Bis(stearoyl) Sulfide: A Stable, Odor-Free Sulfur Precursor for High-Efficiency Metal Sulfide Quantum Dot Photovoltaics

The synthesis of metal sulfide nanocrystals is a crucial step in the fabrication of quantum dot (QD) photovoltaics. Control over the QD size during synthesis allows for precise tuning of their optical and electronic properties, making them an appealing choice for electronic applications. This flexibility has led to the implementation of QDs in both highly-efficient single junction solar cells and other optoelectronic devices including photodetectors and transistors. Most commonly, metal sulfide QDs are synthesized using the hot-injection method utilizing a toxic, and air- and moisture-sensitive sulfur source: bis(trimethylsilyl) sulfide ((TMS)2S). Here, bis(stearoyl) sulfide (St2S) is presented as a new type of air-stable sulfur precursor for the synthesis of sulfide-based QDs, which yields uniform, pure, and stable nanocrystals. Photovoltaic devices based on these QDs are equally efficient as those fabricated by (TMS)2S but exhibit enhanced operational stability. These results highlight that St2S can be widely adopted for the synthesis of metal sulfide QDs for a range of optoelectronic applications

Association of systemic inflammation with shock severity, 30-day mortality, and therapy response in patients with cardiogenic shock

Background: Mortality in cardiogenic shock (CS) remains high even when mechanical circulatory support (MCS) restores adequate circulation. To detect a potential contribution of systemic inflammation to shock severity, this study determined associations between C-reactive protein (CRP) concentrations and outcomes in patients with CS. Methods: Unselected, consecutive patients with CS and CRP measurements treated at a single large cardiovascular center between 2009 and 2019 were analyzed. Adjusted regression models were fitted to evaluate the association of CRP with shock severity, 30-day in-hospital mortality and treatment response to MCS. Results: The analysis included 1116 patients [median age: 70 (IQR 58–79) years, 795 (71.3%) male, lactate 4.6 (IQR 2.2–9.5) mmol/l, CRP 17 (IQR 5–71) mg/l]. The cause of CS was acute myocardial infarction in 530 (48%) patients, 648 (58%) patients presented with cardiac arrest. Plasma CRP concentrations were equally distributed across shock severities (SCAI stage B–E). Higher CRP concentrations were associated with 30-day in-hospital mortality (8% relative risk increase per 50 mg/l increase in CRP, range 3–13%; p < 0.001), even after adjustment for CS severity and other potential confounders. Higher CRP concentrations were only associated with higher mortality in patients not treated with MCS [hazard ratio (HR) for CRP > median 1.50; 95%-CI 1.21–1.86; p < 0.001], but not in those treated with MCS (HR for CRP > median 0.92; 95%-CI 0.67–1.26; p = 0.59; p-interaction = 0.01). Conclusion: Elevated CRP concentrations are associated with increased 30-day in-hospital mortality in unselected patients with cardiogenic shock. The use of mechanical circulatory support attenuates this association

Sex differences in lipidomic and bile acid plasma profiles in patients with and without coronary artery disease

Background: Lipids, including phospholipids and bile acids, exert various signaling effects and are thought to contribute to the development of coronary artery disease (CAD). Here, we aimed to compare lipidomic and bile acid profiles in the blood of patients with and without CAD stratified by sex. Methods: From 2015 to 2022, 3,012 patients who underwent coronary angiography were recruited in the INTERCATH cohort. From the overall cohort, subgroups were defined using patient characteristics such as CAD vs. no CAD, 1st vs. 3rd tertile of LDL-c, and female vs. male sex. Hereafter, a matching algorithm based on age, BMI, hypertension status, diabetes mellitus status, smoking status, the Mediterranean diet score, and the intake of statins, triglycerides, HDL-c and hs-CRP in a 1:1 ratio was implemented. Lipidomic analyses of stored blood samples using the Lipidyzer platform (SCIEX) and bile acid analysis using liquid chromatography with tandem mass spectrometry (LC‒MS/MS) were carried out. Results: A total of 177 matched individuals were analyzed; the median ages were 73.5 years (25th and 75th percentile: 64.1, 78.2) and 71.9 years (65.7, 77.2) for females and males with CAD, respectively, and 67.6 years (58.3, 75.3) and 69.2 years (59.8, 76.8) for females and males without CAD, respectively. Further baseline characteristics, including cardiovascular risk factors, were balanced between the groups. Women with CAD had decreased levels of phosphatidylcholine and diacylglycerol, while no differences in bile acid profiles were detected in comparison to those of female patients without CAD. In contrast, in male patients with CAD, decreased concentrations of the secondary bile acid species glycolithocholic and lithocholic acid, as well as altered levels of specific lipids, were detected compared to those in males without CAD. Notably, male patients with low LDL-c and CAD had significantly greater concentrations of various phospholipid species, particularly plasmalogens, compared to those in high LDL-c subgroup. Conclusions: We present hypothesis-generating data on sex-specific lipidomic patterns and bile acid profiles in CAD patients. The data suggest that altered lipid and bile acid composition might contribute to CAD development and/or progression, helping to understand the different disease trajectories of CAD in women and men. Registration: https://clinicaltrials.gov/ct2/show/NCT04936438, Unique identifier: NCT04936438

Sex differences in lipidomic and bile acid plasma profiles in patients with and without coronary artery disease

Background: Lipids, including phospholipids and bile acids, exert various signaling effects and are thought to contribute to the development of coronary artery disease (CAD). Here, we aimed to compare lipidomic and bile acid profiles in the blood of patients with and without CAD stratified by sex. Methods: From 2015 to 2022, 3,012 patients who underwent coronary angiography were recruited in the INTERCATH cohort. From the overall cohort, subgroups were defined using patient characteristics such as CAD vs. no CAD, 1st vs. 3rd tertile of LDL-c, and female vs. male sex. Hereafter, a matching algorithm based on age, BMI, hypertension status, diabetes mellitus status, smoking status, the Mediterranean diet score, and the intake of statins, triglycerides, HDL-c and hs-CRP in a 1:1 ratio was implemented. Lipidomic analyses of stored blood samples using the Lipidyzer platform (SCIEX) and bile acid analysis using liquid chromatography with tandem mass spectrometry (LC‒MS/MS) were carried out. Results: A total of 177 matched individuals were analyzed; the median ages were 73.5 years (25th and 75th percentile: 64.1, 78.2) and 71.9 years (65.7, 77.2) for females and males with CAD, respectively, and 67.6 years (58.3, 75.3) and 69.2 years (59.8, 76.8) for females and males without CAD, respectively. Further baseline characteristics, including cardiovascular risk factors, were balanced between the groups. Women with CAD had decreased levels of phosphatidylcholine and diacylglycerol, while no differences in bile acid profiles were detected in comparison to those of female patients without CAD. In contrast, in male patients with CAD, decreased concentrations of the secondary bile acid species glycolithocholic and lithocholic acid, as well as altered levels of specific lipids, were detected compared to those in males without CAD. Notably, male patients with low LDL-c and CAD had significantly greater concentrations of various phospholipid species, particularly plasmalogens, compared to those in high LDL-c subgroup. Conclusions: We present hypothesis-generating data on sex-specific lipidomic patterns and bile acid profiles in CAD patients. The data suggest that altered lipid and bile acid composition might contribute to CAD development and/or progression, helping to understand the different disease trajectories of CAD in women and men. Registration: https://clinicaltrials.gov/ct2/show/NCT04936438, Unique identifier: NCT04936438

XMM-Newton observation of the Lockman Hole; I. The X-ray Data

We report on the first deep X-ray survey with the XMM-Newton observatory during the performance verification phase. The field of the Lockman Hole, one of the best studied sky areas over a very wide range of wavelengths, has been observed. A total of ~100 ksec good exposure time has been accumulated. Combining the images of the European Photon Imaging Camera (EPIC) detectors we reach a flux limit of 0.31, 1.4 and 2.4 X 10^{-15} erg cm^{-2} s^{-1}, respectively in the 0.5-2, 2-10, and 5-10 keV band. Within an off-axis angle of 10 arcmin we detect 148, 112 and 61 sources, respectively. The log(N)-log(S) relation in the three bands is compared with previous results. In particular in the 5-10 keV band these observations present the deepest X-ray survey ever, about a factor 20 more sensitive than the previous BeppoSAX observations. Using X-ray spectral diagnostics and the set of previously known, spectroscopically identified ROSAT sources in the field, the new sources can be classified. XMM-Newton detects a significant number (~40%) of X-ray sources with hard, probably intrinsically absorbed X-ray spectra, confirming a prediction of the population synthesis models for the X-ray background.Comment: 6 pages, based on the new A&A style file (included), to be published in A&A 365 (2001, special XMM issue), one page contains color image

High-Redshift Quasars Found in Sloan Digital Sky Survey Commissioning Data II: The Spring Equatorial Stripe

This is the second paper in a series aimed at finding high-redshift quasars from five-color (u'g'r'i'z') imaging data taken along the Celestial Equator by the Sloan Digital Sky Survey (SDSS) during its commissioning phase. In this paper, we present 22 high-redshift quasars (z>3.6) discovered from ~250 deg^2 of data in the spring Equatorial Stripe, plus photometry for two previously known high-redshift quasars in the same region of sky. Our success rate of identifying high-redshift quasars is 68%. Five of the newly discovered quasars have redshifts higher than 4.6 (z=4.62, 4.69, 4.70, 4.92 and 5.03). All the quasars have i* < 20.2 with absolute magnitude -28.8 < M_B < -26.1 (h=0.5, q_0=0.5). Several of the quasars show unusual emission and absorption features in their spectra, including an object at z=4.62 without detectable emission lines, and a Broad Absorption Line (BAL) quasar at z=4.92.Comment: 28 pages, AJ in press (Jan 2000), final version with minor changes; high resolution finding charts available at http://www.astro.princeton.edu/~fan/paper/qso2.htm

The variable XMM-Newton spectrum of Markarian 766

The narrow-line Seyfert 1 galaxy Markarian 766 was observed for 60 ks with the XMM-Newton observatory. The source shows a complex X-ray spectrum. The 2-10 keV spectrum can be adequately represented by a power law and broad Fe Ka emission. Between 0.7 and 2 keV the spectrum is harder and exhibits a flux deficit with respect to the extrapolated medium energy slope. Below 0.7 keV, however, there is a strong excess of emission. The RGS spectrum shows an edge-like feature at 0.7 keV; the energy of this feature is inconsistent with that expected for an OVII edge from a warm absorber. Markarian 766 varies by a factor of ~ 2 in overall count rate in the EPIC and RGS instruments on a timescale of a few thousand seconds, while no significant flux changes are observed in the ultraviolet with the OM. The X-ray variability is spectrally dependent with the largest amplitude variability occurring in the 0.4-2 keV band. The spectral variability can be explained by a change in flux and slope of the medium energy continuum emission, superimposed on a less variable (or constant) low energy emission component.Comment: 6 pages, 6 figures, Accepted by A&A for publication in the Special Issue on 1st science with XMM Newto

Peripheral halo-functionalization in [Cu(N^N)(P^P)]+ emitters: influence on the performances of light-emitting electrochemical cells

A series of heteroleptic [Cu(N^N)(P^P)][PF6] complexes is described in which P^P = bis(2-(diphenylphosphino)phenyl)ether (POP) or 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (xantphos) and N^N = 4,4′-diphenyl-6,6′-dimethyl-2,2′-bipyridine substituted in the 4-position of the phenyl groups with atom X (N^N = 1 has X = F, 2 has X = Cl, 3 has X = Br, 4 has X = I; the benchmark N^N ligand with X = H is 5). These complexes have been characterized by multinuclear NMR spectroscopy, mass spectrometry, elemental analyses and cyclic voltammetry; representative single crystal structures are also reported. The solution absorption spectra are characterized by high energy bands (arising from ligand-centred transitions) which are red-shifted on going from X = H to X = I, and a broad metal-to-ligand charge transfer band with λmax in the range 387–395 nm. The ten complexes are yellow emitters in solution and yellow or yellow-orange emitters in the solid-state. For a given N^N ligand, the solution photoluminescence (PL) spectra show no significant change on going from [Cu(N^N)(POP)]+ to [Cu(N^N)(xantphos)]+; introducing the iodo-functionality into the N^N domain leads to a red-shift in λmaxem compared to the complexes with the benchmark N^N ligand 5. In the solid state, [Cu(1)(POP)][PF6] and [Cu(1)(xantphos)][PF6] (fluoro-substituent) exhibit the highest PL quantum yields (74 and 25%, respectively) with values of τ1/2 = 11.1 and 5.8 μs, respectively. Light-emitting electrochemical cells (LECs) with [Cu(N^N)(P^P)][PF6] complexes in the emissive layer have been tested. Using a block-wave pulsed current driving mode, the best performing device employed [Cu(1)(xantphos)]+ and this showed a maximum luminance (Lummax) of 129 cd m−2 and a device lifetime (t1/2) of 54 h; however, the turn-on time (time to reach Lummax) was 4.1 h. Trends in performance data reveal that the introduction of fluoro-groups is beneficial, but that the incorporation of heavier halo-substituents leads to poor devices, probably due to a detrimental effect on charge transport; LECs with the iodo-functionalized N^N ligand 4 failed to show any electroluminescence after 50 h

Proteomics of spatially identified tissues in whole organs

Spatial molecular profiling of complex tissues is essential to investigate cellular function in physiological and pathological states. However, methods for molecular analysis of biological specimens imaged in 3D as a whole are lacking. Here, we present DISCO-MS, a technology combining whole-organ imaging, deep learning-based image analysis, and ultra-high sensitivity mass spectrometry. DISCO-MS yielded qualitative and quantitative proteomics data indistinguishable from uncleared samples in both rodent and human tissues. Using DISCO-MS, we investigated microglia activation locally along axonal tracts after brain injury and revealed known and novel biomarkers. Furthermore, we identified initial individual amyloid-beta plaques in the brains of a young familial Alzheimer’s disease mouse model, characterized the core proteome of these aggregates, and highlighted their compositional heterogeneity. Thus, DISCO-MS enables quantitative, unbiased proteome analysis of target tissues following unbiased imaging of entire organs, providing new diagnostic and therapeutic opportunities for complex diseases, including neurodegeneration

Phosphane tuning in heteroleptic [Cu(N^N)(P^P)]+ complexes for light-emitting electrochemical cells

The synthesis and characterization of five [Cu(P^P)(N^N)][PF6] complexes in which P^P = 2,7-bis(tert-butyl)-4,5-bis(diphenylphosphino)-9,9-dimethylxanthene (tBu2xantphos) or the chiral 4,5-bis(mesitylphenylphosphino)-9,9-dimethylxanthene (xantphosMes2) and N^N = 2,2'-bipyridine (bpy), 6-methyl-2,2'-bipyridine (6-Mebpy) or 6,6'-dimethyl-2,2'-bipyridine (6,6'-Me2bpy) are reported. Single crystal structures of four of the compounds confirm that the copper(I) centre is in a distorted tetrahedral environment. In [Cu(xantphosMes2)(6-Mebpy)][PF6], the 6-Mebpy unit is disordered over two equally populated orientations and this disorder parallels a combination of two dynamic processes which we propose for [Cu(xantphosMes2)(N^N)]+ cations in solution. Density functional theory (DFT) calculations reveal that the energy difference between the two conformers observed in the solid-state structure of [Cu(xantphosMes2)(6-Mebpy)][PF6] differ in energy by only 0.28 kcal mol‒1. Upon excitation into the MLCT region (λexc = 365 nm), the [Cu(P^P)(N^N)][PF6] compounds are yellow to orange emitters. Increasing the number of Me groups in the bpy unit shifts the emission to higher energies, and moves the Cu+/Cu2+ oxidation to higher potentials. Photoluminescence quantum yields (PLQYs) of the compounds are low in solution, but in the solid state, PLQYs of up to 59% (for [Cu(tBu2xantphos)(6,6'-Me2bpy)]+) are observed. Greatly increased excited-state lifetimes at low temperature are consistent with the complexes exhibiting thermally activated delayed fluorescence (TADF). This is supported by the small energy difference calculated between the lowest-energy singlet and triplet excited states (0.17-0.25 eV). The compounds were tested in simple bilayer light-emitting electrochemical cells (LECs). The optoelectronic performances of complexes containing xantphosMes2 were generally lower with respect to those with tBu2-xantphos, which led to bright and efficient devices. The best performing LECs were obtained for the complex [Cu(tBu2xantphos)(6,6'-Me2bpy)][PF6] due to the increased steric hindrance at the N^N ligand resulting in higher PLQY