An evaluation of metal/metal electronic mixing in the ground and metal-to-metal charge transfer excited states of cyanide-bridged bi-, tri- and tetra-metallic complexes is presented. The ground state ...spectroscopic and electrochemical properties observed for complexes whose M(II) to M(III) oxidation potentials span almost 2eV are surveyed and the variations of their electronic mixings are compared to the patterns expected based on standard perturbation theory models for electronic mixing between donor and acceptor metal ions in bridged complexes. Based on the difference between the electrochemical potentials for oxidation of a D/A pairs containing at least one ruthenium complex and that of an analogous Rh(III) complexes, the extent of electronic mixing, or electronic delocalization is 30–70% larger in these cyanide-bridged D/A complexes than expected based absorption spectra using the standard Hush model. The electronic mixing of the remote or next-nearest-neighbor (NNN) metal centers of tri- and tetra-metallic complexes is largely mediated by a bridging (L)4M(CN)2 moiety; for (L)4 am(m)ine or polypyridine ligands. The extent of this mixing is very strongly dependent on the energy difference between the nearest-neighbor (NN) and the NNN electron transfer excited states. When the donor and acceptor are both polypyridine complexes of ruthenium, the NN and NNN electron transfer excited states can be nearly degenerate. When the diabatic NN and NNN excited states have the same vertical energy (i.e., with respect to the ground state nuclear coordinates), the resulting adiabatic excited states have the same electronic composition and this corresponds to the maximum possible NNN mixing. Many models that treat NNN mixing, “superexchange” coupling models, are obtained for the limit of very weak mixing between well separated electronic states and they are not useful for the limit in which the electron transfer excited states are degenerate or nearly degenerate. The lowest energy electronic excited states of (L)4CrIII{CNRuII(NH3)5}2m+ complexes are also mixed valence donor/acceptor systems, but the electronic configurations of the two D/A pairs involve a metal centered doublet CrIII excited state a metal to metal charge transfer excited state with a low spin triplet CrII species linked by cyanide to RuIII. There are fewer means for probing the mixed valence properties of these excited states; however, their excited state mixed valence properties are complicated by the electronic coupling to other near in energy electronic excited states. Some of the configurational mixing between electronic states appears to help stabilize the triplet CrII electronic configuration.
The synthesis and structural determination of a silver nanocluster Ag20{S2P(OiPr)2}12 (2), which contains an intrinsic chiral metallic core, is produced by reduction of one silver ion from the ...eight‐electron superatom complex Ag21{S2P(OiPr)2}12(PF6) (1) by borohydrides. Single‐crystal X‐ray analysis displays an Ag20 core of pseudo C3 symmetry comprising a silver‐centered Ag13 icosahedron capped by seven silver atoms. Its n‐propyl derivative, Ag20{S2P(OnPr)2}12 (3), can also be prepared by the treatment of silver(I) salts and dithiophosphates in a stoichiometric ratio in the presence of excess amount of BH4−. Crystal structure analyses reveal that the capping silver‐atom positions relative to their icosahedral core are distinctly different in 2 and 3 and generate isomeric, chiral Ag20 cores. Both Ag20 clusters display an emission maximum in the near IR region. DFT calculations are consistent with a description within the superatom model of an 8‐electron Ag135+ core protected by a Ag7{S2P(OR)2}125− external shell. Two additional structural variations are predicted by DFT, showing the potential for isomerism in such Ag20{S2P(OR)2}12 species.
Chiral silver nanocluster: The structure of an intrinsically chiral Ag20 nanocluster was determinded. Containing a silver‐centered icosahedron capped by seven silver atoms, it was rationalized to be an eight‐electron superatom complex. Isomeric Ag20 cores with distinct symmetry were characterized in two derivatives (nPr C1; iPr C3). DFT was used to predict the presence of additional structural variations to show rich isomerism in the Ag20 metallic core.
Hepatitis D virus (HDV) infection increases the risk of hepatocellular carcinoma (HCC) in the natural course of chronic hepatitis B (CHB) patients. Its role in patients treated with ...nucleotide/nucleoside analogues (NAs) is unclear. We aimed to study the role of hepatitis D in the development of HCC in CHB patients treated with NAs. Altogether, 1349 CHB patients treated with NAs were tested for anti-HDV antibody and RNA. The incidence and risk factors of HCC development were analyzed. Rates of anti-HDV and HDV RNA positivity were 2.3% and 1.0%, respectively. The annual incidence of HCC was 1.4 per 100 person-years after a follow-up period of over 5409.5 person-years. The strongest factor association with HCC development was liver cirrhosis (hazard ratio HR/95% confidence interval CI 9.98/5.11-19.46, P < 0.001), followed by HDV RNA positivity (HR/ CI 5.73/1.35-24.29, P = 0.02), age > 50 years old (HR/CI 3.64/2.03-6.54, P < 0.001), male gender (HR/CI 2.69/1.29-5.60, P: 0.01), and body mass index (BMI, HR/CI 1.11/1.03-1.18, P = 0.004). The 5-year cumulative incidence of HCC was 7.3% for patients with HDV RNA negativity compared to that of 22.2% for patients with HDV RNA positivity (P = 0.01). In the subgroup of cirrhotic patients, the factors associated with HCC development were HDV RNA positivity (HR/CI 4.45/1.04-19.09, P = 0.04) and BMI (HR/CI 1.11/1.03-1.19, P = 0.01). HDV viremia played a crucial role in HCC development in CHB patients who underwent NA therapy.
This study investigates the effects of metal addition and doping of a 2-electron silver superatom, Ag
10
{S
2
P(O
i
Pr)
2
}
8
(
Ag
10
). When Ag
+
is added to
Ag
10
in THF solution, Ag
11
{S
2
P(O
i
...Pr)
2
}
8
(OTf) (
Ag
11
) is rapidly formed almost quantitatively. When the same method is used with Cu
+
, a mixture of alloys, Cu
x
Ag
11−
x
{S
2
P(O
i
Pr)
2
}
8
+
(
x
= 1-3,
Cu
x
Ag
11−
x
), is obtained. In contrast, introducing Au
+
to
Ag
10
leads to decomposition. The structural and compositional analysis of
Ag
11
was characterized by single-crystal X-ray diffraction (SCXRD), ESI-MS, NMR spectroscopy, and DFT calculations. While no crystal structure was obtained for
Cu
x
Ag
11−
x
, DFT calculations provide insights into potential sites for copper location. The absorption spectrum exhibits a notable blue shift in the low-energy band after copper doping, contrasting with that of the slight shift observed in 8-electron Cu-doped Ag nanoclusters.
Ag
11
and
Cu
x
Ag
11−
x
are strongly emissive at room temperature, and solvatochromism across different organic solvents is highlighted. This study underscores the profound influence of metal addition and doping on the structural and optical properties of silver nanoclusters, providing important contributions to understanding the nanoclusters and their photophysical behaviors.
The addition of Ag(
i
) and Cu(
i
) by doping of a two-electron silver superatom, Ag
10
(dtp)
8
, leads to the formation of Ag
11
(dtp)
8
+
and Cu
x
Ag
11−
x
(dtp)
8
+
, exhibiting a notable shift in the absorption spectrum.
Background and Aim
The serial serologic changes of hepatitis D virus (HDV) infection among chronic hepatitis B virus (HBV) infected patients who received oral nucleotide/nucleoside analogues are ...elusive.
Methods
Serum anti‐HDV and HDV RNA among chronic hepatitis B (CHB) patients were tested at the time of initiating anti‐HBV therapy and subsequently during the follow‐up period.
Results
The seropositive rate of anti‐HDV and HDV RNA among 2850 CHB patients, was 2.7% and 0.9%, respectively. Factors associated with anti‐HDV seropositivity were platelet counts (odds ratio OR/95% confidence intervals CI: 0.995/0.992–0.999; P = 0.006), HBV DNA levels (OR/CI: 0.81/0.70–0.94; P = 0.005), and hepatitis B e‐antigen (HBeAg) seropositivity (OR/CI: 0.22/0.05–0.95; P = 0.04). The only factor associated with HDV RNA positivity among anti‐HDV seropositive patients was age (OR/CI: 0.95/0.90–1.00; P = 0.03). The spontaneous clearance rate of serum anti‐HDV antibody was 3.0 per 100 person‐years with a median follow‐up period of 3.5 years (range 2–12 years), whereas the seroclearance rate of HDV RNA was 4.3 per 100 person‐years among anti‐HDV seropositive patients after a median follow‐up period of 6.0 years (range 2–11 years). A baseline anti‐HDV titer < 0.5 cut‐off index was the only factor predictive of anti‐HDV seroclearance (hazard ratio HR/CI: 30.11/3.73–242.85; P = 0.001).
Conclusions
HDV infection was not common among patients treated for HBV in Taiwan. Seroclearance of anti‐HDV and HDV RNA did occur over time, albeit the chance is rare.
Vaccination against severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) is one of the best policies to control COVID-19 pandemic. The serological response to COVID-19 vaccination in ...Taiwanese patients with different comorbidities is elusive.
Uninfected subjects who received 3 doses of mRNA vaccines (BNT162b2 Pfizer-BioNTech, BNT and mRNA-1273 Moderna), viral vector-based vaccines (ChAdOx1-S (AZD1222, AZ) or protein subunit vaccines (Medigen COVID-19 vaccine) were prospectively enrolled. The SARS-CoV-2-IgG spike antibody level was determined within three months after the 3rd dose of vaccination. The Charlson Comorbidity Index (CCI) was applied to determine the association between vaccine titers and underlying comorbidities.
A total of 824 subjects were enrolled in the current study. The proportions of CCI scores of 0-1, 2-3 and > 4 were 52.8% (n = 435), 31.3% (n = 258) and 15.9% (n = 131), respectively. The most commonly used vaccination combination was AZ-AZ-Moderna (39.2%), followed by Moderna-Moderna-Moderna (27.8%). The mean vaccination titer was 3.11 log BAU/mL after a median of 48 days after the 3rd dose. Factors associated with potentially effective neutralization capacity (IgG level ≥ 4160 AU/mL) included age ≥ 60 years (odds ratio OR/95% confidence interval CI: 0.50/0.34-0.72, P < 0.001), female sex (OR/CI: 1.85/1.30-2.63, P = 0.001), Moderna-Moderna-based vaccination (compared to AZ-AZ-based vaccination, OR/CI: 6.49/3.90-10.83, P < 0.001), BNT-BNT-based vaccination (compared to AZ-AZ-based vaccination, OR/CI: 7.91/1.82-34.3, P = 0.006) and a CCI score ≥ 4 (OR/CI: 0.53/0.34-0.82, P = 0.004). There was a decreasing trend in antibody titers with increasing CCI scores (trend P < 0.001). Linear regression analysis revealed that higher CCI scores (β: - 0.083; 95% CI: - 0.094-0.011, P = 0.014) independently correlated with low IgG spike antibody levels.
Subjects with more comorbidities had a poor serological response to 3 doses of COVID-19 vaccination.
Air pollution is a risk factor for hepatocellular carcinoma (HCC). However, the effect of air pollution on HCC risk in patients with hepatitis remains unclear.
This cross-sectional study recruited ...348 patients with chronic hepatitis who were tested for serum hepatitis B surface antigen (HBsAg) and for antibodies against hepatitis B core antigen (HBcIgG) and hepatitis C virus (anti-HCV) in 2022. The diagnosis of HCC was based on the International Classification of Diseases, 10th revision (ICD-10). Daily estimates of air pollutants were aggregated into mean estimates for the previous year based on the date of recruitment or HCC diagnosis.
Out of 348 patients, 12 had HCC (3.4%). Patients with HCC were older (71.7 vs 50.9 years; p = 0.004), had higher proportion of HBsAg seropositivity (41.7% vs 5.1%; p < 0.001), and substantially higher levels of particulate matter 2.5 (PM 2.5 ) (21.5 vs 18.2 μg/m 3 ; p = 0.05). Logistic regression analysis revealed that the factors associated with HCC were age (odds ratio OR: 1.10; CI, 1.03-1.17; p = 0.01), PM 2.5 level (OR: 1.51; CI, 1.02-2.23; p = 0.04), and HBsAg seropositivity (OR: 6.60; CI, 1.51-28.85; p = 0.01) ( Table 3 ). There was a combined effect of PM 2.5 and HBsAg seropositivity on the risk of HCC development (OR: 22.17; CI, 3.33-147.45; p = 0.001).
In this study, we demonstrated that PM 2.5 and HBsAg seropositivity were associated with HCC occurrence and had synergistic effects after adjusting for confounding factors.
We aimed to investigate the association between air pollution and advanced fibrosis among patients with metabolic associated fatty liver disease (MAFLD) and chronic hepatitis B virus (HBV) and ...hepatitis C virus (HCV) infections. A total of 1376 participants who were seropositive for HBV surface antigen (HBsAg) or antibodies to HCV (anti‐HCV) or had abnormal liver function in a community screening program from 2019 to 2021 were enrolled for the assessment of liver fibrosis using transient elastography. Daily estimates of air pollutants (particulate matter ≤2.5 μm in diameter PM2.5, nitrogen dioxide NO2, ozone O3 and benzene) were aggregated into mean estimates for the previous year based on the date of enrolment. Of the 1376 participants, 767 (52.8%) and 187 (13.6) had MAFLD and advanced fibrosis, respectively. A logistic regression analysis revealed that the factors associated with advanced liver fibrosis were HCV viremia (odds ratio OR, 3.13; 95% confidence interval CI, 2.05–4.77; p < 0.001), smoking (OR, 1.79; 95% CI, 1.16–2.74; p = 0.01), age (OR, 1.04; 95% CI, 1.02–1.05; p < 0.001) and PM2.5 (OR, 1.10; 95% CI, 1.05–1.16; p < 0.001). Linear regression analysis revealed that LSM was independently correlated with PM2.5 (β: 0.134; 95% CI: 0.025, 0.243; p = 0.02). There was a dose‐dependent relationship between different fibrotic stages and the PM2.5 level (the PM2.5 level in patients with fibrotic stages 0, 1–2 and 3–4: 27.9, 28.4, and 29.3 μg/m3, respectively; trend p < 0.001). Exposure to PM2.5, as well as HBV and HCV infections, is associated with advanced liver fibrosis in patients with MAFLD. There was a dose‐dependent correlation between PM2.5 levels and the severity of hepatic fibrosis.
Background and Aim
Hepatitis B virus (HBV) surface antigen (HBsAg) seroreversion usually occurs during immunosuppressive therapy. The risk and factors of HBsAg seroreversion from resolved HBV ...infection in the general population remained unclear.
Methods
This retrospective study enrolled subjects with resolved HBV infection and who had received at least two times of screening in a longitudinal community screening program. HBsAg, hepatitis B surface antibody (anti‐HBs), and hepatitis C virus antibody (anti‐HCV) were tested every time in all subjects. The primary endpoint was HBsAg seroreversion.
Results
Of the 7630 subjects enrolled, 5158 (67.6%) subjects had positive anti‐HBs at baseline. HBsAg seroreversion occurred in 84 subjects during 42 815‐person‐year follow‐up with an annual incidence of 0.2% and a 10‐year cumulative risk of 1.9%. Anti‐HBV treatment‐experienced subjects had a significantly higher risk of HBsAg seroreversion than anti‐HBV treatment‐naive subjects (83/310 26.8% vs 1/7320 0.01%, P < 0.001). Lower rates of positive anti‐HBs and anti‐HCV were observed in anti‐HBV treatment‐experienced subjects who developed HBsAg seroreversion. Both positive anti‐HBs (hazard ratio/95% confidence interval: 0.56/0.348–0.903, P = 0.017) and positive anti‐HCV (hazard ratio/95% confidence interval: 0.08/0.030–0.234, P < 0.001) were independent factors of HBsAg seroreversion in anti‐HBV treatment‐experienced subjects. Less than 5% of the HBsAg seroreverters had clinical hepatitis flare at HBsAg seroreversion. The HBsAg titer was low, and only transient reappeared in most of the HBsAg seroreverters.
Conclusions
Subjects with resolved HBV infection were at a minimal risk of HBsAg seroreversion, unless with prior anti‐HBV treatment experience. Fortunately, even with a reappearance of HBsAg, it was transient and clinically non‐relevant.
Patients with serious mental illness have a higher risk of hepatitis C virus (HCV) infection but suboptimal HCV care. The current study aimed to facilitate HCV treatment uptake by implementing an ...integrated outreach care model. Multidisciplinary outreach screening followed by HCV reflex testing and onsite treatment for schizophrenia patients was accomplished through the coordination of nongovernmental organizations, remote specialists, and local care providers. The objective was microelimination effectiveness, defined as the multiplication of the rates of anti‐HCV antibodies screening, accurate HCV RNA diagnosis, treatment allocation, treatment completion, and sustained virological response (SVR12; no detectable HCV RNA throughout 12 weeks in the post‐treatment follow‐up period). A total of 1478 of the 2300 (64.3%) psychiatric patients received HCV mass screening. Seventy‐three (4.9%) individuals were seropositive for anti‐HCV antibodies. Of the 73 anti‐HCV seropositive patients, all (100%) received HCV reflex testing, and 29 (37.7%) patients had HCV viremia. Eight patients (34.8%) had advanced liver disease, including 3 with liver cirrhosis and 2 with newly diagnosed hepatocellular carcinoma. Twenty‐three of the 24 (95.8%) patients who stayed in the healthcare system received and completed 8 weeks of glecaprevir/pibrentasvir treatment and post‐treatment follow‐up without significant DDIs or adverse events. The SVR12 rate was 100%. The microelimination effectiveness in the current study was 61.6%. Individuals with serious mental illness are underserved and suffer from diagnostic delays. This patient‐centered and integrated outreach program facilitated HCV care in this marginalized population.
![[Ag20{S2P(OR)2}12]: A Super...](http://api.summon.serialssolutions.com/2.0.0/image/issn/XR4PS5YY4K/0947-6539/small "[Ag20{S2P(OR)2}12]: A Superatom Complex with a Chiral Metallic Core and High Potential for Isomerism")
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