Narrow-bandgap semiconductors with non-centrosymmetric structures, while responsive to visible light, often exhibit limited photocatalytic CO2 reduction performance due to poor quantum efficiency and insufficient thermodynamic driving force. Here, we demonstrate a compelling strategy to repurpose these "dormant" materials as efficient piezocatalysts through mechanical activation. Two-dimensional Cu2MoS4 (CMS), a material with weak photocatalytic activity, exhibits CO-dominant piezocatalytic CO2 reduction under vibration, delivering a CO production rate more than two orders of magnitude higher than that of its photocatalytic counterpart under equivalent nominal power input, together with a substantially improved apparent energy-normalized performance. The piezoelectric properties of CMS were confirmed by piezoelectric force microscopy, piezocurrent measurements, and direct d33 quantification. Finite element analysis indicates that CMS can generate a piezopotential sufficient to drive CO2 reduction, while density functional theory calculations show that mechanical stress induces a more negative conduction band edge, enhances electron density at sulfur active sites, and lowers the Gibbs free energy barrier for the *COOH-to-*CO step. Under optimized conditions, the CMS nanosheets achieved a CO evolution rate of 594.3 μmol g-1 h-1 without cocatalysts. This mechanically driven approach unlocks the catalytic potential of underperforming non-centrosymmetric semiconductors and offers a promising route for sustainable CO2 conversion through mechanical energy harvesting.

Transforming CO2 into value-added chemicals is a key goal for carbon-neutral technologies. Piezocatalytic reduction driven by ambient mechanical energy shows great promise, but its practical deployment is still hindered by the low activity and poor selectivity of existing piezoelectric catalysts. Herein, we present the discovery of the piezoelectric properties of the lamellar inorganic-organic hybrid material ZnS(en)0.5 (ZSE). By utilizing a straightforward UV-lamp irradiation method for activation, we developed a series of piezoelectric catalysts tailored for the catalytic reduction of CO2. Notably, ZSE-254 demonstrated the remarkable capability to reduce CO2 to CO at 100 % selectivity, achieving a maximum yield of 820.8 mu mol g-1 h-1 - the highest reported for piezocatalytic CO production. Comprehensive spectroscopic and crystallographic analyses reveal that the exceptional catalytic performance of ZSE-254 stems from the synergistic effects of several factors, including a high piezoresponse current, abundant sulfur-vacancy active sites, a more negative conduction-band edge, reduced charge-transfer resistance, and an increased carrier concentration compared to pristine ZSE. Finite-element simulations further demonstrate that ZSE-254 generates a piezoelectric potential under liquid-phase vibration that exceeds the CO2 redox potential. Additionally, in-situ diffuse-reflectance infrared Fourier-transform spectroscopy reveals that CO2 is reduced to CO via *COOH as a key intermediate. Density-functional theory calculations show that both compressive and tensile strains applied to ZSE significantly lower the Gibbs free energy of the CO2 intermediate, facilitating the overall reaction. These advance the design of high-performance inorganic-organic hybrid piezocatalysts and deepen our understanding of the mechanism underlying piezocatalytic CO2 reduction.

As biotechnology advances, nucleoside-based active pharmaceutical ingredients (APIs) are emerging as a prominent therapeutic area, owing to their unique biological activities. However, the purification of intermediates such as 5 '-O-dimethoxytrityl-N-benzoyl-deoxycytidine (Bz-Dmt-dC) remains challenging because conventional chromatographic methods are costly and difficult to scale. This study introduces an intensified antisolvent crystallization process utilizing Taylor vortex flow in a Couette-Taylor (CT) crystallizer. Response Surface Methodology (RSM) was employed to systematically optimize key process parameters, including the rotational speed, inner diameter of the crystallizer, and cooling rate, for achieving high crystallinity, narrow particle size distribution, and regular crystal habits. Under optimized conditions, the CT crystallizer yielded short rod-like crystals with a narrow particle size distribution (D50 approximate to 345 mu m) and a crystallinity exceeding 99.87%, significantly outperforming both the mixing-tank (MT) crystallizer and static crystallization approaches. Computational fluid dynamics (CFD) simulations further revealed that the uniform shear field and enhanced mass transfer within Taylor vortices promoted the integration of sterically hindered molecules into the crystal lattice. Overall, this work demonstrates a scalable and efficient alternative for the purification of nucleoside APIs, with the potential for industrial adoption.

As a key intermediate in the synthesis of anticancer agents, 5 '-O-Dimethoxytrityl-N-benzoyl-deoxycytidine (BzDmt-dC) usually presents as a solvate and its purity plays a critical role in the production process. To obtain high purity products quickly and efficiently via crystallization, the solubility data of the compound must first be determined. Therefore, under the premise of ensuring no phase transitions during the measurement process, the solubility of solvates formed by Bz-Dmt-dC in three binary solvent systems (acetonitrile + water, acetone + water, and THF + water) were experimentally determined over the temperature range of 278.15 to 313.15 K at atmospheric pressure using the gravimetric method. The experimental results showed that, for a given solvent type and composition, the solubility of Bz-Dmt-dC increased with increasing temperature. The solubility data of Bz-Dmt-dC were correlated using the modified Apelblat, lambda h, and NRTL equations. Among these, the modified Apelblat model provided the best fitting result, as indicated by the lowest average relative deviation (ARD) values of 0.7%.

Eutectogels hold considerable promise for applications in flexible electronics, soft robotics, and protective systems owing to their combination of the environmental stability of deep eutectic solvents and the mechanical robustness of polymer networks. However, predominantly weak intermolecular interactions among polymer chains within eutectogels restrict their mechanical performance, making it challenging to simultaneously achieve high strength and high toughness. Herein, we propose an inorganic ionic polymerization-anchored polymer network (IIP-APN) strategy to construct ultrastrong and ultratough eutectogels. Specifically, calcium phosphate oligomers (CPO) are incorporated into the polyvinyl alcohol (PVA) chain network to serve as nanoanchors. Through inorganic ionic polymerization, hydroxyapatite nanorivets are generated to anchor PVA chains, forming a hierarchically integrated organic-inorganic composite network. This unique riveting network structure imparts record-breaking ultrahigh toughness (696.4 ± 119.1 MJ m- 3) and high strength (58.02 ± 3.87 MPa) to the resulting PVA/CPO eutectogels, significantly surpassing existing gel materials. Moreover, the PVA/CPO eutectogels demonstrate excellent energy absorption and dissipation, outstanding fatigue resistance over 8000 cycles, and the capacity for damage repair via secondary inorganic ionic polymerization. Consequently, PVA/CPO eutectogels exhibit significant potential for technological applications. The proposed IIP-APN strategy provides a powerful platform for the design and development of high-performance gel materials.

6(5H)-phenanthridinone derivatives, as an important class of alkaloids, have broad application value in drug development and functional material synthesis. In this study, a nickel-catalyzed synthetic strategy was developed, using 2-bromobenzamide compounds as starting materials. Through an intermolecular cyclization reaction, a series of 6(5H)-phenanthridinone derivatives bearing amide substituents was efficiently constructed. The optimal reaction system was identified: Ni(acac)2/Zn as the catalyst, PCy3 as the ligand, toluene as the solvent, Cs2CO3 as the base, under an argon atmosphere at 150 °C for 12 h. The target products were obtained in yields up to 88%. Further substrate scope exploration demonstrated the excellent generality of this method, successfully synthesizing 21 derivatives with various substitution patterns, achieving yields ranging from 51% to 92%, and showing good compatibility with multiple functional groups such as alkyl, aryl, and heterocyclic moieties. Importantly, the reaction remained stable during gram-scale experiments, successfully yielding the desired compound at 85%. This work not only provides an approach for the precise construction of the 6(5H)-phenanthridinone framework but also opens an efficient pathway for the controlled synthesis of amide-substituted derivatives.

Nitroguanidine (NQ), a typical energetic material widely deployed in propellant and explosive formulations, yet it commonly crystallizes into slender needle-like crystals and flocculent aggregates, leading to poor flowability and high...

Deracemization via crystallization traditionally requires alternating dissolution-growth cycles. Although crystal growth has conventionally been regarded as a source of enantiomeric erosion, the emerging "growth-dominated" mechanism fundamentally challenges this view. This study provides the first systematic validation of this novel mechanism in evaporative crystallization. Using N-(2-methylbenzylidene)-phenylglycine amide (NMPA) as a model conglomerate, we reveal that amplification efficiency relies on a delicate interplay between kinetic control and thermodynamic constraints. Kinetically, the evaporation rate is the paramount determinant, as rapid evaporation generates high supersaturation, driving the system far from equilibrium to efficiently couple asymmetric crystal growth with racemization. Thermodynamically, the amplification potential is governed by the proportion of the newly grown material relative to the seeds, necessitating high temperatures and low solid loadings for optimal enantioenrichment. Additionally, the enantiopurity baseline, the competitive growth of the minor enantiomer, and mass transport limitations impose strict boundary conditions on the amplification performance. These findings extend the growth-dominated amplification mechanism to a practical evaporative crystallization environment and provide fundamental insights into the governing principles of asymmetric crystallization.

Abstract Guanidinoacetic acid (GAA), a functional feed additive, has its industrial application hindered by poor powder flowability caused by an unfavorable crystal habit. This study investigates cyanamide-based additives, cyanamide (CA), Dicyandiamide (DICY), and melamine (MA), to regulate the crystal habit of GAA during aqueous crystallization. Increasing supersaturation accelerates crystal growth but does not significantly alter the crystal habit. In contrast, the additives induce a distinct transition from elongated hexagonal to near-equiaxed crystals, significantly improving flowability. Kinetic and surface characterization reveal that the additives selectively inhibit growth of the smooth (111) face, while exerting a weaker inhibitory effect on rough (011) face. This face selectivity originates from distinct growth mechanisms: on the (111) face, additive adsorption induces step pinning and preserves layer growth, whereas on the rough-growing (011) face, the additives weaken interfacial kinetic constraints and enhance solute diffusion near the crystal face, resulting in relatively weak growth inhibition despite stronger adsorption. The habit-modifying efficiency follows the order MA > DICY > CA, which is governed by molecular recognition and interfacial compatibility. These findings provide a mechanistic and practical strategy for industrial crystal habit engineering.

We investigated the deracemization of sodium chlorate in the unique hydrodynamic environment of Taylor vortex flow (TVF) in Couette-Taylor (CT) crystallizer. Our findings revealed a remarkable enhancement in the deracemization due to the effective hydrodynamic attrition of crystals, as compared to conventional mixing tank (MT) crystallizers utilizing the turbulent eddy flow (TEF). So, the deracemization of initial ee = 0 % in the CT crystallizer was significantly enhanced as increasing the rotation speed whereas the deracemization in the MT crystallizer occurred seldom with increase of agitation speed. Using the sparsely soluble solvent, it was demonstrated the TVF was much more effective for the hydrodynamic attrition of the crystals than the TEF. The deracemization depended not only on the flow intensity (viscous energy dissipation) but also the flow pattern. So, the TVF always produced the higher deracemization than the TEF at the same viscous energy dissipation. Also, the flow intensity and flow pattern significantly dictated the crystal agglomeration of homo-chiral (L-form and D-form) and hetero-chiral (L/D-form) forms during the deracemization. Our findings demonstrated the potential of the periodic TVF in the deracemization. The hydrodynamic attrition effect in the CT crystallizer provides a means to enhance enantiomeric purity and offers insights into the design of novel deracemization systems.

Enantioselective crystallization aided by “tailor-made” additives is an important approach of enantiomers purification. However, designing chiral additives with high enantioselectivity, simple synthesis steps and environmental friendliness is a great challenge. Pre-assessment of the conformational matching between additives and target enantiomers by quantum chemistry calculations is an effective screening strategy. In this work, a crystallization resolution of alanine system serves as a case to evaluate the enantioselectivity of chiral ionic liquids (CILs) based on five descriptors (bond distance, bond angle, electron density, Laplacian of electron density, and binding energy) through quantum chemistry calculation. The interaction active sites and strengths of between CILs and alanine enantiomers were qualitatively analyzed and quantitatively assessed by quantum chemical calculation. It was pointed out that two key descriptors, bond angle and Laplacian of electron density, implied the information of conformation and intermolecular interaction strengths, respectively. Moreover, experimental results indicated that under the best conditions, the crystallization resolution yield of alanine with high optical purity (ee% >99.0%) can reach 37.04%, much higher than that without CILs (30.68%). Our work not only brings novel quantum chemistry-assisted screening strategy for “tailor-made” additives, but will also promotes further exploration of the enormous potential of utilizing CILs in enantioselective crystallization.

Image denoising poses a significant challenge in image processing, aiming to remove noise and artifacts from input images. However, current denoising algorithms implemented on electronic chips frequently encounter latency issues and demand substantial computational resources. In this paper, we introduce an all-optical Nonlinear Diffractive Denoising Deep Network (N3DNet) for image denoising at the speed of light. Initially, we incorporate an image encoding and pre-denoising module into the Diffractive Deep Neural Network and integrate a nonlinear activation function, termed the phase exponential linear function, after each diffractive layer, thereby boosting the network’s nonlinear modeling and denoising capabilities. Subsequently, we devise a new reinforcement learning algorithm called regularization-assisted deep Q-network to optimize N3DNet. Finally, leveraging 3D printing techniques, we fabricate N3DNet using the trained parameters and construct a physical experimental system for real-world applications. A new benchmark dataset, termed MIDD, is constructed for mode image denoising, comprising 120K pairs of noisy/noise-free images captured from real fiber communication systems across various transmission lengths. Through extensive simulation and real experiments, we validate that N3DNet outperforms both traditional and deep learning-based denoising approaches across various datasets. Remarkably, its processing speed is nearly 3,800 times faster than electronic chip-based methods.

Stereoselective recognition using “tailor-made” chiral ionic liquids (CILs) is an effective approach to obtaining enantiopure compounds through crystallization resolution. In this study, CILs were used as additives to stereoselectively inhibit the nucleation and growth of unwanted enantiomers via a conformational matching mechanism. Interestingly, a cosolvency phenomenon was found in the threonine-CILs-ethanol solvent system. Based on this, an enhanced stereoselective crystallization resolution strategy that combines ultrasound and cosolvency was proposed. The goal of this strategy was to improve the crystallization yield and enantiomeric purity. The results showed that the crystallization resolution yield of the cosolvency system was 33.43%, higher than that of the pure water system (13.56%). More importantly, the introduction of ultrasonic enhancement further increased the crystallization resolution yield to 39.45%. This work will facilitate the exploration of the unlimited potential of utilizing the cosolvency phenomenon and ultrasonic enhancement for crystallization resolution.

Achieving enantiomeric purification remains challenging due to the remarkably similar physical and chemical properties of enantiomers. Crystallization resolution is one of the most economical and convenient methods for obtaining single enantiomer. In this contribution, we present an intensified method for crystallization resolution by employing polymer additives in conjunction with Taylor-Couette Flow (TCF) which facilitates the chiral resolution of the target enantiomers by exploiting supramolecular interactions of the additive, and strengthening chiral symmetry breaking through TCF. The successful application of TCF in crystallization resolution offers new opportunities for facile and efficient purification of enantiomers from racemic starting materials.

Background/Objectives: Amorphous solid drugs exhibit physical instability and a propensity for crystallization, which leads to reduced solubility and bioavailability. Hence, this study optimized scale manufacturing parameters for producing a physically stable amorphous solid form of nilotinib using neutralization precipitation. Methods: A systematic evaluation of the effects of the solute concentration and filtration rate on amorphous physical stability was conducted using the pair distribution function (PDF), principal component analysis (PCA), and reduced crystallization temperature (Rc) values. Results: It showed concentration-dependent crystallization resistance, with optimal physical stability achieved at a solute concentration of 0.126 mol/L and a 124 mL/min filtration rate. Experiments carried out at a scale of 50 g confirmed the stability of the production process. Conclusions: These findings provide a validated framework for developing lab-scale amorphous drug products with improved shelf-life stability, assessed using indirect indicators (PDF, Rc) and confirmed through accelerated stability tests.

Rational development of biomass-derived porous carbons (BDPCs) is vital for advancing fundamental research and addressing clean energy challenges such as hydrogen purification and supercapacitor energy storage. Current experimental designs are limited by empirical methods, and computational models struggle with the complex function-structure-synthesis relationships of biomass feedstocks. In this study, we introduce a data-driven closed-loop machine learning (ML) workflow integrated with literature-derived BDPC synthesis data sets, enabling inverse design from desired functionalities to optimal structures and synthesis conditions. Our ML framework predicts seven critical synthesis parameters-including precarbonation, physical state, type and amount of activator, activation temperature, time, and heating rate-based on targeted microstructural features. Experimental validations with various biofeedstocks confirm the efficacy of our approach. Notably, AI-S, a BDPC synthesized from sugarcane bagasse under ML guidance, achieves a CO2 working capacity of 12.3 mmol/g at 273 K and 10 bar and a CO2/H2 selectivity of 47.8-the highest reported for BDPCs to date. This ML-driven workflow bridges BDPC properties, microstructure, and synthesis, demonstrating a reliable and predictive method for functionally oriented porous material design and synthesis, thereby accelerating material discovery in energy and environmental applications.

Achieving enantiopure crystallization without the aid of chiral additives or grinding remains a significant challenge in crystallization-based chiral separation. This study demonstrates that periodic Taylor vortex flow (TVF) within a Couette-Taylor crystallizer can drive chiral symmetry breaking (CSB) during the early stages of crystallization, resulting in nearly 100% enantiomeric excess (ee) of hippuric acid as early as the induction period. This performance significantly exceeds that of conventional mixed-tank crystallizers operating under random turbulent flow (RTF). Supersaturation is found to critically influence the extent of CSB. While ee during the induction period under RTF diminishes rapidly with increasing supersaturation, periodic TVF sustains full ee up to a supersaturation of 1.8 and robustly facilitates the dominance of a single enantiomer across all tested conditions, despite the stochastic nature of handedness selection. CFD simulations reveal that Taylor vortices generate coherent flow structures and spatially organized thermal gradients during cooling crystallization, which collectively facilitate molecular alignment and the formation of homochiral prenucleation clusters. These effects favor initial nucleation of a single enantiomer and suppress stochastic, racemic pathways. Importantly, by emphasizing the roles of both homochiral primary nucleation and secondary nucleation, this work extends traditional CSB mechanisms and highlights structured hydrodynamics as a critical regulator of chiral outcomes. This work not only advances the mechanistic understanding of flow-mediated chiral crystallization but also presents a scalable, additive-free strategy for producing enantiopure materials, with broad relevance to pharmaceutical and fine chemical manufacturing.

This study systematically explores the agglomeration behavior of homochiral sodium chlorate crystals in turbulent flow in near equilibrium system. Sodium chlorate, known for forming optically active L- and D-enantiomers through crystallization, serves as an ideal model for examining crystal deracemization processes. The agglomeration of chiral crystals significantly impacts deracemization, as smaller crystals tend to dissolve and redeposit on larger ones. However, the formation of tightly bound agglomerates can hinder this process. This research investigates key factors influencing agglomeration, including seed crystal size, agitation speed, suspension density, and sodium chlorate solubility, using pure enantiomeric seeds. The findings reveal that smaller seed crystals rapidly agglomerate due to supersaturation fluctuations driven by the dissolution of small crystals, whereas larger seed crystals exhibit minimal agglomeration. Sodium chlorate solubility further affects agglomeration; reduced solubility decreases dissolution rates in crystal ripening, thereby limiting agglomeration. Agitation speed is critical, as increased shear stress disrupts aggregates, reducing agglomerate size. Additionally, higher suspension densities increase collision frequency and particle adhesion, enhancing agglomeration. These insights are valuable for optimizing crystallization processes, where controlling particle size and agglomerate formation is crucial, especially in industries requiring precise control over crystal properties to improve drug efficacy, filtration, and process efficiency. The study underscores the delicate balance between dissolution, growth, and breakage in agglomeration, offering a deeper understanding of how to manipulate these factors to enhance deracemization and optimize product quality in various crystallization systems.

This research focused on the precipitation of amorphous forms of nilotinib with high physical stability through the manipulation of various parameters in the neutralization reaction, specifically the quantity of nilotinib, the pH value, and the concentration of HCl. To assess the physical stability of the amorphous nilotinib, various characterization techniques, including PXRD, DSC, and FBRM, were utilized in conjunction with analytical methods such as PDF, PCA, and Rc value. The findings demonstrated that the ideal physical stability was attained with a nilotinib quantity of 0.5 g, a pH value of 11.70, and 7.5 mL of HCl with a concentration of 2.0 mol/L. It is important to acknowledge that this observation is specific to the current experimental configuration and may not hold in the context of a scaled-up experiment. Furthermore, the combination of PDF and Rc was identified as an innovative and effective method for assessing physical stability, demonstrating advantages over traditional accelerated stability testing approaches.

Harnessing ubiquitous mechanical energy for chemical transformations is a grand challenge, primarily impeded by the crystallographic symmetry constraints of conventional piezocatalysts. Here, this long-standing paradigm is shattered by demonstrating potent mechanocatalytic activity in a centrosymmetric material. Synthesized via a facile hydrothermal method, unique SnS nanobelts exhibit a hydrogen evolution rate of 3889 µmol g−1 h−1 under mechanical vibration—achieved without any cocatalysts—a performance substantially surpassing that of most reported piezocatalysts and comparable to state-of-the-art photocatalytic systems. Moreover, the SnS nanobelts were also found to present good cyclic stability. This unprecedented activity was rationalized by the synergy between two effects: sonoluminescence, for which the material’s ideally suited band structure allows efficient photon capture, and flexoelectricity. Furthermore, direct electrical measurements confirmed that SnS generates a flexoelectric current under mechanical deformation, thereby driving the H2 evolution reaction. These findings not only expand the scope of potential mechanocatalysts by unlocking a vast and previously ignored territory of centrosymmetric materials but also offer valuable guidance and insights for designing high-efficiency, mechanically driven chemical reactions.