Time-dependent density-functional study of absorption spectra of open-shell molecules and alkali metal clusters

Thèse numérisée par la Direction des bibliothèques de l'Université de Montréal

Time-dependent density functional study of the electronic potential energy curves and excitation spectrum of the oxygen molecule

Orbital energies, ionization potentials, molecular constants, potential energy curves, and the excitation spectrum of O(2) are calculated using time-dependent density functional theory (TDDFT) with Tamm-Dancoff approximation (TDA). The calculated negative highest occupied molecular orbital energy (-epsilon(HOMO)) is compared with the energy difference ionization potential for five exchange correlation functionals consisting of the local density approximation (LDAxc), gradient corrected Becke exchange plus Perdew correlation (B(88X)+P(86C)), gradient regulated asymptotic correction (GRAC), statistical average of orbital potentials (SAOP), and van Leeuwen and Baerends asymptotically correct potential (LB94). The potential energy curves calculated using TDDFT with the TDA at internuclear distances from 1.0 to 1.8 A are divided into three groups according to the electron configurations. The 1pi(u) (4)1pi(g) (2) electron configuration gives rise to the X (3)Sigma(g) (-), a (1)Delta(g), and b (1)Sigma(g) (+) states; the 1pi(u) (3)1pi(g) (3) electron configuration gives rise to the c (1)Sigma(u) (-), C (3)Delta(u), and A (3)Sigma(u) (+) states; and the B (3)Sigma(u) (-), A (1)Delta(u), and f (1)Sigma(u) (+) states are determined by the mixing of two or more electron configurations. The excitation spectrum of the oxygen molecule, calculated with the aforementioned exchange correlation functionals, shows that the results are quite sensitive to the choice of functional. The LDAxc and the B(88X)+P(86C) functionals produce similar spectroscopic patterns with a single strongly absorbing band positioned at 19.82 and 19.72 eV, respectively, while the asymptotically corrected exchange correlation functionals of the SAOP and the LB94 varieties yield similar excitation spectra where the computed strongly absorbing band is located at 16.09 and 16.42 eV, respectively. However, all of the exchange correlation functionals yield only one strongly absorbing band (oscillator strength greater than 0.1) in the energy interval of 0-20 eV, which is assigned to a X (3)Sigma(g) (-) to (3)Sigma(u) (-) transition. Furthermore, the oxygen molecule has a rich spectrum in the energy range of 14-20 eV and no spin allowed absorption bands are predicted to be observed in the range of 0-6 eV

Different response to 1-methylcyclopropene in two cultivars of Chinese pear fruit with contrasting softening characteristics

In this study, the change in softening and its related genes expression under influence of 500 nl L-1 1-methylcyclopropene (1-MCP) was assessed in the two Chinese pear fruit, ‘Jingbaili’ (Pyrus ussuriensis Maxim) and ‘Yali’ (Pyrus bretschneideri Rehd), which exhibit different softening characteristics. ‘Jingbaili’ pear fruit softened rapidly after harvest, and was strongly inhibited by 1-MCP. In contrast, there was no obvious change of firmness compared to the control after 1-MCP treatment in ‘Yali’ pear fruit. The respiration and ethylene production rates were reduced by 1-MCP at early storage in both two cultivars. ‘Jingbaili’ pear fruit exhibited dramatically increased expression levels of the softening-related genes, i.e., polygalacturonase1 (PG1), polygalacturonase2 (PG2), β-Galactosidase4 (GAL4), α-arabinofuranosidase1 (ARF1) and α-arabinofuranosidase2 (ARF2), and these genes’ expression levels were significantly decreased by 1-MCP treatment. In contrast, ‘Yali’ pear fruit showed lower expression levels of the above-mentioned genes, as well as a relatively smaller inhibition effect by 1-MCP treatment before day 27. These results suggest that ‘Jingbaili’ pear fruit are more sensitive to 1-MCP/ethylene than ‘Yali’ pear fruit during ripening

The influence of 1-MCP on the fruit quality and flesh browning of ‘Red Fuji’ apple after long-term cold storage

This study assessed the influence of 1-MCP treatment on the fruit quality and flesh browning of ‘Red Fuji’ apple at shelf life after long-term cold storage. The ‘Red Fuji’ fruit were stored at 0±0.5 °C for 270 days after treating with 1.0 μL L-1 1-methylcyclopropylene (1-MCP). Fruit quality, browning rate of stem-end flesh, chlorogenic acid content, polyphenol oxidase (PPO) activity were analyzed at shelf-life under 20±0.5 °C, the expression profile of ethylene receptors (MdERS1), phenylalnine ammonia lyase genes (MdPA L1, MdPA L2), quinate hydroxycinnamoyl/hydrxycinnamoyl CoA shi-kimate gene (MdHCT3), polyphenol oxidase genes (MdPPO1, MdPPO5)and lipoxygenase gene (MdLOX) were measured by real-time quantitative PCR. 1-MCP treatment improved the fruit storage quality, decreased stem-end flesh tissue browning, and fruit decay. In addition, the fruit respiration rate and ethylene production rate increased at shelf-life, but this increase could be inhibited by 1-MCP. The same rule was observed in the changes of chlorogenic acid content and PPO activity, the expression of MdERS1, MdPA L1, MdPPO1 and MdLOX were inhibited by 1-MCP as well in the stem-end flesh. Thus, 1-MCP treatment improves the fruit quality of ‘Red Fuji’ apple at shelf-life after long-term cold storage, and inhibits the browning of stem-end flesh by decreasing the chlorogenic acid content and PPO activity. MdPA L1, MdHCT3, MdPPO1 and MdLOX participate in the flesh browning progress

Effect of Preharvest Aminoethoxyvinylglycine Treatment on Fruit Quality and Core Browning in ‘Huangguan’ Pear after Long-Term Cold Storage

In order to prolong the storage period of ‘Huangguan’ pear and reduce the deterioration of fruit quality during long-term storage and subsequent shelf life, this study conducted preharvest treatment with different concentrations of aminoethoxyvinylglycine (AVG) to ‘Huangguan’ pear. Before and after refrigeration for 180 days and after subsequent shelf life for 7 days, quality indicators were tested. The results showed that compared with the control group, preharvest AVG treatment delayed the decline of fruit firmness, maintained higher contents of soluble solids and titratable acids, and effectively inhibited fruit surface browning and core browning, the most pronounced effect being observed at 200 mg/L AVG. During long-term cold storage, the contents of arbutin, chlorogenic acid and total phenols increased with the occurrence of core browning, and the activity of polyphenol oxidase (PPO) increased. The expression levels of PbPAL1, PbPAL2, PbPPO1, PbPPO5, PbLOX1 and PbLOX5 were up-regulated during cold storage, but down-regulated during shelf life. Preharvest treatment with 200 mg/L AVG significantly reduced the consumption of arbutin, chlorogenic acid and total phenols, inhibited the increase of PPO activity along with the expression of PbPAL1, PbPAL2, PbPPO1, PbPPO5 and PbLOX5, and thus effectively reduced core browning in ‘Huangguan’ pear

Effects of Preharvest Aminoethoxyvinylglycine (AVG) Treatment on Fruit Ripening, Core Browning and Related Gene Expression in ‘Huangguan’ Pear (<i>Pyrus bretschneideri</i> Rehd.)

‘Huangguan’ pear (Pyrus bretschneideri Rehd. cv. Huangguan) is a widely planted cultivar in China. However, it is susceptible to core browning after harvest. In this study, aminoethoxyvinylglycine (AVG) was applied at 200 mg L−1 one and two weeks prior to harvest, and its effects on fruit quality, ripening and core browning were investigated during fruit storage at ambient temperature (25 ± 1 °C). The results showed that there was higher firmness, soluble solids content (SSC) and titratable acid (TA) content, but a lower ethylene production rate and core browning index in AVG-treated fruit than in control (water). Compared with the control fruit, AVG treatment decreased the malondialdehyde (MDA) content and polyphenol oxidase (PPO) activity, delayed the peak of chlorogenic acid (CGA) content in the core tissue, and significantly inhibited the expression of genes such as ACC synthase (PbACS2, PbACS3a, PbACS5a and PbASC5b), ACC oxidase (PbACO1 and PbACO2), ethylene receptors (PbETR2 and PbERS1), ethylene response factor (PbERF1), phenylalanine ammonia lyase (PbPAL1), cinnamate 4-hydroxylase (PbC4H4), 4-hydroxycinnamoyl- CoA ligase (Pb4CL2), hydroxycinnamoyl- CoA shikimate hydroxycinnamoyl transferase (PbHCT1 and PbHCT3), and polyphenol oxidase (PbPPO1 and PbPPO5), as well as phospholipase D (PbPLD) and lipoxygenase (PbLOX1 and PbLOX5). Thus, these results suggested that the reduction in core browning by preharvest application of AVG might be due to an inhibitory effect on the expression of genes associated with ethylene biosynthesis and signaling pathways, CGA biosynthesis, PPO and cell membrane degradation in ‘Huangguan’ pear

Scour Evolution Downstream of Submerged Weirs in Clear Water Scour Conditions

Although weirs or dikes in the riverine and coastal environments are frequently overtopped, few studies have hitherto examined the evolution of the scour process downstream of these structures under the submerged condition. This paper presents an experimental investigation on time evolution of the scour process downstream of submerged weirs with a uniform coarse sand. The clear-water scour experiments were carried out in a tilting recirculation flume. Different flow intensities and overtopping ratios (approach flow depth/weir height) were adopted in the experiments. Experimental observations show that the scour hole downstream of submerged weirs develops very fast in the initial stage, before progressing at a decreasing rate and eventually reaching the equilibrium stage. The results show that an increase of the overtopping ratio or flowrate can generate larger scour depth and volume downstream of the weir. Moreover, geometrical similarity of the scour hole that formed downstream of the weir was observed in the tests. Finally, empirical equations for predicting scour hole geometrical evolutions downstream of the submerged weirs were presented. The results of this study are useful in the development of numerical/analytical models capable of estimating the scour depth downstream of weirs in the river or coastal areas, for which the overtopping conditions are present

Scour evolution downstream of submerged weirs in clear water scour conditions

Although weirs or dikes in the riverine and coastal environments are frequently overtopped, few studies have hitherto examined the evolution of the scour process downstream of these structures under the submerged condition. This paper presents an experimental investigation on time evolution of the scour process downstream of submerged weirs with a uniform coarse sand. The clear-water scour experiments were carried out in a tilting recirculation flume. Different flow intensities and overtopping ratios (approach flow depth/weir height) were adopted in the experiments. Experimental observations show that the scour hole downstream of submerged weirs develops very fast in the initial stage, before progressing at a decreasing rate and eventually reaching the equilibrium stage. The results show that an increase of the overtopping ratio or flowrate can generate larger scour depth and volume downstream of the weir. Moreover, geometrical similarity of the scour hole that formed downstream of the weir was observed in the tests. Finally, empirical equations for predicting scour hole geometrical evolutions downstream of the submerged weirs were presented. The results of this study are useful in the development of numerical/analytical models capable of estimating the scour depth downstream of weirs in the river or coastal areas, for which the overtopping conditions are present.Published versio

Low Temperature Conditioning Reduced the Chilling Injury by Regulating Expression of the Dehydrin Genes in Postharvest Huangguan Pear (<i>Pyrus bretschneideri</i> Rehd. cv. Huangguan)

‘Huangguan’ pear (Pyrus bretschneideri Rehd. cv. Huangguan) fruit is sensitive to chilling injury (CI), which exhibits peel browning spots (PBS) during cold storage. Dehydrin (DHN) is considered to be related to cold tolerance in plants, but its function in postharvest pear fruit during storage remains unclear. In this study, six PbDHNs (PbDHN1–6) genes were identified and characterized, and the PbDHN proteins were sorted into YnKn, SKn and YnSKn according to the major conserved motifs related to the number and location of K-segments, S-segments, and Y-segments. In addition, there were five cold-responsive related cis-acting elements in the promoter region of the PbDHNs. The analysis of fruit quality suggested that compared with a storage temperature at 20 °C, a storage temperature of 0 °C results in CI in ‘Huangguan’ pear fruit, while a storage temperature of 10 °C and low temperature conditioning (LTC) alleviates the CI. Moreover, gene expression results indicated that the six PbDHNs were markedly enhanced at low temperatures, especially at 0 °C. The transcripts of PbDHN1, PbDHN4, PbDHN5 and PbDHN6 were also increased in the fruit stored at 10 °C, but they were lower than that at 0 °C except PbDHN5. Compared with low temperature storage at 0 °C, LTC treatment significantly depressed the expression of PbDHN1, PbDHN2, PbDHN3, PbDHN4, and PbDHN6, while enhanced the mRNA amount of PbDHN5. In conclusion, PbDHN1, PbDHN4, PbDHN5, and PbDHN6 were closely related to the CI, and LTC lowered the CI by down-regulating the expression of PbDHN1, PbDHN4, and PbDHN6 and by up-regulating PbDHN5 in ‘Huangguan’ pear fruit