Shifting Lithium Amide Reactivity to the Radical Domain: Regioselective Radical C-H Functionalization of 3-Iodooxetane for the Synthesis of 1,5-Dioxaspiro[2.3]hexanes.

Strained spiro-heterocycles (SSH) have gained significant attention within the medicinal chemistry community as promising (sp3)-rich bioisosteres for their aromatic and non-spirocyclic counterparts. We herein report access to an unprecedented spiro-heterocycle - 1,5-dioxaspiro[2.3]hexane.

Industrial air emissions and breast cancer incidence in a United States-wide prospective cohort.

Background: We evaluated air emissions of industrial compounds, many of which have carcinogenic or endocrine disrupting properties, in relation to breast cancer incidence.

Methods: Using the United States Environmental Protection Agency's Toxics Release Inventory, we quantified air emissions of 28 compounds near Sister Study participants' residences during the 10 years leading up to study enrollment (2003-2006; n=46,150). We used Cox proportional hazards regression to estimate adjusted hazard ratios (HR) and 95% confidence intervals (CI) for associations of residential emission levels of single pollutants with incident breast cancer.

Significant Efficiency Enhancements in Non-Y Series Acceptors by the Addition of Outer Side Chains.

Most current highly efficient organic solar cells utilize small molecules like Y6 and its derivatives as electron acceptors in the photoactive layer. In this work, a small molecule acceptor, SC8-IT4F, is developed through outer side chain engineering on the terminal thiophene of a conjugated 6,12-dihydro-dithienoindeno[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophene (IDTT) central core. Compared to the reference molecule C8-IT4F, which lacks outer side chains, SC8-IT4F displays notable differences in molecule geometry (as shown by simulations), thermal behavior, single-crystal packing, and film morphology.

Personal care product use and risk of adult-onset asthma: findings from the Sister Study.

Background: Personal care products (PCPs) contain endocrine-disrupting chemicals (EDCs) linked to hormonally-sensitive diseases. Population studies have found associations between prenatal EDC exposure and childhood asthma; however, few have investigated adult-onset asthma.

Objectives: We investigated the associations between commonly used PCPs and the risk of adult-onset asthma in a prospective cohort study of U.

Hair Straightener Use in Relation to Prevalent and Incident Fibroids in the Sister Study with a Focus on Black Women.

Background: Uterine fibroids disproportionately affect Black women, and exposure to chemicals from hair relaxers or straighteners ("straighteners") may contribute to fibroid development.

Objectives: We examined the association between straightener use and prevalent young-onset uterine fibroids (diagnosed before age 36 y), as well as incident fibroids (diagnosed age 36-60 y), with a focus on Black women. We also examined differences in associations across birth cohorts as proxies for formulation changes.

Probing the Design Rules for Optimizing Electron Spin Relaxation in Densely Packed Triplet Media for Quantum Applications.

Quantum technologies using electron spins have the advantage of employing chemical qubit media with tunable properties. The principal objective of material engineers is to enhance photoexcited spin yields and quantum spin relaxation. In this study, we demonstrate a facile synthetic approach to control spin properties in charge-transfer cocrystals consisting of 1,2,4,5-tetracyanobenzene (TCNB) and acetylated anthracene.

Mixed Resolution-of-the-Identity Compressed Exchange for Hybrid Mixed Deterministic-Stochastic Density Functional Theory from Low to Extreme Temperatures.

Exact exchange contributions included in density functional theory calculations have rendered excellent electronic structure results on both cold and extremely hot matter. In this work, we develop a mixed deterministic-stochastic resolution-of-the-identity compressed exchange (mRICE) method for efficient calculation of exact and hybrid electron exchange, suitable for applications alongside mixed stochastic-deterministic density functional theory. mRICE offers accurate calculations of the electronic structure at a largely reduced computation time compared to other compression algorithms, such as Lin's adaptive compressed exchange, for the warm dense matter.

Parkinson disease-associated toxic exposures selectively upregulate vesicular glutamate transporter vGlut2 in a model of human cortical neurons.

Parkinson disease (PD) is the second most common neurodegenerative disease, characterized by both motor and cognitive features. Motor symptoms primarily involve midbrain dopaminergic neurons, while cognitive dysfunction involves cortical neurons. Environmental factors are important contributors to PD risk.

Harnessing Oxetane and Azetidine Sulfonyl Fluorides for Opportunities in Drug Discovery.

Four-membered heterocycles such as oxetanes and azetidines represent attractive and emergent design options in medicinal chemistry due to their small and polar nature and potential to significantly impact the physiochemical properties of drug molecules. The challenging preparation of these derivatives, especially in a divergent manner, has severely limited their combination with other medicinally and biologically important groups. Consequently, there is a substantial demand for mild and effective synthetic strategies to access new oxetane and azetidine derivatives and molecular scaffolds.

Do blood contamination reduction devices work? A single institution comparison.

We compare two initial specimen diversion devices evaluated over 3 months to investigate their utility in lowering blood culture contamination rates at or below 1%. Overall contamination rates during trial periods were 2.46% and 2.

Synthesis and Functionalization of Sulfoximine-Bicyclo[1.1.0]butanes: Functionalizable, Tuneable and Cysteine-Selective Chiral Warheads.

Electrophilic covalent warheads with appropriate reactivity and selectivity are crucial to the investigation of protein function and the discovery of therapeutics. Here we report the synthesis of sulfoximine bicyclo[1.1.

Age-related loss of intestinal barrier integrity plays an integral role in thymic involution and T cell ageing.

The intestinal epithelium serves as a physical and functional barrier against harmful substances, preventing their entry into the circulation and subsequent induction of a systemic immune response. Gut barrier dysfunction has recently emerged as a feature of ageing linked to declining health, and increased intestinal membrane permeability has been shown to promote heightened systemic inflammation in aged hosts. Concurrent with age-related changes in the gut microbiome, the thymic microenvironment undergoes a series of morphological, phenotypical and architectural alterations with age, including disorganisation of the corticomedullary junction, increased fibrosis, increased thymic adiposity and the accumulation of senescent cells.

Structure confirmation, reactivity, bacterial mutagenicity and quantification of 2,2,4-tribromo-5-hydroxycyclopent-4-ene-1,3-dione in drinking water.

The presence of two new disinfectant by-product (DBP) groups in the UK was recently shown using non-target analysis, halogenated-hydroxycyclopentenediones and halogenated-methanesulfonic acids. In this work, we confirmed the structure of 2,2,4-tribromo-5-hydroxycyclopent-4-ene-1,3-dione (TBHCD), and quantified it together with dibromomethanesulfonic acid at 122 ± 34 and 326 ± 157 ng L on average in London's drinking water, respectively (n = 21). We found TBHCD to be photolabile and unstable in tap water and at alkaline pH.

Growing Evidence for the Role of Air Pollution in Breast Cancer Development.

In the article that accompanies this editorial, Wu et al., observed that residential exposure to fine particulate matter was associated with higher breast cancer incidence using prospective data from over 58,000 California women in the Multiethnic Cohort Study. These findings, together with a meta-analysis of findings from cohort studies included in the manuscript, highlight the importance of environmental contributors to breast cancer risk.

Fortuitous Enantiomeric Self-Rectification of an Unreported Partial Racemisation in the Synthesis of a Chiral Phosphoric Acid: A Warning to Practitioners.

Racemisation without Consequence: MOM deprotection during a routine synthesis of phosphoric acid 1 promoted partial racemisation of the product BINOL 5. Surprisingly, however, after phosphorylation of the partially racemised BINOL, enantiopure acid 1 was isolated. Further inspection revealed that during phosphorylation, unhydrolysed racemic phosphorochloridate 6 precipitated, thus restoring homochirality in the product phosphoric acid 1.

Synthesis of 3,3-Disubstituted Thietane Dioxides.

4-Membered heterocycles have been increasingly exploited in medicinal chemistry and, as small polar motifs, often show important influence on activity and physicochemical properties. Thietane dioxides similarly offer potential in both agricultural and pharmaceutical applications but are notably understudied. Here we report a divergent approach to 3,3-disubstituted thietane dioxide derivatives by forming carbocations on the 4-membered ring with catalytic Lewis or Brønsted acids.

Current immunotherapy techniques in meningioma.

Introduction: Although meningiomas are the most common primary brain tumor, there are limited treatment options for recurrent or aggressive lesions. Compared to other brain tumors, meningiomas may be uniquely amenable to immunotherapy by virtue of their location outside the blood-brain barrier.

Areas Covered: This review describes our current understanding of the immunology of the meninges, as well as immune cell infiltration and immune signaling in meningioma.

Venous Thromboembolism and Prevention Strategies in Patients with Cushing's Disease: A Systematic Review.

Background: There is a well-documented association between Cushing's syndrome (CS) and hypercoagulability. However, there is limited data on the risk of venous thromboembolic events (VTEs) after surgery for Cushing's disease (CD). There is no consensus on optimal postoperative anticoagulation strategies in this group.

First Simultaneous Measurement of Differential Muon-Neutrino Charged-Current Cross Sections on Argon for Final States with and without Protons Using MicroBooNE Data.

We report the first double-differential neutrino-argon cross section measurement made simultaneously for final states with and without protons for the inclusive muon neutrino charged-current interaction channel. The proton kinematics of this channel are further explored with a differential cross section measurement as a function of the leading proton's kinetic energy that extends across the detection threshold. These measurements use data collected with the MicroBooNE detector from 6.

Cross-coupling of CO and an isocyanide mediated by a tetrameric magnesium hydride cluster.

Sequential addition of CNXyl (Xyl = 2,6-dimethylphenyl) and CO to a tetrametallic magnesium hydride cluster results in stepwise reduction and cross-coupling of these substrates. Cross-coupling results in the formation of an ethene amidolate ligand [OC(H)[double bond, length as m-dash]C(H)NAr] a previously unknown entity which contains a 1,2-difunctionalised carbon chain reminiscent of those found in aminoalcohols and amino acids. To the best of our knowledge, this is the first example of such reactivity with metal hydride precursors.

Bioethics and Neurosurgery: An Overview of Existing and Emerging Topics for the Practicing Neurosurgeon.

Neurosurgery is a field with complex ethical issues. In this article, we aim to provide an overview of key and emerging ethical issues in neurosurgery with a focus on issues relevant to practicing neurosurgeons. These issues include those of informed consent, capacity, clinical trials, emerging neurotechnology, innovation, equity and justice, and emerging bioethics areas including community engagement and organizational ethics.

First Search for Dark-Trident Processes Using the MicroBooNE Detector.

We present a first search for dark-trident scattering in a neutrino beam using a dataset corresponding to 7.2×10^{20} protons on target taken with the MicroBooNE detector at Fermilab. Proton interactions in the neutrino target at the main injector produce π^{0} and η mesons, which could decay into dark-matter (DM) particles mediated via a dark photon A^{'}.