Induced-fit expansion and contraction of a self-assembled nanocube finely responding to neutral and anionic guests

Induced-fit or conformational selection is of profound significance in biological regulation. Biological receptors alter their conformation to respond to the shape and electrostatic surfaces of guest molecules. Here we report a water-soluble artificial molecular host that can sensitively respond to the size, shape, and charged state of guest molecules. The molecular host, i.e. nanocube, is an assembled structure consisting of six gear-shaped amphiphiles (GSAs). This nanocube can expand or contract its size upon the encapsulation of neutral and anionic guest molecules with a volume ranging from 74 to 535 Å3 by induced-fit. The responding property of this nanocube, reminiscent of a feature of biological molecules, arises from the fact that the GSAs in the nanocubes are connected to each other only through the hydrophobic effect and very weak intermolecular interactions such as van der Waals and cation-π interactions

Signal acquisition and analysis of ambulatory electromyographic recordings for the assessment of sleep bruxism : A scoping review

Background Ambulatory electromyographic (EMG) devices are increasingly being used in sleep bruxism studies. EMG signal acquisition, analysis and scoring methods vary between studies. This may impact comparability of studies and the assessment of sleep bruxism in patients. Objectives (a) To provide an overview of EMG signal acquisition and analysis methods of recordings from limited-channel ambulatory EMG devices for the assessment of sleep bruxism; and (b) to provide an overview of outcome measures used in sleep bruxism literature utilising such devices. Method A scoping review of the literature was performed. Online databases PubMed and Semantics Scholar were searched for studies published in English until 7 October 2020. Data on five categories were extracted: recording hardware, recording logistics, signal acquisition, signal analysis and sleep bruxism outcomes. Results Seventy-eight studies were included, published between 1977 and 2020. Recording hardware was generally well described. Reports of participant instructions in device handling and of dealing with failed recordings were often lacking. Basic elements of signal acquisition, for example amplifications factors, impedance and bandpass settings, and signal analysis, for example rectification, signal processing and additional filtering, were underreported. Extensive variability was found for thresholds used to characterise sleep bruxism events. Sleep bruxism outcomes varied, but typically represented frequency, duration and/or intensity of masticatory muscle activity (MMA). Conclusion Adequate and standardised reporting of recording procedures is highly recommended. In future studies utilising ambulatory EMG devices, the focus may need to shift from the concept of scoring sleep bruxism events to that of scoring the whole spectrum of MMA.Peer reviewe

Induced-fit expansion and contraction of a self-assembled nanocube finely responding to neutral and anionic guests

Induced-fit or conformational selection is of profound significance in biological regulation. Biological receptors alter their conformation to respond to the shape and electrostatic surfaces of guest molecules. Here we report a water-soluble artificial molecular host that can sensitively respond to the size, shape, and charged state of guest molecules. The molecular host, i.e. nanocube, is an assembled structure consisting of six gear-shaped amphiphiles (GSAs). This nanocube can expand or contract its size upon the encapsulation of neutral and anionic guest molecules with a volume ranging from 74 to 535 Å3 by induced-fit. The responding property of this nanocube, reminiscent of a feature of biological molecules, arises from the fact that the GSAs in the nanocubes are connected to each other only through the hydrophobic effect and very weak intermolecular interactions such as van der Waals and cation-π interactions.UTokyo FOCUS Press releases掲載「取り込む分子の大きさ・形・電荷に応答して膨らんだり縮んだりする分子カプセル」＜研究成果＞ URI: https://www.u-tokyo.ac.jp/focus/ja/press/z0109_00048.htmlUTokyo FOCUS Press releases "Don’t underestimate the Force Researchers discover weak chemical interactions hold together box of infinite possibilities" URI: https://www.u-tokyo.ac.jp/focus/en/press/z0508_00014.htm

Sulfoxide-Induced Homochiral Folding of o-OPEs by AgI Templating: Structure and Chiroptical Properties

"This is the peer reviewed version of the following article: Resa, S.; et al. Sulfoxide-Induced Homochiral Folding of o-OPEs by AgI Templating: Structure and Chiroptical Properties. Chemistry a European Journal, 2018, which has been published in final form at http://dx.doi.org/10.1002/chem.201704897 . This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving."A new family of homochiral silver complexes based on carbophilic interactions with ortho-phenyleneethynylene (o-OPE) scaffolds containing up to two silver atoms is described. These compounds represent a unique class of complexes with chirality at the metal. Chiral induction is based on the inclusion of chiral sulfoxides which allow an efficient transfer of chirality to the helically folded o-OPE, leading to CPL and VCD active compounds. In the presence of AgI cation carbophilic interactions dominate, promoting helical structures with a defined helicity. This is one of the very scarce examples of the use of such interactions in the attractive field of abiotic foldamers. The switching event has been extensively studied using different chiroptical techniques including CD, CPL and VCD, also representing one of the few CPL switches described in literature.We thank MINECO (FEDER funded grant CTQ2014-53598-R). Computing Center CINECA, Bologna, Italy, Regione Lombardia for the LISA Grant No. “ChiPhyto: HPL13POZE1” and the “Centro de Supercomputación de la UGR” (UGRGRID) are acknowledged for access to computational facilities. Sandra Resa thanks the MECD for a FPU fellowship

Oxidation Catalysis of Au Nano-Particles Immobilized on Titanium(IV)- and Alkylthiol-Functionalized SBA-15 Type Mesoporous Silicate Supports

Novel Au nano-particle catalysts immobilized on both titanium(IV)- and alkylthiol-functionalized SBA-15 type ordered mesoporous silicate supports were developed. The bi-functionalized SBA-15 type support could be synthesized by a one-pot method. To the synthesized supports, Au was immobilized by the reaction of the alkylthiol groups on the supports with AuCl4−, following reduction with NaBH4. The immobilized amount and the formed structures and the electronic property of the Au species depended on the loading of alkylthiol. The moderate size (2–3 nm) nano particulate Au sites formed on Ti(0.5)-SBASH(0.5) were negatively charged. The aerobic alcohol oxidation activity of the catalysts depended on the loading of alkylthiol and the structure of the Au nano-particles. The non-thiol-functionalized catalyst (Au/Ti(0.5)-SBASH(0)) composed of the large (5–30 nm) and the higher thiol-loaded catalyst (Au/Ti(0.5)-SBASH(8)) composed of the small cationic Au species were almost inactive. The most active catalyst was Au/Ti(0.5)-SBASH(0.5) composed of the electron-rich Au nano-particles formed by the electron donation from the highly dispersed thiol groups. Styrene oxidation activity in the presence of 1-phenylethanol with O2 depended on the loadings of titanium(IV) on the Au/Ti(x)-SBASH(0.5). The titanium(IV) sites trapped the H2O2 generated through the alcohol oxidation reaction, and also contributed to the alkene oxidation by activating the trapped H2O2

Supramolecular Assemblies of Dipyrrolyldiketone Cu^II Complexes

Dipyrrolyldiketones are essential building units of anion-responsive π-electronic molecules and ion-pairing assemblies. Here, we demonstrated that they form complexes with CuII characterized by planar geometries. The solid-state stacking assembled structures, as revealed by single-crystal X-ray analysis, were modulated by the substitution of pyrrole units. The rectangular shapes of the CuII complexes resulted in the formation of mesophases upon introduction of aliphatic chains

Supramolecular Assemblies of Dipyrrolyldiketone CuII Complexes

Dipyrrolyldiketones are essential building units of anion-responsive π-electronic molecules and ion-pairing assemblies. Here, we demonstrated that they form complexes with CuII characterized by planar geometries. The solid-state stacking assembled structures, as revealed by single-crystal X-ray analysis, were modulated by the substitution of pyrrole units. The rectangular shapes of the CuII complexes resulted in the formation of mesophases upon introduction of aliphatic chains