41 research outputs found
Theoretical Insights into the Phosphorescence Quantum Yields of Cyclometalated (C<sup>â§</sup>C*) Platinum(II) NHC Complexes: ÏâConjugation Controls the Radiative and Nonradiative Decay Processes
In
this article, the radiative and nonradiative decay processes
of four cyclometalated (C<sup>â§</sup>C*) platinumÂ(II) N-heterocyclic
carbene (NHC) complexes were unveiled via density functional theory
and time-dependent density functional theory. In order to explore
the influence of Ï-conjugation on quantum yields of (NHC)ÂPtÂ(acac)
(NHCî»N-heterocyclic carbene, acac = acetylacetonate) complexes,
the factors that determine the radiative process, including singletâtriplet
splitting energies, transition dipole moments, and spinâorbit
coupling (SOC) matrix elements between the lowest triplet states and
singlet excited states were calculated. In addition, the SOC matrix
elements between the lowest triplet state and the ground state as
well as HuangâRhys factors were also computed to describe the
temperature-independent nonradiative decay processes. Also, the triplet
potential energy surfaces were investigated to elucidate the temperature-dependent
nonradiative decay processes. The results indicate that complex <b>Pt-1</b> has higher radiative decay rate than complexes <b>Pt-2â4</b> due to the larger SOC matrix elements between
the lowest triplet states and singlet excited states. However, complexes <b>Pt-2â4</b> have smaller HuangâRhys factors, smaller
SOC matrix elements between the lowest triplet and the ground states,
and higher active energy barriers than complex <b>Pt-1</b>,
indicating that complexes <b>Pt-2â4</b> have smaller
nonradiative decay rate constants. According to these results, one
may discern why complex <b>Pt-2</b> has higher phosphorescence
quantum efficiency than complex <b>Pt-1</b>; meanwhile, it can
be inferred that the nonradiative decay process plays an important
role in the whole photodeactivation process. In addition, on the basis
of complex <b>Pt-2</b>, <b>Pt-5</b> was designed to investigate
the influence of substitution group on the photodeactivation process
of rigid (NHC)ÂPtÂ(acac) complex
Single-Janus Rod Tracking Reveals the âRock-and-Rollâ of Endosomes in Living Cells
Endosomes in cells
are known to move directionally along microtubules,
but their rotational dynamics have rarely been investigated. Even
less is known, specifically, about the rotation of nonspherical endosomes.
Here we report a single-Janus rod rotational tracking study to reveal
the rich rotational dynamics of rod-shaped endosomes in living cells.
The rotational reporters were Janus rods that display patches of different
fluorescent colors on opposite sides along their long axes. When the
Janus rods are wrapped tightly inside endosomes, their shape and optical
anisotropy allow the simultaneous measurements of all three rotational
angles (in-plane, out-of-plane, and longitudinal) and the translational
motion of single endosomes with high spatiotemporal resolutions. We
demonstrate that endosomes undergo in-plane rotation and rolling during
intracellular transport and that such rotational dynamics are driven
by rapid microtubule fluctuations. We reveal for the first time the
ârock-and-rollâ of endosomes in living cells and how
the intracellular environment modifies such rotational dynamics. This
study demonstrates a unique application of Janus particles as imaging
probes in the elucidation of fundamental biological questions
Table_5_Cuproptosis regulator-mediated patterns associated with immune inïŹltration features and construction of cuproptosis-related signatures to guide immunotherapy.xlsx
BackgroundLiver hepatocellular carcinoma (HCC) is a prevalent cancer that lacks a sufficiently efficient approach to guide immunotherapy. Additionally, cuproptosis is a recently identified regulated cell death program that is triggered by copper ionophores. However, its possible significance in tumor immune cell infiltration is still unclear.MethodsCuproptosis subtypes in HCC were identified using unsupervised consensus cluster analysis based on 10 cuproptosis regulators expressions, and a cuproptosis-related risk signature was generated using univariate and LASSO Cox regression and validated using the ICGC data. Moreover, the relationship between signature and tumor immune microenvironment (TME) was studied through tumor immunotherapy responsiveness, immune cell infiltration, and tumor stem cell analysis. Finally, clinical specimens were analyzed using immunohistochemistry to verify the expression of the three genes in the signature.ResultsTwo subtypes of cuproptosis regulation were observed in HCC, with different immune cell infiltration features. Genes expressed differentially between the two cuproptosis clusters in the TCGA were determined and used to construct a risk signature that was validated using the ICGC cohort. Greater immune and stromal cell infiltration were observed in the high-risk group and were associated with unfavorable prognosis. Elevated risk scores were linked with higher RNA stemness scores (RNAss) and tumor mutational burden (TMB), together with a greater likelihood of benefitting from immunotherapy.ConclusionIt was found that cuproptosis regulatory patterns may play important roles in the heterogeneity of immune cell infiltration. The risk signature associated with cuproptosis can assess each patientâs risk score, leading to more individualized and effective immunotherapy.</p
Table_6_Cuproptosis regulator-mediated patterns associated with immune inïŹltration features and construction of cuproptosis-related signatures to guide immunotherapy.xlsx
BackgroundLiver hepatocellular carcinoma (HCC) is a prevalent cancer that lacks a sufficiently efficient approach to guide immunotherapy. Additionally, cuproptosis is a recently identified regulated cell death program that is triggered by copper ionophores. However, its possible significance in tumor immune cell infiltration is still unclear.MethodsCuproptosis subtypes in HCC were identified using unsupervised consensus cluster analysis based on 10 cuproptosis regulators expressions, and a cuproptosis-related risk signature was generated using univariate and LASSO Cox regression and validated using the ICGC data. Moreover, the relationship between signature and tumor immune microenvironment (TME) was studied through tumor immunotherapy responsiveness, immune cell infiltration, and tumor stem cell analysis. Finally, clinical specimens were analyzed using immunohistochemistry to verify the expression of the three genes in the signature.ResultsTwo subtypes of cuproptosis regulation were observed in HCC, with different immune cell infiltration features. Genes expressed differentially between the two cuproptosis clusters in the TCGA were determined and used to construct a risk signature that was validated using the ICGC cohort. Greater immune and stromal cell infiltration were observed in the high-risk group and were associated with unfavorable prognosis. Elevated risk scores were linked with higher RNA stemness scores (RNAss) and tumor mutational burden (TMB), together with a greater likelihood of benefitting from immunotherapy.ConclusionIt was found that cuproptosis regulatory patterns may play important roles in the heterogeneity of immune cell infiltration. The risk signature associated with cuproptosis can assess each patientâs risk score, leading to more individualized and effective immunotherapy.</p
Table_4_Cuproptosis regulator-mediated patterns associated with immune inïŹltration features and construction of cuproptosis-related signatures to guide immunotherapy.xlsx
BackgroundLiver hepatocellular carcinoma (HCC) is a prevalent cancer that lacks a sufficiently efficient approach to guide immunotherapy. Additionally, cuproptosis is a recently identified regulated cell death program that is triggered by copper ionophores. However, its possible significance in tumor immune cell infiltration is still unclear.MethodsCuproptosis subtypes in HCC were identified using unsupervised consensus cluster analysis based on 10 cuproptosis regulators expressions, and a cuproptosis-related risk signature was generated using univariate and LASSO Cox regression and validated using the ICGC data. Moreover, the relationship between signature and tumor immune microenvironment (TME) was studied through tumor immunotherapy responsiveness, immune cell infiltration, and tumor stem cell analysis. Finally, clinical specimens were analyzed using immunohistochemistry to verify the expression of the three genes in the signature.ResultsTwo subtypes of cuproptosis regulation were observed in HCC, with different immune cell infiltration features. Genes expressed differentially between the two cuproptosis clusters in the TCGA were determined and used to construct a risk signature that was validated using the ICGC cohort. Greater immune and stromal cell infiltration were observed in the high-risk group and were associated with unfavorable prognosis. Elevated risk scores were linked with higher RNA stemness scores (RNAss) and tumor mutational burden (TMB), together with a greater likelihood of benefitting from immunotherapy.ConclusionIt was found that cuproptosis regulatory patterns may play important roles in the heterogeneity of immune cell infiltration. The risk signature associated with cuproptosis can assess each patientâs risk score, leading to more individualized and effective immunotherapy.</p
Triphenylene Discotic Pd(II) Metallomesogens Based on Triazole Ligands Derived from the Click Reaction
Two
palladium complexes (Pd[DiTP-triazole]2Cl2 and Pd[TrTP-triazole]2Cl2) bearing a 1,2,3-triazole segment as ligands
were synthesized. The 1,2,3-triazole moiety in Pd[DiTP-triazole]2Cl2 was synthesized by the Cu(I)-catalyzed azideâalkyne cycloaddition
reaction. Meanwhile, the 1,2,3-triazole in Pd[TrTP-triazole]2Cl2 were synthesized through the Click reaction involving an internal
alkyne and an organic azide. These two complexes feature soft spacers
of comparable length between the triphenylene cores and the 1,2,3-triazole
units, which are designed to enhance the molecular symmetry and improve
the liquid crystalline properties. The structures of both complexes
were fully characterized, with a specific focus on their confirmation
through single-crystal X-ray diffraction (XRD) analysis of two model
molecules, Pd[DiB-triazole]2Cl2 and Pd[TrB-triazole]2Cl2. Additional techniques, such as differential scanning calorimetry
(DSC), polarizing optical microscopy (POM), and powder XRD, were used
to confirm the room temperature discotic liquid crystal (DLC) properties
of all palladium complexes. It was found that both complexes Pd[DiTP-triazole]2Cl2 and Pd[TrTP-triazole]2Cl2 exhibit hexagonal
columnar mesophases at room temperature. Significantly, the temperature
ranges of these mesophases were substantially extended, showing increases
of 70 and 56 °C, respectively, compared to their ligands. Additionally,
upon excitation at 279 nm, all the ligands and complexes emit ultraviolet
to visible blue light as for the critical role of the triphenylene
cores
Table_7_Cuproptosis regulator-mediated patterns associated with immune inïŹltration features and construction of cuproptosis-related signatures to guide immunotherapy.docx
BackgroundLiver hepatocellular carcinoma (HCC) is a prevalent cancer that lacks a sufficiently efficient approach to guide immunotherapy. Additionally, cuproptosis is a recently identified regulated cell death program that is triggered by copper ionophores. However, its possible significance in tumor immune cell infiltration is still unclear.MethodsCuproptosis subtypes in HCC were identified using unsupervised consensus cluster analysis based on 10 cuproptosis regulators expressions, and a cuproptosis-related risk signature was generated using univariate and LASSO Cox regression and validated using the ICGC data. Moreover, the relationship between signature and tumor immune microenvironment (TME) was studied through tumor immunotherapy responsiveness, immune cell infiltration, and tumor stem cell analysis. Finally, clinical specimens were analyzed using immunohistochemistry to verify the expression of the three genes in the signature.ResultsTwo subtypes of cuproptosis regulation were observed in HCC, with different immune cell infiltration features. Genes expressed differentially between the two cuproptosis clusters in the TCGA were determined and used to construct a risk signature that was validated using the ICGC cohort. Greater immune and stromal cell infiltration were observed in the high-risk group and were associated with unfavorable prognosis. Elevated risk scores were linked with higher RNA stemness scores (RNAss) and tumor mutational burden (TMB), together with a greater likelihood of benefitting from immunotherapy.ConclusionIt was found that cuproptosis regulatory patterns may play important roles in the heterogeneity of immune cell infiltration. The risk signature associated with cuproptosis can assess each patientâs risk score, leading to more individualized and effective immunotherapy.</p
Image_2_Cuproptosis regulator-mediated patterns associated with immune inïŹltration features and construction of cuproptosis-related signatures to guide immunotherapy.tif
BackgroundLiver hepatocellular carcinoma (HCC) is a prevalent cancer that lacks a sufficiently efficient approach to guide immunotherapy. Additionally, cuproptosis is a recently identified regulated cell death program that is triggered by copper ionophores. However, its possible significance in tumor immune cell infiltration is still unclear.MethodsCuproptosis subtypes in HCC were identified using unsupervised consensus cluster analysis based on 10 cuproptosis regulators expressions, and a cuproptosis-related risk signature was generated using univariate and LASSO Cox regression and validated using the ICGC data. Moreover, the relationship between signature and tumor immune microenvironment (TME) was studied through tumor immunotherapy responsiveness, immune cell infiltration, and tumor stem cell analysis. Finally, clinical specimens were analyzed using immunohistochemistry to verify the expression of the three genes in the signature.ResultsTwo subtypes of cuproptosis regulation were observed in HCC, with different immune cell infiltration features. Genes expressed differentially between the two cuproptosis clusters in the TCGA were determined and used to construct a risk signature that was validated using the ICGC cohort. Greater immune and stromal cell infiltration were observed in the high-risk group and were associated with unfavorable prognosis. Elevated risk scores were linked with higher RNA stemness scores (RNAss) and tumor mutational burden (TMB), together with a greater likelihood of benefitting from immunotherapy.ConclusionIt was found that cuproptosis regulatory patterns may play important roles in the heterogeneity of immune cell infiltration. The risk signature associated with cuproptosis can assess each patientâs risk score, leading to more individualized and effective immunotherapy.</p
Image_6_Cuproptosis regulator-mediated patterns associated with immune inïŹltration features and construction of cuproptosis-related signatures to guide immunotherapy.tif
BackgroundLiver hepatocellular carcinoma (HCC) is a prevalent cancer that lacks a sufficiently efficient approach to guide immunotherapy. Additionally, cuproptosis is a recently identified regulated cell death program that is triggered by copper ionophores. However, its possible significance in tumor immune cell infiltration is still unclear.MethodsCuproptosis subtypes in HCC were identified using unsupervised consensus cluster analysis based on 10 cuproptosis regulators expressions, and a cuproptosis-related risk signature was generated using univariate and LASSO Cox regression and validated using the ICGC data. Moreover, the relationship between signature and tumor immune microenvironment (TME) was studied through tumor immunotherapy responsiveness, immune cell infiltration, and tumor stem cell analysis. Finally, clinical specimens were analyzed using immunohistochemistry to verify the expression of the three genes in the signature.ResultsTwo subtypes of cuproptosis regulation were observed in HCC, with different immune cell infiltration features. Genes expressed differentially between the two cuproptosis clusters in the TCGA were determined and used to construct a risk signature that was validated using the ICGC cohort. Greater immune and stromal cell infiltration were observed in the high-risk group and were associated with unfavorable prognosis. Elevated risk scores were linked with higher RNA stemness scores (RNAss) and tumor mutational burden (TMB), together with a greater likelihood of benefitting from immunotherapy.ConclusionIt was found that cuproptosis regulatory patterns may play important roles in the heterogeneity of immune cell infiltration. The risk signature associated with cuproptosis can assess each patientâs risk score, leading to more individualized and effective immunotherapy.</p
Image_5_Cuproptosis regulator-mediated patterns associated with immune inïŹltration features and construction of cuproptosis-related signatures to guide immunotherapy.tif
BackgroundLiver hepatocellular carcinoma (HCC) is a prevalent cancer that lacks a sufficiently efficient approach to guide immunotherapy. Additionally, cuproptosis is a recently identified regulated cell death program that is triggered by copper ionophores. However, its possible significance in tumor immune cell infiltration is still unclear.MethodsCuproptosis subtypes in HCC were identified using unsupervised consensus cluster analysis based on 10 cuproptosis regulators expressions, and a cuproptosis-related risk signature was generated using univariate and LASSO Cox regression and validated using the ICGC data. Moreover, the relationship between signature and tumor immune microenvironment (TME) was studied through tumor immunotherapy responsiveness, immune cell infiltration, and tumor stem cell analysis. Finally, clinical specimens were analyzed using immunohistochemistry to verify the expression of the three genes in the signature.ResultsTwo subtypes of cuproptosis regulation were observed in HCC, with different immune cell infiltration features. Genes expressed differentially between the two cuproptosis clusters in the TCGA were determined and used to construct a risk signature that was validated using the ICGC cohort. Greater immune and stromal cell infiltration were observed in the high-risk group and were associated with unfavorable prognosis. Elevated risk scores were linked with higher RNA stemness scores (RNAss) and tumor mutational burden (TMB), together with a greater likelihood of benefitting from immunotherapy.ConclusionIt was found that cuproptosis regulatory patterns may play important roles in the heterogeneity of immune cell infiltration. The risk signature associated with cuproptosis can assess each patientâs risk score, leading to more individualized and effective immunotherapy.</p