Apoptotic Cell Membrane-Inspired Polymer for Immunosuppression

Apoptotic cell death serves important roles in homeostasis by eliminating dangerous, damaged, or unnecessary cells without causing an inflammatory response by externalizing phosphatidylserine to the outer leaflet in the phospholipid bilayer. In this study, we newly designed apoptotic cell membrane-inspired monomer and polymer which have the phosphoryl serine group as the anti-inflammatory functional moiety and demonstrate here for the first time that administration of an apoptotic cell membrane-inspired phosphorylserine polymer can protect murine macrophages (RAW 264.7) from lipopolysaccharide-induced inflammation. Interestingly, statistical copolymers with phosphorylcholine monomer that mimicked more precisely the apoptotic cell membrane result in more effective suppression of macrophage activation. This study provides new insights into the rational design of effective polymeric materials for anti-inflammatory therapies

Highly Fluorescent Slipped-Cofacial Phthalocyanine Dimer as a Shallow Inclusion Complex with α-Cyclodextrin

Supramolecular control of the π-stacked configuration of aqueous phthalocyanine (Zn­[Pc­(SO₃)₄]) was achieved, allowing organization of a J-type slipped-cofacial dimer with per-<i>O</i>-methylated α-cyclodextrin (TMe-α-CDx) by the aid of host–guest interactions. Pristine Zn­[Pc­(SO₃)₄] forms nonfluorescent face-to-face aggregates in water. The π-stacked configuration was controlled in the slipped-cofacial dimer, which was formed as a shallow inclusion complex with TMe-α-CDx, giving remarkably enhanced fluorescence with a very small Stokes shift. Organization of the J-type slipped-cofacial dimer as a 2:2 Zn­[Pc­(SO₃)₄]–TMe-α-CDx complex was achieved through π-stacking of the unencapsulated segment of Zn­[Pc­(SO₃)₄] shallowly encapsulated by a small TMe-α-CDx cavity

Synthesis and Properties of [7]Helicene-like Compounds Fused with a Fluorene Unit

[7]­Helicene-like compounds with a fluorene unit were successfully synthesized using a platinum-catalyzed double cyclization reaction. Crystal structures and photophysical properties of these compounds were also studied. In particular, they were found to exhibit a high fluorescence quantum yield and a relatively large <i>g</i> value (dissymmetric factor) of circularly polarized luminescence (CPL) for small molecules

Time-Resolved Observation of Chiral-Index-Selective Wrapping on Single-Walled Carbon Nanotube with Non-Aromatic Polysilane

In the present paper, we ascertain two novel findings on chiral-index-selective binding/separating of single-walled carbon nanotubes (SWNTs) with a nonaromatic polymer, poly­(dialkylsilane) (PSi). PSi is a typical σ-conjugated polymer, composed of alkyl side chains attached to the silicon (Si)-catenated main chain. First, PSi’s with linear alkyl side chains showed significant diameter-selective wrapping for SWNTs with ca. 0.9 nm in diameter, resulting in the selective separation of (7,6) and (9,4) SWNTs. Its driving force was demonstrated to be cooperative CH−π interactions among the alkyl side chains of PSi’s and the curved graphene of SWNTs. Second, the dynamic wrapping behavior of PSi’s onto SWNTs was elucidated with time-resolved UV spectroscopy. Highly anisotropic UV absorption of PSi along the Si main chain was utilized as a “chromophoric indicator” to monitor the global/local conformations, which enabled us to track kinetic structural changes of PSi’s on SWNTs. Consequently, we concluded that upon wrapping, flexible/helical PSi with an average dihedral angle (φ) of 145° and Kuhn’s segment length (λ^–1) of 2.6 nm interconverted to the more stiffer/planar conformation with 170° and λ^–1 of 7.4 nm. Furthermore, through kinetic analyses of the time-course UV spectra, we discovered the fact that PSi’s involve three distinct structural changes during wrapping. That is, (i) the very fast adsorption of several segments within dead time of mixing (<30 ms), following (ii) the gradual adsorption of loosely wrapped segments with the half-maximum values (τ₁) of 31.4 ms, and (iii) the slow rearrangement of the entire chains with τ₂ of 123.1 ms, coupling with elongation of the segment lengths. The present results may be useful for rational design of polymers toward chiral-index-selective binding/separating of desired (<i>n</i>,<i>m</i>) SWNTs

Koopmans’ Theorem-Compliant Long-Range Corrected (KTLC) Density Functional Mediated by Black-Box Optimization and Data-Driven Prediction for Organic Molecules

Density functional theory (DFT) is a significant computational tool that has substantially influenced chemistry, physics, and materials science. DFT necessitates parametrized approximation for determining an expected value. Hence, to predict the properties of a given molecule using DFT, appropriate parameters of the functional should be set for each molecule. Herein, we optimize the parameters of range-separated functionals (LC-BLYP and CAM-B3LYP) via Bayesian optimization (BO) to satisfy Koopmans’ theorem. Our results demonstrate the effectiveness of the BO in optimizing functional parameters. Particularly, Koopmans’ theorem-compliant LC-BLYP (KTLC-BLYP) shows results comparable to the experimental UV-absorption values. Furthermore, we prepared an optimized parameter dataset of KTLC-BLYP for over 3000 molecules through BO for satisfying Koopmans’ theorem. We have developed a machine learning model on this dataset to predict the parameters of the LC-BLYP functional for a given molecule. The prediction model automatically predicts the appropriate parameters for a given molecule and calculates the corresponding values. The approach in this paper would be useful to develop new functionals and to update the previously developed functionals

Facile Synthetic Route to Highly Luminescent Sila[7]helicene

A facile synthetic route to dimethylsila[7]helicene by using a Lewis acid catalyzed double-cyclization reaction for construction of the twisted two phenanthrene moieties is described. Sila[7]helicene exhibited a high fluorescence quantum yield and a realatively large <i>g</i> value (dissymmetric factor) of circularly polarized luminencence (CPL) for small molecules

Facile Synthetic Route to Highly Luminescent Sila[7]helicene

A facile synthetic route to dimethylsila[7]helicene by using a Lewis acid catalyzed double-cyclization reaction for construction of the twisted two phenanthrene moieties is described. Sila[7]helicene exhibited a high fluorescence quantum yield and a realatively large <i>g</i> value (dissymmetric factor) of circularly polarized luminencence (CPL) for small molecules

Koopmans’ Theorem-Compliant Long-Range Corrected (KTLC) Density Functional Mediated by Black-Box Optimization and Data-Driven Prediction for Organic Molecules

Density functional theory (DFT) is a significant computational tool that has substantially influenced chemistry, physics, and materials science. DFT necessitates parametrized approximation for determining an expected value. Hence, to predict the properties of a given molecule using DFT, appropriate parameters of the functional should be set for each molecule. Herein, we optimize the parameters of range-separated functionals (LC-BLYP and CAM-B3LYP) via Bayesian optimization (BO) to satisfy Koopmans’ theorem. Our results demonstrate the effectiveness of the BO in optimizing functional parameters. Particularly, Koopmans’ theorem-compliant LC-BLYP (KTLC-BLYP) shows results comparable to the experimental UV-absorption values. Furthermore, we prepared an optimized parameter dataset of KTLC-BLYP for over 3000 molecules through BO for satisfying Koopmans’ theorem. We have developed a machine learning model on this dataset to predict the parameters of the LC-BLYP functional for a given molecule. The prediction model automatically predicts the appropriate parameters for a given molecule and calculates the corresponding values. The approach in this paper would be useful to develop new functionals and to update the previously developed functionals

Confinement of Single Polysilane Chains in Coordination Nanospaces

Understanding the intrinsic properties of single conducting polymer chains is of interest, largely for their applications in molecular devices. In this study, we report the accommodation of single polysilane chains with hole-transporting ability in porous coordination polymers (PCPs), [Al­(OH)­(L)]_<i>n</i> (<b>1a</b>; L = 2,6-naphthalenedicarboxylate, channel size = 8.5 × 8.5 Ų, <b>1b</b>; L = 4,4′-biphenyldicarboxylate, channel size = 11.1 × 11.1 Ų). Interestingly, the isolation of single polysilane chains increased the values of carrier mobility in comparison with that in the bulk state due to the elimination of the slow interchain hole hopping. Moreover, even when the chains are isolated one another, the main chain conformation of polysilane could be controlled by changing the pore environment of PCPs, as evidenced by Raman spectroscopy, solid-state NMR measurements, and molecular dynamics simulation. Hence, we succeeded in varying the conducting property of single polysilane chains. Additionally, polysilanes have a drawback, photodegradation under ultraviolet light, which should be overcome for the application of polysilanes. It is noteworthy that the accommodation of polysilane in the nanopores did not exhibit photodegradation. These results highlight that PCP–polysilane hybrids are promising candidates for further use in the field of molecular electronics