bluuebunny/crossref_metadata_2025_split huggingface dataset:
Highly Active Cyclic Zinc(II) Thione Catalyst for C−C and C−N Bond Formation Reactions
Authors: Mannarsamy Maruthupandi , Nandeshwar Muneshwar , Muduli Gopendra , Prabusankar Ganesan 
Published: July 2022

AbstractThe first discrete seven‐membered cyclic zinc(II) complex catalyzed room temperature Knoevenagel condensation reactions, and the synthesis of perimidine derivatives has been reported under mild reaction conditions. The cyclic zinc(II) complex [(L)ZnBr2] (1) was isolated from the reaction between 1‐(2‐hydroxyethyl)‐3‐isopropyl‐benzimidazol‐2‐thione (L) and ZnBr2. Complex 1 was characterized by different analytic techniques such as FT‐IR, CHNS, TGA, NMR, and SCXRD. The mononuclear zinc(II) complex 1 was utilized as a catalyst for Knoevenagel condensation reactions to isolate twenty different substituted methylene malononitriles with excellent yield. Besides, the zinc(II) thione complex 1 was utilized for the synthesis of 2,4‐dihydroperimidine derivatives in a highly efficient manner. Catalyst 1 depicted wide substrate scopes. Overall, twenty different substituted methylene malononitriles and nine different perimidine derivatives were synthesized using catalyst 1 at room temperature. The present investigation features a mild and fast synthetic approach along with excellent functional group tolerance.
Production of retinoic acid by engineered Saccharomyces cerevisiae using an endogenous aldehyde dehydrogenase
Authors: Hu Qiongyue , Yu Hongwei , Ye Lidan 
Published: July 2022

AbstractRetinoic acid (RA), a vitamin A (retinol)‐derived lipophilic compound, is involved in various physiological functions. The demand for RA is growing in the pharmaceutical industry, but RA biosynthesis is still in its infancy compared to other forms of retinoids such as retinol and retinal, largely due to the lack of efficient retinal dehydrogenases. To achieve effective biosynthesis of RA, the catalytic activities of exogenous retinal dehydrogenases were comparatively analyzed in a previously constructed retinoids‐producing Saccharomyces cerevisiae strain, followed by mining of endogenous enzymes with higher retinal dehydrogenase activities using homology‐based search. After confirming the retinal oxidation activity of the endogenous aldehyde dehydrogenase Hfd1 using in vivo and in vitro experiments, it was overexpressed in multiple copies, and the resulting strain produced 99.71 mg/L of RA in shake‐flask cultures. Finally, 545.28 mg/L of RA was produced in fed‐batch fermentation. This study suggests the yeast endogenous Hfd1 as a potent catalyst for RA biosynthesis, and demonstrates the potential of yeast as a platform for RA production.
Simultaneous determination of nirmatrelvir and ritonavir in human plasma using LC–MS/MS and its pharmacokinetic application in healthy Chinese volunteers
Authors: Liu Chenxi , Zhu Miqun , Cao Liyun , Boucetta Hamza , Song Min , Hang Taijun , Lu Yuting 
Published: July 2022

AbstractPaxlovid, a copackaged medication of nirmatrelvir tablets (150 mg) and ritonavir tablets (100 mg) developed by Pfizer, is one of the first orally accessible COVID‐19 antiviral medicines to be approved for emergency usage. In this research, an efficient LC–MS/MS method for simultaneous determination of nirmatrelvir and ritonavir in human plasma was established and validated with remdesivir as an internal standard. Chromatographic separations were carried out on a Thermo BDS Hypersil C18 column (4.6 × 100 mm, 2.4 μm) using deionized water and methanol as mobile phase, both added with 0.1% (v/v) formic acid. Based on the positive electrospray ionization mode, nirmatrelvir and ritonavir were analyzed by selective reaction monitoring. Excellent precision, accuracy, recovery, and linearity were demonstrated, covering the range of 50–5000 ng/mL for nirmatrelvir and 10–1000 ng/mL for ritonavir. Then, the established method was used for determining the pharmacokinetic profile of Paxlovid in healthy Chinese volunteers. The pharmacokinetic parameters, including Cmax, Tmax, t1/2, and AUC0 − ∞ of Western volunteers, correspond well with the results of this pharmacokinetic investigation.
Exploration of the breast ductal carcinoma in situ signature and its prognostic implications
Authors: Zhang Jiao , Lin Hui , Hou Lei , Xiao Hui , Gong Xilong , Guo Xuhui , Cao Xuchen , Liu Zhenzhen 
Published: July 2022

AbstractFollowing the implementation of breast screening programs, the occurrence of ductal carcinoma in situ (DCIS) as an early type of neoplasia has increased. Although the prognosis is promising, 20%–50% of DCIS patients will progress to invasive ductal carcinoma (IDC) if not treated. It is essential to look for promising biomarkers for predicting DCIS prognosis. The Gene Expression Omnibus (GEO) database was used to explore the expression of genes that differed between DCIS and normal tissue in this investigation. Enrichment analysis was performed to characterize the biological role and intrinsic process pathway. The Cancer Genome Atlas Breast Cancer Dataset was used to categorize the hub genes, and the results were confirmed using the Cytoscape plugin CytoHubba and MCODE. The prognostic ability of the core gene signature was determined through time‐dependent receiver operating characteristic (ROC), Kaplan–Meier survival curve, Oncomine databases, and UALCAN databases. In addition, the prognostic value of core genes was verified in proliferation assays. We identified 217 common differentially expressed genes (DEGs) in the present study, with 101 upregulated and 138 downregulated genes. The top genes were obtained from the PPI network (protein–protein interaction). A unique six‐gene signature (containing GAPDH, CDH2, BIRC5, NEK2, IDH2, and MELK) was developed for DCIS prognostic prediction. Centered on the Cancer Genome Atlas (TCGA) cohort, the ROC curve showed strong results in prognosis prediction. The six core gene signatures is often overexpressed in DCIS, with a weak prognosis. Furthermore, when breast cancer cells are transfected with small interfering RNAs, downregulation of core gene expression substantially inhibits cell proliferation, revealing a high potential for employing core genes in DCIS prognosis. In conclusion, the current investigation verified the six core genes signatures for prospective DCIS biomarkers, which may aid clinical decision‐making for individual care.
Daphnetin, a Coumarin in Genus Stellera Chamaejasme Linn: Chemistry, Bioactivity and Therapeutic Potential
Authors: Hang Sijin , Wu Wenhui , Wang Yinan , Sheng Ruilong , Fang Yiwen , Guo Ruihua 
Published: July 2022

AbstractCoumarins is a huge family of phenolic compounds containing a common structure of 2H‐1‐benzopyran‐2‐one. Nowadays, more than 1,300 natural‐based coumarins have been identified in a variety of plants, bacteria and fungi, many of them exhibited promising biomedical performance. Daphnetin (7,8‐dihydroxycoumarin), a typical coumarin, showed a couple of bioactivities such as anti‐cancer, antibacterial, anti‐inflammatory and anti‐arthritis. In the treatment of diseases, it has been verified that daphnetin has outstanding therapeutic effects on diabetes, arthritis, transplant rejection, cancer and even on central nervous system diseases. In China, it is being used for clinical applications, about 93 patent publications were associated with daphnetin. Due to its wide therapeutic potentials in clinical applications, numerous research on the action mechanisms and synthetic methods of daphnetin have been performed to support the future developments. Herein, we summarized the chemical synthetic methodologies, bioactivities, therapeutic potentials and structure‐activity relationships of daphnetin and its derivatives. Moreover, the state‐of‐the‐arts in current daphnetin study and future perspective in this field were discussed. Hopefully, this review would be beneficial for the discovery of new coumarin‐based biomedicine in the near future.
Intriguing mass associated with cleft palate
Authors: Daldoul Malek , Tritar Sirine , Ayachi Samia , Moatemri Ramzi , Kochtali Habib 
Published: July 2022

AbstractNasopharyngeal teratomas are rare and represent only 2% of all teratomas. They can lead to an embryopathogenic mechanical obstacle responsible for a cleft palate with few reported cases of this association in the literature. We report the case of a 14‐month‐old girl with this atypical association.
Trifluoromethoxylation Reactions of (Hetero) arenes, Olefinic Systems and Aliphatic Saturated Substrates
Authors: Barata‐Vallejo Sebastian , Bonesi Sergio M. , Postigo Al 
Published: July 2022

AbstractDirect fluoroalkoxylation reactions of (hetero)arenes, carbon‐carbon multiple bonds, and substitution reactions at Csp3carbon centers by CF3O, CHF2O, and (CF3)2CFO groups are discussed. Emphasis on thermal radical, electron transfer, photocatalytic, electrochemical and redox‐neutral radical methods are placed to accomplish fluoroalkoxylation reactions. All these methods employ either radical fluoroalkoxylating reagents or some nucleophilic trifluoromethoxylating sources of CF3O. A summary of all these methods is provided in Table 2.
Mechanistic Studies for the Rational Design of Multivalent Glycodendrimers
Authors: Manabe Yoshiyuki , Tsutsui Masato , Hirao Kohtaro , Kobayashi Risako , Inaba Hiroshi , Matsuura Kazunori , Yoshidome Daisuke , Kabayama Kazuya , Fukase Koichi 
Published: July 2022

AbstractWe have synthesized B‐antigen‐displaying dendrimers (16‐mers) with different sizes and evaluated their affinity to their IgM antibody in order to investigate which design features lead to effective multivalency. Unexpectedly, the smallest dendrimer, which cannot chelate the multiple binding sites of IgM, clearly exhibited multivalency, together with an affinity similar to or higher than those of the larger dendrimers. These results indicate that the statistical rebinding model, which involves the rapid exchange of clustered glycans, significantly contributes to the multivalency of glycodendrimers. Namely, in the design of glycodendrimers, high‐density glycan presentation to enhance statistical rebinding should be considered in addition to the ability to chelate multiple binding sites. This notion stands in contrast to the currently prevailing scientific consensus, which prioritizes the chelation model. This study thus provides new and important guidelines for molecular design of glycodendrimers.
Structure of Zinc and Nickel Histidine Complexes in Solution Revealed by Molecular Dynamics and Raman Optical Activity
Authors: Hudecová Jana , Kapitán Josef , Dračínský Martin , Michal Pavel , Profant Václav , Bouř Petr 
Published: July 2022

AbstractThe histidine residue has an exceptional affinity for metals, but solution structure of its complexes are difficult to study. For zinc and nickel complexes, Raman and Raman optical activity (ROA) spectroscopy methods to investigate the link between spectral shapes and the geometry were used. The spectra were recorded and interpreted on the basis of ionic equilibria, molecular dynamics, ab initio molecular dynamics, and density functional theory. For zwitterionic histidine the dominant tautomer was determined by the decomposition of experimental spectra into calculated subspectra. An octahedral structure was found to prevail for the ZnHis2 complex in solution, in contrast to a tetrahedral arrangement in the crystal phase. The solution geometry of NiHis2 is more similar to the octahedral structure found by X‐ray. The Raman and ROA structural determinations of metal complexes are dependent on extensive computations, but reveal unique information about the studied systems.
Controlling the Emissive, Chiroptical, and Electrochemical Properties of Double [7] Helicenes through Embedded Aromatic Rings
Authors: Hong Juan , Xiao Xuxian , Liu Haoliang , Dmitrieva Evgenia , Popov Alexey A. , Yu Zidong , Li Ming‐De , Ohto Tatsuhiko , Liu Jun , Narita Akimitsu , Liu Pengcai , Tada Hirokazu , Cao Xiao‐Yu , Wang Xiao‐Ye , Zou Yingping , Müllen Klaus , Hu Yunbin 
Published: July 2022

AbstractWe present here the synthesis and in‐depth physicochemical characterization of a double hetero[7]helicene fused with four triazole rings at both helical ends. The comparison of this triazole‐fused double helicene with the previously reported all‐carbon and thiadiazole‐fused analogs revealed the huge impact of the embedded aromatic rings on the photophysical features. The small structural variation of the terminal rings from thiadiazole to triazole caused a dramatic change of the photoluminescence quantum yields (PLQYs) from <1 % to 96 %, while the replacement of the terminal benzene rings with triazole rings induced a tenfold enhancement of the circularly polarized luminescence dissymmetry factor. These observations were well corroborated with transient absorption analysis and/or theoretic calculations. In addition, the triazole‐fused double helicene exhibited ambipolar redox behavior, enabling the generation of radical cation and anion species by electrochemical and chemical methods and showing its potential for spin‐related applications.
Self‐Assembling Behaviour of Perylene, Perylene Diimide, and Thionated Perylene Diimide Deciphered through Non‐Covalent Interactions
Authors: Parida Sanjukta , Patra Sanjib K. , Mishra Sabyashachi 
Published: July 2022

AbstractThe π‐conjugated supramolecular polymers (SMP) have gained vast popularity in materials chemistry and biomedicine due to their spectacular self‐assembling behaviour. A detailed account of the electronic structure and bonding through quantum theory of atoms‐in‐molecules, non‐covalent interactions, and energy decomposition analysis (EDA) in the oligomers of perylene, perylene diimide (PDI), and thionated‐PDI (t‐PDI) is presented. The oligomers of all three molecules show a slip angle of θ≈62° thus forming H‐aggregates. The stacking pattern in perylene oligomers prefers a slip‐stacked brick‐layer order, while the bulkier PDI and t‐PDI prefer a parallel step‐wise pattern in their oligomers. Successive addition of monomers leads to a consequent rise in the association energy, although to a much greater extent in PDI and t‐PDI than in perylene. While the major contribution to this association energy comes from the dispersion interactions in all three systems, the steric interactions in t‐PDI quench the cooperativity in its SMP formation. A detailed analysis of the non‐covalent interactions reveals the presence of π‐π, π‐hole⋅⋅⋅O=C, and π‐hole⋅⋅⋅S=C electrostatic interactions playing a crucial role in the self‐assembly process, which can be further implemented on developing force field‐based methods for understanding the self‐assembling mechanism in higher degree of oligomers.
Amphiphilic Cationic Phthalocyanines for Photodynamic Therapy of Cancer
Authors: Halaskova Marie , Kostelansky Filip , Demuth Jiri , Hlbocanova Ingrid , Miletin Miroslav , Zimcik Petr , Machacek Miloslav , Novakova Veronika 
Published: July 2022

AbstractEffective interaction with biomembranes is essential for activity of photosensitizers; however, majority of them are highly charged symmetrical species. Amphiphilic cationic phthalocyanines differing in bulkiness of substitution on lipophilic part (‐H, ‐SMe, ‐StBu) were therefore prepared. Compounds had high singlet oxygen production (ΦΔ=0.38–0.46, DMSO), good fluorescence emission (ΦF=0.21–0.26, DMSO), and log P values ranging −0.07–1.1 (1‐octanol/PBS). Study of interaction with liposomes revealed that also bulky ‐StBu derivatives are able to enter biomembranes. Detail in vitro studies (toxicity, subcellular localization, type of cell death, and morphology) were performed. Compounds were characterized by excellent EC50 values in range of dozens of nM (HeLa, EA.hy926, MCF‐7, HCT116), which were dependent on drug‐light interval and reached plateau after 4 h on HeLa cells. Well‐balanced lipophilicity with ability to interact with biomembranes rank these derivatives among perspective photosensitizers, even for vascular‐targeted PDT (VTP) since they kill EA.hy926 without any preincubation time.
Eco‐Friendly Synthesis of 3D Disordered Carbon Materials for High‐Performance Dual Carbon Na‐Ion Capacitors
Authors: Fombona‐Pascual Alba , Díez Noel , Fuertes Antonio B. , Sevilla Marta 
Published: July 2022

AbstractAn eco‐friendly and sustainable salt‐templating approach was proposed for the production of anode materials with a 3D sponge‐like structure for sodium‐ion capacitors using gluconic acid as carbon precursor and sodium carbonate as water‐removable template. The optimized carbon material combined porous thin walls that provided short diffusional paths, a highly disordered microstructure with dilated interlayer spacing, and a large oxygen content, all of which facilitated Na ion transport and provided plenty of active sites for Na adsorption. This material provided a capacity of 314 mAh g−1 at 0.1 A g−1 and 130 mAh g−1 at 10 A g−1. When combined with a 3D highly porous carbon cathode (SBET ≈2300 m2 g−1) synthesized from the same precursor, the Na‐ion capacitor showed high specific energy/power, that is 110 Wh kg−1 at low power and still 71 Wh kg−1 at approximately 26 kW kg−1, and a good capacity retention of 70 % over 10000 cycles.
Calix[n]arenes in Action: Recent Applications in Organocatalysis
Authors: Simões Juliana Baptista , Leite da Silva Daniel , Fernandes Sergio Antonio , de Fátima Ângelo 
Published: July 2022

AbstractThe use of calix[n]arenes as organocatalysts has increasingly been considered a prime focus due to their adjustable three‐dimensional molecular structure, easy synthesis, and versatile structural modification at the upper and lower edges. For instance, these macromolecules have been described as efficient catalysts for asymmetric aldol reactions, asymmetric Michael addition, esterification and transesterification, dehydration, nucleophilic aromatic substitution, and multicomponent reactions. Furthermore, calix[n]arenes also tolerate aqueous or solvent‐free reaction systems and can be supported on solid and/or magnetic particles, showing cost, time and energy savings, easier experimental procedures, and chemical waste reduction.
Direct Functionalization of Lithium Phosphine Oxides Bearing an Alkyne Chain
Authors: Sanaa Hamdi , Samarat Ali , Durandetti Muriel 
Published: July 2022

AbstractAn efficient synthesis of functionalized alkynyl phosphine oxides is described. The current approach is based on the activation of the phosphorus−hydrogen bond (P−H bond) of a secondary phosphine oxide. After the deprotonation step using n‐butyllithium, the in‐situ generated LiP(O)RR’ undergoes further condensation with a wide variety of electrophiles, and without a cyclisation step into the alkyne as a side reaction. In particular, the addition to aldehydes proceeds quickly and gives access to α‐hydroxy phosphine oxides, with a diastereoselectivity rate up to 80/20.
Somatic mutations reveal complex metastatic seeding from multifocal primary prostate cancer
Authors: Carm Kristina T. , Johannessen Bjarne , Bogaard Mari , Bakken Anne Cathrine , Maltau Aase V. , Hoff Andreas M. , Axcrona Ulrika , Axcrona Karol , Lothe Ragnhild A. , Skotheim Rolf I. 
Published: July 2022

AbstractPrimary prostate cancer shows a striking intraorgan molecular heterogeneity, with multiple spatially separated malignant foci in the majority of patients. Metastatic prostate cancer, however, typically reveals more homogenous molecular profiles, suggesting a monoclonal origin of the metastatic lesions. Longitudinal mutational spectra, comparing multiple primary lesions with metastases from the same patients remain poorly defined. We have here analyzed somatic mutations in multisampled, spatio‐temporal biobanked lesions (38 samples from primary foci and 1 sample from each of 8 metastases from seven prostate cancer patients) applying a custom‐designed panel targeting 68 prostate cancer relevant genes. The metastatic samples were taken at time of primary surgery and up to 7 years later, and sampling included circulating tumor DNA in plasma or solid metastatic tissue samples. A total of 282 somatic mutations were detected, with a range of 0 to 25 mutations per sample. Although seven samples had solely private mutations, the remaining 39 samples had both private and shared mutations. Seventy‐four percent of mutations in metastases were not found in any primary samples, and vice versa, 96% of mutations in primary cancers were not found in any metastatic samples. However, for three patients, shared mutations were found suggesting the focus of origin, including mutations in AKT1, FOXA1, HOXB13, RB1 and TP53. In conclusion, the spatio‐temporal heterogeneous nature of multifocal disease is emphasized in our study, and underlines the importance of testing a recent sample in genomics‐based precision medicine for metastatic prostate cancer.
A standardised nomenclature for long non‐coding RNAs
Authors: Seal Ruth L. , Tweedie Susan , Bruford Elspeth A. 
Published: July 2022

AbstractThe HUGO Gene Nomenclature Committee (HGNC) is the sole group with the authority to approve symbols for human genes, including long non‐coding RNA (lncRNA) genes. Use of approved symbols ensures that publications and biomedical databases are easily searchable and reduces the risks of confusion that can be caused by using the same symbol to refer to different genes or using many different symbols for the same gene. Here, we describe how the HGNC names lncRNA genes and review the nomenclature of the seven lncRNA genes most mentioned in the scientific literature.
Biosynthesis of uridine diphosphate N‐Acetylglucosamine: An underexploited pathway in the search for novel antibiotics?
Authors: Wyllie Jessica A. , McKay Mirrin V. , Barrow Andrew S. , Soares da Costa Tatiana P. 
Published: July 2022

AbstractAlthough the prevalence of antibiotic resistance is increasing at an alarming rate, there are a dwindling number of effective antibiotics available. Thus, the development of novel antibacterial agents should be of utmost importance. Peptidoglycan biosynthesis has been and is still an attractive source for antibiotic targets; however, there are several components that remain underexploited. In this review, we examine the enzymes involved in the biosynthesis of one such component, UDP‐N‐acetylglucosamine, an essential building block and precursor of bacterial peptidoglycan. Furthermore, given the presence of a similar biosynthesis pathway in eukaryotes, we discuss the current knowledge on the differences and similarities between the bacterial and eukaryotic enzymes. Finally, this review also summarises the recent advances made in the development of inhibitors targeting the bacterial enzymes.