38 research outputs found
Prato Reaction of M<sub>3</sub>N@<i>I</i><sub><i>h</i></sub>‑C<sub>80</sub> (M = Sc, Lu, Y, Gd) with Reversible Isomerization
The 1,3-dipolar cycloaddition of an azomethine ylide
(Prato reaction)
with M<sub>3</sub>N@<i>I</i><sub><i>h</i></sub>-C<sub>80</sub> (denoted as M<sub>3</sub>N@C<sub>80</sub>; M = Sc,
Lu, Y, Gd) was carried out to obtain fulleropyrrolidinebis(carboxylic
acid) derivatives as scaffolds for the preparation of various functionalized
M<sub>3</sub>N@C<sub>80</sub> materials. The formation of two monoadduct
isomers (the [6,6]- and [5,6]-adducts) were detected by HPLC and identified
by NMR and vis/NIR spectroscopies. In each Prato reaction with M<sub>3</sub>N@C<sub>80</sub>, the initial addition gave a [6,6]-adduct
of the <i>I</i><sub><i>h</i></sub>-C<sub>80</sub> cage, and subsequently, a [5,6]-adduct was obtained by complete
or partial thermal isomerization via a rearrangement reaction. The
reaction rate of the latter thermal conversion of the adducts was
dependent on the size of the metal cluster inside C<sub>80</sub>,
and interestingly, in the reactions of Y<sub>3</sub>N@C<sub>80</sub> and Gd<sub>3</sub>N@C<sub>80</sub>, this conversion was found to
be reversible for the first time. Detailed kinetic studies provided
the enthalpy and entropy barriers for the reactions of the adducts
of Lu<sub>3</sub>N@C<sub>80</sub>, Y<sub>3</sub>N@C<sub>80</sub>,
and Gd<sub>3</sub>N@C<sub>80</sub>. The utility of the obtained Prato
adducts was confirmed by preparation of a highly water-soluble Gd<sub>3</sub>N@C<sub>80</sub> derivative
Covalent Surface Modification of Lipid Nanoparticles by Rapid Potassium Acyltrifluoroborate Amide Ligation
ISSN:0743-7463ISSN:1520-582
Effect of Temperature and Solvent on the Structure of Amide Cavitands
ISSN:0018-019XISSN:1522-267
Micelle vs. vesicle formation controlled by distal functionalization of C-60-PEG conjugates
ISSN:2050-7518ISSN:2050-750
C<sub>60</sub> Pyrrolidine Bis-carboxylic Acid Derivative as a Versatile Precursor for Biocompatible Fullerenes
A C<sub>60</sub> Prato derivative
with bis-<sup><i>t</i></sup>Bu ester was prepared as a stable
and convenient scaffold for
the development of fullerene derivatives such as water-soluble C<sub>60</sub>–PEG conjugates, fulleropeptides <i>via</i> solid phase synthesis, and bis-functionalized C<sub>60</sub>
Essential factors for control of the equilibrium in the reversible rearrangement of M3N@Ih-C80 fulleropyrrolidines: Exohedral functional groups versus endohedral metal clusters
The effects of exohedral moieties and endohedral metal clusters on the isomerization of M3N@Ih-C80 products from the Prato reaction through [1,5]-sigmatropic rearrangement were systematically investigated by using three types of fulleropyrrolidine derivatives and four different endohedral metal clusters. As a result, all types of derivatives provided the same ratios of the isomers for a given trimetallic nitride template (TNT) as the thermodynamic products, thus indicating that the size of the endohedral metal clusters inside C80 was the single essential factor in determining the equilibrium between the [6,6]-isomer (kinetic product) and the [5,6]-isomer. In all the derivatives, the [6,6]- and [5,6]-Prato adducts with larger metal clusters, such as Y3N and Gd3N, were equally stable, which is in good agreement with DFT calculations. The reaction rate of the rearrangement was dependent on both the substituent of exohedral functional groups and the endohedral metal-cluster size. Further DFT calculations and 13C NMR spectroscopic studies were employed to rationalize the equilibrium in the rearrangement between the [6,6]- and [5,6]-fulleropyrrolidine
Infants' looking-time data and Figures
Infants' mean-percentile fixation duration on each of the face types for figures 1 and
Infants prefer the faces of strangers or mothers to morphed faces : an uncanny valley between social novelty and familiarity
母親と他人の狭間 : 赤ちゃんが示す「不気味の谷」現象を発見.京都大学プレスリリース.2012-06-13.The "uncanny valley" response is a phenomenon involving the elicitation of a negative feeling and subsequent avoidant behaviour in human adults and infants as a result of viewing very realistic humanlike robots or computer avatars. It is hypothesised that this uncanny feeling occurs because the realistic synthetic characters elicit the concept of "human" but fail to satisfy it. Such violations of our normal expectations regarding social signals generate a feeling of unease. This conflict-induced uncanny valley between mutually exclusive categories (human and synthetic agent) raises a new question: could an uncanny feeling be elicited by other mutually exclusive categories, such as familiarity and novelty? Given that infants prefer both familiarity and novelty in social objects, we address this question as well as the associated developmental profile. Using the morphing technique and a preferential-looking paradigm, we demonstrated uncanny valley responses of infants to faces of mothers (i.e., familiarity) and strangers (i.e., novelty). Furthermore, this effect strengthened with the infant’s age. We excluded the possibility that infants detect and avoid traces of morphing. This conclusion follows from our finding that the infants equally preferred strangers’ faces and the morphed faces of two strangers. These results indicate that an uncanny valley between familiarity and novelty may accentuate the categorical perception of familiar and novel objects