Mechanistic insights into photoinduced energy and charge transfer dynamics between magnesium-centered tetrapyrroles and carbon nanotubes.

Functionalizing single-walled carbon nanotubes (SWNTs) with light-harvesting molecules is a facile way to construct donor-acceptor nanoarchitectures with intriguing optoelectronic properties. Magnesium-centered bacteriochlorin (MgBC), chlorin (MgC), and porphyrin (MgP) are a series of tetrapyrrole macrocycles comprising a central metal and four coordinated aromatic or antiaromatic five-membered rings linked by methine units, which show excellent visible light absorption. To delineate the effects of the aromaticity of coordinated rings on the optoelectronic properties of the nanocomposites, the photoinduced energy and charge transfer dynamics between Mg-centered tetrapyrroles and SWNTs are explored. The results show that excited energy transfer (EET) can occur within MgP@SWNT ascribed to the stabilization of the highest occupied molecular orbital (HOMO) in MgP with the increase of aromatic coordinated rings, while only electron transfer can take place in MgBC@SWNT and MgC@SWNT. Non-adiabatic dynamics simulations demonstrate that electron and hole transfer from MgP to SWNT is asynchronous. The electron transfer is ultrafast with a timescale of ca. 50 fs. By contrast, the hole transfer is significantly suppressed, although it can be accelerated to some extent when using a lower excitation energy of 2.2 eV as opposed to 3.1 eV. Further analysis reveals that the large energy gaps between charge-donor and charge-acceptor states play a crucial role in regulating photoexcited state relaxation dynamics. Our theoretical insights elucidate the structure-functionality interrelations between Mg-centered tetrapyrroles and SWNTs and provide a comprehensive understanding of the underlying charge transfer mechanism within MgP@SWNT nanocomposites, which paves the way for the forthcoming development of SWNT-based photo-related functional materials with targeted applications.

Near-Infrared Dual-Emission of a Thiolate-Protected Au42 Nanocluster: Excited States, Nonradiative Rates, and Mechanism.

Both DFT and TD-DFT methods are used to elaborate on the excited-state properties and dual-emission mechanism of a thiolate-protected Au42 nanocluster. A three-state model (S0, S1, and T1) is proposed with respect to the results. The intersystem crossing (ISC) process from S1 to T1 benefits from a small reorganization energy due to the similar geometric structures of S1 and T1. However, the ISC process is suppressed by relatively small spin-orbit coupling resulting from the similarity of the electronic structures of S1 and T1. As a result of the counterbalance, the ISC rate is comparable with the fluorescence emission rate. In the T1 state, the phosphorescence emission prevails the reverse ISC process back to the S1 state. Taken together, fluorescence and phosphorescence are achieved simultaneously. The present work provides deep mechanistic insights to aid the rational design of NIR dual-emissive metal nanoclusters.

Interfacial photoinduced carrier dynamics tuned by polymerization of coronene molecules encapsulated in carbon nanotubes: bridging type-I and type-II heterojunctions.

Carbon nanomaterials play important roles in modern scientific research. Integrating different carbon-based building blocks into nano-hybrid architectures not only takes full advantage of each component, but also brings in novel interfacial properties. Herein, we have employed density functional theory (DFT) calculations to investigate the effects of polymerization degree of coronene molecules encapsulated in single-walled carbon nanotubes (SWNTs) (19,0) on their interfacial properties. The present results reveal that the interfacial properties of the formed heterojunctions are remarkably regulated by the polymerization degree. For example, monomer- and dimer-encapsulated SWNTs are type-I heterojunctions in which interfacial excitation energy transfer is preferred, whereas interfacial charge carrier transfer is favorable in trimer- and polymer-encapsulated SWNTs because they are type-II heterojunctions. On the other hand, we have employed the time-domain nonadiabatic dynamics simulation approach to explore the interfacial carrier dynamics in type-II polymer-encapsulated SWNT heterojunctions. It is found that the electron and hole transfer processes are asymmetric and occur in opposite directions and at different rates. The former takes place from polymers to SWNTs in an ultrafast way (ca. 370 fs), whereas the latter occurs slowly from SWNTs to polymers (ca. 24 ps). A closer analysis uncovers the fact that the different carrier transfer rates mainly originate from the different densities of the acceptor states, energy differences and inter-state couplings between the donor and acceptor states. Finally, the present work demonstrates that the polymerization degree could act as a new regulating strategy to tune the interfacial properties of molecule-encapsulated SWNT heterojunctions.

Histone Demethylase KDM4C Is Required for Ovarian Cancer Stem Cell Maintenance.

Ovarian cancer is a highly deadly disease, which is often diagnosed at a late stage with metastases. However, most ovarian cancers relapse after surgery combined with platinum-based chemotherapy. Cancer stem cells (CSCs) are stem-like cells that possess high tumorigenic capability and display higher resistant capability against current therapies. However, our knowledge of ovarian CSCs and their molecular mechanism remains sparse. In the current study, we found that KDM4C, a histone demethylase, was required for ovarian cancer stem cell (CSC) maintenance. Depletion of KDM4C significantly reduced the CSC population and sphere formation in vitro. Moreover, we found that KDM4C can regulate the expression of stem cell factor OCT-4 via binding to its promoter. These data indicate that KDM4C is relevant for ovarian CSC maintenance and underscore its importance as a potential therapeutic target.

Antioxidant epoxydon and benzolactone derivatives from the insect-associated fungus Phoma sp.

One new epoxydon ester (1) and a new benzolactone derivative (2), along with four known compounds (3-6), were isolated from the insect-associated fungus Phoma sp. Their structures were confirmed by extensive MS and NMR spectroscopic analysis and their absolute configurations were determined by a combination of modified Mosher method and Mo2(OCOCH3)4-induced electronic circular dichroism (ECD) experiments. Compounds 1 and 5 were revealed to have potent antioxidant activities, which were approximate to the potency of the positive control trolox. In addition, 1 also exhibited moderate cytotoxic effect against human MGC-803 tumor cell line.[Formula: see text].

Design and Evaluation of a Novel Multiplex Real-Time PCR Melting Curve Assay for the Simultaneous Detection of Nine Sexually Transmitted Disease Pathogens in Genitourinary Secretions.

Background: Sexually transmitted diseases (STD) are a major cause of infertility, long-term disability, ectopic pregnancy, and premature birth. Therefore, the development of fast and low-cost laboratory STD diagnostic screening methods will contribute to reducing STD-induced reproductive tract damage and improve women's health worldwide. In this study, we evaluated a novel multiplex real-time PCR melting curve assay method for the simultaneous detection of 9 STD pathogens, including Chlamydia trachomatis, Neisseria gonorrhoeae, Mycoplasma genitalium, Trichomonas vaginalis, Mycoplasma hominis, Ureaplasma urealyticum, Ureaplasma parvum, and herpes simplex virus. Methods: The analytical performance of the method, including its limit of detection (LOD), specificity, repeatability, and effect on different DNA extraction kits were evaluated. Additionally, we obtained 1,328 clinical specimens from 3 hospitals to detect the 9 STD pathogens using multiplex real-time PCR melting curve and Sanger sequencing, to evaluate the sensitivity, specificity, and consistency of the assay method. Results: The results showed that the analytical sensitivity of the novel multiplex real-time PCR melting curve assay is very excellent, with LOD of DNA corresponding to <200 copies/µL for the DNA of the 9 STDs and 1.00 × 104 color change unit /ml for those of UU and UP. Additionally, this assay demonstrated excellent analytical specificity, excellent repeatability, and its results had no effect of different DNA extraction kits. The performance, in terms of sensitivity (91.06-100%) and specificity (99.14-100%), was remarkable, since the consistency between it and Sanger sequencing was more than 0.85 in the clinic. Conclusion: The novel multiplex real-time PCR melting curve assay method has high sensitivity and specificity, relatively low cost, and simple to use for the simultaneous detection of 9 STD pathogens in genitourinary secretions.

Photoinduced Carrier Dynamics at the Interface of Pentacene and Molybdenum Disulfide.

Understanding of photoinduced interfacial carrier dynamics in organic-transition metal dichalcogenides heterostructures is very important for the enhancement of their potential photoelectronic conversion efficiencies. In this work we have used density functional theory (DFT) calculations and DFT-based fewest-switches surface-hopping dynamics simulations to explore the photoinduced hole transfer and subsequent nonadiabatic electron-hole recombination dynamics taking place at the interface of pentacene and MoS2 in pentacene@MoS2. Upon photoexcitation the electronic transition mainly occurs on the MoS2 monolayer, which corresponds to moving an electron to the MoS2 conduction band. As a result, a hole is left in the valence band. This hole state is energetically lower than certain occupied states of the pentacene molecule; thus, the interfacial hole transfer from MoS2 to pentacene is favorable in energy. In terms of nonadiabatic dynamics simulations, the hole transfer time to the HOMO-1 state of the pentacene is estimated to be about 600 fs; however, the following hole relaxation process from HOMO-1 to HOMO takes much longer time of ca. 15 ps due to the large energy gap between HOMO-1 and HOMO. Moreover, our results also show that the subsequent radiationless recombination process between the hole transferred to the pentacene molecule and the remaining electron on the MoS2 CBM needs about 10.2 ns. The computational results shed important mechanistic insights on the interfacial carrier dynamics of mixed-dimensional pentacene@MoS2. These insights could help to design excellent interfaces for organic-TMDs heterostructures.

Boosting electrocatalytic N2 reduction by MnO2 with oxygen vacancies.

Here, we demonstrate the experimental verification of utilizing a MnO2 with oxygen vacancies (MnOx) nanowire array for high-performance and durable electrocatalytic reduction at neutral pH. Such MnOx nanoarray obtains a high rate of NH3 formation (1.63 × 10-10 mol cm-2 s-1) and a high Faradaic efficiency of 11.40%, which are much higher than those of its pristine MnO2 counterpart (2.3 × 10-11 mol cm-2 s-1; 1.96%). Density functional theory calculations demonstrate that the enhancement of N2 adsorption on the MnOx surface is due to stronger electronic interaction between the N2 molecule and the Mn6c atoms as a result of the oxygen vacancy. This work opens up a new avenue to explore oxygen nonstoichiometry toward the rational design of N2-fixing electrocatalysts with boosted performance for applications.

Theoretical Insights into Interfacial Electron Transfer between Zinc Phthalocyanine and Molybdenum Disulfide.

A comprehensive understanding of interfacial charge transfer dynamics is critical for improving the optoelectronic efficiency of organic-transition metal dichalcogenide heterostructures. In this work we have employed density functional theory (DFT) and developed nonadiabatic dynamics simulation approaches to study the photoinduced electron transfer dynamics at the interface of zinc phthalocyanine (ZnPc) and molybdenum disulfide (MoS2). Our present results show that ZnPc is adsorbed in a parallel orientation on MoS2 through a weak van der Waals interaction. Photoirradiation excites an electron of ZnPc into its lowest unoccupied molecular orbital (LUMO), which is primarily located on ZnPc but has a tail on MoS2. This enhances the vibronic coupling between the LUMO of ZnPc and adiabatic states of MoS2, thereby benefiting the interfacial electron transfer. The LUMO of ZnPc is also calculated to be 0.27 eV higher than the conduction band minimum (CBM) of MoS2 so that the electron transfer from ZnPc to MoS2 is thermodynamically favorable. Further nonadiabatic dynamics simulations verify such ultrafast electron transfer and estimate its time scale of ca. 10 fs. In this process, the low-frequency out-of-plane vibration of MoS2, and low- and high-frequency in-plane and out-of-plane vibrations of ZnPc are found to play an important role in regulating this interfacial electron transfer. In-depth analysis also reveals that atomic motion induced changes of adiabatic states is a dominant factor leading to such ultrafast interfacial electron transfer. These insights could be useful for understanding charge transfer processes at interfaces of heterostructures.

High-performance artificial nitrogen fixation at ambient conditions using a metal-free electrocatalyst.

Conversion of naturally abundant nitrogen to ammonia is a key (bio)chemical process to sustain life and represents a major challenge in chemistry and biology. Electrochemical reduction is emerging as a sustainable strategy for artificial nitrogen fixation at ambient conditions by tackling the hydrogen- and energy-intensive operations of the Haber-Bosch process. However, it is severely challenged by nitrogen activation and requires efficient catalysts for the nitrogen reduction reaction. Here we report that a boron carbide nanosheet acts as a metal-free catalyst for high-performance electrochemical nitrogen-to-ammonia fixation at ambient conditions. The catalyst can achieve a high ammonia yield of 26.57 µg h-1 mg-1cat. and a fairly high Faradaic efficiency of 15.95% at -0.75 V versus reversible hydrogen electrode, placing it among the most active aqueous-based nitrogen reduction reaction electrocatalysts. Notably, it also shows high electrochemical stability and excellent selectivity. The catalytic mechanism is assessed using density functional theory calculations.

The Origin of the Photoluminescence Enhancement of Gold-Doped Silver Nanoclusters: The Importance of Relativistic Effects and Heteronuclear Gold-Silver Bonds.

The weak photoluminescence of silver nanoclusters prevents their broad application as luminescent nanomaterials. Recent experiments, however, have shown that gold doping can significantly enhance the photoluminescence intensity of Ag29 nanoclusters but the molecular and physical origins of this effect remain unknown. Therefore, we have computationally explored the geometric and electronic structures of Ag29 and gold-doped Ag29-x Aux (x=1-5) nanoclusters in the S0 and S1 states. We found that 1) relativistic effects that are mainly due to the Au atoms play an important role in enhancing the fluorescence intensity, especially for highly doped Ag26 Au3 , Ag25 Au4 , and Ag24 Au5 , and that 2) heteronuclear Au-Ag bonds can increase the stability and regulate the fluorescence intensity of isomers of these gold-doped nanoclusters. These novel findings could help design doped silver nanoclusters with excellent luminescence properties.

Increased serum IL-36α and IL-36γ levels in patients with systemic lupus erythematosus: Association with disease activity and arthritis.

IL-36 cytokines (IL-36Ra, IL-36α, IL-36ß and IL-36γ) belong to the IL-1 family and have been linked to several autoimmune diseases. However, little is known about the relationships between systemic lupus erythematosus (SLE) and IL-36 cytokines. In this study, serum IL-36 cytokine levels were determined by enzyme-linked immunosorbent assay (ELISA), and their associations with SLE-related parameters were analyzed in 72 SLE patients and 63 healthy controls. Additionally, IL-36 cytokine mRNA levels were assessed in 30 of 72 SLE patients and 20 of 63 healthy controls using real-time quantitative reverse transcription polymerase chain reaction (RT-PCR). Compared to healthy controls, SLE patients had significantly decreased serum IL-36Ra levels (P = 0.001) and markedly increased serum IL-36α and IL-36γ levels (P = 0.004 and P = 0.001, respectively). Serum IL-36α and IL-36γ levels were significantly higher in active SLE patients [SLE Disease Activity Index (SLEDAI) score ≥ 5] than in inactive patients (SLEDAI score ≤ 4) (P = 0.020 and P = 0.017, respectively). Serum IL-36α and IL-36γ levels were strongly correlated with SLEDAI score (r = 0.308, P = 0.008 and r = 0.400, P = 0.001, respectively) and complement C3 levels (r = -0.276, P = 0.019 and r = -0.314, P = 0.007, respectively). Moreover, SLE patients with arthritis had significantly higher serum IL-36α and IL-36γ levels than those without arthritis (P = 0.001 and P < 0.001, respectively). Our study indicates that the imbalanced antagonist/agonist profile of IL-36 cytokines may be linked to SLE pathogenesis. Furthermore, IL-36α and IL-36γ may participate in arthritis and may be good biomarkers of SLE disease activity.

ID1 promotes hepatocellular carcinoma proliferation and confers chemoresistance to oxaliplatin by activating pentose phosphate pathway.

BACKGROUND: Drug resistance is one of the major concerns in the treatment of hepatocellular carcinoma (HCC). The aim of the present study was to determine whether aberrant high expression of the inhibitor of differentiation 1(ID1) confers oxaliplatin-resistance to HCC by activating the pentose phosphate pathway (PPP). METHODS: Aberrant high expression of ID1 was detected in two oxaliplatin-resistant cell lines MHCC97H-OXA(97H-OXA) and Hep3B-OXA(3B-OXA). The lentiviral shRNA or control shRNA was introduced into the two oxaliplatin-resistant cell lines. The effects of ID1 on cell proliferation, apoptosis and chemoresistance were evaluated in vitro and vivo. The molecular signaling mechanism underlying the induction of HCC proliferation and oxaliplatin resistance by ID1 was explored. The prognostic value of ID1/G6PD signaling in HCC patients was assessed using the Cancer Genome Atlas (TCGA) database. RESULTS: ID1 was upregulated in oxaliplaitin-resistant HCC cells and promoted HCC cell proliferation and oxaliplatin resistance. Silencing ID1 expression in oxaliplaitin-resistant HCC cell lines inhibited cell proliferation and sensitized oxaliplaitin-resistant cells to death. ID1 knockdown significantly decreased the expression of glucose-6-phosphate dehydrogenase (G6PD), a key enzyme of the PPP. Silencing ID1 expression blocked the activation of G6PD, decreased the production of PPP NADPH, and augmented reactive oxygen and species (ROS), thus inducing cell apoptosis. Study of the molecular mechanism showed that ID1 induced G6PD promoter transcription and activated PPP through Wnt/ß-catenin/c-MYC signaling. In addition, ID1/G6PD signaling predicted unfavorable prognosis of HCC patients on the basis of TCGA. CONCLUSIONS: Our study provided the first evidence that ID1 conferred oxaliplatin resistance in HCC by activating the PPP. This newly defined pathway may have important implications in the research and development of new more effective anti-cancer drugs.

QM and QM/MM Studies on Excited-State Relaxation Mechanisms of Unnatural Bases in Vacuo and Base Pairs in DNA.

Semisynthetic alphabet can potentially increase the genetic information stored in DNA through the formation of unusual base pairs such as d5SICS:dNaM. However, recent experiments show that near-visible-light irradiation on the d5SICS and dNaM chromophores could lead to genetic mutations and damages. Until now, their photophysical mechanisms remain elusive. Herein, we have employed MS-CASPT2//CASSCF and QM(MS-CASPT2//CASSCF)/MM methods to explore the spectroscopic properties and excited-state relaxation mechanisms of d5SICS, dNaM, and d5SICS:dNaM in DNA. We have found that (1) the S2 state of d5SICS, the S1 state of dNaM, and the S2 state of d5SICS:dNaM are initially populated upon near-visible-light irradiation and (2) for d5SICS and d5SICS:dNaM, there are several parallel relaxation pathways to populate the lowest triplet state, but for dNaM, a main relaxation pathway is uncovered. Moreover, we have found that the excited-state relaxation mechanism of d5SICS:dNaM in DNA is similar to that of the isolated d5SICS chromophore. These mechanistic insights contribute to the understanding of photophysics and photochemistry of unusual base pairs and to the design of better semisynthetic genetic alphabet.

Laboratory and Molecular Characterization of Dengue Viruses in a 2014 Outbreak in Guangfo Region, Southern China.

Non-specific symptoms and low viremia levels make early diagnosis of dengue virus (DENV) infection challenging. This study aimed to i) identify laboratory markers that can be used to predict a DENV-positive diagnosis and ii) perform a molecular characterization of DENVs from the 2014 Guangdong epidemic. This retrospective study analyzed 1,044 patients from the Guangdong epidemic who were clinically suspected cases of dengue. Viral RNA was detected by real-time RT-PCR, and viral-specific NS1 antigen was detected using enzyme-linked immuno sorbent assay. A molecular phylogenetic analysis was performed for the with the DENV C-prM gene junction. Patients with dengue infection had leukopenia (2.8 × 109/L), thrombocytopenia (109.0 × 109/L), elevated aspartate aminotransferase (56.0 IU/L) and alanine aminotransferase (43.5 IU/L), and prolonged activated partial thromboplastin time (APTT, 33.5 s) (all P ＜ 0.001) compared to patients without dengue. The positive predictive value of leukopenia and thrombocytopenia for DENV infection were 96.9% and 93.0%, respectively. Leukopenia, thrombocytopenia, elevated aminotransferases, and prolonged APTT were useful predictive markers for an early diagnosis of DENV infection. Phylogenetic analysis indicated that the DENVs from the 2014 epidemic were closely related to a 2010 New Delhi strain and a 2013 Guangzhou strain. The 2014 epidemic consisted of co-circulating DENV-1 genotypes I and V from multiple origins. Efficient dengue surveillance can facilitate rapid response to future outbreaks.

Prevalence of human papillomavirus infection among 71,435 women in Jiangxi Province, China.

Cervical cancer is the third most common cancer in women worldwide. Human papillomavirus (HPV) has been identified as an etiological factor for cervical cancer. Data on the prevalence and subtype distribution of HPV infection in Jiangxi Province are incomplete. In this study, we investigated HPV subtype distribution and prevalence in Jiangxi Province between August 1, 2010, and December 31, 2015. A total of 71,435 individuals ranging in age from 16 to 77 years were recruited. Cervicovaginal swabs were collected from each participant, and HPV screening was performed. Our results showed that the HPV prevalence was 22.49% in Jiangxi Province. Overall, 14.99% of individuals were positive for a single HPV type, and 7.49% were positive for multiple types. The most frequently detected low-risk genotypes were HPV-6, and high-risk genotypes were HPV-16, -18, -33, -52, and -58. The prevalence and type distribution of HPV infection exhibits regional and age differences; Yingtan had the highest incidence for high-risk HPV infection (32.00%), and peaks in the frequencies of HPV infections were seen for patients under 20 and over 60 years of age. In conclusion, we present data showing that the HPV prevalence varies significantly with age and regions in Jiangxi Province. These results can serve as valuable reference to guide Jiangxi cervical cancer screening and HPV vaccination programs.

Hepatitis B surface antigen predicts recurrence after radiofrequency ablation in patients with low hepatitis B virus loads.

Radiofrequency ablation (RFA) is a first-line option for the treatment of small liver cancers, but the recurrence remains a problem affecting long-term survival. Hepatitis B virus (HBV) activity is associated with the prognosis of hepatocellular carcinoma (HCC). We investigated the significance of hepatitis B surface antigen (HBsAg) in HCC recurrence after curative RFA treatment in HBV-related small HCC.We enrolled 404 HBV-related patients with small HCC (≤3 cm) who underwent curative RFA. We used univariate and multivariate analyses to investigate the baseline levels of HBsAg, in addition to other known risk factors for HCC recurrence, for association with HCC tumor recurrence after curative RFA.The overall 1-, 2-, and 3-year recurrence-free survival (RFS) rates were 75%, 50%, and 34%, respectively. The median recurrence-free time was 25 months. The level of HBsAg was an independent risk factor for recurrence in patients with lower HBV-DNA levels. In hepatitis Be antigen (HBeAg)-negative patients, the 1-, 2-, and 3-year RFS rates were 79%, 64%, and 44%, respectively, for that with low HBsAg levels, compared with 73%, 50%, and 37%, respectively, for that with high HBsAg levels (P = .039).HBsAg might serve as a valuable marker to evaluate the risk of HCC recurrence in HBeAg-negative patients with low HBV viral load.

Identification of long noncoding RNA expression profile in oxaliplatin-resistant hepatocellular carcinoma cells.

Hepatocellular carcinoma (HCC) is the most prevalent and malignant type of liver cancer. Besides the high incidence, the resistance to chemotherapy is a major problem that leads to the high mortality of HCC. Recently, aberrant expression of long noncoding RNAs (lncRNAs) has been considered as a primary feature of many types of cancer. However, the genome-wide expression pattern and associated functional implications of lncRNAs in chemo-resistant HCC cells remain unknown. In this study, we identified 120 differentially expressed lncRNAs with 61 up-regulated and 59 down-regulated (fold change>2, p<0.05) along with 421 differentially expressed mRNAs with 228 up-regulated and 193 down-regulated (fold change>2, p<0.05) in oxaliplatin-resistant (MHCC97H-OXA) HCC cells, compared to parental oxaliplatin-sensitive (MHCC97H) by microarray. The underlying pathways were related to cell death, proliferation, cellular response to stimulus, including p53 pathway, ErbB pathway and MAPK pathway. Further, 16 lncRNAs were selected for validation of microarray results with quantitative PCR, and a strong correlation was identified between the qPCR results and microarray data. We demonstrated for the first time that ENST00000438347, NR_073453 and ENST00000502804 were up-regulated in MHCC97H-OXA cells as well as chemo-resistant HCC cancerous tissues. Moreover, the expression of ENST00000518376 was significantly associated with the tumor size and differentiation. Overall survival analysis showed that high expression of ENST00000438347 and ENST00000518376 was associated with poor prognosis in HCC patients. Taken together, our results reveal that the expression profile in oxaliplatin-resistant HCC is significantly altered including lncRNAs. And a series of de novo lncRNAs play important functions in HCC oxaliplatin resistance and HCC progression.

Aspirin in combination with TACE in treatment of unresectable HCC: a matched-pairs analysis.

Transarterial chemoembolization (TACE) is the principal therapy for unresectable hepatocellular carcinoma (HCC). However, its efficacy is currently limited owing to tumor progression or treatment failure. It has been shown that aspirin reduces the incidence of multiple malignant tumors including HCC and plays a synergistic role with chemotherapy in the treatment of colon cancer. Therefore, we aimed to investigate the adjuvant effect of aspirin on patients with unresectable HCC who underwent TACE therapy. A retrospective matched-pairs analysis was performed to evaluate the efficacy of aspirin in combination with TACE therapy. A total of 120 patients with HCC, including 60 patients treated with aspirin for treatment of cardiovascular disease, transient ischemic attack, and arthritis, and 60 paired matching HCC patients without aspirin treatment in the same period, were enrolled. Compared with non-aspirin users, patients treated with aspirin showed improved OS (P = 0.050). Specifically, patients treated with a full dose of aspirin showed prolonged OS (P = 0.027), which was an independent factor associated with OS in multivariate analysis (hazard ratio 0.498, 95% confidence interval 0.280-0.888, P = 0.018). Aspirin in combination with TACE might improve OS in patients with unresectable HCC. Thus, the impact of aspirin on patients with HCC warrants further investigation prospectively.

Mechanistic Photochemistry of Methyl-4-hydroxycinnamate Chromophore and Its One-Water Complexes: Insights from MS-CASPT2 Study.

Herein we computationally studied the excited-state properties and decay dynamics of methyl-4-hydroxycinnamate (OMpCA) in the lowest three electronic states, that is, (1)ππ*, (1)nπ*, and S0 using combined MS-CASPT2 and CASSCF electronic structure methods. We found that one-water hydration can significantly stabilize and destabilize the vertical excitation energies of the spectroscopically bright (1)ππ* and dark (1)nπ* excited singlet states, respectively; in contrast, it has a much smaller effect on the (1)ππ* and (1)nπ* adiabatic excitation energies. Mechanistically, we located two (1)ππ* excited-state relaxation channels. One is the internal conversion to the dark (1)nπ* state, and the other is the (1)ππ* photoisomerization that eventually leads the system to a (1)ππ*/S0 conical intersection region, near which the radiationless internal conversion to the S0 state occurs. These two (1)ππ* relaxation pathways play distinct roles in OMpCA and its two one-water complexes (OMpCA-W1 and OMpCA-W2). In OMpCA, the predominant (1)ππ* decay route is the state-switching to the dark (1)nπ* state, while in one-water complexes, the importance of the (1)ππ* photoisomerization is significantly enhanced because the internal conversion to the (1)nπ* state is heavily suppressed due to the one-water hydration.