Development of phase-cycling interface-specific two-dimensional electronic sum frequency generation (2D-ESFG) spectroscopy.

Two-dimensional electronic spectroscopy (2D-ES) has become an important technique for studying energy transfer, electronic coupling, and electronic-vibrational coherence in the past ten years. However, since 2D-ES is not interface specific, the electronic information at surfaces and interfaces could not be demonstrated clearly. Two-dimensional electronic sum-frequency generation (2D-ESFG) is an emerging spectroscopic technique that explores the correlations between different interfacial electronic transitions and is the extension of 2D-ES to surface and interfacial specificity. In this work, we present the detailed development and implementation of phase-cycling 2D-ESFG spectroscopy using an acousto-optic pulse shaper in a pump-probe geometry. With the pulse pair generated by a pulse shaper rather than optical devices based on birefringence or interference, this 2D-ESFG setup enables rapid scanning, phase cycling, and the separation of rephasing and nonrephasing signals. In addition, by collecting data in a rotating frame, we greatly improve experimental efficiency. We demonstrate the method for azo-derivative molecules at the air/water interface. This method could be readily extended to different interfaces and surfaces. The unique phase-cycling 2D-ESFG technique enables one to quantify the energy transfer, charge transfer, electronic coupling, and many other electronic properties and dynamics at surfaces and interfaces with precision and relative ease of use. Our goal in this article is to present the fine details of the fourth-order nonlinear optical technique in a manner that is comprehensive, succinct, and approachable such that other researchers can implement, improve, and adapt it to probe unique and innovative problems to advance the field.

Quantitative Signal Analysis of Sum-Frequency Scattering Experiments from Aerosol Surfaces.

Droplet interfaces are instrumental in processes of biology, engineering, production, and environmental systems. The chemical and physical properties of heterogeneous interfaces are known to be different from those of their underlying bulk phases, and different again when considering the curved surface of submicron aerosol droplets. The recently developed technique of vibrational sum-frequency scattering (VSFS) spectroscopy from airborne particles has emerged as an interface-specific method for the in situ analysis of this unique system. While the technique has shown promise in debut works, a quantitative analysis of the VSFS system has not yet been performed. Here we provide a comprehensive analysis of a VSFS spectrometer with reference to the well-documented planar analog. We decompose the VSFS signal into coherent and incoherent as well as resonant and nonresonant components as a function of incident pulse delay time. We then quantify and compare resonant and nonresonant VSFS and VSFG experimental data using the same laser and detection systems. Using the air/water interface as a guide, we show that the resonant and nonresonant contributions to the SF responses are comparable for the two systems by extracting second-order susceptibilities and hyperpolarizabilities, and using them to estimate single-particle susceptibilities. A quantitative analysis of the signal detection systems for the scattering and planar geometries is made, and conversion efficiencies for VSFG, VSFS, and other nonlinear scattering experiments are compared. Lastly, the possibility of a low-repetition (1 kHz) VSFS spectrometer is considered, determining that it may be possible with modern laser technology but is inevitably less efficient than a high-repetition (100 kHz) system. Though this multistep analysis we obtain a better understanding of the components of the VSFS signal from aerosol particles, further validate the feasibility of the experiments, and provide insight to those wishing to conduct similar experiments and how they may be improved.

Conical Intersections at Interfaces Revealed by Phase-Cycling Interface-Specific Two-Dimensional Electronic Spectroscopy (i2D-ES).

Conical intersections (CIs) hold significant stake in manipulating and controlling photochemical reaction pathways of molecules at interfaces and surfaces by affecting molecular dynamics therein. Currently, there is no tool for characterizing CIs at interfaces and surfaces. To this end, we have developed phase-cycling interface-specific two-dimensional electronic spectroscopy (i2D-ES) and combined it with advanced computational modeling to explore nonadiabatic CI dynamics of molecules at the air/water interface. Specifically, we integrated the phase locked pump pulse pair with an interface-specific electronic probe to obtain the two-dimensional interface-specific responses. We demonstrate that the nonadiabatic transitions of an interface-active azo dye molecule that occur through the CIs at the interface have different kinetic pathways from those in the bulk water. Upon photoexcitation, two CIs are present: one from an intersection of an optically active S2 state with a dark S1 state and the other from the intersection of the progressed S1 with the ground state S0. We find that the molecular conformations in the ground state are different for interfacial molecules. The interfacial molecules are intimately correlated with the locally populated excited state S2 being farther away from the CI region. This leads to slower nonadiabatic dynamics at the interface than in bulk water. Moreover, we show that the nonadiabatic transition from the S1 dark state to the ground state is significantly longer at the interface than that in the bulk, which is likely due to the orientationally restricted configuration of the excited state at the interface. Our findings suggest that orientational configurations of molecules manipulate reaction pathways at interfaces and surfaces.

Identification of lung adenocarcinoma subtypes and a prognostic signature based on activity changes of the hallmark and immunologic gene sets.

Background: Lung adenocarcinoma (LUAD) has a complex tumor heterogeneity. Our research attempts to clearness LUAD subtypes and build a reliable prognostic signature according to the activity changes of the hallmark and immunologic gene sets. Methods: According to The Cancer Genome Atlas (TCGA) - LUAD dataset, changes in marker and immune gene activity were analyzed, followed by identification of prognosis-related differential gene sets (DGSs) and their related LUAD subtypes. Survival analysis, correlation with clinical characteristics, and immune microenvironment assessment for subtypes were performed. Moreover, the differentially expressed genes (DEGs) between different subtypes were identified, followed by the construction of a prognostic risk score (RS) model and nomogram model. The tumor mutation burden (TMB) and tumor immune dysfunction and exclusion (TIDE) of different risk groups were compared. Results: Two LUAD subtypes were determined according to the activity changes of the hallmark and immunologic gene sets. Cluster 2 had worse prognosis, more advanced tumor and clinical stages than cluster 1. Moreover, a prognostic RS signature was established using two LUAD subtype-related DEGs, which could stratify patients at different risk levels. Nomogram model incorporated RS and clinical stage exerted good prognostic performance in LUAD patients. A shorter survival time and higher TMB were observed in the high-risk patients. Conclusions: Our findings revealed that our constructed prognostic signature could exactly predict the survival status of LUAD cases, which was helpful in predicting the prognosis and guiding personalized therapeutic strategies for LUAD.

Present situation and prospect of immunotherapy for unresectable locally advanced esophageal cancer during peri-radiotherapy.

Four major studies (Checkmate577, Keynote-590, Checkmate649 and Attraction-4) of locally advanced esophageal cancer published in 2020 have established the importance of immunotherapy, represented by anti-programmed death protein (PD)-1 in postoperative adjuvant treatment and advanced first-line treatment of locally advanced or advanced esophageal cancer and esophagogastric junction cancer, from the aspects of proof of concept, long-term survival, overall survival rate and progression-free survival. For unresectable or inoperable nonmetastatic esophageal cancer, concurrent radiotherapy and chemotherapy is the standard treatment recommended by various guidelines. Because its curative effect is still not ideal, it is necessary to explore radical radiotherapy and chemotherapy in the future, and it is considered to be promising to combine them with immunotherapeutic drugs such as anti-PD-1. This paper mainly discusses how to combine radical concurrent radiotherapy and chemotherapy with immunotherapy for unresectable local advanced esophageal cancer.

Real-world treatment patterns and survival for locally advanced esophageal squamous cell carcinoma.

The "real world" treatment mode and clinical efficacy of locally advanced esophageal squamous cell carcinoma (LAESCC) are unclear. Meanwhile, the role of immunotherapy in the clinical practice is also puzzling. We conducted the research to investigate the statue of "real world" LAESCC. The clinical data of patients with locally advanced esophageal squamous cell carcinoma which met the criteria from January 2010 to December 2019 have been retrospectively analyzed, and the distribution of clinical treatment patterns has been analyzed. They cover such aspects as dfferences in survival time and further analysis of the differences in overall survival (OS) and progression-free survival (PFS) between patients who received immunotherapy and those who did not receive immunotherapy. What is more, Cox risk regression model has also been used to evaluate the risk factors affecting the prognosis of LAESCC. The cases of a total of 5328 newly diagnosed patients with esophageal cancer were collected, and a total of 363 patients were included in the study, with a median age of (46.2 ± 7.8) years old; 84 (23.1%) and 279 (76.9%) patients received 1L and ≥ 2L, respectively; Concurrent chemoradiotherapy (74.1%) and paclitaxel combined with platinum-based chemotherapy (14.3%) were the main first-line treatment options; fluorouracil combined with cisplatin regimen-based chemotherapy (63.8%) was the main treatment option for ≥ 2L, of which 69 patients (25.3%) received immunization treatment; OS of patients with 1 line of therapy and ≥ 2L were (22.4 ± 7.2) months and (38.7 ± 8.5) months, respectively, and the comparison between groups was statistically significant (P < .05); among 69 patients with ≥ 2L who received immunotherapy, PFS and The OS was (14.6 ± 6.9) and (45.3 ± 9.7) respectively, and the comparison between the groups was statistically significant (all P < .05). Cox multivariate analysis has shown that clinical stage, immunotherapy, concurrent chemoradiotherapy, and ≥ 2L are the main factors affecting OS. and immunotherapy, concurrent chemoradiotherapy, and ≥ 2L are independent factors affecting PFS. Concurrent chemoradiotherapy is currently one of the standard treatments for LAESCC, and most patients are still willing to receive second-line or above treatments. Adding immunotherapy to standard treatment modalities may further optimize clinical treatment modalities and improve patient outcomes.

Development of Two-Dimensional Electronic-Vibrational Sum Frequency Generation (2D-EVSFG) for Vibronic and Solvent Couplings of Molecules at Interfaces and Surfaces.

Many photoinduced excited states' relaxation processes and chemical reactions occur at interfaces and surfaces, including charge transfer, energy transfer, proton transfer, proton-coupled electron transfer, configurational dynamics, conical intersections, etc. Of them, interactions of electronic and vibrational motions, namely, vibronic couplings, are the main determining factors for the relaxation processes or reaction pathways. However, time-resolved electronic-vibrational spectroscopy for interfaces and surfaces is lacking. Here we develop interface/surface-specific two-dimensional electronic-vibrational sum frequency generation spectroscopy (2D-EVSFG) for time-dependent vibronic coupling of excited states at interfaces and surfaces. We further demonstrate the fourth-order technique by investigating vibronic coupling, solvent correlation, and time evolution of the coupling for photoexcited interface-active molecules, crystal violet (CV), at the air/water interface as an example. The two vibronic absorption peaks for CV molecules at the interface from the 2D-EVSFG experiments were found to be more prominent than their counterparts in bulk from 2D-EV. Quantitative analysis of the vibronic peaks in 2D-EVSFG suggested that a non-Condon process participates in the photoexcitation of CV at the interface. We further reveal vibrational solvent coupling for the zeroth level on the electronic state with respect to that on the ground state, which is directly related to the magnitude of its change in solvent reorganization energy. The change in the solvent reorganization energy at the interface is much smaller than that in bulk methanol. Time-dependent center line slopes (CLSs) of 2D-EVSFG also showed that kinetic behaviors of CV at the air/water interface are significantly different from those in bulk methanol. Our ultrafast 2D-EVSFG experiments not only offer vibrational information on both excited states and the ground state as compared with the traditional doubly resonant sum frequency generation and electronic-vibrational coupling but also provide vibronic coupling, dynamical solvent effects, and time evolution of vibronic coupling at interfaces.

In Situ Probing of the Surface Properties of Droplets in the Air.

Surface properties of nanodroplets and microdroplets are intertwined with their immense applicability in biology, medicine, production, catalysis, the environment, and the atmosphere. However, many means for analyzing droplets and their surfaces are destructive, non-interface-specific, not conducted under ambient conditions, require sample substrates, conducted ex situ, or a combination thereof. For these reasons, a technique for surface-selective in situ analyses under any condition is necessary. This feature article presents recent developments in second-order nonlinear optical scattering techniques for the in situ interfacial analysis of aerosol droplets in the air. First, we describe the abundant utilization of such droplets across industries and how their unique surface properties lead to their ubiquitous usage. Then, we describe the fundamental properties of droplets and their surfaces followed by common methods for their study. We next describe the fundamental principles of sum-frequency generation (SFG) spectroscopy, the Langmuir adsorption model, and how they are used together to describe adsorption processes at planar liquid and droplet surfaces. We also discuss the history of developments of second-order scattering from droplets suspended in dispersive media and introduce second-harmonic scattering (SHS) and sum-frequency scattering (SFS) spectroscopies. We then go on to outline the developments of SHS, electronic sum-frequency scattering (ESFS), and vibrational sum-frequency scattering (VSFS) from droplets in the air and discuss the fundamental insights about droplet surfaces that the techniques have provided. Finally, we describe some of the areas of nonlinear scattering from airborne droplets which need improvement as well as potential future directions and utilizations of SHS, ESFS, and VSFS throughout environmental systems, interfacial chemistry, and fundamental physics. The goal of this feature article is to spread knowledge about droplets and their unique surface properties as well as introduce second-order nonlinear scattering to a broad audience who may be unaware of recent progress and advancements in their applicability.

Electric double layer contribution to sum frequency generation signal from Au electrode.

Understanding the electric double layer (EDL) of the metal electrode-electrolyte interface is essential to electrochemistry and relevant disciplines. In this study, potential-dependent electrode Sum Frequency Generation (SFG) intensities of polycrystalline gold electrodes in HClO4 and H2SO4 electrolytes were thoroughly analyzed. The potential of zero charges (PZC) of the electrodes was -0.06 and 0.38 V in HClO4 and H2SO4, respectively, determined from differential capacity curves. Without specific adsorption, the total SFG intensity was dominated by the contribution from the Au surface and increased similar to that of the visible (VIS) wavelength scanning, which pushed the SFG process closer to the double resonant condition in HClO4. However, the EDL contributed about 30% SFG signal with specific adsorption in H2SO4. Below PZC, the total SFG intensity was dominated by the Au surface contribution and increased with potential at a similar slope in these two electrolytes. Around PZC, as the EDL structure became less ordered and the electric field changed direction, there would be no EDL SFG contribution. Above PZC, the total SFG intensity increased much more rapidly with potential in H2SO4 than in HClO4, which suggested that the EDL SFG contribution kept increasing with more specific adsorbed surface ions from H2SO4.

Interface Catalysts of Ni3Fe1 Layered Double Hydroxide and Titanium Carbide for High-Performance Water Oxidation in Alkaline and Natural Conditions.

The electrocatalytic oxygen evolution reaction (OER) is important for many renewable energy technologies. Developing cost-effective electrocatalysts with high performance remains a great challenge. Here, we successfully demonstrate our novel interface catalyst comprised of Ni3Fe1-based layered double hydroxides (Ni3Fe1-LDH) vertically immobilized on a two-dimensional MXene (Ti3C2Tx) surface. The Ni3Fe1-LDH/Ti3C2Tx yielded an anodic OER current of 100 mA cm-2 at 0.28 V versus reversible hydrogen electrode (RHE), nearly 74 times lower than that of the pristine Ni3Fe1-LDH. Furthermore, the Ni3Fe1-LDH/Ti3C2Tx catalyst requires an overpotential of only 0.31 V versus RHE to deliver an industrial-level current density as high as 1000 mA cm-2. Such excellent OER activity was attributed to the synergistic interface effect between Ni3Fe1-LDH and Ti3C2Tx. Density functional theory (DFT) results further reveal that the Ti3C2Tx support can efficiently accelerate the electron extraction from Ni3Fe1-LDH and tailor the electronic structure of catalytic sites, resulting in enhanced OER performance.

Orientational Coupling of Molecules at Interfaces Revealed by Two-Dimensional Electronic-Vibrational Sum Frequency Generation (2D-EVSFG).

Photoinduced relaxation processes at interfaces are intimately related to many fields such as solar energy conversion, photocatalysis, and photosynthesis. Vibronic coupling plays a key role in the fundamental steps of the interface-related photoinduced relaxation processes. Vibronic coupling at interfaces is expected to be different from that in bulk due to the unique environment. However, vibronic coupling at interfaces has not been well understood due to the lack of experimental tools. We have recently developed a two-dimensional electronic-vibrational sum frequency generation (2D-EVSFG) for vibronic coupling at interfaces. In this work, we present orientational correlations in vibronic couplings of electronic and vibrational transition dipoles as well as the structural evolution of photoinduced excited states of molecules at interfaces with the 2D-EVSFG technique. We used malachite green molecules at the air/water interface as an example, to be compared with those in bulk revealed by 2D-EV. Together with polarized VSFG and ESHG experiments, polarized 2D-EVSFG spectra were used to extract relative orientations of an electronic transition dipole and vibrational transition dipoles at the interface. Combined with molecular dynamics calculations, time-dependent 2D-EVSFG data have demonstrated that structural evolutions of photoinduced excited states at the interface have different behaviors than those in bulk. Our results showed that photoexcitation leads to intramolecular charge transfer but no conical interactions in 25 ps. Restricted environment and orientational orderings of molecules at the interface are responsible for the unique features of vibronic coupling.

In Situ Detection of Chemical Compositions at Nanodroplet Surfaces and In-Nanodroplet Phases.

Small-volume nanodroplets play an increasingly common role in chemistry and biology. Such nanodroplets are believed to have unique chemical and physical properties at the interface between a droplet and its surrounding medium, however, they are underexamined. In this study, we present the novel technique of vibrational sum frequency scattering (VSFS) spectroscopy as an interface-specific, high-performance method for the in situ investigation of nanodroplets with sub-micron radii; as well as the droplet bulk through simultaneous hyper-Raman scattering (HRS) spectroscopy. We use laboratory-generated nanodroplets from aqueous alcohol solutions to demonstrate this technique's ability to separate the vibrational phenomena which take place at droplet surfaces from the underlying bulk phase. In addition, we systemically examine interfacial spectra of nanodroplets containing methanol, ethanol, 1-propanol, and 1-butanol through VSFS. Furthermore, we demonstrate interfacial differences between such nanodroplets and their analogous planar surfaces. The sensitivity of this technique to probe droplet surfaces with few-particle density at standard conditions validates VSFS as an analytical technique for the in situ investigation of small nanodroplets, providing breakthrough information about these species of ever-increasing relevance.

In situ analysis of the bulk and surface chemical compositions of organic aerosol particles.

Understanding the chemical and physical properties of particles is an important scientific, engineering, and medical issue that is crucial to air quality, human health, and environmental chemistry. Of special interest are aerosol particles floating in the air for both indoor virus transmission and outdoor atmospheric chemistry. The growth of bio- and organic-aerosol particles in the air is intimately correlated with chemical structures and their reactions in the gas phase at aerosol particle surfaces and in-particle phases. However, direct measurements of chemical structures at aerosol particle surfaces in the air are lacking. Here we demonstrate in situ surface-specific vibrational sum frequency scattering (VSFS) to directly identify chemical structures of molecules at aerosol particle surfaces. Furthermore, our setup allows us to simultaneously probe hyper-Raman scattering (HRS) spectra in the particle phase. We examined polarized VSFS spectra of propionic acid at aerosol particle surfaces and in particle bulk. More importantly, the surface adsorption free energy of propionic acid onto aerosol particles was found to be less negative than that at the air/water interface. These results challenge the long-standing hypothesis that molecular behaviors at the air/water interface are the same as those at aerosol particle surfaces. Our approach opens a new avenue in revealing surface compositions and chemical aging in the formation of secondary organic aerosols in the atmosphere as well as chemical analysis of indoor and outdoor viral aerosol particles.

Treating the primary in low burden metastatic prostate cancer: Where do we stand?

ABSTRACT: On the basis of endocrine therapy for patients with low burden metastatic prostate cancer (LBMP), the clinical efficacy and quality of life were compared between prostate-only directed radiotherapy (PODT) and prostate and metastasis radiotherapy (PMRT).From November 2009 to November 2015, total 91 patients newly diagnosed with LBMP were retrospectively analyzed, of which 52 patients received PODT and 39 patients received PMRT. The biochemical failure free interval (IBF), prostate specific survival (PCSS), and overall survival (OS) time were compared between the 2 groups, and expanded prostate cancer index composite (EPIC) scale was used to evaluate the difference in quality of life between the 2 groups.The median IBF of the PODT group was 31 months, which was significantly lower than the 39 months of the PMRT group (P < .05); the 5-year OS and PCSS were 58.9%, 65.3% in PODT group, and 58.9%, 71.79% in PMRT group, respectively. There was no significant between the 2 groups (P > .05); the side effects of acute radiotherapy in PMRT group were significantly higher than PODT group (P < .05), especially in bone marrow suppression and gastrointestinal reactions; The scores of urinary system function and intestinal system function in PMRT group were significantly higher than PODT group at the end of radiotherapy, 3 months after radiotherapy, and 6 months after radiotherapy (P < .05). The score of sexual function in PMRT group was significantly lower than that in PODT group after radiotherapy (P < .05), and higher than that in PORT group at other follow-up time points (P < .05). The hormone function was decreased at each follow-up time point in 2 groups, and there was no significant difference between the 2 groups (P > .05).Patients with LBMP receiving PMRT can improve IBF, but cannot increase PCSS and OS, and increase the incidence of acute radiation injury.

Interfacial Structure of Water as a New Descriptor of the Hydrogen Evolution Reaction.

Driven by the persisting poor understanding of the sluggish kinetics of the hydrogen evolution reaction (HER) on Pt in alkaline media, a direct correlation of the interfacial water structure and activity is still yet to be established. Herein, using Pt and Pt-Ni nanoparticles we first demonstrate a strong dependence of the proton donor structure on the HER activity and pH. The structure of the first layer changes from the proton acceptors to the donors with increasing pH. In the base, the reactivity of the interfacial water varied its structure, and the activation energies of water dissociation increased in the sequence: the dangling O-H bonds < the trihedrally coordinated water < the tetrahedrally coordinated water. Moreover, optimizing the adsorption of H and OH intermediates can re-orientate the interfacial water molecules with their H atoms pointing towards the electrode surface, thereby enhancing the kinetics of HER. Our results clarified the dynamic role of the water structure at the electrode-electrolyte interface during HER and the design of highly efficient HER catalysts.

Surface configuration of CO adsorbed on nanostructured Pt electrodes probed using broadband sum frequency generation spectroscopy.

Using broadband sum frequency generation (BB-SFG) spectroscopy, the effect of surface structure on the adsorption states of linearly bonded CO (COL) on a Pt electrode was thoroughly analyzed. Two overlapped SFG peaks with different linewidths and electrochemical Stark slopes were identified, which correspond to COL in different surface configurations.

Does brain radiotherapy improve survival in patients with esophageal squamous cell carcinoma with brain metastasis?

BACKGROUND: To investigate the clinical characteristics, influencing factors, and their impact on survival in patients with brain metastases from esophageal squamous cell carcinoma (BM-ESCC). METHODS: A total of 67 patients with patients with newly diagnosed BM-ESCC were retrospectively analyzed from December 2000 to December 2016, in order to examine the correlation between clinicopathological characteristics and brain metastases, and between brain metastases and survival. RESULTS: The number of BM-ESCC was positively correlated with T and N stages (P<0.05). The higher the T and N stages, the higher the incidence. The median survival time was 9.65 months. N stage was an independent risk factor for BM-ESCC. N0 + N1 was associated with a lower risk of brain metastases (P<0.05). Patients with 1 brain metastasis had a significantly longer survival than those with 2 and 3 brain metastases. N stage-stratified analysis revealed that N0 + N1 patients had a longer survival than N2 and N3 patients (P<0.05). Cox regression analysis revealed that mortality in T3 + T4 patients was 2.337 times that of Tis + T1 patients; mortality in N3 patients was 3.486 times that of N0 + N1 patients; and mortality in untreated patients was 2.772 times that of those treated with whole brain radiotherapy. CONCLUSIONS: The number of BM-ESCC is correlated to T and N stages. The higher the N stage, the higher risk of brain metastases. The higher of T and N stages in ESCC, the worse in prognosis. Whole brain radiotherapy could offer greater survival benefits.

Pharmacokinetic interaction between a Chinese herbal formula Huosu Yangwei oral liquid and apatinib in vitro and in vivo.

OBJECTIVES: This study aimed to evaluate the inhibitory effects of Huosu Yangwei oral liquid (HSYW) on cytochrome P450 enzymes (CYPs) and to investigate whether this herbal medicine could modulate the pharmacokinetic behaviour of the co-administered CYP-substrate drug apatinib. METHODS: Cytochrome P450 enzymes inhibition assays were conducted in human liver microsomes (HLM) by a LC-MS/MS method for simultaneous determination of the oxidative metabolites of eight probe substrates for hepatic CYPs. The modulatory effects of HSYW on the oxidative metabolism of apatinib were investigated in both HLM and rat liver microsomes (RLM). The influences of HSYW on the pharmacokinetic behaviour of apatinib were investigated in rats. KEY FINDINGS: Huosu Yangwei oral liquid inhibited all tested CYPs in human liver preparations, with the IC50 values ranged from 0.3148 to 2.642 mg/ml. HSYW could also inhibit the formation of two major oxidative metabolites of apatinib in liver microsomes from both human and rat. In-vivo assays demonstrated that HSYW could significantly prolong the plasma half-life of apatinib by 7.4-fold and increase the AUC0-inf (nm·h) of apatinib by 43%, when HSYW (10 ml/kg) was co-administered with apatinib (10 mg/kg) in rats. CONCLUSIONS: Huosu Yangwei oral liquid could inhibit mammalian CYPs and modulated the metabolic half-life of apatinib both in vitro and in vivo.

Electrochemical CO2 reduction on Cu and Au electrodes studied using in situ sum frequency generation spectroscopy.

As an important pathway for energy storage and a key reaction in the carbon cycle, the CO2 electrochemical reduction reaction has recently gained significant interest. A variety of catalysts have been used to approach this topic experimentally and theoretically; however, the molecular level insight into the reaction mechanism is lacking due to the complexity of the surface processes and the challenges in probing the intermediate species. In this study, CO2 reduction reactions on polycrystalline Cu and Au electrodes were investigated in 0.1 M CO2-saturated NaHCO3 solution. In situ sum frequency generation (SFG) spectroscopy has been adopted to access the intermediates and products on the metal electrodes. On the Au electrode, only linearly adsorbed CO could be detected, and the reduction produced no hydrocarbon species. On the Cu electrode, C-H stretching vibrations corresponding to surface-adsorbed ethoxy species were observed, but no CO vibrations can be detected with SFG. The results revealed that the CO randomly adsorbed on the Cu surface, and the multiple orientations of the adsorbed species may be the reason for the formation of C-C bonding. These results demonstrate direct molecular level evidence for different reaction pathways on the Cu and Au electrodes.