Systematic Tuning of Electronic Ground and Excited States in Donor-Acceptor Dyes; Steps toward Designer Compounds for Modern Technologies.

The vibrational and electronic properties of six systematically altered donor-acceptor dyes were investigated with density functional theory (DFT), spectroscopy, and electrochemical techniques. The dyes incorporated a carbazole donor connected to a dithieno[3,2-b:2',3'-d]thiophene linker at either the C () or C () position. Indane-based acceptors contained either dimalononitrile (), ketone and malononitrile () or diketone () electron accepting groups.

Syntheses and crystal structure of a (2,6-diiso-propyldi-naphtho-[2,1-:1',2'-][1,3]dithiepin-4-yl)(phen-yl)methanol atropisomer.

The racemic title compound, CHOS, comprises an atropisomeric binaphthyl di-thio-acetal substituted at the methyl-ene carbon atom with a chiral benzyl alcohol. The two naphthalene ring systems are additionally substituted at the 3,3'-position with isopropyl groups. The overall stereochemistry is defined as and .

Syntheses and crystal structures of two di-naph-tho[2,1-:1',2'-][1,3]dithiepine atropisomers.

The closely related title compounds, 1-(di-naphtho-[2,1-:1',2'-][1,3]dithiepin-4-yl)-2,2-di-methyl-propan-1-ol, CHOS, and 2-(di-naphtho-[2,1-:1',2'-][1,3]dithiepin-4-yl)-3,3-di-methyl-butan-2-ol, CHOS, , both comprise an atrop-isomeric binaphthyl di-thio-acetal unit substituted at the methyl-ene carbon atom with a chiral neopentyl alcohol grouping. The overall stereochemistry of the racemate in each case is defined as and . In , the hydroxyl group generates inversion dimers pairwise inter-molecular O-H⋯S hydrogen bonds whereas in , the O-H⋯S link is intra-molecular.

-Acylated Flavones in the Alpine Daisy : Intraspecific Variation.

Flavonoids acylated on their core phenolic groups are rare. The Aotearoa New Zealand endemic alpine daisy is widespread, but its flavonoids have not previously been identified. Leaf extracts yielded a series of 8--acylated flavones with combinations of 3-methylbutanoate, 2-methylbutanoate, and 2-methylpropanoate groups and one, two, or three -methyls, all previously unreported.

Efficacy and Safety of Novel Beta-Chitin Patches as Haemostat in Rat Vascular and Neurosurgical Model.

Background: Intraoperative hemorrhage is a major cause of poor post-operative outcome. Beta-chitin patch has previously been found to be an effective haemostat, but whether modifying the patch can improve its efficacy and safety, remains unknown. In this study, beta-chitin patches were modified using polyethylene oxide, Pluronic-F127 (Chi/F127), calcium (Chi/20%Ca), increased thickness (Chi/Thick) or polyphosphate (Chi/PP).

Heterotrimetallic Double Cavity Cages: Syntheses and Selective Guest Binding.

A strategy for the generation of heterotrimetallic double cavity (DC) cages [Pd Pt L ] (DC1: n=1, m=2; and DC2: n=2, m=1) is reported. The DC cages were generated by combining an inert platinum(II) tetrapyridylaldehyde complex with a suitably substituted pyridylamine and Pd ions. H and DOSY nuclear magnetic resonance spectroscopy (NMR) and electrospray ionization mass spectrometry (ESIMS) data were consistent with the formation of the DC architectures.

Synthesis, crystal structure and Hirshfeld surface analysis of 1-ferrocenylundecane-1,11-diol.

The racemic title compound, [Fe(CH)(CHO)], comprises an α,ω-diol-substituted undecyl chain with a ferrocenyl substituent at at one terminus. The alkane chain is inclined to the substituted ring of the ferrocene grouping by 84.22 (13)°.

A comparison between β-tricalcium phosphate and chitosan poly-caprolactone-based 3D melt extruded composite scaffolds.

Melt extrusion 3D printing has become an attractive additive manufacturing technology to construct degradable scaffolds as tissue precursors in order to create clinically relevant medical devices. Towards this end, a commonly used synthetic polyester, poly-caprolactone (PCL), was used to make scaffolds composed of different biomaterial compositions to increase bioactivity using 3D melt pneumatic extrusion technology. Varying ratios of the natural biopolymer, chitosan, or the bioceramic, β-tricalcium phosphate (TCP) were blended with PCL to fabricate support scaffolds with three-dimensional (3D) architecture for human bone-marrow derived mesenchymal stem cell (hBMSC) growth for potential bone regeneration application.

The effect of chemical and structural modifiers on the haemostatic process and cytotoxicity of the beta-chitin patch.

Beta-chitin patch has previously been proven to be an effective haemostat, but whether modifying the patch affects its efficacy and safety, remains unanswered. In this study, the patch was modified using polyethylene oxide, Pluronic-F127, calcium, increased thickness or polyphosphate, and their effect on the process of haemostasis and cytotoxicity was tested and compared with standard-of-care, Surgicel and FloSeal. Whole blood collected from volunteers was applied to the patches to test their whole blood clotting and thrombin generation capacities, whilst platelet isolates were used to test their platelet aggregation ability.

6,6'-Ditriphenylamine-2,2'-bipyridine: Coordination Chemistry and Electrochemical and Photophysical Properties.

A 2,2'-bipyridine with bulky triphenylamine substituents in the 6 and 6' positions of the ligand (6,6'-ditriphenylamine-2,2'-bipyridine, 6,6'-diTPAbpy) was generated. Despite the steric bulk, the ligand readily formed bis(homoleptic) complexes with copper(I) and silver(I) ions. Unfortunately, efforts to use the 6,6'-diTPAbpy system to generate heteroleptic [Cu(6,6'-diTPAbpy)(bpy)] complexes were unsuccessful with only the [Cu(6,6'-diTPAbpy)](PF) complex observed.

A novel approach to increasing community capacity for weight management a volunteer-delivered programme (ActWELL) initiated within breast screening clinics: a randomised controlled trial.

Background: It is estimated that around 30% of breast cancers in post-menopausal women are related to lifestyle. The breast cancer-pooling project demonstrated that sustained weight loss of 2 to 4.5 kg is associated with an 18% lower risk of breast cancer, highlighting the importance of small changes in body weight.

Randomised controlled trial of an augmented exercise referral scheme using web-based behavioural support for inactive adults with chronic health conditions: the e-coachER trial.

Objective: To determine whether adding web-based support (e-coachER) to an exercise referral scheme (ERS) increases objectively assessed physical activity (PA).

Design: Multicentre trial with participants randomised to usual ERS alone (control) or usual ERS plus e-coachER (intervention).

Setting: Primary care and ERS in three UK sites from 2015 to 2018.

Adding web-based behavioural support to exercise referral schemes for inactive adults with chronic health conditions: the e-coachER RCT.

Background: There is modest evidence that exercise referral schemes increase physical activity in inactive individuals with chronic health conditions. There is a need to identify additional ways to improve the effects of exercise referral schemes on long-term physical activity.

Objectives: To determine if adding the e-coachER intervention to exercise referral schemes is more clinically effective and cost-effective in increasing physical activity after 1 year than usual exercise referral schemes.

Peptide Chitosan/Dextran Core/Shell Vascularized 3D Constructs for Wound Healing.

Three-dimensional (3D) bioprinting has emerged to create novel cell-based therapies for regenerative medicine applications. Vascularized networks within engineered constructs are required, and toward this end, we report a promising strategy using core-shell (c/s) extrusion 3D-bioprinting technology that employs biomimetic biomaterials to construct regenerative, prevascularized scaffolds for wound care. A custom-designed cell-responsive bioink consisting of a 13% (w/v) cell-laden gelatin methacryloyl (GelMA) shell surrounding a peptide-functionalized, succinylated chitosan (C)/dextran aldehyde (D) cell-laden core was successfully bioprinted resulting in organized microdesigns exhibiting excellent cell viability and subsequent vessel formation.

Optimisation of the ActWELL lifestyle intervention programme for women attending routine NHS breast screening clinics.

Background: Around 30% of post-menopausal breast cancer is related to excess body fat, alcohol intake and low levels of physical activity. Current estimates suggest that there is a 12% increased risk in post-menopausal breast cancer for every 5 kg/m increase in body mass index (BMI). Despite this evidence there are few lifestyle programmes directed towards breast cancer risk reduction.

Excited-State Switching Frustrates the Tuning of Properties in Triphenylamine-Donor-Ligand Rhenium(I) and Platinum(II) Complexes.

The photophysical properties of a series of rhenium(I) tricarbonyl and platinum(II) bis(acetylide) complexes containing a triphenylamine (TPA)-substituted 1,10-phenanthroline ligand have been examined. The complexes possess both metal-to-ligand charge-transfer (MLCT) and intraligand charge-transfer (ILCT) transitions that absorb in the visible region. The relative energies and ordering of the absorbing CT states have been successfully controlled by changing the metal center and modulating the donating ability of the TPA group through the addition of electron-donating methoxy and electron-withdrawing cyano groups.

Tough polymeric hydrogels using ion-pair comonomers.

Hydrogels with excellent mechanical properties were synthesized by radical photo-polymerization of three different types of ion-pair comonomers (IPC), without requiring any chemical cross-linking agent. Insoluble gels formed only at a specific solution concentration range, which was unique to the particular salt. The gels changed properties after one day soaking in water, becoming less stiff and more extendible, but remained stable after that.

The structure and Hirshfeld surface analysis of the salt 3-methacryl-amido-,,-tri-methyl-propan-1-aminium 2-acryl-amido-2-methyl-propane-1-sulfonate.

The title salt, CHNO·CHNOS, comprises a 3-methacryl-amido-,,-tri-methyl-propan-1-aminium cation and a 2-acryl-amido-2-methyl-propane-1-sulfonate anion. The salt crystallizes with two unique cation-anion pairs in the asymmetric unit of the ortho-rhom-bic unit cell. The crystal studied was an inversion twin with a 0.

Structure and Hirshfeld surface analysis of the salt ,,-trimethyl-1-(4-vinyl-phen-yl)methanaminium 4-vinyl-benzene-sulfonate.

In the title compound, the asymmetric unit comprises an ,,-trimethyl-1-(4-vinyl-phen-yl)methanaminium cation and a 4-vinyl-benzene-sulfonate anion, CHN·CHOS. The salt has a polymerizable vinyl group attached to both the cation and the anion. The methanaminium and vinyl substituents on the benzene ring of the cation subtend angles of 86.

Randomised controlled trial to assess the impact of a lifestyle intervention (ActWELL) in women invited to NHS breast screening.

Introduction: In Scotland, the incidence of breast cancer is predicted to rise significantly in the next few decades and while there are measures to support reductions in morbidity and mortality, the breast cancer community is currently exploring preventative opportunities including supporting weight management programmes in postmenopausal women. This study aims to assess the effectiveness and cost-effectiveness of a theory-based, community delivered, minimal contact, weight management (diet, physical activity and behaviour change techniques) programme (ActWELL) in women with a body mass index (BMI) >25 kg/m attending routine breast cancer screening appointments.

Methods And Analysis: The study will be a four-centre, 1:1 parallel group randomised controlled trial of a 12-month weight management intervention initiated in breast cancer screening centres, delivered by trained Breast Cancer Now lifestyle coaches in community settings.

Multicentred randomised controlled trial of an augmented exercise referral scheme using web-based behavioural support in individuals with metabolic, musculoskeletal and mental health conditions: protocol for the e-coachER trial.

Introduction: Physical activity is recommended for improving health among people with common chronic conditions such as obesity, diabetes, hypertension, osteoarthritis and low mood. One approach to promote physical activity is via primary care exercise referral schemes (ERS). However, there is limited support for the effectiveness of ERS for increasing long-term physical activity and additional interventions are needed to help patients overcome barriers to ERS uptake and adherence.