Synthesis and supramolecular properties of regioisomers of mononaphthylallyl derivatives of γ-cyclodextrin

Monosubstituted derivatives of γ-cyclodextrin (γ-CD) are suitable building blocks for supramolecular polymers, and can also serve as precursors for the synthesis of other regioselectively monosubstituted γ-CD derivatives. We prepared a set of monosubstituted 2I-O-, 3I-O-, and 6I-O-(3-(naphthalen-2-yl)prop-2-en-1-yl) derivatives of γ-CD using two different methods. A key step of the first synthetic procedure is a cross-metathesis between previously described regioisomers of mono-O-allyl derivatives of γ-CD and 2-vinylnaphthalene which gives yields of about 16–25% (2–5% starting from γ-CD). To increase the overall yields, we have developed another method, based on a direct alkylation of γ-CD with 3-(naphthalen-2-yl)allyl chloride as the alkylating reagent. Highly regioselective reaction conditions, which differ for each regioisomer in a used base, gave the monosubstituted isomers in yields between 12–19%. Supramolecular properties of these derivatives were studied by DLS, ITC, NMR, and Cryo-TEM

The topography of rods, cones and intrinsically photosensitive retinal ganglion cells in the retinas of a nocturnal (<i>Micaelamys namaquensis</i>) and a diurnal (<i>Rhabdomys pumilio</i>) rodent - Fig 2

<p>Immunolabelling of melanopsin positive ganglion cells in <i>Micaelamys namaquensis</i> (A, C) and <i>Rhabdomys pumilio</i> (B, D). (A, B) Flattened retinae showing ipRGCs dendritic arbors with beaded varicosities. The upper right insets show putative M2 type ipRGCs, which were faintly labelled and had larger somata. (C, D) Vertical sections of the retina demonstrating that the somata of ipRGCs are situated in the GCL with dendrites stratifying in the outermost margin (OFF sublamina) of the IPL. GCL, ganglion cell layer; INL, inner nuclear layer; IPL, inner plexiform layer; ONL, outer nuclear layer; OPL, outer plexiform layer; R/C, outer segments of rods and cones. The binding sites of the primary antibodies were visualized by a peroxidase anti-peroxidase reaction (diaminobenzidine staining) in (A–C) and by Alexa 488 conjugated secondary antibody in (D). Scale bars; 100 μm.</p

The topography of rods, cones and intrinsically photosensitive retinal ganglion cells in the retinas of a nocturnal (<i>Micaelamys namaquensis</i>) and a diurnal (<i>Rhabdomys pumilio</i>) rodent - Fig 5

<p>Topographical map of the S-cone (left) and M/L-cone density distribution (right) in <i>Micaelamys namaquensis</i>. The filled circles indicate cone density; the irregular outline that is more or less in the centre of the retina indicates the position of the optic nerve head. The dashed line separating the central retina from the peripheral retinal regions designates the areas that were used to calculate photoreceptor ratios between the central and the peripheral retina. D, dorsal; V, ventral; T, temporal; N, nasal.</p

The topography of rods, cones and intrinsically photosensitive retinal ganglion cells in the retinas of a nocturnal (<i>Micaelamys namaquensis</i>) and a diurnal (<i>Rhabdomys pumilio</i>) rodent - Fig 3

<p>Topographical map of the rod density distribution in <i>Rhabdomys pumilio</i> (left) and <i>Micaelamys namaquensis</i> (right). The filled circles indicate rod density; the irregular outline that is more or less in the center of the retina indicates the position of the optic nerve head. The dashed line separating the central retina from the peripheral retinal regions designates the areas that were used to calculate photoreceptor ratios between the central and the peripheral retina. D, dorsal; V, ventral; T, temporal; N, nasal.</p

The topography of rods, cones and intrinsically photosensitive retinal ganglion cells in the retinas of a nocturnal (<i>Micaelamys namaquensis</i>) and a diurnal (<i>Rhabdomys pumilio</i>) rodent - Fig 1

<p>Identification of rods and cones in flat mounted retinae of <i>Rhabdomys pumilio</i> (A–F) and <i>Micaelamys namaquensis</i> (G–I). (A) The retinal photoreceptor mosaic at the level of the inner segments. (B, C) Rod opsin labelled with AO antibody (mid-peripheral retina), the focus is on the transition between rod inner and outer segments (B), and rod outer segments (C). (D, E) Double immunofluorescence labelling of M/L cone opsin (in green) and S-cone opsin (in red). Note that cone densities are much higher in the ventral part of central retina (D) when compared to peripheral retina (E). (F) Higher power photomicrograph showing S-cone densities in central retina. Identification of photoreceptors in <i>M</i>. <i>namaquensis</i> (G–I). (G) Rod opsin labelled with RhoD2 antibody (peripheral retina), the focus is on rod outer segments. (H) Double immunofluorescence labelling of M/L cone opsin (in green) and S-cone opsin (in red) in central retina. (I) Triple immunofluorescence labelling of all cones (PNA labelling, in magenta), M/L-cone opsin (in green) and S-cone opsin (in red) in the central retina. Note that dual cones were not detected in either of the two species and that <i>R</i>. <i>pumilio</i> has much higher cone densities than <i>M</i>. <i>namaquensis</i>. Scale bars; 10 <i>μ</i>m (A–C, F), 50 <i>μ</i>m (D, E, G–I).</p

The topography of rods, cones and intrinsically photosensitive retinal ganglion cells in the retinas of a nocturnal (<i>Micaelamys namaquensis</i>) and a diurnal (<i>Rhabdomys pumilio</i>) rodent - Fig 4

<p>Topographical map of the S-cone (left) and M/L-cone density distribution (right) in <i>Rhabdomys pumilio</i>. The filled circles indicate cone density; the irregular outline that is more or less in the centre of the retina indicates the position of the optic nerve head. The dashed line separating the central retina from the peripheral retinal regions designates the areas that were used to calculate photoreceptor ratios between the central and the peripheral retina. D, dorsal; V, ventral; T, temporal; N, nasal.</p

The topography of rods, cones and intrinsically photosensitive retinal ganglion cells in the retinas of a nocturnal (<i>Micaelamys namaquensis</i>) and a diurnal (<i>Rhabdomys pumilio</i>) rodent - Fig 6

<p>Topographical distribution of melanopsin positive retinal ganglion cells (ipRGCs) in whole mounted retina of <i>Micaelamys namaquensis</i> (left) and <i>Rhabdomys pumilio</i> (right); each dot represents one ipRGC. The enlarged retinal segments (in the top two rectangles) display camera lucida drawings of the photoreceptive nets that are formed the ipRGCs and their overlapping dendrites; the beaded appearance of the dendrites is not shown.</p

List of primary antibodies used in the present study.

<p>List of primary antibodies used in the present study.</p