No abstract

Deep brain stimulation (DBS), a surgical technique to treat certain neurologic and psychiatric conditions, relies on pre-determined stimulation parameters in an open-loop configuration. The major advancement in DBS devices is a closed-loop system that uses neurophysiologic feedback to dynamically adjust stimulation frequency and amplitude. Stimulation-driven neurochemical release can be measured by fast-scan cyclic voltammetry (FSCV), but existing FSCV electrodes rely on carbon fiber, which degrades quickly during use and is therefore unsuitable for chronic neurochemical recording. To address this issue, we developed durable, synthetic boron-doped diamond-based electrodes capable of measuring neurochemical release in humans. Compared to carbon fiber electrodes, they were more than two orders-of-magnitude more physically-robust and demonstrated longevity in vitro without deterioration. Applied for the first time in humans, diamond electrode recordings from thalamic targets in patients (n = 4) undergoing DBS for tremor produced signals consistent with adenosine release at a sensitivity comparable to carbon fiber electrodes. (Clinical trials # NCT01705301).

Maya Blue is a famous indigo-based pigment produced by the ancient Mayas. The organic/inorganic complexes inspired by Maya Blue have led to a new class of surface compounds that have novel applications to pigment industries. Materials analyzed in the present work are made by a synthetic route, and demonstrate chemical stability similar to that of the ancient Maya Blue samples. However, we have learned that stable complexes can be synthesized at much higher dye concentrations than used by the Mayas. Analysis by FT-Raman and FT-IR spectroscopy demonstrates the partial elimination of the selection rules for the centrosymmetric indigo, indicating distortion of the molecule. This distortion accounts for the observed color changes, as the molecular orbital structure is modified, allowing the complex to stabilize. The spectroscopic data also shows the disappearance of the indigo N-H bonding, as the organic molecules incorporate into palygorskite material. A structural change of indigo to dehydroindigo during heating is suggested by this result. Infrared data confirm the loss of zeolitic water and a partial removal of structural water after the heating process. Evidence of bonding between cationic aluminum and dehydroindigo through oxygen and nitrogen is revealed by FT-Raman measurements at higher dye concentrations.

W(0.95)Ti(0.05)O(3) films were fabricated using sputter-deposition onto Si(100) wafers in by varying the growth temperature from room temperature (RT) to 500 °C. X-ray diffraction (XRD), high-resolution scanning electron microscopy (SEM) coupled with energy-dispersive X-ray spectrometry (EDS), and Raman spectroscopy (RS) were performed to investigate the effect of temperature on the growth behavior, crystal structure, texturing, surface morphology, and chemical bonding of W(0.95)Ti(0.5)O(3) films. The results indicate that the effect of temperature is significant on the growth and microstructure of W(0.95)Ti(0.05)O(3) films. XRD results indicate that the effect of Ti is remarkable on the crystallization of WO(3). W(0)(.95)Ti(0.05)O(3) films grown at temperatures <300 °C are amorphous compared to pure WO(3) crystalline films crystallizing at 200 °C. Phase transformation is induced in W(0)(.95)Ti(0.05)O(3) resulting in tetragonal structure at ≥300 °C. The structural changes were also reflected in the intensities of -W-O-W- vibrational modes in RS measurements. The SEM imaging analysis indicates that the phase transformations are accompanied by a characteristic change in surface morphology. Room temperature electrical conductivity of W(0.95)Ti(0.05)O(3) films increases from 0.63 to 27 (Ω m)(-1) with increasing temperature from RT to 400 °C due to improved structural order. Electrical conductivity exhibit a decrease at 500 °C (7.4 (Ω m)(-1)) due to disordering induced by Ti segregation, which is confirmed by XRD and RS measurements.

No abstract

A combined theoretical and experimental analysis of dopamine (DA) is presented in this work with the objective of achieving more accurate detection and monitoring of this neurotransmitter at very low concentrations, specific to physiological levels. Surface-enhanced Raman spectroscopy on silver nanoparticles was employed for recording DA concentrations as low as 10−11 molar. Quantum chemical density functional calculations were carried out using Gaussian-09 analytical suite software. Relatively good agreement between the simulated and experimentally determined results indicates the presence of different DA molecular forms, such as uncharged DA±, anionic DA−, and dopaminequinone. Disappearance of the strongest bands of dopamine around 750 cm−1 and 790 cm−1, which suggests its adsorption onto the metallic surface, is not only consistent with all of these DA configurations, but also provides additional information about the analyte’s redox process and voltammetric detection. On the other hand, occurrence of the abovementioned Raman lines could indicate the formation of multilayers of DA or its presence in a cationic DA+ form. Thus, through coordinated experiment and theory, valuable insights into changes observed in the vibrational signatures of this important neurotransmitter can be achieved for a better understanding of its detection at physiological levels, which is crucial if further optovoltammetric medical device development is envisioned.

Micro-probe Raman and far-infrared absorption spectroscopies were used to prove the existence of optical phonon modes of PbSe nanoparticles prepared by colloidal chemistry and preliminarily characterized by transmission electron microscopy. To the best of our knowledge, this is the first time that evidence of the surface phonon (SP) mode by Raman spectroscopy has been experimentally observed. The wavenumber of the SP mode is consistent with its prediction by a dielectric continuum model. While for different PbSe nanoparticle sizes the observed SP mode does not show any obvious change in its position, there is a clear shift by approximately 4 cm −1 toward higher wavenumber in the appearance of the LO(0) in the Raman spectra from the 3 nm to the 7 nm PbSe nanoparticles. Far-infrared measurements demonstrate the presence of the transverse optical TO(0) and of the coupled phonon modes.

Building on diamond characteristics such as hardness, chemical inertness and low electron emission threshold voltage, the current microscopic, spectroscopic and voltammetric investigations are directed towards improving the properties of electrode coating materials for their future use in clinical studies of deep brain stimulation via fast-scan cyclic voltammetry (FSCV). In this study we combine the capabilities of confocal Raman mapping in providing detailed and accurate analysis of local distributions of material constituents in a series of boron-doped polycrystalline diamond films grown by chemical vapor deposition, with information from the more conventional techniques of scanning electron microscopy (SEM) and infrared absorption spectroscopy. Although SEM images show a uniform distribution of film crystallites, they have the limitation of being unable to differentiate the distribution of boron in the diamond. Values of 1018–1021 atoms/cm3 of boron content have been estimated from the absorption coefficient of the 1290 cm−1 infrared absorption band and from the 500 cm−1 Raman vibration. The observed accumulation of boron atoms and carbon sp2 impurities at the grain boundaries suggests that very high doping levels do not necessarily contribute to improvement of the material’s conductivity, corroborating with voltammetric data. FSCV results also indicate an enhanced stability of analyte detection.