The Diels–Alder (DA) reaction between 3-methyl-3-penten-2-one (MP) and myrcene is experimentally examined and theoretically modeled as part of the Iso E Super synthesis process. The results reveal that the DA reaction between MP and myrcene follows a typical electron-demand mechanism, and the para-product (2) is the most stable structure. With the addition of the AlCl3 catalyst, the reaction energy barrier drops significantly from 132.85 to 61.38 kJ/mol, easing the reaction conditions. The AlCl3 catalyst exhibits the highest catalytic activity among the catalysts tested, especially in isooctane solvent, of which the conversion of myrcene reaches 88.51

Acrolein is an important intermediate for the synthesis of an array of high-value chemicals. Acid-catalyzed dehydration from biomass glycerol provides a green and promising route for the synthesis of acrolein. One of the most pressing issues in this field is the development of efficient and stable catalysts. Herein, a three-dimensional ordered macroporous BPO4 (BPO4-M) was successfully synthesized by a nanocasting method using polybenzoxazine spheres as a hard-template. This catalyst can achieve excellent catalytic performance and robust stability. The glycerol conversion and acrolein selectivity reached 100% and 80%, respectively, and it can be reused more than 7 times, and the total reaction time is over 360 h. Compared with nonporous BPO4, the catalytic efficiency of BPO4-M is increased by more than 10 times.

BACKGROUND:Sucralose (4,1',6'-trichlorogalactosucrose, TGS) has been widely used as a new generation of artificial sweetener, and the loading, release and purification of TGS with edible porous materials such as cyclodextrin metal-organic frameworks (CD-MOF) will pave a new way for the production and application of TGS. RESULTS:K/Na-β-CD-MOFs have been used in the loading, release and purification of TGS. TGS loading capacity of K-β-CD-MOF is higher than that of Na-β-CD-MOF, and the loading ratios increase with the decrease of particle size (the highest ratio is 18.00% below a size of 8.56 μm). Besides, the excellent controllable TGS releasing performance can be found in nano-sized K-β-CD-MOF, during which only 41.12% TGS were released after 24 h. The good loading/releasing performance could be explained by the coordination-driven ligand-exchange (ethanol and TGS) in β-CD-MOFs, during which the weak KOethanol bonds were replaced by relatively strong KClTGS bonds. Finally, these β-CD-MOFs can adsorb DH-4,1'-DGS (3',6'-dehydration-4,1'-dichlorogalactosucralose, main by-product in TGS production) in a TGS/DGS mixture selectively, rending a high separation factor α of 21.39. The remarkable purifying performance stems from the smaller molecular size of DH-4,1'-DGS and less steric hindrance after dehydrating on 3',6'-positions. CONCLUSION:β-CD-MOFs exhibit excellent TGS loading/releasing performance induced by a coordination-driven process, and they can purify the TGS/DGS mixture with high efficiency. The simultaneous realization of loading/purification of TGS on a cheap and edible material will pave a new avenue for the postprocessing of TGS. © 2026 Society of Chemical Industry.

This study investigates the intensified two-phase nitration of toluene-mixed acid by integrating a microimpinging jet (MIJ) mixer with a microchannel reactor. The computational fluid dynamics combined with the population balance model (CFD-PBM) is employed to elucidate local turbulent kinetic energy dissipation and droplet size distributions. The impacts of the volume flow rate (Q), reaction temperatures (T) and volume fractions (phi) on the dispersion and reaction process are systematically investigated. Adjusting Q and T can significantly reduce the mean droplet size from 1.2 mm to 20.3 mu m, yielding up to 36 times increase in the mass transfer coefficient with the corresponding toluene conversion rate boosting from 0.97% to 29.66% after MIJ premixing. Furthermore, lower phi values further amplify the intensification effect. This study offers a scalable strategy for liquid-liquid reaction intensification, which overcomes traditional mixing and mass-transfer limitations.

This study systematically elucidated the flow pattern evolution and dynamic variation mechanism of liquid column length in liquid-liquid two-phase systems within helical microreactors coupled with oscillatory flow. In the absence of oscillation, the main patterns observed were drip flow or plug flow. When oscillation was applied, the flow pattern underwent a distinct transition to intermittent flow or plug flow. Further analysis revealed that intermittent flow tended to form under conditions of low flow ratio, high capillary number, and low oscillation intensity, whereas the opposite conditions favored the formation of plug flow. With respect to the influence of oscillatory parameters on liquid column length, both amplitude and frequency exhibited a "first increase then decrease" trend, which essentially arises from the dynamic equilibrium between coalescence and breakage at the liquid-liquid interface. Additionally, a combination of high flow ratio and small helix diameter effectively extended the liquid column length. Helix diameter modulates liquid column stability independent of flow pattern evolution. Based on the experimental findings, a phase diagram describing flow pattern transitions was established, and a predictive model for liquid column length was derived. The prediction error of the model was constrained within +/- 25%, offering theoretical support and engineering guidance for the precise regulation of liquid-liquid two-phase processes in microreactors.

Styrene epoxide is an important organic intermediate with broad market prospects. Herein, novel homogeneous catalysts bearing pre-constructed diperoxotungstic centers were used in styrene epoxidation. With the increase of diperoxotungstic centers from 2 to 4, the styrene epoxide selectivity increased from 92.80% to 95.5%, the highest activity achieved to date in styrene epoxidation. Notably, the good recyclability of these catalysts helps overcome a key limitation of homogeneous catalysts in this field.

The coming artificial intelligence era calls for the next generation of memories with high density. In this work, four 2,2′‑dithiobis(pyridine N‑oxide) (DTPO) bridged cadmium(II)/halogen coordination polymers, i. e. [Cd2I4(DTPO)3]n (1), [CdBr2(DTPO)(H2O)]n (2), [Cd3Cl6(DTPO)2(CH3OH)2]n, (3) [Cd(SCN)2(DTPO)]n (4) were prepared, which exhibited 1D chain and 2D layers. The coordinated un-saturated Cd centers of 3 and weak Cd–S bond in 4 were prone to be substituted by O-donor of PVP under external voltage. Pristine FTO/Cd complex/Ag memristors can only present dipolar binary resistive switching (RS) behaviors, in which FTO/4/Ag exhibited the best performance (VSet: +1.84 V, ON/OFF ratio: 102.89). After encapsulating into polyvinylpyrrolidone (PVP), FTO/1@PVP/Ag and FTO/2@PVP/Ag remained their binary RS behaviors with enhanced ON/OFF ratio and lower VSet. But FTO/3@PVP/Ag can transfer into WORM (write-once read-many-times) ternary RS behavior. Specially, FTO/4@PVP/Ag illustrated the rare bipolar ternary RS performance (ON2/ON1/OFF ratio: 103.90:101.54:1, VSet1/VSet2/VReset: +1.27/+1.82/-4.83 V), which was more suitable for neuromorphic computing. The ternary RS mechanism was proposed: the OFF→ON1 transition was caused by the carriers trapping/releasing on Cd–O strengthened PVP/Cd complex interfaces, and ON1→ON2 current jump was driven by the 2c-3e S–S bonds. This work provided a new implementing strategy of multilevel memory driven by disulfide bond and PVP encapsulation.

The rapid development of semi-conductor industry calls for the production of organometallic precursors with ultrahigh-purity and low cost. TiO2 film is an important high-k materials, but its atomic layer deposition (ALD) precursor tetrakis(dimethylamino)titanium (TDMAT) still suffers from low industrial synthesis yield and inadequate purity. Herein, by optimizing the lithium displacement method in TDMAT synthesis, much milder synthesis conditions have been achieved with higher yield (91.00%) and ultra-high organic purity (>99.9%). In the purification optimization, a new coupled process combining alkali metal salt and rectification was proposed, based on which ultra-high inorganic purity (99.99993%, Cl- content <10(-)(5), 6N) and high TDMAT yield (93.70%) can be obtained. Finally, by using the as-synthesized precursor, wafer-scale TiO2 film under ALD process has been fabricated, which was characterized by SEM, EDS, AFM, XPS and spectral ellipsometry (SE). Specially, AFM validates its ultra-smooth surface without any extra holes or agglomerations (RMS: 0.303 nm). This work will be significant for the development of ultrahigh-purity semi-conductor materials. (c) 2026 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd. All rights are reserved, including those for text and data mining, AI training, and similar technologies.

Multilevel memory is a feasible solution for the explosive demand for data storage in the Big Data era. In this work, ligand engineering has been implemented in cubane-type Cu4I4L4 clusters to obtain three complexes: Cu4I4L4 (L = P(Ph-p-Cl)3 (1), PPh3 (2), P(Ph-p-OCH3)3 (3)), in which the substitutes on the p-position of benzyl vary from electron-withdrawing (-Cl) to electron-donating (-OCH3) groups. Interestingly, with enhancement of electron-donating ability, the trend of more distorted Cu4I4 cores, enhanced Cu···Cu interactions, and higher structural dimensions can be achieved. Consequently, in FTO/Cu4I4L4/Ag memristors, the electron-withdrawing group (-Cl) and neutral group (-H) exhibit bistable resistive switching performances, and a strong electron-donating group (-OCH3) can give ternary resistive switching behavior (OFF/ON1/ON2 current ratio: 1:102.74:103.73, VSet1/VSet2: 1.09/1.48 V). The mechanism about the elevation from binary to ternary memory behavior in these cubane-like Cu4I4L4 clusters has been clarified: the external voltage-induced I···Cl halogen bonding and C-H···π interaction contribute to the binary resistive switching performances in FTO/1/Ag and FTO/2/Ag, and the presence of the second conductive state in FTO/3/Ag stems from the injected carrier delocalization on the Cu4I4 core due to strong Cu···Cu interactions. The rules drawn in this work can provide a feasible strategy for the design of novel multilevel memories.

The resolution of regioisomers in ionone synthesis to obtain high-purity alpha-/beta-ionone products is highly significant for the perfume industry. In this work, co-crystallization method was applied firstly in highly efficient resolution of alpha-/beta-ionone, which were the cyclization step raw products with different alpha-/beta-ionone ratios. Bisphenol Z (BPZ) was screened as co-former for selective co-crystallization, which can be executed under wide scope of alpha-/beta-ionone ratio (n(alpha): n(beta) from 1:9 to 8:2). The co-crystal was structurally determined as beta-ionone2BPZ by X-ray single crystal diffraction. According to its structure analysis, the stronger H-bond accepting ability of carbonyl on beta-ionone, the bis-hydrogen bond donators provided by phenol groups, and the C-Hpi interaction endowed by cyclohexane ring are the reasons for the high co-crystallization selectivity in alpha-/beta-ionone mixtures. The co-crystallization process has been optimized, based on which high separation efficiency (alpha(X:) 3.29 x 10(-3) similar to 6.91 x 10(-3)) can be achieved. The final yields/purities (alpha-ionone: 98.83%/90.21%; beta-ionone: 98.19%/98.64%) were much higher than those from traditional methods. Co-former BPZ can also be recovered facilely with high yield and purity for next co-crystallization processes. The efficient alpha-/beta-ionone resolution can pave a new avenue for high quality perfume production.

gamma-CuI with zinc blende structure has emerged as a next-generation electrical material, but its current two-step chemical vapor deposition (CVD) method still faces problems including high I-residue/vacancy and low film uniformness. The strategy of one-step CVD using a single-source precursor (SSP) could be a feasible solution. In this work, a tetra-nuclear cubane cluster Cu4I4(TMOP)4 (TMOP = tris(4-methoxyphenyl)phosphine) was constructed and used as SSP in gamma-CuI deposition first. As indicated by structural analysis of this SSP, the introduction of methoxy on the p-position of PPh3 and the absence of pi-pi/C-Hpi interactions can improve its solubility in organic solvent. More importantly, cuprophilic interactions and fluctuant Cu-I bonds can be beneficial for fracture and reconstitution on the substrate surface during the CVD process. Upon optimization of the substrate, deposition sites, gas velocities, and deposition temperatures, the continuous gamma-CuI film with an ultralow roughness (R q = 4.60 nm) under optimal CVD conditions has been obtained, which has been characterized by XRD, SEM, AFM, XPS, and Raman spectra. The {111} preferential growth mechanism of this gamma-CuI has been clarified: the anchoring of Cu4I4 clusters by the size-matched SnO2(110) surface, the Cu-I fracture/reconstitution restricted by cuprophilic interactions, and final growth along the {111} direction. This one-step CVD process using the copper iodide cubane cluster as SSP could pave a new way for the large-scale production of high-quality gamma-CuI films.

In the burgeoning sucralose (TGS) production, the separation bottleneck has hindered its further technology upgrading. In this work, the crystal structural of sucrose-6-acetate chlorination product 4,1 ',6 '-trichlorosucrose-6- acetate hydrate (TSA-6.2H2O) from multi-step recrystallization has been determined, thus the bad separation efficiency of the chlorination process was assigned to the easy incorporation of by-products into the cavities or local defects of the respirable TSA-6.2H2O network. Based on this mechanism, the second cheap organic solvents have been pre-embedded into TSA-6.2H2O to generate stable ternary solvates, i. e. TSA-6.H2Osecond solvent (second solvent = DMF (N,N'-dimethylformamide), DMAc (N, N'-dimethylacetamide), and NMP (N-methyl-2pyrrolidone)). Their cellular-type compacted arrangements were constructed from strong hydrogen bonding interactions between H2O.second solvent guests and TSA-6 networks. Consequently, the free space or local defects for the encapsulation of impurities could be inhibited completely. Upon the optimization of the crystallized process (H2O: NMP = 7: 3, solvent: TSA-6 = 12: 1, operating temperature: 288.2 K), high TSA-6 purity (99.74 % wt) and low sum of alpha x (0.023) can be achieved. Furthermore, under the guidance of ternary phase diagrams (TPD), the second solvents could be facilely removed by modulating the H2O/second solvent ratio (TSA-6 purity: 99.91 % wt in 0.5 h). In all, the clarification on the obscure mechanism and the strategy of pre-embedding second solvents have broken the separation bottleneck in TGS production, which can also be applied in other relative glycosyl halides industries.

d-Allulose, a rare sugar characterized by its high sweetness and low-calorie profile, is gaining attention in the sweetener market. This study introduces an innovative method for converting sucrose into d-allulose through microbial fermentation. An irreversible synthesis pathway was constructed by expressing the scrA, scrB, alsE, and a6PP genes in Escherichia coli JM109 (DE3), enhancing substrate utilization via dual PTS-dependent transport of sucrose and d-fructose. A fructose-1,6-bisphosphatase mutant (GlpX [K29A]) was used to facilitate the influx of fructose-1-phosphate into the synthesis pathway. The Embden-Meyerhof-Parnas (EMP) and pentose phosphate (PP) pathways were weakened by deleting the pfkA and rpiA genes. To further regulate carbon fluxes, a structurally stable antisense RNA (asRNA) was employed to inhibit FbaA expression. The fermentation medium was optimized using response surface methodology. Finally, the d-allulose titer reached 12.8 g/L, with a yield of 0.23 g/g on sucrose, achieved through fed-batch fermentation in a 5 L fermenter.

Multifunctional memristors with a high memory density, low power consumption, flexibility, programmability, and environmental robustness are essential for next-generation memories. In this work, a titanocene-polysulfide complex (Cp2TiS5) with strong S···S interactions and hydrogen bonds was synthesized and integrated with TiO2 to create a novel Cu/TiO2/Cp2TiS5/Ag memristor. This device shows bipolar nonvolatile memory performance with a remarkable ON/OFF ratio (104.8), low switching voltages (VSET, -0.16 V; VRESET, +0.15 V), and low power consumption (2.7 × 10-4 μW). It exhibits multilevel memory behavior, flexibility, optical modulation (VSET decreases from -1.35 to -0.17 V with decreasing irradiation wavelength), and thermal tolerance (up to 200 °C). The electron-rich Cp2TiS5 layer protects the Ag-CFs, while TiO2's oxygen vacancies and unsaturated Ti atoms interact with sulfur from Cp2TiS5, lowering the Schottky barrier and facilitating charge transport. This work offers promising opportunities in flexible memristive devices for neuromorphic computing under extreme conditions.

This study investigates the effect of mechanical vibrations on the pneumatic conveying behavior of nano/micro particles. The minimum pickup velocity (Upu), at which particles are entrained, is experimentally determined for five types of particles (from 20 nm to 275 mu m). Vertical vibrations reduce the Upu for both nano- and microparticles, but the response to vibration differs between large, non-cohesive particles and smaller, more cohesive ones. Larger, non-cohesive particles require weaker vibrations to reduce Upu, while stronger vibrations are needed for nano- and low-micron particles, which are not transported individually but form large agglomerates over 100 mu m, and exhibit irregular and pitted surfaces. A review of current models reveals a lack of a reliable method for accurately predicting the pickup velocities of particles in the nano-to-micro range. To address this, a modified three-zone correlation is proposed to better predict the pickup behavior of nano- and micro-particles under vibration.

The simultaneous achievements of lower aspect ratio and larger crystal size is urgent for the production of high-quality sucralose. In this work, non-toxic ethanol-based anti-solvent crystallization (ASC) of sucralose was conducted, during which carboxylic acids bearing different alkyl lengths (isovaleric acid (IVA), hexanoic acid (HNA), octanoic acid (ONA), decanoic acid (DNA)) were used as anti-solvents. The longer alkyl lengths of carboxylic acids can render higher sucralose yield because the better flexibility can provide larger free void spaces with facilitation of emulsion shrinking, resulting in higher crystallization ratio and rate. Also, the ASC conditions have been optimized, based on which low aspect ratio (1.5585) and small particle size (15.755 mu m) can be obtained using ONA as an anti-solvent. Based on single-crystal structure analysis, the ONA-treated product bearing relatively weaker O-H & ctdot;O/C-H & ctdot;Cl hydrogen bonds was adopted for further ultrasound-assisted ASC process. Interestingly, upon the intermittent sonication mode, the sucralose product with ultra-low aspect ratio (1.244) and larger crystal size (42.722 mu m) can be obtained, which is attributed to the relatively stronger sp3-C-H & ctdot;Cl0 hydrogen bonds on the {011} face than O-H & ctdot;O bonds on the {101}/{110} faces. This work will provide a theoretical guide for the production of high-quality sucralose.

d-Allose has great potential for application in the food and pharmaceutical industries owing to its remarkable physiological properties. Most studies on d-allose production have primarily focused on enzyme catalysis using the Izumoring strategy, which typically requires the use of expensive d-allulose as a substrate. Herein, a metabolically engineered strain of Escherichia coli was developed to synthesize d-allose directly from inexpensive d-glucose. The synthesis pathway was systematically optimized through a modular metabolic engineering. The functionality of the isomerases involved in the conversion of d-allulose to d-allose was confirmed in vivo, while the byproduct and transporter pathways were blocked to positively pull the reversible epimerization. Gene knockouts were employed to weaken glycolytic pathways, redirecting the carbon flux toward product synthesis. Additionally, the nonphosphorylated transport of d-glucose was introduced to enhance substrate utilization. In fed-batch fermentation, the engineered strain achieved a d-allose titer of 4.17 g/L, with a yield of 0.103 g/g from d-glucose. Our achievements are expected to advance the industrial production of d-allose, and this strategy is also applicable for producing other rare sugars.

Bis(fluorosulfonyl)imide triethylamine salt (FSI-HNEt3) is a crucial intermediate for the synthesis of next-generation electrolyte lithium bis(fluorosulfonyl)imide (LiFSI). The NH3-SO2F2-NEt3 route represents a promising approach for LiFSI production but faces challenges, including low efficiency and obscure reaction mechanisms. In this study, we optimize the synthesis of FSI-HNEt3 using NH3-SO2F2-NEt3 route and propose a new process. By capturing the sulfur-fluorine exchange (SuFEx) reaction intermediate with a novel molecular sieve-based method, we clarify the reaction mechanism with direct evidence. The primary mechanism involves a two-step SuFEx process, and we establish the complete pathways for both main and side reactions. Our study further reveals that hydrolysis and self-polymerization reactions during synthesis significantly reduce the yield of FSI-HNEt3. Density functional theory (DFT) calculations demonstrate how triethylamine (NEt3) enhances the nucleophilicity of reactants, confirming the two-step SuFEx mechanism and providing insights into the overall reaction system. These findings offer valuable guidance for the safe and efficient synthesis of FSI-HNEt3.

The design of highly stable and active bifunctional catalysts for electrolytic water remains a significant challenge. In this study, self-supported CoP/CNT/Ni2P bifunctional catalysts with three-phase heterojunction nano- structures were constructed by a multi-step electrodeposition and phosphorylation strategy. X-ray diffraction analysis and transmission electron microscope showed that CoP/CNT/Ni2P was a three-phase heterojunction nanostructure, and scanning electron microscope results of CoP/CNT/Ni2P suggested the successful introduction of carbon nanotube (CNT). The X-ray photoelectron spectroscopy results indicate a shift in the elemental binding energy in CoP/CNT/Ni2P, which is believed to contribute to the electrocatalytic reaction. The incorporation of CNT enhances charge transfer within the multiphase catalyst and maximizes the exposure of catalytically active sites, achieving an increase in catalyst performance. As anticipated, the CoP/CNT/Ni2P catalyst displays high catalytic activity for both the hydrogen evolution reaction (61 mV at 10 mA cm_ 2 ) and the oxygen evolution reaction (342 mV at 100 mA cm_ 2 ), in addition to exhibiting long-term stability at a current density of 10 mA cm_ 2 over 40 h. The electrolyzer comprising CoP/CNT/Ni2P(+,_) necessitates a modest operating voltage of 1.52 V to attain 10 mA cm_ 2 during alkaline water splitting, thereby outperforming the commercial catalyst Pt/C|| IrO2 and earlier reports. This study provides guidance for the development of ultra-high activity and durability catalysts for water splitting.