Vibrational strong coupling (VSC) between molecular vibrations and microcavity photons yields a few polaritons (light-matter modes) and many dark modes (with negligible photonic character). Although ...VSC is reported to alter thermally activated chemical reactions, its mechanisms remain opaque. To elucidate this problem, we followed ultrafast dynamics of a simple unimolecular vibrational energy exchange in iron pentacarbonyl Fe(CO)
under VSC, which showed two competing channels: pseudorotation and intramolecular vibrational-energy redistribution (IVR). We found that under polariton excitation, energy exchange was overall accelerated, with IVR becoming faster and pseudorotation being slowed down. However, dark-mode excitation revealed unchanged dynamics compared with those outside of the cavity, with pseudorotation dominating. Thus, despite controversies around thermally activated VSC modified chemistry, our work shows that VSC can indeed alter chemistry through a nonequilibrium preparation of polaritons.
Long noncoding RNA (lncRNA) have critical roles in various pathophysiological processes, and are frequently dysregulated in many diseases, particularly in cancer. The lncRNA glypican 3 antisense ...transcript 1 (GPC3‐AS1) has been reported to be a potential biomarker for hepatocellular carcinoma (HCC) screening. However, the exact biological functions of GPC3‐AS1 in HCC, and its roles and regulation mechanisms regarding GPC3 are still unknown. In this study, we observed a significant upregulation of GPC3‐AS1 in HCC. Increased expression of GPC3‐AS1 was associated with α‐fetoprotein, tumor size, microvascular invasion, encapsulation, Barcelona Clinic Liver Cancer stage, and worse prognosis of HCC patients. Furthermore, we found that GPC3‐AS1 physically associated with P300/CBP‐associated factor and recruited it to the GPC3 gene body region, consequently inducing an increase in euchromatic histone marks and activating GPC3 transcription. GPC3‐AS1 expression was strongly correlated with GPC3 in HCC tissues. Gain‐of‐function and loss‐of‐function analyses showed that GPC3‐AS1 overexpression enhanced HCC cell proliferation and migration in vitro and xenograft tumor growth in vivo. GPC3‐AS1 knockdown inhibited HCC cell proliferation and migration. Moreover, the effects of GPC3‐AS1 on HCC cell proliferation and migration were dependent on the upregulation of GPC3. Collectively, our studies indicate that GPC3‐AS1 significantly promotes HCC progression via epigenetically activating GPC3, and identifies GPC3‐AS1 as a potential therapeutic target for HCC.
The long noncoding RNA GPC3‐AS1 is significantly upregulated in hepatocellular carcinoma (HCC) and indicates poor prognosis of HCC patients. GPC3‐AS1 physically associates with P300/CBP‐associated factor (PCAF) and recruits it to the GPC3 gene body region, consequently inducing an increase in euchromatic histone marks and activating GPC3 transcription. GPC3‐AS1 overexpression enhances HCC cell proliferation and migration in vitro and xenograft tumour growth in vivo.
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BFBNIB, DOBA, FZAB, GIS, IJS, IZUM, KILJ, NLZOH, NUK, OILJ, PILJ, PNG, SAZU, SBCE, SBMB, SIK, UILJ, UKNU, UL, UM, UPUK
The discovery of borospherenes unveiled the capacity of boron to form fullerene-like cage structures. While fullerenes are known to entrap metal atoms to form endohedral metallofullerenes, few metal ...atoms have been observed to be part of the fullerene cages. Here we report the observation of a class of remarkable metallo-borospherenes, where metal atoms are integral parts of the cage surface. We have produced La
B
and Tb
B
and probed their structures and bonding using photoelectron spectroscopy and theoretical calculations. Global minimum searches revealed that the most stable structures of Ln
B
are hollow cages with D
symmetry. The B
-framework in the Ln
B
cages can be viewed as consisting of two triangular B
motifs connected by three B
units, forming three shared B
rings which are coordinated to the three Ln atoms on the cage surface. These metallo-borospherenes represent a new class of unusual geometry that has not been observed in chemistry heretofore.
Diabetic kidney disease develops in approximately 40% of diabetic patients and is a major cause of chronic kidney diseases (CKD) and end stage kidney disease (ESKD) worldwide. Hydrogen sulfide (H
S), ...the third gasotransmitter after nitric oxide (NO) and carbon monoxide (CO), is synthesized in nearly all organs, including the kidney. Though studies on H
S regulation of renal physiology and pathophysiology are still in its infancy, emerging evidence shows that H
S production by renal cells is reduced under disease states and H
S donors ameliorate kidney injury. Specifically, aberrant H
S level is implicated in various renal pathological conditions including diabetic nephropathy. This review presents the roles of H
S in diabetic renal disease and the underlying mechanisms for the protective effects of H
S against diabetic renal damage. H
S may serve as fundamental strategies to treat diabetic kidney disease. These H
S treatment modalities include precursors for H
S synthesis, H
S donors, and natural plant-derived compounds. Despite accumulating evidence from experimental studies suggests the potential role of the H
S signaling pathway in the treatment of diabetic nephropathy, these results need further clinical translation. Expanding understanding of H
S in the kidney may be vital to translate H
S to be a novel therapy for diabetic renal disease.
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IZUM, KILJ, NUK, PILJ, PNG, SAZU, UL, UM, UPUK
Abstract
Lanthanide (Ln) elements are generally found in the oxidation state +II or +III, and a few examples of +IV and +V compounds have also been reported. In contrast, monovalent Ln(+I) complexes ...remain scarce. Here we combine photoelectron spectroscopy and theoretical calculations to study Ln-doped octa-boron clusters (LnB
8
−
, Ln = La, Pr, Tb, Tm, Yb) with the rare +I oxidation state. The global minimum of the LnB
8
−
species changes from
C
s
to
C
7v
symmetry accompanied by an oxidation-state change from +III to +I from the early to late lanthanides. All the
C
7v
-LnB
8
−
clusters can be viewed as a monovalent Ln(I) coordinated by a η
8
-B
8
2−
doubly aromatic ligand. The B
7
3−
, B
8
2−
, and B
9
−
series of aromatic boron clusters are analogous to the classical aromatic hydrocarbon molecules, C
5
H
5
−
, C
6
H
6
, and C
7
H
7
+
, respectively, with similar trends of size and charge state and they are named collectively as “borozenes”. Lanthanides with variable oxidation states and magnetic properties may be formed with different borozenes.
Silicon carbide (SiC) ceramics, as a kind of candidate material for aero‐engine, its high‐temperature performance is a critical factor to determine its applicability. This investigation focuses on ...studying the high‐temperature properties of SiC ceramics fabricated by using additive manufacturing technology. In this paper, SiC ceramics were prepared by combining selective laser sintering (SLS) with precursor infiltration and pyrolysis (PIP) technique. The microstructure, phase evolution, and failure mechanism after high‐temperature tests were explored. SiC ceramic samples tested at room temperature (RT), 800°C, 1200°C, 1400°C, and 1600°C demonstrated bending strengths of 220.0, 226.1, 234.9, 215.5, and 203.7 MPa, respectively. The RT strength of this material can be maintained at 1400°C, but it decreased at 1600°C. The strength retention at 1400°C and 1600°C were 98% and 92%, respectively. The results indicate that the mechanical properties of SiC ceramics prepared using this method have excellent stability. As the temperature increases, the bending strength of the specimens increased slightly and reached the peak value at 1200°C, and dropped to 203.7 MPa at 1600°C. Such an evolution could be mainly due to the crack healing, and the softening of the glassy phase.
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BFBNIB, FZAB, GIS, IJS, IZUM, KILJ, NLZOH, NUK, OILJ, PILJ, PNG, SAZU, SBCE, SBMB, UL, UM, UPUK
This paper investigates the association between board characteristics and the company's corporate social responsibility (CSR) assurance decision in China. By examining 2054 firm-years of Chinese ...listed companies with CSR reports from 2008 to 2012, we find that firms with a large board size, more female directors, and separation of CEO and chairman positions are more likely to engage in CSR assurance. Gender diversity also influences the CSR assurance provider choice. However, board independence and overseas background of the CEO do not affect the CSR assurance decision. Inconsistent with our prediction, firms with foreign directors are less likely to engage in voluntary CSR assurance. In summary, this research provides in-depth insights into the determinants of Chinese firms' voluntary CSR assurance.
A Cu‐catalyzed vinylation method for alkenyl ethers has been developed. In this strategy, both chain and cyclic alkenyl ether substrates were applicable, and the target products were obtained in up ...to 95% yields and with the E/Z selectivities of >98:2. Furthermore, we have successfully applied this method to directly vinylate the C‐2 position of protected glucals, offering a valuable tool for their functionalization. Moreover, through the utilization of alkenyl alcohols as substrates, we accomplished a 1,2‐alkenyloxylation of alkenyl double bond, enabling the synthesis of functionalized cyclic ether compounds with five or six‐membered rings.
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BFBNIB, FZAB, GIS, IJS, KILJ, NLZOH, NUK, OILJ, SAZU, SBCE, SBMB, UL, UM, UPUK
Despite the success of anti-programmed cell death protein 1 (PD1), anti-PD1 ligand 1 (PDL1) and anti-cytotoxic T lymphocyte antigen 4 (CTLA4) therapies in advanced cancer, a considerable proportion ...of patients remain unresponsive to these treatments (known as innate resistance). In addition, one-third of patients relapse after initial response (known as adaptive resistance), which suggests that multiple non-redundant immunosuppressive mechanisms coexist within the tumour microenvironment. A major immunosuppressive mechanism is the adenosinergic pathway, which now represents an attractive new therapeutic target for cancer therapy. Activation of this pathway occurs within hypoxic tumours, where extracellular adenosine exerts local suppression through tumour-intrinsic and host-mediated mechanisms. Preclinical studies in mice with adenosine receptor antagonists and antibodies have reported favourable antitumour immune responses with some definition of the mechanism of action. Currently, agents targeting the adenosinergic pathway are undergoing first-in-human clinical trials as single agents and in combination with anti-PD1 or anti-PDL1 therapies. In this Review, we describe the complex interplay of adenosine and adenosine receptors in the development of primary tumours and metastases and discuss the merits of targeting one or more components that compose the adenosinergic pathway. We also review the early clinical data relating to therapeutic agents inhibiting the adenosinergic pathway.
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IJS, NUK, SBMB, UL, UM, UPUK
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