bluuebunny/crossref_metadata_2025_split huggingface dataset:
Dihydrogen and Ethylene Activation by a Sterically Distorted Distibene
Authors: Pang Yue , Leutzsch Markus , Nöthling Nils , Cornella Josep 
Published: June 2023

AbstractHerein, we report the synthesis of a sterically distorted distibene ([4]2) and its transition‐metal‐like reactivity towards two fundamental feedstock chemicals: H2 and ethylene. Although [4]2 exhibits an unusually long Sb=Sb distance and noticeable backbone distortion in the solid state, NMR data suggest that [4]2 remains predominantly as a dimer in solution, even at high temperatures. However, it was proposed that the elusive reactivity of [4]2 toward H2 and ethylene results from reversible dissociation of [4]2 into the transient stibinidene ([4]), which could be observed by NMR spectroscopic techniques.
Size exclusion chromatography characterization of poly (ether ether ketone), PEEK, after chemical modification
Authors: Aboelanin Hamza Mahmoud , Arndt Jan‐Hendrik , Macko Tibor , Podzimek Stepan , Brüll Robert 
Published: June 2023

AbstractCharacterization of the molar mass distribution (MMD) of poly (ether ether ketone) (PEEK) is very troublesome due to the insolubility of PEEK in common solvents. The solubility of PEEK may be substantially improved after its sulfonation. Sulfonated PEEK (SPEEK) was prepared by sulfonation of PEEK with 98% concentrated H2SO4 at room temperature. The presence of sulfonic acid group (‐SO3H) in PEEK matrix was confirmed by nuclear magnetic resonance and Fourier transform infrared spectroscopy. The degree of sulfonation (DS ~ 95%) was determined by proton nuclear magnetic resonance in deuterated dimethyl sulfoxide and by thermal analysis methods. The equivalent molar mass and MMD of sulfonated PEEK was determined at 30°C in three polar solvents (N,N‐dimethylacetamide, N,N‐dimethylformamide N‐methyl‐2‐pyrollidone) in PS/DVB column using calibration with PMMA standards. A salt (LiBr) was added to the solvents for suppression of undesired interactions of analytes with the column packing. Moreover, the sulphonated PEEK was separated with size exclusion chromatography (SEC) coupled to a multi‐angle light scattering (MALS) detector. It was found that the absolute average molar mass of SPEEK from the MALS detection is much closer to the value measured by SEC in N,N‐dimethylacetamide +LiBr than the values determined in N,N‐dimethylformamide and N‐methyl‐2‐pyrollidone.
High‐performance flexible piezoelectric nanogenerator with folded structure based on CNTs‐modified BCβZT/P(VDF‐HFP) composite film
Authors: Wang Wei , Cheng Bingnan , Feng Wuwei , He Bin , Liu Shuo 
Published: June 2023

AbstractWith the energy shortage and the increasing awareness of environmental protection, piezoelectric nanogenerator (PENG) has been widely studied in recent years. Polyvinylidene fluoride hexafluoropropylene (P(VDF‐HFP)) is an ideal matrix material because of its piezoelectricity, flexibility, and toughness. Herein, a composite film of carbon nanotubes (CNTs), Ba0.85Ca0.15Zr0.10Ti0.90O3 (BCZT), and P(VDF‐HFP) (CNTs/BCZT/P(VDF‐HFP)) were prepared via the tape casting method. Adding BCZT increased the polar β‐phase in P(VDF‐HFP), reaching a maximum when 40 wt% BCZT was incorporated. Adding CNTs to the matrix provides a conductive path inside the composite. The CNTs/BCZT/P(VDF‐HFP) composite film demonstrated optimal electrical properties when 0.3 wt% CNTs is doped, with the open circuit voltage increased from 22 to 30 V and the short circuit current increased from 3 to 5.9 μA compared with the undoped sample. The output performance of the PENG was further improved with a three‐layer folded structure, achieving an open circuit voltage of 40 V and a maximum power density of 31.5 mW m−2, which easily lit six light‐emitting diodes.
Twenty years of monitoring reveal overfishing of bony fish stocks in the coastal national park Banc d’Arguin, in Mauritania
Authors: Lemrabott Sidi Yahya Cheikhna , El‐Hacen El‐Hacen Mohamed , Piersma Theunis , Sall Amadou Abdarahmane , Sidina Ebaye , Mahmoud Lemhaba Yarba Ahmed , Olff Han , van Leeuwen Anieke 
Published: June 2023

Abstract

Along Africa’s western coast, many local communities rely on the ocean for their livelihood. Over the last decades, introductions of new fishing techniques along with globalizing trade have strongly changed local fishing practices.
The Parc National du Banc d’Arguin (PNBA) in Mauritania had for centuries been subjected to an artisanal, low‐impact, fishery. This fishing was exclusively oriented towards migratory bony fish species, mullet (Mugil cephalus) and meagre (Argyrosomus regius). Since the 1980s, these species have been replaced by illegal catches of internationally traded elasmobranchs (sharks and rays) and by non‐migratory and relict species (resident) such as tilapias (Sarotherodon melanotheron) and catfishes (Arius sp.).
To date, most monitoring and management efforts have been dedicated to evaluating changes in elasmobranch populations and less focus has been on bony fish species. Data from a fishery monitoring programme are used to analyse the trends in effort, catch and catch per unit of effort of bony fish species by fitting non‐parametric generalized additive models to capture changes in the fish community over the last 20 years.
Mullet and meagre became overfished early on, and the contribution of resident species (tilapias and catfishes) increased in the catches. Together with a pattern of increased effort on the traditionally targeted species, such a change in the catch could reflect a change in the fish community.
These results call for the implementation of sustainable fishing practices within PNBA. We propose the need to implement closures of fisheries during the species’ breeding periods as well as the use of biological reference points such as the size at first capture and maximum sustainable yield targets for resident species.
Biosynthesis of diisooctyl 2,5‐furandicarboxylate by Candida antarctica lipase B (CALB) immobilized on a macroporous epoxy resin
Authors: Mang Rongchen , Zhou Yuyang , Du Xuefei , Zhou Hua , Zhu Mingxin 
Published: June 2023

AbstractDiisooctyl 2,5‐furandicarboxylate (DEF), an ester derivative of 2,5‐furandicarboxylic acid (FDCA, a bio‐based platform chemical), resembles the physical and chemical properties of phthalates. Due to its excellent biodegradability, DEF is considered a safer alternative to the hazardous phthalate plasticizers. Although FDCA esters are currently mainly produced by chemical synthesis, the enzymatic synthesis of DEF is a green, promising alternative. The current study investigated the biosynthesis of DEF by Candida antarctica lipase B (CALB) immobilized on macroporous resins. Out of five macroporous resins (NKA‐9, LX‐1000EP, LX‐1000HA, XAD‐7HP, and XAD‐8) evaluated, the LX‐1000EP epoxy resin was identified as the best carrier for CALB, and the XAD‐7HP weakly polar resin was identified as the second best. The optimal immobilization conditions were as follows: CALB (500 μL) and LX‐1000EP (0.1 g) were incubated in phosphate butter (20 mM, pH 6.0) for 10 h at 35°C. The resulting immobilized CALB (EP‐CALB) showed an activity of 639 U/g in the hydrolysis of p‐nitrophenyl acetate, with an immobilization efficiency of 87.8% and an activity recovery rate of 56.4%. Using 0.02 g EP‐CALB as the catalyst in 10 mL toluene, and the molar ratio of 2,5‐dimethyl furanediformate (1 mmol/mL) and isooctyl alcohol (4 mmol/mL) that was 1:4, a DEF conversion rate of 91.3% was achieved after a 24‐h incubation at 50°C. EP‐CALB had similar thermal stability and organic solvent tolerance compared to Novozym 435, and both were superior to CALB immobilized on the XAD‐7HP resin. EP‐CALB also exhibited excellent operational stability, with a conversion rate of 52.6% after 10 repeated uses. EP‐CALB could be a promising alternative to Novozym 435 in the biomanufacturing of green and safe plasticizers such as DEF.
Quantitative dopamine transporter imaging assessment in Parkinson's disease patients carrying GBA gene mutations compared with idiopathic PD patients: A case‐control study
Authors: Grisanti Sara , Fraternali Alessandro , Cavallieri Francesco , Fioravanti Valentina , Casali Massimiliano , Toschi Giulia , Ferri Laura , Sabadini Rossella , Zedde Marialuisa , Salomone Gaetano , Napoli Manuela , Pascarella Rosario , Ferrari Valeria , Scarano Maria , Biagini Giuseppe , Scaglioni Augusto , Moro Elena , Versari Annibale , Valzania Franco 
Published: June 2023

AbstractBackgroundGenetic risk factors impact around 15% of Parkinson's disease (PD) patients and at least 23 variants have been identified including Glucocerebrosidase (GBA) gene variants. Using different clinical and instrumental qualitative‐based data, various studies have been published on GBA‐PD cohorts which suggested possible differences in dopaminergic nigrostriatal denervation pattern, particularly in caudate and putamen nuclei.MethodsThis retrospective study included two consecutive homogenous cohorts of GBA‐PD and idiopathic (I‐PD) patients. Each consecutive GBA‐PD patient has been matched with a 1:1 pairing method with a consecutive I‐PD subject according to age, age at disease onset, sex, Hoehn & Yahr (H&Y) staging scale and comorbidity level (CCI). Semiquantitative volumetric data by the DaTQUANTTM software integrated in the DaTSCAN exam performed at time of the diagnosis (SPECT imaging performed according to current guidelines of I‐123 FPCIT SPECT imaging) were extrapolated. Bilateral specific binding ratios (SBR) at putamen and caudate levels were calculated, using the occipital lobes uptake. The Mann–Whitney test was performed to compare the two cohorts while the Spearman's test was used to find correlations between motor and volumetric data in each group. Bonferroni correction was used to account for multiple comparisons.ResultsTwo cohorts of 25 patients each (GBA‐PD and I‐PD), were included. By comparing GBA‐PD and I‐PD patients, lower SBR values were found in the most affected anterior putamen and left caudate of the GBA‐PD cohort. Furthermore, in the GBA‐PD cohort the SBR of the most affected posterior putamen negatively correlated with the H&Y scale. However, none of these differences or correlations remained significant after Bonferroni correction for multiple comparisons.ConclusionsWe observed differences in SBR values in GBA‐PD patients compared with I‐PD. However, these differences were no longer significant after Bonferroni multiple comparisons correction highlighting the need for larger, longitudinal studies.
Development of cancer surveillance guidelines in ataxia telangiectasia: A Delphi‐based consensus survey of international experts
Authors: Neves Renata , De Dios Perez Blanca , Panek Rafal , Jagani Sumit , Wilne Sophie , Bhatt Jayesh M. , Caputi Caterina , Cirillo Emilia , Coman David J. , Dückers Gregor , Gilbert Donald L. , Kay Koenig Mary , Mansour Lobna , McDermott Elizabeth , Pauni Micaela , Pignata Claudio , Perlman Susan L. , Porras Oscar , Betina Porto Mariela , Schon Katherine , Soler‐Palacin Pere , Nick Russo Sam , Takagi Masatoshi , Tischkowitz Marc , Wainwright Claire , Dandapani Madhumita , Glazebrook Cristine , Suri Mohnish , Whitehouse William P. , Dineen Robert A. 
Published: June 2023

AbstractBackground/ObjectivesAtaxia telangiectasia (A‐T) is a multiorgan disorder with increased vulnerability to cancer. Despite this increased cancer risk, there are no widely accepted guidelines for cancer surveillance in people affected by A‐T. We aimed to understand the current international practice regarding cancer surveillance in A‐T and agreed‐upon approaches to develop cancer surveillance in A‐T.Design/MethodsWe used a consensus development method, the e‐Delphi technique, comprising three rounds. Round 1 consisted of a Delphi questionnaire and a survey that collected the details of respondents' professional background, experience, and current practice of cancer surveillance in A‐T. Rounds 2 and 3 were designed based on previous rounds and modified according to the comments made by the panellists. The pre‐specified consensus threshold was ≥75% agreement.ResultsThirty‐five expert panellists from 13 countries completed the study. The survey indicated that the current practice of cancer surveillance varies widely between experts and centres'. Consensus was reached that evidence‐based guidelines are needed for cancer surveillance in people with A‐T, with separate recommendations for adults and children. Statements relating to the tests that should be included, the age for starting and stopping cancer surveillance and the optimal surveillance interval were also agreed upon, although in some areas, the consensus was that further research is needed.ConclusionThe international expert consensus statement confirms the need for evidence‐based cancer surveillance guidelines in A‐T, highlights key features that the guidelines should include, and identifies areas of uncertainty in the expert community. This elucidates current knowledge gaps and will inform the design of future clinical trials.
Development and validation of a nomogram for predicting the overall survival of patients with testicular cancer
Authors: Yu Haohui , Feng Bin , Zhang Yunrui , Lyu Jun 
Published: June 2023

AbstractBackgroundThe purpose of this study was to develop and validate a nomogram to predict survival in testicular cancer patients.MethodsTesticular cancer patients diagnosed between 2004 and 2015 from the Surveillance, Epidemiology, and End Results (SEER) database were selected for this study. A random sampling method was used to divide patients into training and validation cohorts, which accounted for 30% and 70% of the total sample, respectively. The nomogram was developed using the training cohort and evaluated using the C index, calibration chart, and area under the receiver operating characteristic curve (AUC).ResultsSeven risk factors that affect the survival of testicular cancer patients (AJCC stage, marital status, age at diagnosis, race, SEER historic stage A, surgery status, and origin) were identified using Cox proportional hazard regression analysis. The nomogram has a higher C index (0.897) and AUC when compared with the AJCC staging system. The results of the calibration chart of the nomogram show that the predicted survival of testicular cancer patients at 3, 5, and 10 years after diagnosis is very close to their actual survival.ConclusionsWe developed and validated a nomogram for predicting the survival rate of testicular cancer patients at 3, 5, and 10 years after diagnosis. This nomogram has better discrimination, calibration, and clinical validity than the AJCC staging system. This indicates that the nomogram can be used to predict the survival of testicular cancer patients effectively, and provide a reference for patient treatment strategies.
CH3CN@open‐C60: An Effective Inner‐Space Modification and Isotope Effect Inside a Nano‐Sized Flask
Authors: Huang Guanglin , Ide Yuki , Hashikawa Yoshifumi , Hirose Takashi , Murata Yasujiro 
Published: June 2023

AbstractDespite several small molecules being encapsulated inside cage‐opened fullerene derivatives, such species have not considerably affected the structures and properties of the outer carbon cages. Herein, we achieved an effective inner‐space modification for an open‐cage C60 derivative by insertion of a neutral CH3CN molecule into the cavity. The CH3CN@open‐C60 thus obtained showed an enhanced polarity, thus affording an easy separation from a mixture containing the empty cage by column chromatography on silica gel, without the preparative HPLC that was needed for previous cases. The less negative reduction potentials with respect to those of empty cage reflect the decreased energy level of the LUMO, which is supported by the DFT calculations. NMR spectroscopy, single‐crystal X‐ray analysis, and theoretical calculations revealed that both the presence of the encapsulated CH3CN and cage deformation caused by the CH3CN play an essential role in the change of the electronic properties. Furthermore, the favored binding affinity of deuterated acetonitrile CD3CN with internal C60 surface is discussed.
Light‐Cleavable Auxiliary for Diselenide–Selenoester Ligations of Peptides and Proteins
Authors: Schrems Maximilian , Kravchuk Alexander V. , Niederacher Gerhard , Exler Florian , Bello Claudia , Becker Christian F. W. 
Published: June 2023

AbstractDiselenide–selenoester ligations are increasingly used for the synthesis of proteins. Excellent ligation rates, even at low concentrations, in combination with mild and selective deselenization conditions can overcome some of the most severe challenges in chemical protein synthesis. Herein, the versatile multicomponent synthesis and application of a new ligation auxiliary that combines a photocleavable scaffold with the advantages of selenium‐based ligation strategies are presented. Its use was investigated with respect to different ligation junctions and describe a novel para‐methoxybenzyl deprotection reaction for the selenol moiety. The glycine‐based auxiliary enabled successful synthesis of the challenging target protein G‐CSF.
Inept N2 Activation of Tri‐Nuclear Nickel Complex with Labile Sulfur Ligands Facilitates Selective N2H4 Formation in Electrocatalytic Conversion of N2**
Authors: Kumar Ray Anuj , Paul Ankan 
Published: June 2023

AbstractConversion of N2 to the energy vector N2H4 under benign conditions is highly desirable. However, such N2 fixation processes are extremely rare. It has been recently reported that N2 to N2H4 conversion can be achieved electrochemically by using a trinuclear [Ni3(S2C3H6)4]2− complex (named as [Ni3S8]2−). There are hardly any precedents of Nitrogen Reduction Reaction (NRR) by molecular catalysts having Ni and the highly unusual selectivity for N2H4 over NH3 makes this electrochemical reduction unique. A systematic theoretical study employing calibrated Density Functional Theory to unearth the mechanisms of NRR (4e−/4H+) and Hydrogen Evolution Reaction (2e−/2H+) was conducted for the aforementioned trinuclear Ni complex. Our findings unravel a curious case of ligand lability working in tandem with metal centers in facilitating this unprecedented electrocatalytic activity. Furthermore, it is shown that the poor N−N bond activation property of Ni is responsible for this unusual selectivity. Additionally, the Hydrogen Evolution Reaction (HER) mechanistic pathways have also been delineated in this report. The mechanistic intricacies thus unearthed in this study may assist in developing more efficient electrocatalysts for N2H4 production through NRR.
Mechanism of Acyl Group Migration in Carbohydrates
Authors: Lassfolk Robert , Leino Reko 
Published: June 2023

AbstractAcyl group migration has been the subject of several studies. Such migration processes may cause problems during synthesis, isolation, and purification of different acyl‐bearing compounds, and have biological relevance, for example, in the metabolism of pharmaceuticals. Considering the recent evidence of acyl group migration being possible even over glycosidic bonds, it could be hypothesized to be involved also in the regulation of biological activity of natural polysaccharides in the host cells. Migrations are mostly observed in carbohydrates, typically having several hydroxyl groups near each other. Several studies have investigated the migration in a single or only a few different carbohydrate molecules, providing different suggestions for the mechanisms of migration, seldom supported by comprehensive computational investigations. In this concept article we discuss the recent progress on the mechanistic aspects of acyl group migration, with carbohydrates in particular focus.
N‐Heterocyclic Carbene Boranes: Dual Reagents for the Synthesis of Gold Nanoparticles
Authors: Hippolyte Laura , Sadek Omar , Ba Sowid Salem , Porcheron Alexandre , Bridonneau Nathalie , Blanchard Sébastien , Desage‐El Murr Marine , Gatineau David , Gimbert Yves , Mercier Dimitri , Marcus Philippe , Chauvier Clément , Chanéac Corinne , Ribot François , Fensterbank Louis 
Published: June 2023

AbstractN‐Heterocyclic carbenes (NHCs) have drawn considerable interest in the field of nanomaterials chemistry as highly stabilizing ligands enabling the formation of strong and covalent carbon–metal bonds. Applied to gold nanoparticles synthesis, the most common strategy consists of the reduction of a preformed NHC‐AuI complex with a large excess of a reducing agent that makes the particle size difficult to control. In this paper, we report the straightforward synthesis of NHC‐coated gold nanoparticles (NHC‐AuNPs) by treating a commercially available gold(I) precursor with an easy‐to‐synthesize NHC‐BH3 reagent. The latter acts as both the reducing agent and the source of surface ligands operating under mild conditions. Mechanistic studies including NMR spectroscopy and mass spectrometry demonstrate that the reduction of gold(I) generates NHC‐BH2Cl as a by‐product. This strategy gives efficient control over the nucleation and growth of gold particles by varying the NHC‐borane/gold(I) ratio, allowing unparalleled particle size variation over the range of 4.9±0.9 to 10.0±2.7 nm. Our strategy also allows an unprecedented precise and controlled seeded growth of gold nanoparticles. In addition, the as‐prepared NHC‐AuNPs exhibit narrow size distributions without the need for extensive purification or size‐selectivity techniques, and are stable over months.
Meroterpenoids Possessing Diverse Rearranged Skeletons with Anti‐inflammatory Activity from the Mangrove‐Derived Fungus Penicillium sp. HLLG‐122
Authors: Qin Yu‐Yue , Li Wan‐Shan , Zhang Xuan , Yu Zhang‐Xin , Li Xiao‐Bao , Chen Han‐Yi , Lv Yan‐Ru , Han Chang‐Ri , Chen Guang‐Ying 
Published: June 2023

Comprehensive SummaryFifteen new meroterpenoids, littoreanoids A—O (1—15), including three rearranged skeleton meroterpenoids (1—3), were isolated from the mangrove‐derived fungus Penicillium sp. HLLG‐122. Compound 1 was a novel berkeleyacetal‐derived meroterpenoid featuring an unusual spirocyclic 2‐oxaspiro[5.5]undeca‐4,7‐dien‐3‐one moiety. Compound 2 possessed an unusual 6/6/6/6/6 pentacyclic system with a novel 1‐hydroxy‐7,7‐dimethyl‐2‐oxabicyclo[2.2.2]octan‐5‐yl acetate moiety. Compound 3 was an unusual 6/7/6/5/6/5/4 polycyclic systems containing a β‐lactone ring. The structures and absolute configurations of new compounds were elucidated by HRESIMS, NMR spectroscopy, single crystal X‐ray diffraction analysis, and electronic circular dichroism calculations. The plausible biosynthetic pathways of 1—3 were also proposed. Compounds 6 and 11 exhibited anti‐inflammatory effects with IC50 values of 30.41 and 19.02 μmol/L, respectively. The bioactive compound 11 was selected for the investigation of preliminary mechanism using molecular docking and Western blotting experiments. Compound 11 could suppress the levels of TNF‐α and IL‐6, and down‐regulate the protein expression of iNOS and COX‐2 in RAW 264.7 cells.