bluuebunny/crossref_metadata_2025_split huggingface dataset:
Bending, Twisting, and Propulsion of Photoreactive Crystals by Controlled Gas Release
Authors: Yu Chunjiao , Jiang Xiaofan , Al‐Handawi Marieh B. , Naumov Panče , Li Liang , Yu Qi , Wang Guoming 
Published: March 2024

AbstractThe rapid release of gas by a chemical reaction to generate momentum is one of the most fundamental ways to elicit motion that could be used to sustain and control the motility of objects. We report that hollow crystals of a three‐dimensional supramolecular metal complex that releases gas by photolysis can propel themselves or other objects and advance in space when suspended in mother solution. In needle‐like regular crystals, the reaction occurs mainly on the surface and results in the formation of cracks that evolve due to internal pressure; the expansion on the cracked surface of the crystal results in bending, twisting, or coiling of the crystal. In hollow crystals, gas accumulates inside their cavities and emanates preferentially from the recess at the crystal terminus, propelling the crystals to undergo directional photomechanical motion through the mother solution. The motility of the object which can be controlled externally to perform work delineates the concept of “crystal microbots”, realized by photoreactive organic crystals capable of prolonged directional motion for actuation or delivery. Within the prospects, we envisage the development of a plethora of light‐weight, efficient, autonomously operating robots based on organic crystals with high work capacity where motion over large distances can be attained due to the large volume of latent gas generated from a small volume of the crystalline solid.
A Cytochrome P450 Catalyzes Oxidative Coupling Formation of Insecticidal Dimeric Indole Piperazine Alkaloids
Authors: He Qian , Zhang Hua‐Ran , Zou Yi 
Published: March 2024

AbstractCytochrome P450 (CYP450)‐catalyzed oxidative coupling is an efficient strategy for using simple building blocks to construct complex structural scaffolds of natural products. Among them, heterodimeric coupling between two different monomers is relatively scarce, and the corresponding CYP450s are largely undiscovered. In this study, we discovered a fungal CYP450 (CpsD) and its associated cps cluster from 37208 CYP450s of Pfam PF00067 family member database and subsequently identified a group of new skeleton indole piperazine alkaloids (campesines A−G) by combination of genome mining and heterologous synthesis. Importantly, CYP450 CpsD mainly catalyzes intermolecular oxidative heterocoupling of two different indole piperazine monomers to generate an unexpected 6/5/6/6/6/6/5/6 eight‐ring scaffold through the formation of one C−C bond and two C−N bonds, illuminating its first dimerase role in this family of natural products. The proposed catalytic mechanism of CpsD was deeply investigated by diversified substrate derivatization. Moreover, dimeric campesine G shows good insecticidal activity against the global honeybee pest Galleria mellonella. Our study shows a representative example of discovering new skeleton monomeric and dimeric indole piperazine alkaloids from microbial resources, expands our knowledge of bond formation by CYP450s and supports further development of the newly discovered and engineered campesine family compounds as potential biopesticides.
Hydrogen‐Bonded Organic Framework Supporting Atomic Bi−N2O2 Sites for High‐Efficiency Electrocatalytic CO2 Reduction
Authors: Wang Changli , Lv Zunhang , Liu Yarong , Liu Rui , Sun Caiting , Wang Jinming , Li Liuhua , Liu Xiangjian , Feng Xiao , Yang Wenxiu , Wang Bo 
Published: March 2024

AbstractSingle atomic catalysts (SACs) offer a superior platform for studying the structure–activity relationships during electrocatalytic CO2 reduction reaction (CO2RR). Yet challenges still exist to obtain well‐defined and novel site configuration owing to the uncertainty of functional framework‐derived SACs through calcination. Herein, a novel Bi−N2O2 site supported on the (1 1 0) plane of hydrogen‐bonded organic framework (HOF) is reported directly for CO2RR. In flow cell, the target catalyst Bi1‐HOF maintains a faradaic efficiency (FE) HCOOH of over 90 % at a wide potential window of 1.4 V. The corresponding partial current density ranges from 113.3 to 747.0 mA cm−2. And, Bi1‐HOF exhibits a long‐term stability of over 30 h under a successive potential‐step test with a current density of 100–400 mA cm−2. Density function theory (DFT) calculations illustrate that the novel Bi−N2O2 site supported on the (1 1 0) plane of HOF effectively induces the oriented electron transfer from Bi center to CO2 molecule, reaching an enhanced CO2 activation and reduction. Besides, this study offers a versatile method to reach series of M−N2O2 sites with regulable metal centers via the same intercalation mechanism, broadening the platform for studying the structure–activity relationships during CO2RR.
Large‐Area Ultrathin Metal–Organic Framework Membranes Fabricated on Flexible Polymer Supports for Gas Separations
Authors: Liang Yueyao , Zhang Zhengqing , Chen Aibing , Yu Caijiao , Sun Yuxiu , Du Juan , Qiao Zhihua , Wang Zhi , Guiver Michael D. , Zhong Chongli 
Published: March 2024

AbstractUltrathin continuous metal–organic framework (MOF) membranes have the potential to achieve high gas permeance and selectivity simultaneously for otherwise difficult gas separations, but with few exceptions for zeolitic‐imidazolate frameworks (ZIF) membranes, current methods cannot conveniently realize practical large‐area fabrication. Here, we propose a ligand back diffusion‐assisted bipolymer‐directed metal ion distribution strategy for preparing large‐area ultrathin MOF membranes on flexible polymeric support layers. The bipolymer directs metal ions to form a cross‐linked two‐dimensional (2D) network with a uniform distribution of metal ions on support layers. Ligand back diffusion controls the feed of ligand molecules available for nuclei formation, resulting in the continuous growth of large‐area ultrathin MOF membranes. We report the practical fabrication of three representative defect‐free MOF membranes with areas larger than 2,400 cm2 and ultrathin selective layers (50–130 nm), including ZIFs and carboxylate‐linker MOFs. Among these, the ZIF‐8 membrane displays high gas permeance of 3,979 GPU for C3H6, with good mixed gas selectivity (43.88 for C3H6/C3H8). To illustrate its scale‐up practicality, MOF membranes were prepared and incorporated into spiral‐wound membrane modules with an active area of 4,800 cm2. The ZIF‐8 membrane module presents high gas permeance (3,930 GPU for C3H6) with acceptable ideal gas selectivity (37.45 for C3H6/C3H8).
Stepwise Dissipative Control of Multimodal Motion in a Silver(I) Catenate
Authors: Elramadi Emad , Kundu Sohom , Mondal Debabrata , Paululat Thomas , Schmittel Michael 
Published: March 2024

AbstractStepwise dissipative control of two distinct motions, i.e., shuttling and sliding, is demonstrated in a single multicomponent device. When [2]rotaxane 1, which acts as a biped, and deck 2 were treated with AgBF4/PhCH2Br+NEt3 as chemical fuel, the transient catenate [Ag(1)]+ ⋅ [Ag3(2)]3+ was instantly generated showing multimodal motion and autonomous return to 1 and 2. In the dissipative process, catenate [Ag(1)]+ ⋅ [Ag3(2)]3+ cleanly transformed into the follow‐up transient device (1) ⋅ [Ag3(2)]3+ exhibiting only sliding motion. Two interference‐free dissipative cycles proved the resilience and robustness of the process.
Orthogonal Photoswitching in a Porous Organic Framework
Authors: Sheng Jinyu , Perego Jacopo , Bracco Silvia , Cieciórski Piotr , Danowski Wojciech , Comotti Angiolina , Feringa Ben L. 
Published: March 2024

AbstractThe development of photoresponsive systems with non‐invasive orthogonal control by distinct wavelengths of light is still in its infancy. In particular, the design of photochemically triggered‐orthogonal systems integrated into solid materials that enable multiple dynamic control over their properties remains a longstanding challenge. Here, we report the orthogonal and reversible control of two types of photoswitches in an integrated solid porous framework, that is, visible‐light responsive o‐fluoroazobenzene and nitro‐spiropyran motifs. The properties of the constructed material can be selectively controlled by different wavelengths of light thus generating four distinct states providing a basis for dynamic multifunctional materials. Solid‐state NMR spectroscopy demonstrated the selective transformation of the azobenzene switch in the bulk, which in turn modulates N2 and CO2 adsorption.
Radical‐Induced Photochromic Silver(I) Metal–Organic Frameworks: Alternative Topology, Dynamic Photoluminescence and Efficient Photothermal Conversion Modulated by Anionic Guests
Authors: Liao Pei‐Yu , Li Jia‐Xin , Liu Jia‐Chuan , Xiong Qi , Ruan Ze‐Yu , Li Tao , Deng Wei , Jiang Shang‐Da , Jia Jian‐Hua , Tong Ming‐Liang 
Published: March 2024

AbstractPhotogenerated radicals are an indispensable member of the state‐of‐the‐art photochromic material family, as they can effectively modulate the photoluminescence and photothermal conversion performance of radical‐induced photochromic complexes. Herein, two novel radical‐induced photochromic metal–organic frameworks (MOFs), [Ag(TEPE)](AC) ⋅ 7/4H2O ⋅ 5/4EtOH (1) and [Ag(TEPE)](NC) ⋅ 3H2O ⋅ EtOH (2), are reported. Distinctly different topological networks can be obtained by judiciously introducing alternative π‐conjugated anionic guests, including a new topological structure (named as sfm) first reported in this work, describing as 4,4,4,4‐c net. EPR data and UV–Vis spectra prove the radical‐induced photochromic mechanism. Dynamic photochromism exhibits tunability in a wide CIE color space, with a linear segment from yellow to red for 1, while a curved coordinate line for 2, resulting in colorful emission from blue to orange. Moreover, photogenerated TEPE* radicals effectively activate the near‐infrared (NIR) photothermal conversion effect of MOFs. Under 1 W cm−2 808 nm laser irradiation, the surface temperatures of photoproducts 1* and 2* can reach ~160 °C and ~120 °C, respectively, with competitive NIR photothermal conversion efficiencies η=51.8 % (1*) and 36.2 % (2*). This work develops a feasible electrostatic compensation strategy to accurately introduce photoactive anionic guests into MOFs to construct multifunctional radical‐induced photothermal conversion materials with tunable photoluminescence behavior.
Bioinspired Total Synthesis of Cephalotaxus Diterpenoids and Their Structural Analogues
Authors: Shao Hui , Ma Zhi‐Hua , Cheng Yang‐Yang , Guo Xiao‐Feng , Sun Ya‐Kui , Liu Wen‐Jie , Zhao Yu‐Ming 
Published: March 2024

AbstractHerein, we present a unified chemical synthesis of three subgroups of cephalotaxus diterpenoids. Key to the success lies in adopting a synthetic strategy that is inspired by biosynthesis but is opposite in nature. By employing selective one‐carbon introduction and ring expansion operations, we have successfully converted cephalotane‐type C18 dinorditerpenoids (using cephanolide B as a starting material) into troponoid‐type C19 norditerpenoids and intact cephalotane‐type C20 diterpenoids. This synthetic approach has enabled us to synthesize cephinoid H, 13‐oxo‐cephinoid H, 7‐oxo‐cephinoid H, fortalpinoid C, 7‐epi‐fortalpinoid C, cephanolide E, and 13‐epi‐cephanolide E. Furthermore, through the development of an intermolecular asymmetric Michael reaction between β‐oxo esters and β‐substituted enones, we have achieved the enantioselective synthesis of advanced intermediates within our synthetic sequence, thus formally realizing the asymmetric total synthesis of the cephalotaxus diterpenoids family.
Atropisomeric Carboxylic Acids Synthesis via Nickel‐Catalyzed Enantioconvergent Carboxylation of Aza‐Biaryl Triflates with CO2
Authors: Chen Xiao‐Wang , Li Chao , Gui Yong‐Yuan , Yue Jun‐Ping , Zhou Qi , Liao Li‐Li , Yang Jing‐Wei , Ye Jian‐Heng , Yu Da‐Gang 
Published: March 2024

AbstractUpgrading CO2 to value‐added chiral molecules via catalytic asymmetric C−C bond formation is a highly important yet challenging task. Although great progress on the formation of centrally chiral carboxylic acids has been achieved, catalytic construction of axially chiral carboxylic acids with CO2 has never been reported to date. Herein, we report the first catalytic asymmetric synthesis of axially chiral carboxylic acids with CO2, which is enabled by nickel‐catalyzed dynamic kinetic asymmetric reductive carboxylation of racemic aza‐biaryl triflates. A variety of important axially chiral carboxylic acids, which are valuable but difficult to obtain via catalysis, are generated in an enantioconvergent version. This new methodology features good functional group tolerance, easy to scale‐up, facile transformation and avoids cumbersome steps, handling organometallic reagents and using stoichiometric chiral materials. Mechanistic investigations indicate a dynamic kinetic asymmetric transformation process induced by chiral nickel catalysis.
Evaluating preference displacement of edible stimuli and social interactions for typically developing preschool children
Authors: Lasinski N. R. , Klatt K. P. 
Published: March 2024

AbstractEdible and leisure items are often used in behavioral intervention to teach skills or reduce problem behavior. Social interactions, however, have also been shown to function as reinforcers for both typically developing children and children diagnosed with autism. Previous research has been conducted investigating preference displacement between edible, leisure and social items. The current study included edible stimuli and social interactions to evaluate whether patterns of displacement would appear with typically developing children. Multiple stimulus without replacement preference assessments were conducted to identify highly preferred stimuli from both edible item and social interaction classes to use in combined assessments to evaluate displacement. Three of six participants showed complete displacement of social interactions by edible items and three participants showed patterns of partial displacement. Two of the participants demonstrating patterns of partial displacement showed a disproportionate preference for social interactions.
An innovative hybrid modeling approach for simultaneous prediction of cell culture process dynamics and product quality
Authors: Polak Jakub , Huang Zhuangrong , Sokolov Michael , von Stosch Moritz , Butté Alessandro , Hodgman C. Eric , Borys Michael , Khetan Anurag 
Published: March 2024

AbstractThe use of hybrid models is extensively described in the literature to predict the process evolution in cell cultures. These models combine mechanistic and machine learning methods, allowing the prediction of complex process behavior, in the presence of many process variables, without the need to collect a large amount of data. Hybrid models cannot be directly used to predict final product critical quality attributes, or CQAs, because they are usually measured only at the end of the process, and more mechanistic knowledge is needed for many classes of CQAs. The historical models can instead predict the CQAs better; however, they cannot directly relate manipulated process parameters to final CQAs, as they require knowledge of the process evolution. In this work, we propose an innovative modeling approach based on combining a hybrid propagation model with a historical data‐driven model, that is, the combined hybrid model, for simultaneous prediction of full process dynamics and CQAs. The performance of the combined hybrid model was evaluated on an industrial dataset and compared to classical black‐box models, which directly relate manipulated process parameters to CQAs. The proposed combined hybrid model outperforms the black‐box model by 33% on average in predicting the CQAs while requiring only around half of the data for model training to match performance. Thus, in terms of model accuracy and experimental costs, the combined hybrid model in this study provides a promising platform for process optimization applications.
Profiling Key Aroma Compounds of Senecio glaucus L. and their Antimicrobial and Antioxidant Activities: Multiplex of GC‐MS, NMR and In Silico Studies
Authors: Elghonemy Mai M. , Essa Ahmed F. , Osman Abeer F. , Khalaf Doaa D. , El‐Nasser G. El Gendy Abd , Abd‐ElGawad Ahmed M. , Umeyama Akemi , Elshamy Abdelsamed I. 
Published: March 2024

AbstractThe essential oils of Senecio plants have been used to treat a wide range of ailments. The current study aimed to extract the essential oil of Senecio glaucus obtained from Egypt's Nile delta and determine its chemical profile using GC‐MS and NMR analysis. Then, the antimicrobial activity of the oil has been investigated against different fungal and bacterial strains. In addition, its activity as radical scavenger has been evaluated using DPPH, ABTS, and metal chelating techniques. The results revealed the identification of 50 compounds representing 98.80 % of the oil total mass. Sesquiterpenes, including dehydrofukinone (27.15 %) and 4,5‐di‐epi‐aristolochene (10.27 %), as well as monoterpenes, including p‐cymene (4.77 %), represented the most predominant constituents. The dehydrofukinone has been isolated and structurally confirmed using 1D and 2D NMR techniques. The oil has showed remarkable antifungal activity against Candida glabrata and C. albicans where the minimum inhibitory concentration (MIC) and minimum fungicidal concentration (MFC) values were 3.13 μg/mL and 1.50 μg/mL and 12.50 μg/mL and 6.30 μg/mL, respectively that could be attributed to the sesquiterpene ketones present in the aerial tissues of the plant. Also, this oil inhibited the growth of the tested bacteria with MIC ranging from 12.50–100.00 μg/mL. In comparison to ascorbic acid and Trolox, the EO had remarkable scavenging activity of DPPH, ABTS and metal chelating with IC50 values of 313.17±13.4, 493.83±20.1, and 409.13±16.7 μg/mL. The docking studies of the identified compounds of the oil to different microbial targets, including Gyrase B and α‐sterol demethylase, showed that the phytol possessed the best binding affinities toward the active sites of both enzymes with ΔG=−7.42 and −7.78 kcal/mol, respectively. In addition, the phytol revealed the highest binding affinity to tyrosine kinase Hck with ΔG=−7.44 kcal/mol.
Recurrent hypo‐attenuated leaflet thickening after TAVR: Clinical implications
Authors: Takla Andrew , Sourial Kirolus , Sharma Gaurav 
Published: March 2024

AbstractSubclinical bioprosthetic valve thrombosis (BPVT) is a relatively common finding in asymptomatic patients during follow‐up imaging. However, its clinical significance is unclear. Data from registries associate BPVT with elevated valve gradients, thromboembolic complications, recurrence, and valve degeneration. Given the dynamic nature of the disease process, management is challenging. The duration of anticoagulation is unpredictable, and the need for frequent monitoring of BPVT, even in subclinical scenarios, is unclear. Our report is shedding the light on the clinical implications BPVT.
Biocatalytic Synthesis of l‐Pipecolic Acid by a Lysine Cyclodeaminase: Batch and Flow Reactors
Authors: Stalder Kaja , Benítez‐Mateos Ana I. , Paradisi Francesca 
Published: March 2024

Abstractl‐Pipecolic Acid (l‐PA) is a valuable building block for the synthesis of pharmaceuticals such as anesthetics and immunosuppressants. Thus, more efficient and greener strategies are desired for its production. Herein, we have applied a previously engineered variant of the Lysine Cyclodeaminase from Streptomyces pristinaespiralis (e‐SpLCD) for the bioconversion of l‐Lysine into l‐PA. The reaction can be performed by the free e‐SpLCD reaching full conversion to 50 mM l‐PA. From a biotechnological perspective, the process scale‐up has been trialed in a SpinChem® reactor, albeit with lower conversion yields. To further enhance the biocatalyst stability, we present a detailed study of the e‐SpLCD immobilization on microparticles. This enabled the integration of the immobilized biocatalyst into a packed‐bed reactor for the continuous flow synthesis of l‐PA. The full conversion was achieved in 90 min, maintaining also high operational stability. Remarkably, the addition of exogenous cofactor was not needed for the flow reaction, although the long‐term operational stability was improved by the addition of NAD+.
Electrodeposition of Fractal Structured Nickel for Hydrogen Evolution Reaction in Alkaline
Authors: Harada Yuya , Hua Qi , Harris Lauren C. , Yoshida Tsukasa , Gewirth Andrew A. 
Published: March 2024

AbstractTo accelerate the practical application of water splitting in alkaline media, it is imperative to enhance the electrocatalytic performance for the Hydrogen Evolution Reaction (HER). In this context, we demonstrate that a simple (one‐pot, one‐step) electrodeposition process of nickel (Ni) in the presence of 3,5‐diamino1,2,4‐triazole (DAT) results in the formation of fractally structured Ni films with a significantly increased surface area. The Electrochemically active surface area (ECSA) increases with the electrodeposition charge passed, with the film electrodeposited at 14 C cm−2 achieving a reduction in overpotential at −10 mA cm−2 (η10) to 65.7 mV, coupled with a remarkable increase in ECSA (114‐fold greater than that of Ni‐foil). Additionally, nickel deposited in the presence of DAT effectively mitigates deactivation during electrolysis, exhibiting a 3.6‐fold lower overpotential degradation compared to that of the smooth Ni foil. This simple electrodeposition technique, applicable to a variety of conductive substrates, is distinguished by its high catalytic performance in the HER, a feature of considerable significance.
Facilitating Electron Transfer by Resizing Cyclocarbon Acceptor from C18 to C16
Authors: Stasyuk O. A. , Voityuk A. A. , Stasyuk A. J. 
Published: March 2024

AbstractRecent advances in synthetic methods, combined with tip‐induced on‐surface chemistry, have enabled the formation of numerous cyclocarbon molecules. Here, we investigate computationally the experimentally studied C16 and C18 molecules as well as their van der Waals (vdW) complexes with several typical donor and acceptor molecules. Our results demonstrate a remarkable electron‐withdrawing ability of cyclocarbon molecules. The vdW complexes of C16 and C18 exhibit a thermodynamically favorable photoinduced electron transfer (ET) from the donor partner to the cyclocarbons that occurs on a picosecond time scale. The lower reorganization energy of C16 compared to C18 leads to a significant acceleration of the ET reactions.
One‐pot Synthesis of PdCuAg and CeO2 Nanowires Hybrid with Abundant Heterojunction Interface for Ethylene Glycol Electrooxidation
Authors: Fan Dongping , Zheng Jinyu , Xiang Xin , Xu Dongdong 
Published: March 2024

AbstractIntroducing CeO2 into Pd‐based nanocatalysts for electrocatalytic reactions is a good way to solve the intermediate toxicity problem and improve the catalytic performance. Here we reported a simple strategy to synthesize the PdCuAg and CeO2 nanowires hybrid via a one‐pot synthesis process under strong nanoconfined effect of specific surfactant as templates. Owing to the structural (ultrathin nanowires, abundant heterojunction/interfaces between metal and metal oxide) and compositional (Pd, Cu, Ag, CeO2) advantages, the hybrid showed significantly enhanced catalytic activity (6.06 A mgPd−1) and stability, accelerated reaction rate, and reduced activation energy toward electrocatalytic ethylene glycol oxidation reaction.