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Gu, Wenyuan; Wang, Juanjuan; Chen, Biao; Chen, Mingyang; Chao, Xiaolian; Jia, Yanmin
doi: 10.1039/d5cp03979gpmid: 41528234
High-performance ferroelectric materials are pivotal to the operation of advanced technologies in sensing, data storage, and beyond. A variety of conventional approaches with thermal annealing and chemical doping have been extensively adopted in order to further improve the ferroelectric properties. An ingenious method involves external pressure followed by structural deformation to regulate ferroelectric behavior. This review summarizes pressure-induced modulation of ferroelectric behavior and highlights the structure transformations and ultimate characteristics. The relevant polarization, Curie temperature, and phase transitions are discussed based on their crystal structure changes in different systems under various ultrahigh-pressure conditions such as uniaxial stress, hydrostatic pressure, and supercritical CO2 isostatic pressure. In particular, the challenges and opportunities in developing ferroelectric materials under ultrahigh-pressure are provided as future research directions.
doi: 10.1039/d5cp04258epmid: 41533431
The selective conversion of methane, a highly stable molecule, remains a central challenge in catalysis. Plasmonic antenna-reactor systems offer a promising strategy for light-driven methane activation, yet the role of single-atom dopants in modulating their activity is not fully understood. Here we show, through dynamic simulations of plasmon-induced bond-length variations, that single-atom dopants on Ag20 plasmonic nanoparticles can dramatically enhance C–H bond activation. In particular, Ga dopants induce strong orbital coupling with the adsorbed methane molecule, enabling bond activation at significantly lower laser intensities than undoped systems. These findings reveal a new mechanism by which atomic-scale modifications control plasmon–molecule interactions and provide design principles for next generation light-driven catalysts.
Xiao, Zhehui; Yu, Shuangwei; Bian, Zihan; Dong, Qianqian; Yuan, Haohao; Gong, Xue; He, Xiong; Jiang, Daochuan; Sun, Zijun
doi: 10.1039/d5cp02984hpmid: 41493021
Tailoring the electronic structure of oxygen evolution catalysts (OECs) integrated on BiVO4 is essential for achieving efficient photoelectrochemical (PEC) water splitting, yet remains challenging. Herein, we demonstrate that the substitution of sulfonic acid, due to its strong electron-withdrawing properties, could effectively tailor the electronic structure of cobalt phthalocyanine (CoPc) on BiVO4. This electronic structure regulation enhances the interface coupling between CoPc and BiVO4, promotes the adsorption and activation of OH− intermediates at the central Co active site, and simultaneously enhances the hydrophilicity of the photoanode surface, leading to improved PEC performance. Compared to CoPc/BiVO4 (2.9 mA cm−2 at 1.23 VRHE), the sulfonic acid-functionalized derivative (CoPcTs)/BiVO4 achieves a significantly higher photocurrent density of 3.9 mA cm−2 at 1.23 VRHE. This work not only provides an efficient molecular electronic structure engineering strategy for designing high-performance metal complex OECs, but also significantly contributes to overcoming key kinetic and interfacial challenges in practical PEC water splitting.
Jegamohan, Shabeena; Jafari, Maziar; Bérubé, Frédérique; Bourgault, Steve; Gaudreault, Roger
doi: 10.1039/d5cp04100gpmid: 41525708
Proteins and peptides spontaneously assemble into various structured supramolecular entities that perform vital physiological functions. In pathology and biopharmaceutics, protein assemblies can form cytotoxic oligomers or protofibrils. Most studies focus on aggregation and inhibition processes in bulk solutions. However, local surface interactions are largely responsible for protein structural changes leading to aggregation. To date, research on surface-induced protein aggregation remains insufficient to comprehend underlying mechanisms. This work reports a systematic process to produce islet amyloid polypeptide (IAPP), exclusively surface-induced fibrils, on mica and polyethylene glycol (PEG)-, poly-hydroxyethyl methacrylate (pHEMA)- and polystyrene (PS) polymeric-coated substrates. IAPP adsorbed and generated protofibrils, fibrils or spherical nanoscale particles, contingent upon the type of polymeric-coated surfaces. Polyphenols are known to alter structures and inhibit protein aggregation, preventing oligomeric cytotoxicity. This study further explores the effect of corilagin on surface-induced aggregation. Overall, corilagin exhibited differing inhibitory effects on the surface-induced IAPP structures, depending on the type of surfaces.
Yamagishi, Akihiko; Yoshida, Jun; Sato, Hisako
doi: 10.1039/d5cp03773epmid: 41536199
Converting photon energy in a green solvent is a challenge for developing environmentally friendly technologies. Triplet–triplet annihilation up-conversion (TTA-UC) in R-limonene is one such attempt. Since R-limonene is a nonpolar medium, conventional organic compounds or neutral metal complexes are used as a donor. In this study, cationic chiral iridium(iii) complexes are used for the first time. The studies were based on the finding that a cyclometalated cationic iridium(iii) complex in a chiral form, Δ- or Λ-[Ir(piq)2(dmbpy)]+ (piqH = 1-phenyisoquinoline, dmbpy = 4,4′-dimethyl-2,2′-bipyridine), was soluble enough in R-limonene to perform TTA-UC. Conversely, its racemic form was barely soluble due to its high crystallinity. When an R-limonene solution containing chiral [Ir(piq)2(dmbpy)]PF6 (ca. 2 × 10−5 M) and DPA (0.3–2.6 mM) was irradiated with laser light at 445 nm, the up-conversion of photon energy to 430 nm was achieved with a quantum yield as high as 4.5% under air. Despite the slight difference in solubility between the enantiomers, no stereoselectivity was observed in TTA-UC. The effects of long alkyl chains attached to a donor molecule, or Δ- or Λ- [Ir(piq)2(Cnbpy)]+ (Cnbpy = 4,4′-nonyl (C9)- or 4,4′-nonyldecyl (C19)-2,2′-bipyridine), were investigated on the solubility and efficiency of TTA-UC.
Carreras, Abel; Orús, Román; Casanova, David
doi: 10.1039/d5cp03907jpmid: 41527830
Variational quantum eigensolvers (VQEs) are among the most promising quantum algorithms for solving electronic structure problems in quantum chemistry, particularly during the noisy intermediate-scale quantum (NISQ) era. In this study, we investigate the capabilities and limitations of VQE algorithms implemented on current quantum hardware for determining molecular ground-state energies, focusing on the adaptive derivative-assembled pseudo-Trotter ansatz VQE (ADAPT-VQE). To address the significant computational challenges posed by molecular Hamiltonians, we explore various well known strategies to simplify the Hamiltonian, optimize the ansatz, and improve classical parameter optimization through modifications of the COBYLA optimizer. These enhancements are integrated into a tailored quantum computing implementation designed to minimize the circuit depth and computational cost. Using benzene as a benchmark system, we demonstrate the application of these optimizations on an IBM quantum computer. Despite these improvements, our results highlight the limitations imposed by current quantum hardware, particularly the impact of quantum noise on state preparation and energy measurement. The noise levels in today's devices prevent meaningful evaluations of molecular Hamiltonians with sufficient accuracy to produce reliable quantum chemical insights. Finally, we extrapolate the requirements for future quantum hardware to enable practical and scalable quantum chemistry calculations using VQE algorithms. This work provides an assessment of current quantum algorithms for molecular modeling on real quantum hardware, highlighting the impact of noise and hardware limitations on the achievable accuracy.
Herzog, Raoul E.; Janke, Philipp; Fischer, Paul M.; Heckmeier, Philipp J.; Wei, Chongyao; Nag, Probal; Hartmann, Sina J.; Mulder, Matthias; Stierli, Fabienne; Standfuss, Jörg; Schapiro, Igor; Hamm, Peter
doi: 10.1039/d5cp03982gpmid: 41527851
Light-oxygen-voltage (LOV) domain proteins represent a versatile class of photoreceptors capable of regulating a wide range of light-dependent biological functions. While a lot of studies have focused on the photochemistry of LOV domains, the mechanisms of signal generation and propagation in multidomain LOV proteins remain incompletely understood. Here, we investigated two multidomain proteins, using time-resolved infrared spectroscopy. The measurements resolve the entire photocycle dynamics from picoseconds to hours and uncover distinct patterns of local and global structural responses. The two multidomain proteins under study, YF1 and PAL, exhibit nearly identical dynamics during excitation and intersystem crossing on the nanosecond timescale, reflecting conserved local interactions between the chromophore and its highly conserved binding pocket. Multiscale simulations attribute minor spectral differences in this regime to a phenylalanine residue located near the chromophore present only in one of the two LOV domains. The similarities, however, end at the microsecond timescale, where adduct formation already involves global structural adaptations. By experimentally isolating the response of the histidine kinase effector domain in the synthetic photoreceptor YF1, we show that major structural adaptions of the effector domain occur concurrently with cysteine-adduct formation and that the Jα-helix putatively mediates unidirectional communication between domains. In PAL, light-induced opening of the RNA binding site during the adduct formation is additionally followed by a subsequent rearrangement in the distal PAS domain after 3 s. This highlights the pivotal yet distinct roles of the Jα-helix in signal transmission, which depend on the domain topology. Ultimately, our study not only deepens the current understanding of signal transduction in full-length LOV proteins, but also contributes to the fundamental framework for the future application of LOV domains in optogenetic engineering.
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