Inspired by the distinguished regulated photochemical and photophysical properties of 2-(2′-hydroxyphenyl)benzazole derivatives, in this work, the novel bis(2′-benzothiazolyl)hydroquinone (BBTHQ) ...fluorophore is explored, looking at its photo-induced behaviors associated with different substituted atomic electronegativities, i.e., BBTHQ-SO, BBTHQ-SS and BBTHQ-Se compounds. From the structural changes, infrared (IR) vibrational variations and simulated core-valence bifurcation (CVB) indexes for the dual hydrogen bonds for the three BBTHQ derivatives, we see that low atomic electronegativity could be conducive to enhancing hydrogen bonding effects in the S1 state. Particularly, the O4-H5⋯N6 of BBTHQ-SO and the O1-H2⋯N3 of BBTHQ-SSe could be strengthened to be more intensive in the S1 state, respectively. Looking into the charge recombination induced by photoexcitation, we confirm a favorable ESDPT trend deriving from the charge reorganization of the dual hydrogen bonding regions. By constructing the potential energy surfaces (PESs) along with the ESDPT paths for the BBTHQ-SO, BBTHQ-SS and BBTHQ-Se compounds, we not only unveil stepwise ESDPT behaviors, but also present an atomic electronegativity-regulated ESDPT mechanism.
An in-depth understanding of the relationship between innovation factor allocation, the institutional environment, and high-quality economic development can help us better comprehend how better ...productivity promotes high-quality, regionally coordinate, and balanced economic development. Using panel data of 30 provincial-level regions in China from 2011 to 2019, we explore the effect of innovation factor allocation on high-quality economic development and the moderating effects of different institutional environments. First, we construct a comprehensive indicator system for innovation factor allocation and a new model to calculate the weights of various indicators of innovation factors. Second, we apply TOPSIS and grey correlation to measure the level of innovation factor allocation, and construct a modified gravity model to generate a directed weighted spatial association network of this allocation as a spatial weight matrix. Finally, we use the spatial Durbin model to empirically test the spatial effects of innovation factor allocation on high-quality economic development under different institutional environments. We find that: First, innovation factor allocation significantly positively affects the high-quality development of the local economy, while it has negative spatial spillover effects on neighboring areas. The impact of different types of institutional environments on high-quality economic development exhibits an inverted “U” shape. China's institutional environment has not crossed the critical threshold of this “U" shaped relationship. Thus, different types of institutional environments can still effectively strengthen the role of innovation factor allocation in promoting high-quality economic development. In particular, the strengthening effect of online government is the strongest and its negative impact is the weakest. Overall, this study is of great significance for optimizing innovation factor allocation in various regions and promoting high-quality economic development.
In this work, we theoretically investigate the sequential excited state double proton transfer (ESDPT) mechanism of a representative intramolecular hydroxyl (OH)-type hydrogen molecule ...2,2′-bipyridyl-3,3′-diol (BP(OH)2). We mainly adopt three kinds of different polar solvents (nonpolar cyclohexane (CYH), polar acetonitrile (ACN), and moderate chloroform (CHCl3)) to explore solvent effects on this system. Two intramolecular hydrogen bonds of BP(OH)2 are testified to be strengthened in the S1 state, which provides possibility for ESDPT process. Explorations of charge redistribution and potential energy surfaces (PESs) reveal ESDPT process. Searching transition state (TS) structures in different polar aprotic solvents, we successfully regulate and control the stepwise ESDPT behaviors of BP(OH)2 through solvent polarity.
The excited state intramolecular proton transfer (ESIPT) mechanisms of 2-(2-hydroxyphenyl)benzoxazole (HBO), bis-2,5-(2-benzoxazolyl)-hydroquinone (BBHQ) and ...2,5-bis(5'-tert-butyl-benzoxazol-2'-yl)hydroquinone (DHBO) have been investigated using time-dependent density functional theory (TDDFT). The calculated vertical excitation energies based on the TDDFT method reproduced the experimental absorption and emission spectra well. Three kinds of stable structures were found on the S1 state potential energy surface (PES). A new ESIPT mechanism that differs from the one proposed previously (Mordzinski et al., Chem. Phys. Lett., 1983, 101, 291. and Lim et al., J. Am. Chem. Soc., 2006, 128, 14542.) is proposed. The new mechanism includes the possibility of simultaneous double proton transfer, or successive single transfers, in addition to the accepted single proton transfer mechanism. Hydrogen bond strengthening in the excited state was based on primary bond lengths, angles, IR vibrational spectra and hydrogen bond energy. Intramolecular charge transfer based on the frontier molecular orbitals (MOs) also supports the proposed mechanism of the ESIPT reaction. To further elucidate the proposed mechanism, reduced dimensionality PESs of the S0 and S1 states were constructed by keeping the O-H distance fixed at a series of values. The potential barrier heights among the local minima on the S1 surface imply competitive single and double proton transfer branches in the mechanism. Based on the new ESIPT mechanism, the observed fluorescence quenching can be satisfactorily explained.
Presents the first theoretical and methodological shift in the measurement of area deprivation in NZ since the 1990s and describes the development of the New Zealand Index of Multiple Deprivation ...(IMD). Describes briefly the development of Data Zones, an intermediary geographical scale, before outlining the development of the New Zealand Index of Multiple Deprivation (IMD), which uses routine data sets and methods comparable to current international deprivation indices. Identifies 28 indicators of deprivation from national health, social development, taxation, education, police databases, geospatial data providers and the 2013 Census, all of which represented seven domains of deprivation : employment; income; crime; housing; health; education; and geographical access Source: National Library of New Zealand Te Puna Matauranga o Aotearoa, licensed by the Department of Internal Affairs for re-use under the Creative Commons Attribution 3.0 New Zealand Licence.
Celotno besedilo
Dostopno za:
DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
Two excited state proton transfer mechanisms of 3-hydroxyisoquinoline (3HIQ) in cyclohexane and acetic acid (ACID) were investigated based on the time-dependent density functional theory (TDDFT), ...suggesting a different double-proton transfer mechanism from the one proposed previously (
J. Phys. Chem. B
, 1998,
102
, 1053). Instead of the formation of keto-enol complexes for 3HIQ self-association in cyclohexane, our theoretical results predicted that 3HIQ self-association exists in two forms: the normal form (enol/enol) and the tautomer form (keto/keto) in cyclohexane. A high barrier (37.023 kcal mol
−1
) between the 3HIQ enol monomer and 3HIQ keto monomer form indicated that the 3HIQ keto monomer in the ground state should not exist. In addition, the constructed potential energy surfaces of the ground state and excited state have been used to explain the proton transfer process. Upon optical excitation, the enol/enol form is excited to the first excited state, then transfers one proton, in turn, transition to the ground state to transfer another proton. A relatively low barrier (8.98 kcal mol
−1
) demonstrates two stable structures in the ground state. In view of the acetic acid solvent effect, two protons of 3HIQ/ACID transfer along the dihydrogen bonds in the first excited state, which is a different transfer mechanism to 3HIQ self-association. In addition, the proton transfer process provides a possible explanation for the fluorescence quenching observed.
Two excited state proton transfer mechanisms of 3-hydroxyisoquinoline (3HIQ) in cyclohexane and acetic acid (ACID) were investigated.
The excited state intramolecular proton transfer (ESIPT) mechanisms of 1,8-dihydroxydibenzoa,hphenazine (DHBP) in toluene solvent have been investigated based on time-dependent density functional ...theory (TD-DFT). The results suggest that both a single and double proton transfer mechanisms are relevant, in constrast to the prediction of a single one proposed previously (Piechowska et al. J. Phys. Chem. A 2014, 118, 144–151). The calculated results show that the intramolecular hydrogen bonds were formed in the S0 state, and upon excitation, the intramolecular hydrogen bonds between −OH group and pyridine-type nitrogen atom would be strengthened in the S1 state, which can facilitate the proton transfer process effectively. The calculated vertical excitation energies in the S0 and S1 states reproduce the experimental UV–vis absorption and fluorescence spectra well. The constructed potential energy surfaces of the S0 and S1 states have been used to explain the proton transfer process. Four minima have been found on the S1 state surface, with potential barriers between these excited-state minima of less than 10 kcal/mol, which supports concomitant single and double proton transfer mechanisms. In addition, the fluorescence quenching can be explained reasonably based on the proton transfer process.
Abstract
Background
Studies had shown that social integration was related to the utilization of medical services. Few studies investigated the relationship between social integration and medical ...returns among the elderly. None research had ever clarified the effect of social integration on medical returns among the migrant elderly following children (MEFC) to new cities. This study aimed to explore the association between social integration and medical returns among the MEFC in Jinan, China.
Method
This cross-sectional study included 627 MEFC in Jinan China. Social integration was evaluated by economic integration, acculturation, and identification. Medical return was assessed by asking the subjects whether go back to hometown to use the medical services when ill. Chi-squared test and multivariable logistic regression were applied to analyze the association between social integration and medical returns of the MEFC.
Results and discussion
It was found that 20.3% of the MEFC had a medical return. As for social integration, those who had not joined local medical insurance (OR = 3.561, 95% CI 1.577–8.039,
p
= 0.002) and were unwilling to stay for a long time (OR = 2.600, 95% CI 1.620–4.174,
p
= 0.001) were more likely to have a medical return. Furthermore, our findings showed that the MEFC who were accompanied by one or more (OR = 1.568, 95% CI 1.027–2.392,
p
= 0.037) were more likely to have a medical return than those who migrated alone.
Conclusion
Negative relationship between social integration and medical returns was found among the MEFC, which means the better social integration of the MEFC would generally have fewer medical return, as well as the better refunding connections of the medical insurance between the current residence and hometown.
Celotno besedilo
Dostopno za:
DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
Drought causes osmotic stress and rapidly triggers abscisic acid (ABA) accumulation in plants. The roles of various ABA receptors in drought tolerance and molecular mechanisms regulating ABA receptor ...stability needs to be elucidated. Here, we report that Arabidopsis plants overexpressing PYL9, one of the 14 pyrabactin resistance (PYR)/pyrabactin resistance-like (PYL)/regulatory component of ABA receptors (RCAR) family ABA receptors, gained drought tolerance trait. Osmotic stress induced accumulation of the PYL9 protein, which was regulated by the 26S proteasome. PYL9 interacted with two highly homologous plant U-box E3 ubiquitin ligases PUB22 and PUB23. In the cell-free degradation assay, the degradation of GST-PYL9 was accelerated in protein extract from plants overexpressing PUB22 but slowed down in protein extract from the
double mutant. The in vivo decay of Myc-PYL9 was significantly reduced in the
double mutant as compared with the wild-type. Additionally, PUB22 also interacted with other ABA receptors such as PYL5, PYL7 and PYL8. Considering the improved drought tolerance in the
double mutant in previous studies, our results suggest that PUB22 and PUB23 negatively regulate drought tolerance in part by facilitating ABA receptors degradation.
Hepatocellular carcinoma (HCC) is one of the most common malignant tumors in adults. Basic leucine zipper and W2 domains 2 (BZW2) is a member of the basic‐region leucine zipper (bZIP) superfamily of ...transcription factors. Here, we found that BZW2 expression was substantially increased in both human HCC tissues and cell lines, which was correlated with the clinical progression of patients with HCC. Silence of BZW2 in HCC cells by infecting with the lentivirus for delivering BZW2 shRNA (short hairpin RNA), prohibits cell progression, as determined by the suppressed cell proliferation, clonality, invasion, and increased cell apoptosis. Furthermore, overexpression of BZW2 promotes drug resistance of HCC cells, as shown by the attenuated suppression of cell viability and invasion following rapamycin (RAPA) treatment. Mechanistically, overexpression (or silence) of BZW2 in HCC cells significantly stimulates (or decreases) the activation of the PI3K/AKT/mTOR signaling pathway, which is responsible for HCC progression. Thus, increased BZW2 expression in HCC can induce HCC progression and drug resistance via stimulating the PI3K/AKT/mTOR pathway, which may represent a new therapeutic target for HCC.
BZW2 expression was substantially increased in both human hepatocellular carcinoma (HCC) tissues and cell lines. BZW2 expression in HCC can induce HCC progression and drug resistance via stimulating the PI3K/AKT/mTOR pathway, which may represent a new therapeutic target for HCC.
PDF
