Expression of 5-HT3 receptors and TTX resistant sodium channels (NaV1.8) on muscle nerve fibers in pain-free humans and patients with chronic myofascial temporomandibular disorders

Background

Previous studies have shown that 5-HT₃-antagonists reduce muscle pain, but there are no studies that have investigated the expression of 5-HT₃-receptors in human muscles. Also, tetrodotoxin resistant voltage gated sodium-channels (Na_V) are involved in peripheral sensitization and found in trigeminal ganglion neurons innervating the rat masseter muscle. This study aimed to investigate the frequency of nerve fibers that express 5-HT_3A-receptors alone and in combination with Na_V1.8 sodium-channels in human muscles and to compare it between healthy pain-free men and women, the pain-free masseter and tibialis anterior muscles, and patients with myofascial temporomandibular disorders (TMD) and pain-free controls.

Methods

Three microbiopsies were obtained from the most bulky part of the tibialis and masseter muscles of seven and six healthy men and seven and six age-matched healthy women, respectively, while traditional open biopsies were obtained from the most painful spot of the masseter of five female patients and from a similar region of the masseter muscle of five healthy, age-matched women. The biopsies were processed by routine immunohistochemical methods. The biopsy sections were incubated with monoclonal antibodies against the specific axonal marker PGP 9.5, and polyclonal antibodies against the 5-HT_3A-receptors and Na_V1.8 sodium-channels.

Results

A similar percentage of nerve fibers in the healthy masseter (85.2%) and tibialis (88.7%) muscles expressed 5-HT_3A-receptors. The expression of Na_V1.8 by 5-HT_3A positive nerve fibers associated with connective tissue was significantly higher than nerve fibers associated with myocytes (P < .001). In the patients, significantly more fibers per section were found with an average of 3.8 ± 3 fibers per section in the masseter muscle compared to 2.7 ± 0.2 in the healthy controls (P = .024). Further, the frequency of nerve fibers that co-expressed Na_V1.8 and 5-HT_3A receptors was significantly higher in patients (42.6%) compared to healthy controls (12.0%) (P < .001).

Conclusions

This study showed that the 5-HT_3A-receptor is highly expressed in human masseter and tibialis muscles and that there are more nerve fibers that express 5-HT_3A-receptors in the masseter of women with myofascial TMD compared to healthy women. These findings indicate that 5-HT₃-receptors might be up-regulated in myofascial TMD and could serve as potential biomarkers of chronic muscle pain.     

Endogenous assessment of chronic myocardial infarction with T1ρ-mapping in patients

Background

Detection of cardiac fibrosis based on endogenous magnetic resonance (MR) characteristics of the myocardium would yield a measurement that can provide quantitative information, is independent of contrast agent concentration, renal function and timing. In ex vivo myocardial infarction (MI) tissue, it has been shown that a significantly higher T_1ρ is found in the MI region, and studies in animal models of chronic MI showed the first in vivo evidence for the ability to detect myocardial fibrosis with native T_1ρ-mapping. In this study we aimed to translate and validate T_1ρ-mapping for endogenous detection of chronic MI in patients.

Methods

We first performed a study in a porcine animal model of chronic MI to validate the implementation of T_1ρ-mapping on a clinical cardiovascular MR scanner and studied the correlation with histology. Subsequently a clinical protocol was developed, to assess the feasibility of scar tissue detection with native T_1ρ-mapping in patients (n = 21) with chronic MI, and correlated with gold standard late gadolinium enhancement (LGE) CMR. Four T_1ρ-weighted images were acquired using a spin-lock preparation pulse with varying duration (0, 13, 27, 45 ms) and an amplitude of 750 Hz, and a T_1ρ-map was calculated. The resulting T_1ρ-maps and LGE images were scored qualitatively for the presence and extent of myocardial scarring using the 17-segment AHA model.

Results

In the animal model (n = 9) a significantly higher T_1ρ relaxation time was found in the infarct region (61 ± 11 ms), compared to healthy remote myocardium (36 ± 4 ms) . In patients a higher T_1ρ relaxation time (79 ± 11 ms) was found in the infarct region than in remote myocardium (54 ± 6 ms). Overlap in the scoring of scar tissue on LGE images and T_1ρ-maps was 74%.

Conclusion

We have shown the feasibility of native T_1ρ-mapping for detection of infarct area in patients with a chronic myocardial infarction. In the near future, improvements on the T_1ρ -mapping sequence could provide a higher sensitivity and specificity. This endogenous method could be an alternative for LGE imaging, and provide additional quantitative information on myocardial tissue characteristics.     

Menthol Enhances an Antiproliferative Activity of 1α,25-Dihydroxyvitamin D3 in LNCaP Cells

1α,25-dihydroxyvitamin D₃ [1α,25(OH)₂D₃], the most active form of vitamin D₃, and its analogues have therapeutic benefits for prostate cancer treatment. However, the development of hypercalcemia is an obstacle to clinical applications of 1α,25(OH)₂D₃ for cancer therapy. In this study, we provide evidence that menthol, a key component of peppermint oil, increases an anti-proliferation activity of 1α,25(OH)₂D₃ in LNCaP prostate cancer cells. We found that menthol per se does not exhibit antiproliferative activity, but it is able to enhance 1α,25(OH)₂D₃-mediated growth inhibition in LNCaP cells. Fluorometric assays using Fura-2 showed that 1α,25(OH)₂D₃ does not induce acute Ca²⁺ response, whereas menthol evokes an increase in [Ca²⁺]_i, which suggests that cross-talks of menthol-induced Ca²⁺ signaling with 1α,25(OH)₂D₃-mediated growth inhibition pathways. In addition, Western blot analysis revealed that 1α,25(OH)₂D₃ and menthol cooperatively modulate the expression of bcl-2 and p21 which provides the insight into the molecular mechanisms underlying the enhanced 1α,25(OH)₂D₃-mediated growth inhibition by menthol. Thus, our findings suggest that menthol may be a useful natural compound to enhance therapeutic effects of 1α,25(OH)₂D₃.     

From inverse sandwich Ta2B7+ and Ta2B8 to spherical trihedral Ta3B12−: prediction of the smallest metallo-borospherene

Transition-metal-doped boron nanoclusters exhibit interesting structures and bonding. Inspired by the experimentally discovered inverse sandwich D_6h Ta₂B₆ and spherical trihedral D_3h La₃B₁₈⁻ and based on extensive first-principles theory calculations, we predict herein the structural transition from perfect di-metal-doped inverse sandwich D_7h Ta₂B₇⁺ (1) and D_8h Ta₂B₈ (2) to tri-metal-doped spherical trihedral D_3h Ta₃B₁₂⁻ (3). As the smallest metallo-borospherene reported to date, Ta₃B₁₂⁻ (3) contains three octa-coordinate Ta atoms as integral parts of the cage surface coordinated in three equivalent η⁸-B₈ rings which share two eclipsed equilateral B₃ triangles on the top and bottom interconnected by three B₂ units on the waist. Detailed orbital and bonding analyses indicate that both Ta₂B₇⁺ (1) and Ta₂B₈ (2) possess σ + π dual aromaticity, while Ta₃B₁₂⁻ (3) is σ + π + δ triply aromatic in nature. The IR, Raman, and UV-vis or photoelectron spectra of the concerned species are computationally simulated to facilitate their future spectroscopic characterizations.

Structural transition from inverse sandwich Ta₂B₇⁺ (1) and Ta₂B₈ (2) with σ + π dual aromaticity to the smallest metallo-borospherene D_3h Ta₃B₁₂⁻ (3) which is σ + π + δ triply aromatic in nature.     

Blocking the A2B adenosine receptor alleviates myocardial damage by inhibiting spleen-derived MDSC mobilisation after acute myocardial infarction

BackgroundMyeloid-derived suppressor cell (MDSC) mobilisation is an important immune event in acute myocardial infarction (AMI). The A_2B adenosine receptor (A_2BAR) plays key role in regulating MDSC function, but its specific involvement in MDSC mobilisation in AMI remains unclear.MethodsIn AMI patients, the circulating MDSC ratio and A_2BAR mRNA expression were measured. A mouse AMI model was established by left anterior descending coronary artery (LADCA) ligation. MDSCs were analysed by FACS and immunofluorescence staining (of heart tissue). A_2BAR mRNA expression was assessed by qRT-PCR. Myocardial injury was detected by HE staining. Myocardial cell apoptosis was analysed by immunohistochemistry. Cardiac systolic function was evaluated by transthoracic echocardiography.ResultsIn AMI patients, the circulating MDSC ratio was increased and positively correlated with A_2BAR mRNA expression (r = 0.86, p < 0.01). In AMI model mice, the percentage of MDSCs was increased in the circulation and infarcted heart and decreased in the spleen. MRS-1754-mediated A_2BAR inhibition decreased the MDSC ratio in the circulation and infarcted heart and prevented the decrease in MDSC number in the spleens of mice with AMI. A_2BAR blockade inhibited myocardial cell apoptosis, alleviated myocardial inflammatory injury, and improved myocardial systolic function in the AMI mouse model. Similar results were found in mice after splenectomy. Additionally, spleen-derived MDSC injection increased the MDSC ratio in the infarcted heart, increased myocardial cell apoptosis, aggravated myocardial injury, and decreased cardiac systolic function in mice with AMI.ConclusionBlocking A_2BAR alleviates myocardial damage and improves myocardial systolic function through inhibition of spleen-derived MDSC mobilisation after AMI.

Key Messages

• Spleen-derived MDSC mobilisation aggravates myocardial inflammatory injury within 24 h of AMI.
• A_2BAR promotes spleen-derived MDSC mobilisation within 24 h of AMI.
• Blocking A_2BAR improves myocardial systolic function through inhibition of spleen-derived MDSC mobilisation.

     

Metal-centered monocyclic carbon wheel clusters with record coordination numbers in planar species

The highest coordination number identified to date in planar species is CN = 10 in metal-centered monocyclic boron wheel clusters D_10h M©B₁₀⁻ (M = Ta and Nb) (Galeev et. al., Angew. Chem. Int. Ed., 2012, 51, 2101). Extensive global minimum searches and first-principles theory calculations performed herein indicate that the experimentally observed LaC₁₃⁺ and LaC₁₄⁺ possess the well-defined global minima of perfect metal-centered monocyclic carbon wheel D_13h La©C₁₃⁺ (1) and slightly off-centered C_2v La©C₁₄⁺ (4) (¹A₁) with record coordination numbers of CN = 13 and 11 in planar structures, respectively, further pushing the boundary of our understanding of chemical structures and bonding. Detailed molecular orbital, nucleus-independent chemical shift, and ring current analyses indicate that D_13h La©C₁₃⁺ (1) is σ + π dually aromatic in nature, with 14 totally delocalized in-plane σ electrons and 14 totally delocalized out-of-plane π electrons each matching the 4N + 2 aromatic rule (N_σ = N_π = 3). Similar σ + π dually aromatic metal-centered monocyclic wheel clusters D_13h Ca©C₁₃ (2), C_13v Ac©C₁₃⁺ (3), C_2v Y©B₆C₆⁺ (5), and C_2v Sc©B₅C₆ (6) have also been obtained with CN = 13, 13, 12, and 11, respectively. The results obtained in this work effectively enrich the chemical structures and bonding patterns of planar hypercoordinated complexes.

First-principle theory calculations reveal record coordination numbers of CN = 13 in D_13h La©C₁₃⁺, CN = 12 in C_2v Y©B₆C₆⁺, and CN = 11 in C_2v Sc©B₅C₆ in planar species, effectively enriching the chemical structures and bonding patterns of planar hypercoordinated complexes.     

High-resolution X-ray diffraction determination of the electron density of 1-(8-PhSC10H6)SS(C10H6SPh-8′)-1′ with the QTAIM approach: evidence for S4 σ(4c–6e) at the naphthalene peri-positions

An extended hypervalent S₄ σ(4c–6e) system was confirmed for the linear ^BS-∗-^AS-∗-^AS-∗-^BS interaction in 1-(8-Ph^BSC₁₀H₆)^AS–^AS(C₁₀H₆^BSPh-8′)-1′ (1) via high-resolution X-ray diffraction determination of electron densities. The presence of bond critical points (BCPs; ∗) on the bond paths confirms the nature and extent of this interaction. The recently developed QTAIM dual functional analysis (QTAIM-DFA) approach was also applied to elucidate the nature of the interaction. Total electron energy densities H_b(r_c) were plotted versus H_b(r_c) − V_b(r_c)/2 for the interaction at the BCPs, where V_b(r_c) represents the potential energy densities at the BCP. The results indicate that although the data for an interaction in the fully optimized structure corresponds to a static nature, the data obtained for the perturbed structures around it represent the dynamic nature of the interaction in QTAIM-DFA. The former classifies the interaction and the latter characterises it. Although ^AS-∗-^AS in 1 is classified by a shared shell interaction and exhibits weak covalent character, ^AS-∗-^BS is characterized as having typical hydrogen-bond nature with covalent properties in the region of the regular closed shell interactions. The experimental results are supported by matching theoretical calculations throughout, particularly for the extended hypervalent E₄ σ(4c–6e) (E = S) interaction.

The nature of S₄ σ(4c–6e) at the 1,8-positions of naphthalene is elucidated via a high-resolution X-ray method with the QTAIM approach.     

Evaluation of a Subject specific dual-transmit approach for improving B1 field homogeneity in cardiovascular magnetic resonance at 3T

Background

Radiofrequency (RF) shading artifacts degrade image quality while performing cardiovascular magnetic resonance (CMR) at higher field strengths. In this article, we sought to evaluate the effect of local RF (B₁ field) shimming by using a dual-source–transmit RF system for cardiac cine imaging and to systematically evaluate the effect of subject body type on the B₁ field with and without local RF shimming.

Methods

We obtained cardiac images from 37 subjects (including 11 patients) by using dual-transmit 3T CMR. B₁ maps with and without subject-specific local RF shimming (exploiting the independent control of transmit amplitude and phase of the 2 RF transmitters) were obtained. Metrics quantifying B₁ field homogeneity were calculated and compared with subject body habitus.

Results

Local RF shimming across the region encompassed by the heart increased the mean flip angle (μ) in that area (88.5 ± 15.2% vs. 81.2 ± 13.3%; P = 0.0014), reduced the B₁ field variation by 42.2 ± 13%, and significantly improved the percentage of voxels closer to μ (39% and 82% more voxels were closer to ± 10% and ± 5% of μ, respectively) when compared with no RF shimming. B₁ homogeneity was independent of subject body type (body surface area [BSA], body mass index [BMI] or anterior-posterior/right-left patient width ratio [AP/RL]). Subject specific RF (B₁) shimming with a dual-transmit system improved local RF homogeneity across all body types.

Conclusion

With or without RF shimming, cardiac B1 field homogeneity does not depend on body type, as characterized by BMI, BSA, and AP/RL. For all body types studied, cardiac B₁ field homogeneity was significantly improved by performing local RF shimming with 2 independent RF-transmit channels. This finding indicates the need for subject-specific RF shimming.     

Impact of motion correction on reproducibility and spatial variability of quantitative myocardial T2 mapping

Background

To evaluate and quantify the impact of a novel image-based motion correction technique in myocardial T₂ mapping in terms of measurement reproducibility and spatial variability.

Methods

Twelve healthy adult subjects were imaged using breath-hold (BH), free breathing (FB), and free breathing with respiratory navigator gating (FB + NAV) myocardial T₂ mapping sequences. Fifty patients referred for clinical CMR were imaged using the FB + NAV sequence. All sequences used a T₂ prepared (T₂prep) steady-state free precession acquisition. In-plane myocardial motion was corrected using an adaptive registration of varying contrast-weighted images for improved tissue characterization (ARCTIC). DICE similarity coefficient (DSC) and myocardial boundary errors (MBE) were measured to quantify the motion estimation accuracy in healthy subjects. T₂ mapping reproducibility and spatial variability were evaluated in healthy subjects using 5 repetitions of the FB + NAV sequence with either 4 or 20 T₂prep echo times (TE). Subjective T₂ map quality was assessed in patients by an experienced reader using a 4-point scale (1-non diagnostic, 4-excellent).

Results

ARCTIC led to increased DSC in BH data (0.85 ± 0.08 vs. 0.90 ± 0.02, p = 0.007), FB data (0.78 ± 0.13 vs. 0.90 ± 0.21, p < 0.001), and FB + NAV data (0.86 ± 0.05 vs. 0.90 ± 0.02, p = 0.002), and reduced MBE in BH data (0.90 ± 0.40 vs. 0.64 ± 0.19 mm, p = 0.005), FB data (1.21 ± 0.65 vs. 0.63 ± 0.10 mm, p < 0.001), and FB + NAV data (0.81 ± 0.21 vs. 0.63 ± 0.08 mm, p < 0.001). Improved reproducibility (4TE: 5.3 ± 2.5 ms vs. 4.0 ± 1.5 ms, p = 0.016; 20TE: 3.9 ± 2.3 ms vs. 2.2 ± 0.5 ms, p = 0.002), reduced spatial variability (4TE: 12.8 ± 3.5 ms vs. 10.3 ± 2.5 ms, p < 0.001; 20TE: 9.7 ± 3.5 ms vs. 7.5 ± 1.4 ms) and improved subjective score of T₂ map quality (3.43 ± 0.79 vs. 3.69 ± 0.55, p < 0.001) were obtained using ARCTIC.

Conclusions

The ARCTIC technique substantially reduces spatial mis-alignment among T₂-weighted images and improves the reproducibility and spatial variability of in-vivo T₂ mapping.     

Perfect cubic La-doped boron clusters La6&[La@B24]+/0 as the embryos of low-dimensional lanthanide boride nanomaterials

La-doped boron nanoclusters have received considerable attention due to their unique structures and bonding. Inspired by recent experimental observations of the inverse sandwich D_8h La₂B₈ (1) and triple-decker C_2v La₃B₁₄⁻ (2) and based on extensive global searches and first-principles theory investigations, we present herein the possibility of the perfect cubic La-doped boron clusters O_h La₆&[La@B₂₄]⁺ (3, ¹A_1g) and O_h La₆&[La@B₂₄] (4, ²A_2g) which appear to be the embryos of the metallic one-dimensional La₁₀B₃₂ (5) nanowire, two-dimensional La₃B₁₀ (6) nanosheet, and three-dimensional LaB₆ (7) nanocrystal, facilitating a bottom-up approach to build cubic lanthanide boride nanostructures from gas-phase clusters. Detailed molecular orbital and bonding analyses indicate that effective (d–p)σ, (d–p)π and (d–p)δ covalent coordination interactions exist in La₆&[La@B₂₄]^+/0 (3/4) clusters, while the 1D La₁₀B₃₂ (5), 2D La₃B₁₀ (6), and 3D LaB₆ (7) crystals exhibit mainly electrostatic interactions between the trivalent La centers and cubic B₂₄ frameworks, with weak but discernible coordination contributions from La (5d) ← B (2p) back-donations. The IR and Raman spectra of La₆&[La@B₂₄]^+/0 (3/4) and band structures of La₁₀B₃₂ (5) and La₃B₁₀ (6) are computationally simulated to facilitate their future characterizations.

Perfect cubic clusters O_h La₆&[La@B₂₄]^+/0 are predicted at first-principles levels to be the embryos of 1D La₁₀B₃₂, 2D La₃B₁₀, and 3D LaB₆ lanthanide boride nanomaterials in a bottom-up approach.     

Strategic tuning of excited-state properties of electroluminescent materials with enhanced hot exciton mixing

Deep blue emitters with excellent stability, high quantum yield and multifunctionality are the major issues for full-color displays. In line with this, new multifunctional, thermally stable blue emitters viz., N-(4-(10-(1-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-1H-phenanthro[9,10-d]imidazol-2-yl)anthracen-9-yl)phenyl)-N-phenylbenzenamine (DPIAPPB) and 2-(10-(9H-carbazol-9-yl)anthracen-9-yl)-1-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-1H-phenanthro[9,10-d]imidazole (CADPPI) with hybridized local charge transfer state (HLCT) and hot exciton properties have been synthesized. These molecules show high photoluminescence quantum yield (Φ_s/f): (DPIAPPB – 0.82/0.70 and CADPPI – 0.91/0.83). The CADPPI based device (EL – 467 nm) shows high efficiencies [η_c – 9.85 cd A⁻¹; η_p – 10.84 lm W⁻¹; η_ex – 4.78% at 2.8 V; CIE (0.15, 0.10)] compared to the DPIAPPB device (EL − 472 nm) [η_c – 6.56 cd A⁻¹; η_p – 6.16 lm W⁻¹; η_ex – 4.15% at 2.8 V with CIE (0.15, 0.12)]. The green device with CADPPI:Ir(ppy)₃ exhibits a maximum L – 59 012 cd m⁻²; η_ex – 16.8%; η_c – 37.3 cd A⁻¹; η_p – 39.8 lm W⁻¹ with CIE (0.30, 0.60) and the red device with CADPPI:Ir(MDQ)₂(acac) shows a maximum L – 43 456 cd m⁻²; η_ex – 21.9%; η_c – 36.0 cd A⁻¹; η_p – 39.6 lm W⁻¹ with CIE (0.64, 0.35).

The CADPPI:Ir(ppy)₃ device exhibits L – 90 12 cd m⁻²; η_ex – 18.8%; η_c − 27.3 cd A⁻¹; η_p – 29.8 lm W⁻¹; CIE (0.30, 0.60).     

The unique sandwich K6Be2B6H6 cluster with a real borozene B6H6 core

Theoretical evidence is reported for a boron-based K₆Be₂B₆H₆ sandwich cluster, showing a perfectly D_6h B₆H₆ ring, being capped by two tetrahedral K₃Be ligands. Due to the comfortable charge transfer, the sandwich is viable in [K₃Be]³⁺[B₆H₆]⁶⁻[BeK₃]³⁺ ionic complex in nature. The [B₆H₆]⁶⁻ core with 6π aromaticity vividly imitates the benzene (C₆H₆), occurring as a real borozene. In contrast, the tetrahedral [K₃Be]³⁺ ligand is 2σ three-dimensional aromatic, acting as the simple superatom. Thus, this complex possesses a collectively three-fold 2σ/6π/2σ aromaticity. The interlaminar interaction is governed by the robust electrostatic attraction. The unique chemical bonding gives rise to interesting dynamic fluxionality.

The fascinating sandwich K₆Be₂B₆H₆ cluster with a real borozene ring, being stabilized collectively by three-fold 2σ/6π/2σ aromaticity.     

Surfactant protein A genetic variants associate with severe respiratory insufficiency in pandemic influenza A virus infection

Introduction

Inherited variability in host immune responses influences susceptibility and outcome of Influenza A virus (IAV) infection, but these factors remain largely unknown. Components of the innate immune response may be crucial in the first days of the infection. The collectins surfactant protein (SP)-A1, -A2, and -D and mannose-binding lectin (MBL) neutralize IAV infectivity, although only SP-A2 can establish an efficient neutralization of poorly glycosylated pandemic IAV strains.

Methods

We studied the role of polymorphic variants at the genes of MBL (MBL2), SP-A1 (SFTPA1), SP-A2 (SFTPA2), and SP-D (SFTPD) in 93 patients with H1N1 pandemic 2009 (H1N1pdm) infection.

Results

Multivariate analysis showed that two frequent SFTPA2 missense alleles (rs1965708-C and rs1059046-A) and the SFTPA2 haplotype 1A⁰ were associated with a need for mechanical ventilation, acute respiratory failure, and acute respiratory distress syndrome. The SFTPA2 haplotype 1A¹ was a protective variant. Kaplan-Meier analysis and Cox regression also showed that diplotypes not containing the 1A¹ haplotype were associated with a significantly shorter time to ICU admission in hospitalized patients. In addition, rs1965708-C (P = 0.0007), rs1059046-A (P = 0.0007), and haplotype 1A⁰ (P = 0.0004) were associated, in a dose-dependent fashion, with lower PaO₂/FiO₂ ratio, whereas haplotype 1A¹ was associated with a higher PaO₂/FiO₂ ratio (P = 0.001).

Conclusions

Our data suggest an effect of genetic variants of SFTPA2 on the severity of H1N1pdm infection and could pave the way for a potential treatment with haplotype-specific (1A¹) SP-A2 for future IAV pandemics.     

Promotional effect of silver nanoparticle embedded Ga–Zr-codoped TiO2 as an alternative anode for efficient blue,green and red PHOLEDs

Efficient blue, green and red phosphorescent OLEDs have been harvested from silver nanoparticles embedded at a glass:Ga–Zr-codoped TiO₂ interface. The embedded silver nanoparticles at the interface removed the non productive hole current and enhanced the efficiencies. The blue emitting device (456 nm) with emissive layer Ir(fni)₃ exhibits a maximum luminance (L) of 40 512 cd m⁻² (ITO – 37 623 cd m⁻²), current efficiency (η_c) of 41.3 cd A⁻¹ (ITO – 40.5 cd A⁻¹) and power efficiency (η_p) of 43.1 lm w⁻¹ (ITO – 39.8 lm w⁻¹) and external quantum efficiency (η_ex) of 19.4% (ITO – 6.9%). A newly fabricated green device based on emissive layer Ir(tfpdni)₂(pic) shows intensified emission at 514 nm, luminance of 46 435 cd m⁻² (ITO – 40 986 cd m⁻²), current efficiency of 49.7 cd A⁻¹ (ITO – 47.3 cd A⁻¹), power efficiency of 48.6 lm w⁻¹ (ITO – 41.4 lm w⁻¹) and external quantum efficiency of 17.5% (ITO – 14.9%). The red device (618 nm) with emissive layer Ir(bbt)₂(acac) shows luminance of 8936 cd m⁻² (ITO – 8043 cd m⁻²), current efficiency of 6.9 cd A⁻¹ (ITO – 4.6 cd A⁻¹), power efficiency of 5.7 lm w⁻¹ (ITO – 4.9 lm w⁻¹) and external quantum efficiency of 9.3% (ITO – 6.9%).

Efficient blue, green and red phosphorescent OLEDs have been harvested from silver nanoparticles embedded at a glass:Ga–Zr-codoped TiO₂ interface.     

Cs2NaGaBr6: a new lead-free and direct band gap halide double perovskite

In this work, we have studied new double perovskite materials, A₂¹⁺B²⁺B³⁺X₆¹⁻, where A₂¹⁺ = Cs, B²⁺ = Li, Na, B³⁺ = Al, Ga, In, and X₆¹⁻. We used the all electron full-potential linearized augmented plane wave (FP-LAPW+lo) method within the framework of density functional theory. We used the mBJ approximation and WC-GGA as exchange–correlation functionals. We optimized the lattice constants with WC-GGA. Band structures were calculated with and without spin–orbit coupling (SOC). Further, band structures for Cs₂LiGaBr₆ and Cs₂NaGaBr₆ were calculated with SOC + mBJ to correct the band gap values with respect to experimental value. We obtained direct bandgaps at Γ-point of 1.966 eV for Cs₂LiGaBr₆ and 1.762 eV for Cs₂NaGaBr₆, which are similar to the parent organic–inorganic perovskite (MAPI) CH₃NH₃PbI₃ (E_g = 1.6 eV). Total and partial density of states were analyzed to understand the orbital contribution of Cs, Na, Li, Ga and Br near the Fermi level. The optical properties in terms of real and imaginary ε, refractive index n, extinction coefficient k, optical conduction σ, absorption I, and reflectivity R were calculated. A study of the elastic and mechanical properties shows that both materials are thermodynamically stable. A stable, direct bandgap and a gap value close to those of MAPI make Cs₂NaGaBr₆ a great competitor in the Pb-free hybrid perovskite solar cells world.

In this work, we have studied new double perovskite materials, A₂¹⁺B²⁺B³⁺X₆¹⁻, where A₂¹⁺ = Cs, B²⁺ = Li, Na, B³⁺ = Al, Ga, In, and X₆¹⁻.     

Donor–acceptor duality of the transition-metal-like B2 core in core–shell-like metallo-borospherenes La3&[B2@B17]− and La3&[B2@B18]−

Transition-metal doping induces dramatic structural changes and leads to earlier planar → tubular → spherical → core–shell-like structural transitions in boron clusters. Inspired by the newly discovered spherical trihedral metallo-borospherene D_3h La₃&B₁₈⁻ (1) (Chen, et al., Nat. Commun., 2020, 11, 2766) and based on extensive first-principles theory calculations, we predict herein the first and smallest core–shell-like metallo-borospherenes C_2v La₃&[B₂@B₁₇]⁻ (2) and D_3h La₃&[B₂@B₁₈]⁻ (3) which contain a transition-metal-like B₂ core at the cage center with unique donor–acceptor duality in La₃&B_n⁻ spherical trihedral shells (n = 17, 18). Detailed energy decomposition and bonding analyses indicate that the B₂ core in these novel complexes serves as a π-donor in the equatorial direction mainly to coordinate three La atoms on the waist and a π/σ-acceptor in the axial direction mainly coordinated by two B₆ triangles on the top and bottom. These highly stable core–shell complexes appear to be spherically aromatic in nature in bonding patterns. The IR, Raman, and photoelectron spectra of 2 and 3 are computationally simulated to facilitate their spectroscopic characterizations.

The smallest core–shell-like metallo-borospherenes C_2v La3&[B₂@B₁₇]⁻ and D_3h La₃&[B₂@B₁₈]⁻ have been predicted at first-principles theory level which contain a transition-metal-like B₂ core with unique donor–acceptor duality.     

Efficient full-colour organic light-emitting diodes based on donor–acceptor electroluminescent materials with a reduced singlet–triplet splitting energy gap

A series of efficient blue-emitting materials, namely, Cz-DPVI, Cz-DMPVI, Cz-DEPVI and TPA-DEPVI, possessing a donor–acceptor architecture with dual carrier transport properties and small singlet–triplet splitting is reported. These compounds exhibit excellent thermal properties with a very high glass-transition temperature (T_g), and thus, a stable uniform thin film was formed during device fabrication. Among the weak donor compounds, specifically, Cz-DPVI, Cz-DMPVI and Cz-DEPVI, the Cz-DEPVI-based device showed the maximum efficiencies (L: 13 955 cd m⁻², η_ex: 4.90%, η_c: 6.0 cd A⁻¹, and η_p: 5.4 lm W⁻¹) with CIE coordinates of (0.15, 0.06) at 2.8 V. The electroluminescent efficiencies of Cz-DEPVI were higher than that of the strong donor TPA-DEPVI-based device (L: 13 856 cd m⁻², η_ex: 4.70%, η_c: 5.7 cd A⁻¹, and η_p: 5.2 lm W⁻¹). Furthermore, these blue emissive materials were used as hosts to construct efficient green and red phosphorescent OLEDs. The green device based on Cz-DEPVI:Ir(ppy)₃ exhibited the maximum L of 8891 cd m⁻², η_ex of 19.3%, η_c of 27.9 cd A⁻¹ and η_p of 33.4 lm W⁻¹ with CIE coordinates of (0.31, 0.60) and the red device based on Cz-DEPVI:Ir(MQ)₂(acac) exhibited the maximum L of 40 565 cd m⁻², η_ex of 19.9%, η_c of 26.0 cd A⁻¹ and η_p of 27.0 lm W⁻¹ with CIE coordinates of (0.64, 0.37).

The Cz-DEPVI device showed high efficiencies of L: 13955 cd m⁻², η_ex: 4.90%, η_c: 6.0 cd A⁻¹, η_p: 5.4 lm W⁻¹ and CIE coordinates of (0.15, 0.06) at 2.8 V.     

Myocardial T1 and T2 mapping at 3?T: reference values,influencing factors and implications

Background

Myocardial T₁ and T₂ mapping using cardiovascular magnetic resonance (CMR) are promising to improve tissue characterization and early disease detection. This study aimed at analyzing the feasibility of T₁ and T₂ mapping at 3 T and providing reference values.

Methods

Sixty healthy volunteers (30 males/females, each 20 from 20–39 years, 40–59 years, 60–80 years) underwent left-ventricular T₁ and T₂ mapping in 3 short-axis slices at 3 T. For T₂ mapping, 3 single-shot steady-state free precession (SSFP) images with different T₂ preparation times were acquired. For T₁ mapping, modified Look-Locker inversion recovery technique with 11 single shot SSFP images was used before and after injection of gadolinium contrast. T₁ and T₂ relaxation times were quantified for each slice and each myocardial segment.

Results

Mean T₂ and T₁ (pre-/post-contrast) times were: 44.1 ms/1157.1 ms/427.3 ms (base), 45.1 ms/1158.7 ms/411.2 ms (middle), 46.9 ms/1180.6 ms/399.7 ms (apex). T₂ and pre-contrast T₁ increased from base to apex, post-contrast T₁ decreased. Relevant inter-subject variability was apparent (scatter factor 1.08/1.05/1.11 for T₂/pre-contrast T₁/post-contrast T₁). T₂ and post-contrast T₁ were influenced by heart rate (p < 0.0001, p = 0.0020), pre-contrast T₁ by age (p < 0.0001). Inter- and intra-observer agreement of T₂ (r = 0.95; r = 0.95) and T₁ (r = 0.91; r = 0.93) were high. T₂ maps: 97.7% of all segments were diagnostic and 2.3% were excluded (susceptibility artifact). T₁ maps (pre-/post-contrast): 91.6%/93.9% were diagnostic, 8.4%/6.1% were excluded (predominantly susceptibility artifact 7.7%/3.2%).

Conclusions

Myocardial T₂ and T₁ reference values for the specific CMR setting are provided. The diagnostic impact of the high inter-subject variability of T₂ and T₁ relaxation times requires further investigation.     

Structure characterization and anticoagulant activity of a novel polysaccharide from Leonurus artemisia (Laur.) S. Y. Hu F

An acidic polysaccharide, named LAP-1, was extracted and isolated from Leonurus artemisia (Laur.), and was further purified with ion exchange chromatography and gel chromatography. The extraction conditions of the crude polysaccharides were optimized by single-factor experiments and response surface methodology. The primary structure of the purified polysaccharide was measured by FT-IR, GC-MS, and NMR. The results showed that LAP-1 was mainly composed of galacturonic acid (GalA), mannose (Man), xylose (Xyl), rhamnose (Rha), arabinose (Ara), glucose (Glc), galactose (Gal), fucose (Fuc), ribose (Rib), and glucuronic acid (GlcA) in the molar ratio of 8.74 : 3.45 : 1.02 : 1 : 2.11 : 5.60 : 4.73 : 1.08 : 1.09 : 1.47. Primary structure analysis results indicated that LAP-1 contained characteristic glycosyl linkages such as →1)-α-d-Manp, →1)-α-d-Glcp, →1)-α-d-Arap-(2→, →1)-β-d-Galp-(3→, →1)-β-d-Manp-(4→, →1)-β-d-Galp-(4→, →1)-β-d-Glcp-(4→, →1)-β-d-GalAp-(4→, →1)-β-d-GlcAp-(4→, →1)-β-d-Manp-(4,6→, →1)-β-d-Manp-(3,4→. The M_w/M_n (PDI), M_n, M_z and M_w of LAP-1 were determined to be 1.423, 6.979 × 10³ g mol⁻¹, 1.409 × 10⁴ g mol⁻¹, and 9.930 × 10³ g mol⁻¹ by HPSEC-MALLS-RID and DLS. SEM, TEM and AFM results indicated that LAP-1 was a highly branched structure. LAP-1 showed mild anticoagulant activity, low toxicity, and less spontaneous bleeding compared with heparin sodium. These results demonstrated the effective coagulation activity of Leonurus artemisia polysaccharides. Thus, the purified LAP-1 could be explored as a promising anticoagulant agent for the treatment of coagulation disorders.

An acidic polysaccharide, denoted LAP-1 was extracted, isolated and purified from Leonurus artemisia (Laur.), in addition to its structure and anticoagulant activity were explored.