Rational Design Research Articles

Reduced thermal conductivity and enhanced TE performance in CrSb2via Fe-Bi co-substitution.

The efficiency of thermoelectric (TE) technology relies on the performance of TE materials. Substitution with heavy elements is an effective strategy in TE for enhancing phonon scattering without much affecting electrical transport properties. However, selecting suitable dopants to achieve a high TE figure-of-merit (ZT) poses a significant challenge. Thus, in this study, the efficacy of combined (Fe and Bi) co-substitution in CrSb2is investigated as a promising strategy to enhance ZT by lowering thermal conductivity. A series of co-substituted Cr1-xFexBiySb2-y(x= 0, 0.25, 0.50, 0.75, 1 andy= 0.10, 0.15, 0.20,0.25) samples were synthesized via furnace reaction followed by spark plasma sintering technique. Phase analysis and temperature dependence TE transport properties were systematically studied on synthesized samples. Furthermore, to analyze the impact of disorder induced by Bi/Fe substitution, electronic structure calculation was performed using the projector augmented-wave method. Notably, Cr0.75Fe0.25Bi0.15Sb1.85exhibited a low thermal conductivity of ∼2.5 W m-1K-1at 300 K, which reduced to half compared to that of pristine CrSb2(∼5 W m-1K-1). This reduction is attributed to the introduction of significant mass fluctuations and point defects along with the presence of Bi at grain boundaries by co-substitution. Consequently, a remarkable 90% enhancement inZT(∼0.021) at 350 K was achieved for Cr0.75Fe0.25Bi0.15Sb1.85compared to that of pristine CrSb2(ZT∼ 0.012). This study can provide valuable insights into the rational design of effective dopants in other TE materials also.

Plasmonic Pt-PPCN/TiN Ohmic Junction for Photo-Thermo Catalytic Hydrogen Production.

The rational design of photocatalysts for improving the conversion of solar energy into hydrogen is a promising route for achieving carbon neutrality. Herein, we couple plasmonic titanium nitride (TiN) with highly crystalline potassium-doped polymeric carbon nitride (PPCN) to construct a PPCN/TiN ohmic junction. Such an ohmic junction not only broadens the absorption spectrum but also inhibits the recombination of electrons and holes. In addition, Pt nanoparticles are introduced into this ohmic junction to form plasmonic Pt-PPCN/TiN, improving the capture of hot electrons generated by TiN and thereby promoting the dissociation of the O-H bond in H2O. The energy barrier decreases from 0.7 to 0.2 eV. Enhanced separation of carrier, activation of water molecules, and capture of hot electrons are jointly promoting photo-thermo catalytic hydrogen production. Therefore, under full-spectrum irradiation, the hydrogen production rate of Pt-PPCN/TiN reaches 19 085 μmol g-1 h-1. This novel plasmonic photocatalyst is promising for full-spectrum photo-thermo catalytic hydrogen production.

A Connected Convolutional Neutral Network Protocol for Design of Two-Dimensional Materials Based on Modified Graphdiyne.

In materials science, doping plays a crucial role in manipulating the electronic properties of materials. Conventional screening via a trial-and-error strategy is challenging owing to the enormous chemical space. We proposed a connected convolutional neutral network (CCNN) for quick screening of boron nitrogen (B-N) codoped graphdiyne in terms of band gap. A paired-atomic localized matrix (PALM) descriptor was designed to describe the local chemical environment of materials with the matrix form adapted to a neutral network. An attribution analysis was conducted, and a quantitative relationship between structure and band gap is proposed, which reveals more significant influence of B-N doping at sp2 hybridized sites than at sp hybridized sites on broadening of the band gap of GDY. The accuracy and efficiency of the proposed approach implicate its potential in promoting the design of graphdiyne-based optoelectronic devices and catalysts with expected electronic properties, opening a new avenue for rational design of novel materials.

Confining Conversion Chemistry in Intercalation Host for Aqueous Batteries.

Conversion-type anode materials with high theoretical capacities play a pivotal role in developing future aqueous rechargeable batteries (ARBs). However, their sustainable applications have long been impeded by the poor cycling stability and sluggish redox kinetics. Here we show that confining conversion chemistry in intercalation host could overcome the above challenges. Using sodium titanates as a model intercalation host, an integrated layered anode material of iron oxide hydroxide-pillared titanate (FeNTO) is demonstrated. The conversion reaction is spatially and kinetically confined within sub-nano interlayer, enabling superlow redox polarization (ca. 4-6 times reduced), ultralong lifespan (up to 8700 cycles) and excellent rate performance. Notably, the charge compensation of interlayer via universal cation intercalation into host endows FeNTO with the capability of operating well in a broad range of aqueous electrolytes (Li+, Na+, K+, Mg2+, Ca2+, etc.). We further demonstrate the large-scale synthesis of FeNTO thin film and powder, and rational design of quasi-solid-state high-voltage ARB pouch cells powering wearable electronics against extreme mechanical abuse. This work demonstrates a powerful confinement means to access disruptive electrode materials for next-generation energy devices.

Unveiling the potential of triphenylphosphine salts in tuning organic room temperature phosphorescence.

Triphenylphosphine (TPP) salt derivatives, with their rich chemistry of core-substitution, have emerged as promising candidates for ultralong room temperature phosphorescence (RTP) materials owing to their distinct molecular structures, high quantum efficiency and exceptional phosphorescence properties. This feature article highlights the vast potential of TPP salt derivatives in tunable RTP properties by exploring some factors such as the alkyl chains, halogen anions, through-space charge transfer states, etc., and recent advancements in multi-level information encryption, high-level anticounterfeiting tags and X-ray imaging applications. We anticipate that this article will assist in directing future analyses based on the mechanisms underlying the RTP behavior of TPP derivatives and offer guidance for the rational design of high-performance RTP materials.

Advancing Electrically Conductive Metal-Organic Frameworks for Photocatalytic Energy Conversion.

ConspectusPhotocatalytic energy conversion is a pivotal process for harnessing solar energy to produce chemicals and presents a sustainable alternative to fossil fuels. Key strategies to enhance photocatalytic efficiency include facilitating mass transport and reactant adsorption, improving light absorption, and promoting electron and hole separation to suppress electron-hole recombination. This Account delves into the potential advantages of electrically conductive metal-organic frameworks (EC-MOFs) in photocatalytic energy conversion and examines how manipulating electronic structures and controlling morphology and defects affect their unique properties, potentially impacting photocatalytic efficiency and selectivity. Moreover, with a proof-of-concept study of photocatalytic hydrogen peroxide production by manipulating the EC-MOF's electronic structure, we highlight the potential of the strategies outlined in this Account.EC-MOFs not only possess porosity and surface areas like conventional MOFs, but exhibit electronic conductivity through d-p conjugation between ligands and metal nodes, enabling effective charge transport. Their narrow band gaps also allow for visible light absorption, making them promising candidates for efficient photocatalysts. In EC-MOFs, the modular design of metal nodes and ligands allows fine-tuning of both the electronic structure and physical properties, including controlling the particle morphology, which is essential for optimizing band positions and improving charge transport to achieve efficient and selective photocatalytic energy conversion.Despite their potential as photocatalysts, modulating the electronic structure or controlling the morphology of EC-MOFs is nontrivial, as their fast growth kinetics make them prone to defect formation, impacting mass and charge transport. To fully leverage the photocatalytic potential of EC-MOFs, we discuss our group's efforts to manipulate their electronic structures and develop effective synthetic strategies for morphology control and defect healing. For tuning electronic structures, diversifying the combinations of metals and linkers available for EC-MOF synthesis has been explored. Next, we suggest that synthesizing ligand-based solid solutions will enable continuous tuning of the band positions, demonstrating the potential to distinguish between photocatalytic reactions with similar redox potentials. Lastly, we present incorporating a donor-acceptor system in an EC-MOF to spatially separate photogenerated carriers, which could suppress electron-hole recombination. As a synthetic strategy for morphology control, we demonstrated that electrosynthesis can modify particle morphology, enhancing electrochemical surface area, which will be beneficial for reactant adsorption. Finally, we suggest a defect healing strategy that will enhance charge transport by reducing charge traps on defects, potentially improving the photocatalytic efficiency.Our vision in this Account is to introduce EC-MOFs as an efficient platform for photocatalytic energy conversion. Although EC-MOFs are a new class of semiconductor materials and have not been extensively studied for photocatalytic energy conversion, their inherent light absorption and electron transport properties indicate significant photocatalytic potential. We envision that employing modular molecular design to control electronic structures and applying effective synthetic strategies to customize morphology and defect repair can promote charge separation, electron transfer to potential reactants, and mass transport to realize high selectivity and efficiency in EC-MOF-based photocatalysts. This effort not only lays the foundation for the rational design and synthesis of EC-MOFs, but has the potential to advance their use in photocatalytic energy conversion.

'Accelerated' Deactivation of Carbon Nitride Photocatalyst for Solar Hydrogen Evolution.

Carbon nitride photocatalysts are among the most studied candidates for efficient solar hydrogen (H2) production due to their abundance of precursors, suitable bandgap, and visible light utilization. However, the polymeric nature of carbon nitride materials raises concerns regarding the self-decomposition during photocatalytic redox processes. Yet, the operational stability of carbon nitride photocatalysts for solar H2 production remains under-explored. Here we evaluate the photostability of carbon nitride photocatalysts with platinum (Pt) as the co-catalyst for solar H2 evolution and significant deactivation of this photocatalyst is observed under'accelerated' testing conditions. It is demonstrated that the detachment of the Pt co-catalyst on the surface of carbon nitride is the major reason for this deactivation, which can be attributed to a synergistic effect of photo-corrosion and mechanical stirring. The photo-corrosion weakens the interfacial bonding between carbon nitride and Pt co-catalyst, while continuous collisions from the mechanical stirring promote the detachment of co-catalysts from the surface of carbon nitride. These understandings provide insights into the rational design of photocatalysts and photocatalytic systems for improved operational stability.

Multiscale Computational Study of Cellulose Acetate-Water Miscibility: Insights from Molecularly Informed Field-Theoretic Modeling.

Cellulose acetate (CA), a prominent water-soluble derivative of cellulose, is a promising biodegradable ingredient that has applications in films, membranes, fibers, drug delivery, and more. In this work, we present a molecularly informed field-theoretic model for CA to explore its phase behavior in aqueous solutions. By integrating atomistic details into large-scale field-theoretic simulations via the relative entropy coarse-graining framework, our approach enables efficient calculations of CA's miscibility window as a function of the degree of substitution (DS) of cellulose hydroxyl groups with acetate side chains. This allows us to capture the intricate phase behavior of CA, particularly its unique miscibility at intermediate substitution, without relying on experimental input. Additionally, the model directly probes CA solution behavior specific to the relative DS at C2, C3, and C6 alcohol sites, providing insights for the rational design of water-soluble CA for diverse applications. This work demonstrates a promising integration of molecularly informed field theories, complementing wet-lab experimentation, for engineering the next-generation polymeric materials with precisely tailored properties.

Steering the Site Distance of Atomic Cu‐Cu Pairs by First‐Shell Halogen Coordination Boosts CO2‐to‐C2 Selectivity

Electrocatalytic reduction of CO2 into C2 products of high economic value provides a promising strategy to realize resourceful CO2 utilization. Rational design and construct dual sites to realize the CO protonation and C‐C coupling to unravel their structure‐performance correlation is of great significance in catalysing electrochemical CO2 reduction reactions. Herein, Cu‐Cu dual sites with different site distance coordinated by halogen at the first‐shell are constructed and shows a higher intramolecular electron redispersion and coordination symmetry configurations. The long‐range Cu‐Cu (Cu‐I‐Cu) dual sites show an enhanced Faraday efficiency of C2 products, up to 74.1%, and excellent stability. In addition, the linear relationships that the long‐range Cu‐Cu dual site is accelerated to C2H4 generation and short‐range Cu‐Cu (Cu‐Cl‐Cu) dual site is beneficial for C2H5OH formation are disclosed. In situ electrochemical attenuated total reflection surface enhanced infrared absorption spectroscopy, in situ Raman and theoretical calculations manifest that long‐range Cu‐Cu dual sites can weaken reaction energy barriers of CO hydrogenation and C‐C coupling, as well as accelerating deoxygenation of *CH2CHO. This study uncovers the exploitation of site‐distance‐dependent electrochemical property to steer the CO2 reduction pathway, as well as a potential generic tactic to target C2 synthesis by constructing the desired Cu‐Cu dual sites.

Steering the Site Distance of Atomic Cu-Cu Pairs by First-Shell Halogen Coordination Boosts CO2-to-C2 Selectivity.

Electrocatalytic reduction of CO2 into C2 products of high economic value provides a promising strategy to realize resourceful CO2 utilization. Rational design and construct dual sites to realize the CO protonation and C-C coupling to unravel their structure-performance correlation is of great significance in catalysing electrochemical CO2 reduction reactions. Herein, Cu-Cu dual sites with different site distance coordinated by halogen at the first-shell are constructed and shows a higher intramolecular electron redispersion and coordination symmetry configurations. The long-range Cu-Cu (Cu-I-Cu) dual sites show an enhanced Faraday efficiency of C2 products, up to 74.1%, and excellent stability. In addition, the linear relationships that the long-range Cu-Cu dual site is accelerated to C2H4 generation and short-range Cu-Cu (Cu-Cl-Cu) dual site is beneficial for C2H5OH formation are disclosed. In situ electrochemical attenuated total reflection surface enhanced infrared absorption spectroscopy, in situ Raman and theoretical calculations manifest that long-range Cu-Cu dual sites can weaken reaction energy barriers of CO hydrogenation and C-C coupling, as well as accelerating deoxygenation of *CH2CHO. This study uncovers the exploitation of site-distance-dependent electrochemical property to steer the CO2 reduction pathway, as well as a potential generic tactic to target C2 synthesis by constructing the desired Cu-Cu dual sites.

Regulating the Double-Way Traffic of Cations and Anions in Ambipolar Polymer Cathodes for High-Performing Aluminum Dual-Ion Batteries.

The strong Coulombic interactions between Al3+ and traditional inorganic crystalline cathodes present a significant obstacle in developing high-performance rechargeable aluminum batteries (RABs) that hold promise for safe and sustainable stationary energy storage. While accommodating chloroaluminate ions (AlCl4 -, AlCl2+, etc.) in redox-active organic compounds offers a promising solution for RABs, the issues of dissolution and low ionic/electronic conductivities plague the development of organic cathodes. Herein, electron donors are synthetically connected with acceptors to create crosslinked, bipolar-conjugated polymer cathodes. These cathodes exhibit overlapped redox potential ranges for both donors and acceptors in highly concentrated AlCl3-based ionic liquid electrolytes. This approach strategically enables on-site doping of the polymer backbones during redox reactions involving both donor and acceptor units, thereby enhancing the electron/ion transfer kinetics within the resultant polymer cathodes. Based on the optimal donor/acceptor combination, the bipolar polymer cathodes can deliver a high specific capacity of 205mAhg-1 by leveraging the co-storage of AlCl4 - and AlCl2+. The electrodes exhibit excellent rate performance, a stable cycle life of 60000 cycles, and function efficiently at high mass loadings, i.e., 100mg cm-2, and at low temperatures, i.e., -30°C. The findings exemplify the exploration of high-performing conjugated polymer cathodes for RABs through rational structural design.

A comprehensive study on three typical photoacid generators using photoelectron spectroscopy and abinitio calculations.

Conducting a comprehensive molecular-level evaluation of a photoacid generator (PAG) and its subsequent impact on lithography performance can facilitate the rational design of a promising 193nm photoresist tailored to specific requirements. In this study, we integrated spectroscopy and computational techniques to meticulously investigate the pivotal factors of three prototypical PAG anions, p-toluenesulfonate (pTS-), 2-(trifluoromethyl)benzene-1-sulfonate (TFMBS-), and triflate (TF-), in the lithography process. Our findings reveal a significant redshift in the absorption spectra caused by specific PAG anions, attributed to their involvement in electronic transition processes, thereby enhancing the transparency of the standard PAG cation, triphenylsulfonium (TPS+), particularly at ∼193nm. Furthermore, the electronic stability of PAG anions can be enhanced by solvent effects with varying degrees of strength. We observed the lowest vertical detachment energy of 6.6eV of pTS- in PGMEA solution based on the polarizable continuum model, which prevents anion loss at 193nm lithography. In addition, our findings indicate gas-phase proton affinity values of 316.4 kcal/mol for pTS-, 308.1 kcal/mol for TFMBS-, and 303.2 kcal/mol for TF-, which suggest the increasing acidity strength, yet even the weakest acid pTS- is still stronger than strong acid HBr. The photolysis of TPS+-based PAG, TPS+·pTS-, generated an excited state leading to homolysis bond cleavage with the lowest reaction energy of 83 kcal/mol. Overall, the PAG anion pTS- displayed moderate acidity, possessed the lowest photolysis reaction energy, and demonstrated an appropriate redshift. These properties collectively render it a promising candidate for an effective acid producer.

Visualization of Electrooxidation on Palladium Single Crystal Surfaces via In Situ Raman Spectroscopy.

The electrooxidation of catalyst surfaces is across various electrocatalytic reactions, directly impacting their activity, stability and selectivity. Precisely characterizing the electrooxidation on well-defined surfaces is essential to understanding electrocatalytic reactions comprehensively. Herein, we employed in situ Raman spectroscopy to monitor the electrooxidation process of palladium single crystal. Our findings reveal that the Pd surface's initial electrooxidation process involves forming *OH intermediate and ClO4- ions facilitate the deprotonation process, leading to the formation of PdOx. Subsequently, under deep electrooxidation potential range, the oxygen atoms within PdOx contribute to creating surface-bound peroxide species, ultimately resulting in oxygen generation. The adsorption strength of *OH and the coverage of ClO4- can be adjusted by the controllable electronic effect, resulting in different oxidation rates. This study offers valuable insights into elucidating the electrooxidation mechanisms underlying a range of electrocatalytic reactions, thereby contributing to the rational design of catalysts.

Water disinfection: Advances in photocatalysis and piezo/triboelectric catalysis with progressively enhanced energy utilization

AbstractIncreasing climate‐related extreme weather events and conflicts hinder safe water sanitation for vulnerable populations. In developing areas, centralized water systems are impractical due to high costs and poor infrastructure. Thus, technologies utilizing renewable energy like solar and mechanical energy for water treatment hold promise. It is critical to develop photocatalysts and piezoelectric/triboelectric catalysts that capture solar energy as well as mechanical energy to generate disinfectants to maximize energy utilization. The latest advancements in principles, materials, and processes utilizing solar and mechanical energy for water disinfection are highlighted in this review. First, we elucidate both direct and indirect mechanisms of sunlight‐mediated water disinfection, discuss the evolution of photocatalysts from simple UV absorption to visible‐light utilization, and even near‐infrared light exploitation to enhance solar spectrum utilization efficiency. Furthermore, we delve into the fundamental principles of piezoelectricity and triboelectricity relying on mechanical energy conversion as well as summarize the development of piezo/triboelectric catalysts from being driven by high‐frequency energy to utilizing low‐frequency mechanical energy from the environment. Finally, challenges and directions for efficient systems are outlined to inspire rational design strategies and accelerate the production of superior catalytic systems applicable across a broad range.

Statistical Survey of Chemical and Geometric Patterns on Protein Surfaces as a Blueprint for Protein‐Mimicking Nanoparticles

Despite recent breakthroughs in understanding how protein sequence relates to structure and function, considerably less attention has been paid to the general features of protein surfaces beyond those regions involved in binding and catalysis. This article provides a systematic survey of the universe of protein surfaces and quantifies the sizes, shapes, and curvatures of the positively/negatively charged and hydrophobic/hydrophilic surface patches as well as correlations between such patches. It then compares these statistics with the metrics characterizing nanoparticles functionalized with ligands terminated with positively and negatively charged ligands. These particles are of particular interest because they are also surface patchy and have been shown to exhibit both antibiotic and anticancer activities—via selective interactions against various cellular structures—prompting loose analogies to proteins. The analyses support such analogies in several respects (e.g., patterns of charged protrusions and hydrophobic niches similar to those observed in proteins), although there are also significant differences. Looking forward, this work provides a blueprint for the rational design of synthetic nano‐objects with further enhanced mimicry of proteins’ surface properties.

Micro-Structure Engineering in Pd-InOx Catalysts and Mechanism Studies for CO2 Hydrogenation to Methanol

Significant interest has emerged for the application of Pd-In2O3 catalysts as high-performance catalysts for CO2 hydrogenation to CH3OH. However, precise active site control in these catalysts and understanding their reaction mechanisms remain major challenges. In this investigation, a series of Pd-InOx catalysts were synthesized, revealing three distinct types of active sites: In-O, Pd-O(H)-In, and Pd2In3. Lower Pd loadings exhibited Pd-O(H)-In sites, while higher loadings resulted in Pd2In3 intermetallic compounds. These variations impacted catalytic performance, with Pd-O(H)-In catalysts showing heightened activity at lower temperatures due to the enhanced CO2 adsorption and H2 activation, and Pd2In3 catalysts performing better at elevated temperatures due to the further enhanced H2 activation. In situ DRIFTS studies revealed an alteration in key intermediates from *HCOO over In-O bonds to *COOH over Pd-O(H)-In and Pd2In3 sites, leading to a shift in the main reaction pathway transition and product distribution. Our findings underscore the importance of active site engineering for optimizing catalytic performance and offer valuable insights for the rational design of efficient CO2 conversion catalysts.

A lamellar-morphology-based computational modeling for predicting the thermal conductivity of semicrystalline polymers

Molecular-scale design of crystal structures is an emerging approach for significantly improving the intrinsic properties of polymers. In this study, we performed computational modeling to quantitatively predict the thermal conductivity of polymers based on their crystal morphology. Polyethylene lamellae with alternating crystalline and amorphous phases were prepared using isothermal crystallization within a coarse-grained molecular dynamics framework. The crystalline bulk, transient, and amorphous regions were clearly distinguished based on the distribution of the Steinhardt-bond order parameter. The thermal conductivity of the local regions was estimated discretely by applying a steady heat flow, facilitating a bottom-up prediction of the thermal response depending on the morphology of the lamellae. In particular, the integration with homogenization theory can evaluate the effective thermal conductivity of the system in terms of crystallinity, temperature, lamella thickness and orientation. The modeling successfully provided quantitative predictions for two representative hierarchical structures: spherulites and oriented crystals. Therefore, this study serves as a theoretical guide for molecular-level rational design of semicrystalline materials with high thermal conductivity.

Enhancement of Electromagnetic Wave Attenuation through Polarization Loss Induced by Hybridization of Rare‐Earth 4f and Mo‐4d Orbitals in Liquid Plasma

AbstractThe incorporation of large‐sized rare earth (RE) elements with high coordination characteristics into transition metal dichalcogenide (TMD) absorbers while preserving a high 1T phase content during post‐processing poses a significant challenge. To address this, a novel strategy involving the confinement of RE elements within the 1T‐MoS2 lattice via liquid plasma assistance, is proposed. This approach effectively mitigates the environmental impact on the 1T phase of MoS2, yielding a remarkable 1T phase content of 82.69% for Ce20‐D7 (20 wt.% Cerium trinitrate and 7 kV applied voltage). Combining experimental and theoretical investigations reveals that the multi‐orbital characteristics of RE elements facilitate hybridization between the RE‐4f and Mo‐4d orbitals on the MoS2 surface, leading to the occupation of weakly bound electrons in bonding orbitals with short‐distance motion, enhanced inter‐orbital electron‐electron interactions, and induced polarization loss. Notably, the results demonstrate that the Pr15‐D7 sample (15 wt.% praseodymium nitrate and 7 kV applied voltage) exhibits an effective absorption bandwidth (EAB) of 7.12 GHz at 2.6 mm, with a minimum reflection loss of ‐52.02 dB while the Ce20‐D7 sample achieves an EAB of 6.96 GHz at 2.7 mm. These findings provide valuable insights for the rational design and development of high‐performance TMD absorbers leveraging RE‐modified materials.

Advances in the structural basis for angiotensin-1 converting enzyme (ACE) inhibitors.

Human somatic angiotensin-converting enzyme (ACE) is a key zinc metallopeptidase that plays a pivotal role in the renin-angiotensin-aldosterone system (RAAS) by regulating blood pressure and electrolyte balance. Inhibition of ACE is a cornerstone in the management of hypertension, cardiovascular diseases, and renal disorders. Recent advances in structural biology techniques have provided invaluable insights into the molecular mechanisms underlying ACE inhibition, facilitating the design and development of more effective therapeutic agents. This review focuses on the latest advancements in elucidating the structural basis for ACE inhibition. High-resolution crystallographic studies of minimally glycosylated individual domains of ACE have revealed intricate molecular details of the ACE catalytic N- and C-domains, and their detailed interactions with clinically relevant and newly designed domain-specific inhibitors. In addition, the recently elucidated structure of the glycosylated form of full-length ACE by cryo-electron microscopy (cryo-EM) has shed light on the mechanism of ACE dimerization and revealed continuous conformational changes which occur prior to ligand binding. In addition to these experimental techniques, computational approaches have also played a pivotal role in elucidating the structural basis for ACE inhibition. Molecular dynamics simulations and computational docking studies have provided atomic details of inhibitor binding kinetics and energetics, facilitating the rational design of novel ACE inhibitors with improved potency and selectivity. Furthermore, computational analysis of the motions observed by cryo-EM allowed the identification of allosteric binding sites on ACE. This affords new opportunities for the development of next-generation allosteric inhibitors with enhanced pharmacological properties. Overall, the insights highlighted in this review could enable the rational design of novel ACE inhibitors with improved efficacy and safety profiles, ultimately leading to better therapeutic outcomes for patients with hypertension and cardiovascular diseases.

Improving Photophysical Properties of Deazaflavin Derivatives by Acrylaldehyde Bridging: A Theoretical Investigation

AbstractThe electronic structure and photophysical properties of several acrylaldehyde‐bridged deazaflavin derivatives (cFLs) were investigated theoretically. The impact of acrylaldehyde bridging on photophysical properties of deazaflavin (cFL) is strongly site‐dependent. Specifically, the change of adiabatic energy of electronic transitions(ΔEad) and vibronic coupling promote fluorescent emission to be comparable to internal conversion of cFL and cFL4 (both C5−C6 and C9−N10 bridged, but C9−N10 bridged by propene), turning them eligible as fluorescent sensors. As El‐Sayed's rule is satisfied in cFL1(C5−C6 bridged), cFL2(C9−N10 bridged) and cFL3(both C5−C6 and C9−N10 bridged), intersystem crossing from first singlet excited state to triplet excited states (Tn) become dominant and the evolution of excited cFLs from T1 appears vital. The rate constants of photophysical processes indicate these cFLs are of dominantly high steady state T1 concentration and are potential triplet sensitizers. We expect the findings would pave the way for rational design of novel cFLs with extraordinary photophysical properties.