Luvega1572

The transitions between these wetting/dewetting states are strongly dependent on the intrinsic wettability (E in), the initial location of the water droplet, the height of the nanotextures (H 1), and the spacing between nanotextures (W 1). Notably, E in-H 1 and E in-W 1 diagrams show that regions of rich wetting/dewetting states can be identified, including regions where between one to five states can coexist.Highly efficient persistent (lifetime > 0.1 s) room-temperature phosphorescence (pRTP) chromophores are important for futuristic high-resolution afterglow imaging for state-of-the-art security, analytical, and bioimaging applications. Suppression of the radiationless transition from the lowest triplet excited state (T1) of the chromophores is a critical factor to access the high RTP yield and RTP lifetime for desirable pRTP. Logical explanations for factor suppression based on chemical structures have not been reported. Here we clarify a strategy to reduce the radiationless transition from T1 based on chemical backbones and yield a simultaneous high RTP yield and high RTP lifetime. Yellow phosphorescence chromophores that contain a coronene backbone were synthesized and compared with yellow phosphorescent naphthalene. One of the designed coronene derivatives reached a RTP yield of 35%, which is the best value for chromophores with a RTP lifetime of 2 s. The optically measured rate constant of a radiationless transition from T1 was correlated precisely with a multiplication of vibrational spin-orbit coupling (SOC) at a T1 geometry and with the Franck-Condon chromophore factor. The agreement between the experimental and theoretical results confirmed that the extended two-dimensional fused structure in the coronene backbone contributes to a decrease in vibrational SOC and Franck-Condon factor between T1 and the ground state to decrease the radiationless transition. A resolution-tunable afterglow that depends on excitation intensity for anticounterfeit technology was demonstrated, and the resultant chromophores with a high RTP yield and high RTP lifetime were ideal for largely changing the resolution using weak excitation light.Polymer colloids arise in a variety of contexts ranging from synthetic to natural systems. The structure of polymeric colloids is crucial to their function and application. Hence, understanding the mechanism of structure formation in polymer colloids is important to enabling advances in their production and subsequent use as enabling materials in new technologies. Here, we demonstrate how the specific pathway from precipitation to vitrification dictates the resulting morphology of colloids fabricated from polymer blends. Through continuum simulations, free energy calculations, and experiments, we reveal how colloid structure changes with the trajectory taken through the phase diagram. We demonstrate that during solvent exchange, polymer-solvent phase separation of a homogeneous condensate can precede polymer-polymer phase separation for blends of polymers that possess some degree of miscibility. For less-miscible, higher-molecular-weight blends, phase separation and kinetic arrest compete to determine the final morphology. Such an understanding of the pathways from precipitation to vitrification is critical to designing functional structured polymer colloids.The electronic, optical, and redox properties of thiophene-based materials have made them pivotal in nanoscience and nanotechnology. However, the exploitation of oligothiophenes in photodynamic therapy is hindered by their intrinsic hydrophobicity that lowers their biocompatibility and availability in water environments. Here, we developed human serum albumin (HSA)-oligothiophene bioconjugates that afford the use of insoluble oligothiophenes in physiological environments. UV-vis and electrophoresis proved the conjugation of the oligothiophene sensitizers to the protein. The bioconjugate is water-soluble and biocompatible, does not have any "dark toxicity", and preserves HSA in the physiological monomeric form, as confirmed by dynamic light scattering and circular dichroism measurements. In contrast, upon irradiation with ultralow light doses, the bioconjugate efficiently produces reactive oxygen species (ROS) and leads to the complete eradication of cancer cells. Real-time monitoring of the photokilling activity of the HSA-oligothiophene bioconjugate shows that living cells "explode" upon irradiation. Photodependent and dose-dependent apoptosis is one of the primary mechanisms of cell death activated by bioconjugate irradiation. The bioconjugate is a novel theranostic platform able to generate ROS intracellularly and provide imaging through the fluorescence of the oligothiophene. It is also a real-time self-reporting system able to monitor the apoptotic process. The induced phototoxicity is strongly confined to the irradiated region, showing localized killing of cancer cells by precise light activation of the bioconjugate.Thanks to their photophysical properties, both organic molecular fluorophores (MFs) and inorganic quantum dots (QDs) are extensively used for bioimaging applications. see more However, limitations such as photobleaching for the former or blinking, size, and toxicity for the latter still constitute a challenge for numerous applications. We report here that embedding MFs in graphitic carbon dots (GDs) results in fluorophores which entirely tackle this challenge. Characterized by ultranarrow, bright, and excitation-independent emission devoid of blinking and photobleaching, these hybrid-featured nanoparticles also demonstrate their unique photophysical performances at the single-nanoparticle scale, making them appealing candidates for bioimaging applications.Proteins are dynamic entities that intermittently depart from their ground-state structures and undergo conformational transitions as a critical part of their functions. Central to understanding such transitions are the structural rearrangements along the connecting pathway, where the transition state plays a special role. Using NMR relaxation at variable temperature and pressure to measure aromatic ring flips inside a protein core, we obtain information on the structure and thermodynamics of the transition state. We show that the isothermal compressibility coefficient of the transition state is similar to that of short-chain hydrocarbon liquids, implying extensive local unfolding of the protein. Our results further indicate that the required local volume expansions of the protein can occur not only with a net positive activation volume of the protein, as expected from previous studies, but also with zero activation volume by compaction of remote void volume, when averaged over the ensemble of states.Ruthenium(II) polypyridine complexes are among the most popular sensitizers in photocatalysis, but they face some severe limitations concerning accessible excited-state energies and photostability that could hamper future applications. In this study, the borylation of heteroleptic ruthenium(II) cyanide complexes with α-diimine ancillary ligands is identified as a useful concept to elevate the energies of photoactive metal-to-ligand charge-transfer (MLCT) states and to obtain unusually photorobust compounds suitable for thermodynamically challenging energy transfer catalysis as well as oxidative and reductive photoredox catalysis. B(C6F5)3 groups attached to the CN - ligands stabilize the metal-based t2g-like orbitals by ∼0.8 eV, leading to high 3MLCT energies (up to 2.50 eV) that are more typical for cyclometalated iridium(III) complexes. Through variation of their α-diimine ligands, nonradiative excited-state relaxation pathways involving higher-lying metal-centered states can be controlled, and their luminescence quantum yields and MLCT lifetimes can be optimized. These combined properties make the respective isocyanoborato complexes amenable to photochemical reactions for which common ruthenium(II)-based sensitizers are unsuited, due to a lack of sufficient triplet energy or excited-state redox power. Specifically, this includes photoisomerization reactions, sensitization of nickel-catalyzed cross-couplings, pinacol couplings, and oxidative decarboxylative C-C couplings. Our work is relevant in the greater context of tailoring photoactive coordination compounds to current challenges in synthetic photochemistry and solar energy conversion.Regioselective access to heterohelicenes through the 1,3-dipolar cycloaddition of sydnones with arynes is described. Novel access to sydnones and poly(hetero)aromatic aryne precursors allowed the introduction of chemical diversity over multiple positions of the helical scaffolds. The origins of the unconventional regioselectivity during the cycloaddition steps was systematically investigated using density functional theory (DFT) calculations, unveiling the key features that control this reactivity, namely, face-to-face (π···π) or edge-to-face (C-H···π) interactions, primary orbital interactions and distortion from coplanarity in the transition structures (TSs) of the transformation. From the library of 24 derivatives synthesized, a pyridyl containing derivative displayed reversible, red-shifted, pH-triggered chiroptical switching properties, with CPL-sign reversal. It is found that protonation of the helicene causes a change of the angle between the electric and magnetic dipole moments related to the S1 → S0 transition, resulting in this rare case of reversible CPL sign inversion upon application of an external stimulus.Target properties of CO2 capture adsorbents that would ensure economic viability of bioenergy with carbon capture and storage (BECCS) are defined. The key role of sorbent lifetime in the process cost is demonstrated, and an optimal heat of adsorption for BECCS is postulated through a balance of adsorbent-adsorbate affinity and regeneration energy demand. Using an exponential decay model of sorbent capacity increases the process cost and results in an optimum sorbent lifetime. To ensure a levelized cost of carbon below $100/tonne-CO2, adsorbents should be designed to have working capacities above 0.75 mol/kg, lifetimes over 2 years, heats of adsorption of approximately -40 kJ/mol, and exponential degradation decay constants below 5 × 10-6 cycle-1 (equivalent to a half-life of 1.3 years). Our model predicts a BECCS process cost of $65/t-CO2 can be achieved with a degradation-resistant adsorbent, $40/kg sorbent cost, 2.0 mol/kg working capacity, -40 kJ/mol heat of adsorption, and at least a 2 year lifetime.The discovery of clustered regularly interspaced short palindromic repeats and their associated proteins (Cas) has revolutionized the field of genome and epigenome editing. A number of new methods have been developed to precisely control the function and activity of Cas proteins, including fusion proteins and small-molecule modulators. Proteolysis-targeting chimeras (PROTACs) represent a new concept using the ubiquitin-proteasome system to degrade a protein of interest, highlighting the significance of chemically induced protein-E3 ligase interaction in drug discovery. Here, we engineered Cas proteins (Cas9, dCas9, Cas12, and Cas13) by inserting a Phe-Cys-Pro-Phe (FCPF) amino acid sequence (known as the π-clamp system) and demonstrate that the modified CasFCPF proteins can be (1) labeled in live cells by perfluoroaromatics carrying the fluorescein or (2) degraded by a perfluoroaromatics-functionalized PROTAC (PROTAC-FCPF). A proteome-wide analysis of PROTAC-FCPF-mediated Cas9FCPF protein degradation revealed a high target specificity, suggesting a wide range of applications of perfluoroaromatics-induced proximity in the regulation of stability, activity, and functionality of any FCPF-tagging protein.