Medically responsive amyloidogenic giant sellar-parasellar prolactinoma.

Background: Giant prolactinomas are rare; among them, the amyloidogenic variant, prolactinomas with extensive spherical amyloid deposits, are rare, with only 30 cases reported with recommendations of surgical management contrary to the routine prolactinoma's medical management. Case Description: We report here a case of giant amyloidogenic prolactinoma in a 32-year-old male patient who had a very atypical presentation in terms of clinical, radiological, and pathological features and responded to dopamine agonist therapy like a normal prolactinoma. Conclusion: Amyloidogenic giant prolactinomas are rare. Contrary to usual belief, even they remain medically responsive; however, more literature is required to decide their ideal management.

Raman Evidence of Multiple Adsorption Sites and Structural Transformation in ZIF-4.

The zeolitic imidazolate framework, ZIF-4, exhibits soft porosity and is known to show pore volume changes with temperatures, pressures, and guest adsorption. However, the mechanism and adsorption behavior of ZIF-4 are not completely understood. In this work, we report an open to narrow pore transition in ZIF-4 around T ∼ 253 K upon lowering the temperature under vacuum (10-6 Torr) conditions, facilitated by C-H···π interactions. In the gaseous environment of N2 and CO2 around the framework, characteristic Raman peaks of adsorbed gases were observed under ambient conditions of 293 K and 1 atm. A guest-induced transition at ∼153 K resulting in the opening of new adsorption sites was inferred from the Raman spectral changes in the C-H stretching modes and low-frequency modes (<200 cm-1). In contrast to a single vibrational mode generally reported for entrapped N2, we show three Raman modes of adsorbed N2 in ZIF-4. The adsorption is facilitated by dispersive and quadrupolar interactions. From our temperature-dependent Raman results and theoretical analysis based on the density functional tight-binding approach, we conclude that the C-Hs are the preferred adsorption sites on ZIF-4 in the following order: C4-H, C5-H > C2-H > center of the Im ring (interacting with C-H centers) > center of the cavity. We also show that with an increasing concentration of N2 adsorbed at low temperatures, the ZIF-4 structure undergoes shear distortion of the window formed by 4-imidazole rings and consequent volumetric expansion. Our results have immediate implications in the field of porous materials and could be vital in identifying subtle structural transformations that may favor or hinder guest adsorption.

Raman spectroscopy, an ideal tool for studying the physical properties and applications of metal-organic frameworks (MOFs).

Metal-organic frameworks (MOFs) are a unique family of materials constructed by coordinating metal ions or clusters to bridging organic ligands. Many of these materials are well known for their intricate structures, and exceptional gas adsorption properties, and have potential applications in the separation of alkanes, catalysis, energy storage, surface-enhanced Raman spectroscopy (SERS) based detections, and diagnostics. In situ or in operando Raman spectroscopic studies provide real-time information about the different processes and associated structural changes in MOFs. In the last few decades, there has been phenomenal growth in the publications on MOFs containing insights from Raman spectroscopy. Such studies have helped the research community in identifying the adsorption sites, defect sites, structural or spin transitions, reaction centers, intermediates, etc. In this review, we present the current research status of Raman spectroscopy in probing the structure, guest adsorption, catalytic activity, and reaction mechanisms of MOFs, and their application in energy storage and SERS detection. We highlight the advancements in the Raman spectroscopy technique that have facilitated in situ studies in atmosphere as well as various chemical environments. We briefly discuss the relevance of computational studies in understanding phonon modes and predicting the stability of MOFs. Although this review is particularly focussed on works related to Raman spectroscopy of MOFs, we do discuss infrared studies on MOFs, where such results or analyses are missing from the Raman studies. These discussions have been provided with the intent to develop similar analysis techniques or methods in Raman spectroscopy research.

Interscapular pain with Chiari Type I malformation attributed to atypical spinal accessory neuralgia.

BACKGROUND: The spinal accessory nerve (XI) is traditionally considered a motor nerve. However, as some studies have documented the presence of nociceptive fibers in XI, vascular XI neural compression may lead to an atypical neuralgia. CASE DESCRIPTION: A 27-year-old male presented with a Chiari Type I malformation contributing to interscapular pain. Following a posterior fossa and microvascular decompression of XI, the patient improved, thus confirming the underlying diagnosis of a XI atypical neuralgia. CONCLUSION: Unilateral, posterior-interscapular deep pain may be due to an atypical spinal accessory nerve (XI) neuralgia rather than a Chiari Type I malformation or syrinx. Posterior fossa decompression, subpial tonsillar resection, and XI nerve microvascular decompression resolved this patient's complaints. In the future, CTA or MRA vascular studies along with a balanced steady-state gradient echo MRI sequence would be better to document the presence of XI nerve neurovascular compromise.

Photocatalytic Surface Restructuring in Individual Silver Nanoparticles.

Light absorption and scattering by metal nanoparticles can drive catalytic reactions at their surface via the generation of hot charge carriers, elevated temperatures, and focused electromagnetic fields. These photoinduced processes can substantially alter the shape, surface structure, and oxidation state of surface atoms of the nanoparticles and therefore significantly modify their catalytic properties. Information on such local structural and chemical change in plasmonic nanoparticles is however blurred in ensemble experiments, due to the typical large heterogeneity in sample size and shape distributions. Here, we use single-particle dark-field and Raman scattering spectroscopy to elucidate the reshaping and surface restructuring of individual silver nanodisks under plasmon excitation and during photocatalytic CO2 hydrogenation. We show that silver nanoparticles reshape significantly in inert N2 atmosphere, due to photothermal effects. Furthermore, by collecting the inelastic scattering during laser irradiation in a reducing gas environment, we observe intermittent light emission from silver clusters transiently formed at the nanoparticle surface. These clusters are likely to modify the photocatalytic activity of silver nanodisks and to enable detection of reaction products by enhancing their Raman signal. Our results highlight the dynamic nature of the catalytic surface of plasmonic silver nanoparticles and demonstrate the power of single-particle spectroscopic techniques to unveil their structure-activity relationship both in situ and in real time.

Plasmon-driven synthesis of individual metal@semiconductor core@shell nanoparticles.

Most syntheses of advanced materials require accurate control of the operating temperature. Plasmon resonances in metal nanoparticles generate nanoscale temperature gradients at their surface that can be exploited to control the growth of functional nanomaterials, including bimetallic and core@shell particles. However, in typical ensemble plasmonic experiments these local gradients vanish due to collective heating effects. Here, we demonstrate how localized plasmonic photothermal effects can generate spatially confined nanoreactors by activating, controlling, and spectroscopically following the growth of individual metal@semiconductor core@shell nanoparticles. By tailoring the illumination geometry and the surrounding chemical environment, we demonstrate the conformal growth of semiconducting shells of CeO2, ZnO, and ZnS, around plasmonic nanoparticles of different morphologies. The shell growth rate scales with the nanoparticle temperature and the process is followed in situ via the inelastic light scattering of the growing nanoparticle. Plasmonic control of chemical reactions can lead to the synthesis of functional nanomaterials otherwise inaccessible with classical colloidal methods, with potential applications in nanolithography, catalysis, energy conversion, and photonic devices.

In situ formation of catalytically active graphene in ethylene photo-epoxidation.

Ethylene epoxidation is used to produce 2 × 107 ton per year of ethylene oxide, a major feedstock for commodity chemicals and plastics. While high pressures and temperatures are required for the reaction, plasmonic photoexcitation of the Ag catalyst enables epoxidation at near-ambient conditions. Here, we use surface-enhanced Raman scattering to monitor the plasmon excitation-assisted reaction on individual sites of a Ag nanoparticle catalyst. We uncover an unconventional mechanism, wherein the primary step is the photosynthesis of graphene on the Ag surface. Epoxidation of ethylene is then promoted by this photogenerated graphene. Density functional theory simulations point to edge defects on the graphene as the sites for epoxidation. Guided by this insight, we synthesize a composite graphene/Ag/α-Al2O3 catalyst, which accomplishes ethylene photo-epoxidation under ambient conditions at which the conventional Ag/α-Al2O3 catalyst shows negligible activity. Our finding of in situ photogeneration of catalytically active graphene may apply to other photocatalytic hydrocarbon transformations.

Watching Visible Light-Driven CO2 Reduction on a Plasmonic Nanoparticle Catalyst.

Photocatalytic reduction of carbon dioxide (CO2) by visible light has the potential to mimic plant photosynthesis and facilitate the renewable production of storable fuels. Accomplishing desirable efficiency and selectivity in artificial photosynthesis requires an understanding of light-driven pathways on photocatalyst surfaces. Here, we probe with single-nanoparticle spatial resolution the dynamics of a plasmonic silver (Ag) photocatalyst under conditions of visible light-driven CO2 reduction. In situ surface-enhanced Raman spectroscopy captures discrete adsorbates and products formed dynamically on single photocatalytic nanoparticles, most prominent among which is a surface-adsorbed hydrocarboxyl (HOCO*) intermediate critical to further reduction of CO2 to carbon monoxide (CO) and formic acid (HCOOH). Density functional theory simulations of the captured adsorbates reveal the mechanism by which plasmonic excitation activates physisorbed CO2 leading to the formation of HOCO*, indicating close interplay between photoexcited states and adsorbate/metal interactions.

Nano-morphology induced additional surface plasmon resonance enhancement of SERS sensitivity in Ag/GaN nanowall network.

The GaN nanowall network, formed by opening the screw dislocations by kinetically controlled MBE growth, possesses a large surface and high conductivity. Sharp apexed nanowalls show higher surface electron concentration in the band-tail states, in comparison to blunt apexed nanowalls. Uncapped silver nanoparticles are vapor deposited on the blunt and sharp GaN nanowall networks to study the morphological dependence of band-edge plasmon-coupling. Surface enhanced Raman spectroscopy studies performed with a rhodamine 6G analyte on these two configurations clearly show that the sharp nanowall morphology with smaller Ag nanoparticles shows higher enhancement of the Raman signal. A very large enhancement factor of 2.8 × 10(7) and a very low limit of detection of 10(-10) M is observed, which is attributed to the surface plasmon resonance owing to the high surface electron concentration on the GaN nanowall in addition to that of the Ag nanoparticles. The significantly higher sensitivity with same-sized Ag nanoparticles confirms the unconventional role of morphology-dependent surface charge carrier concentration of GaN nanowalls in the enhancement of Raman signals.

Temperature induced structural transformations and gas adsorption in the zeolitic imidazolate framework ZIF-8: a Raman study.

Here we have used Raman spectroscopy to investigate molecular level changes in the zeolitic imidazolate framework ZIF-8 (a prototypical zeolite-like porous metal organic framework) as a function of temperature. Temperature dependent Raman spectra suggest that at low temperature the softening of the C-H stretching frequencies is due to the decrease in steric hindrance between the methyl groups of methyl imidazole. The larger separation between the methyl groups opens the window for increased nitrogen and methane uptake at temperatures below 153 K. The appearance of Raman bands at 2323 cm(-1) and 2904 cm(-1) at or below 153 K in ZIF-8 are characteristic signatures of the adsorbed nitrogen and methane gases respectively. Nanoscale ZIF-8 uptakes more molecules than bulk ZIF-8, and as a result we could provide evidence for encaged CO2 at 203 K yielding its Raman mode at 1379 cm(-1).

Unusual room temperature CO2 uptake in a fluoro-functionalized MOF: insight from Raman spectroscopy and theoretical studies.

We herein report an unusual CO(2) adsorption behavior in a fluoro-functionalized MOF {[Zn(SiF(6))(pyz)(2)]·2MeOH}(n) (1) with a 1D channel system, which is made up of pyrazine and SiF(6)(2-) moieties. Surprisingly, desolvated 1 (1') adsorbs higher amounts of CO(2) at 298 K than at 195 K, which is in contrast to the usual trend. Combined Raman spectroscopic and theoretical studies reveal that slanted pyrazine rings in 1' with an angle of 17.2° with respect to the (200) Zn(II)-Si plane at low temperature block the channel windows and thus reduce the uptake amount.

New Nano Architecture for SERS Applications.

Silver silica gold sandwich nanoparticles were synthesized by a multistep seeded growth process and were characterized by UV-vis spectroscopy, transmission electron microscopy, and X-ray diffraction. Gold islands allow passage of light through the crevices into the silica layer, and the silver core-silica shell behaves like a mirror, thus reflecting the light incident on it. These structures facilitate light amplification due to mixing of light waves from the multiple reflections. Sandwich nanoparticles show SERS enhancement of ∼10(6). This enhancement factor is 6-fold larger in magnitude than that of similar nanoparticles without the silver core under identical experimental conditions.