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Micrometer-sized single crystal cathodes have garnered significant interest as promising cathode materials for lithium-ion batteries due to their ability to reduce surface area exposure to electrolytes and suppress side reactions, thereby enhancing electrochemical performance. One of the challenging issues with single crystal cathode materials is synthesizing monodisperse and discrete single crystals rather than agglomerated quasi-single crystals. However, conventional solid-state synthesis of most single crystals results in severe agglomeration and cation mixing, as it requires high temperatures to promote particle growth to several micrometers. In this study, a novel morphology-conserving reaction strategy that employs octahedron single crystal intermediates is introduced to synthesize discrete, monodisperse LiNi 0.97 Co 0.02 Mn 0.01 O 2 octahedron single crystals. This scalable and cost-effective approach involves using rock-salt Ni 0.97 Co 0.02 Mn 0.01 O 1+ x octahedrons as single crystal intermediates, which are transformed in unreactive unary lithium salt melts (LiCl and Li 2 SO 4 ) from spherical Ni 0.97 Co 0.02 Mn 0.01 (OH) 2 obtained via coprecipitation. These intermediates are then subjected to a stoichiometric amount of Li precursor in a conventional solid-state synthesis to produce layered LiNi 0.97 Co 0.02 Mn 0.01 O 2 . This process is a morphology-conserving lithiation reaction, leading to the formation of discrete and monodisperse LiNi 0.97 Co 0.02 Mn 0.01 O 2 octahedron single crystals. The resultant LiNi 0.97 Co 0.02 Mn 0.01 O 2 single crystals demonstrate superior electrochemical performance, including stable capacity retention over 150 cycles, which surpasses that of typical quasi-single crystals produced through conventional methods. This is attributed to negligible crack formation during cycling, in contrast to significant cracking observed in conventional quasi-single crystals. This implies that single-crystal forms are preferred over agglomerated quasi-single crystal forms for enhancing cycle performance. These findings provide valuable insights into the industrial synthesis of discrete and monodisperse ultrahigh-nickel oxide cathode materials.

The mononuclear phagocytic system clears the circulating inorganic nanomaterials from the bloodstream, which raises concerns about the chronic toxicity of the accumulated metal species. A better understanding of the behavior of each metal after systemic injection is thus required for clinical translations. This study investigates the significance of the metal-ligand interaction on the accumulation of cerium and demonstrates that only the form in which cerium is coordinated to a multidentate chelator with a strong binding affinity does not accumulate in major organs. Specifically, cerium complexed with diethylenetriamine pentaacetic acid (DTPA) forms renally excretable nanoparticles in vivo to circumvent the leaching of cerium ions, whereas weakly coordinated cerium-based nanomaterials produce insoluble precipitates upon encountering physiological phosphate anions. Ceria-based renally clearable nanoparticles (CRNs) derived from cerium-DTPA are utilized as the antioxidant pair with iron-DTPA, in which their combination leverages the Fenton reaction to synergistically scavenge hydrogen peroxide. This reduces the gene expression of pro-inflammatory factors in the macrophages activated with lipopolysaccharide as well as improves the survival rate of septic mice by alleviating the systemic inflammatory response and its downstream tissue injury in the liver, spleen, and kidneys. This study demonstrates that CRNs combined with iron-DTPA can be utilized as nonaccumulative nanomedicines for treating systemic inflammation, thereby overcoming the limitations of conventional ceria nanoparticle-based treatments.

Regulators of G-protein signaling (RGS) are a family of approximately 30 proteins that bind to and deactivate the alpha subunits of G-proteins (G α ) by accelerating their GTP hydrolysis rates, which terminates G-protein coupled receptor (GPCR) signaling. Thus, RGS proteins are essential in regulating GPCR signaling, and most members are implicated as critical nodes in human diseases such as hypertension, depression, and others. Regulator of G-protein signaling 2 (RGS2), a member of the R4 family of RGS proteins, is overexpressed in many solid breast cancers, and its levels in prostate cancer significantly correlate with the metastatic stage and poor prognosis. We sought to develop RGS2 inhibitors as potential chemotherapeutic agents utilizing structure-based drug design approaches. Available structures of the RGS2-G α complex were used to extract a pharmacophore model for searching chemical databases. Docking of identified hits to RGS2 as well as other RGS structures was used to screen the hits for potent and selective RGS2 inhibitors. Whole cell assays showed the top 10 ranking compounds, AJ-1-AJ-10, to inhibit RGS2-G αq interactions. Differential scanning fluorimetry showed AJ-3 to bind RGS2 but not G αq . All 10 compounds inhibited the growth of several RGS2 expressing cancers in cell culture assays. In addition, AJ-3 inhibited the migration of LNCaP prostate cancer cells in wound healing assays. This is the first group of RGS2 inhibitors identified by structure-based approaches and that show anticancer activity. These results highlight the potential RGS2 inhibitors have to be a new class of chemotherapeutic agents.

Raman spectroscopy has emerged as a pivotal analytical instrument, valued for its nondestructive capabilities and its capacity to provide essential material-specific insights. However, the excessive costs associated with commercially available Raman instruments present a barrier to their accessibility for many academic institutions and broader usage. Herein, we introduce an affordable and accessible approach to constructing a versatile Raman instrument capable of accommodating both spectroscopic and microscopic analyses. Through this multimodal approach that concurrently captures Raman signal and image data, we demonstrate color-based alcohol detection, showcase a high signal-to-noise ratio achieved through meticulous hardware design and signal processing, and present a cost-effective, modular design utilizing 3D printing technology. This system offers adaptability to address diverse research needs and requirements. We systematically detail the fabrication process, including the utilization of a 3D printer to produce necessary components, ultimately resulting in the assembly of a functional Raman probe system. Our experiments and subsequent analyses substantiate the accuracy and reliability of the constructed system. Specifically, we conducted experiments involving three distinct samples: water, ethanol, and methanol using the Raman probe, successfully confirming their unique Raman spectra. Furthermore, our Raman probe accurately identified ethanol concentration by assessing mixed samples with varying water-to-ethanol ratios and demonstrated a coefficient of determination value of 0.9993. This underscores the performance of the constructed Raman probe and positions it as a viable option for characterization, particularly in regions where access to conventional Raman probe may be limited., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

Ni-rich layered oxides have received significant attention as promising cathode materials for Li-ion batteries due to their high reversible capacity. However, intergranular and intragranular cracks form at high state-of-charge (SOC) levels exceeding 4.2 V (vs. Li/Li + ), representing a prominent failure mechanism of Ni-rich layered oxides. The nanoscale crack formation at high SOC levels is attributed to a significant volume change resulting from a phase transition between the H2 and H3 phases. Herein, in contrast to the electrochemical crack formation at high SOC levels, another mechanism of chemical crack and pit formation on a nanoscale is directly evidenced in fully lithiated Ni-rich layered oxides (low SOC levels). This mechanism is associated with intergranular stress corrosion cracking, driven by chemical corrosion at elevated temperatures. The nanoscopic chemical corrosion behavior of Ni-rich layered oxides during aging at elevated temperatures is investigated using high-resolution transmission electron microscopy, revealing that microcracks can develop through two distinct mechanisms: electrochemical cycling and chemical corrosion. Notably, chemical corrosion cracks can occur even in a fully discharged state (low SOC levels), whereas electrochemical cracks are observed only at high SOC levels. This finding provides a comprehensive understanding of the complex failure mechanisms of Ni-rich layered oxides and provides an opportunity to improve their electrochemical performance.

The high theoretical capacity (∼2000 mAh g -1 ) of silicon suboxide (SiO x , with 1 < x < 2) can solve the energy density issue of the graphite anode in Li-ion batteries. In addition, it has an advantage in terms of volume expansion or side reactions compared to pure Si or Li metals, which are considered as next-generation anode materials. However, the loading content of SiO x is limited in commercial anodes because of its low cycle stability and initial coulombic efficiency. In this study, a nitrogen-doped carbon layer with Cu beads (N-C/Cu) derived from copper phthalocyanine (CuPc) is applied to a SiO x electrode to improve its electrochemical performance. The SiO x electrode is simultaneously coated with a Cu- and N-doped carbon layer using CuPc. N-C/Cu synergistically enhances the electric conductivity of the electrode, thus improving its electrochemical performance. The SiO x /N-C/Cu composite has better cyclability and higher capacity (1095.5 mAh g -1 ) than the uncoated electrode, even after 200 cycles in the 0.5 C condition. In full-cell cycling with NCM811 cathodes, the SiO x (60 wt % of SiO x , with a n/p ratio of 1.1) and graphite-mixed (7.8 wt % of SiO x , with a n/p ratio of 1.1) anodes also show improved electrochemical performances in the same conditions.

Salt concentration-dependent structure of complex coacervate core micelles (C3Ms), formed by polyether-based block copolyelectrolytes containing cationic ammonium (A) or anionic sulfonate (S) groups in aqueous media, is investigated by light scattering and small-angle X-ray/neutron scattering (SAX/NS). As the salt concentration increases, both a core radius ( R core ) and an aggregation number ( N agg ) significantly decrease, but a corona thickness ( L corona ) is nearly unchanged. Larger salt concentrations can lower the interfacial tension between the coacervate cores and aqueous media, resulting in an increased interfacial area per chain and a more relaxed conformation of the core blocks. Based on the structure characterization, the scaling relationship between structure parameters (i.e., R core , N agg , and L corona ) and salt concentration is obtained and compared to the theoretical description estimated by the free energy balance between the entropic penalty of core stretching and the interfacial energy. We propose that the free energy contribution of the core block stretching is not negligible in C3Ms because of the highly swollen cores caused by water.

Oxide semiconductors (OS) are attractive materials for memory and logic device applications owing to their low off-current, high field effect mobility, and superior large-area uniformity. Recently, successful research has reported the high field-effect mobility (μ FE ) of crystalline OS channel transistors (above 50 cm 2 V -1 s -1 ). However, the memory and logic device application presents challenges in mobility and stability trade-offs. Here, we propose a method for achieving high-mobility and high-stability by lowering the grain boundary effect. A DBADMIn precursor was synthesized to deposit highly c -axis-aligned C(222) crystalline 3 nm thick In 2 O 3 films. In this study, the 250 °C deposited 3 nm thick In 2 O 3 channel transistor exhibited high μ FE of 41.12 cm 2 V -1 s -1 , V th of -0.50 V, and SS of 150 mV decade -1 with superior stability of 0.16 V positive shift during PBTS at 100 °C, 3 MV cm -1 stress conditions for 3 h.

Monolayered transition-metal dichalcogenides (TMDs) are easily exposed to air, and their crystal quality can often be degraded via oxidation, leading to poor electronic and optical device performance. The degradation becomes more severe in the presence of defects, grain boundaries, and residues. Here, we report crack propagation in pristine TMD monolayers grown by chemical vapor deposition under ambient conditions and light illumination. Under a high relative humidity (RH) of ∼60% and white light illumination, the cracks appear randomly. Photo-oxidative cracks gradually propagated along the grain boundaries of the TMD monolayers. In contrast, under low RH conditions of ∼2%, cracks were scarcely observed. Crack propagation is predominantly attributed to the accumulation of water underneath the TMD monolayers, which is preferentially absorbed by hygroscopic alkali metal-based precursor residues. Crack propagation is further accelerated by the cyclic process of photo-oxidation in a basic medium, leading to localized tensile strain. We also found that such crack propagation is prevented after the removal of alkali metals via the transfer of the sample to other substrates.

We explored trans - and cis -2-aminocycloheptanecarboxylic acid (ACHpC) as potential building blocks for helical foldamers. trans -ACHpC does not show sufficient folding propensity in unnatural peptides. cis -ACHpC promotes nontraditional helices of two unnatural peptide backbones: the 11/9-helix for 1:1 α/β-peptides and the 12/10-helix for β-peptides with interconvertible handedness. The two opposite-handed 12/10-helices rapidly interconvert in solution by pseudorotation of the two twist chair forms of the cycloheptane moiety in each cis -ACHpC residue.

The scaling relationship of complex coacervate core micelles (C3Ms) has been investigated experimentally and theoretically. The C3Ms are formed by mixing two oppositely charged block copolyelectrolyte solutions (i.e., AB + AC system) and are characterized by small-angle neutron (SANS) and X-ray scattering (SAXS). Scaling relationships for micellar structure parameters, including core radius, total radius, corona thickness, and aggregation number, all with respect to the core block length, are determined. A scaling theory is also proposed by minimizing the free energy per chain, leading to four regimes depending on the core and corona chain conformations. Although the corona block is significantly longer than the core block, the structure of our C3Ms is consistent with that of the crew-cut I regime. A highly swollen core by water enables the core blocks to be stretched significantly and corona chains to be minimally overlapped.

Recent advancements in wearable electronics offer seamless integration with the human body for extracting various biophysical and biochemical information for real-time health monitoring, clinical diagnostics, and augmented reality. Enormous efforts have been dedicated to imparting stretchability/flexibility and softness to electronic devices through materials science and structural modifications that enable stable and comfortable integration of these devices with the curvilinear and soft human body. However, the optical properties of these devices are still in the early stages of consideration. By incorporating transparency, visual information from interfacing biological systems can be preserved and utilized for comprehensive clinical diagnosis with image analysis techniques. Additionally, transparency provides optical imperceptibility, alleviating reluctance to wear the device on exposed skin. This review discusses the recent advancement of transparent wearable electronics in a comprehensive way that includes materials, processing, devices, and applications. Materials for transparent wearable electronics are discussed regarding their characteristics, synthesis, and engineering strategies for property enhancements. We also examine bridging techniques for stable integration with the soft human body. Building blocks for wearable electronic systems, including sensors, energy devices, actuators, and displays, are discussed with their mechanisms and performances. Lastly, we summarize the potential applications and conclude with the remaining challenges and prospects.

Solar energy is the most promising, efficient, environmentally friendly energy source with the potential to meet global demand due to its non-polluting nature. Herein, a porous Zn 1- x Cd x Se/ZnO nanorod (NR) heterojunction was synthesized by hydrothermal and low-temperature solvothermal methods. First, the ZnO NR was grown on a Zinc foil, and an inorganic-organic hybrid ZnSe(en) 0.5 material was developed by the low-temperature solvothermal method. In this work, the ZnO NR acted as a base material and a building block for the growth of ZnSe(en) 0.5 . Moreover, after the solvothermal process, the reduced Se 2- reacts with the ZnO NR and forms inorganic-organic hybrid ZnSe(en) 0.5 . After the selenization process, the obtained material shows a red brick color due to the absorbance of excessive Se metal particles during the solvothermal process. Furthermore, in order to enhance the photoelectrochemical properties, the Cd 2+ ion exchange method was applied at various temperatures (140, 160, and 180 °C for 3 h) to produce a precursor material to a porous Zn 1- x Cd x Se/ZnO NR nanostructure. The optimum Zn 1- x Cd x Se/ZnO NR-160 photoanode showed a high photocurrent density of 7.8 mA·cm -2 at -0.5 V vs . Ag/AgCl with a hydrogen evolution rate of 199 μmol·cm -2 /3 h. The improved photocurrent performance was attributed to effective light absorption and prolonged recombination lifetime.

Temperature plays a crucial role in the preparation of polyvinyl chloride (PVC) gels for optical applications. Incorrect temperature selection can lead to various issues such as poor surface roughness, inadequate light transmission, and insufficient solution for optical devices. To address this challenge, this study focuses on the preparation of PVC gel samples by combining PVC powder ( n = 3000), eco-friendly dibutyl adipate, and tetrahydrofuran at different stirring temperatures ranging from 40 to 70 °C. The PVC gel preparation process is categorized into four groups ( T 40, T 50, T 60, and T 70) based on the mixing temperatures, employing a controlled test method with specific temperature conditions. The prepared PVC gel samples are then subjected to analysis to evaluate various properties including surface morphology, tensile strength, light transmittance, and electrical response time. Among the samples, the PVC gel prepared at 60 °C (referred to as T60) exhibits excellent optical properties, with a transmittance of 91.2% and a tensile strength of 2.07 MPa. These results indicate that 60 °C is an optimal reaction temperature. Notably, the PVC gel microlenses produced at this temperature achieve their maximum focal length (ranging from -8 to -20 mm) within approximately 60 s, and they recover their initial state within around 80 s after the power is switched off. This focal length achievement is twice as fast as reported in previous studies on microlenses. It is observed that the reaction temperature significantly influences the solubility of the resin-based raw materials and the homogeneity of the gel. Consequently, these findings open up possibilities for utilizing PVC gel microlenses in novel commercial optics applications, thanks to their desirable properties., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Herein, we present the iron-catalyzed oxidative cyclization of alcohol/methyl arene with 2-amino styrene to synthesize polysubstituted quinoline. Low-oxidation level substrates such as alcohols and methyl arenes are converted to aldehydes in the presence of an iron catalyst and di- t -butyl peroxide. Then, the quinoline scaffold is synthesized through imine condensation/radical cyclization/oxidative aromatization. Our protocol showed a broad substrate scope, and various functionalization and fluorescence applications of quinoline products demonstrated its synthetic ability.

Postsurgical treatment of glioblastoma multiforme (GBM) by systemic chemotherapy and radiotherapy is often inefficient. Tumor cells infiltrating deeply into the brain parenchyma are significant obstacles to the eradication of GBM. Here, we present a potential solution to this challenge by introducing an injectable thermoresponsive hydrogel nanocomposite. As a liquid solution that contains drug-loaded micelles and water-dispersible ferrimagnetic iron oxide nanocubes (wFIONs), the hydrogel nanocomposite is injected into the resected tumor site after surgery. It promptly gelates at body temperature to serve as a soft, deep intracortical drug reservoir. The drug-loaded micelles target residual GBM cells and deliver drugs with a minimum premature release. Alternating magnetic fields accelerate diffusion through heat generation from wFIONs, enabling penetrative drug delivery. Significantly suppressed tumor growth and improved survival rates are demonstrated in an orthotopic mouse GBM model. Our system proves the potential of the hydrogel nanocomposite platform for postsurgical GBM treatment.

α-Alkyl and α-olefin nitriles are very important for organic synthesis and medicinal chemistry. However, different types of catalysts are employed to achieve either α-alkylation of nitriles by borrowing hydrogen or α-olefination by dehydrogenative coupling methods. Designing and developing high-performance earth-abundant catalysts that can procure different products from the same starting materials remain a great challenge. Herein, we report an iron(0) catalyst system that achieves chemoselectivity between borrowing hydrogen and dehydrogenative coupling protocols by simply changing the base. A broad range of nitriles and alcohols, including benzylic, linear aliphatic, cycloaliphatic, heterocyclic, and allylic alcohols, were selectively and efficiently converted to the corresponding products. Mechanistic studies reveal that the reaction mechanism proceeds through a dehydrogenative pathway. This iron catalytic protocol is environmentally benign and atom-efficient with the liberation of H 2 and H 2 O as green byproducts.

High pressure or strain is an effective strategy for generating phase transformations in van der Waals (vdW) layered materials without introducing defects, but this approach remains difficult to perform consistently. We present a scalable and facile method for achieving phase transformation in vdW materials, wherein solid vdW materials are subject to internal thermal stress within a molten metal mantle as it undergoes cooling. This internal thermal stress is principally the product of differential thermal expansion between mantle and core and can be tuned by the mantle material and temperature conditions. We validated this approach by achieving phase transformation of red phosphorus to black phosphorus, and metallic 1T'- to semiconducting 2H-MoTe 2 crystals. We further demonstrate quantum electronic phase transformation of suppressed charge density wave in TiSe 2 by means of electron-phonon coupling using the same system.

Melicoptelines, natural cyclopeptides containing a 3a-hydroxy hexahydropyrrolo[2,3- b ]indole (HPI) moiety, exhibit anti-influenza activity. Herein, we report the first total synthesis of melicoptelines C-E ( 1-3 , respectively). The core 3a-hydroxy HPIs were synthesized in a diastereoselective manner from l-tryptophan using dimethyldioxirane-mediated oxidation. Subsequently, sequential peptide couplings and cyclization completed the synthesis of melicoptelines C-E and unnatural melicopteline 4 . The synthesized melicoptelines were evaluated for their anti-influenza activity, and melicopteline E showed the most potent inhibition of cytopathic effects.

Vertical van der Waals heterostructures (vdWhs), which are made by layer-by-layer stacking of two-dimensional (2D) materials, offer great opportunities for the development of extraordinary physics and devices such as topological superconductivity, robust quantum Hall phenomenon, electron-hole pair condensation, Coulomb drag, and tunneling devices. However, the size of vdWhs is still limited to the order of a few micrometers, which restricts the large-scale roll-to-roll processes for industrial applications. Herein, we report the sequential growth of a 14 in. vertical vdWhs on a rollable Al foil via chemical vapor deposition. By supplying chalcogen precursors to liquid transition-metal precursor-coated Al foils, we grew a wide range of individual 2D transition-metal dichalcogenide (TMD) films, including MoS 2 , VS 2 , ReS 2 , WS 2 , SnS 2 , WSe 2 , and vanadium-doped MoS 2 . Additionally, by repeating the growth process, we successfully achieved the layer-by-layer growth of ReS 2 /MoS 2 and SnS 2 /ReS 2 /MoS 2 vdWhs. The chemically inert Al native oxide layer inhibits the diffusion of chalcogen and metal atoms into Al foils, allowing for the growth of diverse TMDs and their vdWhs. The conductive Al substrate enables the effective use of vdWhs/Al as a hydrogen evolution reaction electrocatalyst with a transfer-free process. This work provides a robust route for the commercialization of 2D TMDs and their vdWhs at a low cost.

The study of Alzheimer's disease (AD), the most common cause of dementia, faces challenges in terms of understanding the cause, monitoring the pathogenesis, and developing early diagnoses and effective treatments. Rapid and accurate identification of AD biomarkers in the brain is critical to providing key insights into AD and facilitating the development of early diagnosis methods. In this work, we developed a platform that enables a rapid screening of AD biomarkers by employing graphene-assisted Raman spectroscopy and machine learning interpretation in AD transgenic animal brains. Specifically, we collected Raman spectra on slices of mouse brains with and without AD and used machine learning to classify AD and non-AD spectra. By contacting monolayer graphene with the brain slices, the accuracy was increased from 77% to 98% in machine learning classification. Further, using a linear support vector machine (SVM), we identified a spectral feature importance map that reveals the importance of each Raman wavenumber in classifying AD and non-AD spectra. Based on this spectral feature importance map, we identified AD biomarkers including Aβ and tau proteins and other potential biomarkers, such as triolein, phosphatidylcholine, and actin, which have been confirmed by other biochemical studies. Our Raman-machine learning integrated method with interpretability will facilitate the study of AD and can be extended to other tissues and biofluids and for various other diseases.

Single-conformation IR and UV spectroscopy of the prototypical capped γ-peptide Ac-γ 4 -Phe-NHMe (γ 4 F) was carried out under jet-cooled conditions in the gas phase in order to understand its innate conformational preferences in the absence of a solvent. We obtained conformer-specific IR and UV spectra and compared the results with calculations to make assignments and explore the differences between the γ 2 - and γ 4 -substituted molecules. We found four conformers of γ 4 F in our experiment. Three conformers form nine-membered hydrogen-bonded rings (C9) enclosed by an NH···O═C H-bond but differing in their phenyl ring positions (a, g+, and g-). The fourth conformer forms a strained seven-membered hydrogen-bonded ring in which the amide groups lie in a nominally anti-parallel arrangement stacked on top of one another (labeled S7). This conformer is a close analogue of the amide-stacked conformer (S) found previously in γ 2 F, in which the Phe side chain is substituted at the γ 2 position, Ac-γ2-Phe-NHMe ( J. Am. Chem. Soc. 2009, 131, 14243-14245). IR population transfer spectroscopy was used to determine the fractional abundances of the γ 4 F conformers in the expansion. A combination of force field and density functional theory calculations is used to map out the conformational potential energy surfaces for γ 4 F and compare it with its γ 2 F counterpart. Based on this analysis, the phenyl ring prefers to take up structures that facilitate NH···π interactions in γ 4 F or avoid phenyl interactions with the C═O group in γ 2 F. The disconnectivity graph for γ 4 F reveals separate basins associated with the C9 and amide-stacked conformational families, which are separated by a barrier of about 42 kJ/mol. The overall shape of the potential energy surface bears a resemblance to peptides and proteins that have a misfolding pathway that competes with the formation of the native structure.

An urgent need in chemodynamic therapy (CDT) is to achieve high Fenton catalytic efficiency at small doses of CDT agents. However, simple general promotion of the Fenton reaction increases the risk of damaging normal cells along with the cancer cells. Therefore, a tailored strategy to selectively enhance the Fenton reactivity in tumors, for example, by taking advantage of the characteristics of the tumor microenvironment (TME), is in high demand. Herein, a heterogeneous CDT system based on copper-iron peroxide nanoparticles (CFp NPs) is designed for TME-mediated synergistic therapy. CFp NPs degrade under the mildly acidic conditions of TME, self-supply H 2 O 2 , and the released Cu and Fe ions, with their larger portions at lower oxidation states, cooperatively facilitate hydroxyl radical production through a highly efficient catalytic loop to achieve an excellent tumor therapeutic efficacy. This is distinct from previous heterogeneous CDT systems in that the synergism is closely coupled with the Cu + -assisted conversion of Fe 3+ to Fe 2+ rather than their independent actions. As a result, almost complete ablation of tumors at a minimal treatment dose is demonstrated without the aid of any other therapeutic modality. Furthermore, CFp NPs generate O 2 during the catalysis and exhibit a TME-responsive T 1 magnetic resonance imaging contrast enhancement, which are useful for alleviating hypoxia and in vivo monitoring of tumors, respectively.

Injectable hydrogels show high potential for in vivo biomedical applications owing to their distinctive mode of administration into the human body. In this study, we propose a material design strategy for developing a multifunctional injectable hydrogel with good adhesiveness, stretchability, and bioresorbability. Its multifunctionality, whereupon multiple reactions occur simultaneously during its injection into the body without requiring energy stimuli and/or additives, was realized through meticulous engineering of bioresorbable precursors based on hydrogel chemistry. The multifunctional injectable hydrogel can be administered through a minimally invasive procedure, form a conformal adhesive interface with the target tissue, dynamically stretch along with the organ motions with minimal mechanical constraints, and be resorbed in vivo after a specific period. Further, the incorporation of functional nanomaterials into the hydrogel allows for various in vivo diagnostic and therapeutic applications, without compromising the original multifunctionality of the hydrogel. These features are verified through theranostic case studies on representative organs, including the skin, liver, heart, and bladder.

The catalog of enzymes known to catalyze the nucleophile-assisted formation of C-C bonds is extremely small, and there is presently no definitive example of a biological Rauhut-Currier reaction. Biosynthesis of the polyketide insecticide spinosyn A in Saccharopolyspora spinosa involves a [4 + 2]-cycloaddition and a subsequent intramolecular C-C bond formation catalyzed by SpnF and SpnL, respectively. Isotope tracer experiments and kinetic isotope effects, however, imply that the SpnL-catalyzed reaction proceeds without initial deprotonation of the substrate. The crystal structure of SpnL exhibits high similarity to SAM-dependent methyltransferases as well as SpnF. The residue Cys60 is also shown to reside in the SpnL active site, and the Cys60Ala SpnL mutant is found to be devoid of activity. Moreover, SpnL is covalently modified at Cys60 and irreversibly inactivated when it is coincubated with a fluorinated substrate analogue designed as a suicide inactivator of nucleophile-assisted C-C bond formation. These results suggest that SpnL catalyzes a biological Rauhut-Currier reaction.

The instability of van der Waals (vdW) materials leads to spontaneous morphological and chemical transformations in the air. Although the passivation of vdW materials with other resistive materials is often used to solve stability issues, this passivation layer can block carrier injection and thus interfere with charge transfer doping. In this study, a facile method is proposed for n-doping and mediation of Se vacancies in tungsten diselenide (WSe 2 ) by poly(vinylpyrrolidone) (PVP) coating. The major carrier type of the PVP-coated WSe 2 -based field-effect transistor (FET) was converted from hole (p-type) to electron (n-type). Furthermore, the vacancy-induced interface trap density was reduced by approximately 500 times. This study provides a practical doping and passivation method for the van der Waals materials, as well as a comprehensive understanding of the chemical reaction and electronic transport in these materials.

Evaporation-induced particle aggregation in drying droplets is of significant importance in the prevention of pathogen transfer due to the possibility of indirect fomite transmission of the infectious virus particles. In this study, particle aggregation was directionally controlled using contact line dynamics (pinned or slipping) and geometrical gradients on microstructured surfaces by the systematic investigation of the evaporation process on sessile droplets and sprayed microdroplets laden with virus-simulant nanoparticles. Using this mechanism, we designed robust particle capture surfaces by significantly inhibiting the contact transfer of particles from fomite surfaces. For the proof-of-concept, interconnected hexagonal and inverted pyramidal microwall were fabricated using ultraviolet-based nanoimprint lithography, which is considered to be a promising scalable manufacturing process. We demonstrated the potentials of an engineered microcavity surface to limit the contact transfer of particle aggregates deposited with the evaporation of microdroplets by 93% for hexagonal microwall and by 96% for inverted pyramidal microwall. The particle capture potential of the interconnected microstructures was also investigated using biological particles, including adenoviruses and lung-derived extracellular vesicles. The findings indicate that the proposed microstructured surfaces can reduce the indirect fomite transmission of highly infectious agents, including norovirus, rotavirus, or SARS-CoV-2, via respiratory droplets.

Molecular exchange dynamics between spherical complex coacervate core micelles (C3Ms) are documented using time-resolved small-angle neutron scattering measurements (TR-SANS), and the effects of salt concentration, type of charges, and core block polydispersity to the chain exchange are quantified. Isotopically labeled block copolyelectrolytes were prepared by postpolymerization modification of two nearly identical poly(ethylene oxide- b -allyl glycidyl ether), one with normal and the other with deuterated PEO blocks (i.e., hPEO-PAGE and dPEO-PAGE). The observed rates at multiple salt concentrations are consolidated using time-salt superposition shift factors representing chain exchange rates and analyzed. Our comprehensive analytical relaxation function based on the sticky-Rouse model and the thermodynamic barrier for core block extraction successfully describes the molecular exchange kinetics between the isotopically labeled C3Ms. We believe this work provides fundamental design criteria for C3Ms with engineered chain exchange dynamics.

A spherical hollow carbon framework decorated with functional heteroatoms is designed and synthesized using ultrasonic spray pyrolysis as a potential anode material for lithium metal batteries (LMBs). The pore structure of the hollow carbon framework can be tailored by melamine, which is a functional additive for integrating abundant nanopores and the uniform decoration of heteroatoms in the structure. The large surface area and pore volume of the hollow carbon framework offer enhanced reversibility and capability for metallic Li storage. In addition, the dendritic growth of Li and volume changes induced by repeated Li plating and stripping can be effectively suppressed during cycling. More importantly, atomic-scale decorations of heteroatoms can effectively lower the overpotential for the nucleation and growth of metallic Li inside the hollow carbon framework. It is mainly responsible for improving the cycle performance and rate capability, even at a high current density. Finally, the hollow carbon framework anode shows stable behavior toward Li plating and stripping without significant capacity fading in the LMBs than conventional Li metal anodes.

While the hydrolytic cleavage of ester groups is widely exploited in degradable hydrogels, the scission in the midst of chain backbones can bring dramatic changes in the mechanical properties of the hydrogels. However, the predictive design of the mechanical profile of the hydrogels is a complex task, mainly due to the randomness of the location of chain scission. To overcome this challenge, we herein present degradable ABA triblock poly(ethylene oxide)-based hydrogels containing an A-block bearing acetal pendant, which provides systematically tunable mechano-temporal properties of the hydrogels. In particular, hydrophobic endocyclic tetrahydropyranyl or exocyclic 1-(cyclohexyloxy)ethyl acetal pendants are gradually cleaved by acidic hydrolysis, leading to the gel-to-sol transition at room temperature. Most importantly, a series of dynamic mechanical analyses coupled with ex situ NMR spectroscopy revealed that the hydrolysis rate can be orthogonally and precisely tuned by changing the chemical structure and hydrophobicity of acetal pendants. This study provides a platform for the development of versatile degradable hydrogels in a highly controllable manner.

Self-assembly of gold nanoparticles (AuNPs) into highly ordered superstructures provides a promising route toward fabricating materials with new functionalities or enhanced physical properties. Although self-assembly of AuNPs has garnered significant research attention recently, a highly ordered superlattice of AuNPs under a low concentration in a confined geometry formed by nonfunctionalized materials has not been reported. Herein, we investigate the self-assembly of a 2D AuNPs superlattice in a polymer vesicle layer using hydrophobic interactions, which exhibits centered rectangular lattice symmetry. To create the highly ordered AuNPs superlattice, the P(EG x - b -iPGE y ) block copolymers that form the thickness of the hydrophobic vesicle layer comparable to the size of the AuNP are used as a template to control the AuNP degree of freedom. To the best of our knowledge, this study provides the first demonstration of a centered rectangular structure formation of AuNPs at the vesicle layer in 2D confined geometry.

Over the past several decades, tin monoxide (SnO) has been studied extensively as a p-type thin film transistor (TFT). However, its TFT performance is still insufficient for practical use. Many studies suggested that the instability of the valence state of Sn (Sn 2+ /Sn 4+ ) is a critical reason for the poor performance such as limited mobility and low on/off ratio. For SnO, the Sn 5s-O 2p hybridized state is a key component for obtaining p-type conduction. Thus, a strategy for stabilizing the SnO phase is essential. In this study, we employ a variety of analytical methods such as X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and Hall measurement to identify the main contributors to the physical properties of SnO. It is revealed that precision control of the process temperature is needed to achieve both the crystallinity and thermal stability of SnO. In other words, it would be ideal to obtain high-quality SnO thin films at low temperature. We find that atomic layer deposition (ALD) is a quite advantageous process for obtaining high-quality SnO thin films by the following two-step process: (i) growth of highly c -axis oriented SnO at the initial stage and (ii) further crystallization along the in-plane direction by a postannealing process. Consequently, we obtained a highly dense SnO thin film (film density: 6.4 g/cm 3 ) with a high Hall mobility of ∼5 cm 2 /(V·s). The fabricated SnO TFTs exhibit a field-effect mobility of ∼6.0 cm 2 /(V·s), which is a quite high value among the SnO TFTs reported to date, with long-term stability. We believe that this study demonstrates the validity of the ALD process for SnO TFTs.

Tau aggregation is believed to have a strong association with the level of cognitive deficits in Alzheimer's disease (AD). Thus, optical brain imaging of tau aggregates has recently gained substantial attention as a promising tool for the early diagnosis of AD. However, selective imaging of tau aggregates is a major challenge due to sharing similar β-sheet structures with homologous Aβ fibrils. Herein, four quinoline-based fluorescent probes (Q-tau) were judiciously designed using the donor-acceptor architecture for selective imaging of tau aggregates. In particular, probe Q-tau 4 exhibited a strong intramolecular charge transfer and favorable photophysical profile, such as a large Stokes' shift and fluorescence emission wavelength of 630 nm in the presence of tau aggregates. The probe also displayed a "turn-on" fluorescence behavior toward tau fibrils with a 3.5-fold selectivity versus Aβ fibrils. In addition, Q-tau 4 exhibited nanomolar binding affinity to tau aggregates ( K d = 16.6 nM), which was 1.4 times higher than that for Aβ fibrils. The mechanism of "turn-on" fluorescence was proposed to be an environment-sensitive molecular rotor-like response. Moreover, ex vivo labeling of human AD brain sections demonstrated favorable colocalization of Q-tau 4 and the phosphorylated tau antibody, while comparable limited staining was observed with Aβ fibrils. Molecular docking was conducted to obtain insights into the tau-binding mode of the probe. Collectively, Q-tau 4 has successfully been used as a tau-specific fluorescent imaging agent with lower background interference.

Atomic layer deposition (ALD) is a promising deposition method to precisely control the thickness and metal composition of oxide semiconductors, making them attractive materials for use in thin-film transistors because of their high mobility and stability. However, multicomponent deposition using ALD is difficult to control without understanding the growth mechanisms of the precursors and reactants. Thus, the adsorption and surface reactivity of various precursors must be investigated. In this study, InGaO (IGO) semiconductors were deposited by plasma-enhanced atomic layer deposition (PEALD) using two sets of In and Ga precursors. The first set of precursors consisted of In(CH 3 ) 3 [CH 3 OCH 2 CH 2 NHtBu] (TMION) and Ga(CH 3 ) 3 [CH 3 OCH 2 CH 2 NHtBu]) (TMGON), denoted as TM-IGO; the other set of precursors was (CH 3 ) 2 In(CH 2 ) 3 N(CH 3 ) 2 (DADI) and (CH 3 ) 3 Ga (TMGa), denoted as DT-IGO. We varied the number of InO subcycles between 3 and 19 to control the chemical composition of the ALD-processed films. The indium compositions of TM-IGO and DT-IGO thin films increased as the InO subcycles increased. However, the indium/gallium metal ratios of TM-IGO and DT-IGO were quite different, despite having the same InO subcycles. The steric hindrance of the precursors and different densities of the adsorption sites contributed to the different TM-IGO and DT-IGO metal ratios. The electrical properties of the precursors, such as Hall characteristics and device parameters of the thin-film transistors, were also different, even though the same deposition process was used. These differences might have resulted from the growth behavior, anion/cation ratios, and binding states of the IGO thin films.

Herein, we propose the topotactic and self-templated fabrication of Zn 1- x Cd x Se porous nanobelt-ZnO nanorod (termed as ZnCdSe/ZnO) photoelectrode via the cadmium (Cd 2+ ) ion-exchange process on zinc (Zn) foil. Inorganic-organic hybrid ZnSe(en) 0.5 nanobelt (NB) was synthesized on Zn foil by a facial solvothermal method at different temperatures of 140, 160, and 180 °C for 12 h. The interfacial properties and photoelectrochemical (PEC) performance of inorganic-organic ZnSe(en) 0.5 NB fabricated through the Cd 2+ ion-exchange method at different time durations of 6, 12, 18, and 24 h at 140 °C were investigated. The TEM analysis results indicate that the inorganic-organic ZnSe(en) 0.5 NB transformed into ZnCdSe and a self-assembled ZnO formed on the Zn foil. In particular Cd 2+ ion temperature (140 °C/18 h), the optimized ZnCdSe/ZnO-(F) photoelectrode shows an excellent photocurrent density of 14 mA·cm -2 at 0 V vs Ag/AgCl with 219 μmol·cm -2 hydrogen gas evolution for 3 h under 1 sun illumination. The higher photocurrent value resulted from the optimum growth of ZnO, the formation of porous ZnCdSe, and the effective electrolyte penetration for electron-hole pair separation. The photoluminescence spectroscopy shows that the photoexcited charged carriers promoted a longer lifetime. Furthermore, we provide a full account of the possible charge-transfer mechanism during PEC hydrogen production.

Elastin-like polypeptides (ELPs) are stimulus-responsive protein-based biopolymers, and some ELP block copolymers can assemble into spherical nanoparticles with thermosensitivity. In this study, two different ELP diblock copolymers, each composed of a hydrophobic and a charged moiety, were synthesized, and the dependence of their physical properties on pH, temperature, and salt concentration was investigated. A series of analyses revealed that hydrophobic core micelles could be generated in response to a change in their surroundings and that micelles did not self-aggregate, a phenomenon due to the repulsive forces between like-charged molecules on the surface. We also demonstrated that self-assembly behavior was closely dependent on the character of the charged amino acid and the specific anion in solution.

Various antibody-redirected immunotherapeutic approaches, including antibody-drug conjugates (ADCs), bispecific antibodies (bsAbs), and chimeric antigen receptor-T (CAR-T) cells, have been devised to produce specific activity against various cancer types. Using genetically encoded unnatural amino acids, we generated a homogeneous Her2-targeted ADC, a T cell-redirected bsAb, and a FITC-modified antibody capable of redirecting anti-FITC CAR-T (switchable CAR-T; sCAR-T) cells to target different Her2-expressing breast cancers. sCAR-T cells showed activity against Her2-expressing tumor cells comparable to that of conventional anti-Her2 CAR-T cells and superior to that of ADC- and bsAb-based approaches. To prevent antigen escape, we designed bispecific sCAR-T cells targeting both the Her2 receptor and IGF1R, which showed an overall improved activity against cancer cells with low Her2 expression. This study increases our understanding of various explored cancer therapeutics and underscores the efficient application of sCAR-T cells as a promising therapeutic option for breast cancer patients with low or heterogeneous antigen expression.

Zwitterionic polymers have extraordinary properties, that is, significant hydration and the so-called antipolyelectrolyte effect, which make them suitable for biomedical applications. The hydration induces an antifouling effect, and this has been investigated significantly. The antipolyelectrolyte effect refers to the extraordinary ion-responsive behavior of particular polymers that swell and hydrate considerably in physiological solutions. This actuation begins to attract attention to achieve in vivo antifouling that is challenging for general polyelectrolytes. In this study, we established the sophisticated cornerstone of the antipolyelectrolyte effect in detail, including (i) the essential parameters, (ii) experimental verifications, and (iii) effect of improving antifouling performance. First, we find that both osmotic force and charge screening are essential factors. Second, we identify the antipolyelectrolyte effect by visualizing the swelling and hydration dynamics. Finally, we verify that the antifouling performance can be enhanced by exploiting the antipolyelectrolyte effect and report reduction of 85% and 80% in ex and in vivo biofilm formation, respectively.

Natural killer (NK) cells have been recognized as a next-generation therapy for cancer as they are less likely to trigger adverse events ( e.g ., cytokine storm or graft-versus-host disease) than T cell-based therapeutics. Although NK cell activation strategies through genetic engineering and cytokine treatment have been actively studied for successful cancer treatment, the approaches are inefficient, expensive, and involve complex processing. Here, we developed a facile and efficient method of activating NK cells using cationic nanoparticles (cNPs). The cytotoxic activity of cNP-treated primary NK and NK-92MI cells against triple-negative breast cancer cells was over 2-fold higher than that of control NK cells in vitro . Molecular biological analyses confirmed that cNPs altered the expression of CCR4 and CXCR4 of NK cells that function as chemokine receptors. In vitro live cell imaging showed that the NK cells treated with cNPs were better than control NK cells at interacting with cancer cells. Consistent with these in vitro results, cNP-treated NK cells effectively inhibited tumor growth in an in vivo tumor animal model of triple-negative breast cancer. Additionally, NK cells treated with cNPs were tracked effectively in vivo by magnetic resonance imaging. Thus, cNP-mediated activation of NK cells has great potential as an NK cell-based cancer immunotherapy. Most of all, activating NK cells using cNPs has a great advantage over conventional methods in that immune cells can be activated by a one-step facile process with exogenously charged nanomaterials, without the need for genetic engineering or cytokine treatment.

Stimuli-responsive smart hydrogels have garnered considerable interest for their potential in biomedical applications. While widely utilized, little is known about the rheological and mechanical properties of the hydrogels with respect to the type of cross-linker in a systematic manner. In this study, we present a facile synthetic route toward ABA triblock copolymer hydrogels based on poly(ethylene oxide) (PEO). Two classes of hydrogels were prepared by employing the functional allyl glycidyl ether (AGE) monomer during the polymerization followed by the subsequent post-polymerization modification of prepared PAGE- b -PEO- b -PAGE via respective hydrogenation or thiol-ene reaction: (1) chemically cross-linked hydrogels responsive to redox stimuli and (2) physically cross-linked hydrogels responsive to temperature. A series of dynamic mechanical analyses revealed the relaxation dynamics of the associative A block. Most interestingly, the redox-responsive hydrogels demonstrated a highly tunable nature by introducing reducing and oxidizing agents, which provided the self-healing property and injectability. Together with superior biocompatibility, these smart hydrogels offer the prospect of advancing biomedical applications.

The iron-catalyzed hydrogen transfer strategy has been applied to the redox condensation of o -hydroxynitrobenzene with alcohol, leading to the formation of benzoxazole derivatives. A wide range of 2-substituted benzoxazoles were synthesized in good to excellent yields without the addition of an external redox agent. A series of control experiments provided a plausible mechanism. Furthermore, the reaction system was successfully extended to the synthesis of benzothiazoles and benzimidazoles.

Dual-modular imaging approaches combining near-infrared (NIR) fluorescence (FLI) and photoacoustic imaging (PAI) require suitable contrast agents to produce dual-modular signals. Although nanoparticles have been used to develop PAI agents, small molecule-based imaging agents have not been extensively studied, highlighting the need to design new fluorophores with an enhanced multifunctional ability. Thus, in this study, we designed a novel squaraine (SQ)-based dye and reported its rational preparation and conjugation with a cancer targeting peptide. Specifically, benzoindole-derived SQ (BSQ) showed strong absorption and fluorescence properties at above 650 nm under aqueous conditions, with a maximum absorption and emission at 665 and 680 nm, respectively. Moreover, PA signal scanning experiments revealed a maximum signal intensity in the range 680-700 nm. BSQ was also conjugated with cyclic arginine-glycine-aspartic acid (cRGD) to improve its active targeting ability for the α v β 3 integrin, which is overexpressed in various cancer and angiogenic cells. A series of in vitro , in vivo , and ex vivo FLI studies showed that the cRGD conjugated BSQ (BSQ-RGD 2 ) successfully stained and targeted α v β 3 integrin-overexpressing tumor cells and xenografts, which were clearly visualized by FLI and PAI. Therefore, BSQ-RGD 2 can successfully be applied to dual-modular imaging of the specific biomarker in living animals.

We prepared MoS 2 monolayers on Au nanodot (ND) and nanohole (NH) arrays. Both these sample arrays exhibited enhanced photoluminescence intensity compared with that of a bare SiO 2 /Si substrate. The reflectance spectra of MoS 2 /ND and MoS 2 /NH had clear features originating from excitation of localized surface plasmon and propagating surface plasmon polaritons. Notably, the surface photovoltages (SPV) of these hybrid plasmonic nanostructures had opposite polarities, indicating negative and positive charging at MoS 2 /ND and MoS 2 /NH, respectively. Surface potential maps, obtained by Kelvin probe force microscopy, suggested that the potential gradient led to a distinct spatial distribution of photo-generated charges in these two samples under illumination. Furthermore, the local density of photo-generated excitons, as predicted from optical simulations, explained the SPV spectra of MoS 2 /ND and MoS 2 /NH. We show that the geometric configuration of the plasmonic nanostructures modified the polarity of photo-generated excess charges in MoS 2 . These findings point to a useful means of optimizing optoelectronic characteristics and improving the performance of MoS 2 -based plasmonic devices.

We fabricated plasmonic hybrid nanostructures consisting of MoS 2 monolayer flakes and Au nanogratings with a period of 500 nm. The angle-resolved reflectance and photoluminescence spectra of the hybrid nanostructures clearly indicated a coupling between surface plasmon polaritons (SPPs) and incoming photons. The surface photovoltage (SPV) maps could visualize the spatial distribution of net charges while shining light on the sample. Considerable polarization and wavelength dependence of the SPV signals suggested that the SPP mode enhanced the light-matter interaction and resulting exciton generation in the MoS 2 monolayer. From the photoluminescence spectra and the morphology of the suspended MoS 2 region, it could be noted that light irradiation did not much raise the temperature of the MoS 2 monolayers on the nanogratings. Nanoscopic SPV and surface topography measurements could reveal the local optoelectronic and mechanical properties of MoS 2 monolayers. This work provided us insights into the proposal of a high-performance MoS 2 /metal optoelectronic devices, based on the understanding of the SPP-photon and SPP-exciton coupling.

We present structural analysis of spherical diblock copolymer micelles where core blocks have bottlebrush architecture. The dependence of the core radius ( R core ) and the corona thickness ( L corona ) on the core block length ( N core ) is investigated using small-angle X-ray scattering (SAXS) and discussed in terms of the stiffness of a core-forming polymer posed by its long fluoroalkyl side chains. The conformation of the core block is strongly stretched, and the measured exponents α and β from power-law correlations, R core ∼ N core α and L corona ∼ N core β , respectively, are greater than those from any scaling predictions for block copolymer micelles with a flexible, linear core-block. Such deviations are attributed to the appreciable chain stiffness of the bottlebrush core block, and a simple model is suggested to understand how the core block stiffness influences both the dimensions of core and corona.

Sensory adaptation is an essential part of biological neural systems for sustaining human life. Using the light-induced halide phase segregation of CsPb(Br 1- x I x ) 3 perovskite, we introduce neuromorphic phototransistors that emulate human sensory adaptation. The phototransistor based on a hybrid structure of perovskite and transition-metal dichalcogenide (TMD) emulates the sensory adaptation in response to a continuous light stimulus, similar to the neural system. The underlying mechanism for the sensory adaptation is the halide segregation of the mixed halide perovskites. The phase separation under visible-light illumination leads to the segregation of I and Br into separate iodide- and bromide-rich domains, significantly changing the photocurrent in the phototransistors. The devices are reversible upon the removal of the light stimulation, resulting in near-complete recovery of the photosensitivity before the phase segregation (sensitivity recovery of 96.65% for 5 min rest time). The proposed phototransistor based on the perovskite-TMD hybrid structure can be applied to other neuromorphic devices such as neuromorphic photonic devices, intelligent sensors, and selective light-detecting image sensors.

The inherent conformational preferences of the neutral β-peptide foldamer series, Ac-(ACHC) n -NHBn, n = 2-4, are studied in the gas phase using conformation-specific IR-UV double resonance methods. The cyclically constrained chiral β-amino acid cis -2-aminocyclohexane carboxylic acid (ACHC) is designed to bring both right- and left-handed helices into close energetic proximity. Comparison of the infrared spectra in the NH stretch and amide I/II regions with the predictions of DFT calculations lead to the unambiguous assignment of four out of the six observed conformations of the molecules in this series, while corroborating computational and spectral evidence, affords tentative assignments of the remaining two conformers for which IR data were not recorded. The observed structures fall into one of two conformational families: a right-handed 12/10-mixed helix or its "cap-disrupted" left-handed helical analogue, which coexist with significant populations. Site-specific and stereospecific methylation on the cyclohexane backbone at the dipeptide ( n = 2) level is also tested as a means to sterically lock in a predetermined cyclohexane chair conformation. These substitutions are proven to be a means of selectively driving formation of one helical screw sense or the other. Calculated relative energies and free energies of all possible structures for the molecules provide strong supporting evidence that the rigid nature of the ACHC residue confers unusual stability to the 12/10-mixed helix conformation, regardless of local environment, temperature, or C-terminal capping unit. The simultaneous presence of both handed helices offers unique opportunities for future studies of their interconversion.

In the medical industry, zwitterionic brushes have received significant attention owing to their antifouling effect that arose from their hydration ability. However, sufficient understanding of the hydration dynamics of zwitterionic brushes is required to fabricate the precisely controlled antifouling medical devices. In this paper, we successfully show that hydration, the interaction between water molecules and zwitterionic brushes, and its dynamics can be evaluated logically and quantitatively using (i) water contact angle, (ii) molecular dynamics simulation, and (iii) Raman spectroscopy. Based on the intuitive results on hydration, we precisely optimized the antifouling property of the model medical device, a removable orthodontic retainer, with various grafting efficiencies of 2-methacryloyloxyethyl phosphate choline. As a result, the model device reduced nonspecific adsorption of proteins and bacteria, indicating an improved antifouling effect, and also inhibited the formation of a biofilm. Furthermore, the device showed excellent physical properties desirable for application in the orthodontic field, meaning the balance between the antibacterial property and mechanical strength.

Hybrid organic-inorganic perovskites and MoS 2 are highly attractive as emerging materials for various kinds of optoelectronic devices. Here, we first report perovskite photodiode-solar cell nanosystems (PPSNs) by employing bilayer (BL) MoS 2 and triethylenetetramine-doped graphene (TETA-GR) as the electron-transport layer (ETL) and transparent conductive electrode (TCE), respectively. The rigid/flexible PPSNs exhibit 0.42/0.40 AW -1 responsivity ( R ), 37.2/80.1 pW Hz -1/2 noise equivalent power, 1.1 × 10 10 /5.0 × 10 9 cm Hz 1/2 W -1 specific detectivity at a zero-bias photodiode mode (i.e., self-power operation), similar to or even greater than those of previous reports, and 14.27/12.12% power conversion efficiency at a photovoltaic mode. The PPSNs show high long-term stabilities by maintaining more than 78% of the initial R for 30 days. The flexible PPSNs maintain about 80% of the original R during 1000 bending tests at 4 mm radius of curvature, indicating excellent mechanical properties. These high performances result from the enhanced TCE properties, well-matched band offsets at the cathode/ETL/active layer interfaces, and the reduced carrier recombination/charge-transfer resistance by the use of TETA-GR TCE and BL-MoS 2 ETL.