Insights into brain microstructure from the T2 distribution

T2 weighting is particularly sensitive, but notoriously unspecific, to a wide range of brain pathologies. However, careful measurement and analysis of the T2 decay curve from brain tissue promise to provide much improved pathological specificity. In vivo T2 measurement requires accurate 180 pulses and appropriate manipulation of stimulated echoes; the most common approach is to acquire multiple echoes from a single slice. The T2 distribution, a plot of component amplitude as a function of T2, can be estimated using an algorithm capable of fitting a multi-exponential T2 decay with no a priori assumptions about the number of exponential components. T2 distributions from normal brain show peaks from myelin water, intra/extracellular water and cerebral spinal fluid; they can be used to provide estimates of total water content (total area under the T2 distribution) and myelin water fraction (MWF, fractional area under the myelin water peak), a measure believed to be related to myelin content. Experiments on bovine brain suggest that magnetization exchange between water pools plays a minor role in the T2 distribution. Different white matter structures have different MWFs. In normal white matter (NWM), MWF is not correlated with the magnetization transfer ratio (MTR) or the diffusion tensor fractional anisotropy (FA); hence it provides unique information about brain microstructure. Normal-appearing white matter (NAWM) in multiple sclerosis (MS) brain possesses a higher water content and lower MWF than controls, consistent with histopathological findings. Multiple sclerosis lesions demonstrate great heterogeneity in MWF, presumably due to varying myelin contents of these focal regions of pathology. Subjects with schizophrenia were found to have significantly reduced MWF in the minor forceps and genu of the corpus callosum when compared to controls, suggesting that reduced frontal lobe myelination plays a role in schizophrenia. In normal controls, frontal lobe myelination was positively correlated with both age and education; this result was not observed in subjects with schizophrenia. A strong correlation between MWF and the optical density from the luxol fast blue histological stain for myelin was observed in formalin-fixed brain, supporting the use of the MWF as an in vivo myelin marker.     

Orthogonal self-assembly of low molecular weight hydrogelators and surfactants

The concurrent self-assembly of new 1,3,5-trisamide-cyclohexane-based low molecular weight hydrogelators and various surfactants in water leads to the formation of self-assembled fibrillar networks with encapsulated micelles. This prototype system presents an example of orthogonal self-assembly, that is, the independent formation of two different supramolecular structures, each with their own characteristics that coexist within a single system.     

Performance of biodegradable microcapsules of poly(butylene succinate), poly(butylene succinate-co-adipate) and poly(butylene terephthalate-co-adipate) as drug encapsulation systems

Poly(butylene succinate) (PBSu), poly(butylene succinate-co-adipate) (PBSA) and poly(butylene terephthalate-co-adipate) (PBTA) microcapsules were prepared by the double emulsion/solvent evaporation method. The effect of polymer and poly(vinyl alcohol) (PVA) concentration on the microcapsule morphologies, drug encapsulation efficiency (EE) and drug loading (DL) of bovine serum albumin (BSA) and all-trans retinoic acid (atRA) were all investigated. As a result, the sizes of PBSu, PBSA and PBTA microcapsules were increased significantly by varying polymer concentrations from 6 to 9%. atRA was encapsulated into the microcapsules with an high level of approximately 95% EE. The highest EE and DL of BSA were observed at 1% polymer concentration in values of 60 and 37%, respectively. 4% PVA was found as the optimum concentration and resulted in 75% EE and 14% DL of BSA. The BSA release from the capsules of PBSA was the longest, with 10% release in the first day and a steady release of 17% until the end of day 28. The release of atRA from PBSu microcapsules showed a zero-order profile for 2 weeks, keeping a steady release rate during 4 weeks with a 9% cumulative release. Similarly, the PBSA microcapsules showed a prolonged and a steady release of atRA during 6 weeks with 12% release. In the case of PBTA microcapsules, after a burst release of 10% in the first day, showed a parabolic release profile of atRA during 42 days, releasing 36% of atRA.     

IR,Raman, and UV/Vis Spectra of Corannulene for Use in Possible Interstellar Identification

The spectroscopic characterization of corannulene (C₂₀H₁₀) is carried out by several techniques. The high purity of the material synthesized for this study was confirmed by gas chromatography‐mass spectrometry (GC‐MS). During a high‐performance liquid chromatography (HPLC) process, the absorption spectrum of corannulene in the ultraviolet (UV) and visible (vis) ranges is obtained. The infrared (IR) absorption spectrum is measured in CsI pellets, and the Raman scattering spectrum is recorded for pure crystal grains. In addition to room temperature measurements, absorption spectroscopy in an argon matrix at 12 K is also performed in the IR and UV/Vis ranges. The experimental spectra are compared with theoretical Raman and IR spectra and with calculated electronic transitions. All calculations are based on the density functional theory (DFT), either normal or time‐dependent (TDDFT). Our results are discussed in view of their possible application in the search for corannulene in the interstellar medium.     

Spectroscopy of Dibenzorubicene: Experimental Data for a Search in Interstellar Spectra

We report on the characterization of dibenzo[cde,opq]rubicene (C₃₀H₁₄). The molecule was studied in solution at room temperature with absorption spectroscopy in the visible (vis) and ultraviolet (UV) wavelength ranges, and with emission spectroscopy. The infrared (IR), visible, ultraviolet, and vacuum ultraviolet (VUV) absorption spectra of a thin film were measured also at room temperature. In addition, the UV/vis absorption spectrum was measured at cryogenic temperatures using the matrix isolation spectroscopy technique. The interpretation of spectra was supported by theoretical calculations based on semiempirical and ab initio models, as well as on density functional theory. Finally, the results of the laboratory study were compared with interstellar spectra.     

Reaktionen auf der Spur

A new technique, desorption electrospray ionization coupled to mass spectrometry (DESI‐MS), has been used as a tool for reaction analysis. Charged droplets of a reagent are sprayed onto the catalyst, which has previously been deposited on a surface in front of a mass analyzer. The reaction starts as the droplets impact the catalyst on the surface and continues inside secondary microdroplets that are desorbed from the surface. These are directed toward the mass spec inlet. Using this technique, the very first milliseconds of a reaction can be observed. The first example describes the discovery of an extremely short‐lived intermediate in a C‐H amination reaction cycle. Another example describes how DESI‐MS has been used to identify catalyst arrest mechanisms in ruthenium catalyzed C‐H hydroxylation.