Search

The role of hepatitis C virus (HCV) infection statuses in the development of type 2 diabetes mellitus (T2DM) has not been completely understood. To evaluate the prevalence of T2DM in patients with different HCV infection statuses. We conducted a systematic study on T2DM risk in five types of individuals with different HCV infection statuses: non-HCV controls, HCV-cleared patients, chronic HCV patients without cirrhosis, patients with HCV cirrhosis and patients with decompensated HCV cirrhosis. Studies published from 2010 to 2019 were selected. Both pairwise and network meta-analyses were employed to compare the T2DM risk among patients with different HCV infection statuses. The pairwise meta-analysis showed that non-HCV (OR = 0.60, 95% CI [0.47–0.78]) had a lower risk of T2DM compared with CHC, while cirrhosis had a significant higher risk (OR = 1.90, 95% CI [1.60–2.26]). Network meta-analysis further demonstrated patients with HCV infection were at a significantly higher risk of T2DM than those without HCV infection or with HCV clearance, while decompensated cirrhosis had a significant higher T2DM risk than non-HCV (OR = 3.84, 95% CI [2.01–7.34]), patients with HCV clearance (OR = 3.17, 95% CI [1.49–6.73]), and CHC patients (OR = 2.21, 95% CI [1.24–3.94]). HCV infection is a significant risk factor for developing T2DM. CHC, cirrhosis, and decompensated cirrhosis contribute to an increasingly greater risk of T2DM, but HCV clearance spontaneously or through clinical treatment may immediately reduce the risk of the onset and development of T2DM.

The electroreductive dechlorination of γ-hexachlorocyclohexane (lindane) was investigated in non-aqueous media using as a catalyst the dirhodium complex Rh2(dpf)4, where dpf = the anion of N, N′-diphenylformamidinate. Rh2(dpf)4 undergoes two reversible one-electron redox processes in pyridine and/or N,N′-dimethylformamide (DMF), corresponding respectively to Rh24+/Rh25+ and Rh24+/Rh23+. Electrochemical and spectroelectrochemical measurements indicate that lindane reacts with the Rh23+ center in singly reduced [Rh2(dpf)4]−, giving a transient carbon-bonded dirhodium complex along with Cl−. Further catalytic dechlorination of lindane subsequently occurs with the activity of Rh2(dpf)4 as a catalyst depending upon the solvent conditions. Rh2(dpf)4 shows a higher catalytic reduction current in pyridine than in DMF for the degradation of lindane. This catalytic current can be further enhanced if 6% water (v/v) is added to the pyridine solution. Bulk controlled-potential electrolysis combined with GC–MS verified that although the addition of water to the neat pyridine increased the catalytic activity of Rh2(dpf)4, neat pyridine is still a better solvent for the formation of more extensively dechlorinated products of lindane. In neat pyridine, lindane can be converted stepwise to tetrachlorocyclohexene, dichlorobenzene isomers, chlorobenzene and the fully dechlorinated product benzene, the last of which becomes predominant at the end of the electrolysis. In pyridine having 6% added water, other than those dechlorinated products seen above, trichlorobenzene isomers are formed upon lindane degradation. Meanwhile, the relative concentrations of dichlorobenzene isomers and chlorobenzene become higher, while the yield of benzene becomes lower than the corresponding results obtained in neat pyridine. Based on the measured distribution of the products under the different solvent conditions, an overall pathway for the degradation of lindane is proposed.

BackgroundCoronavirus disease 2019 (COVID-19) has brought major harm and challenges to the world. Although many studies have suggested that IFN-I could affect the life cycle of the virus by regulating the expression level of microRNAs, the expression characteristics of plasma IFN-I signaling-related miRNAs at the acute and recovery phase of COVID-19 remain unclear.MethodsDemographic characteristics and fasting blood samples were collected from the acute and recovery phases of 29 COVID-19 patients and 29 healthy controls matched by age (± 5years) and gender (1:1). Expression levels of 12 IFN signaling-related miRNAs were analyzed using RT-qPCR. The receptor-binding domain (RBD) IgG antibody in the convalescent plasma samples was detected using competitive ELISA.ResultsCompared with healthy controls, patients with COVID-19 presented increased levels of miR-29b-3p (~ 5.91-fold), miR-497-5p (~ 2.28-fold), and miR-1246 (~ 7.97-fold), and decreased expression levels of miR-186-5p (~ 6.39-fold) and miR-15a-5p (~ 3.26-fold) at the acute phase of infection. However, the expression levels of miR-29b-3p and miR-1246, which significantly elevated at the acute phase, were not different between individuals at the recovery phase and healthy controls. The expression levels of miR-30b-5p, miR-497-5p, miR-409-3p and miR-548c-5p in convalescent plasma samples were significantly lower than those in healthy controls. However, the concentration of miR-186-5p in the convalescent plasma samples was significantly higher than that in healthy controls and patients with acute infection. Furthermore, competitive ELISA results showed that the plasma level of miR-497-5p at the acute phase positively correlated with RBD-IgG antibody response (r=0.48, P=0.038).ConclusionsThe present study firstly reported that timely and appropriate regulation of IFN signaling-related miRNA expression plays a critical role during both acute and recovery phase of SARS-CoV-2 infection. Furthermore, the circulating miR-497-5p level was positively correlated to RBD-IgG antibody response in COVID-19 patients.

Background KIR/HLA-C signaling pathway influences the innate immune response which is the first defense to hepatitis C virus (HCV) infection. The aim of this study was to determine the association between the genetic polymorphisms of KIR/HLA-C genes and the outcomes of HCV infection in a high-risk Chinese population. Methods In this case-control study, four single nucleotide polymorphisms (SNPs) of KIR/HLA-C genes (KIR2DS4/KIR2DS1/KIR2DL1 rs35440472, HLA-C rs2308557, HLA-C rs1130838, and HLA-C rs2524094) were genotyped by TaqMan assay among drug users and hemodialysis (HD) patients including 1,378 uninfected control cases, 307 subjects with spontaneous viral clearance, and 217 patients with persistent HCV infection. Bioinformatics analysis was used to functionally annotate the SNPs. Results After logistic regression analysis, the rs35440472-A and rs1130838-A alleles were found to be associated with a significantly elevated risk of HCV infection (OR = 1.562, 95% CI: 1.229–1.987, P < 0.001; OR = 2.134, 95% CI: 1.180–3.858, P = 0.012, respectively), which remained significant after Bonferroni correction (0.05/4). The combined effect of their risk alleles and risk genotypes (rs35440472-AA and rs1130838-AA) were linked to the increased risk of HCV infection in a locus-dosage manner (all P trend < 0.001). Based on the SNPinfo web server, rs35440472 was predicted to be a transcription factor binding site (TFBS) while rs1130838 was predicted to have a splicing (ESE or ESS) function. Conclusion KIR2DS4/KIR2DS1/KIR2DL1 rs35440472-A and HLA-C rs1130838-A variants are associated with increased susceptibility to HCV infection in a high-risk Chinese population.

Hypertension is a common comorbidity in COVID-19 patients. However, the association of hypertension with the severity and fatality of COVID-19 remain unclear. In the present meta-analysis, relevant studies reported the impacts of hypertension on SARS-CoV-2 infection were identified by searching PubMed, Elsevier Science Direct, Web of Science, Wiley Online Library, Embase and CNKI up to 20 March 2020. As the results shown, 12 publications with 2389 COVID-19 patients (674 severe cases) were included for the analysis of disease severity. The severity rate of COVID-19 in hypertensive patients was much higher than in non-hypertensive cases (37.58%vs19.73%, pooled OR: 2.27, 95% CI: 1.80–2.86). Moreover, the pooled ORs of COVID-19 severity for hypertensionvs.non-hypertension was 2.21 (95% CI: 1.58–3.10) and 2.32 (95% CI: 1.70–3.17) in age vs.non-hypertension was 6.43 (95% CI: 3.40–12.17) and 2.66 (95% CI: 1.27–5.57) in age

To investigate whether nuclear factor-kappa B1 (NFKB1) gene polymorphisms are associated with the outcomes of hepatitis C virus (HCV) infection in a Chinese high-risk population.In this case-control study, 984 HCV-uninfected controls, 221 infected individuals with spontaneous HCV clearance, and 456 with persistent HCV infection were enrolled. Rs28362491 and rs72696119 were genotyped using the ABI TaqMan allelic discrimination assay. The functional annotation of the identified single nucleotide polymorphisms (SNPs) were further evaluated by bioinformatics analysis.Significant differences were observed among the three groups (P 0.001) in terms of the frequency of rs28362491 SNP. In logistic regression analysis, rs28362491-ATTG deleted (D) was associated with a significantly increased risk of HCV infection compared to the major-type rs28362491-ATTG inserted (I) (dominant model: adjusted OR = 1.332, 95% CI = 1.059-1.674, P = 0.014; additive model: adjusted OR = 1.181, 95% CI = 1.021-1.367, P = 0.025), after adjusting for age, gender, and route of infection. Based on the in silico prediction, the RegulomeDB score for SNP rs28362491 was 3a, indicating that it can potentially regulate the transcription and expression of NFKB1 gene.NFKB1 rs28362491-D allele was functionally associated with the increased risk of susceptibility to HCV infection in the Chinese Han population.

Mounting evidence has shown that microRNAs (miRNAs), a class of small non-coding RNAs, are frequently deregulated in human malignancies and have pivotal roles in diverse biological processes including cancer cell proliferation. Herein, we investigated the expression pattern of miR-383 in 64 hepatocellular carcinoma (HCC) tissues and 4 HCC cell lines and found that miR-383 was downregulated in HCC tissues and cell lines. Moreover, miR-383 expression in HCC was significantly correlated with tumor size and tumor-node-metastasis (TNM) stage. Kaplan-Meier analysis showed that decreased miR-383 expression was associated with poor overall survival of HCC patients. In addition, Cox regression analysis indicated that miR-383 was an independent prognostic factor for HCC patients. Then, functional studies demonstrated that ectopic miR-383 expression could significantly suppress the in vitro proliferation of HCC cells, as well as induce cell cycle arrest and cell apoptosis. Luciferase reporter assay further identified that a proliferation-inducing ligand (APRIL), a member in the tumor necrosis factor (TNF) superfamily, was a novel target gene for miR-383. Subsequent investigation revealed that miR-383 expression was inversely correlated with APRIL messenger RNA (mRNA) expression in HCC tissues. Besides, recombinant human APRIL (rhAPRIL) could rescue HCC cell proliferation inhibited by miR-383. Taken together, our present study provided the first evidence that miR-383 was decreased in HCC and associated with tumor progression and prognosis of HCC patients. Furthermore, our findings confirmed that miR-383 might inhibit HCC cell proliferation partially via downregulating APRIL expression. Thus, this study might provide a promising strategy by targeting with the miR-383-APRIL axis in the treatment of HCC.

Background Hepatitis B virus (HBV) G1896A mutation was associated with HBeAg seronegativity and hepatitis B related acute-on-chronic liver failure. In this study, we developed Taqman amplification refractory mutation system (Taqman-ARMS) and established a strict control system to detect HBV G1896A mutant. Methods HBV viral DNA was isolated from 60 patient serum samples, and full-length HBV genome was cloned. Then, Taqman-ARMS was used to detect HBV G1896A mutant. Results The assay has the sensitivity of 1E+3 IU/ml G1896A template, and 0.1% weak population virus with G1896A could be found in mixtures. Total of all 60 clinical samples random collected were detected by Taqman-ARMS, the results were consistent with those by DNA sequencing. Conclusion The proposed Taqman-ARMS real-time PCR method for the detection of G1896A mutation of HBV was rapid, simple, sensitive, specific, and applicable in the clinical setting.

Iron(II) 2,3- and 3,4-tetrapyridinoporphyrazine complexes (2,3-PyD and 3,4-PyD) were synthesized and characterized as to their electrochemistry, UV-visible spectroelectrochemistry and catalytic properties towards the reductive dechlorination of 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (p,p′-DDT) in pyridine, dimethyl sulfoxide (DMSO), N,N′-dimethylacetamide (DMA) and N,N′-dimethylformamide (DMF). These properties were compared with those of the unsubstituted iron(II) phthalocyanine ((Pc) Fe ). Electrochemistry indicates that there are up to three reductions and one oxidation in the three investigated derivatives. The easiest reduction takes place for 3,4-PyD while the most difficult one occurs for (Pc) Fe in all of the solvents investigated. The first reduction is metal-centered corresponding to the formation of [P(-2)Fe(I)]- while the second and third reductions are ring-centered leading stepwise to the generation of [P(-3)Fe(I)]2- · and [P(-4)Fe(I)]3- , where P = phthalocyanine or tetrapyridinoporphyrazine rings. Aggregation exists in the solutions of all three iron complexes and its extent depends upon the nature and concentration of the iron compounds and the binding property of each solvent. The order of the extent of aggregation for the three iron derivatives is 3,4-PyD > 2,3-PyD > (Pc) Fe . Stronger binding solvents such as pyridine and DMSO do not favor the aggregation. The singly and doubly reduced species of investigated complexes, [P(-2)Fe(I)]- and [P(-3)Fe(I)]2- · , are active in DDT reductive dechlorination, the latter of which has better catalytic performance. As a result, three products, 1,1-bis(4-chlorophenyl)-2,2-dichloroethane (p,p′-DDD), 1,1-bis(4-chlorophenyl)-2,2-dichloroethylene (p,p′-DDE), and 1,1-bis(4-chlorophenyl)-2-chloroethylene (p,p′-DDMU), were obtained after the dechlorination of DDT catalyzed by each iron complex. The increasing order of catalytic performance is 3,4-PyD < 2,3-PyD < (Pc) Fe in pyridine, which is superior to DMSO and DMA for the DDT dechlorination reaction. An overall electrocatalytic mechanism is proposed for DDT reductive degradation based on the electrochemical and UV-visible spectroelectrochemical results.

The mechanical properties and flame retardancy of linear low-density polyethylene/ethylene-propylene-diene terpolymer thermoplastic elastomers (TPEs) containing magnesium hydroxide sulfate hydrate (MHSH) whiskers and their corresponding un-vulcanized blends (UVBs) were evaluated using static tensile measurements, cone calorimetry and limiting oxygen index (LOI) tests. TPEs exhibited better fire-resistant properties in reducing peak heat release rate and improving LOI values to UVBs. Scanning electron microscopy (SEM) images showed that TPE sample left a more compact char after cone test. Results from tensile tests confirmed that TPEs had superior mechanical properties to UVBs due to the better compatibility between MHSH whiskers and polymer matrix.

Neutral cobalt(II) phthalocyanine and 2,3- and 3,4-tetrapyridoporphyrazine complexes were examined in pyridine, dimethyl sulfoxide and N,N-dimethylformamide to evaluate their catalytic properties in the reductive dechlorination of 1,1-bis(4-chlorophenyl)-2,2,2-trichloroethane (p,p'-DDT). Cyclic voltammetry, controlled potential bulk electrolysis and thin-layer UV-visible spectroelectrochemistry of each compound in the presence of DDT indicated that both the singly and doubly reduced species, [Co(I)]- and [Co(I)]2- , can catalyze the dechlorination of DDT through the formation of, and a photoinduced or electrochemically induced cleavage of, the Co-C bond in the organometallic intermediates. GC-MS analysis revealed that DDT was converted to 1,1-bis(4-chlorophenyl)-2, 2-dichloroethane (p,p'-DDD), 1,1-bis(4-chlorophenyl)-2,2-dichloroethylene (p,p'-DDE) and 1,1-bis(4-chlorophenyl)-2-chloroethylene (p,p'-DDMU), upon dechlorination. The catalytic performance of the three cobalt complexes depends upon the reactive nature of each compound, the solvent, the reaction time and the equivalence of DDT. In addition, either DDD or DDE can be catalytically dechlorinated to generate DDMU, possibly through a similar mechanism.

Two cobalt porphyrazines, 2,3-tetrapyridoporphyrazine and 3,4-tetrapyridoporphyrazine, were examined in N,N-dimethylformamide, dimethyl sulfoxide and pyridine solutions as to their electrochemical, spectroelectrochemical and ESR spectroscopic properties. These results were compared with those of the unsubstituted cobalt phthalocyanine. At high concentrations, aggregation was observed for each investigated compound in the three solvents. The intensity of ESR signals of each derivative depends upon the extent of aggregation in its solution. The g values shift towards high field with an increase in the strength of the axial ligand and the number of axial ligands on the cobalt center. Both tetrapyridoporphyrazine complexes undergo one oxidation and three reductions in N,N-dimethylformamide, dimethyl sulfoxide or pyridine solution. Thin-layer UV-visible spectroelectrochemical results confirmed that the first oxidation and first reduction of both compounds are metal-centered while the second and third reductions are ring-centered. An overall electron transfer mechanism for both porphyrazine derivatives is proposed.

The cyclic voltammetric studies on ER(2)[(eta(5)-C(5)H(4))Fe(L(2))Me](2) (L(2) = dppe; ER(2) = CH(2) (1a), SiMe(2) (2a), GeMe(2) (3a), SnMe(2) (4a) revealed two well resolved reversible waves [(1)E(1/2) = -0.33 V, (2)E(1/2) = -0.20 V (for 1a); (1)E(1/2) = -0.35 V, (2)E(1/2) = -0.21 V (for 2a);(1)E(1/2) = -0.36 V, (2)E(1/2) = -0.23 V (for 3a);(1)E(1/2) = -0.36 V, (2)E(1/2) = -0.22 V (for 4a)] in CH(2)Cl(2) suggesting electronic communication between two iron centers which is seen for the first time in this family of organometallic complexes. The resolution between two reversible waves increases in the order of 1a < 2a < 3a < 4a; however, coordinating solvents such as pyridine, PhCN, DMSO and DMF decreased these interactions attributable to the stabilization of cationic species formed after the first oxidation. UV/Vis spectroelectrochemistry of 1a-4a revealed two distinct absorbance patterns for both redox processes and reflected the stepwise oxidation. Homobimetallic complexes containing ferrocenyl groups, (eta(5)-C(5)H(5))Fe(L(2))ER(2)Fc [ER(2) = none, L(2) = cis-dppen (5a), ER(2) = SiMe(2), L(2) = cis-dppen (6a), dppm (6b); ER(2) = GeMe(2), L(2) = cis-dppen (7a), dppm (7b); ER(2) = Sn(t)Bu(2), L(2) = dmpe (8a); Fc = (eta(5)-C(5)H(4))Fe(eta(5)4-C(5)H(5))] were prepared and studied in terms of electrochemistry. The cyclic voltammogram of 5a exhibited two well resolved one electron reversible waves at (1)E(1/2) = -0.21 V and (2)E(1/2) = 0.58 V corresponding to oxidation of the Fe(P-P) and Fc iron atoms respectively. Other complexes in this series (6a/6b, 7a/7b, 8a) containing direct Fe-E-Fc (E = Si, Ge and Sn) bridging units were not stable under electrochemical conditions and rupture of the Fe-E bonds was observed.

The synthesis and redox properties of a series of free-base and metal(II) quinoxalino[2,3-b']porphyrins and their use in an investigation of the substituent effects on the degree of communication between the porphyrin and its beta,beta'-fused quinoxalino component are reported. ESR, thin-layer spectroelectrochemistry, and quantum chemical calculations of the resultant radical anions from one-electron reduction indicate that localization of the unpaired electron across both the porphyrin and the fused quinoxalino group can be controlled, the system as a whole behaving as a highly polarizable pi-expanded porphyrin radical anion. ESR studies on the radical anions of zinc(II) quinoxalino[2,3-b']porphyrin derivatives indicate that nitrogen-atom spin distribution changes as a function of chemical substitution: 27% quinoxaline character when the porphyrin ring bears a 7-nitro substituent, 34% quinoxaline character in the unsubstituted parent, and 51-61% nitroquinoxaline character when the quinoxalino unit has one or more nitro groups. Close analogies are found between the calculated and observed nitrogen-atom spin distributions, indicating that the calculations embody the key chemical effects. The calculations also indicate that the nitrogen-atom spin distributions closely parallel the important total porphyrin, quinoxaline, and nitro spin distributions, indicating that the observed quantities realistically depict the change in the nature of the delocalization of the radical anion as a function of chemical substitution. The profound effects observed indicate long-range communication of the type that is essential in molecular electronics applications.

A series of free-base corroles with different electron-donating or electron-withdrawing substituents were reacted with piperidine, 4-aminopyridine, 2-methylimidazole, 2-aminopyridine or pyridine in PhCN and the UV-visible spectral changes monitored during conversion of ( Cor ) H 3 to [( Cor ) H 2]- as a function of the concentration and strength of the added organic base. Analysis of the UV-visible spectral changes as a function of the added base concentration enabled calculation of equilibrium constants ( logK ) for deprotonation of each corrole under the given experimental conditions. Relationships are examined between the experimentally measured logK values and previously published spectroscopic and structural properties of the compounds.

Protonated meso-substituted free-base macrocycles of the form [(Cor)H4]+, [(Cor)H5]2+, and [(Cor)H6]3+ where Cor is the trianion of a given corrole, were chemically generated from neutral (Cor)H3 in benzonitrile by addition of trifluoroacetic acid (TFA) and characterized as to their relative acidity, electrochemistry, and spectroelectrochemistry. Three types of protonated free-base corroles with different electron-donating or electron-withdrawing substituents at the meso positions of the macrocycle were investigated. One is protonated exclusively at the central nitrogens of the corrole forming [(Cor)H4]+ from (Cor)H3, while the second and third types of corroles undergo protonation at one or two meso pyridyl substituents prior to protonation of the central nitrogens and give as the final products [(Cor)H5]2+ and [(Cor)H6]3+, respectively. Altogether the relative deprotonation constants (pKa) for 10 different corroles were determined in benzonitrile and analyzed with respect to the molecular structure and/or type of substituents on the three meso positions of the macrocycle. Mechanisms for oxidation and reduction of the protonated corroles are proposed in light of the electrochemical and spectroelectrochemical data.

To investigate the role of Src family kinases (Fgr, Hck, Lyn) and the major protein kinase C substrate SSeCKS in non-alcoholic steatohepatitis (NASH) and determine the possible mechanism regulating differential expression.Kupffer cells were stimulated with CCL4 and effect on SSeCKS, Hck, Fgr, and Lyn expression was detected by real-time reverse transcription-PCR. Male Sprague-Dawley rats were used to create a NASH model by feeing a high fat diet. The modeled rats were divided into a model group and a normal group. After sacrifice, the extent of hepatic steatosis and inflammation was assessed, and the expression levels of SSeCKS and Hck, Fgr, Lyn were detected by immunohistochemical staining.Expression of Lyn and Hck was decreased in the CCL4-stimulated Kupffer cells and the change in expression level was positively associated with levels of inflammatory stimuli (P0.01). The change in expression of SSeCKS in the CCL4-stimulated Kupffer cells was negatively correlated with inflammatory stimuli (P0.01). Fgr expression was very low in the unstimulated Kupffer cells and was not affected by the exposure to inflammatory stimuli. The number of inflammatory cells in the liver tissues of rars were negatively correlated with expression of Lyn, Hck and SSeCKS (P0.01), with low negative correlation for Lyn (r =-0.398, P0.01) and moderate negative correlation for Hck (r=-0.508, P0.01); the Lyn and Hck expression levels were highly positively correlated (r =0.942, P0.01).Src family kinases (Lyn, Hck and Fgr) and SSeCKS are involved in development and progression of NASH, and their differential expression patterns are associated to a certain extent. The factors may represent potential targets of therapy for NASH-related inflammation.

An electron donor–acceptor linked compound containing Zn(II) and Au(III) porphyrins ( ZnPQ - AuPQ + PF 6 - ) has been designed and synthesized to examine its electrochemical and photophysical properties. Time-resolved transient absorption spectra of ZnPQ–AuPQ + were measured by nanosecond laser photolysis in toluene and cyclohexane. The observed transient absorption bands at 600–800 nm are assigned to the charge-shift state (ZnPQ + –AuPQ). The charge-shifted state decays via back electron transfer (BET) to the ground state rather than to the triplet excited state. The BET rate was determined from the disappearance of the absorption band at 750 nm due to ZnPQ + in ZnPQ + –AuPQ. The decay of the absorption band obeys first-order kinetics. The k BET value in cyclohexane is determined as 1.0 × 10 5 s −1 , which corresponds to a lifetime of 10μs, whereas the lifetime becomes much shorter (250 ps) in benzonitrile. The charge-shift state is also observed for a zinc porphyrin–free base porphyrin–gold porphyrin triad (ZnPQ–2HPQ–AuPQ + ), which has a longer lifetime of 14 μs in cyclohexane. The detailed photodynamics of ZnPQ–AuPQ + and ZnPQ–H 2 PQ–AuPQ + are also reported. We have successfully attained long-lived charge-shift states in nonpolar solvents using the ZnPQ–AuPQ + dyad and the ZnPQ–H 2 PQ–AuPQ + triad. This photoinduced electron-transfer in low dielectric environment mimics a key feature of photosynthetic reaction centers.

A new synthesis is reported for hexadecafluorophthalocyanineruthenium(II), F16Pc (2-) RuIIand hexadecachlorophthalocyanineruthenium(II), Cl16Pc (2-) RuII, is reported for the first time. These paramagnetic species, which contain no axial ligand, are quite reasonably soluble in a range of common organic solvents. We report and discuss electronic and vibrational (infrared and resonance Raman) spectroscopic, MALDI-TOF and magnetic data. In addition we report electrochemical data and use spectroelectrochemical methods to obtain the electronic spectra of these species in the phthalocyanine(1-), (3-) and (4-) oxidation states.

Two α-substituted vanadium-oxo phthalocyanines, [( OC 6 H 3(t- Bu )2)4Pc] VO and [( OC 8 H 17)4Pc] VO , where OC 6 H 3(t- Bu )2 is 2,4-di-tert-butylphenoxy and OC 8 H 17 is 2,2,4-tri-methyl-3-pentoxy, were synthesized and characterized by elemental analysis, mass spectrometry, UV-visible, IR, ESR spectroscopy and electrochemistry. Both complexes have good solubility and do not aggregate in polar or non-polar solvents. Three reductions and two oxidations can be observed in DMF containing 0.2 M TBAP. A HOMO-LUMO gap of ~1.4 V is seen for both complexes. The first two one-electron reductions and first oxidation are reversible diffusion controlled electrode processes under the given experimental conditions. The effects of solvent and phthalocyanine macrocycle substituents on the Q bands of the electronic absorption spectra are discussed.

Three series of cobalt(III) corroles were tested as catalysts for the electroreduction of dioxygen to water. One was a simple monocorrole represented as (Me(4)Ph(5)Cor)Co, one a face-to-face biscorrole linked by an anthracene (A), biphenylene (B), 9,9-dimethylxanthene (X), dibenzofuran (O) or dibenzothiophene (S) bridge, (BCY)Co(2) (with Y = A, B, X, O or S), and one a face-to-face bismacrocyclic complex, (PCY)Co(2), containing a Co(II) porphyrin and a Co(III) corrole also linked by one of the above rigid spacers (Y = A, B, X, or O). Cyclic voltammetry and rotating ring-disk electrode voltammetry were both used to examine the catalytic activity of the cobalt complexes in acid media. The mixed valent Co(II)/Co(III) complexes, (PCY)Co(2), and the biscorrole complexes, (BCY)Co(2), which contain two Co(III) ions in their air-stable forms, all provide a direct four-electron pathway for the reduction of O(2) to H(2)O in aqueous acidic electrolyte when adsorbed on a graphite electrode, with the most efficient process being observed in the case of the complexes having an anthracene spacer. A relatively small amount of hydrogen peroxide was detected at the ring electrode in the vicinity of E(1/2) which was located at 0.47 V vs SCE for (PCA)Co(2) and 0.39 V vs SCE for (BCA)Co(2). The cobalt(III) monocorrole (Me(4)Ph(5)Cor)Co also catalyzes the electroreduction of dioxygen at E(1/2) = 0.38 V with the final products being an approximate 50% mixture of H(2)O(2) and H(2)O.

Quinoxalino[2,3-b]porphyrins are laterally-extended porphyrins with aromatic ring systems fused to the β,β'-positions of a pyrrolic ring of the macrocycle. They are building blocks for coplanar laterally-extended oligoporphyrins with applications in molecular electronics. The electrochemistry and spectroelectrochemistry of four such quinoxalinoporphyrins containing metal(II) ions and one free-base quinoxalinoporphyrin dissolved in nonaqueous media have been investigated and the data are compared to that seen for the same derivatives of the parent macrocycle lacking the fused quinoxaline ring. The investigated compounds are represented as (P)M and (PQ)M, where P = 5 ,10,15,20-tetrakis(3,5-di-tert-butylphenyl)porphyrin, PQ = 5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)quinoxalino[2,3-b]porphyrin and M = 2 H , Zn , Cu , Ni or Pd . The complexes all undergo two ring-centered reductions and one or two ring-centered oxidations in PhCN , CH 2 Cl 2, pyridine or THF . Additional redox reactions are also seen for the quinoxaline group in THF . The fusion of an electroactive quinoxaline group to the porphyrin macrocycle results in an 80 to 270 mV shift of E 1/2 towards easier reductions and the appearance of a third reduction which is assigned as a quinoxaline-centered redox process. The average HOMO-LUMO gap for the ( P ) M and ( PQ ) M derivatives is 2.26 ± 0.09 V and 2.14 ± 0.08 V , respectively. Both values are smaller than the average separation of 2.33 ± 0.13 V for the corresponding derivatives of tetraphenylporphyrin. The electrochemistry and UV-visible spectroelectrochemcal data indicate that moderate communication exists between the quinoxaline unit and the porphyrin π-ring system.

The synthesis, catalytic properties, UV-visible spectra and electrochemistry of β-pyrrole brominated porphyrins are summarized in this brief review. The effect of the Br substituents of the porphyrin ring on the redox behavior, and on axial CO or pyridine binding to the porphyrins is also discussed.

Ten meso-tetraphenylporphyrin-type heterodimers containing a partly or completely β-brominated subunit were synthesized and characterized by UV-visible spectroscopy, cyclic voltammetry and spectroelectrochemistry, showing the presence of low electronic interactions between the two subunits. The investigated compounds are represented as M [( tripp - tpp ( Br 4)] M and M [ tripp - tpp ( Br 8)] M ( M = 2 H , Zn , Ni , Co and Cu ) where tripp - tpp ( Br 4) is the tetraanion of 1-[5-(10,15,20-triphenylporphyrinyl)]-4-[10-(2,3,12,13-tetrabromoporphyrinyl)]-benzene and tripp - tpp ( Br 8) is the tetraanion of 1-[5-(10,15,20-triphenylporphyrinyl)]-4-[10-(2,3,7,8,12,13,17,18-octabromoporphyrinyl)]-benzene. One of the synthesized dimers, H 2[ tripp - tpp ( Br 8)] H 2, was characterized by a single-crystal X-ray investigation.

A bacteriochlorin-C60 dyad (H2BCh-C60) and a zinc chlorin dyad (ZnCh-C60) with the same short spacer have been synthesized. The rate constants for the charge-separation (CS) processes in these dyads were determined by fluorescence lifetime measurements of the dyads. The charge-recombination (CR) rate constants of the dyads were determined using laser flash photolysis. The photoexcitation of the zinc chlorin-C60 dyad results in formation of the long-lived radical ion pair, which has absorption maxima at 790 and 1000 nm due to the zinc chlorin radical cation and the C60 radical anion, respectively. Photoexcitation of the free-base bacteriochlorin-C60 dyad with the same short linkage leads to formation of the radical ion pair, which decays quickly to the triplet excited state of the bacteriochlorin moiety. The driving force dependence of the electron-transfer rate constants of these dyads with a short spacer affords a small reorganization energy (λ = 0.51 eV) as compared with the λ value (0.66 eV) of zinc po...

Two diruthenium(III,III) corrole dimers, [(Et 6 Me 2 Cor)Ru] 2 and [(Me 6 Et 2 Cor)Ru] 2 , where Et 6 Me 2 Cor and Me 6 Et 2 Cor are the 2,3,8,12,17,18-hexaethyl-7,13-dimethylcorrole and 8,12-diethyl-2,3,7,13,17,18-hexamethylcorrole trianions, respectively, were synthesized and characterized as to their spectroscopic and electrochemical properties. They exhibit up to three oxidations and two reductions by cyclic voltammetry in CH 2 Cl 2 or pyridine containing 0.1 M TBAP, almost all of which are electrochemically reversible on the voltammetric and/or thin-layer spectroelectrochemical timescale. The two reductions and the first two oxidations involve one-electron transfer processes which are separated from each other by 770–880 mV upon reduction and by 350–420 mV upon oxidation. The UV–vis spectroelectrochemical data suggest that the first two one-electron oxidations occur at the diruthenium metal centers while the third oxidation (seen only in CH 2 Cl 2 ) is proposed to be macrocycle-based, leading to the formation of a Ru 2 (IV,IV) corrole species. The formation of a Ru(III,IV) complex after abstraction of one electron is also suggested by the rhombic ESR spectrum of singly oxidized [(Me 6 Et 2 Cor)Ru] 2 at 77 K. The first one-electron reduction is also assigned as metal-centered and leads to the formation of a Ru 2 (III,II) complex. Finally, a comparison of electrochemical properties between the investigated diruthenium(III,III) corroles and an earlier characterized diruthenium(II,II) octaethylporphyrin, [(OEP)Ru] 2 , is presented.

The synthesis, photophysical, and photochemical properties of a series of stable bacteriochlorins containing a fused six-member anhydride or an imide ring are discussed. The Q y band (a 1 u → e g x transition) in the near-infrared region (NIR) lies between 788 and 831 nm depending upon the macrocycle substituents. Compounds with such a long-wavelength absorption are highly promising for their potential use in photodynamic therapy. Fluorescence maxima are also observed in the long-wavelength region of the spectrum, between 804 and 842 nm, and have lifetimes between 1.1 and 1.4 ns. The phosphorescence maxima are red-shifted to 840-870 nm. The triplet-triplet transient absorption spectra are observed to have maxima between 570 and 640 nm with lifetimes between 72 and 150 μs. The triplet excited states are efficiently quenched by oxygen to produce singlet oxygen. The quantum yields of the generated singlet oxygen were determined to be in the range of 0.33-0.55, The bacteriochlorin derivatives are easy to oxidize by one electron, and reversible half-wave potentials range between 0.65 and 0.82 V vs SCE in benzonitrile containing 0.1 M tetra-n-butylammonium perchlorate (TBAP). The second oxidation is irreversible and occurs at a rather constant potential of 1.17-1.22 V independent of the macrocycle substituents. The bacteriochlorin derivatives are also easy to reduce, and the reversible first and second one-electron reduction potentials range between -0.53 and -0.80 V and between -0.95 and -1.28 V vs SCE, respectively. Spectroelectrochemical measurements reveal the expected π radical cation and π radical anion marker bands of the bacteriochlorin derivatives. The electron spin resonance (ESR) spectra of the radical cations and radical anions produced by the chemical oxidation and reduction are reported, and the experimental and calculated spin densities are compared to each other.

Previous studies have identified a number of microRNAs (miRNAs) that were aberrantly expressed in hepatocellular carcinoma (HCC) tissues. Nevertheless, their diagnostic and prognostic value in serum has not been fully evaluated. Herein, the levels of five serum miRNAs, namely, miR-182, miR-331-3p, miR-197, miR-492, and miR-581, were detected in 103 HCC patients, 95 benign liver diseases, and 40 healthy controls using real-time PCR technique. The results showed that, compared with benign liver diseases and healthy controls, the levels of serum miR-182 and miR-331-3p were significantly increased in HCC patients, both P

Three related diruthenium complexes containing four symmetrical anionic bridging ligands were synthesized and characterized as to their electrochemical and spectroscopic properties. The examined compounds are represented as Ru2(dpb)4Cl, Ru2(dpb)4(CO), and Ru2(dpb)4(NO) in the solid state, where dpb = diphenylbenzamidinate anion. Different forms of Ru2(dpb)4Cl are observed in solution depending on the utilized solvent and the counteranion added to solution. Each Ru2(5+) form of the compound undergoes multiple redox processes involving the dimetal unit. The reversibility as well as potentials of these diruthenium-centered electrode reactions depends upon the solvent and the bound axial ligand. The Ru2(5+/4+) and Ru2(5+/6+) processes of Ru2(dpb)4Cl were monitored by UV-vis spectroscopy in both CH2Cl2 and PhCN. A conversion of Ru2(dpb)4Cl to [Ru2(dpb)4(CO)](+) was also carried out by simply bubbling CO gas through a CH2Cl2 solution of Ru2(dpb)4Cl at room temperature. The chemically generated [Ru2(dpb)4(CO)](+) complex undergoes several electron transfer processes in CH2Cl2 containing 0.1 M TBAClO4 under a CO atmosphere, and the same reactions were seen for a chemically synthesized sample of Ru2(dpf)4(CO) in CH2Cl2, 0.1 M TBAClO4 under a N2 atmosphere, where dpf = N,N'-diphenylformamidinate anion. Ru2(dpb)4(NO) undergoes two successive one-electron reductions and a single one-electron oxidation, all of which involve the diruthenium unit. The CO and NO adducts of Ru2(dpb)4 were further characterized by FTIR spectroelectrochemistry, and the IR spectral data of these compounds are discussed in light of results for previously characterized Ru2(dpf)4(CO) and Ru2(dpf)4(NO) derivatives under similar solution conditions.

The photochemical and electrochemical properties of four chlorin-C60 or porphyrin-C60 dyads having the same short spacer between the macrocycle and the fullerene are examined. In contrast with all the previous results on porphyrin-fullerene dyads, the photoexcitation of a zinc chlorin-C60 dyad results in an unusually long-lived radical ion pair which decays via first-order kinetics with a decay rate constant of 9.1 x 10(3) x s(-1). This value is 2-6 orders of magnitude smaller than values reported for all other porphyrin or chlorin donor-acceptor of the molecule dyad systems. The formation of radical cations of the donor part and the radical anion of the acceptor part was also confirmed by ESR measurements under photoirradiation at low temperature. The photoexcitation of other dyads (free-base chlorin-C60, zinc porphyrin-C60, and free-base porphyrin-C60 dyads) results in formation of the ion pairs which decay quickly to the triplet excited states of the chlorin or porphyrin moiety via the higher lying radical ion pair states as is expected from the redox potentials.