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Pancreatic cancer (PC) is a deadly malignant digestive tumor with poor prognoses and a lack of effective treatment options. Cuproptosis, a recently identified copper-dependent programmed cell death type, has been implicated in multiple cancers. Long non-coding RNAs (lncRNAs) are also linked to the progression of PC. However, the role and prognostic values of cuproptosis-related lncRNAs in pancreatic adenocarcinoma (PAAD) remain unclear. In this study, we systemically analyzed the differential expressions and prognostic values of 672 cuproptosis-related lncRNAs in PAAD. Based on this, a prognostic signature including four lncRNAs (LINC00853, AC099850.3, AC010719.1, and AC006504.7) was constructed and was able to divide PAAD patients into high- and low-risk groups with significantly different prognoses. Next, we focused on lncRNA LINC00853. The differential expressions of LINC00853 between normal tissue and PAAD samples were validated by qRT-PCR. LINC00853 was knocked down by siRNA in PC cell lines BxPC-3 and PANC-1 and the oncogenic role of LINC00853 was validated by CCK8, colony formation, and EdU assays. Subsequently, LINC00853 knockdown cells were subjected to tumor xenograft tests and exhibited decreased tumor growth in nude mice. Mechanistically, knockdown of LINC00853 significantly reduced cellular glycolysis and enhanced cellular mitochondrial respiration levels in PC cells. Moreover, knockdown of LINC00853 decreased the protein level of a glycolytic kinase PFKFB3. Finally, glycolysis tests and functional tests using LINC00853 and HA-PFKFB3 indicated that the effects of LINC00853 on glycolysis and cell proliferation were mediated by PFKFB3. In conclusion, our systemic analyses have highlighted the important roles of cuproptosis-related lncRNAs in PAAD while the prognostic signature based on them showed excellent performance in PAAD patients and is expected to provide clinical guidance for individualized treatment. In addition, our findings provide a novel mechanism by which the LINC00853-PFKFB3 axis critically regulates aerobic glycolysis and cell proliferation in PC cells.

Platinum catalysts supported on metal oxidesupports (CeO2–ZrO2, CeO2, ZrO2 and Al2O3) were prepared by a facile impregnation method. Significant differences in properties (medium strong acid density, Pt0 species content, Pt dispersion and oxygen density, etc.) were observed among these catalysts. The highest density of medium-strong acid sites, Pt dispersion, and content of metallic Pt0 species were observed in Pt/Al2O3 catalyst, and Pt/CeO2–ZrO2 catalyst gave the highest density of oxygen vacancy. Moreover, the activity orders of these Pt catalysts for ethyl acetate oxidation were very different from that of toluene. The T99 of ethyl acetate oxidation over the Pt/CeO2–ZrO2, Pt/CeO2, Pt/ZrO2 and Pt/Al2O3 catalysts are at 190, 210, 230 and 250 °C, respectively. Ethyl acetate oxidation activity is in the order: Pt/CeO2–ZrO2 > Pt/CeO2 > Pt/ZrO2 > Pt/Al2O3. The T99 of toluene oxidation over the Pt/CeO2–ZrO2, Pt/CeO2, Pt/ZrO2 and Pt/Al2O3 catalysts are 220, 260, 190 and 250 °C, respectively. Toluene oxidation activity is in order: Pt/ZrO2> Pt/CeO2–ZrO2 > Pt/Al2O3 > Pt/CeO2. The catalytic activities of these Pt catalysts for ethyl acetate mainly depend on the oxygen vacancy density, while the synergistic catalysis of Pt0 species and oxygen vacancies play an important role in toluene oxidation. This work could deepen our understanding to differentiate the dominant roles of catalyst properties on ethyl acetate and toluene oxidation over Pt catalysts.

Thyroid Hürthle cell carcinoma, known as thyroid eosinophilic carcinoma, is a rare pathological type of differentiated thyroid cancer (DTC), representing 3-4% of all thyroid cancers. However, given the high risk of invasion and metastasis, thyroid Hürthle cell carcinoma has a relatively poor prognosis. Traditional treatment methods have limited effects on patients with metastatic thyroid cancers. Developing a valuable therapy for advanced thyroid carcinomas is an unfilled need, and immunotherapy could represent another choice for these tumors. We herein reported the case of a patient with recurrent advanced thyroid Hürthle cell cancer and positive programmed death-ligand 1 (PD-L1) expression, who suffered tumor progression after re-surgery, radiotherapy, and targeted therapy. It is encouraging that PD-1 inhibitors in combination with GM-CSF and stereotactic body irradiation (SBRT) on metastatic disease have a significant anti-tumor effect.

Development of shape memory materials are very important due to their scientific and technological values. Typically, poly(lactic acid) (PLA) has received increasing attentions because of shape memory properties and biodegradability, however, its semi-crystalline structure restricts its shape recovery ratio and toughness both. Herein, we report a reinforced PLA-based elastomer material prepared by physical blending with different weight ratios of polyamide elastomer (PAE). After the modification, PLA/PAE elastomers show excellent shape recovery (> 99%) from ~ 25 to ~ 70 °C and toughness (impact strength ~ 50 kJ/m2). By regulating the weight ratio of PAE at 10 wt%, the resulting PLA/PAE elastomers showed relative low glass transition temperature (Tg) at ~ 61 °C versus pure PLA (~ 65 °C). Besides, the storage modulus (E′) decreased to ~ 8000 MPa (at 10 wt% PAE) indicated that PAE weakened the PLA crystallinity and promoted its toughness. Comparing with pure PLA, PLA/PAE elastomers showed almost 45% decrease on loss modulus (E″), which indicated that elasticity and shape recovery behavior have been promoted. With the increase of PAE ratio in PLA/PAE elastomers, the initial recovery temperature of blends showed decreasing trend, which indicated that blends are more helpful for shape recovery actuated by temperature. This work provided a new PLA/PAE elastomer with stronger toughness and faster thermo-induced shape recovery that may show great potential for fundamental research and biomedical applications.

Background Since December 2019, a novel corona virus disease named COVID-19 outbreak in Wuhan, China and spread worldwide then. Active prevention and control measures have been carried out in China, such as vigorous publicity, active screening and rapid isolation. As the major epidemic area, the passages in and out of Wuhan were temporarily closed since January 23. We aimed to demonstrate the effectiveness of rigorous measures by comparing the characteristics of patients hospitalized before and after implementation of vital measures. Methods Clinical data of patients admitted to hospital with COVID-19 during January 17-23 (Phase I) and February 3-9 (Phase II) were collected and compared. The cut-off date for follow-up was March 13, 2020. Results Of 176 patients with COVID-19, 97 were admitted in Phase I (43 [44.3%] male; mean age: 47.7), and 79 were in Phase II (33 [41.8%] male; mean age: 50.1). The proportions of severe cases were 21.6% and 10.1% respectively. Fewer patients had comorbidities (13 [16.5%] vs. 7 [7.2%]) and more asymptomatic patients were in Phase II (27.8% vs. 13.9%). Patients in Phase II had less fever (53.2% vs. 70.1%), cough (34.2% vs. 52.6%) and myalgia (11.4% vs.28.9%), while more diarrhea (11.4% vs. 2.1%). Lymphopenia and elevated CRP, as well as eosinopenia and elevated SAA were common in two groups, but all of that were significantly better in Phase II. More patients in Phase II preformed normal CT image on admission (10 [12.7%] vs. 7 [7.2%]). And lower CT scores (3 [2-4] vs. 2 [1-3]) were observed in Phase II. Up to cut-off date, average response time on CT image were 11.2 and 8.1 days in Phase I and II respectively. Shorter average hospitalized days were in Phase II (18.9 vs. 23.3 days). Four patients (4.1%) in Phase I and two (2.5%) in Phase II died. Conclusions Various actions (including vigorous publicity, active screening and rapid isolation) prompted more early patients with COVID-19 found, diagnosed and remedied, leading to good prognosis. Call for pretty attention to the epidemics of COVID-19 and timely measures around the world.

Designing the electron-rich palladium active site is of great importance to enhance the selectivity of ethylene in acetylene semi-hydrogenation. In this work, ionic liquids, the effective electronic modifier, were mingled with palladium solution to be immobilized on Al2O3 by incipient impregnation method. X-ray photoelectron spectra characterization was conducted to characterize the structure of catalysts, suggesting that some ionic liquids can form unique carbene structure. The catalytic results showed that those immobilized ionic liquids that can form unique carbene structure exhibited much higher selectivity of ethylene than those cannot. The above results were obtained because carbene can donor the electron to palladium, enriching the electron density of palladium and therefore facilitating the desorption of ethylene. The findings of the unique carbene structure derived from ionic liquids in this work provide an efficient strategy to design the catalyst to improve the selectivity of the intermediate in other partial hydrogenationreactions.

Gold on activated carbon (Au/AC) materials are promising alternative catalysts for ethyne hydrochlorination. The preparation of active, stable Au/AC catalysts without aqua regia for ethyne hydrochlorination remains a significant challenge. A novel catalyst preparation protocol involving impregnation using a H 2 O 2 /HCl mixture is established for highly active Au/AC catalysts comprising primarily of single-site cationic Au species, as identified by systematic X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR) analyses and transmission electron microscopy (TEM) imaging. In addition, evaluation of the Au-C interface by temperature-programmed desorption (TPD) analyses showed that the oxidation of activated carbon by the H 2 O 2 /HCl mixture, which creates surface oxygen-containing functional groups (SOGs), is a crucial step for the formation of active Au/AC catalysts. The structure determination and comprehensive experimental evidence allow density functional theory (DFT) to predict that single-site cationic AuCl species stabilized by SOGs via -O- linkages are efficient active sites for Au-catalyzed ethyne hydrochlorination. In addition, these catalysts can be reused for several times with negligible changes in performance after treatment with the H 2 O 2 /HCl mixture. The H 2 O 2 /HCl mixture is thus envisioned as a viable, green alternative to toxic aqua regia for the preparation of Au/AC catalysts for ethyne hydrochlorination.

Mercuric chloride supported on activated carbon (HgCl2/AC) is used as an industrial catalyst for the hydrochlorination of acetylene. Loss of HgCl2 by sublimating from the surface of activated carbon causes the irreversible deactivation of mercury catalyst and environmental pollution. In this work, a ligand coordination approach based on the Principle of Hard and Soft Acids and Bases (HSAB) was employed to design more stable low-mercury catalyst. The low-mercury catalysts (4% HgCl2 loading) were prepared by using HgCl2 and potassium halides (KX, X = Cl, I) as precursors. The HgCl2-4KI/AC catalyst showed best catalytic stability than HgCl2/AC and HgCl2-4KCl/AC in the hydrochloriantion of acetylene. HgCl2 could form more stable complex with KI, K2HgI4 as the main active component of the HgCl2-4KI/AC catalyst. The characterizations of XRD and EDX analysis illustrated that the active component of HgCl2-4KI/AC was highly dispersed on the surface of activated carbon. The sublimation rates of HgCl2 from the catalysts verified that the active component with larger stability constant had better thermal stability. Using Hg(II) complexes with high stability constant as the active component may be the research direction of developing highly stable low-mercury catalyst for the hydrochlorination of acetylene.

In this paper, we demonstrate that the less toxic, relatively safe, and recyclable organic aqua regia (OAR) can be employed as a greener alternative solvent to conventional aqua regia to activate Au/AC catalysts for the hydrochlorination of acetylene. We show that Au-based catalysts prepared with HAuCl4 as precursor can be prepared initially in water (Au(H2O)/AC). Although catalysts prepared from aqueous HAuCl4 showed poor activity, it can be significantly enhanced by catalyst activation in OAR (Au(H2O)/AC(OAR)). In contrast to the catalyst activation procedure using aqua regia (Au(aq)/AC), we demonstrate that the new activation procedure leads to both improved activity and stability of the resulting Au(H2O)/AC(OAR) catalyst. Further analyses of X-ray diffraction (XRD), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS) show that the variations of Au particle size and chemical state caused by OAR treatment promote Au oxidation and high dispersion. In addition, temperature-programmed reduction (TPR) and temperature-programmed desorption (TPD) indicated that the presence of residual sulfur and nitrogen species may help stabilize the cationic Au3+ species and generate a catalyst less prone to deactivation by increasing the reduction temperature of the Au3+ species and enhancing the adsorption of hydrogen chloride over the Au(H2O)/AC(OAR) catalyst. These results suggest that OAR can be substituted for conventional solvents to activate Au/AC catalysts for the hydrochlorination of acetylene.

We studied the acetylene hydrochlorination in gas&ndash, liquid phase reactions using ionic liquids (IL) as the reaction media and CuCl2 as the catalyst. The Cu-IL catalyst showed strong synergy between the IL and the Cu(II) active catalytic species. For [PrMIm]Cl, the Cu-IL catalyst exhibited significant enhancement of the catalytic activity in comparison with the CuCl2 catalyst supported on activated carbon and the IL alone as the catalyst. We have also performed DFT calculations of the reaction process, which provides a good explanation of our experimental results and for the synergetic effect. Our result suggests that ILs may be used to improve the activity of other metallic catalysts for the hydrochlorination reaction of acetylene.

Development of a sustainable process for designing and synthesising an active and stable catalyst for hydrochlorination of acetylene is challenging, yet crucial, for industrial vinyl chloride monomer (VCM) production. Herein, direct synthesis of bimetallic AuCu catalysts using organic aqua regia (OAR) preparation methods was investigated. In comparison with conventional aqua regia (AR), bimetallic AuCu catalysts synthesised from OAR exhibit enhanced activity and stability. After careful characterisation of the catalyst samples using X-ray diffraction patterns (XRD), Scanning transmission electron microscopy (STEM), X-ray photoelectron spectroscopy (XPS), and Temperature-programmed desorption (TPD), this observation was justified for the following reasons: 1) the existence of sulphur and nitrogen atoms stabilised the cationic Au active sites, and 2) OAR helped to sustain the function of the Cu promotor by stabilising it. Advanced understanding on the importance of promoter stability has unveiled new perspectives for this research area.

Acetylene hydrochlorination is an attractive chemical reaction for the manufacture of polyvinyl chloride (PVC), and the development efforts are focused on the search for non-mercury catalyst systems. Supported Pd-based catalysts have relatively high activity in the catalytic hydrochlorination of acetylene but are still deactivated rather quickly. Herein, we demonstrated that the atomically dispersed (NH4)2PdCl4 complex, distributed on activated carbon, enabled the highly active and stable production of the vinyl chloride monomer (VCM) through acetylene hydrochlorination under low temperature conditions. We found that the presence of nitrogen-containing ligands in the structure of the active center could remarkably improve the stability of the Pd-based catalysts when compared with the case of the conventional PdCl2 catalyst. Further analyses via X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and temperature-programmed reduction (TPR) show that the variations in the Pd dispersion, chemical state and reduction property are caused by the nitrogen-containing ligands. Temperature-programmed desorption (TPD) characterizations illustrated that the N-containing ligands over the (NH4)2PdCl4/AC catalyst might enhance the adsorption of HCl. These findings suggest that in addition to strategies that target the doping modification of support materials, optimization of the structure of the active center complexes provides a new path for the design of highly active and stable Pd-based catalysts.

Commercialization of acetylene hydrochlorination using AuCl3 catalysts has been impeded by its poor stability. We have been studying that nitrogen-modified Au/NAC catalyst delivered a stable performance which can improve acetylene hydrochlorination activity and has resistance to catalytic deactivation. Here we show that nitrogen and sulfur co-doped activated carbon supported AuCl3 catalyst worked as efficient catalysts for the hydrochlorination of acetylene to vinyl chloride. Au/NSAC catalyst demonstrated high activity comparative to Au/AC catalyst. Furthermore, it also delivered stable performance within the selectivity of acetylene, reaching more than 99.5%, and there was only a 3.3% C2H2 conversion loss after running for 12 h under the reaction conditions of a temperature of 180 °C and a C2H2 hourly space velocity of 1480 h−1. The presence of the sulfur atoms may serve to immobilize/anchor the Au and also help prevent reduction and sintering of the Au and hence improve the catalytic activity and stability. The excellent catalytic performance of the Au/NSAC catalyst demonstrated its potential as an alternative to mercury chloride catalysts for acetylene hydrochlorination.

An efficient and stable heterogeneous Zeolite Supported Ionic Liquid Catalyst (IL/CaX) has been explored in acetylene hydrochlorination reaction. The IL/CaX catalyst exhibits excellent space time yields of vinyl chloride (VCM), when compared to the benchmark of Au/C systems. Through characterization and kinetic studies, the reaction follows a two-site mechanism, which is described as the adsorbed hydrogen chloride on the Ca2+ in zeolite, reacting with the adsorbed acetylene on the cation of ionic liquid to form vinyl chloride. The catalytic reaction takes place at the IL/CaX interface, whilst the upper interphase IL/CaX is not active. The deactivation of the catalyst is caused by the dissolving byproducts in the ionic liquid layer, which can be reactivated by a simple vacuum procedure. It is of great significance to study and develop green non-mercury catalysts, in acetylene hydrochlorination.

It is important to understand the behaviour of ionic liquids (ILs) in nanoscale pores, as application of supported ionic liquid phase (SILP) materials has attracted much attention. The main intention of this investigation is to study the dispersion performance of ionic liquid on activated carbons with different surface oxygen groups. Several active carbons with diverse oxygenated surface groups were obtained by oxidation and reduction methods. All samples were impregnated with [Bmim]Cl at different loadings. The blocked porosity of ionic liquid on SILP materials mainly depends on the amount of ionic liquid and surface oxygen content. In addition, stability of the supported IL in water was tested by analyzing the leached amount of IL. We found that the supported IL is not easily leached from the interface of carbon with low amount of surface oxygen. This may be due to the high free π-electron density of oxygen-free supports, forming more CH–π bonds with H atoms at the C2 position of the acidic cation. In addition, we propose that dispersion of ionic liquid in the pores depends on the density of surface free π-electrons of carbon materials.

An equation of state (EOS) for square-well chain molecules with variable range developed on the basis of statistical mechanics for chemical association in our previous work is employed for the calculations of pVT properties and vapor–liquid equilibria (VLE) of pure non-associating fluids. The molecular parameters for 73 normal substances and 46 polymers are obtained from saturated vapor pressure and liquid molar volume data for normal fluids or pVT data for polymers. Linear relations are found for the molecular parameters of normal fluids with their molecular weight of homologous compounds. This indicates that the model parameters of homologous series, subsequently pVT and VLE, can be predicted when experimental data are not available. The predicted saturated vapor pressures and/or liquid volumes are satisfactory through the generalized model parameters. The calculated VLE and pVT for normal fluids and polymers by this EOS are compared with those from other engineering models, respectively.

A new equation of state (EOS) for square-well chain molecules and their mixtures with variable well-width range (SWCF-VR-EOS) has been developed based on the sticky-point model for chemical association. Two important modifications have been made. Firstly, a new dispersion contribution to the Helmholtz function of monomers due to square-well potential with variable well-width range of 1.1 ≤ λ ≤ 3 was established by combining the second-order perturbation theory and Chiew's PY2 approximation of the integral equation. Secondly, the contribution of chain formation to the Helmholtz function is divided into two parts: One is from the hard sphere, and the other is from the effect of square-well potential described via the nearest-neighbor and next-to-nearest-neighbor residual cavity correlation functions (CCFs). The predicted compressibility factors and vapor–liquid coexistence curves for square-well fluids as well as for their mixtures are in good agreement with simulations. The new EOS has been applied to real non-associating fluids and the corresponding mixtures by adopting one-fluid mixing rule. The pVT and vapor–liquid equilibria (VLE) can be correlated satisfactorily. The model parameters for some homologous compounds are found to be linear with the molar mass indicating that the pVT and VLE of those homologous compounds can be predicted even if no accurate data are available.