Solvent Effects and Internal Functions Control Molecular Recognition of Neutral Substrates in Functionalized Self-Assembled Cages.

suite of internally functionalized FeL cage complexes has been synthesized with lipophilic end groups to allow dissolution in varied solvent mixtures, and the scope of their molecular recognition of a series of neutral, nonpolar guests has been analyzed. The lipophilic end groups confer cage solubility in solvents with a wide range of polarities, from hexafluoroisopropanol (HFIP) to tetrahydrofuran, and the hosts show micromolar affinities for neutral guests, despite having no flat panels enclosing the cavity. These hosts allow interrogation of the effects of an internal functional group on guest binding properties, as well as solvent-based driving forces for recognition.

Unusually Rapid Isomerization of Aspartic Acid in Tau.

Spontaneous chemical modifications in long-lived proteins can potentially change protein structure in ways that impact proteostasis and cellular health. For example, isomerization of aspartic acid interferes with protein turnover and is anticorrelated with cognitive acuity in Alzheimer's disease. However, few isomerization rates have been determined for Asp residues in intact proteins.

Forensic science capacity development: A case study of Timor-Leste.

Forensic science is socially constructed within particular contexts, with notable challenges for countries of the Global South. This study explored forensic capacity development taking place under a bilateral agreement between the governments of Timor-Leste and Australia through the Timor-Leste Police Development Program. Data were collected through in-country site visits, observations, and interviews with key personnel from both countries.

Chromophore Optimization in Organometallic Au(III) Cys Arylation of Peptides and Proteins for 266 nm Photoactivation.

Cysteine is the most reactive naturally occurring amino acid due to the presence of a free thiol, presenting a tantalizing handle for covalent modification of peptides/proteins. Although many mass spectrometry experiments could benefit from site-specific modification of Cys, the utility of direct arylation has not been thoroughly explored. Recently, Spokoyny and co-workers reported a Au(III) organometallic reagent that robustly arylates Cys and tolerates a wide variety of solvents and conditions.

Assessing Full Stomach Prevalence with Ultrasound Following Preoperative Fasting in Diabetic Patients with Dysautonomia: A Comparative Observational Study.

Background: Traditionally, diabetics have been considered patients with a high risk of aspiration due to having delayed gastric emptying; However, the evidence concerning residual gastric volume (GV) in fasting diabetic patients is inconsistent. This study aimed to compare the fasting GV of diabetic patients with or without dysautonomia with control patients scheduled for elective surgery using gastric ultrasound.

Methods: This bicentric prospective single-blinded case-control study was conducted at 2 university hospitals in Spain.

T-cell Responses to Individualized Neoantigen Therapy mRNA-4157 (V940) Alone or in Combination with Pembrolizumab in the Phase 1 KEYNOTE-603 Study.

mRNA-4157 (V940) is an individualized neoantigen therapy targeting up to 34 patient-specific tumor neoantigens to induce T-cell responses and potentiate antitumor activity. We report mechanistic insights into the immunogenicity of mRNA-4157 via characterization of T-cell responses to neoantigens from the first-in-human, phase 1, KEYNOTE-603 study (NCT03313778) in patients with resected non-small cell lung cancer (Part A: 1-mg mRNA-4157, n = 4) or resected cutaneous melanoma (Part D: 1-mg mRNA-4157 + 200-mg pembrolizumab, n = 12). Safety, tolerability, and immunogenicity were assessed.

Healing the Past by Nurturing the Future: trauma-aware, healing-informed care to improve support for Aboriginal and Torres Strait Islander families - implementation and evaluation study protocol.

Introduction: Complex trauma can have serious impacts on the health and well-being of Aboriginal and Torres Strait Islander families. The perinatal period represents a 'critical window' for recovery and transforming cycles of trauma into cycles of healing. The Healing the Past by Nurturing the Future (HPNF) project aims to implement and evaluate a programme of strategies to improve support for Aboriginal and Torres Strait islander families experiencing complex trauma.

Localizing Isomerized Residue Sites in Peptides with Tandem Mass Spectrometry.

Isomerized amino acid residues have been identified in many peptides extracted from tissues or excretions of humans and animals. These isomerized residues can play key roles by affecting biological activity or by exerting an influence on the process of aging. Isomerization occurs spontaneously and does not result in a mass shift.

A systematic review of the relationship between muscle oxygen dynamics and energy rich phosphates. Can NIRS help?

Background: Phosphocreatine dynamics provide the gold standard evaluation of in-vivo mitochondrial function and is tightly coupled with oxygen availability. Low mitochondrial oxidative capacity has been associated with health issues and low exercise performance.

Methods: To evaluate the relationship between near-infrared spectroscopy-based muscle oxygen dynamics and magnetic resonance spectroscopy-based energy-rich phosphates, a systematic review of the literature related to muscle oxygen dynamics and energy-rich phosphates was conducted.

Concurrent Validity and Reliability of In-Field Vertical Jump Performance Measures on Sand Surfaces.

Wirtz, S, Julian, R, Schmale, R, and Eils, E. Concurrent validity and reliability of in-field vertical jump performance measures on sand surfaces. J Strength Cond Res 38(4): 687-693, 2024-Beach sports, such as handball, volleyball, and soccer, involve dynamic actions, primarily jumps.

Organ-specific characteristics govern the relationship between histone code dynamics and transcriptional reprogramming during nitrogen response in tomato.

Environmental stimuli trigger rapid transcriptional reprogramming of gene networks. These responses occur in the context of the local chromatin landscape, but the contribution of organ-specific dynamic chromatin modifications in responses to external signals remains largely unexplored. We treated tomato seedlings with a supply of nitrate and measured the genome-wide changes of four histone marks, the permissive marks H3K27ac, H3K4me3, and H3K36me3 and repressive mark H3K27me3, in shoots and roots separately, as well as H3K9me2 in shoots.

Understanding the challenges of disaster victim identification: perspectives of Australian forensic practitioners.

Disaster victim identification (DVI) is an important process in the aftermath of disasters to provide answers for the families and communities of victims. Australian forensic practitioners contribute to such processes internationally under difficult post-disaster circumstances. The aim of the study was to better understand the challenges experienced by forensic practitioners in international DVI operations.

Catalytic Inhibition of Base-Mediated Reactivity by a Self-Assembled Metal-Ligand Host.

Spacious M L tetrahedra can act as catalytic inhibitors for base-mediated reactions. Upon adding only 5 % of a self-assembled Fe L cage complex, the conversion of the conjugate addition between ethylcyanoacetate and β-nitrostyrene catalyzed by proton sponge can be reduced from 83 % after 75 mins at ambient temperature to <1 % under identical conditions. The mechanism of the catalytic inhibition is unusual: the octacationic Fe L cage increases the acidity of exogenous water in the acetonitrile reaction solvent by favorably binding the conjugate acid of the basic catalyst.

Fragment Ion Abundance Reveals Information about Structure and Charge Localization in Highly Charged Proteins.

Top-down mass spectrometry (MS) is a versatile tool that has been employed to investigate both protein sequence and structure. Although a variety of different fragmentation methods are available in top-down MS that can potentially yield structural information, quantifying differences between spectra remains challenging. Herein, we show that subtle differences in spectra produced by a variety of fragmentation methods are surprisingly sensitive to protein structure and/or charge localization, even in highly unfolded proteins observed in high charge states.

Improving menstrual health literacy in sport.

Menstrual health represents a state of complete physical, mental, and social well-being in relation to a woman's menstrual cycle. From a health literacy perspective, knowledge acquisition and expertise are dependent upon the degree to which an individual can find, access, understand, critically analyse, and apply health information. Therefore, menstrual health literacy can be used to describe the state of knowledge acquisition and application specific to menstrual health-related issues.

Statistical Framework for Identifying Differences in Similar Mass Spectra: Expanding Possibilities for Isomer Identification.

Isomeric molecules are important analytes in many biological and chemical arenas, yet their similarity poses challenges for many analytical methods, including mass spectrometry (MS). Tandem-MS provides significantly more information about isomers than intact mass analysis, but highly similar fragmentation patterns are common and include cases where no unique / peaks are generated between isomeric pairs. However, even in such situations, differences in peak intensity can exist and potentially contain additional information.

Randomized Phase II Trial of Ficlatuzumab With or Without Cetuximab in Pan-Refractory, Recurrent/Metastatic Head and Neck Cancer.

Purpose: Primary or acquired resistance to cetuximab, an antiepidermal growth factor receptor monoclonal antibody (mAb), minimizes its utility in recurrent/metastatic head and neck squamous cell carcinoma (HNSCC). Aberrant hepatocyte growth factor/cMet pathway activation is an established resistance mechanism. Dual pathway targeting may overcome resistance.

Decoding the Fucose Migration Product during Mass-Spectrometric analysis of Blood Group Epitopes.

Fucose is a signaling carbohydrate that is attached at the end of glycan processing. It is involved in a range of processes, such as the selectin-dependent leukocyte adhesion or pathogen-receptor interactions. Mass-spectrometric techniques, which are commonly used to determine the structure of glycans, frequently show fucose-containing chimeric fragments that obfuscate the analysis.

RDD-HCD Provides Variable Fragmentation Routes Dictated by Radical Stability.

Radical-directed dissociation (RDD) is a fragmentation technique in which a radical created by selective 213/266 nm photodissociation of a carbon-iodine bond is reisolated and collisionally activated. In previous RDD experiments, collisional activation was effected by ion-trap collision-induced dissociation (CID). Higher-energy collisional dissociation (HCD) differs from CID both in terms of how ions are excited and in the number, type, or abundance of fragments that are observed.

A Novel Use of the Exoscope for In-Vivo Microvascular Free Flaps.

Recent innovations in camera and display technologies have created a new potential modus for the microvascular surgeon. An exoscope consists of cameras mounted to a flexible arm that broadcasts the image to a nearby high-definition monitor. This article details the experience using this emerging technology to perform microvascular anastomosis for 46 cases of head and neck free flaps reconstruction.

The Effects of Fixture Congestion on Injury in Professional Male Soccer: A Systematic Review.

Background: Professional soccer teams are often required to compete with ≤ 4 days recovery between matches. Since congested schedules reduce recovery time between matches, players are possibly at an increased injury risk. To date, there are no published systematic reviews on the impact of match congestion on injuries during professional male soccer.

Gated, Selective Anion Exchange in Functionalized Self-Assembled Cage Complexes.

Appending functional groups to the exterior of Zn L self-assembled cages allows gated control of anion binding. While the unfunctionalized cages contain aryl groups in the ligand that can freely rotate, attaching inert functional groups creates a "doorstop", preventing rotation and slowing the guest exchange rate, even though the interiors of the host cavities are identically structured. The effects on anion exchange are subtle and depend on multiple factors, including anion size, the nature of the leaving anion, and the electron-withdrawing ability and steric bulk of the pendant groups.