Light Intensity-Selective Photopolymerization and Photoisomerization for Creating Colorful Polymer-Stabilized Cholesteric Liquid Crystal Patterns.

Polymer-stabilized cholesteric liquid crystal (PSCLC) films have been widely studied for their application as sensors, polarizers, and reflective windows. However, the preparation of programmable and colorful patterns based on the structural color is still challenging. Herein, the photochromic CLC mixtures were prepared by adding a photoisomerizable chiral additive (CA) and a photoinitiator in the nematic liquid crystal LC242. Under UV irradiation with weak intensity, photoisomerization of the CA was carried out and photopolymerization was suppressed by oxygen inhibition. With extending the irradiation time, the helical pitch of the CLC film increased and the selective Bragg reflection band tended to redshift. Under strong UV irradiation, oxygen inhibition was overcome and photopolymerization dominates the reaction. Therefore, the colorful-patterned PSCLC films were able to be prepared using masks. The results shown here not only give us a better understanding of the effect of oxygen inhibition but also lay the foundations for practical applications such as decoration and optical devices.

Stereostructure Dependence Phenomenon on the Self-Assembly of Ala-Ala-Ala Lipotripeptides.

A series of lipotripeptide stereoisomers based on alanine were synthesized, and their self-assembling behaviors were studied by means of circular dichroism spectra, ATR-IR, temperature-dependent 1H NMR, and X-ray diffraction patterns. In the mixed solvent of hexafluoroisopropanol/H2O (1/9, v/v), eight lipotripeptides were able to self-assembled into nanoflakes or nanoribbons driven by the hydrophobic association of alkyl chains, intermolecular hydrogen bonding among carboxyl groups at C-terminal and amide groups of alanine moieties in the peptide segment. It was found that the stacking chirality of carbonyl groups was determined by the chirality of alanine residue at C-terminal (i.e., "C-terminal determination" rule). Moreover, our research also highlighted the intermolecular hydrogen bonding on amide groups of each alanine residue, terminal carboxyl as well as the molecular packing structures can be subtly manipulated by changing the stereochemical sequence of peptide segment.

Circularly polarized luminescence from structurally coloured polymer films.

Structurally coloured polymer films with circularly polarized luminescence (CPL) properties were prepared by the photopolymerization of cholesteric liquid crystal mixtures doped with aggregation-induced emission (AIE)-active tetraphenylethylene. The films show good CPL performance with the luminescence dissymmetry factor up to 0.58 and enhanced fluorescence efficiency.

Circularly polarized luminescence of single-handed helical tetraphenylethylene-silica nanotubes.

Two single-handed helical tetraphenylethylene-silica nanotubes with circularly polarized luminescence (CPL) properties and enhanced fluorescence efficiency were fabricated through a supramolecular templating approach using the self-assemblies of chiral gelators as templates. This work provides a facile strategy for constructing CPL-active organic-inorganic hybrid nanomaterials with single-handed helical morphologies.

Helicity of perfluoroalkyl chains controlled by the self-assembly of the Ala-Ala dipeptides.

Four Ala-Ala dipeptides with a perfluoroalkyl chain at the N-terminal were synthesized. They were able to self-assemble into helical nanofibers and/or twisted nanobelts in a mixture of DMSO/H2 O. The handedness of nanofibers and nanobelts was controlled by the chirality of the alanine at the N-terminal. The stacking handedness of the phenylene groups and the helicity of the perfluoroalkyl chain were studied using circular dichroism spectroscopy and vibrational circular dichroism, respectively. The chirality of the alanine at N-terminal controlled the stacking handedness of the neighboring phenylene groups. Moreover, due to the low potential barrier between M- and P-helices of the perfluorocarbon chain, the handedness of the organic self-assemblies eventually controlled the helicity of the perfluorocarbon chain. X-ray diffraction indicated that a lamellar structure was formed by the dimers of the dipeptides.

bola-Type Ala-Ala Dipeptides: Odd-Even Effect in Molecular Packing Structures.

A series of bola-type Ala-Ala dipeptides with different alkylene bridges (n = 10-15) were synthesized. In methanol, the molecules with even-numbered carbon bridges self-assembled into twisted nanoribbons, while those with odd-numbered carbon bridges self-assembled into straight belts. The morphology displays a pronounced odd-even dependence upon the number of carbons (n) in the connecting alkylene bridge. The circular dichroism spectra of the self-assemblies showed that molecules with even- and odd-numbered carbon bridges stacked in different structures. FT-IR spectra indicated that the dipeptides with even-numbered carbon bridges formed hydrogen bonds between the amide group and carboxyl ester group, while those with odd-numbered carbon bridges formed hydrogen bonds only between the amide groups. X-ray diffraction patterns revealed that molecules with odd- and even-numbered carbon bridges stacked in monoclinic and triclinic structures, respectively.

Allosteric Inhibition of Ubiquitin-like Modifications by a Class of Inhibitor of SUMO-Activating Enzyme.

Ubiquitin-like (Ubl) post-translational modifications are potential targets for therapeutics. However, the only known mechanism for inhibiting a Ubl-activating enzyme is through targeting its ATP-binding site. Here we identify an allosteric inhibitory site in the small ubiquitin-like modifier (SUMO)-activating enzyme (E1). This site was unexpected because both it and analogous sites are deeply buried in all previously solved structures of E1s of ubiquitin-like modifiers (Ubl). The inhibitor not only suppresses SUMO E1 activity, but also enhances its degradation in vivo, presumably due to a conformational change induced by the compound. In addition, the lead compound increased the expression of miR-34b and reduced c-Myc levels in lymphoma and colorectal cancer cell lines and a colorectal cancer xenograft mouse model. Identification of this first-in-class inhibitor of SUMO E1 is a major advance in modulating Ubl modifications for therapeutic aims.

Alignment of twisted nanoribbons formed by C17H35CO-Val-Ala sodium salts.

C17H35CO-l-Val-l-Ala and C17H35CO-d-Val-d-Ala sodium salts can form physical gels in water, and self-assemble into right- and left-handed twisted nanoribbons, respectively. FT-IR and 1H NMR spectra indicate that the H-bonding between the neighboring valine residues and electrostatic interactions of carboxylate groups play important roles in the formation of helical nanoribbons. Circular dichroism characterization and theoretical chemical calculations indicate that the dipeptide segments pack in a helical manner. X-ray diffraction patterns and theoretical chemical simulations indicate an interdigitated bilayer structure. The hydrogels exhibit a thixotropic behavior. The twisted nanoribbons are able to align under directional force.

Left-handed helical polymer resin nanotubes prepared by using N-palmitoyl glucosamine.

Although the preparation of single-handed helical inorganic and hybrid organic-inorganic nanotubes is well developed, approaches to the formation of single-handed organopolymeric nanotubes are limited. Here, left-handed helical m-phenylenediamine-formaldehyde resin and 3-aminophenol-formaldehyde resin nanotubes were prepared by using N-palmitoyl glucosamine that can self-assemble into left-handed twisted nanoribbons in a mixture of methanol and water. In the reaction mixture, the helical pitch of the nanoribbons decreased with increasing reaction time. The resin nanotubes were obtained after removing the N-palmitoyl glucosamine template, and circular dichroism spectroscopy indicated that the organopolymeric nanotubes had optical activity. Carbonaceous nanotubes were then prepared by carbonization of the 3-aminophenol-formaldehyde resin nanotubes.

Aggregation-Induced Chirality: Twist and Stacking Handedness of the Biphenylene Groups of n-C12H25O-BP-CO-Ala-Ala Dipeptides.

In mixtures of water and dimethyl sulfoxide, 4'-(n-dodecyloxy)-1,1'-biphenyl-4-carbonyl Ala-Ala dipeptides can self-assemble into tubular structures that are formed by coiled nanoribbons. The twist and stacking handedness of biphenylene groups were studied using circular dichroism and confirmed by theoretical chemical calculations. The handedness of the coiled nanoribbons and the stacking handedness of biphenylene groups are controlled by the chirality of alanine at the C-terminus, whereas the twist handedness of biphenylene groups is determined by the chirality of alanine at the N-terminus. 1H NMR spectra indicated that the hydrogen bond formed by the N-H group of alanine at the N-terminus plays an important role in the formation of organic self-assemblies. On the basis of small-angle X-ray scattering characterization, a dimer structure was proposed to form through the terminal COOH groups.

Chirality-Driven Parallel and Antiparallel ß-Sheet Secondary Structures of Phe-Ala Lipodipeptides.

Four Phe-Ala lipodipeptides with different stereochemical structures are observed to self-assemble into twisted nanoribbons in water. The handedness of the twisted nanoribbons is controlled by the chirality of the phenylalanine near the alkyl chain, while the stacking handedness of the phenyl and carbonyl groups is determined by the alanine at the C-terminal. The homochiral and heterochiral lipodipeptides self-assemble into parallel and antiparallel ß-sheet structures, respectively. The 1H NMR, FTIR, X-ray diffraction, and circular dichroism characterizations indicate that these phenomena are mainly driven by the interaction between neighboring phenyl groups and H-bonding among the amide groups.

Synthesis of Helical Phenolic Resin Bundles through a Sol-Gel Transcription Method.

Chiral and helical polymers possess special helical structures and optical property, and may find applications in chiral catalysis and optical devices. This work presents the preparation and formation process of helical phenolic resins through a sol-gel transcription method. A pair of bola-type chiral low-molecular-weight gelators (LMWGs) derived from valine are used as templates, while 2,4-dihydroxybenzoic acid and formaldehyde are used as precursors. The electron microscopy images show that the phenolic resins are single-handed helical bundles comprised of helical ultrafine nanofibers. The diffused reflection circular dichroism spectra indicate that the helical phenolic resins exhibit optical activity. A possible formation mechanism is proposed, which shows the co-assembly of the LMWGs and the precursors.

Control of the Handedness of Self-assemblies of Dipeptides by the Chirality of Phenylalanine and Steric Hindrance of Phenylglycine.

Eight dipeptides, composed of phenylalanine and phenylglycine, that are able to self-assemble into twisted nanoribbons in deionized water are synthesized. The handedness of the nanoribbons is controlled by the chirality of the phenylalanine and the steric hindrance owing to the phenyl group of the phenylglycine. When the phenylalanine is at the C-terminal, π-π stacking by the phenyl groups, hydrogen bonding by the NH group of the phenylalanine, and hydrophobic associations of the alkyl chains control the stacking of the molecules. When phenylglycine is at the C-terminal, the chiral π-π stacking by the phenyl groups of the phenylalanines is suppressed. The hydrogen bonds formed by the NH groups of the phenylalanines had a greater contribution on forming organic self-assemblies than those formed by the NH groups of the phenylglycines.

Preparation of Carbonaceous Hemispheres Using a Hard Templating Approach.

Silica spheres prepared using a Stöber method were covered with 4,4'-biphenylene-bridged polybissilsesquioxane to form a core-shell structure. After carbonization, and the removal of the silica, carbonaceous hemispheres were obtained. The hemispheres were formed because of the collapse and shrinkage of the hollow spheres. The obtained samples were characterized using field-emission scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, X-ray diffraction, and nitrogen sorption measurements. The carbon was amorphous. Large numbers of micropores were identified in the hemispheres. The micropores were formed because of the removal of the silica. Spheres with a rattle-type structure were also found during the formation of the hollow carbonaceous spheres.

Achiral Polydialkylsilane Aggregates That Record Stirring Direction.

Achiral polysilane aggregates can recognize the chirality of low-molecular-weight compounds. It was found that they can also record the stirring direction. Poly(n-decyl-2-methylpropylsilane), poly(n-nonyl-2-methylpropylsilane), poly(n-decyl-2-ethylbutylsilane), and poly(n-decyl-(S)-2-methylbutylsilane) aggregates were prepared in a mixture of tetrahydrofuran/isopropanol. Although the optical activity of the aggregates of the polysilane with chiral side chains was not tunable by changing the direction of the vortex flow, that of the aggregates of the optically inactive polysilane had a strong relationship to the direction, time, and rate of the vortex flow. The chiral stacked polysilanes were proposed to exist at the surfaces of the aggregates. The optically inactive polysilanes also exhibited optical activity under shear force with a distinct signal in the linear dichroism (LD) spectra of the achiral aggregates in vortex flows. However, the LD signals did not have a significant influence on the circular dichroism signals.

Helical Polybissilsesquioxane Bundles Prepared Using a Self-Templating Approach.

Polybissilsesquioxanes with single-handed helical morphologies attracted much attention during the last decade, which could be applied as asymmetric catalysts and chiral stationary phases. Herein, a pair of chiral biphenylene-bridged bissilsesquioxanes were synthesized. They self-assembled into helical bundles in ethanol, behavior that was confirmed in field emission scanning electron microscopy images. Circular dichroism analysis indicated that the biphenylene groups twisted in a single-handed fashion. Single-handed helical polybissilsesquioxane bundles were prepared via polycondensation of the bissilsesquioxanes, using a self-templating approach. Because of the shrinkage that occurred during polycondensation, the helical pitches of the bundles were shorter than those of their corresponding organic self-assemblies. The wide-angle X-ray diffraction pattern indicated that there were no π-π interactions among the diphenylene groups. The circular dichroism spectra indicated that the chirality was successfully transferred from the bissilsesquioxane self-assemblies to the polybissilsesquioxane. The polybissilsesquioxanes displayed a capacity for the adsorption of nitrobenzene and had potential application for enantioseparation.

A Novel Class of HIV-1 Antiviral Agents Targeting HIV via a SUMOylation-Dependent Mechanism.

We have recently identified a chemotype of small ubiquitin-like modifier (SUMO)-specific protease (SENP) inhibitors. Prior to the discovery of their SENP inhibitory activity, these compounds were found to inhibit HIV replication, but with an unknown mechanism. In this study, we investigated the mechanism of how these compounds inhibit HIV-1. We found that they do not affect HIV-1 viral production, but significantly inhibited the infectivity of the virus. Interestingly, virions produced from cells treated with these compounds could gain entry and carry out reverse transcription, but could not efficiently integrate into the host genome. This phenotype is different from the virus produced from cells treated with the class of anti-HIV-1 agents that inhibit HIV protease. Upon removal of the SUMO modification sites in the HIV-1 integrase, the compound no longer alters viral infectivity, indicating that the effect is related to SUMOylation of the HIV integrase. This study identifies a novel mechanism for inhibiting HIV-1 integration and a new class of small molecules that inhibits HIV-1 via such mechanism that may contribute a new strategy for cure of HIV-1 by inhibiting the production of infectious virions upon activation from latency.

Chirality of 4,4'-Biphenylene Bridged Polybissilsesquioxane Nanotubes Using the Dipeptides Derived from Valine.

Four dipeptides with alkyl chains derived from L- and D-valines were synthesized, the handedness of their self-assemblies were controlled by the valine chirality at the terminals. The stacking of the carbonyl groups plays an important in the formation of chiral organic self-assemblies. Chiral 4,4'-biphenylene bridged polybissilsesquioxane nanotubes were prepared using the self-assemblies of these dipeptides as the templates. The chirality of the polysilsesquioxane nanotubes was mainly controlled by the valines at the terminals of the dipeptides, which was transferred from the valines at the terminals through electrostatic interaction. The valines near the alkyl chains could also affect the polysilsesquioxane chirality through hydrogen bonding.

Inner Surface Chirality of Single-Handed Twisted Carbonaceous Tubular Nanoribbons.

Single-handed twisted 4,4'-biphenylene-bridged polybissilsesquioxane tubular nanoribbons and single-layered nanoribbons were prepared by tuning the water/ethanol volume ratio in the reaction mixture at pH = 11.6 through a supramolecular templating approach. The single-layered nanoribbons were formed by shrinking tubular nanoribbons after the removal of the templates. In addition, solvent-induced handedness inversion was achieved. The handedness of the polybissilsesquioxanes could be controlled by changing the ethanol/water volume ratio in the reaction mixture. After carbonization at 900 °C for 4.0 h and removal of silica, single-handed twisted carbonaceous tubular nanoribbons and single-layered nanoribbons with micropores in the walls were obtained. X-ray diffraction and Raman spectroscopy analyses indicated that the carbon is predominantly amorphous. The circular dichroism spectra show that the twisted tubular nanoribbons exhibit optical activity, while the twisted single-layered nanoribbons do not. The results shown here indicate that chirality is transferred from the organic self-assemblies to the inner surfaces of the 4,4'-biphenylene-bridged polybissilsesquioxane tubular nanoribbons and subsequently to those of the carbonaceous tubular nanoribbons.

Chirality of Single-Handed Twisted Titania Tubular Nanoribbons Prepared Through Sol-gel Transcription.

Single-handed twisted titania tubular nanoribbons were prepared through sol-gel transcription using a pair of enantiomers. Handedness was controlled by that of the template. The obtained samples were characterized using field-emission electron microscopy, transmission electron microscopy, diffuse reflectance circular dichroism (DRCD), and X-ray diffraction. The DRCD spectra indicated that the titania nanotubes exhibit optical activity. Although the tubular structure was destroyed after being calcined at 700 °C for 2.0 h, DRCD signals were still identified. However, the DRCD signals disappeared after being calcined at 1000 °C for 2.0 h. The optical activity of titania was proposed to be due to chiral defects. Previous results showed that straight titania tubes could be used as asymmetric autocatalysts, indicating that titania exhibit chirality at the angstrom level. Herein, it was found that they also exhibit DRCD signals, indicating that there are no obvious relationships between morphology at the nano level and chirality at the angstrom level. The nanotube chirality should originate from the chiral defects on the nanotube inner surface. The Fourier transform infrared spectra indicated that the chirality of the titania was transferred from the gelators through the hydrogen bonding between N-H and Ti-OH.