Aromatic Saddles Containing Two Heptagons

Soluble derivatives of C₇₀H₂₆ (<b>1a</b>,<b>b</b>) and C₇₀H₃₀ (<b>2a</b>,<b>b</b>), two new saddle-shaped polycyclic arenes containing two heptagons, were successfully synthesized from saddle-shaped diketones (<b>3a</b>,<b>b</b>), whose carbonyl groups are the key in the reactions to extend the polycyclic π-framework. As found from the crystal structures, the polycyclic backbone of <b>1b</b> has a deep saddle shape, while that of <b>2b</b> is even more distorted because of the existence of two [4]-helicene moieties. On the basis of crystal structures, local aromaticity and nonplanarity of individual rings in the saddle-shaped π-backbone were analyzed, and were found to follow Clar’s rule in general. It was found that <b>1b</b> and <b>3b</b> behaved as p-type semiconductors in solution-processed thin film transistors while the amorphous films of <b>2b</b> appeared insulating

Aromatic Saddles Containing Two Heptagons

Soluble derivatives of C₇₀H₂₆ (<b>1a</b>,<b>b</b>) and C₇₀H₃₀ (<b>2a</b>,<b>b</b>), two new saddle-shaped polycyclic arenes containing two heptagons, were successfully synthesized from saddle-shaped diketones (<b>3a</b>,<b>b</b>), whose carbonyl groups are the key in the reactions to extend the polycyclic π-framework. As found from the crystal structures, the polycyclic backbone of <b>1b</b> has a deep saddle shape, while that of <b>2b</b> is even more distorted because of the existence of two [4]-helicene moieties. On the basis of crystal structures, local aromaticity and nonplanarity of individual rings in the saddle-shaped π-backbone were analyzed, and were found to follow Clar’s rule in general. It was found that <b>1b</b> and <b>3b</b> behaved as p-type semiconductors in solution-processed thin film transistors while the amorphous films of <b>2b</b> appeared insulating

Curved Polycyclic Aromatic Molecules That Are π‑Isoelectronic to Hexabenzocoronene

Reported here are two types of curved π-molecules that are π-isoelectronic to planar hexabenzocoronene (HBC) but are forced out of planarity either by an embedded seven-membered ring or by atom crowding at the fjord region. Embedding a heptagon in HBC leads to a novel saddle-shaped molecule 1, whose π-backbone is slightly less curved than the previously reported [7]­circulene in terms of the average Gauss curvature, but surprisingly much more rigid than [7]­circulene. Overcrowded fjord regions in novel derivatives of hexabenzoperylene (HBP) 2a,b lead to both chiral twisted and antifolded conformers. The successful synthesis of 1 and 2a,b is related to introducing alkoxyl groups to unprecedented positions of hexaphenylbenzenes. It is found that the red twisted isomer of 2b isomerizes at elevated temperature to the yellow anti-folded conformer. This finding along with the study on the thermodynamics and kinetics of the thermal isomerization has improved the early understandings on the conformation of HBP. In the crystals, 1 lacks π–π interactions between neighboring molecules, while twisted-2a exhibits both face-to-face and edge-to-face π–π interactions. Twisted-2b is found to function as a p-type semiconductor in thin film transistors, but the thin films of 1 appear insulating presumably due to lacking π–π interactions. By exploring three different types of curvatures in 1 and the two isomers of 2b, this study has revealed that the curvature of π-face plays a role in determining the frontier molecular orbital energy levels and π–π interactions and thus needs to be considered when one designs new organic semiconductors

Pile defect assessment using distributed temperature sensing: fundamental questions examined

Thermal integrity testing has been successfully used to assess the quality of cast-in-place piles for the past decade. It employs temperature data measured during concrete curing to identify defects along the piles’ length. However, the uptake of this technology has been rather limited in the piling industry. The main concerns are that the method is not standardised and its reliability is not well understood. In order to address these, there are a number of fundamental questions that need to be explored in more detail, including (a) the optimum time to conduct the assessment, (b) the defect thermal impact, (c) the zone of influence on temperature sensors, (d) the minimum detectable size of a defect and (e) the associated optimum sensor location required. In this paper, experimental and numerical studies were conducted to examine these questions. Fibre optic sensors were employed on model concrete piles in laboratory tests to provide fully distributed temperature data throughout the curing process. The test results showed that the optimum time to assess the defects is approximately at 60% of the time to reach peak temperature and the minimal detectable defect size, using the currently available optical fibre sensor technology, is 4% of the cross-sectional area. In addition, the thermal influence of different defect sizes is presented. Following this, it is shown in the paper that the minimum numbers of sensor cables required to identify defects with cross-sectional areas of 4%, 5% and 8% are eight, six and four cables, respectively. The optimum layout of these sensor cables within a pile cross-section has also been discussed. When specifying pile instrumentation for integrity assessment, the findings of this paper enable practising engineers to make informed judgements in relation to the size of defects they would like to detect (and hence the associated risk this entails) together with the corresponding instrumentation layout required.</p

Curved Polycyclic Aromatic Molecules That Are π‑Isoelectronic to Hexabenzocoronene

Reported here are two types of curved π-molecules that are π-isoelectronic to planar hexabenzocoronene (HBC) but are forced out of planarity either by an embedded seven-membered ring or by atom crowding at the fjord region. Embedding a heptagon in HBC leads to a novel saddle-shaped molecule <b>1</b>, whose π-backbone is slightly less curved than the previously reported [7]­circulene in terms of the average Gauss curvature, but surprisingly much more rigid than [7]­circulene. Overcrowded fjord regions in novel derivatives of hexabenzoperylene (HBP) <b>2a</b>,<b>b</b> lead to both chiral twisted and antifolded conformers. The successful synthesis of <b>1</b> and <b>2a</b>,<b>b</b> is related to introducing alkoxyl groups to unprecedented positions of hexaphenylbenzenes. It is found that the red twisted isomer of <b>2b</b> isomerizes at elevated temperature to the yellow <i>anti</i>-folded conformer. This finding along with the study on the thermodynamics and kinetics of the thermal isomerization has improved the early understandings on the conformation of HBP. In the crystals, <b>1</b> lacks π–π interactions between neighboring molecules, while twisted-<b>2a</b> exhibits both face-to-face and edge-to-face π–π interactions. Twisted-<b>2b</b> is found to function as a p-type semiconductor in thin film transistors, but the thin films of <b>1</b> appear insulating presumably due to lacking π–π interactions. By exploring three different types of curvatures in <b>1</b> and the two isomers of <b>2b</b>, this study has revealed that the curvature of π-face plays a role in determining the frontier molecular orbital energy levels and π–π interactions and thus needs to be considered when one designs new organic semiconductors

Curved Polycyclic Aromatic Molecules That Are π‑Isoelectronic to Hexabenzocoronene

Reported here are two types of curved π-molecules that are π-isoelectronic to planar hexabenzocoronene (HBC) but are forced out of planarity either by an embedded seven-membered ring or by atom crowding at the fjord region. Embedding a heptagon in HBC leads to a novel saddle-shaped molecule <b>1</b>, whose π-backbone is slightly less curved than the previously reported [7]­circulene in terms of the average Gauss curvature, but surprisingly much more rigid than [7]­circulene. Overcrowded fjord regions in novel derivatives of hexabenzoperylene (HBP) <b>2a</b>,<b>b</b> lead to both chiral twisted and antifolded conformers. The successful synthesis of <b>1</b> and <b>2a</b>,<b>b</b> is related to introducing alkoxyl groups to unprecedented positions of hexaphenylbenzenes. It is found that the red twisted isomer of <b>2b</b> isomerizes at elevated temperature to the yellow <i>anti</i>-folded conformer. This finding along with the study on the thermodynamics and kinetics of the thermal isomerization has improved the early understandings on the conformation of HBP. In the crystals, <b>1</b> lacks π–π interactions between neighboring molecules, while twisted-<b>2a</b> exhibits both face-to-face and edge-to-face π–π interactions. Twisted-<b>2b</b> is found to function as a p-type semiconductor in thin film transistors, but the thin films of <b>1</b> appear insulating presumably due to lacking π–π interactions. By exploring three different types of curvatures in <b>1</b> and the two isomers of <b>2b</b>, this study has revealed that the curvature of π-face plays a role in determining the frontier molecular orbital energy levels and π–π interactions and thus needs to be considered when one designs new organic semiconductors

Table5_Integrating Network Pharmacology and Metabolomics to Elucidate the Mechanism of Action of Huang Qin Decoction for Treament of Diabetic Liver Injury.docx

Huang Qin Decoction (HQD), is used for the treatment of diabetic liver injury (DLI) and in this study, its mechanisms were evaluated by metabonomics and system pharmacology. To study the anti-DLI effects of HQD. The 48 male db/db mice were fed adaptively for one week, and a random blood glucose test was performed twice. The db/db mice with a blood glucose level of more than 11.1mol/l were separated into four groups: the model group, the active control group, the high-dose HQD group the low-dose HQD group, the control group consisted of db/m mice. Using the UHPLC/Q-TOF-MS metabolomics approach, 18 metabolites were found to be profoundly altered in the model group, and the levels of these biomarkers were significantly recovered after treatment with HQD. 8 signaling pathways related to HQD, including the Sphingolipid metabolism, Taurine and hypotaurine metabolism, Phenylalanine metabolism, Glutathione metabolism and Glycerophospholipid metabolism, etc. were explored. In addition, the system pharmacology paradigm revealed that HQD contains 141 active ingredients and is related to 265 genes, and 1404 disease genes are related to DLI. The construction of the HQD composition-target-DLI network identified a total of 161 intersection genes. We identified 10 key genes, which is partially compatible with the results of metabolomics. The integrated approach metabolomics and network pharmacology revealed that additional detailed investigation focused on five major targets, including CAT, PTGS2, MAPK3, AKT1, and MAPK8, and their essential metabolites (sphinganine, sphingosine, Glutahione, Oxidized gutahione, Dihydrolipoamide) and pathway (glycerol phospholipid metabolism and tryptophan metabolism). The significant affinity of the primary target for the HQD was confirmed by molecular docking. The results demonstrate that the combination of metabolomics and network pharmacology could be used to reflect the effects of HQD on the biological network and metabolic state of DLI and to evaluate the drug efficacy of HQD and its related mechanisms.</p

Table3_Integrating Network Pharmacology and Metabolomics to Elucidate the Mechanism of Action of Huang Qin Decoction for Treament of Diabetic Liver Injury.docx

Huang Qin Decoction (HQD), is used for the treatment of diabetic liver injury (DLI) and in this study, its mechanisms were evaluated by metabonomics and system pharmacology. To study the anti-DLI effects of HQD. The 48 male db/db mice were fed adaptively for one week, and a random blood glucose test was performed twice. The db/db mice with a blood glucose level of more than 11.1mol/l were separated into four groups: the model group, the active control group, the high-dose HQD group the low-dose HQD group, the control group consisted of db/m mice. Using the UHPLC/Q-TOF-MS metabolomics approach, 18 metabolites were found to be profoundly altered in the model group, and the levels of these biomarkers were significantly recovered after treatment with HQD. 8 signaling pathways related to HQD, including the Sphingolipid metabolism, Taurine and hypotaurine metabolism, Phenylalanine metabolism, Glutathione metabolism and Glycerophospholipid metabolism, etc. were explored. In addition, the system pharmacology paradigm revealed that HQD contains 141 active ingredients and is related to 265 genes, and 1404 disease genes are related to DLI. The construction of the HQD composition-target-DLI network identified a total of 161 intersection genes. We identified 10 key genes, which is partially compatible with the results of metabolomics. The integrated approach metabolomics and network pharmacology revealed that additional detailed investigation focused on five major targets, including CAT, PTGS2, MAPK3, AKT1, and MAPK8, and their essential metabolites (sphinganine, sphingosine, Glutahione, Oxidized gutahione, Dihydrolipoamide) and pathway (glycerol phospholipid metabolism and tryptophan metabolism). The significant affinity of the primary target for the HQD was confirmed by molecular docking. The results demonstrate that the combination of metabolomics and network pharmacology could be used to reflect the effects of HQD on the biological network and metabolic state of DLI and to evaluate the drug efficacy of HQD and its related mechanisms.</p

Table4_Integrating Network Pharmacology and Metabolomics to Elucidate the Mechanism of Action of Huang Qin Decoction for Treament of Diabetic Liver Injury.docx

Huang Qin Decoction (HQD), is used for the treatment of diabetic liver injury (DLI) and in this study, its mechanisms were evaluated by metabonomics and system pharmacology. To study the anti-DLI effects of HQD. The 48 male db/db mice were fed adaptively for one week, and a random blood glucose test was performed twice. The db/db mice with a blood glucose level of more than 11.1mol/l were separated into four groups: the model group, the active control group, the high-dose HQD group the low-dose HQD group, the control group consisted of db/m mice. Using the UHPLC/Q-TOF-MS metabolomics approach, 18 metabolites were found to be profoundly altered in the model group, and the levels of these biomarkers were significantly recovered after treatment with HQD. 8 signaling pathways related to HQD, including the Sphingolipid metabolism, Taurine and hypotaurine metabolism, Phenylalanine metabolism, Glutathione metabolism and Glycerophospholipid metabolism, etc. were explored. In addition, the system pharmacology paradigm revealed that HQD contains 141 active ingredients and is related to 265 genes, and 1404 disease genes are related to DLI. The construction of the HQD composition-target-DLI network identified a total of 161 intersection genes. We identified 10 key genes, which is partially compatible with the results of metabolomics. The integrated approach metabolomics and network pharmacology revealed that additional detailed investigation focused on five major targets, including CAT, PTGS2, MAPK3, AKT1, and MAPK8, and their essential metabolites (sphinganine, sphingosine, Glutahione, Oxidized gutahione, Dihydrolipoamide) and pathway (glycerol phospholipid metabolism and tryptophan metabolism). The significant affinity of the primary target for the HQD was confirmed by molecular docking. The results demonstrate that the combination of metabolomics and network pharmacology could be used to reflect the effects of HQD on the biological network and metabolic state of DLI and to evaluate the drug efficacy of HQD and its related mechanisms.</p

Table2_Integrating Network Pharmacology and Metabolomics to Elucidate the Mechanism of Action of Huang Qin Decoction for Treament of Diabetic Liver Injury.docx

Huang Qin Decoction (HQD), is used for the treatment of diabetic liver injury (DLI) and in this study, its mechanisms were evaluated by metabonomics and system pharmacology. To study the anti-DLI effects of HQD. The 48 male db/db mice were fed adaptively for one week, and a random blood glucose test was performed twice. The db/db mice with a blood glucose level of more than 11.1mol/l were separated into four groups: the model group, the active control group, the high-dose HQD group the low-dose HQD group, the control group consisted of db/m mice. Using the UHPLC/Q-TOF-MS metabolomics approach, 18 metabolites were found to be profoundly altered in the model group, and the levels of these biomarkers were significantly recovered after treatment with HQD. 8 signaling pathways related to HQD, including the Sphingolipid metabolism, Taurine and hypotaurine metabolism, Phenylalanine metabolism, Glutathione metabolism and Glycerophospholipid metabolism, etc. were explored. In addition, the system pharmacology paradigm revealed that HQD contains 141 active ingredients and is related to 265 genes, and 1404 disease genes are related to DLI. The construction of the HQD composition-target-DLI network identified a total of 161 intersection genes. We identified 10 key genes, which is partially compatible with the results of metabolomics. The integrated approach metabolomics and network pharmacology revealed that additional detailed investigation focused on five major targets, including CAT, PTGS2, MAPK3, AKT1, and MAPK8, and their essential metabolites (sphinganine, sphingosine, Glutahione, Oxidized gutahione, Dihydrolipoamide) and pathway (glycerol phospholipid metabolism and tryptophan metabolism). The significant affinity of the primary target for the HQD was confirmed by molecular docking. The results demonstrate that the combination of metabolomics and network pharmacology could be used to reflect the effects of HQD on the biological network and metabolic state of DLI and to evaluate the drug efficacy of HQD and its related mechanisms.</p