Evaluation of the Expression of Infection-Related Long Noncoding RNAs among COVID-19 Patients: A Case-Control Study.

Background and Aims: Severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2), a worldwide pandemic, activates signaling cascades and leads to innate immune responses and secretion of multiple chemokines and cytokines. Long noncoding RNAs (lncRNAs) have a crucial role in inflammatory pathways. Through our search on the PubMed database, we discovered that existing research has primarily focused on examining the regulatory impacts of five lncRNAs in the context of viral infections. However, their role in regulating other conditions, including SARS-CoV-2, has not been explored. Therefore, this study aimed to investigate the expression pattern of lncRNAs in the peripheral blood mononuclear cells (PBMC) and their potential roles in SARS-CoV-2 infection. Potentially significant competing endogenous RNA (ceRNA) networks of these five lncRNAs were found using online in-silico techniques. Methods: Ethylenediaminetetraacetic acid (EDTA) blood samples of the control group consisted of 45 healthy people, and a total of 53 COVID-19-infected patients in case group, with a written informed consent, was collected. PBMCs were extracted, and then, the RNA extraction and complementary DNA (cDNA) synthesis was performed. The expression of five lncRNAs (lnc ISR, lnc ATV, lnc PAAN, lnc SG20, and lnc HEAL) was assessed by real-time PCR. In order to evaluate the biomarker roles of genes, receiver operating characteristic (ROC) curve was drawn. Results: Twenty-four (53.3%) and 29 (54.7%) of healthy and COVID-19-infected participants were male, respectively. The most prevalent symptoms were as follows: cough, general weakness, contusion, headache, and sore throat. The results showed that three lncRNAs, including lnc ISR, lnc ATV, and lnc HEAL, were expressed dramatically higher in the case group compared to healthy controls. According to ROC curve analysis, lnc ATV has a higher AUC and is a better biomarker to differentiate COVID-19 patients from the healthy controls. Then, using bioinformatics methods, the ceRNA network of these lncRNAs enabled the identification of mRNAs and miRNAs with crucial functions in COVID-19. Conclusion: The considerable higher expression of ISR, ATV, and HEAL lncRNAs and the significant area under curve (AUC) in ROC curve demonstrate that these RNAs probably have a potential role in controlling the host innate immune responses and regulate the viral replication of SARS-CoV-2. However, these assumptions need further in vitro and in vivo investigations to be confirmed.

Evaluation of S100A12 and Apo-A1 plasma level potency in untreated new relapsing-remitting multiple sclerosis patients and their family members.

Multiple sclerosis is an inflammatory disease of the spinal cord and brain. Receptor for advanced glycation end products and Apolipoprotein A1 (Apo-AI) have been recommended to have a pathogenic role in the neuroinflammatory disorder as multiple sclerosis. The purpose of this research was to measure the plasma levels of S100A12 and Apo-A1 in the first-degree family of relapsing-remitting multiple sclerosis (RRMS) patients. Plasma levels of S100A12 & Apo-A1 were evaluated via enzyme-linked immunosorbent assay in the thirty-five new cases of untreated patients with deterministic RRMS according to the McDonald criteria, twenty-four healthy controls, and twenty-six first-degree members of untreated RRMS patients (called them as high-risk group). The main findings of this study were as follows: the plasma level of S100A12 was significantly lower in the new cases of untreated RRMS (P ≤ 0.05; 0.045) and high-risk (P ≤ 0.05; 0.001) groups. Although the plasma protein level of Apo-A1 was reduced significantly in the high-risk group (P < 0.05, P = 0.003) as compared to the healthy control group, there was no significant difference in the untreated RRMS patients (P = 0.379). The plasma level of vitamin D3 in both RRMS patients and high-risk groups displayed significance reduction, although, there was no significant association between vitamin D and S100A12 & Apo-A1 levels. Given the role of S100A12 and Apo-A1 in the inflammatory process performed in the first-degree family members of the RRMS patients, which revealed a significant decrease in this group, we concluded that they can be considered as one of the contributing factors in the pathogenesis of MS, though more research is needed before assuming them as predictive biomarkers.

Fast Proton Transfer and Hydrogen Evolution Reactivity Mediated by [Co13C2(CO)24]4.

A common approach to speeding up proton transfer (PT) by molecular catalysts is manipulation of the secondary coordination sphere with proton relays and these enhance overall reaction rates by orders of magnitude. In contrast, heterogeneous electrocatalysts have band structures that promote facile PT concerted with electron transfer (ET), known as the Volmer mechanism. Here, we show that [Co13C2(CO)24]4-, containing multiple Co-Co bonds to statistically enhance observed rates of PT, promotes PT on the order of 2.3 × 109 M-1 s-1 which suggests a diffusion-limited rate. The fast ET and PT chemistry is attributed to the delocalized electronic structure of [Co13C2(CO)24]4-. Electrochemical characterization of [Co13C2(CO)24]4- in the presence and absence of protons reveals ET kinetics and diffusion behavior similar to other small clusters such as nanomaterials and fullerenes.

Making C-H bonds with CO2: production of formate by molecular electrocatalysts.

Molecular approaches to the electrocatalytic reduction of CO2 to formate are varied and versatile in their methods. We discuss recent efforts to catalyse this reaction including significant progress made in the last 5 years. This Feature Article begins with a survey of molecular electrocatalysts that produce CO or H2, but have been observed under certain conditions to afford some formate. These examples are included because they provide valuable mechanistic insight for design of catalysts that produce hydrogenated products selectively from CO2. The subsequent discussion describes catalyst properties that favour C-H bond formation with CO2 and this is followed by recent advances that have been made in developing these catalysts. The focus on specific catalyst systems includes recently reported Ir PCP-type pincer complexes and Fe carbonyl clusters, such as [Fe4N(CO)12](-), that selectively produce formate from CO2 in aqueous solution. A discussion of the relevant thermochemical properties of the catalysts in the context of formate production is included.

Tailoring Electrocatalysts for Selective CO2 or H(+) Reduction: Iron Carbonyl Clusters as a Case Study.

The design of electrocatalysts that will selectively transfer hydride equivalents to either H(+) or CO2 to afford H2 or formate is a long-standing goal in molecular electrocatalysis. In this Forum Article, we use experimentally determined thermochemical parameters, hydricity and pKa values, to rationalize our observations that the carbide-containing iron carbonyl cluster [Fe4C(CO)12](2-) reduces H(+) to H2 in the presence of CO2 in either acetonitrile (MeCN), MeCN with 5% water, or buffered water (pH 5-13), with no traces of formate or other carbon-containing products observed. Our previous work has shown that the closely related nitride-containing clusters [Fe4N(CO)12](-) and [Fe4N(CO)11(PPh3)](-) will also reduce H(+) to H2 in either MeCN with 5% water or buffered water (pH 5-13), but upon the addition of CO2, they selectively generate formate. The thermochemical measurements on [Fe4C(CO)12](2-) predict that the free energy for transfer of hydride, in MeCN, from the intermediate [HFe4C(CO)12](2-) to CO2 is thermoneutral and to H(+) is -32 kcal mol(-1). In water, these values are less than -19.2 and -8.6 kcal mol(-1), respectively. These results suggest that generation of both H2 and formate should be favorable in aqueous solution and that kinetic effects, such as a fast rate of H2 evolution, must influence the observed selectivity for generation of H2. The hydride-donating ability of [HFe4N(CO)12](-) is lower than that of [HFe4C(CO)12](2-) by 5 kcal mol(-1) in MeCN and by at least 3 kcal mol(-1) in water, and we speculate that this more modest reactivity provides the needed selectivity to obtain formate. We also discuss predictions that may guide future catalyst design.

Temperature dependent iodide oxidation by MLCT excited states.

The metal-to-ligand charge transfer (MLCT) excited states of two related heteroleptic Ru(ii) compounds [Ru(bpy)2(deeb)](2+) and [Ru(bpy)2(deebq)](2+), where bpy is 2,2'-bipyridine, deeb is 4,4'-(CO2CH2CH3)2-2,2'-bipyridine and deebq is 4,4'-(CO2CH2CH3)2-2,2'-biquinoline, were characterized in fluid acetonitrile by temperature dependent photoluminescence spectroscopies as well as quenching by iodide ions. Photoluminescence emanates from a manifold of thermally equilibrated excited states referred to as the thexi states. Evidence for activated internal conversion to a 4(th) MLCT excited state was garnered from an Arrhenius analysis of temperature dependent lifetime data. The activation energy was found to be 550 cm(-1) for [Ru(bpy)2(deeb)](2+)* and 1200 cm(-1) for [Ru(bpy)2(deebq)](2+)*. The pre-exponential factor abstracted from the Arrhenius analysis of the [Ru(bpy)2(deebq)](2+)* data suggested that ligand field excited states might be populated, however there was no evidence for ligand loss photochemistry under the conditions studied. The excited states were found to quench iodide by a dynamic process in good agreement with the Stern-Volmer model. Transient absorption data showed that the quenching mechanism was electron transfer to generate an iodine atom and a reduced ruthenium compound as products. The quenching rate constants abstracted from temperature dependent Stern-Volmer quenching data were corrected for diffusion and activated complex formation to yield electron transfer rate constants that were found to increase markedly with temperature. An Arrhenius analysis of the electron transfer data revealed that electron transfer from iodide to the d-orbitals of the excited state was an activated process with an Ea of 2400 cm(-1) for [Ru(bpy)2(deeb)](2+) and 3300 cm(-1) for [Ru(bpy)2(deebq)](2+).

Long-wavelength sensitization of TiO2 by ruthenium diimine compounds with low-lying π* orbitals.

The role of low-lying π* orbitals in dye-sensitized solar cells based on mesoporous thin films of anatase TiO(2) nanocrystallites remains unknown. Herein we report three ruthenium compounds, cis-Ru(dcbq)(2)(NCS)(2), cis-Ru(dcbq)(bpy)(NCS)(2), and cis-Ru(dcb)(bq)(NCS)(2), where bpy is 2,2'-bipyridine, dcb is 4,4'-(CO(2)H)(2)-2,2'-bipyridine, bq is 2,2'-biquinoline, and dcbq is 4,4'-(CO(2)H)(2)-2,2'-biquinoline, that were synthesized, characterized, and contrasted with the well-known N3 compound (i.e., cis-Ru(dcb)(2)(NCS)(2)) in dye-sensitized solar cells. These compounds maintain the same cis-Ru(NCS)(2) core with a systematic variation in the energy of the π* orbitals of the diimine ligand: bpy > dcb > bq > dcbq. The lowered π* orbitals resulted in enhanced red absorption relative to N3. With HCl pretreated TiO(2) in regenerative solar cells, sensitization from 400 to 900 nm was realized with cis-Ru(dcb)(bq)(NCS)(2) and global power conversion efficiencies as high as 6.5% were achieved under 1 sun of AM 1.5 irradiation. The energy conversion efficiency was found to be acutely sensitive to the presence of p-tert-butylpyridine (TBP) in a 0.5 M LiI/0.05 M I(2) acetonitrile electrolyte. Nanosecond transient absorption studies revealed that the addition of TBP decreased the excited-state injection yield for the compounds with biquinoline ligands. Spectro-electrochemical studies showed that the HCl pretreatment lowered the effective density of TiO(2) acceptor states and confirmed that the presence of TBP raised them toward the vacuum level. There was no spectroscopic data to support the hypothesis that the π* levels of the diimine ligand mediate back-electron transfer to the oxidized dye or the redox mediator was found.