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The emergence of new viral threats, wide applications of viruses in biotechnology and challenges associated with viral contamination necessitate multiple types of virustatic agents. Here, we show that highly biocompatible tapered CuS nanoparticles efficiently agglutinate COVID virus with binding affinity dependent on chirality of surface ligands and particle shape. L-penicillamine-stabilized nanoparticles with left-handed curved apexes display half-maximal inhibitory concentration as low as 0.57 pM for authentic SARS-CoV-2 viruses, which is ca 15 times greater than for antibodies. Exposure to elevated temperatures causes no change in activity or biocompatibility of nanoparticles while completely deactivating antibodies. Testing with mice indicates that the chirality-optimized nanoparticles can serve as analogs of high antiviral molecular weight biologics complementing the current spectrum of virustatic agents. Their thermal and chemical stability simplifies their applications in biomedical and biotechnological processes.

Chiral metasurface with orthogonal nanohelical metal arrays provide strong optical rotation but demands multi-step nanofabrication at low-pressure and/or high-temperature conditions, which is incompatible with many substrates and high-throughput assessment. Submillimeter local photonic patterns with various optical polarization were also hitherto unattainable over the same substrate. Here, we demonstrate direct substrate-tolerant printing of silver nanohelicoids with a locally variable optical activity using circularly polarized light (CPL), producing centimeter-scale chiral metasurface within minutes. The light-illuminated sites on the substrate immersed in an aqueous silver ion solution are activated for heterogeneous nucleation at room temperature. Subsequent CPL-induced asymmetric site-selective deposition and self-assembly of the silver nanoparticles (NPs) sculpt the orthogonal silver helicoids at the interface as one-pot synthesis. The ellipticity and wavelength of the incident photons control the handedness and size of the printed silver helicoids, realizing on-the-fly modulation of optical polarization while printing local patterns. Processing simplicity, high polarization rotation, and fine spatial resolution of the light-driven printing can provide a pathway to the sustainable production of chiral plasmonic metasurfaces, accelerating the development of chiral photonics for health and information technologies.

Small extracellular vesicles, often termed as “exosomes” carry informative cargo containing proteins and lipids, reflective of their cellular origin. Thus, they are promising biomarkers for early diagnosis of cancer. However, conventional profiling methods like quantitative polymerase chain reaction (qPCR) require complex procedures, thereby limiting the analytical sensitivity of exosomes for liquid biopsies. Here, we demonstrate a sensitive microfluidic device (CDEXO) that isolates and profiles cancer-associated exosomes directly from blood plasma using assembled chiral gold nanoparticles (AuNPs). The unique changes in chiral signals are associated with specific biomolecules on the exosomes’ membranes. Thus, we can distinguish exosomes of lung cancer patients from those of healthy individuals and detect mutated EGFR proteins on the membrane. Hence, this low-cost microfluidic device is an attractive technique for rapid, sensitive, and versatile profiling of various extracellular vesicles. Methods: The top layer of CDEXO devices were fabricated by soft lithography using polydimethylsiloxane (PDMS). The bottom glass slide was functionalized with a layer-by-layer assembly of cationic poly(dimethyl diallyl ammonium chloride) and anionic polystyrene sulfonate. AuNPs were prepared by adding gold nanoplates to a growth solution. Next, AuNPs were conjugated with biotinylated Annexin-V, using Neutravidin-biotin chemistry. Exosomes were harvested from lung cancer cell lines (A549, H1650, H3255) and lung fibroblasts (MRC5) and spiked into the CDEXO chip. EDTA was used to release the captured exosomes and quantified using nanoparticle tracking analysis (NTA). CD spectra were measured by spectrometry. Imaging of AuNPs and exosomes were done using scanning electron microscope (SEM). Results: CDEXO captures cancer-associated exosomes with an efficiency of 81.1±1.5%. H3255 derived exosomes that exhibited EGFR point mutation showed the greatest change in spectral signals from the baseline, followed by A549 (wild type), H1650, (EGFR exon19 deletion) and MRC5 (healthy). The CD responses were measurable at exosome numbers as low as 100. Further validation with 19 lung cancer patients showed an average 40% change in chiral signals from isolated exosomes that were 5.6 times higher in patients than healthy donors. Conclusions: A microfluidic device with chiral AuNPs allows sensitive and accurate detection of lung cancer-associated exosomes by conjugation with Annexin V. The resulting strong CD peaks that arise from specific interactions between exosomal surface proteins and chiral AuNPs facilitate in-depth profiling of target exosomes, including EGFR mutation expression. Citation Format: Yoon-Tae Kang, Ji-Young Kim, Emine Sumeyra Turali-Emre, Hee-Jeong Jang, Minjeong Cha, Abha Kumari, Colin Palacios-Rolston, Chitra Subramanian, Emma Purcell, Sarah Owen, Chung-Man Lim, Rishindra Reddy, Shruthi Jolly, Nithya Ramnath, Nicholas A. Kotov, Sunitha Nagrath. Chiroptical detection and mutation analysis of cancer-associated extracellular vesicles in microfluidic devices with oriented chiral nanoparticles [abstract]. In: Proceedings of the American Association for Cancer Research Annual Meeting 2023; Part 1 (Regular and Invited Abstracts); 2023 Apr 14-19; Orlando, FL. Philadelphia (PA): AACR; Cancer Res 2023;83(7_Suppl):Abstract nr 994.

Chirality is a geometrical property described by continuous mathematical functions.1–5 However, in chemical disciplines chirality is often treated as a binary left/right characteristic of molecules rather than a continuity of chiral shapes. While being theoretically possible, a family of stable chemical structures with the same shape and progressively tunable chirality is yet unknown. Here we present such structures in the form of nanostructured microparticles with anisotropic bowtie shape and widely tunable twist angle, pitch, size, 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 conditions.6 The bowties nanoassemblies display multiple strong circular dichroism peaks originating from absorptive and scattering phenomena. Unlike classical chiral molecules, these particles display 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 tunable positive/negative polarization signatures for light detection and ranging (LIDAR) devices.

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., Organic photovoltaics suffer from degradation. Here, Nam et al. develop a quaternary blend and fabricate devices which lose 28% of their initial efficiency after one year of operation at 65 °C.

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.

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.

The conversion and manipulation of light via luminescent down-shifting (LDS) show promise in numerous applications. An elegant combination of lanthanide-doped polymer-derived ceramics incorporated with versatile nanopatterns is demonstrated using direct nanoimprint techniques. The prompt formation of nanoscale photonic structures enhances the fluorescence emission from the LDS while retaining the material's optical transparency. The functionality of this material is further expanded to accommodate surface energy modulation by nanopatterns. The practical applicability of this platform in photovoltaic devices is evaluated, showing distinctively enhanced efficiency and lifetime mainly attributed to the nanopattern assisted strong LDS property. Moreover, to efficiently combine two lanthanide emissions, so called a “double imprint” approach is devised by superpositioning two LDS nanopatterned arrays. Combined with the multi-functionality such as prominent LDS characteristics, color tunability, and surface energy modulation, the developed LDS platform offers promise for esthetic building-integrated photovoltaics.