bluuebunny/crossref_metadata_2025 huggingface dataset:
Multidimension‐Regulated Dynamic Timing Control Over Multicolor Emission of Host–Guest Assemblies for Information Encryption and Advanced Anti‐Counterfeiting
Authors: Zhang Qi , Chang Zhidong , Han Weiqiang , Wang Chaofan , Liu Guoxin , Li Hongjuan , Sun Shiguo , Xu Yongqian
Published: May 2024

Dynamical control over molecular luminescence, especially in a time‐dependent manner, holds great promise for the development of smart luminescent materials for anti‐counterfeiting and preventing information leakage. Herein, a series of self‐assembled systems are reported using pillar[5]arene (DMP[5]) and spiropyran derivatives (SP‐C4‐Py). The assemblies rely on the time‐encoded locking and unlocking ring‐switching and fluorescence resonance energy transfer (FRET) units for information camouflage and multilevel encryption. DMP[5] with cyan solid fluorescence color acts as the host and energy transfer (EnT) donor, while photochromic SP‐C4‐Py with the ring‐opened and closed isomers acts as guest and EnT acceptor. When irradiated, the assemblies undergo a time‐dependent luminescence color change ranging from cyan to yellow to red through a FRET process. The molar ratio of host and guest in the assembly systems affects the FRET efficiency, and the power of the irradiation source influences the isomerization degree and rate of SP‐C4‐Py, allowing for precise control over the fluorescent color transition time. The combination of molecular composition and external stimuli governs the kinetics of color change, resulting in a difference in the appearance time of a specific fluorescent color pre‐designed as correct authorized information. By combining these diverse assembles in one label, information encryption and dynamic information identification are achieved in the dimensions of time, ratio, and light power. This time‐dependent feature offers the assembly materials with a multilevel security and provides new possibilities for anti‐counterfeiting and blocking information leakage.
Multilayer Graphene/Epitaxial Silicon Near‐Infrared Self‐Quenched Avalanche Photodetectors
Authors: Li Zongwen , Cao Xiaoxue , Zhang Zhixiang , Qiao Baoshi , Tian Feng , Dai Yue , Bodepudi Srikrishna Chanakya , Liu Xinyu , Chai Jian , Liu Dajian , Anwar Muhammad Abid , Han Xun , Xue Fei , Fang Wenzhang , Dan Yaping , Zhao Yuda , Hu Huan , Yu Bin , Gao Chao , Xu Yang
Published: May 2024

2D materials and their heterostructures exhibit considerable potential in the development of avalanche photodetectors (APDs) with high gain, response, and signal‐to‐noise ratio. These materials hold promise in addressing inherent technical challenges associated with APDs, such as low light absorption coefficient, elevated noise current, and substantial power consumption due to high bias resulting in only moderate current gain. In this work, a macro‐assembled graphene nanofilm (nMAG)/epitaxial silicon (epi‐Si) vertical heterostructure photodetector with a responsivity of 0.38 A W−1 and a response time of 1.4 µs is reported. The photodetectors use high‐quality nMAG as the absorption layer and a lightly‐doped epi‐Si layer as the multiplication region under the avalanche mode to provide a high responsivity (2.51 mA W−1) and detectivity (2.67 × 109 Jones) at 1550 nm, which can achieve high‐resolution imaging. In addition, the APD displays a weak noise level and an avalanche gain of M = 1123. It can work with relatively low avalanche turn‐on voltages and achieve self‐quenching by switching from illumination to dark during avalanche multiplication, with a real‐time data transfer rate of 38 Mbps in near‐infrared light communication data links. The proposed structure enables the fabrication of high‐performance APDs in the infrared range using complementary‐metal‐oxide‐semiconductor (CMOS)‐compatible processes.
Bifunctional Squaramide‐Catalyzed Oxidative Kinetic Resolution: Simultaneous Access to Axially Chiral Thioether and Sulfoxide
Authors: Wen Wei , Yang Chang‐Lin , Wu Zhu‐Lian , Xiao Dong‐Rong , Guo Qi‐Xiang
Published: May 2024

Axially chiral thioethers and sulfoxides emerge as two pivotal classes of ligands and organocatalysts, which have remarkable features in the stereoinduction of various asymmetric transformations. However, the lack of easy methods to access such molecules with diverse structures has hampered their broader utilization. Herein, an oxidative kinetic resolution for sulfides using a chiral bifunctional squaramide as the catalyst with cumene hydroperoxide as the terminal oxidant is established. This asymmetric approach provides a variety of axially chiral thioethers as well as sulfoxides bearing both axial and central chirality, with excellent diastereo‐ and enantioselectivities. This catalytic system also successfully extends to the kinetic resolution of benzothiophene‐based sulfides. Preliminary mechanism investigation indicates that the multiple hydrogen bonding interactions between the bifunctional squaramide catalyst and substrates play a crucial role in determining the enantioselectivity and reactivity.
High‐Entropy and Multiphase Cathode Materials for Sodium‐Ion Batteries
Authors: Li Ranran , Qin Xuan , Li Xiaolei , Zhu Jianxun , Zheng Li‐Rong , Li Zhongtao , Zhou Weidong
Published: May 2024

Cycling stability is the biggest challenge for cathodes of sodium‐ion batteries (SIBs), which is directly affected by the structure design. Herein, the combination of high‐entropy (HE) and multiphase structure is demonstrated to be helpful for maintaining the structure and improving the cycling stability. In the Ni/Mn/Cu/Ti/Sn five‐component HE multiphase cathode, the multiple elements at transition metal sites can enlarge the lattice and stabilize the structure simultaneously without causing an obvious capacity drop, achieving the synergistic effect of multi‐cations. In the HE cathodes consisting of P2 and O3 phases, the harmful phase transition in high‐voltage is suppressed and the cycling performance is improved. A capacity retention of 77.3 mAh g−1 after 300 cycles is delivered, and an improved rate performance of 88.7 mAh g−1 at 750 mA g−1 is observed, better than that of the low‐entropy multiphase cathode(P2 and O3) and the HE oxide single O3‐phase cathode. The weighted average ionic radius(WAIR) of all transition metals is demonstrated critical for the formation of the phase composition in HE composites. Through comparing a series of HE and multiphase cathodes, an empirical range of WAIR is obtained, which shows guidance for the design of other cathode materials.
Association between the severity of hypothermia and in‐hospital mortality in patients with infectious diseases: The J‐Point registry
Authors: Shiozumi Tadaharu , Miyamoto Yuki , Morita Sachiko , Ehara Naoki , Miyamae Nobuhiro , Okada Yohei , Jo Takaaki , Sumida Yasuyuki , Okada Nobunaga , Watanabe Makoto , Nozawa Masahiro , Tsuruoka Ayumu , Fujimoto Yoshihiro , Okumura Yoshiki , Kitamura Tetsuhisa , Matsuyama Tasuku
Published: May 2024

Aim

Hypothermia is associated with poor prognosis in patients with sepsis. However, no studies have explored the correlation between the severity of hypothermia and prognosis.

Methods

Using data from the Japanese accidental hypothermia network registry (J‐Point registry), we examined adult patients aged ≥18 years with infectious diseases whose initial body temperature was ≤35°C from April 1, 2011 to March 31, 2016, in 12 centers. Patients were divided into three groups according to their body temperature: Tertile 1 (T1) (32.0–35.0°C), Tertile 2 (T2) (28.0–31.9°C), and Tertile 3 (T3) (<28.0°C). In‐hospital mortality was employed as a metric to assess outcomes. We conducted a multivariate logistic regression analysis to investigate the relationship between the three categories and the occurrence of in‐hospital mortality.

Results

A total of 572 patients were registered, and 170 eligible patients were identified. Of these patients, 55 were in T1 (32.0–35.0°C), 76 in T2 (28.0–31.9°C), and 39 in T3 (<28.0°C) groups. The overall in‐hospital mortality rate in accidental hypothermia (AH) patients with infectious diseases was 34.1%. The in‐hospital mortality rates in the T1, T2, and T3 groups were 34.5%, 36.8%, and 28.2%, respectively. The multivariable analysis demonstrated no significant differences regarding in‐hospital mortality among the three groups (T2 vs. T1, adjusted odds ratio [OR]: 1.29; 95% confidence interval [CI]: 0.58–2.89 and T3 vs. T1, adjusted OR: 0.83; 95% CI: 0.30–2.31).

Conclusion

In this multicenter retrospective observational study, hypothermia severity was not associated with in‐hospital mortality in AH patients with infectious diseases.
Characteristics and outcomes of out‐of‐hospital cardiac arrest in a hilly area: Utstein Registry data from the Nagasaki Medical Region, Japan
Authors: Zmushka Valeryia , Tajima Goro , Iyama Keita , Hayakawa Koichi , Yamashita Kazunori , Inokuma Takamitsu , Izumino Hiroo , Otaguro Takanobu , Uemura Eri , Ueki Tomohiro , Murahashi Shimon , Yamano Shuhei , Takahashi Kensuke , Aoki Yoshihiro , Tachikawa Atsuko , Tasaki Osamu
Published: May 2024

Aim

To analyze characteristics and investigate prognostic indicators of out‐of‐hospital cardiac arrest (OHCA) in a hilly area in Japan.

Methods

A retrospective population‐based study was conducted using the Utstein Registry for 4280 OHCA patients in the Nagasaki Medical Region (NMR) registered over the 10‐year period from 2011 to 2020. The main outcome measure was a favorable cerebral performance category (CPC 1–2). Sites at which OHCA occurred were classified into “sloped places (SPs)” (not easily accessible by emergency medical services [EMS] personnel due to slopes) and “accessible places (APs)” (EMS personnel could park an ambulance close to the site). The characteristics and prognosis based on CPC were compared between SPs and APs, and multivariable analysis was performed.

Results

No significant improvement in prognosis occurred in the NMR from 2011 to 2020. Prognosis in SPs was significantly worse than that in APs. However, multivariable analysis did not identify SP as a prognostic indicator. The following factors were associated with survival and CPC 1–2: age group, witness status, first documented rhythm, bystander‐initiated cardiopulmonary resuscitation (CPR) and automated external defibrillator (AED) use, use of mechanical CPR (m‐CPR) device or esophageal obturator airway (EOA), and year. Both m‐CPR and EOA use were associated with a poor prognosis.

Conclusion

In a hilly area, OHCA patients in SPs had a worse prognosis than those in APs, but SPs was not significantly associated with prognosis by multivariable analysis. Interventions to increase bystander‐initiated CPR and AED use could potentially improve outcomes of OHCA in the NMR.
Elevated Water Oxidation by Cation Leaching Enabled Tunable Surface Reconstruction
Authors: Luo Songzhu , Dai Chencheng , Ye Yike , Wu Qian , Wang Jiarui , Li Xiaoning , Xi Shibo , Xu Zhichuan J.
Published: May 2024

Water electrolysis is one promising and eco‐friendly technique for energy storage, yet its overall efficiency is hindered by the sluggish kinetics of oxygen evolution reaction (OER). Therefore, developing strategies to boost OER catalyst performance is crucial. With the advances in characterization techniques, an extensive phenomenon of surface structure evolution into an active amorphous layer was uncovered. Surface reconstruction in a controlled fashion was then proposed as an emerging strategy to elevate water oxidation efficiency. In this work, Cr substitution induces the reconstruction of NiFexCr2‐xO4 during cyclic voltammetry (CV) conditioning by Cr leaching, which leads to a superior OER performance. The best‐performed NiFe0.25Cr1.75O4 shows a ~1500 % current density promotion at overpotential η=300 mV, which outperforms many advanced NiFe‐based OER catalysts. It is also found that their OER activities are mainly determined by Ni : Fe ratio rather than considering the contribution of Cr. Meanwhile, the turnover frequency (TOF) values based on redox peak and total mass were obtained and analysed, and their possible limitations in the case of NiFexCr2‐xO4 are discussed. Additionally, the high activity and durability were further verified in a membrane electrode assembly (MEA) cell, highlighting its potential for practical large‐scale and sustainable hydrogen gas generation.
Selective Macrocyclization of Unprotected Peptides with an Ex Situ Gaseous Linchpin Reagent
Authors: Ding Yuxuan , Pedersen Simon S. , Wang Haofan , Xiang Baorui , Wang Yixian , Yang Zhi , Gao Yuxiang , Morosan Emilia , Jones Matthew R. , Xiao Han , Ball Zachary T.
Published: May 2024

Peptide cyclization has dramatic effects on a variety of important properties, enhancing metabolic stability, limiting conformational flexibility, and altering cellular entry and intracellular localization. The hydrophilic, polyfunctional nature of peptides creates chemoselectivity challenges in macrocyclization, especially for natural sequences without biorthogonal handles. Herein, we describe a gaseous sulfonyl chloride derived reagent that achieves amine–amine, amine–phenol, and amine–aniline crosslinking through a minimalist linchpin strategy that affords macrocyclic urea or carbamate products. The cyclization reaction is metal‐mediated and involves a novel application of sulfine species that remains unexplored in aqueous or biological contexts. The aqueous method delivers unique cyclic or bicyclic topologies directly from a variety of natural bioactive peptides without the need for protecting‐group strategies.
Biocatalytic Strategy for the Highly Stereoselective Synthesis of Fluorinated Cyclopropanes
Authors: Villada Juan D. , Majhi Jadab , Lehuédé Valentin , Hendricks Michelle E. , Neufeld Katharina , Tona Veronica , Fasan Rudi
Published: May 2024

Fluorinated cyclopropanes are highly desired pharmacophores in drug discovery owing to the rigid nature of the cyclopropane ring and the beneficial effects of C−F bonds on the pharmacokinetic properties, cell permeability, and metabolic stability of drug molecules. Herein a biocatalytic strategy for the stereoselective synthesis of mono‐fluorinated and gem‐difluoro cyclopropanes is reported though the use of engineered myoglobin‐based catalysts. In particular, this system allows for a broad range of gem‐difluoro alkenes to be cyclopropanated in the presence of diazoacetonitrile with excellent diastereo and enantiocontrol (up to 99 : 1 d.r. and 99 % e.e.), thereby enabling a transformation not currently accessible with chemocatalytic methods. The synthetic utility of the present approach is further exemplified through the gram‐scale synthesis of a key gem‐difluorinated cyclopropane intermediate useful for the preparation of fluorinated bioactive molecules.
Acyl hydrazone‐based supramolecular polymer for ultrasensitive detection of Fe3+, Pd2+, H2PO4− and its application for Suzuki coupling reactions
Authors: Wu Shang , Fu Shuaishuai , Wang Jiajia , Sun Xin , Zhang Guangwu , Wang Ningning , He Yuan , Wang Zhe , Wang Yanbin , Su Qiong , Yang Quanlu
Published: May 2024

A novel acylhydrazide‐based gelator (BE) was successfully built without the use of traditional fluorescent groups. Surprisingly, in 1,2‐propanediol, the BE can further self‐assemble into a stable supramolecular gel (OBE) and display significant blue‐white aggregation‐induced enhanced emission (AIEE). Interestingly, based on the excellent coordination capacity of acyl hydrazone bonds, the OBE demonstrated a sensitive response to Pd2+ and Fe3+, with corresponding lowest limits of detection of 21.8 and 37.3 ppb, respectively. More interesting, H2PO4− could only be constantly recognized by the Pd‐OBE (Pd2+ coordinated with OBE). Fourier transform infrared (FT‐IR), scanning electron microscopy (SEM), X‐ray diffraction (XRD), density functional theory (DFT) and rheological measurements, the self‐assembly process of OBE, and the ion recognition sensing mechanism were extensively examined. Moreover, xerogel OBE as supporter, a novel heterogeneous catalyst Pd/OBE is prepared. The catalyst displays outstanding activity and stability for Suzuki coupling reactions in water. It can be easily reused for at least five runs with no decrease in the catalytic activity.
Methanol Steam Reforming for Hydrogen Production over Ni‐Based Catalysts: State‐Of‐The‐Art Review and Future Prospects
Authors: Hu Bin , Shu Riyang , Khairun Hafila S. , Tian Zhipeng , Wang Chao , Kumar Gupta Navneet
Published: May 2024

With increasing global emphasis on environmental sustainability, the reliance on traditional energy sources such as coal, natural gas, and oil are encountering significant challenges. H2, known for its high energy content and pollution‐free usage, emerges as a promising alternative. However, despite the great potential of H2, approximately 95 % of hydrogen production still depends on non‐renewable resources. Hence, the shift towards producing H2 from renewable sources, particularly through methods like steam reforming of methanol – a renewable resource – represents a beacon of hope for advancing sustainable energy practices. This review comprehensively examines recent advancements in efficient H2 production using Ni‐based catalysts in methanol steam reforming (MSR) and proposes the future prospects. Firstly, the fundamental principles of MSR technology and the significance in clean energy generation are elucidated. Subsequently, the design, synthesis techniques, and optimization strategies for enhancing the catalytic performance of Ni‐based catalysts are discussed. Through the analysis of various catalyst compositions, structural adjustments, surface active sites, and modification methods, the review uncovers effective approaches for boosting the activity and durability of MSR reactions. Moreover, the review investigates the causes of deactivation in Ni‐based catalysts during MSR reactions and proposes strategies for extending catalyst lifespan through fine design and optimization of operation parameters. Lastly, this review outlines the current research challenges and anticipates the future trends and potential applications of Ni‐based catalysts in MSR hydrogen production. By offering a comprehensive critical analysis, this review serves as a valuable reference to enhance MSR hydrogen production efficiency and catalyst performance.
Multi‐event‐based distributed cooperative predictive control for the multi‐agent system
Authors: Zhang Guangchen , Gao Han , He Shuping
Published: May 2024

In this paper, we provide the detailed distributed cooperative predictive control scheme for the multi‐agent system (MAS) affected by the network delays. Firstly, we restate the distributed cooperative predictive control problem by introducing iterative learning‐based MAS, which can guarantee the cooperative predictive control of the MAS. To alleviate the unfavorable network constrains, the multi‐event‐triggered conditions are formulated via considering the predictive and error data sufficiently. With these preparations, the well‐posed Roesser‐type two‐dimensional (2D) system is achieved equivalently to the distributed iterative learning predictive system. On this basis, we employ 2D predictive system analysis and control theory to realize the predictive control for the equivalent 2D system and then obtain the collaborative predictive control for the MAS under multi‐event‐triggered mechanism. The corresponding stability criteria, controller, and observer gains are provided by the executable matrix constraints and algorithms design. To conclude the paper, the numerical example is proposed to illustrate the effectiveness and practicability of the provided methods and algorithms.
High expression of SLC7A1 in high‐grade serous ovarian cancer promotes tumor progression and is involved in MAPK/ERK pathway and EMT
Authors: You Shijing , Han Xiahui , Xu Yuance , Sui Lei , Song Kejuan , Yao Qin
Published: May 2024

Our previous studies have shown that upregulation of SLC7A1 in epithelial ovarian cancer (EOC) tumor cells significantly increases cancer cell proliferation, migration, and cisplatin resistance; however, the molecular mechanism by which SLC7A1 functions in EOC remains unknown. In later studies, we found that SLC7A1 is also highly expressed in the interstitial portion of high‐grade serous ovarian cancer (HGSOC), but the significance of this high expression in the interstitial remains unclear. Here, we showed the Interstitial high expression of SLC7A1 in HGSOC by immunohistochemistry. SLC7A1 enriched in cancer‐associated fibroblasts (CAFs) was upregulated by TGF‐β1. Transwell assay, scratch assay, cck8 assay and cell adhesion assay showed that SLC7A1 highly expressed in CAFs promoted tumor cells invasion, migration and metastasis in vitro. The effect of SLC7A1 on MAPK and EMT pathway proteins in ovarian cancer (OC) was verified by RNA sequencing and western blotting. Overexpression of SLC7A1 in OC is involved in MAPK/ ERK pathway and EMT. In general, in HGSOC, CAFs overexpressing SLC7A1 supported the migration and invasion of tumor cells; SLC7A1 is highly expressed in ovarian cancer and is involved in ERK phosphorylation and EMT signaling in MAPK signaling pathway. This suggests that SLC7A1 may be a potential therapeutic target for OC metastasis.
Case study with dosimetric analysis: Total body irradiation to a patient with a left ventricular assist device
Authors: Webster Matthew , Dona Lemus Olga M. , Zheng Dandan , Wancura Joshua N. , Tanny Sean , Sakthivel Gukan , Constine Louis
Published: May 2024

Key Clinical Message

A patient presented with cardiogenic shock, requiring the implantation of a left ventricular assist device (LVAD), and acute myeloblastic leukemia. This necessitated total body irradiation (TBI) while balancing dose reduction to the LVAD components to avoid potential radiation damage. Here we outline our treatment approach and dose estimates to the LVAD.

This case report discusses the delivery of TBI to a patient with an LVAD. This treatment required radiation‐dose determinations and consequential reductions for the heart, LVAD, and an external controller connected to the LVAD. The patient was treated using a traditional 16MV anterior posterior (AP)/posterior anterior (PA) technique at a source‐to‐surface‐distance of 515 cm for 400 cGy in two fractions. A 3 cm thick Cerrobend block was placed on the beam spoiler to reduce dose to the heart and LVAD to 150 cGy. The external controller was placed in a 1 cm thick acrylic box to reduce neutron dose and positioned as far from the treatment fields as achievable. In vivo measurements were made using optically stimulated luminescence dosimeters (OSLDs) placed inside the box at distances of 2 cm, 8.5 cm, and 14 cm from the field edge, and on the patient along the central axis and centered behind the LVAD block. Further ion chamber measurements were made using a solid water phantom to more accurately estimate the dose delivered to the LVAD. Neutron dose measurements were also conducted. The total estimated dose to the controller ranged from 135.3 cGy to 91.5 cGy. The LVAD block reduced the surface dose to the patient to 271.6 cGy (68.1%). The block transmission factors of the 3 cm Cerrobend block measured in the phantom were 45% at 1 cm depth and decreased asymptotically to around 30% at 3 cm depth. Applying these transmission factors to the in vivo measurements yielded a dose of 120 cGy to the implanted device. The neutron dose the LVAD region is estimated around 0.46 cGy. Physical limitations of the controller made it impossible to completely avoid dose. Shielding is recommended. The block had limited dose reduction to the surface, due to secondary particles, but appropriately reduced the dose at 3 cm and beyond. More research on LVADs dose limits would be beneficial.
Successful management of gingival recession with creeping attachment: A case report
Authors: Assimi Sihame , Ismaili Zouheir , Dghoughi Saloua
Published: May 2024

Key Clinical Message

A successful management of a mandibular recession with creeping attachment using free gingival graft. This case highlights the “wait‐and‐see” approach in the treatment plan, emphasizing the root coverage.

This clinical report describes the case of a 23‐year‐old female patient with gingival recession of the mandibular left central incisor. The patient's symptoms included hypersensitivity and cosmetic improvements. After thorough examination, the patient was diagnosed with plaque‐induced gingivitis on a reduced periodontium with acquired mucogingival deformities. Gingival recession was classified as Miller class II or Cairo Recession Type 1. The treatment plan consisted of a nonsurgical phase, followed by a surgical phase using a free gingival graft. The surgical procedure involved harvesting the graft from the palatal mucosa and placing it in the recipient site. Post‐operative care and instructions were provided and a comprehensive follow‐up schedule was established. At the 12‐month evaluation, the patient exhibited healthy periodontal conditions with creeping attachment and complete root coverage. The success of the treatment approach demonstrates its effectiveness in addressing hypersensitivity and cosmetic concerns, while improving periodontal health. Factors influencing the achievement of creeping attachment are discussed, including recession width, graft position, bone support, tooth position, patient hygiene, graft thickness, and root surface treatment.
Enhanced Low‐Temperature Resistance of Lithium‐Metal Rechargeable Batteries Based on Electrolyte Including Ethyl Acetate and LiDFOB Additives
Authors: Wang Kang , Gao Song , Li Li , Wang Liying , Yang Xijia , Li Xuesong , Lü Wei
Published: May 2024

To meet the demand for higher energy density in lithium‐ion batteries and expand their application range, coupling lithium metal anodes with high‐voltage cathodes is an ideal solution. However, the compatibility between lithium metal batteries and electrolytes affects their applicability. In this study, proposes a locally concentrated electrolyte based on ethyl acetate (EA) as the solvent, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as the lithium salt, and lithium difluorooxoborate (LiDFOB) as a sacrificial agent to enhance the low‐temperature and high‐voltage endurance of Li//Lithium cobalt oxide (LCO) batteries. The Li//LCO battery can operate within the voltage range of 3 to 4.5 V, with an initial discharge specific capacity of 174.5 mAh g−1 at 20 °C. At −40 °C, after 200 cycles, the capacity retention rate is 87.7 %. It can operate under extreme conditions of −70 °C, with a discharge specific capacity of 112.6 mAh g−1. Additionally, LCO//HC batteries using this electrolyte demonstrate excellent performance. Present work provides a new perspective for the optimization of electrolytes for low‐temperature lithium‐ion batteries.
Rationalization of a Streptavidin Based Enantioselective Artificial Suzukiase: An Integrative Computational Approach
Authors: Tiessler‐Sala Laura , Maréchal Jean‐Didier , Lledós Agustí
Published: May 2024

An Artificial Metalloenzyme (ArM) built employing the streptavidin‐biotin technology has been used for the enantioselective synthesis of binaphthyls by means of asymmetric Suzuki‐Miyaura cross‐coupling reactions. Despite its success, it remains a challenge to understand how the length of the biotin cofactors or the introduction of mutations to streptavidin leads the preferential synthesis of one atropisomer over the other. In this study, we apply an integrated computational modeling approach, including DFT calculations, protein‐ligand dockings and molecular dynamics to rationalize the impact of mutations and length of the biotion cofactor on the enantioselectivities of the biaryl product. The results unravel that the enantiomeric differences found experimentally can be rationalized by the disposition of the first intermediate, coming from the oxidative addition step, and the entrance of the second substrate. The work also showcases the difficulties facing to control the enantioselection when engineering ArM to catalyze enantioselective Suzuki‐Miyaura couplings and how the combination of DFT calculations, molecular dockings and MD simulations can be used to rationalize artificial metalloenzymes.
Employment Survey for European Chemists (ESEC3) How Diverse is Europe's Chemical Workforce?
Authors: Salzer Reiner , Hrastelj Nineta , Smith Anthony
Published: May 2024

Understanding diversity is the foundation for progress on inclusion. Diversity covers a wide range of characteristics, not just gender. Does the training meet the current needs of the workplace? What role does gender discrimination play in the chemical workforce? To what extent are partners treated equally when caring for a family member? Three Employment Surveys for European Chemists (ESEC1 – ESEC3) were conducted between 2013 and 2020. The online questionnaires were open to chemists from all countries. 9747 responses were collected for all three surveys together. The reports for ESEC1 and ESEC2 are freely available.[1,2] The questionnaires from ESEC1 to ESEC3 were continuously adapted to reflect the latest discussions in our societies, for example diversity, which was specifically addressed in ESEC3. The results are reported here. The Royal Society of Chemistry asked similar questions.[3] Graduates from the last 15 years are particularly important for two reasons. They are the largest group of ESEC participants, with 59 % of the responses, and they represent the labour market with the greatest future prospects. Their situation is of particular importance for real decisions about the chemistry labour market. For this reason, the current report focuses exclusively on graduates of the last 15 years.
European Employment Survey for Chemists (ESEC3) Careers of Chemistry Graduates in Europe
Authors: Salzer Reiner , Hrastelj Nineta , Smith Anthony
Published: May 2024

What are the country‐specific differences in the education of chemistry students across the EU? How do students’ preferred careers change with the level of their qualifications? Do students have sufficient information to make good career choices? Which media are now considered most effective for job searches? What do students currently consider to be a successful career?

Three Employment Surveys for European Chemists (ESEC1−ESEC3) were conducted between 2013 and 2020. The web‐based questionnaires were open to chemists from all countries. A total of 9747 responses were received. The reports for ESEC1 and ESEC2 are freely available.[1,2] Subsequent questionnaires have been continuously adapted to reflect the latest discussions in our societies. In particular, ESEC3 focused on students’ careers. The results are reported here. Where results from earlier surveys are included, this is explicitly stated.

Graduates of the last 15 years are particularly important for two reasons. They represent the largest group of ESEC participants, with 59 % of the responses, and they represent the labour market with the greatest future prospects. Their situation is of particular importance for real decisions about the chemistry labour market. For this reason, this report focuses exclusively on graduates of the last 15 years.
Photo‐triggered Phase Transition of Crystals and Photoactuation
Authors: Hagiwara Yuki , Takanabe Akifumi , Asahi Toru , Koshima Hideko
Published: May 2024

Photo‐triggered phase transition is a new type of phase transition in which a photochromic crystal with a thermal phase transition transforms into an identical high‐temperature phase in a temperature region lower than the thermal phase transition temperature upon light irradiation. Here, we report a second crystal that exhibits a photo‐triggered phase transition, thereby demonstrating that the photo‐triggered phase transition is a general phenomenon that occurs in crystals. When the chiral salicylidenephenylethylamine crystal was irradiated with ultraviolet (UV) light, the photo‐triggered phase transition occurred in the temperature range −30 to −10 °C. The photo‐triggered phase transition is induced by local stress due to trans‐keto molecules produced by photoisomerization near the irradiated surface. Crystal cantilevers exhibited stepwise bending by the combination of the photo‐triggered phase transition and photoisomerization. Alternate irradiation with UV and visible light achieved locomotion of single crystals driven by repeated stepwise bending. Finally, a detailed comparison of photo‐triggered and non‐photo‐triggered phase transition crystals revealed that a sufficient molecular conformation change in affordable crystal voids, smooth photoisomerization, and most likely a chiral molecular arrangement are required for inducing the photo‐triggered phase transition.
Unusually Short H⋅⋅⋅H Contacts in Intramolecularly Cyclized Helically Fused Anthracenes
Authors: Fukuda Hiroki , Tsurumaki Eiji , Wakamatsu Kan , Toyota Shinji
Published: May 2024

The intramolecular coupling of dichloro‐substituted helically fused anthracenes using the Yamamoto coupling yielded cyclized products with sterically congested molecular structures. The X‐ray analysis and DFT calculations showed that the aromatic framework adopted a nonplanar structure with a twisted conformation about the newly formed single bond, which acts as a chiral axis. Interestingly, the X‐ray structure obtained through the Hirshfeld atom refinement revealed short interatomic distances between the inner hydrogen atoms (1.648–1.692 Å), much shorter than the sum of their van der Waals radii. Owing to these unusually short contacts, the 1H NMR spectrum exhibited a significant deshielding (12.5 ppm) and a large nuclear Overhauser effect (44 %). Additionally, the IR spectrum displayed a high‐frequency shift of the C−H stretching vibration. These observations, along with the noncovalent interaction plot indicative of a characteristic steric environment, strongly support the presence of steric hindrance. Moreover, dynamic NMR measurement of the mesityl‐substituted derivative yielded a barrier to helical inversion of 84 kJ mol−1. The optical properties and crystal packing of the cyclized products are also reported.
Backbone Modification in a Protein Hydrophobic Core
Authors: Lin Yuhan , Horne W. Seth
Published: May 2024

Targeted protein backbone modification can recreate tertiary structures reminiscent of folds found in nature on artificial scaffolds with improved biostability. Incorporation of altered monomers in such entities is typically limited to sites distant from the hydrophobic core to avoid potential disruptions to folding. This is limiting, as it is advantageous in some applications to incorporate artificial connectivity at buried sites. Here, we report an examination of protein backbone modification targeted specifically to hydrophobic core positions and its impacts on tertiary folded structure and fold stability. Different artificial monomer types are placed at core, core‐flanking, or solvent‐exposed positions in a compact three‐helix protein. Effects on structure and folding energetics are assessed by NMR spectroscopy and biophysical methods. Results show that artificial residues can be well accommodated in the hydrophobic core of a defined tertiary fold, with effects on stability only modestly larger than identical changes at solvent‐exposed sites. Collectively, these results provide new insights into folding behavior of protein‐like artificial chains as well as strategies for the design of such molecules.
Prodrug Approach to Exploit (S)‐Alanine Amide as Arginine Mimic Moiety in the Development of Protein Arginine Methyltransferase 4 Inhibitors
Authors: Milite Ciro , Sarno Giuliana , Pacilio Ida , Cianciulli Agostino , Viviano Monica , Iannelli Giulia , Gazzillo Erica , Feoli Alessandra , Cipriano Alessandra , Giovanna Chini Maria , Castellano Sabrina , Bifulco Giuseppe , Sbardella Gianluca
Published: May 2024

Protein arginine methyltransferase (PRMT) 4 (also known as coactivator‐associated arginine methyltransferase 1; CARM1) is involved in a variety of biological processes and is considered as an emerging target class in oncology and other diseases. A successful strategy to identify PRMT substrate‐competitive inhibitors has been to exploit chemical scaffolds able to mimic the arginine substrate. (S)‐Alanine amide moiety is a valuable arginine mimic for the development of potent and selective PRMT4 inhibitors; however, its high hydrophilicity led to derivatives with poor cellular outcomes. Here, we describe the development of PRMT4 inhibitors featuring a central pyrrole core and an alanine amide moiety. Rounds of optimization, aimed to increase lipophilicity and simultaneously preserve the inhibitory activity, produced derivatives that, despite good potency and physicochemical properties, did not achieve on‐target effects in cells. On the other hand, masking the amino group with a NAD(P)H:quinone oxidoreductase 1 (NQO1)‐responsive trigger group, led to prodrugs able to reduce arginine dimethylation of the PRMT4 substrates BRG1‐associated factor 155 (BAF155). These results indicate that prodrug strategies can be successfully applied to alanine‐amide containing PRMT4 inhibitors and provide an option to enable such compounds to achieve sufficiently high exposures in vivo.
Evaluation of the Clinical Drug‐Drug Interaction Potential of Pritelivir on Transporters and CYP450 Enzymes Using a Cocktail Approach
Authors: de Vries Michiel , Bonsmann Susanne , Pausch Jörg , Sumner Melanie , Birkmann Alexander , Zimmermann Holger , Kropeit Dirk
Published: May 2024

Pritelivir is a novel viral helicase‐primase inhibitor active against herpes simplex virus. In vitro drug‐drug interaction studies indicated that pritelivir has the potential for clinically relevant interactions on the cytochrome P450 (CYP) enzymes 2C8, 2C9, 3A4, and 2B6, and intestinal uptake transporter organic anion transporting polypeptide (OATP) 2B1 and efflux transporter breast cancer resistance protein (BCRP). This was evaluated in 2 clinical trials. In 1 trial the substrates flurbiprofen (CYP2C9), bupropion (CYP2B6), and midazolam (CYP3A4) were administered simultaneously as part of the Geneva cocktail, while the substrate celiprolol (OAPT2B1) was administered separately. In another trial, the substrates repaglinide (CYP2C8) and rosuvastatin (BCRP) were administered separately. Exposure parameters of the substrates and their metabolites (flurbiprofen and bupropion only) were compared after administration with or without pritelivir under therapeutic concentrations. The results of these trials indicated that pritelivir has no clinically relevant effect on the exposure of substrates for the intestinal uptake transporter OATP2B1 and the CYP enzymes 3A4, 2B6, 2C9, and 2C8, and has a weak inhibitory effect on the intestinal efflux transporter BCRP. In summary, the results suggest that pritelivir has a low drug‐drug interaction potential.
Self‐Assembly of the Porphyrin Monomer on the Surface of Fe/Graphene Material: A Novel Sensing Material for the Detection of Chloramphenicol Antibiotic in Aqueous solution
Authors: Nguyen Quynh Xuan Thi , Manh Khong Hung , Duc La Duong , Dang Trung‐Dung
Published: May 2024

Currently, electrochemical sensors are being developed and widely used in various fields, and new materials are being explored to enhance the precision and selectivity of the sensors. The present investigation involved the fabrication of a Fe/graphene/porphyrin nanocomposite through self‐assembly, wherein the individual porphyrin molecules were arranged on the Fe/graphene nanomaterials′ surface. The Fe/graphene nanoparticles were synthesized utilizing a green approach, wherein leaf extract was employed as the reducing agent. The resulting materials underwent comprehensive characterization using a range of contemporary techniques, including scanning electron microscopy (SEM), X‐ray diffraction (XRD), Fourier‐transform infrared spectroscopy (FTIR), and Raman spectroscopy. The study‘s findings revealed that the nanocomposites of Fe/graphene/porphyrin comprised zero‐valent iron nanoparticles, exhibiting an average particle size ranging from 15 to 60 nm. These nanoparticles were seen to be evenly dispersed across the graphene sheets. The presence of nanostructure porphyrin nanofibers, measuring 20 nm in diameter, was also shown to exhibit strong integration with the surface of the Fe/graphene nanomaterials. The electrochemical properties of the Fe/graphene/porphyrin nanocomposite were also investigated, demonstrating that the prepared material could be effectively employed as a sensing electrode in the electrochemical sensor for detecting Chloramphenicol (CAP) through CV, EIS, and DPV techniques using a three‐electrode electrochemical system. Under optimal conditions, Fe/graphene/porphyrin exhibited a high current response when detecting CAPs. Electrochemical sensors created using Fe/graphene/porphyrin nanocomposite have high stability and repeatability, and they hold promise in developing sensors capable of identifying other antibiotic residues in agriculture.
Sequence of Monomers and Position of Stereocenters Matter for Thermal Properties of Stereocontrolled Oligourethanes
Authors: Forysiak Weronika , Lizak Agnieszka , Szweda Róża
Published: May 2024

Polyurethanes are commodity materials used for multiple applications. In recent years, a new category of polyurethane material has emerged, characterized by the lack of polymer molar mass dispersity, control of the monomer arrangement in the chain, and even full stereocontrol. Various multistep synthesis strategies have been developed to fabricate sequence‐defined polyurethanes. However, synthesizing stereocontrolled polyurethanes with a controlled sequence is still a challenge. Polyurethanes with structural precision, as represented by biopolymers, i. e. proteins or nucleic acids, have opened new application directions for these groups of materials. It has been shown that polyurethanes can be used as biomimetics, information carriers, molecular tags, and materials with strictly controlled properties. Precise synthesis of macromolecules allows us to fine‐tune the properties of polymers to specific needs. Therefore, it is essential to collect information on the sequence‐structure relationship of polymers. In our work, we present synthetic pathways to make sequence and stereo‐defined oligourethanes. We demonstrate that structural details, i. e., the monomer sequences and position of the stereocenter, have a tremendous effect on the thermal properties of model oligourethanes. We show that the introduction of chirality by constitutional isomerization can be used to program the thermal characteristics of polymers, which are key features for material applications.
Optimizing Clinical Translation of Bispecific T‐cell Engagers through Context Unification with a Quantitative Systems Pharmacology Model
Authors: Liao Xiaozhi , Qi Timothy , Zhou Jiawei , Liu Can , Cao Yanguang
Published: May 2024

Bispecific T‐cell engagers (bsTCEs) have emerged as a promising class of cancer immunotherapy. BsTCEs enable physical connections between T cells and tumor cells to enhance T‐cell activity against cancer. Despite several marketing approvals, the development of bsTCEs remains challenging, especially at early clinical translational stages. The intricate design of bsTCEs makes their pharmacologic effects and safety profiles highly dependent on patient's immunological and tumor conditions. Such context‐dependent pharmacology introduces considerable uncertainty into translational efforts. In this study, we developed a Quantitative Systems Pharmacology (QSP) model, through context unification, that can facilitate the translation of bsTCEs preclinical data into clinical activity. Through characterizing the formation dynamics of immunological synapse (IS) induced by bsTCEs, this model unifies a broad range of contexts related to target affinity, tumor characteristics, and immunological conditions. After rigorous calibration using both experimental and clinical data, the model enables consistent translation of drug potency observed under diverse experimental conditions into predictable exposure–response relationships in patients. Moreover, the model can help identify optimal target‐binding affinities and minimum efficacious concentrations across different clinical contexts. This QSP approach holds significant promise for the future development of bsTCEs.
Recombinant Human Proteoglycan Aggrecan‐G1 Domain‐induced Arthritis (GIA) Mouse Model
Authors: Olasz Katalin , Boldizsar Ferenc
Published: May 2024

The recombinant human proteoglycan aggrecan‐G1 domain (rhG1)‐induced arthritis (GIA) mouse model is a complex model of rheumatoid arthritis (RA). In GIA, autoimmune arthritis is induced by repeated intraperitoneal immunization of genetically susceptible BALB/c mice with the rhG1 antigen emulsified in the adjuvant dimethyldioctadecylammonium (DDA). This article describes the steps for producing and purifying the rhG1 antigen, the immunization protocol, methods for following the clinical picture of arthritis, and the evaluation of relevant laboratory parameters. In this model, the autoimmune arthritis develops stepwise, similar to RA: First is the preclinical stage (after the first immunization, days 0‐20) with no sign of inflammation but detectable T and B cell activation; next, the stage of early arthritis (after the second immunization, days 21‐41), where the first definitive signs of arthritis appear together with autoantibody production; and then the severe late‐stage arthritis (after the third immunization, after day 42), which presents with massive inflammation of the limbs, leading to cartilage and bone destruction and finally ankylosis. The protocols described here provide sufficient information for investigators to use the GIA model to study different aspects of autoimmune arthritis. © 2024 The Authors. Current Protocols published by Wiley Periodicals LLC.

Basic Protocol: Induction of recombinant human proteoglycan aggrecan‐G1 domain (rhG1)‐induced arthritis (GIA)

Support Protocol 1: Production of rhG1‐Xa‐mFc2a fusion protein with CHOK1 mammalian expression system

Support Protocol 2: Purification of the rhG1‐Xa‐mFc2a fusion protein by affinity chromatography

Support Protocol 3: Preparation of DDA adjuvant

Support Protocol 4: Clinical assessment of arthritis

Support Protocol 5: Measurement of serum antibody levels and cytokines

Support Protocol 6: Measurement of rhG1‐induced proliferation and cytokine production in spleen cell culture

Support Protocol 7: Histological assessment of arthritic limbs

Support Protocol 8: Evaluation of arthritis with micro‐computed tomography
Improved Compatibility of α‐NaMnO2 Cathodes at the Interface with Ionic Liquid Electrolytes
Authors: Maresca Giovanna , Ottaviani Michela , Ryan Kevin M. , Brutti Sergio , Appetecchi Giovanni B.
Published: May 2024

The behaviour and compatibility of monoclinic sodium manganite, α‐NaMnO2, cathodes at the interface with electrolytes based on the 1‐ethyl‐3‐methylimidazolium bis(fluorosulfonyl)imide (EMIFSI) and N‐trimethyl‐N‐butylammonium bis(fluorosulfonyl)imide (N1114FSI) ionic liquids is presented and discussed. The Na+ insertion process was analysed through cyclic voltammetry tests combined with impedance spectroscopy measurements and the cell performance was tested by charge‐discharge cycles. XPS and FIB‐SEM measurements allowed analysis of the surface composition and the morphology of post‐mortem cathodes. Overall, the α‐NaMnO2 cathode showed high reversibility in N1114FSI‐based electrolyte, delivering 60 % of the initial capacity after 1200 cycles in conjunction with a Coulombic efficiency above 99 %. To our knowledge, these very promising results are the best result obtained till now for monolithic α‐NaMnO2 cathodes, are ascribable to the formation of a stable passive layer onto the electrode surface, as confirmed by spectroscopic analysis.