bluuebunny/crossref_metadata_2025_split huggingface dataset:
Aspirin Use and Incidence of Colorectal Cancer According to Lifestyle Risk
Authors: Sikavi Daniel R. , Wang Kai , Ma Wenjie , Drew David A. , Ogino Shuji , Giovannucci Edward L. , Cao Yin , Song Mingyang , Nguyen Long H. , Chan Andrew T. 
Published: August 2024

ImportanceAspirin reduces the risk of colorectal cancer (CRC). Identifying individuals more likely to benefit from regular aspirin use for CRC prevention is a high priority.ObjectiveTo assess whether aspirin use is associated with the risk of CRC across different lifestyle risk factors.Design, Setting, and ParticipantsA prospective cohort study among women in the Nurses’ Health Study (1980-2018) and men in the Health Professionals Follow-Up Study (1986-2018) was conducted. Data analysis was performed from October 1, 2021, to May 22, 2023.ExposuresA healthy lifestyle score was calculated based on body mass index, alcohol intake, physical activity, diet, and smoking with scores ranging from 0 to 5 (higher values corresponding to a healthier lifestyle). Regular aspirin use was defined as 2 or more standard tablets (325 mg) per week.Main Outcome and MeasuresOutcomes included multivariable-adjusted 10-year cumulative incidence of CRC, absolute risk reduction (ARR), and number needed to treat associated with regular aspirin use by lifestyle score and multivariable-adjusted hazard ratios for incident CRC across lifestyle scores.ResultsThe mean (SD) baseline age of the 107 655 study participants (63 957 women from the Nurses’ Health Study and 43 698 men from the Health Professionals Follow-Up Study) was 49.4 (9.0) years. During 3 038 215 person-years of follow-up, 2544 incident cases of CRC were documented. The 10-year cumulative CRC incidence was 1.98% (95% CI, 1.44%-2.51%) among participants who regularly used aspirin compared with 2.95% (95% CI, 2.31%-3.58%) among those who did not use aspirin, corresponding to an ARR of 0.97%. The ARR associated with aspirin use was greatest among those with the unhealthiest lifestyle scores and progressively decreased with healthier lifestyle scores (P &amp;lt; .001 for additive interaction). The 10-year ARR for lifestyle scores 0 to 1 (unhealthiest) was 1.28%. In contrast, the 10-year ARR for lifestyle scores 4 to 5 (healthiest) was 0.11%. The 10-year number needed to treat with aspirin was 78 for participants with lifestyle scores 0 to 1, 164 for score 2, 154 for score 3, and 909 for scores 4 to 5. Among the components of the healthy lifestyle score, the greatest differences in ARR associated with aspirin use were observed for body mass index and smoking.Conclusions and RelevanceIn this cohort study, aspirin use was associated with a greater absolute reduction in risk of CRC among individuals with less healthy lifestyles. The findings of the study suggest that lifestyle risk factors may be useful to identify individuals who may have a more favorable risk-benefit profile for cancer prevention with aspirin.
Discussion Addendum for: Rh(I)‐Catalyzed Allenic Pauson–Khand Reaction
Authors: Deihl Eric D. , Haghighi Fatemeh , Brummond Kay M. 
Published: August 2024

AbstractThe intramolecular Rh(I)‐catalyzed allenic Pauson–Khand reaction (APKR) is a powerful synthetic method for constructing ring‐fused cyclopentenones. This discussion addendum informs on a few recent advances made regarding expansion of the scope of the APKR and its application to target‐oriented synthesis. In this chapter, the authors divided addendum into the following topics: Asymmetric Allenic Pauson–Khand Reaction; Transfer of Allene Axial Chirality in APKR; Rh(I)‐Catalyzed APKR Double Bond Selectivity, Mechanism, and Reaction Optimization; and APKR Approach to Natural Products and Other Bioactive Compounds. In summary, the APKR has played an important role in target‐oriented organic synthesis. Amongst different metals including Fe, Mo, and Co being used as the catalyst in APKR, Rh is the most prominent in the recent advances in this area. For additional insight and information on the APKR several reviews have been published.
Synthesis of NH‐Sulfoximines from Sulfides Using Ammonium Carbamate and (Diacetoxyiodo)benzene to Transfer NH and O
Authors: Tota Arianna , Spennacchio Mauro , Briggs Edward L. , Ma Tsz‐Kan , Zhong Zhenhao , Degennaro Leonardo , Bull James A. , Luisi Renzo 
Published: August 2024

AbstractThis chapter presents the procedure for synthesis of NH‐sulfoximines from sulfides using ammonium carbamate and (diacetoxyiodo) benzene to transfer NH and O. Sulfoximines are emerging motifs in the life sciences and have shown application in asymmetric synthesis as chiral auxiliaries, ligands and catalysts. Their Lewis basic character has also made them interesting directing groups for C‐H functionalization. In 2017, the authors reported an operationally simple metal‐free protocol for the straightforward preparation of NH‐sulfoximines from sulfides using ammonium carbamate as a convenient source of ammonia and (diacetoxyiodo) benzene as the oxidant. This protocol was applied by them (and others) for the preparation of NH‐sulfoximines and for the NH‐ and O‐transfer to sulfenamides to access sulfonimidamides. In conclusion, the authors expect this metal‐free protocol from sulfides to be widely applicable, with the demonstrated compound presenting an attractive building block for further derivatization.
N
‐(Benzyloxy)‐
N
‐(pivaloyloxy)‐4‐(trifluoromethyl)‐benzamide
Authors: Berger Kathleen J. , Dherange Balu D. , Morales Megan , Driscoll Julia L. , Tarhan A. Kaan , Levin* Mark D. 
Published: August 2024

Abstract

This chapter presents the procedure for the N‐(Benzyloxy)‐N‐(pivaloyloxy)‐4‐(trifluoromethyl)‐benzamide which belongs to the N‐(alkoxy)‐N‐(acyloxy)benzamide class of anomeric amides. In this class of compounds, in order to satisfy the electron demand of the two oxygen substituents, the resonance of the nitrogen lone pair with the amide carbonyl is largely diminished. This results in an sp
3
configuration and pyramidalization at nitrogen. The authors have used N‐(Benzyloxy)‐N‐(pivaloyloxy)‐4‐(trifluoromethyl)‐benzamide to selectively edit secondary amines containing a range of functional groups and heterocycles. Nitrogen deletion of cyclic secondary amines results in a ring contraction, which has been applied to give substituted cyclobutene products from pyrrolidine precursors. This methodology also enabled a new synthetic route to the chemotherapeutic Pemetrexed and enabled the late‐stage editing of the kinase inhibitor Lapatinib.
Synthesis of Potassium 5‐Bromopentyltrifluoroborate via Hydroboration of a Haloalkene
Authors: Burke Sarah J. , Alhthlol Latifah M. , Gamrat James M. , Mancini Giulia , Orme Christopher L. , Santhouse Jacqueline R. , Tomares Dylan T. , Tomsho* John W. 
Published: August 2024

AbstractThis chapter presents the procedure for synthesis of potassium 5‐bromopentyltrifluoroborate via hydroboration of a haloalkene. While investigating nucleophilic substitution reactions involving boron‐containing electrophiles as a method to synthesize new pharmaceutical agents, the authors found boron's vacant p‐orbital caused problems in their syntheses. To overcome these difficulties, trifluoroborate salt electrophiles were explored as a method to mask the vacant p‐orbital. In conclusion, the authors have developed and reported a convenient, sequential synthesis as a general method for the preparation of potassium haloalkyltrifluoroborate salts through hydroboration with dichloroborane followed by treatment of the crude hydroboration products with potassium hydrogen difluoride. The reported procedure provided high yields and easy separation from disiloxane, a rarely mentioned hydroboration byproduct. This technique improves upon those that have been reported in terms of yield, reproducibility, atom economy, convenience, and cost for the generation of a series of potassium haloalkyltrifluoroborate salts.
Preparation of (
S
)‐5,5′,6,6′,7,7′,8,8′‐Octahydro‐1,1'‐bi‐2‐naphthol [(
S
)‐H
8
BINOL]
Authors: Chen Jiong , Zhu Yuan‐Yuan , Gu Shuang‐Xi 
Published: August 2024

Abstract

This chapter presents the procedure for the preparation of (
S
)‐5,5',6,6',7,7',8,8'‐octahydro‐1,1'‐bi‐2‐naphthol [(
S
)‐H
8
BINOL]. 1,1'‐Binaphthyl‐based chiral molecules have been extensively employed in asymmetric catalysis and molecular recognition. In the past two decades, a number of groups have used the enantiomerically pure BINOL as the starting material to prepare BINOL‐based fluorescent probes for chiral recognition. 5,5',6,6',7,7',8,8'‐octahydro‐[1,1'‐binaphthalene]‐2,2'‐diol (H
8
BINOL), the selectively partially hydrogenated BINOL, and other derivatives based on this structural motifs have also been investigated and shown higher enantioselectivity than BINOL‐based probes in many cases. Therefore, it is expected that the investigation of H
8
BINOL‐based probes might yield probes with significant fluorescent properties.
Fast Photoactuation Driven by Supramolecular Polymers Integrated into Covalent Networks
Authors: Cezan S. Doruk , Li Chuang , Kupferberg Jacob , Ðorđević Luka , Aggarwal Aaveg , Palmer Liam C. , Olvera de la Cruz Monica , Stupp Samuel I. 
Published: August 2024

AbstractThe design of robotic soft matter capable of emulating the complex movements of living organisms such as mechanical actuation, shape transformation, and autonomous translation remains a grand challenge in soft materials science. Functionalized hydrogels are excellent candidates for such materials since they can operate in water and are highly responsive to their environment, but their response times can be slow. This work investigates fast photoactuation of hybrid bonding hydrogels composed of peptide amphiphile (PA) supramolecular nanofibers bonded covalently to merocyanine‐based (MCH+) photoresponsive networks. By incorporating ionizable acrylic acid (AA) co‐monomers in these networks, photoactuation at nearly neutral pH is observed, which in turn enables a new mechanism to accelerate the response by triggering the bundling of supramolecular nanofibers by rapid proton exchange reactions. Furthermore, this rapid response and its consequent large shape transformations lead to hydrogels capable of spontaneously tracking external light sources inspired by pedicellariae, defensive organs present in echinoderms like the starfish and the sea urchin. This work suggests that hybrid bonding polymers (HBPs), which leverage the interplay between supramolecular assemblies and covalent networks, offer novel strategies to design rapidly actuating soft robotic materials.
Nucleation Behavior of SnS2 on Thiol Functionalized SAMs During Solution‐Based Atomic Layer Deposition
Authors: Götz Klaus , Prihoda Annemarie , Shen Chen , Dierner Martin , Dallmann Johannes , Prusch Saskia , Zahn Dirk , Spiecker Erdmann , Unruh Tobias 
Published: August 2024

AbstractSolution‐based atomic layer deposition (sALD) is an emerging technique that transfers the principle of traditional atomic layer deposition (ALD) from the gas phase into a wet chemical environment. This new preparation technique has new and unique properties and requirements. A large number of new surfaces and reactants are available to produce active 2D materials.In this work a reproducible procedure to coat silicon wafers with a densely packed monolayer of (3‐Mercaptopropyl)trimethoxysilane (MPTMS) molecules is presented. These highly functionalized surfaces can be used to seed the nucleation of SnS2 in a solution‐based ALD procedure. A coating routine for the production of SnS2 is adapted from ALD to sALD and insight into the nucleation behavior of the reactands is given. X‐ray reflectometry (XRR) is used to resolve the nucleation process of SnS2 on an MPTMS self assembled monolayer (SAM) during the first three cycles of an sALD procedure. The comparison of ex situ XRR, in situ XRR, grazing incidence wide‐angle X‐ray scattering (GIWAXS), atomic force microscopy (AFM), energy dispersive X‐ray spectroscopy (EDX) measurements, and density functional theory (DFT) calculations find that SnS2 first forms a closed layer and then continues to grow in islands on thiol functionalized silane SAMs. Subsequent coating cycles will continue the growth of the islands laterally and in height.
4‐Aminobenzotriazole (ABTA) Directed Palladium‐Catalyzed Cascade Reaction for Synthesis of Benzofulvenes Through C−H Bond Activation Involving Inner Alkynes
Authors: Li Chengqian , Wang Zhuo , Song Zhiguang 
Published: August 2024

AbstractA route for the construction of benzofulvenes derivatives through 4‐Aminobenzotriazole (ABTA) directed Pd‐catalyzed cascade reactions of amides with inner alkynes was developed. This method afforded a diverse array of benzofulvene derivatives in yields ranging from 34% to 91%. The control experiments indicated that the substrate reacts with alkynes in tandem to synthesize 1,3‐diene intermediates, and ultimately 1,3‐diene underwent intramolecular cyclization to produce benzofulvene derivatives. Furthermore, the directing group can be removed.
Unconventional Light‐Matter Interactions Between Giant Atoms and Structured Baths with Next‐Nearest‐Neighbor Couplings
Authors: Wang Pengfei , Huang Lei , Zhang Hanxiao , Yang Hong , Yan Dong 
Published: August 2024

AbstractIn this paper, the unconventional light‐matter interactions between giant atoms and structured baths (i.e., lattices) are studied with either Hermitian or non‐Hermitian next‐nearest‐neighbor coupling terms. Essentially different dynamics of the atoms and the propagating field in the Hermitian and non‐Hermitian cases is revealed, which can be further engineered by tuning parameters such as the atomic transition frequency and the (synthetic) magnetic field associated to the coupling terms. The next‐nearest‐neighbor couplings play an important role in controlling the emission direction and the field distribution in the lattice, thus providing opportunities for tailoring exotic dipole–dipole interactions. The results in this paper have potential applications in, e.g., engineering unconventional quantum networks and simulating quantum many‐body systems.
Universal C‐MAC® videolaryngoscope use in adult patients: a single‐centre experience
Authors: Penders R. , Kelly F. E. , Cook T. M. 
Published: August 2024

SummaryUniversal use of Storz C‐MAC® videolaryngoscopes was implemented for adult tracheal intubations in the operating theatres, intensive care unit and emergency department at Royal United Hospitals Bath NHS Foundation Trust in 2017. We report data from 1099 intubations from March 2020 to March 2022, collected contemporaneously and anonymously using a smartphone app, representing an estimated 18% of intubations in operating theatres and 30% of intubations in other locations during this period. Intubation success was 100%. The first‐pass success rate was 87.3% overall: 87% with a Macintosh videolaryngoscope, 92% with a hyperangulated videolaryngoscope and 81% for users with ≤ 20 previous uses. First‐pass success without complications was 87% overall: 87% in operating theatres (836/962), 93% in the emergency department (38/41) and 83% in the intensive care unit (73/88). Complications occurred during 0.6% of intubations: 0/962 in operating theatres and 7/137 in non‐theatre locations. The rate of complications was unaltered by blade type (Macintosh 5/994 vs. hyperangulated 2/105, p = 0.14); intubator experience with the device (≤ 20 previous clinical uses 2/260 vs. > 20 previous uses 5/832, p = 0.67) and use of airborne personal protective equipment (PPE 6/683 vs. no‐PPE 1/410, p = 0.27). Complication rates increased outside theatres (theatres 0/963 vs. non‐theatre 7/136, p < 0.001) and during rapid sequence induction (RSI 6/379 (1.6%) vs. non‐RSI 1/720 (0.1%), p = 0.008).
A comparative assessment of age‐related nicotinamide adenine dinucleotide phosphate‐diaphorase positivity in the spinal cord and medulla oblongata of pigeons, rats, and mice
Authors: Jia Yunge , Li Yinhua , Hou Wei , Wei Zichun , Zhang Tianyi , Wang Xinghang , Wang Jie , Tan Huibing 
Published: August 2024

AbstractNicotinamide adenine dinucleotide phosphate (NADPH)‐diaphorase (N‐d) positive neurons have been extensively studied across various animals, and N‐d neurodegenerative neurites have been detected in some aged animal models. However, detailed knowledge on N‐d positivity and aging‐related alterations in the spinal cord and medulla oblongata of pigeons is limited. In this study, we investigated N‐d positivity and age‐related changes in the pigeon's spinal cord and medulla oblongata and compared them to those in rats and mice. Pigeons, had more N‐d neurons in the dorsal horn, around the central canal, and in the column of Terni in the thoracic and lumbar segments, with scattered neurons found in the ventral horn of the spinal segments. N‐d neurons were also present in the white matter of the spinal cord. Morphometric analysis revealed that the size of N‐d soma in the lumbosacral, cervical, and thoracic regions was substantially altered in aged pigeons compared to young birds. Furthermore, the lumbar to sacral segments underwent significant morphological alterations. The main findings of this study were the presence of age‐related N‐d positive bodies (ANB) in aged pigeons, predominantly in the external cuneate nucleus (CuE) and occasionally in the gracilis and CuEs. ANBs were also identified in the gracile nuclei and spinal cord in the aged rats and mice, whereas in aged rats, ANBs were detected in the CuE spinal nucleus. Immunohistochemistry showed that the age‐related alterations occurred in the cell types and neuropeptides in old animals. The results suggest weak inflammatory response and neuronal dysfunction in the spinal cord in aged pigeons. Our results suggested that the ANB could be a potential aging marker for the central nervous system.
Changes in high school students attitudes toward health sciences following a hands‐on outreach STEM program
Authors: Masamoto Maia , Stevens Courtney , Ettinger Lucas 
Published: August 2024

AbstractDespite attempts to diversify healthcare workplaces and education, racial and ethnic minorities (REM) remain underrepresented in these fields. This study investigated changes in high school students' health science interest following a single exposure, hands‐on anatomy laboratory visit. One hundred and eighty‐eight high school students participated in a single day, one‐hour visit to a human anatomy laboratory on a university campus. Participants engaged in hands‐on activities centered around both human and animal specimens led by university mentors. Using a modified Science Technology Engineering and Mathematics—Career Interest Survey (STEM‐CIS) questionnaire, health science STEM interest was calculated before and after the visits and compared using a paired t‐test (α = 0.05). A 2 × 2 ANOVA (α = 0.05) was run on pre‐to‐post‐visit interest score differences with factors of Race (White/REM) and Gender (Male/Female) to determine if race/ethnicity and/or gender moderated the gains observed. Overall, health science STEM interest increased significantly from pre‐ to post‐visit (p < 0.001), and these gains were greater in REM students (p < 0.05) but did not differ as a function of gender. These findings indicate that a single visit to an anatomy laboratory with hands‐on activities can be used as a tool to engage high school aged students in STEM and may be particularly beneficial for racial/ethnic minority students, potentially influencing health science STEM interest.
Synthesis, Structure, Spectral, Redox, and Theoretical Studies of Sterically Crowded Decaaryl Triphyrin(2.1.1)s
Authors: Alka A. , Sharma Akrti , Ravikanth Mangalampalli 
Published: August 2024

AbstractFirst examples of sterically crowded β‐ and meso‐arylated decaaryl triphyrin(2.1.1)s were synthesized by reacting β‐hexabromo meso‐tetraaryl triphyrin(2.1.1) with five different aryl boronic acids in THF/toluene/H2O (1 : 1 : 1) in the presence of catalytic amount of Pd(PPh3)4/Na2CO3 at 80 °C for 12–24 h. The X‐ray structure obtained for one of the decaaryl triphyrin(2.1.1)s revealed that the macrocycle exhibited saddle type of distortion due to steric crowding by bulky aryl substituents introduced at the six β‐carbons of meso‐tetraaryl triphyrin(2.1.1) unlike almost planar structure observed for β‐unsubstituted meso‐tetraaryl triphyrin(2.1.1). The absorption bands of decaaryl triphyrin(2.1.1)s were broadened and bathochromically shifted compared to meso‐tetraaryl triphyrin(2.1.1) and the redox potentials were dependent on the kind of aryl substituents present at the β‐pyrrole carbons in decaaryl triphyrin(2.1.1)s. DFT and TD‐DFT studies helped in understanding the alteration in the structure, spectral, and redox properties in decaaryl triphyrin(2.1.1)s compared to meso‐tetraaryl triphyrin(2.1.1).
Fisetin is a selective adenosine triphosphate‐competitive inhibitor for mitogen‐activated protein kinase kinase 4 to inhibit lipopolysaccharide‐stimulated inflammation
Authors: He Ziyu , Uto Takuhiro , Tanigawa Shunsuke , Sakao Kozue , Kumamoto Takuma , Xie Kun , Pan Xuchi , Wu Shusong , Yang Yili , Komatsu Masaharu , Hou De‐Xing 
Published: August 2024

AbstractThe mitogen‐activated protein kinase kinase 4 (MKK4), a member of the MAP kinase kinase family, directly phosphorylates and activates the c‐Jun NH2‐terminal kinases (JNK), in response to proinflammatory cytokines and cellular stresses. Regulation of the MKK4 activity is considered to be a novel approach for the prevention and treatment of inflammation. The aim of this study was to identify whether fisetin, a potential anti‐inflammatory compound, targets MKK4‐JNK cascade to inhibit lipopolysaccharide (LPS)‐stimulated inflammatory response. RAW264 macrophage pretreated with fisetin following LPS stimulation was used as a cell model to investigate the transactivation and expression of related‐inflammatory genes by transient transfection assay, electrophoretic mobility shift assay (EMSA), or enzyme‐linked immunosorbent assay (ELISA), and cellular signaling as well as binding of related‐signal proteins by Western blot, pull‐down assay and kinase assay, and molecular modeling. The transactivation and expression of cyclooxygenase‐2 (COX‐2) gene as well as prostaglandin E2 (PGE2) secretion induced by LPS were inhibited by fisetin in a dose‐dependent manner. Signaling transduction analysis demonstrated that fisetin selectively inhibited MKK4‐JNK1/2 signaling to suppress the phosphorylation of transcription factor AP‐1 without affecting the NF‐κB and Jak2‐Stat3 signaling as well as the phosphorylation of Src, Syk, and TAK1. Furthermore, in vitro and ex vivo pull‐down assay using cell lysate or purified protein demonstrated that fisetin could bind directly to MKK4. Molecular modeling using the Molecular Operating Environment™ software indicated that fisetin docked into the ATP‐binding pocket of MKK4 with a binding energy of −71.75 kcal/mol and formed a 1.70 Å hydrogen bound with Asp247 residue of MKK4. The IC50 of fisetin against MKK4 was estimated as 2.899 μM in the kinase assay, and the ATP‐competitive effect was confirmed by ATP titration. Taken together, our data revealed that fisetin is a potent selective ATP‐competitive MKK4 inhibitor to suppress MKK4‐JNK1/2‐AP‐1 cascade for inhibiting LPS‐induced inflammation.