ABSTRACT
Chirality is a geometrical property described by continuous mathematical functions1-5. However, in chemical disciplines, chirality is often treated as a binary left or right characteristic of molecules rather than a continuity of chiral shapes. Although they are theoretically possible, a family of stable chemical structures with similar shapes and progressively tuneable chirality is yet unknown. Here we show that nanostructured microparticles with an anisotropic bowtie shape display chirality continuum and can be made with widely tuneable twist angle, pitch, width, thickness and length. The self-limited assembly of the bowties enables high synthetic reproducibility, size monodispersity and computational predictability of their geometries for different assembly conditions6. The bowtie nanoassemblies show several strong circular dichroism peaks originating from absorptive and scattering phenomena. Unlike classical chiral molecules, these particles show a continuum of chirality measures2 that correlate exponentially with the spectral positions of the circular dichroism peaks. Bowtie particles with variable polarization rotation were used to print photonically active metasurfaces with spectrally tuneable positive or negative polarization signatures for light detection and ranging (LIDAR) devices.
ABSTRACT
Chiral plasmonic surfaces with 3D "forests" from nanohelicoids should provide strong optical rotation due to alignment of helical axis with propagation vector of photons. However, such three-dimensional nanostructures also demand multi-step nanofabrication, which is incompatible with many substrates. Large-scale photonic patterns on polymeric and flexible substrates remain unattainable. Here, we demonstrate the substrate-tolerant direct-write printing and patterning of silver nanohelicoids with out-of-plane 3D orientation using circularly polarized light. Centimeter-scale chiral plasmonic surfaces can be produced within minutes using inexpensive medium-power lasers. The growth of nanohelicoids is driven by the symmetry-broken site-selective deposition and self-assembly of the silver nanoparticles (NPs). The ellipticity and wavelength of the incident photons control the local handedness and size of the printed nanohelicoids, which enables on-the-fly modulation of nanohelicoid chirality during direct writing and simple pathways to complex multifunctional metasurfaces. Processing simplicity, high polarization rotation, and fine spatial resolution of the light-driven printing of stand-up helicoids provide a rapid pathway to chiral plasmonic surfaces, accelerating the development of chiral photonics for health and information technologies.
ABSTRACT
The incessant mutations of viruses, variable immune responses, and likely emergence of new viral threats necessitate multiple approaches to novel antiviral therapeutics. Furthermore, the new antiviral agents should have broad-spectrum activity and be environmentally stable. Here, we show that biocompatible tapered CuS nanoparticles (NPs) efficiently agglutinate coronaviruses with binding affinity dependent on the chirality of surface ligands and particle shape. L-penicillamine-stabilized NPs with left-handed curved apexes display half-maximal inhibitory concentrations (IC50) as low as 0.66 pM (1.4 ng/mL) and 0.57 pM (1.2 ng/mL) for pseudo-type SARS-CoV-2 viruses and wild-type Wuhan-1 SARS-CoV-2 viruses, respectively, which are about 1,100 times lower than those for antibodies (0.73 nM). Benefiting from strong NPs-protein interactions, the same particles are also effective against other strains of coronaviruses, such as HCoV-HKU1, HCoV-OC43, HCoV-NL63, and SARS-CoV-2 Omicron variants with IC50 values below 10 pM (21.8 ng/mL). Considering rapid response to outbreaks, exposure to elevated temperatures causes no change in the antiviral activity of NPs while antibodies are completely deactivated. Testing in mice indicates that the chirality-optimized NPs can serve as thermally stable analogs of antiviral biologics complementing the current spectrum of treatments.
Subject(s)
COVID-19 , Coronavirus OC43, Human , Humans , Animals , Mice , SARS-CoV-2/genetics , Antibodies/pharmacology , Antiviral Agents/pharmacology , Antiviral Agents/therapeutic useABSTRACT
Chirality is an essential geometric property unifying small molecules, biological macromolecules, inorganic nanomaterials, biological microparticles, and many other chemical structures. Numerous chirality measures have attempted to quantify this geometric property of mirror asymmetry and to correlate these measures with physical and chemical properties. However, their utility has been widely limited because these correlations have been largely notional. Furthermore, chirality measures also require prohibitively demanding computations, especially for chiral structures comprised of thousands of atoms. Acknowledging the fundamental problems with quantification of mirror asymmetry, including the ambiguity of sign-variable pseudoscalar chirality measures, we revisit this subject because of the significance of quantifying chirality for quantitative biomimetics and describing the chirality of nanoscale materials that display chirality continuum and scale-dependent mirror asymmetry. We apply the concept of torsion within the framework of differential geometry to the graph theoretical representation of chiral molecules and nanostructures to address some of the fundamental problems and practical limitations of other chirality measures. Chiral gold clusters and other chiral structures are used as models to elaborate a graph-theoretical chirality (GTC) measure, demonstrating its applicability to chiral materials with different degrees of chirality at different scales. For specific cases, we show that GTC provides an adequate description of both the sign and magnitude of mirror asymmetry. The direct correlations with macroscopic properties, such as chiroptical spectra, are enhanced by using the hybrid chirality measures combining parameters from discrete mathematics and physics. Taking molecular helices as an example, we established a direct relation between GTC and optical activity, indicating that this chirality measure can be applied to chiral metamaterials and complex chiral constructs.
ABSTRACT
The prokaryotic global transcription factor CRP has been considered to be an ideal model for in-depth study of both the allostery of the protein and the differential utilization of the homologous cyclic nucleotide second messengers cAMP and cGMP. Here, atomic details from the crystal structures of two inactive CRP species, an apo form and a cGMP-bound form, in comparison with a known active conformation, the cAMP-CRP complex, provide macroscopic and microscopic insights into CRP allostery, which is coupled to specific discrimination between the two effectors. The cAMP-induced conformational transition, including dynamic fluctuations, can be driven by the fundamental folding forces that cause water-soluble globular proteins to construct an optimized hydrophobic core, including secondary-structure formation. The observed conformational asymmetries underlie a negative cooperativity in the sequential binding of cyclic nucleotides and a stepwise manner of binding with discrimination between the effector molecules. Additionally, the finding that cGMP, which is specifically recognized in a syn conformation, induces an inhibitory conformational change, rather than a null effect, on CRP supports the intriguing possibility that cGMP signalling could be widely utilized in prokaryotes, including in aggressive inhibition of CRP-like proteins.
Subject(s)
C-Reactive Protein/chemistry , Second Messenger Systems , Allosteric Regulation , Base Sequence , Cyclic AMP/chemistry , Cyclic GMP/chemistry , DNA Primers , Protein Structure, SecondaryABSTRACT
Bispecific antibodies expressed and assembled from a single upstream culture require the correct balance and pairing of four different heavy and light chains (HC and LC). The increased potential for chain-mispaired species challenges the downstream purification of this new format. While clearance of HC-mispaired species, including homodimers and half-antibodies, has been assessed, removal of LC mispairs requires a more stringent approach. Here, we report two case studies in which separation is achieved, as well as the structural basis of these separations: (A) In the first case, a main species with a positively charged patch in the correctly formed variable fragment (Fv) is disrupted when paired with the wrong LC. This LC-mispaired variant binds more weakly to a cation exchange resin and can be washed off in a chromatography step. (B) A second molecule whose LC mispair introduces a negative-charge patch and hydrophobic patch in close proximity, presenting increased binding to a multimodal anion exchange resin. This LC-mispaired variant can be retained on the column under conditions in which the bispecific is recovered. In both case studies, the molecular structural analysis by protein surface properties models correlated well with the chromatography experiments. The comprehensive interpretation of experimental and computational results has provided a better understanding of strategies and potential applications for predicting the downstream purification of complex molecules.
Subject(s)
Antibodies, Bispecific , Immunoglobulin Light Chains , Antibodies, Bispecific/chemistry , Antibodies, Bispecific/isolation & purification , Immunoglobulin Light Chains/chemistry , Immunoglobulin Light Chains/isolation & purification , Chromatography, Ion Exchange/methods , Animals , CHO Cells , Cricetulus , Models, MolecularABSTRACT
Despite the commonality of static holograms, the holography with multiple information layers and reconfigurable grey-scale images at communication frequencies remain a confluence of scientific challenges. One well-known difficulty is the simultaneous modulation of phase and amplitude of electromagnetic wavefronts with a high modulation depth. A less appreciated challenge is scrambling of the information and images with hologram bending. Here, this work shows that chirality-guided pixelation of plasmonic kirigami sheets enables tunable multiplexed holography at terahertz (THz) frequencies. The convex and concave structures with slanted Au strips exhibit gradual variations in geometries facilitating modulation of light ellipticity reaching 40 deg. Real-time switching of 3D images of the letter "M" and the Mona Lisa demonstrates the possibility of complex grey-scale information content and importance of continuously variable mirror asymmetry. Microscale chirality measures of each pixel experiences little change with bending while retaining controllable reconfigurability upon stretching, which translates to remarkable resilience of chiral holograms to bending. Simplicity of their design with local chirality measures opens the door to information technologies with fault-tolerant THz encryption, wearable holographic devices, and new communication technologies.
ABSTRACT
The Columbia Suicide Severity Rating Scale (C-SSRS) is considered the gold standard for collecting information on suicidal ideation and behavior by the Food and Drug Administration (FDA) of the United States. To determine the accuracy of the C-SSRS compared to the Beck Scale for Suicidal Ideation (BSS) for collecting suicide attempt history in the schizophrenia population, 202 participants aged 18-40 with schizophrenia spectrum disorders were administered the C-SSRS, followed by the BSS. Medical charts were reviewed to confirm the lifetime history of actual suicide attempts. The BSS had an 83.5% accuracy in reporting single suicide attempts and 81.7% for multiple suicide attempts; while the C-SSRS had 84.1% and 83.9% accuracy respectively. This difference was not statistically significant (p = 0.849). Both the BSS and C-SSRS demonstrated high sensitivity and specificity in collecting suicide attempt history for young patients with psychosis, with no significant differences. Future investigators may choose the scale that is best suited to the level of detail required.
Subject(s)
Psychotic Disorders , Schizophrenia , Humans , Young Adult , Suicidal Ideation , Reproducibility of Results , Suicide, AttemptedABSTRACT
Reconfiguration of chiral ceramic nanostructures after ion intercalation should favor specific nanoscale twists leading to strong chiroptical effects. In this work, V2 O3 nanoparticles are shown to have "built-in" chiral distortions caused by binding of tartaric acid enantiomers to the nanoparticle surface. As evidenced by spectroscopy/microscopy techniques and calculations of nanoscale chirality measures, the intercalation of Zn2+ ions into the V2 O3 lattice results in particle expansion, untwist deformations, and chirality reduction. Coherent deformations in the particle ensemble manifest as changes in sign and positions of circular polarization bands at ultraviolet, visible, mid-infrared (IR), near-IR (NIR), and IR wavelengths. The g-factors observed for IR and NIR spectral diapasons are ≈100-400 times higher than those for previously reported dielectric, semiconductor, and plasmonic nanoparticles. Nanocomposite films layer-by-layer assembled (LBL) from V2 O3 nanoparticles reveal cyclic-voltage-driven modulation of optical activity. Device prototypes for IR and NIR range problematic for liquid crystals and other organic materials are demonstrated. High optical activity, synthetic simplicity, sustainable processability, and environmental robustness of the chiral LBL nanocomposites provide a versatile platform for photonic devices. Similar reconfigurations of particle shapes are expected for multiple chiral ceramic nanostructures, leading to unique optical, electrical, and magnetic properties.
ABSTRACT
Biomimetic nanoparticles are known to serve as nanoscale adjuvants, enzyme mimics and amyloid fibrillation inhibitors. Their further development requires better understanding of their interactions with proteins. The abundant knowledge about protein-protein interactions can serve as a guide for designing protein-nanoparticle assemblies, but the chemical and biological inputs used in computational packages for protein-protein interactions are not applicable to inorganic nanoparticles. Analysing chemical, geometrical and graph-theoretical descriptors for protein complexes, we found that geometrical and graph-theoretical descriptors are uniformly applicable to biological and inorganic nanostructures and can predict interaction sites in protein pairs with accuracy >80% and classification probability ~90%. We extended the machine-learning algorithms trained on protein-protein interactions to inorganic nanoparticles and found a nearly exact match between experimental and predicted interaction sites with proteins. These findings can be extended to other organic and inorganic nanoparticles to predict their assemblies with biomolecules and other chemical structures forming lock-and-key complexes.
ABSTRACT
Chiral inorganic nanostructures have high circular dichroism, but real-time control of their optical activity has so far been achieved only by irreversible chemical changes. Field modulation is a far more desirable path to chiroptical devices. We hypothesized that magnetic field modulation can be attained for chiral nanostructures with large contributions of the magnetic transition dipole moments to polarization rotation. We found that dispersions and gels of paramagnetic Co3O4 nanoparticles with chiral distortions of the crystal lattices exhibited chiroptical activity in the visible range that was 10 times as strong as that of nonparamagnetic nanoparticles of comparable size. Transparency of the nanoparticle gels to circularly polarized light beams in the ultraviolet range was reversibly modulated by magnetic fields. These phenomena were also observed for other nanoscale metal oxides with lattice distortions from imprinted amino acids and other chiral ligands. The large family of chiral ceramic nanostructures and gels can be pivotal for new technologies and knowledge at the nexus of chirality and magnetism.
ABSTRACT
A major impediment to the commercialization of organic photovoltaics (OPVs) is attaining long-term morphological stability of the bulk heterojunction (BHJ) layer. To secure the stability while pursuing optimized performance, multi-component BHJ-based OPVs have been strategically explored. Here we demonstrate the use of quaternary BHJs (q-BHJs) composed of two conjugated polymer donors and two fullerene acceptors as a novel platform to produce high-efficiency and long-term durable OPVs. A q-BHJ OPV (q-OPV) with an experimentally optimized composition exhibits an enhanced efficiency and extended operational lifetime than does the binary reference OPV. The q-OPV would retain more than 72% of its initial efficiency (for example, 8.42-6.06%) after a 1-year operation at an elevated temperature of 65 °C. This is superior to those of the state-of-the-art BHJ-based OPVs. We attribute the enhanced stability to the significant suppression of domain growth and phase separation between the components via kinetic trapping effect.
ABSTRACT
Graphene has recently attracted much interest as a material for flexible, transparent electrodes or active layers in electronic and photonic devices. However, realization of such graphene-based devices is limited due to difficulties in obtaining patterned graphene monolayers on top of materials that are degraded when exposed to a high-temperature or wet process. We demonstrate a low-temperature, dry process capable of transfer-printing a patterned graphene monolayer grown on Cu foil onto a target substrate using an elastomeric stamp. A challenge in realizing this is to obtain a high-quality graphene layer on a hydrophobic stamp made of poly(dimethylsiloxane), which is overcome by introducing two crucial modifications to the conventional wet-transfer method - the use of a support layer composed of Au and the decrease in surface tension of the liquid bath. Using this technique, patterns of a graphene monolayer were transfer-printed on poly(3,4-ethylenedioxythiophene):polystyrene sulfonate and MoO3, both of which are easily degraded when exposed to an aqueous or aggressive patterning process. We discuss the range of application of this technique, which is currently limited by oligomer contaminants, and possible means to expand it by eliminating the contamination problem.
ABSTRACT
We report a novel method for the synthesis of a self-reducible (thermally reducible without a reducing atmosphere) and alcohol-soluble copper-based metal-organic decomposition (MOD) ink for printed electronics. Alcohol-solvent-based conductive inks are necessary for commercial printing processes such as reverse offset printing. We selected copper(II) formate as a precursor and alkanolamine (2-amino-2-methyl-1-propanol) as a ligand to make an alcohol-solvent-based conductive ink and to assist in the reduction reaction of copper(II) formate. In addition, a co-complexing agent (octylamine) and a sintering helper (hexanoic acid) were introduced to improve the metallic copper film. The specific resistivity of copper-based MOD ink (Cuf-AMP-OH ink) after heat treatment at 350 °C is 9.46 µΩ·cm, which is 5.5 times higher than the specific resistivity of bulk copper. A simple stamping transfer was conducted to demonstrate the potential of our ink for commercial printing processes.