Data_Sheet_1_Open Debates Conducive for Vaccination Rate Flatlines: A Scoping Review and Convergent Cross Mapping.xlsx

COVID-19 pandemic is fueling digital health transformation—accelerating innovations of digital health services, surveillance, and interventions, whereas hastening social contagion of deliberate infodemic. The USA and many other countries are experiencing a resurgent wave of the COVID-19 pandemic with vaccination rate slowdown, making policymaking fraught with challenges. Political leaders and scientists have publicly warned of a “pandemic of the unvaccinated,” reinforcing their calls for citizens to get jabs. However, some scientists accused elites of stigmatizing the unvaccinated people and undermining the moral pillars of public health. Following the PRISMA-ScR guidelines, we first reviewed the nuances of stakeholders involved in the ongoing debates and revealed the potential consequences of divisive pronouncements to provide perspectives to reframe extensible discussions. Then, we employed the convergent cross mapping (CCM) model to reveal the uncharted knock-on effects of the contentious tsunami in a stakeholders-oriented policymaking framework, coupled with rich metadata from the GDELT project and Google Trends. Our experimental findings suggest that current news coverage may shape the mindsets of the vaccines against the unvaccinated, thereby exacerbating the risk of dualistic antagonism in algorithmically infused societies. Finally, we briefly summarized how open debates are conducive to increasing vaccination rates and bolstering the outcomes of impending policies for pandemic preparedness.</p

Data_Sheet_2_Open Debates Conducive for Vaccination Rate Flatlines: A Scoping Review and Convergent Cross Mapping.pdf

COVID-19 pandemic is fueling digital health transformation—accelerating innovations of digital health services, surveillance, and interventions, whereas hastening social contagion of deliberate infodemic. The USA and many other countries are experiencing a resurgent wave of the COVID-19 pandemic with vaccination rate slowdown, making policymaking fraught with challenges. Political leaders and scientists have publicly warned of a “pandemic of the unvaccinated,” reinforcing their calls for citizens to get jabs. However, some scientists accused elites of stigmatizing the unvaccinated people and undermining the moral pillars of public health. Following the PRISMA-ScR guidelines, we first reviewed the nuances of stakeholders involved in the ongoing debates and revealed the potential consequences of divisive pronouncements to provide perspectives to reframe extensible discussions. Then, we employed the convergent cross mapping (CCM) model to reveal the uncharted knock-on effects of the contentious tsunami in a stakeholders-oriented policymaking framework, coupled with rich metadata from the GDELT project and Google Trends. Our experimental findings suggest that current news coverage may shape the mindsets of the vaccines against the unvaccinated, thereby exacerbating the risk of dualistic antagonism in algorithmically infused societies. Finally, we briefly summarized how open debates are conducive to increasing vaccination rates and bolstering the outcomes of impending policies for pandemic preparedness.</p

A Proton-Induced N-1 to η² Migration of the Fluxional Pyrazine in the [Ru^II(hedta)(pz)]^- Complex

[RuII(hedta)(D2O)]-, hedta3- = N-(hydroxyethyl)ethylenediaminetriacetate, reacts with pyrazine in D2O at 25 °C to yield several isomers and ≤20% of the pyrazine-bridged binuclear complex. Two isomers of 56.2% combined abundance have differentiated α (near) and β (remote) 1H NMR pyrazine resonances at 9.09 ppm (α or H2, H6 pair) and 8.33 ppm (β or H3, H5 pair). The other isomer of ca. 24% abundance exhibits only a singlet at 8.76 ppm, indicative of fluxional pyrazine movement from N-1 to N-4. This is believed to be the cis-polar isomer. Within 24 h the differentiated isomers convert to the fluxional isomer, which remains fluxional in 50% D2O/50% CD3OD down to 237 K. The fluxional isomer has all equivalent 13C NMR resonances at 152.44 ppm, 5.18 ppm downfield of free pyrazine. Comparison with the bridged binuclear ion {[Ru(hedta)]2(pz)}2- revealed fortuitously similar shifts; the 1H NMR spectrum shows a singlet at 8.76 ppm, and the 13C NMR spectrum, a singlet at 152.40 ppm. These species have different electrochemical signatures, however, with the 1:1 fluxional complex having a RuII/III wave at 0.20 V that shifts to 0.35 V upon protonation of the N-4 position, whereas the binuclear complex has two waves at 0.18 and 0.33 V which are independent of pH. 1H NMR indicates stereochemically rigid coordination of 2-methylpyrazine (2-CH3pz) at N-4 with the 2-CH3 position remote in the major species (65.5%) and at N-2 with the 2-CH3 site adjacent (34.4%) in the lesser isomer. The proton resonances are as follows. Remote isomer (N-4):  H2, 8.22 ppm; H3, 8.97 ppm; H5, 8.88 ppm; CH3, 2.53 ppm. Adjacent (N-1) isomer:  H2, 8.73 ppm; H3, 8.42 ppm, H5, 8.50 ppm; CH3, 2.45 ppm. A slow conversion of the strained adjacent isomer to the remote isomer is observed. Remote and adjacent isomers were also prepared for [(NH3)5Ru(2-CH3pz)]2+ in 87.7% and 12.3% yield. Protonation of [Ru(hedta)(pz)]- yields nonfluxional complexes:  a major species (63%) bound η2(1,2) with four complicated resonance patterns at 8.72, 8.57, 8.00, and 7.91 ppm, each signal having across-the-ring couplings which require couplings to at least two different ring protons and a minor N-1-coordinated N-4 protonated species (16%) with α and β proton pairs resonating at 8.81 and 8.25 ppm. An η2(2,3) isomer is also detectable (20%) which has four types of 1H resonances at 9.51, 9.01, 8.85, and 8.15 ppm. The weakened σ bonding from pzH+ and enhanced π-acceptor capacity power of pzH+ combine to induce a switch in coordination to either η2(1,2) or η2(2,3)

Recycling Acetic Acid from Polarizing Film of Waste Liquid Crystal Display Panels by Sub/Supercritical Water Treatments

Waste liquid crystal display (LCD) panels mainly contain inorganic materials (glass substrate) and organic materials (polarizing film and liquid crystal). The organic materials should be removed first since containing polarizing film and liquid crystal is to the disadvantage of the indium recycling process. In the present study, an efficient and environmentally friendly process to obtain acetic acid from waste LCD panels by sub/supercritical water treatments is investigated. Furthermore, a well-founded reaction mechanism is proposed. Several highlights of this study are summarized as follows: (i) 99.77% of organic matters are removed, which means the present technology is quite efficient to recycle the organic matters; (ii) a yield of 78.23% acetic acid, a quite important fossil energy based chemical product is obtained, which can reduce the consumption of fossil energy for producing acetic acid; (iii) supercritical water acts as an ideal solvent, a requisite reactant as well as an efficient acid–base catalyst, and this is quite significant in accordance with the “Principles of Green Chemistry”. In a word, the organic matters of waste LCD panels are recycled without environmental pollution. Meanwhile, this study provides new opportunities for alternating fossil-based chemical products for sustainable development, converting “waste” into “fossil-based chemicals”

¹⁵N NMR and Electrochemical Studies of [Ru^II(hedta)]^- Complexes of NO, NO⁺, NO₂^-, and NO^-

[RuII(hedta)L]n- complexes (hedta3- = N-(hydroxyethyl)ethylenediaminetriacetate; L = NO+, n = 0; L = NO, n = 1; L = NO-, n = 2) have been prepared by the displacement of H2O/D2O via NO(g) or NO2-. This is the first reported entire set of NO+, NO, and NO- as ligands for the same metal center in a constant oxidation state and with a constant ligand environment (here RuII and the amino carboxylate hedta3-). From the NO stretching frequencies of isolated salts, the net influence of back-donation by RuII and its σ-withdrawal was observed to be that the bond order for the NO+ complex is virtually the same (ca. 2.46) as that for the NO complex (ca. 2.48). The back-donation to NO- is also small, as is that to NO, but orbital mixing of NO- and RuII is sufficiently important to induce a singlet NO- complex. Values for the νNO in cm-1 for the 14N- and 15N-labeled complexes, respectively, are as follows:  NO+, 1846, 1827; NO, 1858, 1842; NO-, 1383, 1370. Combined results of 15N, 13C, and 1H NMR spectra of the complexes in D2O show that [RuII(hedta)(15NO+)] is a single cis-equatorial isomer with its 15NO+ resonance at 249.6 ppm vs [15N]formamide. The two-electron-reduced [RuII(hedta)(15NO-)]2- complex exists as trans- and cis-equatorial isomers having 15NO- resonances at 609.4 and 607.4 ppm. The 15N resonances appear at 260.0 ppm for the 15NO+ ligand and at 348.8 ppm for the bound 15NO2- ligand in the [RuII(hedta)(15NO2-)(15NO+)(D2O)] complex. Differential pulse voltammetric waves for the [RuII(hedta)L]n- series occur at −0.37 V for the RuII(NO-)/RuII(NO) couple, at −0.10 V for the RuII(NO)/RuII(NO+) couple, and at +0.98 V for the RuII(NO+)/RuIII(NO+) couple. The coordinated nitrosyl ion/nitro equilibrium (L‘)RuII(NO+) + 2OH- ⇌ (L‘)RuII(NO2-) + H2O (KNO2−) was observed for L‘ = hedta3-, as for previous examples with L‘ = violurate, polypyridyl ligands, and (CN-)5 and (NH3)5 ligand sets. KNO2− = 1.44 × 1013 for L‘ = hedta3-. log(KNO2−) is linearly related through the ion-pairing equilibrium constant expression to −z1z2, the charge product of the reacting ions (here the (L‘)Ru(NO+) complex and OH-) from −4 through +3, excluding the (NH3)m ammine series with m = 4 and 5. The opposite behavior of the ammines is attributed to strong solvent H-bonding that changes for reactant and product in the nitrosyl/nitro equilibrium. The pKa of coordinated nitrous acid in [RuII(hedta)(HONO)]- is calculated to be −0.80, a 3.85 log unit enhancement over free HONO due to the RuII charge. An MO explanation is presented to interrelate the {FeIII−(NO- triplet)} complexes, the {RuII−(NO- singlet)} type observed for [RuII(hedta)(15NO-)]2-, and the NO+ complexes of other strong-field metals. When both dz2 and dx2-y2 metal orbitals reside below the NO π* pair, the electronic repulsions favor a bent NO- triplet ligand. If both metal orbitals reside above the NO π* pair, the orbital mixing and back-donation induce a coordinated NO- singlet ligand, and if the NO π* pair reside between the two σ-based d orbitals, an NO+ ligand and reduced metal center obtain

<i>N</i>-1- and η²-Pyrimidine Linkage Isomers in Complexes of [Ru^II(hedta)]^-

[RuII(hedta)(H2O)]-, hedta3- = N-hydroxyethylethylenediaminetriacetate, forms N-1-bound pyrimidine complexes via a kinetically controlled substitution at N-1 with pyrimidine (pym), 4-methylpyrimidine (4CH3pym), and 4,6-dimethylpyrimidine (Me2pym); k = 31 M-1 s-1 for pym. Subsequent to N-1 coordination, an intramolecular redistribution of RuII−pyrimidine linkage isomers occurs with the formation of η2 attachments, reaching equilibrium with t1/2's of 28.8 (pym), 24 (4CH3pym), and 1 h for Me2pym. The N-1 forms exhibit normal RuII/III waves at 0.14 (pym), 0.10 (4CH3pym), and 0.16 V (Me2pym) whereas the η2 forms shift to more positive values indicative of better π-acceptor attachments:  0.50 (pym) and 0.44 V (4CH3pym). The ratio of isomers was determined to be as follows by 1H NMR and 13C NMR methods:  (pym) η2(1,2):η2(5,6):η2(1,6):N-1 of 43:22:33:2; (4CH3pym) η2(1,2):η2(5,6):N-1 of 10:33:57; (Me2pym) η2(1,2):η2(5,6):N-1 of 6:26:68. 1H NMR assignments have been made for all the observed N-1, η2(1,2), η2(5,6), and η2(1,6) isomers. 13C NMR shifts have been identified for the major isomers of pym and 4CH3pym and confirmed HH COSY and HC COSY methods. Several important conclusions are drawn:  (1) η2 isomers of the η2(1,2) type exhibit significant downfield shifts of H2 of ca 1.20 ppm; (2) 13C NMR shifts of carbon centers in η2-bound diazine rings are downfield of the free ligand by up to +9 ppm and not 40−80 ppm upfield as for η2-olefinic complexes; (3) η2 protons of the η2(5,6) type shift significantly less upfield than those for η2-olefin complexes (ca. 0.4−0.8 ppm vs 1.0−2.0 ppm). It was established that the formation of η2-bound pyrimidines of [RuII(hedta)]- occurs concomitantly with the dissociation of a carboxylate donor of the hedta3- ligand. 13C NMR spectra reveal the predicted weighted percentage of freed carboxylates based on the isomer distribution between N-1 with all three glycinato arms of hedta3- bound to RuII (13C resonance at 188 ppm) vs η2 forms with two bound glycinato groups and one free glycinato group of hedta3- (resonating near 174 ppm)

Simultaneous Determination of Flonicamid and its Metabolites in Tea by Liquid Chromatography–Tandem Mass Spectrometry

An analytical method was established to simultaneously quantify flonicamid and its metabolites 4-trifluoromethylnicotinic acid (TFNA), N-(4-trifluoromethylnicotinoyl) glycine (TFNG), and 4-trifluoromethylnicotinamide (TFNA-AM) in tea using orthogonal experimental design and liquid chromatography–tandem mass spectrometry (LC–MS/MS). Residues were extracted from the samples with acetonitrile containing 1% acetic acid and were purified with graphitized carbon black. The linearity of the method was excellent in the concentration range of 0.01–10 µg/mL, producing correlation coefficients greater than 0.996 for the target compounds. The limits of detection and quantification of all analytes in tea were 0.0013–0.013 mg/kg and 0.004–0.040 mg/kg, respectively. The average recoveries of flonicamid, TFNA, TFNG, and TFNA-AM ranged from 75.14 to 92.72%, with intra- and interday relative standard deviations of 1.07–9.75%. The proposed method was successfully applied to the terminal residue determination of flonicamid and its metabolites in dry tea processed from three field trials’ fresh samples. The determined total terminal residue concentrations of flonicamid 10 days after the last application at all three sites were below the maximum residue limit (MRL) set by the European Union (0.1 mg/kg) and the residues in all samples were lower than the MRL established by the United States Environmental Protection Agency (EPA) (8 mg/kg). This method may be used to meet the requirements for the determination of flonicamid and its metabolites that could provide guidance for establishing a MRL for flonicamid in tea in China.</p

Table_1_Unraveling genetic causality between metformin and myocardial infarction on the basis of Mendelian randomization.xlsx

BackgroundIn recent years, several studies have explored the effect of metformin on myocardial infarction (MI), but whether metformin has an improvement effect in patients with MI is controversial. This study was aimed to investigate the causal relationship between metformin and MI using Mendelian randomization (MR) analysis.MethodsThe genome-wide significant (P-8) single-nucleotide polymorphisms (SNPs) in patients with metformin and patients with MI were screened from the Open genome-wide association study (GWAS) project as instrumental variables (IVs). The study outcomes mainly included MI, old MI, acute MI, acute transmural MI of inferior wall, and acute transmural MI of anterior wall. The inverse variance weighted (IVW) method was applied to assess the main causal effect, and weighted median, simple mode, weighted mode methods, and MR-Egger regression were auxiliary applied for supplementary proof. The causal relationship between metformin and MI was assessed using odds ratios (OR) and 95% confidence intervals (95% CI). A leave-one-out method was used to explore the effect of individual SNPs on the results of IVW analyses, and a funnel plot was used to analyze the potential bias of the study results, thus ensuring the robustness of the results.ResultsIn total, 16, 84, 39, 26, and 34 SNPs were selected as IVs to assess the genetic association between metformin and outcomes of MI, old MI, acute MI, acute transmural MI of inferior wall, and acute transmural MI of anterior wall, respectively. Treatment with metformin does not affect the risk of acute transmural MI of anterior wall at the genetic level (P>0.05; OR for inverse variance weighted was 1.010). In the cases of MI, old MI, acute MI, and acute transmural MI of inferior wall, metformin may even be a risk factor for patients (PConclusionMetformin is not protective against the risk of myocardial infarction in patients and may even be a risk factor for MI, old MI, acute MI, and acute transmural MI of inferior wall.</p

Dissipation, residues and risk assessment of oxine-copper and pyraclostrobin in citrus

An efficient, sensitive, simple and fast method for the simultaneous determination of oxine-copper and pyraclostrobin in citrus fruit was developed and validated. The method uses ethylene diamine tetra-acetic acid as a competitive ligand to convert oxine-copper to soluble 8-hydroxyquinoline for analysis by QuEChERS and LC-MS/MS. Linear relationships were determined with correlation coefficients ranging from 0.9904 to 0.9998. The limits of detection for the analytes were 0.012–0.8 μg kg−1, and the limits of quantitation were 0.04–2.6 μg kg−1 in citrus. The average recoveries were 79.1–114.9% with relative standard deviations of less than 7.4%. The analyses of dissipation indicated that the half-lives of oxine-copper and pyraclostrobin were 1.94–3.67 and 1.79–2.48 days and the terminal residues were −1, respectively. The risk quotients of oxine-copper and pyraclostrobin were 0.026–0.199 and 0.003–0.022, respectively. This risk assessment provides a reference for the safe and reasonable use of oxine-copper and pyraclostrobin and may help to establish maximum residue limits for these pesticides in China.</p

Iodide-Dependent Selective Dehydroaromatization Affording Maleimide-Fused 9,10-Phenanthrenes and Their Analogues

A novel and selective synthesis of polycyclic fused maleimides from easily available raw materials under metal-free conditions is presented. This cascade protocol involves self-condensation of cyclohexanones, followed by Diels–Alder reaction with maleimides, intramolecular dehydration, and selective dehydroaromatization in a one-pot fashion, affording maleimide-fused 9,10-phenanthrenes and their analogues in satisfactory yields. Notably, iodide reagents play a critical role in switching the selectivity toward full or partial dehydrogenation compounds