Near-infrared (NIR)-emitting materials have been extensively studied due to their important applications in biosensing and bioimaging. Luminescent metal-organic frameworks (LMOFs) are a new class of ...highly emissive materials with strong potential for utilization in biomedical related fields because of their nearly unlimited structural and compositional tunability. However, very little work has been reported on organic linker-based NIR-MOFs and their emission properties. In the present work, a series of yttrium-tetracarboxylate-based LMOFs (HIAM-390X) are prepared
via
judicious linker design to achieve NIR emission with diverse structures. The introduction of an amino group not only offers the remarkable emission bathochromic shift from 521 nm, 665 nm to 689 nm for the resultant MOFs, but also influences the linker conformations, leading to the topology evolution from (4,12)-c ftw, (4,8)-c scu, which is rarely reported in rare earth element-based MOFs, to an unprecedented topology hlx for HIAM-3901 (without an amino group), HIAM-3905 (with one amino group) and HIAM-3906 (with two amino groups). Among these MOFs, HIAM-3907 shows an emission maximum at ∼790 nm, with the emission tail close to 1000 nm. The NIR emission may be attributed to the combination of the strongly electron-donating amino group and the strongly electron-withdrawing acceptor naphtho2,3-
c
1,2,5selenadiazole. This work sheds light on the rational design of organic linker-based LMOFs with controlled structures and NIR emission, and inspires future interest in biosensing and bioimaging related applications of NIR-MOFs.
Introduction of amino groups into linkers will not only induce a significant emission red-shift to near-infrared, but also increase structural diversity of resultant LMOFs, leading to structural change from
ftw
,
scu
to an unprecedented topology
hlx
.
Luminescent metal–organic frameworks (LMOFs) have been extensively studied for their potential applications in lighting, sensing and biomedicine-related areas due to their high porosity, unlimited ...structure and composition tunability. However, methodical development in systematically tuning the emission properties of fluorescent organic linker-based LMOFs to facilitate the rational design and synthesis of target-specific materials has remained challenging. Herein we attempt to build an emission library by customized synthesis of LMOFs with targeted absorption and emission properties using donor–acceptor–donor type organic linkers. By tuning the acceptor groups ( i.e. 2,1,3-benzothiadiazole and its derivatives), donor groups (including modification of original donors and use of donors with different metal–linker connections) and bridging units between acceptor and donor groups, an emission library is developed for LMOFs with their emissions covering the entire visible light range as well as the near-infrared region. This work may offer insight into well controlled design of organic linkers for the synthesis of LMOFs with specified functionality.
Chronic obstructive pulmonary disease (COPD) is a major cause of morbidity and mortality in chronic lung disease patients throughout the world. Mesenchymal stem cells (MSCs) have been shown to ...regulate immunomodulatory, anti-inflammatory, and regenerative responses. However, the effects of human-umbilical-cord-derived mesenchymal stem cells (hUC-MSCs) on the lung pathophysiology of COPD remain unclear. We aimed to investigate the role of hUC-MSCs in emphysema severity and Yes-associated protein (Yap) phosphorylation (p-Yap) in a porcine-pancreatic-elastase (PPE)-induced emphysema model. We observed that the emphysema percentages (normalized to the total lung volume) measured by chest computed tomography (CT) and exercise oxygen desaturation were significantly reduced by hUC-MSCs at 107 cells/kg body weight (BW) via intravenous administration in emphysematous mice (p < 0.05). Consistently, the emphysema index, as assessed by the mean linear intercept (MLI), significantly decreased with hUC-MSC administration at 3 × 106 and 107 cells/kg BW (p < 0.05). Changes in the lymphocytes, monocytes, and splenic cluster of differentiation 4-positive (CD4+) lymphocytes by PPE were significantly reversed by hUC-MSC administration in emphysematous mice (p < 0.05). An increasing neutrophil/lymphocyte ratio was reduced by hUC-MSCs at 3 × 106 and 107 cells/kg BW (p < 0.05). The higher levels of tumor necrosis factor (TNF)-α, keratinocyte chemoattractant (KC), and lactate dehydrogenase (LDH) in bronchoalveolar lavage fluid (BALF) were significantly decreased by hUC-MSC administration (p < 0.05). A decreasing p-Yap/Yap ratio in type II alveolar epithelial cells (AECII) of mice with PPE-induced emphysema was significantly increased by hUC-MSCs (p < 0.05). In conclusion, the administration of hUC-MSCs improved multiple pathophysiological features of mice with PPE-induced emphysema. The effectiveness of the treatment of pulmonary emphysema with hUC-MSCs provides an essential and significant foundation for future clinical studies of MSCs in COPD patients.
Colorectal cancer (CRC) is among the most common malignant cancers worldwide, and its development is influenced by inflammation, nutrition, and the immune status. Therefore, we combined C-reactive ...protein (CRP), albumin, and lymphocyte, which could reflect above status, to be the CRP-albumin-lymphocyte (CALLY) index, and evaluated its association with overall survival (OS) in patients with CRC.
The clinicopathological and laboratory characteristics of 1260 patients with CRC were collected from the Investigation on Nutrition Status and Clinical Outcome of Common Cancers (INSCOC) study. Cox regression analysis was performed to assess the association between the CALLY index and OS. A nomogram including sex, age, the CALLY index and TNM stage was constructed. The Concordance Index (C-index) was utilized to evaluate the prognostic value of the CALLY index and classical CRC prognostic factors, such as modified Glasgow prognostic score (mGPS), neutrocyte to lymphocyte ratio (NLR), systemic immune inflammation index (SII), and platelet to lymphocyte ratio (PLR), as well as to assess the prognostic value of the nomogram and TNM stage.
Multivariate Cox regression analyses demonstrated that the CALLY index was independently associated with OS in patients with CRC Hazard ratio (HR) = 0.91, 95% confidence interval (CI) = 0.87-0.95,
<0.001. The CALLY index showed the highest prognostic value (C-index = 0.666, 95% CI = 0.638-0.694,
<0.001), followed by mGPS, NLR, SII, and PLR. The nomogram demonstrated higher prognostic value (C-index = 0.784, 95% CI = 0.762-0.807,
<0.001) than the TNM stage.
The CALLY index was independently associated with OS in patients with CRC and showed higher prognostic value than classical CRC prognostic factors. The nomogram could provide more accurate prognostic prediction than TNM stage.
Metal–organic frameworks (MOFs) exhibit strong potential for applications in molecular adsorption and separation because of their highly tunable structures and large specific surface areas and have ...also been used for iodine capture. However, most works on MOF-based iodine capture focus on the adsorption capacity while taking little consideration of the capture rate and efficiency. Herein, we report the design of a saddle-shaped tetratopic carboxylic acid containing four thiophene groups (H4COTTBA) and the synthesis of a 4,8-connected flu-type zirconium MOF (HIAM-4014) using this linker. HIAM-4014 exhibits highly efficient iodine capture. The large cagelike pore structure, OH– groups on the unsaturated Zr6 clusters, electron-rich nature of the thiophene group in the linker, and high surface area are all attributed to the tetrahedral geometry of H4COTTBA, which endows HIAM-4014 with a relatively high iodine adsorption capacity of 2.50 g/g within 2 h and an equilibrium adsorption capacity of 2.68 g/g after 5 h. Coupled with a high elution ratio and great recyclability, HIAM-4014 is a good candidate for the efficient removal of waste iodine.
Hepatocellular carcinoma (HCC) is closely associatedwith chronic liver diseases, particularly liver cirrhosis, which has an altered extracellular matrix (ECM) composition. The influence and its ...mechanism of the cirrhotic-ECM on the response of HCC to immune checkpoint inhibitor (ICI) remains less clarified.
In silico, proteomic and pathological assessment of alteration of cirrhotic-ECM were applied in clinical cohort. Multiple pre-clinical models with ECM manipulation were used to evaluate cirrhotic-ECM's effect on ICI treatment. In silico, flow cytometry and IHC were applied to explore how cirrhotic-ECM affect HCC microenvironment. In vitro and in vivo experiments were carried out to identify the mechanism of how cirrhotic-ECM undermined ICI treatment.
We defined "a pro-tumor cirrhotic-ECM" which was featured as the up-regulation of collagen type 1 (Col1). Cirrhotic-ECM/Col1 was closely related to impaired T cell function and limited anti PD-1 (aPD-1) response of HCC patients from the TCGA pan cancer cohort and the authors' institution, as well as in multiple pre-clinical models. Mechanically, cirrhotic-ECM/Col1 orchestrated an immunosuppressive microenvironment (TME) by triggering Col1-DDR1-NFκB-CXCL8 axis, which initiated neutrophil extracellular traps (NETs) formation to shield HCC cells from attacking T cells and impede approaching T cells. Nilotinib, an inhibitor of DDR1, reversed the neutrophils/NETs dominant TME and efficiently enhanced the response of HCC to aPD-1.
Cirrhotic-ECM modulated a NETs enriched TME in HCC, produced an immune suppressive TME and weakened ICI efficiency. Col1 receptor DDR1 could be a potential target synergically used with ICI to overcome ECM mediated ICI resistance. These provide a mechanical insight and novel strategy to overcome the ICI resistance of HCC.
Herein, three tritopic carboxylic acids were used to construct three Zr-MOFs, HIAM-4033, HIAM-4034, and HIAM-4035, to investigate the effect of carboxyl position on the MOF structures. The results ...showed that HIAM-4033 and HIAM-4034 possess (3,9)-c models with different underlying nets, whereas HIAM-4035 exhibits the same underlying net as UiO-68. Nanosized HIAM-4033 exhibits excellent sensitivity and selectivity for detecting aromatic acids, such as benzoic acid and 2-fluorobenzoic acid, compared with aliphatic acids and inorganic acids. This study offers new insights into achieving an organic linker directed structure evolution of Zr-MOFs, which might facilitate the discovery of unprecedented underlying nets.
Zr-MOFs with different topologies were constructed by changing carboxyl group positions on thiophene moiety of tritopic carboxylic acids, which provides new insights into investigating organic linker directed structure evolution of Zr-MOFs.
We demonstrate the assembly of a mononuclear metal center, a hexanuclear cluster, and a V-shaped, trapezoidal tetracarboxylate linker into a microporous metal–organic framework featuring an ...unprecedented 3-nodal (4,4,8)-c lyu topology. The compound, HIAM-302, represents the first example that incorporates both a primary building unit and a hexanuclear secondary building unit in one structure, which should be attributed to the desymmetrized geometry of the organic linker. HIAM-302 possesses optimal pore dimensions and can separate monobranched and dibranched alkanes through selective molecular sieving, which is of significant value in the petrochemical industry.
Herein, we demonstrate that linker installation (LI) through postsynthesis is an effective strategy to insert emissive second linkers into single-linker-based metal–organic frameworks (MOFs) to tune ...the emission properties of multicomponent MOFs. Full-color emission, including white-light emission, can be achieved via such a LI process.
