A study of dye anchoring points in half-squarylium dyes for dye-sensitized solar cells

This paper reports the synthesis of a series of new half-squaraine dyes (Hf-SQ) based around a common chromophoric unit consisting of linked indoline and squaric acid moieties. Carboxylate groups have been incorporated onto this core structure at four different points to study the influence of the anchoring group position on dye-sensitized solar cell (DSC) device performance. Dyes have been linked to TiO2 directly through the squaric acid moiety, through a modified squaric acid unit where a vinyl dicyano group has replaced one carbonyl, via an alkyl carboxylate attached to the indole N or through a carboxylate attached to the 4 position of a benzyl indole. Contact angle measurements have been studied to investigate the hydrophobic/hydrophilic properties of the dyes and the results have been compared to N719 and Z907. Full characterization data of all the dyes and synthetic intermediates are reported including single-crystal X-ray structural analysis for dye precursors; the indole (2a) and the half-squarylium esters (3a) and (6b), as well as the dyes (4c), (8) and (12). Dye colours range from yellow to red/brown in solution (λmax range from 430 to 476 nm) with ε ranging from 38 000 to 133 100 M−1 cm−1. The performance of the dyes in DSCs shows the highest efficiency yet reported for a Hf-SQ dye (η = 5.0%) for 1 cm2 devices with a spectral response ranging from 400 to 700 nm depending on the dye substituents. Co-sensitization of half-squarylium dye (7b) with squaraine dye (SQ2) resulted in a broader spectral response and an improved device efficiency (η = 6.1%). Density functional theory (DFT) calculations and cyclic voltammetry have been used to study the influence of linker position on dye HOMO–LUMO levels and the data has been correlated with I–V and EQE data

Epidermal Notch1 recruits RORγ+ group 3 innate lymphoid cells to orchestrate normal skin repair

Notch has a well-defined role in controlling cell fate decisions in the embryo and the adult epidermis and immune systems, yet emerging evidence suggests Notch also directs non-cell-autonomous signalling in adult tissues. Here, we show that Notch1 works as a damage response signal. Epidermal Notch induces recruitment of immune cell subsets including RORγ + ILC3s into wounded dermis; RORγ + ILC3s are potent sources of IL17F in wounds and control immunological and epidermal cell responses. Mice deficient for RORγ + ILC3s heal wounds poorly resulting from delayed epidermal proliferation and macrophage recruitment in a CCL3-dependent process. Notch1 upregulates TNFα and the ILC3 recruitment chemokines CCL20 and CXCL13. TNFα, as a Notch1 effector, directs ILC3 localization and rates of wound healing. Altogether these findings suggest that Notch is a key stress/injury signal in skin epithelium driving innate immune cell recruitment and normal skin tissue repair

Para-infectious brain injury in COVID-19 persists at follow-up despite attenuated cytokine and autoantibody responses

To understand neurological complications of COVID-19 better both acutely and for recovery, we measured markers of brain injury, inflammatory mediators, and autoantibodies in 203 hospitalised participants; 111 with acute sera (1–11 days post-admission) and 92 convalescent sera (56 with COVID-19-associated neurological diagnoses). Here we show that compared to 60 uninfected controls, tTau, GFAP, NfL, and UCH-L1 are increased with COVID-19 infection at acute timepoints and NfL and GFAP are significantly higher in participants with neurological complications. Inflammatory mediators (IL-6, IL-12p40, HGF, M-CSF, CCL2, and IL-1RA) are associated with both altered consciousness and markers of brain injury. Autoantibodies are more common in COVID-19 than controls and some (including against MYL7, UCH-L1, and GRIN3B) are more frequent with altered consciousness. Additionally, convalescent participants with neurological complications show elevated GFAP and NfL, unrelated to attenuated systemic inflammatory mediators and to autoantibody responses. Overall, neurological complications of COVID-19 are associated with evidence of neuroglial injury in both acute and late disease and these correlate with dysregulated innate and adaptive immune responses acutely

Whole-genome sequencing reveals host factors underlying critical COVID-19

Critical COVID-19 is caused by immune-mediated inflammatory lung injury. Host genetic variation influences the development of illness requiring critical care1 or hospitalization2,3,4 after infection with SARS-CoV-2. The GenOMICC (Genetics of Mortality in Critical Care) study enables the comparison of genomes from individuals who are critically ill with those of population controls to find underlying disease mechanisms. Here we use whole-genome sequencing in 7,491 critically ill individuals compared with 48,400 controls to discover and replicate 23 independent variants that significantly predispose to critical COVID-19. We identify 16 new independent associations, including variants within genes that are involved in interferon signalling (IL10RB and PLSCR1), leucocyte differentiation (BCL11A) and blood-type antigen secretor status (FUT2). Using transcriptome-wide association and colocalization to infer the effect of gene expression on disease severity, we find evidence that implicates multiple genes—including reduced expression of a membrane flippase (ATP11A), and increased expression of a mucin (MUC1)—in critical disease. Mendelian randomization provides evidence in support of causal roles for myeloid cell adhesion molecules (SELE, ICAM5 and CD209) and the coagulation factor F8, all of which are potentially druggable targets. Our results are broadly consistent with a multi-component model of COVID-19 pathophysiology, in which at least two distinct mechanisms can predispose to life-threatening disease: failure to control viral replication; or an enhanced tendency towards pulmonary inflammation and intravascular coagulation. We show that comparison between cases of critical illness and population controls is highly efficient for the detection of therapeutically relevant mechanisms of disease

Simulation Studies of the Latency Measures of Components of Event-Related Brain Potentials

We compared the accuracy of P300 latency estimates obtained with different procedures under several simulated signal and noise conditions. Both preparatory and signal detection techniques were used. Preparatory techniques included frequency filters and spatial filters (single electrode selection and Vector filter). Signal detection techniques included peak‐picking, cross‐correlation, and Woody filter. Accuracy in the latency estimation increased exponentially as a function of the signal‐to‐noise ratio. Both Woody filter and cross‐correlation provided better estimates than peak‐picking, although this advantage was reduced by frequency filtering. For all signal detection techniques, Vector filter provided better estimates than single electrode selection. Large component overlap impaired the accuracy of the estimates obtained with both single electrode selection and Vector filter, but with Vector filter impairment occurred only when the overlapping component had a scalp distribution that was similar to the scalp distribution of the signal component. The effects of varying noise characteristics, P300 duration and latency, and the parameters of Vector filter were also investigated

Multiple linker half-squarylium dyes for dye-sensitized solar cells; are two linkers better than one?

The synthesis and full characterization of new half-squaraine dyes (Hf-SQ) containing two or three carboxylate-based linker units is reported and these dyes tested in dye-sensitized solar cell (DSC) devices. The data show improved device efficiency for a Hf-SQ dye with two linkers (η = 5.5%) compared to the highest efficiency Hf-SQ previously reported which had only a single linker (η = 5.0%); this is mainly due to improved Voc. To understand the effects of using multiple dye linker groups, device I–V data have been correlated with single crystal X-ray structural analysis and dye electrical properties (both in solution and adsorbed to TiO2) using UV-visible and ATR-IR spectroscopy along with cyclic voltammetry, and also theoretical studies using density functional theory (DFT) calculations. These data show that positioning the linkers near the dye LUMO and so that this enables complete linker chemisorption are key factors for device performance