Phosphine-Free Synthesis of High-Quality CdSe Nanocrystals in Noncoordination Solvents: “Activating Agent” and “Nucleating Agent” Controlled Nucleation and Growth

CdSe nanocrystals (NCs) are prepared in noncoordination solvents (1-octadecene (ODE) and paraffin liquid) with long-chain primary alkylamine as the sole ligand, ODE-Se, and cadmium fatty acid salt as precursors. The obtained NCs meet the four fundamental parameters for high-quality NCs: high crystallinity, narrow size distribution, moderate photoluminescence quantum yield, and broad range size tunableness. Further, by simply regulating the relative molar ratio of alkylamine to cadmium precursor, the regular sized “nuclei” and final obtained NCs can be produced predictably within a certain size range. The size distribution of regular sized “nuclei” is very narrow (fwhm = 23 ± 1 nm), and the following focusing growth procedure vanishes. This indicates a different nucleation and growth kinetics from that of the well-established “focusing” and “defocusing” theory. By analyzing the conversion factor of precursors and the concentration of magic sized nanoclusters and regular sized “nuclei”, a subtle secondary nucleation mechanism, “quantized fusion”, was proposed. First, magic sized nanoclusters are formed as the critical nuclei; second, quantized critical nuclei will couple together and fuse into perfect regular sized “nuclei” by combining with stoichiometric monomers. The “quantized fusion” transformation could be regulated by the nature and ratios of the “activating agent” and the “nucleating agent”. These transition processes are very rapid and should be kinetically controlled. The molecular mechanism for monomer formation may be based on the traditional ester aminolysis reaction

Microwave Spectroscopic Investigation and Structural Determination of the Ar–Difluoropyridine van der Waals Complexes

The ground state rotational spectra of the van der Waals dimers of 2,3-, 2,4-, 2,5-, 2,6-, and 3,5-difluoropyridine with argon were investigated in the range of 4 to 26 GHz using both Fourier transform microwave (FTMW) and chirped pulse Fourier transform microwave (cp-FTMW) spectroscopy. The spectroscopic parameters derived from fitting the observed transitions were used to estimate the van der Waals coordinates of the five weakly bound complexes and to quantitatively describe their internal dynamics using a pseudodiatomic model. The experimental structures are in fair agreement with MP2 calculations (6-311++G­(2d, 2p)) and have the centers of mass of the two moieties separated by 3.486 to 3.545 Å with the Ar atom lying 2–10° from the <i>c</i>′ axis of the ring monomer

Rotational Spectra and Structures of the van der Waals Dimers of Argon with 2‑Fluoropyridine and 3‑Fluoropyridine

The ground state rotational spectra of the van der Waals dimers of 2-fluoropyridine and 3-fluoropyridine with argon have been investigated using both Fourier transform microwave (FTMW) and chirped-pulse Fourier transform microwave (cp-FTMW) spectroscopies between 4 and 26 GHz. The rotational constants and ¹⁴N nuclear quadrupole coupling constants derived from fitting the observed transitions were used to estimate the van der Waals coordinates of the two complexes. These are in good agreement with the lowest energy structures determined via MP2 calculations (6-311++G­(2d, 2p)) and have the Ar atom sitting above the plane of the aromatic ring. The center of mass separation of the two moieties in the dimers is between 3.5 and 3.6 Å and the Ar atom lies 5–11° off the monomer <i>c</i>′-axis toward the nitrogen atom of the pyridine backbone

DataSheet_1_Evaluating effects of changing sampling protocol for a long-term ichthyoplankton monitoring program.docx

Abundance indices play a crucial role in monitoring and assessing fish population dynamics. Fishery-independent surveys are commonly favored for deriving abundance indices because they follow standardized or randomized designs, ensuring spatiotemporal consistency in representative and unbiased sampling. However, modifications to the survey protocol may be necessary to accommodate changes in survey goals and logistic difficulty. When the survey undergoes changes, calibration is often needed to remove variability that is unrelated to changes in abundance. We evaluated a long-term monitoring program, the Long River Survey (LRS) in the Hudson River Estuary (HRE), to illustrate the process of calibrating survey data to account for the effects of changing sampling protocol. The LRS provided valuable ichthyoplankton data from 1974 to 2017, but inconsistencies in sampling timing, location, and gears resulted in challenges in interpreting and comparing the fish abundance data in the HRE. Generalized Additive Models were developed for five species at various life stages, aiming to mitigate the impact of sampling protocol changes. Model validation results suggest the consistent performance of the developed models with varying lengths of time series. This study indicates that changes in the sampling protocol can introduce biases in the estimates of abundance indices and that the model-based estimates can improve the reliability and accuracy of the survey abundance indices. The model-estimated sampling effects for each species and life stage provide critical information and valuable insights for designing future sampling protocols.</p

Microwave Rotational Spectra and Structures of 2-Fluoropyridine and 3-Fluoropyridine

The ground state rotational spectra of 2-fluoropyridine and 3-fluoropyridine have been investigated using both Fourier transform microwave (FTMW) and chirped pulse Fourier transform microwave (cp-FTMW) spectroscopies. In addition to the parent species, the spectra of the ¹³C and ¹⁵N singly substituted isotopologues were recorded in the 8–23 GHz region in natural abundance. The rotational constants determined for the seven isotopologues of each were used to calculate relevant geometric parameters including the bond distances and angles of the pyridine ring backbone. The derived structures show a more pronounced deviation from the pyridine ring geometry when the fluorine substituent is <i>ortho</i> to nitrogen which is consistent with <i>ab initio</i> predictions at various levels of theory. Analysis of the ¹⁴N hyperfine structure provided an additional source of information about the electronic structure surrounding the nitrogen atom as a function of fluorine substitution. Together, the experimental results are consistent with a bonding model that involves hyperconjugation whereby fluorine donates electron density from its lone pair into the π-system of pyridine

DataSheet2_Calreticulin as a prognostic biomarker and correlated with immune infiltrate in kidney renal clear cell carcinoma.ZIP

Background: Calreticulin (CALR) has been investigated in several malignant diseases and is associated with immune-cell infiltration. However, the prognostic value of CALR in kidney renal clear cell carcinoma (KIRC) is still unknown.Methods: Based on the computational analysis, data from 530 KIRC cases and 72 normal kidney samples from The Cancer Genome Atlas (TGCA-KIRC) database were analyzed in this study. The expression of CALR mRNA in pan-cancer and immune infiltrates was analyzed using the Tumor Immune Estimation Resource (TIMER) database. The CALR protein expression was obtained from the UALCAN and Human Protein Atlas (HPA) databases. Survival, functional, and statistical analyses were conducted using R software.Results: The CALR expression was higher in KIRC cases than in normal kidneys. A high CALR expression was correlated with TNM stage, pathological stage, and histological grade. Kaplan–Meier survival analysis showed that a high CALR expression was associated with poor overall survival, disease-specific survival, and progression-free interval. Gene set enrichment analysis (GSEA) indicated that CALR was enriched in IL-6 and IL-2 signaling, interferon signaling, TNF signaling, inflammatory response, apoptosis, and the p53 pathway. CALR is correlated with immune-infiltrating cells. A significant correlation was observed between CALR expression and immunomodulators.Conclusion: We identified CALR as a prognostic biomarker of KIRC. Meanwhile, the CALR expression associated with immune infiltration indicated that CALR might be a potential immunotherapy target for patients with KIRC.</p

Investigation of Structural Trends in Mono‑, Di‑, and Pentafluorobenzonitriles Using Fourier Transform Microwave Spectroscopy

The ground state rotational spectra of a series of fluorinated benzonitriles (BN), namely, 2-fluorobenzonitrile (2FBN), 3-fluorobenzonitrile (3FBN), 2,3-difluorobenzonitrile (23DFBN), 2,4-difluorobenzonitrile (24DFBN), and pentafluorobenzonitrile (PFBN), have been investigated between 4 and 24 GHz using Fourier transform microwave (FTMW) spectroscopy. The assigned transitions include those due to the parent as well as the ¹³C and ¹⁵N singly substituted isotopologues which were observed in natural abundance. The spectroscopic analysis allowed the derivation of substitution (<i>r</i>_s) and effective ground state structures (<i>r</i>₀) to investigate the effect of mono-, di-, and pentafluoro substitution on the geometry of the BN backbone and are compared here with ab initio values of the equilibrium parameters (<i>r</i>_e) obtained from MP2/6-311++G­(2d,2p) calculations. Analysis of the ¹⁴N hyperfine structure provides additional information about the electronic structure surrounding the nitrogen atom. The observed geometry changes relative to the reference BN compound are interpreted using natural bond orbital (NBO) analysis to describe differences in the hybridization at various sites and contributions from plausible resonance structures

DataSheet1_Calreticulin as a prognostic biomarker and correlated with immune infiltrate in kidney renal clear cell carcinoma.PDF

Background: Calreticulin (CALR) has been investigated in several malignant diseases and is associated with immune-cell infiltration. However, the prognostic value of CALR in kidney renal clear cell carcinoma (KIRC) is still unknown.Methods: Based on the computational analysis, data from 530 KIRC cases and 72 normal kidney samples from The Cancer Genome Atlas (TGCA-KIRC) database were analyzed in this study. The expression of CALR mRNA in pan-cancer and immune infiltrates was analyzed using the Tumor Immune Estimation Resource (TIMER) database. The CALR protein expression was obtained from the UALCAN and Human Protein Atlas (HPA) databases. Survival, functional, and statistical analyses were conducted using R software.Results: The CALR expression was higher in KIRC cases than in normal kidneys. A high CALR expression was correlated with TNM stage, pathological stage, and histological grade. Kaplan–Meier survival analysis showed that a high CALR expression was associated with poor overall survival, disease-specific survival, and progression-free interval. Gene set enrichment analysis (GSEA) indicated that CALR was enriched in IL-6 and IL-2 signaling, interferon signaling, TNF signaling, inflammatory response, apoptosis, and the p53 pathway. CALR is correlated with immune-infiltrating cells. A significant correlation was observed between CALR expression and immunomodulators.Conclusion: We identified CALR as a prognostic biomarker of KIRC. Meanwhile, the CALR expression associated with immune infiltration indicated that CALR might be a potential immunotherapy target for patients with KIRC.</p

Table_1_The Association Between Cancer and Dementia: A National Cohort Study in Sweden.DOCX

Background: Previous studies have found that the incidence of dementia is lower in patients with cancer. However, the impact of survival bias, as well as the confounding by medical treatment, have not been fully addressed. We aimed to explore the subsequent risk of dementia in different follow-up intervals among patients with cancer, as well as the risk before the diagnosis of cancer.Methods: By using the Swedish Cancer Register and the Swedish Hospital Discharge Register, we systematically examined the risk of dementia among patients diagnosed with 35 different types of cancer. Standardized incidence ratios (SIRs) were used to calculate the relative risk.Results: The subsequent risk of dementia in patients with cancer decreased by 21% compared to matched cancer-free controls (SIR = 0.79, 95% CI 0.78–0.80). For specific cancer sites, 21 of them had a significantly lower risk of subsequent dementia. The decreased risk of dementia was also significant before the diagnosis of cancer. However, the risk was higher among patients with cancer who survived for more than 10 years' post-diagnosis (SIR = 1.37, 95% CI 1.32–1.41).Conclusions: In this population-based study, we found that the risk of dementia was lower among patients with cancer, and the risk was also lower before the diagnosis of cancer. This suggests that lower dementia risk is not simply due to bias. However, the underlying mechanisms need to be explored further.</p

High-Capacitance γ‑rGO/MXene Cathode and Rapid Na⁺‑Transfer Dynamics Sodium Titanate Anode for a Quasi-Solid-State Sodium-Ion Capacitor

Sodium-ion capacitors (SICs) bear the advantages of secondary batteries and supercapacitors and are regarded as promising energy-storage devices. However, the matching of the respective Na+-transfer kinetics of the anode and the cathode and the low energy density are still a challenge. Herein, to achieve a high-capacity cathode, 2D V2C MXene nanosheets were introduced into γ-ray-reduced graphene oxide (γ-rGO), and the γ-rGO/V2C MXene foam (GMF) was fabricated. The GMF provides a high specific capacitance of 391.4 mF cm–2 (130.5 F g–1) at a high current density of 60 mA cm–2 (20 A g–1). Meanwhile, the structure-directing strategy combining multiple nanocarbon composites accelerates the Na+-transfer kinetics of sodium titanate (NTO). The as-fabricated CNT film-supported sodium titanate nanowires encapsulated by the graphene (CNTF@NTO-G) anode deliver a specific capacity of 109 mA h g–1 at a high current density of 10 A g–1. As a result, the assembled quasi-solid-state SIC displays an energy density of 5.61 mW h cm–3 (56.1 W h kg–1) at a power density of 1 W cm–3 (10 kW kg–1) with excellent cycle stability (87.3% capacitance retention after 10,000 cycles)