From nano to micro: synthesis and optical properties of homogeneous spheroidal gold particles and their superlattices

Iodide ions have been used as an additive to fabricate homogeneous gold spheres with a la carte dimensions, ranging from the nano- (50 nm) to the microscale (ca. 1 μm). Due to the high uniformity and surface functionalization of the produced materials, they undergo spontaneous assembly into organized superlattices upon solvent drying. Thus, optical properties of the particles including localized surface plasmon resonances and surface enhanced Raman scattering (SERS) response, both in solution and organized into superlattices, are also reported.     

Switchable Self‐Assembly of a Bioinspired Alkyl Catechol at a Solid/Liquid Interface: Competitive Interfacial,Noncovalent, and Solvent Interactions

The large tendency of catechol rings to adsorb on surfaces has been studied by STM experiments with molecular resolution combined with molecular‐dynamics simulations. The strong adhesion is due to interactions with the surface and solvent effects. Moreover, the thermodynamic control over the differential adsorption of 1 and the nonanoic solvent molecules has been used to induce a new temperature‐induced switchable interconversion. Two different phases that differ in their crystal packing and the presence of solvent molecules coexist upon an increase or decrease in the temperature. These results open new insight into the behavior of catechol molecules on surfaces and 2D molecular suprastructures.     

Synthesis of 11‐cis‐Retinoids by Hydrosilylation–Protodesilylation of an 11,12‐Didehydro Precursor: Easy Access to 11‐ and 12‐Mono‐ and 11,12‐Dideuteroretinoids

An expeditious, highly efficient approach to 11‐cis‐retinoids was achieved by semihydrogenation of a readily available 11‐yne precursor through a hydrosilylation–protodesilylation protocol. The complete chemo‐, regio‐, and syn‐stereoselectivity of the method also allowed direct access to 11‐ and 12‐monodeutero‐, and 11,12‐dideutero‐11‐cis‐retinoids. The analogous trans series was not accessible by this route, and was synthesized by means of Hiyama coupling.     

Grafted squaramide monoamine nanoparticles as simple systems for sulfate recognition in pure water

New simple systems formed by a chain containing a squaramide function and a quaternised amine group attached to boehmite or silica-coated boehmite nanoparticles are able to discriminate anions in pure water.     

The role of intraoperative magnetic resonance imaging in complex meningioma surgery

Intraoperative magnetic resonance imaging (iMRI) has gained importance in the treatment of gliomas and sellar tumors. In intracranial meningiomas, the extent of surgical tumor removal is one of the most important factors in the prevention of tumor recurrence and patient survival. Complex meningiomas located at the skull base or near eloquent brain regions show higher recurrence rates, morbidity and mortality. The aim of this study was to evaluate whether iMRI contributes to more extensive surgical resection in these tumors. Patients undergoing complex meningioma resection using iMRI from January 2007 to January 2011 were included in this study. The indication for iMRI-guided tumor resection included patients presenting with meningiomas located in the skull base or compressing eloquent brain areas in whom a radical resection was considered to be difficult. Intraoperative 0.15-T MRI scan (PoleStar; Medtronic Navigation, Louisville, CO, USA) was performed before and after maximal possible resection using standard microsurgical and neuronavigation techniques. All patients underwent fluorescence-guided resection. The following data were analyzed: tumor localization, histological grade, Simpson resection grade, duration of the procedure, iMRI scan time, iMRI findings, resection extent based on postresection iMRI, hospitalization time, surgical complications and outcome, and MRI follow-up 2–27 months postoperation. Twenty-seven consecutive patients undergoing complex meningioma resection using iMRI were included. In this series, only one patient (3.4%) underwent resection of tumor remnant after iMRI, although without improvement of the Simpson resection grade. Temporary neurologic deficits were found in 8 patients (27.6%) postoperatively, whereas 11 patients (37.9%) had permanent postoperative neurologic deficits. In one case (3.4%), fatal postoperative bleeding occurred which was not detected by iMRI. Our results show that iMRI has no influence on intraoperative strategy in terms of resection grade or detection of early postoperative complications. The benefits of iMRI in complex meningioma surgery are therefore doubtful; however, it may still prove to be effective in certain subsets of complex meningiomas.     

A remark on homomorphisms from right-angled Artin groups to mapping class groups

We study rigidity properties of certain homomorphisms from right-angled Artin groups to mapping class groups. As an application, we show that if $\Gamma ?\mathrm{Map}(S)$ is a subgroup that contains some power of every Dehn twist, then any injective homomorphism $\Gamma \to \mathrm{Map}(S)$ is a restriction of an automorphism of $\mathrm{Map}(S)$.     

Modeling detergent organization around aquaporin-0 using small-angle X-ray scattering

Solubilization of integral membrane proteins in aqueous solutions requires the presence of amphiphilic molecules like detergents. The transmembrane region of the proteins is then surrounded by a corona formed by these molecules, ensuring a hydrophilic outer surface. The presence of this corona has strongly hampered structural studies of solubilized membrane proteins by small-angle X-ray scattering (SAXS), a technique frequently used to monitor conformational changes of soluble proteins. Through the online combination of size exclusion chromatography, SAXS, and refractometry, we have determined a precise geometrical model of the n-dodecyl β-d-maltopyranoside corona surrounding aquaporin-0, the most abundant membrane protein of the eye lens. The SAXS data were well-fitted by a detergent corona shaped in an elliptical toroid around the crystal structure of the protein, similar to the elliptical shape recently reported for nanodiscs (Skar-Gislinge et al. J. Am. Chem. Soc. 2010, 132, 13713-13722). The torus thickness determined from the curve-fitting protocol is in excellent agreement with the thickness of a lipid bilayer, while the number of detergent molecules deduced from the volume of the torus compares well with those obtained on the same sample from refractometry and mass analysis based on SAXS forward scattering. For the first time, the partial specific volume of the detergent surrounding a protein was measured. The present protocol is a crucial step toward future conformational studies of membrane proteins in solution.