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Donor engineering of diphenylamine-substituted tris(2,4,6-trichlorophenyl)methyl (TTM) radicals triggers the switching of the TTM-based radicals from the photoluminescent to NIR photothermal mode.

Three novel BN-embedded V-shaped polycyclic aromatic hydrocarbons with different π-conjugation lengths were designed and successfully synthesized. Their single-crystal structures were confirmed by X-ray crystallographic analysis, and it is found that the molecular stacking structure can be effectively tuned by extending the length of π conjugation. Meanwhile, owing to the unique V-shaped molecular geometry, they exhibit moderate host-guest supramolecular interactions with both fullerenes C

The solution-phase synthesis of (hetero)cycloarenes with a well-defined size and geometric structure remains a challenging topic in organic chemistry and materials science. Herein, two novel nonplanar N,S-heterocycloarenes (PTZ1 and PTZ2) containing two/three alternate phenothiazine

A series of closed-shell kekulene homologues and an open-shell carbonylated cycloarene derivative were synthesized successfully by controlling the temperature and gas atmosphere of a Bi(OTf)3-catalyzed cyclization reaction.

Cycloarenes and heterocycloarenes display unique physical structures and hold great potential as organic semiconductors. However, the synthesis of (hetero)cycloarenes remains a big challenge, and there are limited reports on their applications. Herein, a series of nitrogen- and sulfur-codoped cycloarenes

Cyclopenta[b]thiopyran, isomeric to benzo[b]thiophene while isoelectronic to azulene, is involved as a building block to construct soluble organic semiconductors for field-effect transistors. Two series of angular-shaped heteroarenes based on cyclopenta[b]thiopyran, that is, Cn-SS (n = 4, 6, 8, 10) with different linear alkyl groups and C8-SS-Clm (m = 2, 3, 4) with chlorides substituted at different positions, have been straightforward synthesized. The obtained seven S-heteroarenes exhibit intriguing and similar photophysical and electrochemical properties, such as near-infrared absorption and high-energy levels of the highest occupied molecular orbitals. Nevertheless, the S-heteroarenes with identical π-conjugated skeletons demonstrate completely different molecular packing structures, which is proofed to be the key determinate factor for the charge carrier mobilities. Upon the engineering of the pendant alkyl lengths, the highest hole mobility in the Cn-SS series is achieved for C8-SS (1.1 cm2 V-1 s-1) with moderate alkyl length. The further incorporation of chlorides on C8-SS results in the shortened intermolecular H···S contacts and the interplane distances. Most interestingly, when chlorine-containing chloroform and chlorobenzene are used as crystallization solvents, single crystals of C8-SS-Clm with different packing structures are produced owing to the intermolecular interactions among the solute and solvent molecules. Upon further engineering of the chlorination position and the crystallization solvent, the maximum hole mobility in the ambient air improves to 2.7 cm2 V-1 s-1 for C8-SS-Cl2 crystallized from chlorobenzene, suggesting that the introduction of the accessible chlorides is a feasible pathway to engineering the crystal structures and controlling the charge transport characteristics.

Low-bandgap π-conjugated small molecules have multiple applications. However, it is still a big challenge to develop such materials because of the scarcity of effective synthetic strategies. In this study, we adopt a feasible strategy, by extending the π-conjugation of the termini in quinoidal compounds, to construct low-bandgap π-conjugated small molecules. With this strategy, we synthesized four indandione-terminated quinoidal compounds, i.e., QIDT-H, QIDT-4F, QSiIDT-H and QSiIDT-4F. Owing to their closed-shell structures, which were confirmed by X-ray crystallographic analysis and 1H NMR spectroscopy, these compounds showed good air stability. Absorption spectroscopy revealed that the terminal benzene rings effectively extended the π-conjugation of these compounds and endowed them with a low bandgap. QIDT-H and QSiIDT-H showed similar bandgaps of ∼1.23 eV, which was smaller than that of a dicyanomethylene-terminated analogue (1.38 eV). Introducing fluorine atoms on the terminal benzene rings further reduced the bandgap, thus QIDT-4F and QSiIDT-4F showed very small bandgaps of 1.06 and 0.91 eV, respectively. These values are among the lowest reported to date for small molecules. The lowest unoccupied molecular orbital energy levels of these compounds were below −4.0 eV, giving them good electron-transport characteristics in organic thin-film transistors. Our findings demonstrate that extending the π-conjugation of the termini in quinoidal compounds is an effective strategy for developing low-bandgap π-conjugated small molecules.

A proton nuclear magnetic resonance (NMR)-based metabolomic study was used to characterize 2009, 2010, 2011, and 2012 vintages of Cabernet Sauvignon wines from Ningxia, which were vinified using the same fermentation technique. The pattern recognition methods of principal component analysis (PCA), partial least squares discriminant analysis (PLS-DA), and orthogonal PLS-DA (OPLS-DA) clearly distinguished between the different vintages of wine driven by the following metabolites: valine, 2,3-butanediol, ethyl acetate, proline, succinic acid, lactic acid, acetic acid, glycerol, gallic acid, and choline. The PLS-DA loading plots also differentiated among the metabolites of different vintages. In the 2009 vintage wines, we found the highest levels of gallic acid, valine, proline, and 2,3-butanediol. The 2011 vintage wines contained the highest levels of lactic acid, and the highest levels of ethyl acetate, succinic acid, glycerol, and choline were observed in the 2012 vintage wines. We selected eight metabolites from the 1H NMR spectra that were quantified according to their peak areas, and the concentrations were in agreement with the results of PLS-DA and OPLS-DA analyses.

A feasible approach against the low yield of microalgae biomass involves the use of a stimulator for microalgal growth. In this research, vanillic acid present in the hydrolysate of agricultural waste, was applied to the cultivation of unicellular microalga Euglena gracilis. At the optimal dosage of 800 mg L−1 vanillic acid, biomass yield at treatment increased 2.08-fold. Correspondingly, the content of chlorophyll a and carotenoids was 3.48 and 2.69 fold than of the control ground, respectively. Increased in cell aspect ratio demonstrated that the alga was more active after vanillic acid treatment. Furthermore, relative lipid and carbohydrate content were analyzed using Fourier transform infrared spectroscopy, the result showed that vanillic acid increased the lipid content in algal cells without sacrificing biomass, which would be a promising way for future biofuel production.

Miniature air bubbles with a diameter of less than 200 nm were generated by a nanobubble aerator, and nanobubble water (NBW) was eventually obtained using the gas-liquid mixing system with hydrodynamic function. As the air bubbles have long lifetime and high gas solubility in the liquids, NBW is stable in nature and inside contains sufficient dissolved oxygen. At present, there is no report on the use of NBW to replace ordinary water to cultivate microalgae. In this research, effect of NBW on the growth and metabolism of different microalgae, including Haematococcus lacustris and Botryococcus braunii was investigated. The result demonstrated that the growth of H. lacustris and B. braunii was increased by NBW and the highest promotion ratio was up to 44% and 26%, respectively. For H. lacustris, the astaxanthin content in the NBW treatment group was also improved compared to the control group. As the main product of B. braunii, lipid content in the dry matter was decreased after the treatment of NBW, but total lipid production was significantly higher than that of the control group. In general, NBW could serve as the potentially effective tool to promote the growth of microalgae in the future.

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A feasible approach against the low yield of microalgae biomass involves the use of a stimulator for microalgal growth. In this research, vanillic acid present in the hydrolysate of agricultural waste, was applied to the cultivation of unicellular microalga Euglena gracilis. At the optimal dosage of 800 mg L

The development of efficient, environmentally friendly, low-cost approaches used to boost the growth of microalgae is urgently required to meet the increasing demands for food supplements, cosmetics, and biofuels. In this study, the growth promotion effects of protocatechuic acid (PCA) in the freshwater microalga Euglena gracilis were confirmed for the first time. PCA is a simple phenolic compound derived from natural plants and has a range of biological functions. The highest biomass yield, 3.1-fold higher than that of the control, used at 1.3 g&middot, L&minus, 1, was obtained at 800 mg&middot, 1 of PCA. The yields of the metabolites chlorophyll a, carotenoids, and paramylon in the presence of PCA at 800 mg&middot, 1 were 3.1, 3.3, and 1.7 times higher than those of the control group, respectively. The highest paramylon yield was achieved at a lower dosage of PCA (100 mg&middot, 1), which is considered to be feasible for economic paramylon production. The growth and biosynthesis of metabolites stimulated by phytochemicals such as PCA could be an efficient and cost-effective strategy to enhance the productivity of microalgae in large-scale cultivations.

Introducing biomass-derived additives into microalgae cultivation to increase its yield has been regarded as a more cost-effective and environment-friendly method compared with gene-editing and nutrients supplementation. In this research, feasibility of three major phenolic compounds from lignin’s basic structures (guaiacyl-, hydroxyphenyl- and syringyl- types) for freshwater microalga Euglena gracilis cultivation was evaluated. The results indicated that trans-4-hydroxy-3-methoxycinnamic acid (HMA), 4-hydroxybenzaldehyde (HBA), and syringaldehyde (SRA) could all promote microalgae growth in a phytohormone-like role, and the highest promotion effect was achieved under HMA treatment. HMA at 0.5 g·L−1 enhanced the cell biomass yield by 2.30 times, while HBA and SRA at the concentration of 0.1 g·L−1 increased the yield by 1.30 and 1.21 times, respectively. In addition, increased carotenoids and lipid biosynthesis were also observed under the treatments of phenolic compounds, which would contribute to the microalgae biofuel production, since the growth and lipid accumulation of E. gracilis were simultaneously enhanced.

A significant promotion of growth and accumulation of metabolites of freshwater microalga Euglena gracilis was obtained by adding phytic acid to the culture. Phytic acid concentration of 0.05% (v/v) showed a maximum biomass increase of 1.6-fold compared to the control group. Synchronous variation in the content and proportion of photosynthetic pigments was also observed. The total chlorophyll content increased with phytic acid concentration, suggesting the enhanced capacity of absorbing light. Cell length, an important biomarker for E. gracilis, was prolonged to a certain extent under light condition, indicating the state of the cells was more active. Since phytic acid is derived from agro waste of rice bran, it is promising as a low-cost but high-efficient growth promoter of E. gracilis.

The recovery of algal biomass is one of the critical steps involved in the commercial production of beneficial metabolites fromPA: Phytic acid; PUFAs: Polyunsaturated fatty acids; FAO: Food and Agriculture Organization; γ-PGA: Poly (γ-glutamic acid); CNF: Cellulose nanofibrils; NIES: National Institute for Environmental Studies; SOT

The metabolites that provide the aroma and flavor to wine are the products of several influences, such as grape cultivar, geographic location and associated environmental features, viticultural practices, and vinification techniques, which are central to production protocols, quality evaluation and development of wine regions. Accordingly, we initiated the requisite studies to investigate the differences in the dry red wine metabolites of different grape varieties. The proton-nuclear magnetic resonance technique (1H-NMR) combined with multivariate statistical analysis was used to investigate the changes of metabolite levels in Cabernet Sauvignon, Merlot and Cabernet Gernischt dry red wines vinified in Changli, Hebei province, China, in 2017. The results showed that the types of metabolites in different varieties of dry red wines were similar, but the content was significantly different. The main contributors to the differences in Cabernet Sauvignon, Merlot and Cabernet Gernischt dry red wines were ethyl acetate, lactic acid, alanine, succinic acid, proline, malic acid, and gallic acid, indicating 1H-NMR method combined with multivariate statistical analysis can distinguish these three types of dry red wines from each other. It provides a benchmark for further comparative study on wine quality and the verification of wine authenticity.

Metabolomics technology based on proton nuclear magnetic resonance (1H NMR) spectroscopy combined with pattern recognition analysis was used to characterize the Cabernet Sauvignon and Shiraz dry red wines vinified in the Linfen of Shanxi Province, China, in 2016. The results showed that there was a very significant difference between the metabolites of Cabernet Sauvignon and Shiraz dry red wines from the area of Linfen. Compared with Shiraz dry red wines, Cabernet Sauvignon dry red wines contained higher levels of proline, valine, tartaric acid, citric acid, malic acid, gallic acid, β-glucose and ethyl acetate, whereas 2,3-butanediol, lactic acid, choline, glycerol, α-D-glucuronic acid, succinic acid and alanine were present in lower levels. Application of NMR spectroscopy combined with pattern recognition analysis showed the discriminative power between wine varietals from the same production area. The loading plot from partial least squares discriminant analysis (PLs-DA) indicated that the key biomarkers for this differentiation were proline, tartaric acid, glycerol, lactic acid, choline, succinic acid and gallic acid, which was consistent with the result of quantitative analysis.

The recovery of algal biomass is one of the critical steps involved in the commercial production of beneficial metabolites from Arthrospira platensis. Efficient and safe harvesting methods that do not sacrifice quality of final product are important for commercial application. Phytic acid (PA) is a natural non-toxic phytochemical widely distributed in plant tissues. Effect of PA from rice bran on the growth, trichome morphology such as spiral number and algal filament length, and harvesting efficiency of A. platensis were investigated. Cells aggregated into large cell flocs after the addition of PA in the medium, and algal spiral number and filament length increased. UV-vis spectra indicated the interactions between PA and algal cells. Adding PA at stationary growth phase is a good strategy for harvesting, since no adverse effect to biomass growth and harvesting efficiency. Harvesting efficiency of 95.69% at 0.5% (v/v) PA was superior to other conventional harvesting methodologies. Abbreviations PA: Phytic acid; PUFAs: Polyunsaturated fatty acids; FAO: Food and Agriculture Organization; γ-PGA: Poly (γ-glutamic acid); CNF: Cellulose nanofibrils; NIES: National Institute for Environmental Studies; SOT: Spirulina–Ogawa–Terui; CG: Control group; pI: Isoelectric point.

Miniature air bubbles with a diameter of less than 200 nm were generated by a nanobubble aerator, and nanobubble water (NBW) was eventually obtained using the gas-liquid mixing system with hydrodynamic function. As the air bubbles have long lifetime and high gas solubility in the liquids, NBW is stable in nature and inside contains sufficient dissolved oxygen. At present, there is no report on the use of NBW to replace ordinary water to cultivate microalgae. In this research, effect of NBW on the growth and metabolism of different microalgae, including Haematococcus lacustris and Botryococcus braunii was investigated. The result demonstrated that the growth of H. lacustris and B. braunii was increased by NBW and the highest promotion ratio was up to 44% and 26%, respectively. For H. lacustris, the astaxanthin content in the NBW treatment group was also improved compared to the control group. As the main product of B. braunii, lipid content in the dry matter was decreased after the treatment of NBW, but total lipid production was significantly higher than that of the control group. In general, NBW could serve as the potentially effective tool to promote the growth of microalgae in the future.

To better understand the promotion effect of phytic acid and its uptake mechanism in freshwater microalga Euglena gracilis, cell growth, photosynthetic pigment content and cell morphology of E. gracilis were evaluated under four conditions: phosphorus deficient group (CMP−), single phosphate treatment group (CMP+), single phytic acid treatment group (CMPA−), and phosphate-phytic acid mixed treatment group (CMPA+). The results showed that phytic acid could serve as the sole phosphorus source for the growth of E. gracilis, and phytase which catalyzes the hydrolysis of phytic acid was discovered for the first time in E. gracilis. Fourier transform infrared spectroscopy combined with multivariate analysis showed the good recognition of metabolites from different culture conditions especially focusing on relative carbohydrate or lipid contents. Phytic acid derived from agro-wastes is a cheap growth promoter for E. gracilis, and this E. gracilis with high nutritional value is applicable to animal feed while minimizing environmental impact.

The study aimed to investigate the effect of five inactive yeasts on the metabolites of Chardonnay dry white wines vinified in 2016 in Shacheng Manor Wine Co. Ltd., Hebei province, China. In this research, proton nuclear magnetic resonance (NMR) spectroscopy coupled multivariate analysis (1H NMR-PCA/PLS-DA) were applied to identify and discriminate the different wine products. The results of principle component analysis (PCA) showed that there was significant difference between the metabolites of sample wines with different inactive yeasts, among them, the content of polyols, organic acids, amino acids and choline was notably influenced. The results of partial least squares discrimination analysis (PLS-DA) confirmed that the metabolites contributed to the discrimination of the wines were 2,3-butanediol, ethyl acetate, malic acid, valine, succinic acid, lactic acid, tartaric acid, glycerol, gallic acid, choline, proline, and alanine.

Cellulose was extracted from rice husk (RH) using an integrated delignification process using alkaline treatment and acid hydrolysis (concentrated HNO3) for lignocellulosic biomass dissolution. Cellulose yield and quality were assessed through analysis of lignocellulosic content, thermogravimetric, functional group, X-ray diffraction, and surface morphology. HNO3 treatment showed an increment (2.01–fold) in the cellulose content and some enhancement in the crystallinity of cellulose (up to 40.8%). A slight increase was observed in thermal properties from 334.6 °C to 339.3 °C. Economic analysis showed chlorine extraction produce higher cellulose recovery (58%) as compared to HNO3 (26.7%) with the total cost of operation using HNO3 was double compared to chlorine extraction. The economic feasibility of HNO3 can be improved using various progress in the pre-treatment process, chemical recycling and cellulose recovery process since adopting it is crucial for environmental sustainability.

Biomass derived supplements have been recognized as environment-friendly and cost-effective sources of stimulants which can promote growth and valuable metabolites biosynthesis of microalgae. In this research, effect of lignosulfonates (LIGNs) on the growth, cell morphological changes, and valuable products accumulation of microalga Euglena gracilis was explored. At the optimal concentration of 5000 mg·L−1, LIGNs could promote the growth of E. gracilis up to 1.95 folds, and increase the yield of chlorophyll a, chlorophyll b and carotenoids by 3.50, 1.59 and 3.48 times, respectively. Cell morphological changes in aspect ratio and size caused by LIGNs were also observed. Fourier transform infrared spectroscopy measurements followed by multivariate analysis revealed difference in metabolic patterns and prominent metabolites with LIGNs treatment. LIGNs improved the lipid yield since both cell density and lipid content increased, which could contribute to the biofuel production in the future.

It is an effective solution to overcome the bottlenecks of commercial production of microalgal biomass by providing cost-effective and environment-friendly organic carbon sources for microalgal mixotrophic growth. In this study, effects of lignocellulose-related mannitol and xylitol on the growth, photosynthetic pigment content, cell morphology, and metabolites biosynthesis of freshwater microalga Euglena gracilis were investigated. The results revealed that both mannitol and xylitol effectively promoted the growth of E. gracilis, and at the optimal dosage of 4 g·L−1, the biomass yield was increased by 4.64-fold and 3.18-fold, respectively. Increase of cell aspect ratio was only observed in mannitol treatment groups, indicating that E. gracilis had different physiological responses to mannitol and xylitol. Fourier transform infrared spectroscopy combined with multivariate analysis was applied to analyze the cellular components. The lipid content of E. gracilis was significantly promoted by these two sugar alcohols, which would increase its potential in biofuel production.

15 An H NMR-based metabolomic study was used to characterize 2009, 2010, 2011, and 2012 16 vintages of Cabernet Sauvignon wines from NingxXia that were vinified in the same 17 fermentation technique. The pattern recognition methods of principal component analysis (PCA) 18 and partial least squares discriminant analysis (PLS-DA) clearly distinguished vintages of wine, 19 driven by the following metabolites: valine, 2,3-butanediol, ethyl acetate, proline, succinic acid, 20 lactic acid, acetic acid, glycerol, gallic acid and choline. The PLS-DA loading plots also 21 differentiated between the metabolites of different vintages. In the 2009 vintage wines we found 22 gallic acid , valine, proline and 2,3-butanediol provide the highest levels. The 2011 vintage wines 23 contained the highest level of lactic acid, and the highest levels of ethyl acetate, succinic acid, 24 glycerol and choline were detected in the 2012 vintage wines. We picked out 8 metabolites from 25 the H NMR spectra, quantified according to the peak areas in total, concentrations in agreement 26 with the PLS-DA results. 27 Subjects Food Science and Technology, Metabolomic 28

T cell activation requires the import of NF-AT transcription factors to the nucleus, a process promoted by calcineurin-dependent dephosphorylation and inhibited by poorly understood protein kinases. Here, we report the identification of two protein kinases that oppose NF-AT4 nuclear import. Casein kinase Ialpha directly binds and phosphorylates NF-AT4, resulting in the inhibiton of NF-AT4 nuclear translocation. MEKK1 indirectly suppresses NF-AT4 nuclear import by stabilizing the interaction between NF-AT4 and CKIalpha. CKIalpha thus acts to establish an intramolecular masking of the nuclear location signal on NF-AT4, while MEKK1 augments this mechanism, and may further provide a link to signal transduction pathways regulating NF-AT4.

The Abl tyrosine kinase contains nuclear-import and -export signals and undergoes nucleo-cytoplasmic shuttling in proliferating cells. The nuclear Abl is activated by DNA damage or tumor necrosis factor to promote cell death through transcription-dependent and -independent mechanisms. The oncogenic BCR-ABL tyrosine kinase is defective in nuclear import and functions as an inhibitor of apoptosis in the cytoplasm. If allowed to function in the nucleus, BCR-ABL also induces cell death. Abl interacts with several different types of death effectors. However, the precise mechanism by which Abl tyrosine kinase regulates cell death remains to be determined.

The TRP73 gene, a member of the p53 family, encodes several variants through differential splicing and use of alternative promoters. At the N terminus, two different promoters generate the full-length and the DeltaN isoforms, with or without the transactivating domain. At the C terminus, seven isoforms generated through alternative splicing have been cloned. Previous studies have demonstrated that DeltaN-p73 interferes with p73-induced apoptosis. However, there has been no evidence for functional diversity of the C-terminal p73 variants. In this study, we found that p73alpha and p73beta exerted differential effect on the differentiation of C2C12 myoblasts. Although p73beta lacked any detectable effect on differentiation, p73alpha caused a substantial delay in the expression of muscle-specific genes. In co-transfection experiments p73alpha, but not p73beta, attenuated the transcriptional activity of MyoD. Microarray-based gene profiling confirmed the protraction of MyoD-dependent gene expression in C2C12 cells stably expressing p73alpha. Notwithstanding the differential effect on differentiation, p73alpha and p73beta showed similar activity in sensitizing C2C12 myoblasts to cisplatin-induced cell death. These results demonstrated a functional diversity between the two C-terminal variants of p73 and suggested that p73alpha can regulate cellular differentiation in addition to its role in stimulating cell death.

Publisher Summary This chapter examines the regulation of Abl sub-cellular location and the location-dependent functions of Abl tyrosine kinase. In the cytoplasm, Abl regulates F-actin and promotes mitogenic signaling in response to extracellular matrix (ECM) and growth factors. In the nucleus, Abl inhibits differentiation and induces apoptosis in response to DNA damage or death receptor signals. The chapter mentions that the Breakpoint Cluster Region (BCR-ABL) oncoprotein resides exclusively in the cytoplasm and causes chronic myelogenous leukemia. When trapped in the nucleus, BCR-ABL kinase behaves like an anti-oncoprotein by activating the suicide program to kill leukemic cells. The ABL protein is excluded from the nucleus of anaplastic thyroid cancer cells. Enforced nuclear accumulation and activation of Abl kinase also induces p73-dependent apoptosis in these cancer cells. The current results are consistent with a simple model: nuclear accumulation of activated Abl tyrosine kinase causes cell death; nuclear export or inhibition of nuclear import prevents Abl from killing cells. Therefore, death by Abl is regulated by the sub-cellular location of this tyrosine kinase.

The p73alpha protein is a functional homolog of the p53 tumor suppressor. Although the TP53 gene is frequently mutated in human cancers, the TP73 gene is rarely inactivated. We have found that p73alpha is highly expressed in a significant fraction of anaplastic thyroid cancer, whereas it is not detectable in normal thyroid epithelial cells or in papillary and follicular thyroid cancer cells. Interestingly, the tumor suppression function of p73alpha is actively restrained in anaplastic thyroid cancer cells. We have also found that c-Abl tyrosine kinase, an activator of p73, is excluded from the nucleus of p73alpha-positive thyroid cancer cells; whereas c-Abl undergoes nuclear-cytoplasmic shuttling in normal thyroid and p73-negative thyroid cancer cells. We constructed an AblNuk-FK506-binding protein (FKBP) fusion protein to enforce the nuclear accumulation of an inducible Abl kinase. Activation of this nuclear AblNuk-FKBP by dimerization with AP20187 in anaplastic thyroid cancer cells increased the levels of p73alpha and p21Cip1 and caused p73-dependent apoptosis. These results suggest subcellular segregation of c-Abl from p73 to be a strategy for disrupting the tumor suppression function of p73alpha.