at 761, 1249 and 1426 cm-1) after the intermediate structures are formed. This delayed formation of FF-MNTs supports a nucleation process. The formation via nucleation of FF-MNTs is further corroborated by a simulation of the Raman spectra based on a 2-step kinetic model and the respective vibrational Raman modes are identified using Density Functional Theory vibrational calculations. Our results indicate that the driving force for the FF-MNT patterning process is the electric dipole re-orientation originating from the FF dipeptide unit connectivity over time.

Rapid and noninvasive technique to assess the metabolomics profile of bovine embryos produced in vitro by Raman spectroscopy.

Morphological assessments are used to select embryos with the highest implantation potential, however it is still very limited. The development of new technologies, such as Raman spectroscopy have improved quantitative and qualitative analysis, and consequently led to a better characterization of embryos and improvements on the prediction of their potential. Therefore, we propose a method based on the conventional in vitro culture system of bovine embryos, and the subsequent analysis of the culture media drops by Raman spectroscopy. Our results obtained by PCA analysis clearly showed a separation of the spectral profiles from culture media drops with and without embryos.

Relaxation dynamics of deeply supercooled confined water in L,L-diphenylalanine micro/nanotubes.

The temperature dependence (10-290 K) of the low-frequency (20-150 cm(-1)) Raman-active phonon modes of deeply supercooled confined water in L,L-diphenylalanine micro/nanotubes was analyzed. The isolated dynamics of a specific geometry of a water cluster (pentamer) in a supercooled confined regime was studied in detail. A fragile-to-strong transition at 204 K was observed and related to the crossing of the Widom line. Analysis of peptide vibrational modes coupled to water hydrogen bonds indicated that hydrogen bond fluctuations play an irrelevant role in this system. Our results are in agreement with the second critical point of water existence hypothesis.

Unusual specific heat of almost dry L-cysteine and L-cystine amino acids.

A detailed quantitative analysis of the specific heat in the 0.5- to 200-K temperature range for almost dry L-cysteine and its dimer, L-cystine, amino acids is presented. We report the occurrence of a sharp first-order transition at ∼76 K for L-cysteine associated with the thiol group ordering which was successfully modeled with the two-dimensional Ising model. We demonstrated that quantum rotors, two-level systems (TLS), Einstein oscillators, and acoustic phonons (the Debye model) are essential ingredients to correctly describe the overall experimental data. Our analysis pointed out the absence of the TLS contribution to the low temperature specific heat of L-cysteine. This result was similar to that found in other noncrystalline amorphous materials, e.g., amorphous silicon, low density amorphous water, and ultrastable glasses. L-cystine presented an unusual nonlinear acoustic dispersion relation ω(q)=vq0.95 and a Maxwell-Boltzmann-type distribution of tunneling barriers. The presence of Einstein oscillators with ΘE∼70 K was common in both systems and adequately modeled the boson peak contributions.

Boson peak as a probe of quantum effects in a glassy state of biomolecules: the case of L-cysteine.

Some physical properties of hydrated biomolecules, e.g., the occurrence of a boson peak, have been recognized to resemble those of glassy states. The present work shows that quantum fluctuations play a fundamental role in describing the glassy state of biomolecules, particularly at lower hydration levels. There is a linear relationship between the quantumness and the slope of the temperature dependence of the boson peak frequency, which is used to classify the extent of quantum contributions to the glassy state of glasses in general. Lastly, we demonstrate that the boson peak two-band spectral structure that is observed in some cases can be directly linked to the anisotropy of the elastic properties of the material. The amino acid L-cysteine is studied in detail. The findings are compared with previously reported data for other macromolecules.

Anharmonic transitions in nearly dry L-cysteine I.

Two special dynamical transitions of universal character have recently been observed in macromolecules (lysozyme, myoglobin, bacteriorhodopsin, DNA and RNA) at T* ~100-150 K and T(D) ~180-220 K. The underlying mechanisms governing these transitions have been the subject of debate. In the present work, a survey is reported on the temperature dependence of structural, vibrational and thermodynamical properties of a nearly anhydrous amino acid (orthorhombic polymorph of the amino acid l-cysteine at a hydration level of 3.5%). The temperature dependence of x-ray powder diffraction patterns, Raman spectra and specific heat revealed these two transitions at T* = 70 K and T(D) = 230 K for this sample. The data were analyzed considering amino acid-amino acid, amino acid-water, water-water phonon-phonon interactions and molecular rotor activation. Our results indicated that the two referred temperatures define the triggering of very simple and particular events that govern all the interactions of the biomolecular: activation of CH(2) rigid rotors (T < T* ), phonon-phonon interactions between specific amino acid and water dimer vibrational modes (T* < T < T(D)), and water rotational barriers surpassing (T > T(D)).

Evidence for a subtle structural symmetry breaking in EuB(6).

This work presents a systematic Raman scattering study and first-principles calculations for the EuB(6) system. Evidence for the presence of an incipient (∼1 × 10(-4) Å) tetragonal symmetry break of its crystalline structure was found. Forbidden Raman modes at ω(fRm(1))∼1170 cm(-1), ω(fRm(2))∼1400 cm(-1), and ω(fRm(3))∼1500  cm(-1) were observed. The tetragonal symmetry of ω(fRm(2)) and ω(fRm(3)) together with spin-polarized first-principles simulations of the structural and magnetic properties fully support such a break of symmetry. Our data and calculations explain the occurrence of ferromagnetism in Eu hexaborides, previously reported.

Study of normal colorectal tissue by FT-Raman spectroscopy.

FT-Raman spectroscopy was employed to study normal human colorectal tissues in vitro with the aim of evaluating the spectral differences of the complex colon mucous in order to establish a characteristic Raman spectrum. The samples were collected from 39 patients, providing 144 spectra for the statistical analysis. The results enable one to establish three well-defined spectroscopic groups of non-altered colorectal tissues that were consistently checked by statistical (clustering) and biological (histopathology) analyses: group 1 is represented by samples with the presence of epithelial layer, connective tissue papillae, and smooth muscle tissue; group 2 comprises tissues with epithelial layer and connective tissue papillae; group 3 presented mostly fatty and slack conjunctive tissue. The study reveals the existence of an intrinsic spectral variability for each patient that must be considered when sampling tissues fragments to build a spectral database. This is the first step for future studies and applications of Raman spectroscopy to optical biopsy and diagnosis of colorectal cancer.

Unconventional metallic magnetism in LaCrSb3.

Neutron-diffraction measurements in LaCrSb3 show a coexistence of ferromagnetic and antiferromagnetic sublattices below T(C)=126 K, with ordered moments of 1.65(4) and 0.49(4)mu(B)/formula unit, respectively (T=10 K), and a spin-reorientation transition at approximately 95 K. No clear peak or step was observed in the specific heat at T(C). Coexisting localized and itinerant spins are suggested.

Dramatic changes in the magnetic coupling mechanism for La-doped CaMnO3.

The exchange interactions in polycrystalline samples of Ca1-xLaxMnO3 (0.00< or =x< or =0.05) are studied by means of Raman scattering and electron paramagnetic resonance. Dramatic reductions in the spin-phonon interactions and magnetic correlations are observed for La doping levels as small as approximately 2%-3%. These results show that the charge carriers play an important role in the overall exchange coupling in the electron-doped manganites, even at very low doping levels.

Reliability of bilateral differences in electrodermal activity.

To evaluate the reliability of electrodermal lateralization, skin conductance response (SCR) and skin potential response (SPR) amplitudes were recorded bilaterally in 11 right-handed male students during 4 identical experimental sessions each a week apart. After a rest period of 5 min, a set of auditory stimuli (1000 Hz, 100 dB, 1 s) was delivered. Results of both recordings showed a significant lateralization for all sets of response in the majority of subjects, but the reliability of the right-left (R-L) differences was low from one session to another. However, results suggest the existence of different degrees in stability according to subjects. Otherwise, the R-L differences appear to be recording technique dependent. These results have implications for the influence of central and peripheral factors on electrodermal activity laterality.

Instrumental conditioning of skin potential responses in curarized cats: non specific effects of a punishment procedure.

This study evaluates the effects of a punishment paradigm upon electrodermal activity (EDA) in curarized cats. In ten experimental subjects, any skin potential response (SPR) exceeding threshold value was punished by an electric shock. Ten control subjects received an electric shock or an electric stimulation of the mesencephalic reticular formation unrelated to the EDA. The results show that: a) No significant modifications of EDA occurred in subjects characterized by low initial activity; b) The frequency of SPR significantly decreased in high activity subjects used both for the experiments and the controls. Therefore, this diminution, in experimental subjects, cannot be due to a learning process. Neither can it be related to level of curarization or to rate of artificial ventilation. It is suggested that this effect results from a non-specific cortical inhibitory mechanism acting on the reticular activating system. The results obtained in three decorticated cats submitted to a punishment procedure are in accordance with such an hypothesis. Consequently the existence of operant autonomic learning remains unproven.

Adrenal versus nonadrenal sympathetic preganglionic neurones in the lower thoracic intermediolateral nucleus of the cat: physiological properties.

Adrenal and nonadrenal sympathetic preganglionic neurones (SPNs) in the intermediolateral nucleus of spinal segments T8-T10 in the cat were compared according to a number of physiological properties. An SPN was classified as "adrenal" (n = 37) if it could be antidromically activated by electrical stimulation of the adrenal medulla. An SPN that could not be activated from the adrenal medulla yet could be antidromically activated by electrical stimulation of the greater splanchnic nerve was classified as "nonadrenal" (n = 123). Approximately 50% of adrenal SPNs (17 out of 37) were activated antidromically by stimulation of both the greater splanchnic nerve and adrenal medulla, suggesting that these neurones projected to the adrenal medulla via the greater splanchnic nerve, with the other adrenal SPNs taking a different route. The mean conduction velocities of adrenal (6.7 +/- 1.8 (SD) m/s) and nonadrenal (6.7 +/- 1.5 m/s) sympathetic preganglionic axons were similar. Over 80% of adrenal (31 out of 37) and nonadrenal (104 out of 116) SPNs were spontaneously active. The two types of neurone were indistinguishable in terms of the rates and patterns of discharge. Adrenal SPNs discharged with a mean rate of 1.4 +/- 1.1 spikes/s, and nonadrenal SPNs discharged with a mean rate of 1.8 +/- 1.4 spikes/s. With both types of SPN, the pattern of spontaneous activity was either irregular or phasic. With the latter pattern, periodic bursts of discharge were at the same frequency as oscillations in arterial pressure, frequency of ventilation, or phrenic nerve discharge. These data suggest that adrenal and nonadrenal sympathetic preganglionic neurones in the intermediolateral nucleus in caudal thoracic segments share a number of common physiological properties.

Adrenal versus nonadrenal sympathetic preganglionic neurones in the lower thoracic intermediolateral nucleus of the cat: effects of serotonin, substance P, and thyrotropin-releasing hormone.

Adrenal and nonadrenal sympathetic preganglionic neurones (SPNs) in the intermediolateral nucleus of spinal segments T8-T10 in the cat were compared according to their responses to iontophoretic application of serotonin, substance P, and thyrotropin-releasing hormone (TRH). Responses of both types of SPN to iontophoretic application of serotonin were characterized by an increase in the rate of discharge that was slow in onset (mean +/- SD = 36 +/- 21 s) and prolonged in afterdischarge (115 +/- 70 s) following termination of application. Depression was never observed and responses were similar whether using serotonin at a pH of 3.3 or 4.5, suggesting that the absence of a depressant effect cannot be accounted for by pH, as has been reported with cortical neurones. Iontophoretic application of methysergide resulted in a decrease in the rate of discharge of both types of SPN and blocked the excitatory responses to serotonin. Adrenal and nonadrenal SPNs were excited by iontophoretic application of substance P. Responses of both types of SPN were similar and were characterized by a gradual increase in the rate of discharge that was slow in onset (42 +/- 27 s) and prolonged in afterdischarge (96 +/- 42 s). Finally, adrenal and nonadrenal SPNs were also weakly excited by iontophoretic application of TRH. These responses were slow in onset (48 +/- 27 s) and prolonged in afterdischarge (78 +/- 35 s). These data indicate that serotonin, substance P, and TRH exert excitatory effects on functionally dissimilar sympathetic preganglionic neurones and support the possibility that they may be chemical mediators of synaptic transmission in the intermediolateral nucleus. In addition, these data may be interpreted to support the notion that serotonin, substance P, and TRH are involved in global activation of the sympathetic nervous system.