Recent Advances in the 3D Chiral Plasmonic Nanomaterials.

From the view of geometry, chirality is that an object cannot overlap with its mirror image, which has been a fundamental scientific problem in biology and chemistry since the 19th century. Chiral inorganic nanomaterials serve as ideal templates for investigating chiral transfer and amplification mechanisms between molecule and bulk materials, garnering widespread attentions. The chiroptical property of chiral plasmonic nanomaterials is enhanced through localized surface plasmon resonance effects, which exhibits distinctive circular dichroism (CD) response across a wide wavelength range. Recently, 3D chiral plasmonic nanomaterials are becoming a focal research point due to their unique characteristics and planar-independence. This review provides an overview of recent progresses in 3D chiral plasmonic nanomaterials studies. It begins by discussing the mechanisms of plasmonic enhancement of molecular CD response, following by a detailed presentation of novel classifications of 3D chiral plasmonic nanomaterials. Finally, the applications of 3D chiral nanomaterials such as biology, sensing, chiral catalysis, photology, and other fields have been discussed and prospected. It is hoped that this review will contribute to the flourishing development of 3D chiral nanomaterials.

Controlling 1D Nanostructures and Handedness by Polar Residue Chirality of Amphiphilic Peptides.

Peptide assemblies are promising nanomaterials, with their properties and technological applications being highly hinged on their supramolecular architectures. Here, how changing the chirality of the terminal charged residues of an amphiphilic hexapeptide sequence Ac-I4 K2 -NH2 gives rise to distinct nanostructures and supramolecular handedness is reported. Microscopic imaging and neutron scattering measurements show thin nanofibrils, thick nanofibrils, and wide nanotubes self-assembled from four stereoisomers. Spectroscopic and solid-state nuclear magnetic resonance (NMR) analyses reveal that these isomeric peptides adopt similar anti-parallel ß-sheet secondary structures. Further theoretical calculations demonstrate that the chiral alterations of the two C-terminal lysine residues cause the formation of diverse single ß-strand conformations, and the final self-assembled nanostructures and handedness are determined by the twisting direction and degree of single ß-strands. This work not only lays a useful foundation for the fabrication of diverse peptide nanostructures by manipulating the chirality of specific residues but also provides a framework for predicting the supramolecular structures and handedness of peptide assemblies from single molecule conformations.

Surfactant like peptides for targeted gene delivery to cancer cells.

Surfactant like peptides (SLPs) are a class of amphiphilic peptides widely used for drug delivery and tissue engineering. However, there are very few reports on their application for gene delivery. The current study was aimed at development of two new SLPs, named (IA)4K and (IG)4K, for selective delivery of antisense oligodeoxynucleotides (ODNs) and small interfering RNA (siRNA) to cancer cells. The peptides were synthesized by Fmoc solid phase synthesis. Their complexation with nucleic acids was studied by gel electrophoresis and DLS. The transfection efficiency of the peptides was assessed in HCT 116 colorectal cancer cells and human dermal fibroblasts (HDFs) using high content microscopy. The cytotoxicity of the peptides was assessed by standard MTT test. The interaction of the peptides with model membranes was studied using CD spectroscopy. Both SLPs delivered siRNA and ODNs to HCT 116 colorectal cancer cells with high transfection efficiency which was comparable to the commercial lipid-based transfection reagents, but with higher selectivity for HCT 116 compared to HDFs. Moreover, both peptides exhibited very low cytotoxicity even at high concentrations and long exposure time. The current study provides more insights into the structural features of SLPs required for nucleic acid complexation and delivery and can therefore serve as a guide for the rational design of new SLPs for selective gene delivery to cancer cells to minimize the adverse effects in healthy tissues.

Effect of Achiral Glycine Residue on the Handedness of Surfactant-Like Short Peptide Self-Assembly Nanofibers.

Surfactant-like short peptides are a kind of ideal model for the study of chiral self-assembly. At present, there are few studies on the chiral self-assembly of multicharged surfactant-like peptides. In this study, we adopted a series of short peptides of Ac-I4KGK-NH2 with different combinations of L-lysine and D-lysine residues as the model molecules. TEM, AFM and SANS results showed that Ac-I4LKGLK-NH2, Ac-I4LKGDK-NH2, and Ac-I4DKGLK-NH2 formed the morphologies of nanofibers, and Ac-I4DKGDK-NH2 formed nanoribbons. All the self-assembled nanofibers, including the intermediate nanofibers of Ac-I4DKGDK-NH2 nanoribbons, showed the chirality of left handedness. Based on the molecular simulation results, it has been demonstrated that the supramolecular chirality was directly dictated by the orientation of single ß strand. The insertion of glycine residue demolished the effect of lysine residues on the single strand conformation due to its high conformational flexibility. The replacement of L-isoleucine with Da-isoleucine also confirmed that the isoleucine residues involved in the ß-sheet determined the supramolecular handedness. This study provides a profound mechanism of the chiral self-assembly of short peptides. We hope that it will improve the regulation of chiral molecular self-assembly with achiral glycine, as well.

Investigation on the Mechanism of PAL (100) Surface Modified by APTES.

The interfacial mechanism has always been a concern for 3-aminopropyltriethoxysilane (APTES)-grafted palygorskite (PAL). In this research, the mechanism of graft modification for grafting of APTES to the surface of PAL (100) was studied using density functional theory (DFT) calculation. The results illustrated that different grafting states of the APTES influence the inter- and intramolecular interactions between APTES/PAL (100), which are reflected in the electronic structures. For single-, double-, and three-toothed state APTES-PAL (100), the charge transfer rates from the PAL (100) surface to APTES were 0.68, 1.02, and 0.77 e, respectively. The binding energy results show that PAL (100) modification performance in the double-tooth state is the best compared to the other states, with the lowest value of -181.91 kJ/mol. The double-toothed state has lower barrier energy (94.69, 63.11, and 153.67 kJ/mol) during the modification process. This study offers theoretical insights into the chemical modification of the PAL (100) surface using APTES coupling agents, and can provide a guide for practical applications.

Peptide Self-Assemblies from Unusual α-Sheet Conformations Based on Alternation of d/l Amino Acids.

Peptide self-assembly is a hierarchical process during which secondary structures formed in the initial stages play a critical role in determining the subsequent assembling processes and final structural ordering. Unusual secondary structures hold promise as a source to develop novel supramolecular architectures with unique properties. In this work, we report the design of a new peptide self-assembly strategy based on unusual α-sheet secondary structures. In light of the strong propensity of leucine toward forming helical conformations and its high hydrophobicity, we design two short amphiphilic peptides Ac-LDLLDLK-NH2 and Ac-DLLDLLDK-NH2 with alternating l- and d-form amino acids. Microscopic imaging, neutron scattering, and spectroscopic measurements indicate that the two heterochiral peptides form highly ordered wide nanotubes and helical ribbons with monolayer thickness, in sharp contrast to twisted nanofibrils formed by the homochiral peptide Ac-LLLLK-NH2. Molecular dynamics simulations from monomers to trimers reveal that the two heteropeptides fold into α-sheets instead of ß-sheets, which readily pack into tubular architectures in oligomer simulations. Simulated circular dichroism spectra based on α-sheet oligomers validate the proposed α-sheet secondary structures. These results form an important basis for the rational design of higher-order peptide assemblies with novel properties based on unusual α-sheet secondary structures.

Broad Spectral Response Z-Scheme Three-Dimensional Ordered Macroporous Carbon Quantum Dots/TiO2/g-C3N4 Composite for Boosting Photocatalysis.

Photocatalytic degradation technology is one of the effective protocols to solve environmental problems. TiO2 has always been favored for its photostability and low cost. However, the insufficient photocatalytic activity of TiO2 limits its application due to the severe recombination of photogenerated electrons and holes and a narrow light response range. Therefore, 3DTCN, a TiO2/g-C3N4 composite with a three-dimensional ordered macroporous structure was prepared by a colloidal crystal template technique to form a heterojunction for inhibiting the photogenerated electron-hole recombination. On 3DTCN, carbon quantum dots (CQDs) were loaded by impregnation to obtain x % CQDs/3DTCN with a broad spectral response to light. The physical and chemical properties of samples were investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy (TEM), high-resolution-TEM, energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller analysis, photoluminescence spectroscopy, and ultraviolet-visible diffuse reflectance spectroscopy. The photocatalytic activity was evaluated via degrading the rhodamine B (RhB) dye, and the degradation efficiency of 1% CQDs/3DTCN (98%) was found to be much higher than that of 3DTCN (42%) in 80 min under simulated sunlight irradiation. Furthermore, it also possessed excellent durability. Meanwhile, the sample also showed an outstanding photoelectric property. Finally, the proposed mechanism of the composites had been mainly analyzed by density functional theory calculations. This work thus provides an idea to form a 3D structure heterojunction and further improve the photocatalytic activity.

Core-Shell Structures from the Coassembly of Lipoprotein-like Nanoparticles and Plasmid DNA for Gene Delivery.

We reported self-assembled core-shell nanoparticles (NPs) based on lipoprotein-like NPs and plasmid DNA (pDNA). Lipoprotein-like NPs were prepared using cholic acid (CA)-modified lipopeptides. We designed six different lipopeptides with different peptide segments to construct a series of NPs. It was proven that these NPs have different positive surface charges. These NPs could bind pDNA through electrostatic interaction to form core-shell complexes. The interactions between NPs and pDNA were systematically investigated. The number of NP charges determines the strength of the interaction between NPs and pDNA. Thus, various types of core-shell structures, such as loose and dense core-shell NPs, were found in this system. Cytotoxicity test confirmed that the carriers had no toxicity. We also proved that the core-shell structures have a good cell transfection effect. This study would expand the application of lipopeptide assemblies in the gene delivery field, which may lead to the development of peptide-based gene vectors for therapeutic application.

Ordered Packing of ß-Sheet Nanofibrils into Nanotubes: Multi-hierarchical Assembly of Designed Short Peptides.

Although it is well-known proteins and their complexes are hierarchically organized and highly ordered structures, it remains a major challenge to replicate their hierarchical self-assembly process and to fabricate multihierarchical architectures with well-defined shapes and monodisperse characteristic sizes via peptide self-assembly. Here we describe an amphiphilic short peptide Ac-I3GGHK-NH2 that first preassembles into thin, left-handed ß-sheet nanofibrils, followed by their ordered packing into right-handed nanotubes. The key intermediate morphology and structures featuring the hierarchical process are simultaneously demonstrated. Further mechanistic exploration with the variants Ac-I3GGGK-NH2, Ac-I3GGFK-NH2, and Ac-I3GGDHDK-NH2 reveals the vital role of multiple His-His side chain interactions between nanofibrils in mediating higher-order assembly and architectures. Altogether, our findings not only advance current understanding of hierarchical assembly of peptides and proteins but also afford a paradigm of how to take advantage of side chain interactions to construct higher-order assemblies with enhanced complexities.

Coassembly Behavior and Rheological Properties of a ß-Hairpin Peptide with Dicarboxylates.

To understand the molecular interaction mechanism and develop peptide-based hydrogels, a ß-hairpin peptide CBHH was used as the model peptide, and its coassembly performance with succinic, malic, and tartaric dicarboxylates has been investigated with circular dichroism spectroscopy (CD) and atomic force microscopy (AFM). The rheological properties and cell culture performance of the coassembled hydrogels have also been assessed. The results showed that the dicarboxylates could induce the folding and self-assembly of the ß-hairpin peptide and promote its gelation at low pH. The effects of the dicarboxylates on peptide self-assembly and hydrogel properties were correlated to their hydroxyl group number. The toxicity of the hydrogel has been assessed with NIH-3T3 cells by MTT and Calcein-AM/PI experiments, and it was confirmed that the hydrogel was biocompatible and could be used as cell culture scaffolds. We hope that this study would provide a novel way for biomaterial fabrication in cell and tissue engineering.

pH-Responsive Self-Assemblies from the Designed Folic Acid-Modified Peptide Drug for Dual-Targeting Delivery.

Targeting delivery is a promising technique for the therapy of cancers. A molecule FA-EEYSV-NH2, which consists of target recognition site folic acid (FA), dipeptide linker, and peptide drug, was designed as a novel anticancer prodrug. The molecules could self-assemble into nanoparticles at pH 7.0 and nanofibers at pH 5.0. By the aid of pH-responsiveness, the self-assemblies were used purposefully as targeted vehicles of self-delivery prodrugs. The results of cell toxicity and internalization assays have proved that the self-assemblies have good cancer cell selectivity. The selection was mainly attributed to the pH-responsive structure transition of self-assemblies and the FA active-targeting effect. We hope that our work could provide a useful strategy for finely tuning the properties and activities of peptide-based supramolecular nanomaterials, thus optimizing nanomedicines with enhanced performance.

Ordered Nanofibers Fabricated from Hierarchical Self-Assembling Processes of Designed α-Helical Peptides.

Peptide self-assembly is fast evolving into a powerful method for the development of bio-inspired nanomaterials with great potential for many applications, but it remains challenging to control the self-assembling processes and nanostrucutres because of the intricate interplay of various non-covalent interactions. A group of 28-residue α-helical peptides is designed including NN, NK, and HH that display distinct hierarchical events. The key of the design lies in the incorporation of two asparagine (Asn) or histidine (His) residues at the a positions of the second and fourth heptads, which allow one sequence to pack into homodimers with sticky ends through specific interhelical Asn-Asn or metal complexation interactions, followed by their longitudinal association into ordered nanofibers. This is in contrast to classical self-assembling helical peptide systems consisting of two complementary peptides. The collaborative roles played by the four main non-covalent interactions, including hydrogen-bonding, hydrophobic interactions, electrostatic interactions, and metal ion coordination, are well demonstrated during the hierarchical self-assembling processes of these peptides. Different nanostructures, for example, long and short nanofibers, thin and thick fibers, uniform metal ion-entrapped nanofibers, and polydisperse globular stacks, can be prepared by harnessing these interactions at different levels of hierarchy.

Construction and Characterization of a Mirror-Image l-DNA i-Motif.

The first thermally stable and pH-responsive quadruplex intercalated motif (i-motif) structure formed by l-DNA is presented. Although this l-type i-motif exhibits the same physiochemical properties as its d isomer, its inverted chirality and good enzymatic resistance potentially open the way to the development of new DNA materials of pharmaceutical and biological interest.

Effects of Conventional Surfactants on the Activity of Designed Antimicrobial Peptide.

In this article, the interaction between a designed antimicrobial peptide (AMP) G(IIKK)3I-NH2 (G3) and four typical conventional surfactants (sodium dodecyl sulfonate (SDS), hexadecyl trimethyl ammonium bromide (C16TAB), polyoxyethylene (23) lauryl ether (C12EO23), and tetradecyldimethylamine oxide (C14DMAO)) has been studied through surface tension measurement and circular dichroism (CD) spectroscopy. The antimicrobial activities of AMP/surfactant mixtures have also been studied with Gram-negative Escherichia coli, Gram-positive Staphylococcus aureus, and the fungus Candida albicans. The cytotoxicity of the AMP/surfactant mixtures has also been assessed with NIH 3T3 and human skin fibroblast (HSF) cells. The surface tension data showed that the AMP/SDS mixture was much more surface-active than SDS alone. CD results showed that G3 conformation changed from random coil, to ß-sheet, and then to α-helix with increasing SDS concentration, showing a range of structural transformation driven by the different interactions with SDS. The antimicrobial activity of G3 to Gram-negative and Gram-positive bacteria decreased in the presence of SDS due to the strong interaction of electrostatic attraction between the peptide and the surfactant. The interactions between G3 and C16TAB, C12EO23, and C14DMAO were much weaker than SDS. As a result, the surface tension of surfactants with G3 did not change much, neither did the secondary structures of G3. The antimicrobial activities of G3 were little affected in the presence of C12EO23, slightly improved by C14DMAO, and clearly enhanced by cationic surfactant C16TAB due to its strong cationic and antimicrobial nature, consistent with their surface physical activities as binary mixtures. Although AMP G3 did not show activity to fungus, the mixtures of AMP/C16TAB and AMP/C14DMAO could kill C. albicans at high surfactant concentrations. The mixtures had rather high cytotoxicity to NIH 3T3 and HSF cells although G3 is nontoxic to cells. Cationic AMPs can be formulated with nonionic, cationic, and zwitterionic surfactants during product development, but care must be taken when AMPs are formulated with anionic surfactants, as the strong electrostatic interaction may undermine their antimicrobial activity.

Modulation of Antimicrobial Peptide Conformation and Aggregation by Terminal Lipidation and Surfactants.

The function and properties of peptide-based materials depend not only on the amino acid sequence but also on the molecular conformations. In this paper, we chose a series of peptides Gm(XXKK)nX-NH2 (m = 0, 3; n = 2, 3; X = I, L, and V) as the model molecules and studied the conformation regulation through N-terminus lipidation and their formulation with surfactants. The structural and morphological transition of peptide self-assemblies have also been investigated via transmission electron microscopy, atomic force microscopy, circular dichroism spectroscopy, and small-angle neutron scattering. With the terminal alkylation, the molecular conformation changed from random coil to ß-sheet or α-helix. The antimicrobial activities of alkylated peptide were different. C16-G3(IIKK)3I-NH2 showed antimicrobial activity against Streptococcus mutans, while C16-(IIKK)2I-NH2 and C16-G3(IIKK)2I-NH2 did not kill the bacteria. The surfactant sodium dodecyl sulfonate could rapidly induce the self-assemblies of alkylated peptides (C16-(IIKK)2I-NH2, C16-G3(IIKK)2I-NH2, C16-G3(VVKK)2V-NH2) from nanofibers to micelles, along with the conformation changing from ß-sheet to α-helix. The cationic surfactant hexadecyl trimethyl ammonium bromide made the lipopeptide nanofibers thinner, and nonionic surfactant polyoxyethylene (23) lauryl ether (C12EO23) induced the nanofibers much more intensively. Both the activity and the conformation of the α-helical peptide could be modulated by lipidation. Then, the self-assembled morphologies of alkylated peptides could also be further regulated with surfactants through hydrophobic, electrostatic, and hydrogen-bonding interactions. These results provided useful strategies to regulate the molecular conformations in peptide-based material functionalization.

Examining the predictive information of CBOE OVX on China's oil futures volatility: Evidence from MS-MIDAS models.

This study evaluates whether CBOE crude oil volatility index (OVX) owns forecasting ability for China's oil futures volatility using Markov-regime mixed data sampling (MS-MIDAS) models. In-sample empirical result shows that, OVX can significantly lead to high future short-term, middle-term and long-term volatilities with regard to Chinese oil futures market. Moreover, our proposed model, the Markov-regime MIDAS with including the OVX (MS-MIDAS-RV-OVX), significantly outperforms the MIDAS and other competing models. Unsurprising results further confirm that OVX indeed contain predictive information for oil realized volatility (especially significant and robust in middle-term and long-term horizons) and regime switching is useful to deal with the structural break within the energy market. We carry out economic value analysis and discuss OVX's asymmetric effects concerning different trading hours and good (bad) OVX, and find OVX performs better in day-time trading hours and the good OVX is more predictive for the oil futures RV than the bad OVX. The further discussion also confirms our previous conclusions are robust during the highly volatile period of the COVID-19 pandemic.

The role of the IDEMV in predicting European stock market volatility during the COVID-19 pandemic.

The main purpose of this paper is to investigate whether the Infectious Disease EMV tracker (IDEMV) proposed by Baker et al. (2020) has additional predictive ability for European stock market volatility during the COVID-19 pandemic. The three European stock markets we consider are France, UK and Germany. Our investigation is based on the HAR and its augmented models. We find that the IDEMV has stronger predictive power for the France and UK stock markets volatilities during the global pandemic, and the VIX has also superior predictive ability for the three European stock markets during this period.

Effect of Aggregation and Adsorption Behavior on the Flow Resistance of Surfactant Fluid on Smooth and Rough Surfaces: A Many-Body Dissipative Particle Dynamics Study.

To study the effect of surfactant on the resistance of wall-bound flow, the adsorption and aggregation behaviors of surfactant fluid on both smooth and groove-patterned rough surface are investigated through many-body dissipative particle dynamics (MDPD) simulation. The MDPD models of surfactants were carefully parametrized and have been validated to be able to simulate the aggregation and adsorption behavior of surfactants. The simulation results show that the surfactant in laminar flow can only increase the flow resistance on the smooth surface. On the rough surface, surfactant with strong adsorption performance on the channel wall shows a drag reduction effect at moderate concentration. The surfactant with weak adsorption properties can enhance the flow resistance, which is even more significant than that of those surfactants with no adsorption capacity. Although heating (high temperature) can generally reduce the viscosity and flow resistance of surfactant fluid, it would cause a poor drag reduction efficiency. It may arise from the destruction of the adsorption layer and the interruption of the fluid/boundary interface. Surfactant adsorption can tune the roughness of the fluid boundary on either the smooth or rough surface in a different manner, which turns out to be highly correlated to the change in flow resistance. Compared with the adsorption layer, surfactant in the bulk fluid makes a greater contribution to enhancing the flow resistance as the concentration rises. This study is expected to be helpful in guiding the application of surfactants on the micro- and nanoscale such as lab-on-a-chip nanodevices and EOR in a low-permeability porous medium.

Preparation and Properties of Semi-Self-Assembled Lipopeptide Vesicles.

Novel lipopeptide vesicles are prepared from self-assembled nanomembranes through an extrusion method. The size of vesicles can be controlled by the pore diameter of the extrusion filter. The vesicles are rather stable because hydrogen bonds exist among the peptide headgroups. When doxorubicin hydrochloride (DOX·HCl) is encapsulated in the vesicles, it could be released sustainably, and its side effect would also be reduced due to encapsulation. The leakage rate of DOX·HCl depends on the pH via charge regulation. As drug carriers, lipopeptide vesicles have been proved to have nontoxicity to normal cells. A magnetic surfactant CH3(CH2)14CH2N(CH3)3+ [FeCl3Br]- (CTAFe) was mixed with lipopeptide to modify the vesicles. Also, the results demonstrated that the vesicles is endowed with magnetic property after the addition of CTAFe. We believe that the strategy of lipopeptide vesicle preparation would enrich the drug carrier family and expand the application of lipopeptide materials.

Light- and pH-Controlled Hierarchical Coassembly of Peptide Amphiphiles.

The coassembly behavior of peptide amphiphiles (PAs) C4-Bhc-EE-NH2 and C14-FKK-NH2 has been investigated by transmission electron microscopy, atomic force microscopy, fluorescence microscopy, circular dichroism, Fourier transform infrared spectroscopy, and 1H nuclear magnetic resonance. These two PAs coassembled into nanofibers by electrostatic and π-π stacking interactions at a low concentration and further aggregated into nanofiber bundles via charge complementation on the surface of nanofibers. As the charge number varied with pH, the bundles could be disassembled/assembled with pH regulation. More interestingly, as C4-Bhc-EE-NH2 was a photodegradable molecule, the bundles could also be responsive to both ultraviolet (UV) and near-infrared (NIR) light. In contrast to the reversible pH-dependent response, the light responses were irreversible as C4-Bhc-EE-NH2 broke under UV or NIR radiation. The highlight of this article is that structural changes were realized for control at the aggregate level, not only at the molecular level. With this inspiration, we hope that we can support the novel biomaterial construction and exploitation of new functions of biomaterials.