A new physical method was proposed to control the liquid properties of room temperature ionic liquids (RT-ILs) in combination with nanoporous materials; the melting point of ILs confined in nanopores remarkably decreases in proportion to the inverse of the pore size.
X-ray diffraction measurements for 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid ([BMIM][PF6])-CO2 systems were carried out at high pressures with a newly developed polymer cell. The intermolecular distribution functions (g(inter)(r)) were obtained at 25 degrees C for neat [BMIM][PF6] and its solutions saturated with CO2 at 4 and 15 MPa, where the mole fractions (x) of CO2 correspond to 0.5 and 0.7, respectively. In g(inter)(r) for x = 0.5, two peaks appeared at around 2.8 and 3.2 A. These two peaks in g(inter)(r) appreciably increased for x = 0.7; moreover, there was another peak observed at approximately 3.8 A. Only assuming the correlations between CO2 and [PF6]-, it is reasonably determined that the nearest-neighbor P([PF6]-). . .C(CO2) distances are 3.57 and 3.59 A with the coordination numbers being 1.8 and 4.0 for x = 0.5 and 0.7, respectively. It is concluded that CO2 molecules are preferentially solvated to the [PF6]- anion.
A newly designed high-pressure NMR flow cell has been developed for studies of supercritical fluids. By using the high-pressure cell, 1 H chemical shifts of nonpolar (n-hexane and benzene) and polar (dichloromethane, chloroform, acetonitrile, water, methanol, and ethanol) solute molecules in gaseous and supercritical carbon dioxide were measured in the wide pressure range between 2 and 30 MPa at 313.3 K. The chemical shifts of hydroxyl protons of water, methanol, and ethanol in carbon dioxide at 20.0 MPa were shifted to higher frequency due to intermolecular hydrogen bonding with increasing concentration. A comparison of the concentration dependence with relevant data in carbon tetrachloride indicated a specific interaction between alcohol and carbon dioxide molecules. The corrected 1 H chemical shifts of nonpolar and polar solute molecules at infinite dilution, where the bulk magnetic susceptibility contribution was subtracted, were shifted to higher frequency with increasing density of carbon dioxide. The observed density dependence, represented by a polynomial equation of the third power of density, was interpreted in terms of three distinct density regions, i.e., gaslike, intermediate, and liquidlike. In the gaslike and liquidlike states the solvation structure rapidly varies as the bulk density increases, whereas in the intermediate state the solvation structure remains almost unchanged despite the drastic change in the bulk density. It was demonstrated that the 1 H chemical shift is quite a sensitive probe to a variation of surroundings. The solvent-induced 1 H chemical shifts were analyzed on the basis of two different models.
The electric conductivities and self-diffusion coefficients in dried and water-saturated 1-butyl-3-methylimidazolium hexafluorophosphate, [BMIM][PF6], were measured at 25 and 40 °C. Although the presence of water can remarkably induce acceleration of transport properties in the ionic liquid, the ionic dissociation remains almost unchanged.
Recent studies have shown that the tumor microenvironment plays a significant role in the progression of solid tumors. As an abundant component of the tumor microenvironment, cancer‐associated fibroblasts (CAFs) have been shown to promote tumorigenesis and cancer aggressiveness, but their molecular characteristics remain poorly understood. In the present study, paired CAFs and normal fibroblasts (NFs) were isolated from five colorectal cancer (CRC) tissues from patients who underwent surgical resection. The gene expression profiles of CAFs and NFs identified by RNA sequencing were compared to understand the complex role of CAFs in cancer progression. Gene Set Enrichment Analysis revealed that the gene sets related to the Wnt signaling pathway were highly enriched in CAFs, as well as TGFβ signaling, which is considered to be a regulator of CAFs. Among the components of this pathway, Wnt2 was specifically expressed. The observations led us to speculate that Wnt2 is extremely involved in regulating CRC progression by CAFs. Thus, we performed immunohistochemical analysis on Wnt2 in 171 patients who underwent surgery for colorectal adenocarcinoma. Positive staining for Wnt2 was mainly observed in cancer stroma, although the immunoreactivity was weak in cancer cells. Wnt2 expression in CAFs was significantly correlated with depth of tumor (P < .001), lymph node metastasis (P = .044), TNM stage (P = .010), venous invasion (P < .001), and recurrence (P = .013). Subsequent in vitro analyses were conducted using conditioned medium (CM) from immortalized CAFs transfected with siRNA targeting Wnt2. As a result, cancer cell invasion and migration were significantly decreased in the CM from immortalized CAFs transfected with siRNA targeting Wnt2. Our findings indicated that Wnt2 protein released from CAFs enhances CRC cell invasion and migration. In conclusion, Wnt2 secreted by CAFs plays a key role in cancer progression and is a potential therapeutic target for CRC.
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