Characterizing X-Ray and Solution State Conformations for a Model Qubit System: {CrNi} Ring Rotaxanes on a Mixed Metal Triangle.

The synthesis of a series of [4]rotaxanes, each consisting of three [2]rotaxanes joined via a central {CrNi} triangular linker, is reported. The resultant four [4]rotaxanes were characterized by single crystal X-ray diffraction and electron paramagnetic resonance (EPR) spectroscopy. Orientation-selective 4-pulse double electron-electron resonance (DEER) measurements between the three {CrNi} rings incorporated in each [4]rotaxane reveal that each system is conformationally fluxional in solution, with the most abundant conformations found to differ significantly from the crystal structure geometry for each compound.

Weak Exchange Interactions in Multispin Systems: EPR Studies of Metalloporphyrins Decorated with {CrNi} Rings.

Both metalloporphyrins and heterometallic {CrNi} rings are of significant research interest due to their proposed roles in quantum information processing devices. In this study, we present a series of complexes in which [CrNiF(Etglu)(OCBu)] (-EtgluH = -ethyl-dglucamine) heterometallic rings are coordinated to metalloporphyrin linkers: the symmetric [M(TPyP)] for M = Cu, VO, and HTPyP = 5,10,15,20-tetra(4-pyridyl)porphyrin; and the asymmetric [{VO}(TrPPyP)] for H(TrPPyP) = 5,10,15-(triphenyl)-20-(4-pyridyl)porphyrin. The magnetic interactions present in these complexes are unraveled using the continuous wave (CW) electron paramagnetic resonance (EPR) technique.

Two- and Three-Spin Hybrid Inorganic-Organic [2]Rotaxanes Containing Metallated Salen Groups.

Mono- and bis-salen functionalised [2]rotaxanes have been synthesised from the esterification of [2]rotaxanes containing phenol-terminated threads (salen=N,N'-bis(salicylidene)ethylenediamine). The [2]rotaxanes have general formula [RH][CrNiF(OCBu)], where [RH] is a thread with a central secondary ammonium site that templates a [CrNiF(OCBu)] ring. The threads are terminated at one or both ends by carboxylic acid functionalised salen groups.

A ring of rotaxanes: studies of a large paramagnetic assembly in solution.

Here we report the synthesis and structural characterization of four [7]rotaxanes formed by coordinating hybrid inorganic-organic [2]rotaxanes to a central {Ni} core. X-ray single crystal diffraction demonstrate that [7]rotaxanes are formed, with a range of conformations in the crystal. Small angle X-ray scattering supported by molecular dynamic simulations demonstrates that the large molecules are stable in solution and also show that the conformers present in solution are not those found in the crystal.

Correction: Synthesis and characterization of heterometallic rings templated through alkylammonium or imidazolium cations.

Correction for 'Synthesis and characterization of heterometallic rings templated through alkylammonium or imidazolium cations' by Rajeh Alotaibi , , 2023, , 7473-7481, https://doi.org/10.1039/D3DT00982C.

Control and Transferability of Magnetic Interactions in Supramolecular Structures: Trimers of {Cr Ni} Antiferromagnetic Rings.

A synthetic strategy is demonstrated to prepare two distinct trimers of antiferromagnetically coupled {Cr Ni} rings, substantially varying the magnetic interactions between the spin centres. The interactions were studied using multi-frequency cw EPR: in a trimer linked via non-covalent H-bonding interactions no measurable interaction between rings was seen, while in a trimer linked via iso-nicotinate groups isotropic and anisotropic exchange interactions of +0.42 and -0.

Synthesis and characterization of heterometallic rings templated through alkylammonium or imidazolium cations.

We report the synthesis and structural characterization of a series of heterometallic rings templated alkylammonium or imidazolium cations. The template and preference of each metal's coordination geometry can control the structure of heterometallic compounds, leading to octa-, nona-, deca-, dodeca-, and tetradeca-metallic rings. The compounds were characterized by single-crystal X-ray diffraction, elemental analysis, magnetometry, and EPR measurements.

How do we differentiate not demonise - Is there a role for healthier processed foods in an age of food insecurity? Proceedings of a roundtable event.

The 'ultra-processed food' (UPF) concept, with classification of foods by 'level of processing' rather than nutrient profiles, and its relationship with health outcomes, is currently a topic of debate among academics and increasingly referred to in the media. The British Nutrition Foundation convened a virtual roundtable on 6th July 2022 to gather views on the use of the term (and current definitions of) UPF for public health messaging, seeking to establish areas of consensus and disagreement and identify topics for further research. A small group of invited expert stakeholders attended, including representatives from academia, policy, behavioural science, communications, health, food science, retail and consumer interests.

A vein bypass first versus a best endovascular treatment first revascularisation strategy for patients with chronic limb threatening ischaemia who required an infra-popliteal, with or without an additional more proximal infra-inguinal revascularisation procedure to restore limb perfusion (BASIL-2): an open-label, randomised, multicentre, phase 3 trial.

Background: Chronic limb-threatening ischaemia is the severest manifestation of peripheral arterial disease and presents with ischaemic pain at rest or tissue loss (ulceration, gangrene, or both), or both. We compared the effectiveness of a vein bypass first with a best endovascular treatment first revascularisation strategy in terms of preventing major amputation and death in patients with chronic limb threatening ischaemia who required an infra-popliteal, with or without an additional more proximal infra-inguinal, revascularisation procedure to restore limb perfusion.

Methods: Bypass versus Angioplasty for Severe Ischaemia of the Leg (BASIL)-2 was an open-label, pragmatic, multicentre, phase 3, randomised trial done at 41 vascular surgery units in the UK (n=39), Sweden (n=1), and Denmark (n=1).

Decorating polymer beads with 10 inorganic-organic [2]rotaxanes as shown by spin counting.

Polymer beads have been used as the core of magnetic particles for around twenty years. Here we report studies to attach polymetallic complexes to polymer beads for the first time, producing beads of around 115 microns diameter that are attached to 10 hybrid inorganic-organic [2]rotaxanes. The bead is then formally a [10] rotaxane.

Templating metallocycles with a macrocycle: synthesis, structures and magnetic studies of {CrM} complexes.

Addition of 1,4,8,11-tetrazacyclotetradecane (cyclam) to a reaction that produces octametallic rings when simpler amines are used, produces {CrM} "pretzels" (M = Zn or Cu) where the cyclam coordinates to the M ion which then sits at the centre of a twelve-metal macrocycle. Magnetic studies were fitted using the finite-temperature Lanczos method (FTLM), and the results demonstrate that exchange interactions are transferable from previous exchange-coupled Cr rings.

Five-Spin Supramolecule for Simulating Quantum Decoherence of Bell States.

We report a supramolecule that contains five spins of two different types and with, crucially, two different and predictable interaction energies between the spins. The supramolecule is characterized, and the interaction energies are demonstrated by electron paramagnetic resonance (EPR) spectroscopy. Based on the measured parameters, we propose experiments that would allow this designed supramolecule to be used to simulate quantum decoherence in maximally entangled Bell states that could be used in quantum teleportation.

Walnut consumption and health outcomes with public health relevance-a systematic review of cohort studies and randomized controlled trials published from 2017 to present.

Context: Considering the accumulation of recent studies investigating the health effects of walnut consumption, both including and beyond cardiovascular health effects, a systematic review of this literature to investigate the strength of the evidence is warranted.

Objective: To investigate associations between walnut consumption and outcomes with public health relevance (specifically all-cause mortality, type 2 diabetes, CVD, metabolic syndrome, obesity, cancer, neurological and mental health, musculoskeletal, gastrointestinal, and maternal disorders) and the effect on associated disease risk markers, reported in studies published from 2017 to present.

Data Sources: MEDLINE, FSTA, CENTRAL, and Scopus were searched from 1 January 2017 to 5 May 2021.

Targeting molecular quantum memory with embedded error correction.

The implementation of a quantum computer requires both to protect information from environmental noise and to implement quantum operations efficiently. Achieving this by a fully fault-tolerant platform, in which quantum gates are implemented within quantum-error corrected units, poses stringent requirements on the coherence and control of such hardware. A more feasible architecture could consist of connected memories, that support error-correction by enhancing coherence, and processing units, that ensure fast manipulations.

Gold(i) bridged dimeric and trimeric heterometallic {CrNi}-based qubit systems and their characterization.

Gold(i) bridged dimeric and trimeric structures of a ground state spin S = 1/2 heterometallic {CrNi} wheel have been prepared and studied by continuous wave (CW) and pulsed wave EPR spectrometry. The {CrNi} relaxation time constants (T and T) show rates matching well with previous observations. Four pulse Double Electron Resonance (DEER) studies suggest presence of more than one conformations.

The Synthesis and Characterisation of a Molecular Sea-Serpent: Studies of a {Cr Cu } Chain.

A finite chain of thirty-one paramagnetic centers is reported, synthesized by reaction of hydrated chromium fluoride, copper carbonate and pivalic acid in the presence of 1,4,7,10-tetrazacyclododecane (cyclen). Magnetic studies show predominantly anti-ferromagnetic exchange leading to a high density of low-lying spin states and large saturation field.

We will remember them: The Canadian Armed Forces's Casualty Identification Program.

The 2003 discovery of two sets of human skeletal remains of Canadian soldiers killed in action during the First World War revitalized the Canadian Armed Forces's responsibility for identifying and burying its war dead from the First and Second World Wars. In 2007, the Casualty Identification Program was formally established with a mandate of identifying newly discovered remains of Canadian soldiers and airmen. The Program is now also responsible for adjudicating research into identifying remains previously interred as an "unknown" soldier or airman.

The role of probiotics on the roadmap to a healthy microbiota: a symposium report.

The ninth International Yakult Symposium was held in Ghent, Belgium in April 2018. Keynote lectures were from Professor Wijmenga on using biobanks to understand the relationship between the gut microbiota and health; and Professor Hill on phage-probiotic interactions. Session one included talks from Professor Plӧsch on epigenetic programming by nutritional and environmental factors; Professor Wilmes on the use of "omics" methodologies in microbiome research and Professor Rescigno on the gut vascular barrier.

Conformational Flexibility of Hybrid [3]- and [4]-Rotaxanes.

The synthesis, structures, and properties of [4]- and [3]-rotaxane complexes are reported where [2]-rotaxanes, formed from heterometallic {CrNi} rings, are bound to a fluoride-centered {CrNi} triangle. The compounds have been characterized by single-crystal X-ray diffraction and have the formulas [CrNi(F)(OCBu)]{(H)[CrNiF(OCBu)]} () and [CrNi(F)(OCBu)(THF)]{(H)[CrNiF(OCBu)]} (), where = py-CHCHNHCHCHSCH. The [4]-rotaxane is an isosceles triangle of three [2]-rotaxanes bound to the central triangle while the [3]-rotaxane contains only two [2]-rotaxanes bound to the central triangle.

Close Encounters of the Weak Kind: Investigations of Electron-Electron Interactions between Dissimilar Spins in Hybrid Rotaxanes.

We report a family of hybrid [2]rotaxanes based on inorganic [CrNiF(OCBu)] ("{CrNi}") rings templated about organic threads that are terminated at one end with pyridyl groups. These rotaxanes can be coordinated to [Cu(hfac)] (where Hhfac = 1,1,1,5,5,5-hexafluoroacetylacetone), to give 1:1 or 1:2 Cu:{CrNi} adducts: {[Cu(hfac)](py-CHNHCHCHPh)[CrNiF(OCBu)]}, {[Cu(hfac)][py-CHNHCHCH][CrNiF(OCBu)]}, {[Cu(hfac)]([py-CHCHNHCHCHSCH][CrNiF(OCBu)])}, {[Cu(hfac)]([py-CH-CHNH(CH)Ph][CrNiF(OCBu)])}, and {[Cu(hfac)]([3-py-CHCHNH(CH)SCH][CrNiF(OCBu)])}, the structures of which have been determined by X-ray diffraction. The {CrNi} rings and Cu ions both have electronic spin = 1/2, but with very different -values.

Hybrid Organic-Inorganic Rotaxanes, Including a Hetero-Hybrid [3]Rotaxane Featuring Two Distinct Heterometallic Rings and a Molecular Shuttle.

[2] and [3] hybrid rotaxanes are reported based on {Ti M} rings (M is a trivalent metal such as Fe or Ga ). NMR studies show that [2]rotaxanes can act as molecular shuttles, while EPR studies of [3]rotaxanes show weak interactions between the paramagnetic components of the supramolecular assemblies.

Structural Characterization of Lithium and Sodium Bulky Bis(silyl)amide Complexes.

Alkali metal amides are vital reagents in synthetic chemistry and the bis(silyl)amide {N(SiMe₃)₂} (N′′) is one of the most widely-utilized examples. Given that N′′ has provided landmark complexes, we have investigated synthetic routes to lithium and sodium bis(silyl)amides with increased steric bulk to analyse the effects of R-group substitution on structural features. To perform this study, the bulky bis(silyl)amines {HN(SiBuMe₂)(SiMe₃)}, {HN(SiPr₃)(SiMe₃)}, {HN(SiBuMe₂)₂}, {HN(SiPr₃)(SiBuMe₂)} and {HN(SiPr₃)₂} () were prepared by literature procedures as colourless oils; on one occasion crystals of were obtained.

Apolipoprotein E (epsilon) genotype has a greater impact on apoB-48 than apoB-100 responses to dietary fat manipulation-insights from the SATgenε study.

Scope: To determine the contribution of intestinally and liver-derived lipoproteins to the postprandial plasma triacylglycerol (TAG) response in APOE3/E3 and E3/E4 individuals following chronic dietary fat manipulation.

Methods And Results: In sequential order, participants (n = 12 E3/E3, n = 11 E3/E4) followed low fat; high-fat, high-saturated fat (HSF); and HSF with 3.45 g/day docosahexaenoic acid (HSF-DHA) diets, each for 8 weeks.