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1.
Plants (Basel) ; 13(5)2024 Mar 04.
Artigo em Inglês | MEDLINE | ID: mdl-38475568

RESUMO

Uridine diphosphate glycosyltransferases (UDP-GTs, UGTs), which are regulated by UGT genes, play a crucial role in glycosylation. In vivo, the activity of UGT genes can affect the availability of metabolites and the rate at which they can be eliminated from the body. UGT genes can exert their regulatory effects through mechanisms such as post-transcriptional modification, substrate subtype specificity, and drug interactions. Phoebe bournei is an economically significant tree species that is endemic to southern China. Despite extensive studies on the UGT gene family in various species, a comprehensive investigation of the UGT family in P. bournei has not been reported. Therefore, we conducted a systematic analysis to identify 156 UGT genes within the entire P. bournei genome, all of which contained the PSPG box. The PbUGT family consists of 14 subfamilies, consistent with Arabidopsis thaliana. We observed varying expression levels of PbUGT genes across different tissues in P. bournei, with the following average expression hierarchy: leaf > stem xylem > stem bark > root xylem > root bark. Covariance analysis revealed stronger covariance between P. bournei and closely related species. In addition, we stressed the seedlings with 10% NaCl and 10% PEG-6000. The PbUGT genes exhibited differential expression under drought and salt stresses, with specific expression patterns observed under each stress condition. Our findings shed light on the transcriptional response of PbUGT factors to drought and salt stresses, thereby establishing a foundation for future investigations into the role of PbUGT transcription factors.

2.
Dalton Trans ; 52(46): 17485-17492, 2023 Nov 28.
Artigo em Inglês | MEDLINE | ID: mdl-37955433

RESUMO

Nickel chloride and thiolate complexes supported by benzene-pyridine-based nonsymmetrical PCN pincer ligands, [2-(tBu2PO)-6-(2-pyrindinyl-4-R)-C6H3]NiX (R = H, CH3, CF3; X = Cl, SH, SPh), were synthesized and fully characterized. The structures of these complexes and the catalytic reactivity of the chloride complexes were investigated along with the related POCOP counterparts [2,6-(tBu2PO)2C6H3]NiX (X = Cl, SH). It was found that the composition and substitution of the pincer backbone evidently influence the structures and catalytic reactivity. The Ni-P and Ni-Cipso bond lengths in the PCN complexes are significantly shorter than those in the POCOP complex. The Ni-Cl and Ni-S bond lengths in the PCN complexes are longer than those in the POCOP complexes. An electron rich pyrindinyl ring in the PCN complexes makes the Ni-Cl bond longer. The Ni-N bond length is more sensitive to the auxiliary ligand compared with the Ni-P bond length in the PCN complexes. The PCN chloride complexes were found to be active catalysts for selective hydration of nitriles to primary amides in the presence of NaOH at 80 °C and the catalytic activity increases with the increase of electron richness of the pyridinyl ring. However, the corresponding POCOP counterpart is inactive under the same conditions.

3.
Plants (Basel) ; 12(10)2023 May 21.
Artigo em Inglês | MEDLINE | ID: mdl-37653964

RESUMO

GRAS genes are important transcriptional regulators in plants that govern plant growth and development through enhancing plant hormones, biosynthesis, and signaling pathways. Drought and other abiotic factors may influence the defenses and growth of Phoebe bournei, which is a superb timber source for the construction industry and building exquisite furniture. Although genome-wide identification of the GRAS gene family has been completed in many species, that of most woody plants, particularly P. bournei, has not yet begun. We performed a genome-wide investigation of 56 PbGRAS genes, which are unequally distributed across 12 chromosomes. They are divided into nine subclades. Furthermore, these 56 PbGRAS genes have a substantial number of components related to abiotic stress responses or phytohormone transmission. Analysis using qRT-PCR showed that the expression of four PbGRAS genes, namely PbGRAS7, PbGRAS10, PbGRAS14 and PbGRAS16, was differentially increased in response to drought, salt and temperature stresses, respectively. We hypothesize that they may help P. bournei to successfully resist harsh environmental disturbances. In this work, we conducted a comprehensive survey of the GRAS gene family in P. bournei plants, and the results provide an extensive and preliminary resource for further clarification of the molecular mechanisms of the GRAS gene family in P. bournei in response to abiotic stresses and forestry improvement.

4.
Int J Food Microbiol ; 403: 110298, 2023 Oct 16.
Artigo em Inglês | MEDLINE | ID: mdl-37392609

RESUMO

As a widely distributed food-borne pathogenic fungus, Aspergillus flavus and its secondary metabolites, mainly aflatoxin B1 (AFB1), pose a great danger to humans. It is urgent to reveal the complex regulatory network of toxigenic and virulence of this fungus. The bio-function of Set9, a SET-domain-containing histone methyltransferase, is still unknown in A. flavus. By genetic engineering means, this study revealed that, through catalyzing H4K20me2 and -me3, Set9 is involved in fungal growth, reproduction, and mycotoxin production via the orthodox regulation pathway, and regulates fungal colonization on crop kernels through adjusting fungal sensitivity reactions to oxidation stress and cell wall integrity stress. Further domain deletion and point mutation inferred that the SET domain is the core element in catalyzing H4K20 methylation, and D200 site of the domain is the key amino acid in the active center of the methyltransferase. Combined with RNA-seq analysis, this study revealed that Set9 regulates the aflatoxin gene cluster by the AflR-like protein (ALP), other than traditional AflR. This study revealed the epigenetic regulation mechanism of fungal morphogenesis, secondary metabolism, and pathogenicity of A. flavus mediated by the H4K20-methyltransferase Set9, which might provide a potential new target for early prevention of contamination of A. flavus and its deadly mycotoxins.


Assuntos
Aflatoxinas , Aspergillus flavus , Humanos , Aspergillus flavus/metabolismo , Metabolismo Secundário , Epigênese Genética , Aflatoxina B1 , Metiltransferases/genética , Proteínas Fúngicas/genética , Proteínas Fúngicas/metabolismo
5.
Inorg Chem ; 62(12): 4971-4979, 2023 Mar 27.
Artigo em Inglês | MEDLINE | ID: mdl-36922906

RESUMO

In order to develop efficient protocols for CO2 reduction with less expensive and more convenient hydrogen sources, the catalytic reactivities of group 10 metal hydride complexes supported by a PNCNP pincer ligand, [2,6-(tBu2PNH)2C6H3]MH (M = Ni, 1a; Pd, 1b; Pt, 1c), against the hydroboration of CO2 with NH3·BH3 and NaBH4 have been explored. Both 1a and 1b readily react with CO2 at room temperature to form the corresponding formato complexes, [2,6-(tBu2PNH)2C6H3]MOC(O)H (M = Ni, 2a; Pd, 2b), in nearly quantitative yields. Treatment of NH3·BH3 with CO2 (1 atm) in 1,4-dioxane or THF at room temperature in the presence of 0.05-1.0 mol % of 1b followed by hydrolysis of the resulting mixtures produces formic acid in 105-186% yields, and initial turnover frequencies of up to 2000 h-1 are observed. In the presence of 1.0 mol % of 1b, NaBH4 reacts with CO2 (1 atm) in THF at room temperature to form NaB[OC(O)H]4 (3) in 87% isolated yield. In situ NMR spectroscopy indicates that the reactions proceed through the insertion of the C═O bond in CO2 into the Pd-H bond in 1b to form 2b, which sequentially reacts with the hydrides in NH3·BH3 or NaBH4 to produce boron formato species and regenerate 1b. This work represents one of the rare examples of catalytic transfer hydrogenation of CO2 with NH3·BH3 to the formic acid level under very mild conditions without any additives and also the first example of 4 equiv of CO2 uptake by NaBH4 in a reaction.

6.
Cell ; 186(3): 560-576.e17, 2023 02 02.
Artigo em Inglês | MEDLINE | ID: mdl-36693374

RESUMO

Downward social mobility is a well-known mental risk factor for depression, but its neural mechanism remains elusive. Here, by forcing mice to lose against their subordinates in a non-violent social contest, we lower their social ranks stably and induce depressive-like behaviors. These rank-decline-associated depressive-like behaviors can be reversed by regaining social status. In vivo fiber photometry and single-unit electrophysiological recording show that forced loss, but not natural loss, generates negative reward prediction error (RPE). Through the lateral hypothalamus, the RPE strongly activates the brain's anti-reward center, the lateral habenula (LHb). LHb activation inhibits the medial prefrontal cortex (mPFC) that controls social competitiveness and reinforces retreats in contests. These results reveal the core neural mechanisms mutually promoting social status loss and depressive behaviors. The intertwined neuronal signaling controlling mPFC and LHb activities provides a mechanistic foundation for the crosstalk between social mobility and psychological disorder, unveiling a promising target for intervention.


Assuntos
Habenula , Status Social , Camundongos , Animais , Recompensa , Comportamento Social , Habenula/fisiologia , Depressão
7.
J Org Chem ; 87(24): 16230-16235, 2022 Dec 16.
Artigo em Inglês | MEDLINE | ID: mdl-36414318

RESUMO

The preparation of primary amines from nitriles has been a subject of continuing interest, and many different methods have been reported for this process. We report in this paper an alternative method for transforming nitriles into primary amines. In this work, a wide range of nitriles were reduced to primary amines by 1.2 equiv of ammonia borane under thermal decomposition conditions without any catalyst and the corresponding primary amines were isolated in good to excellent yields. The reactions are environmentally benign with H2 and NH3 generated as byproducts. The reactions are also tolerant of many functional groups. Nitriles are likely reduced by the in situ-generated aminodiborane, the application of which in organic synthesis has never been reported before. By using our protocol, primary amines containing multifluorinated aromatic rings, which are greatly important in pharmaceutical synthesis and have rarely been prepared via catalytic processes, were successfully prepared.

8.
Dalton Trans ; 51(46): 17602-17608, 2022 Nov 29.
Artigo em Inglês | MEDLINE | ID: mdl-36345989

RESUMO

A palladium(II) hydride complex supported by a benzene-based PNCNP pincer ligand, [2,6-(tBu2PNH)2C6H3]PdH (1), has been synthesized via two different routes: the reaction of the corresponding chloride complex with LiAlH4 and the reaction of the corresponding nitrate complex with KOCH3. Complex 1 exhibits strong deprotonating ability and versatile catalytic activity. Acetamide can be readily deprotonated by complex 1 to form the corresponding acetamido complex, [2,6-(tBu2PNH)2C6H3]PdNHC(O)CH3, in high yield. Complex 1 is an active catalyst for both the dehydrogenation of methanol to formaldehyde under mild conditions and direct hydration of nitriles to primary amides. Particularly, the direct hydration of nitriles to primary amides catalysed by complex 1 represents the most efficient palladium catalytic system for this type of reaction. A wide range of nitriles have been successfully hydrated to primary amides with 100% selectivity and good to excellent isolated yields. The possible reaction mechanisms are discussed.

9.
ACS Omega ; 7(27): 23717-23726, 2022 Jul 12.
Artigo em Inglês | MEDLINE | ID: mdl-35847272

RESUMO

We performed serum metabolome analysis of di(2-ethylhexyl)phthalate (DEHP)-exposed and control pregnant mice. Pregnant mice (n = 5) were fed a DEHP-containing diet (0.1% or 0.2% DEHP) or a normal diet (control) from gestational days 0-18. After maternal exposure to 0.2% DEHP there were no surviving fetuses, indicating its strong fetal lethality. There were no significant differences in the numbers of fetuses and placentas between the 0.1% DEHP and control groups, although fetal viability differed significantly between them, suggesting that maternal exposure to 0.1% DEHP could inhibit fetal growth. Metabolomics successfully detected 169 metabolites in serum. Principal component analysis (PCA) demonstrated that the three groups were clearly separated on PCA score plots. The biological interpretation of PC1 was fetal lethality, whereas PC2 meant metabolic alteration of pregnant mice via DEHP exposure without fetal lethality. In particular, the first component was significantly correlated with fetal viability, demonstrating that maternal metabolome changes via DEHP exposure were strongly related to fetal lethality. Levels of some amino acids were significantly increased in the DEHP-exposed groups, whereas those of some fatty acids, nicotinic acid, and 1,5-anhydroglucitol were significantly decreased in the DEHP groups. DEHP-induced increases in glycine levels could cause fetal neurological disorders, and decreases in nicotinic acid could inhibit fetal growth. In addition, a machine-learning Random forest could determine 16 potential biomarkers of DEHP exposure, and data-driven network analysis revealed that nicotinic acid was the most influential hub metabolite in the metabolic network. These findings will be useful for understanding the effects of DEHP on the maternal metabolome in pregnancy and their relationship to fetal lethality.

10.
Dalton Trans ; 51(30): 11507-11514, 2022 Aug 02.
Artigo em Inglês | MEDLINE | ID: mdl-35833572

RESUMO

The coordination mode of the BH4- ligand in transition metal tetrahydroborate complexes is mainly dominated by the nature of the metal centres. However, other factors can also play important roles sometimes. In order to rationalize the coordination modes and the stability of the BH4- ligand in group 10 metal tetrahydroborate pincer complexes, [2,6-(tBu2PO)2C6H3]Pt(η1-HBH3) and [C6H4-o-(NCH2PtBu2)2B]M(η2-H2BH2) (M = Ni, Pt) were prepared and characterized. A structural comparison of [2,6-(tBu2PCH2)2C6H3]Ni(BH4), [2,6-(tBu2PO)2C6H3]M(BH4) and [C6H4-o-(NCH2PtBu2)2B]M(BH4) (M = Ni, Pd, and Pt) indicates that the M-P bond length, the P-M-P bite angle and the trans-influence of the central atom in the pincer platform also affect the coordination mode of the BH4- ligand. The nickel complexes tend to adopt a monodentate coordination mode while the palladium and platinum complexes can adopt either the monodentate or the bidentate mode depending on the structural features of the pincer platforms. Longer M-P bonds and smaller P-M-P bite angles favour the bidentate mode. The stability of the BH4- ligand is influenced by both the coordination mode and the nature of the metal centre. The BH3 species is released more easily from complexes with less electron rich metal centres. Following the series of Ni, Pd, and Pt, complexes with the same pincer ligand more easily lose a BH3 moiety.

11.
Dalton Trans ; 51(6): 2304-2312, 2022 Feb 08.
Artigo em Inglês | MEDLINE | ID: mdl-35041735

RESUMO

Diphosphino-boryl-based PBP pincer platinum thiolate complexes, [Pt(SR){B(NCH2PtBu2)2-1,2-C6H4}] (R = H, 1a; Ph, 1b), and benzene-based bisphosphinite POCOP pincer platinum thiolate complexes, [Pt(SR)(tBu2PO)2-1,3-C6H3] (R = H, 2a; Ph, 2b), were prepared and fully characterized by multinuclear NMR, X-ray crystallography, HRMS and elemental analyses. The application of these complexes in the catalytic hydrosilylation of aldehydes and ketones was investigated. It was found that these platinum thiolate complexes are efficient catalysts for the hydrosilylation of aldehydes and ketones at 65-75 °C. Comparatively, the PBP complexes are more active than the corresponding POCOP complexes. Both phenylsilane and polymethylhydrosiloxane (PMHS) can be used as silyl reagents. The expected alcohols were obtained in good to excellent yields after the basic hydrolysis of the hydrosilylation products and many functional groups were not affected. With turnover frequencies (TOFs) of up to 67 000 h-1, the present catalytic system represents the most effective platinum catalytic system for the hydrosilylation of carbonyl compounds. The reactions were likely catalysed by the in situ generated platinum hydride species.

12.
J Sci Food Agric ; 102(7): 2792-2804, 2022 May.
Artigo em Inglês | MEDLINE | ID: mdl-34716586

RESUMO

BACKGROUND: Flavor is a key element affecting the popularity of French fries (FFs). When oil is heated, the changes in oil quality can affect the flavor of the food directly. RESULTS: The flavor of FFs showed three crucial stages: the break-in (3.0% to 6.8% of total polar compounds (TPC)), optimum (7.0% to 19% of TPC), and degrading (above 19.5% of TPC) stages. To distinguish the key aroma compounds in the three stages, the FFs, prepared in palm oil (PO) at TPC of 3.0% (FF3), 7.5% (FF8), 19.5% (FF20), and their relevant oils (PO3, PO8, PO20), were selected for molecular sensory science analysis. The results indicated that the concentration of (E, E)-2,4-decadienal linked with the deep-fried odor was low in FF3, which led to a lower sensory score in the FF3 sample. The FF8 sample had a high (E, E)-2,4-decadienal content and received a high sensory score. The FF20 sample possessed high hexanoic acid, heptanoic acid (sweaty odor), benzaldehyde (stale odor), octanoic acid (sweaty odor), (E)-2-undecenal (fatty odor), and trans-4,5-epoxy-(E)-2-decenal (metallic odor) content, thus leading to FFs having an undesirable flavor and PO20 showed high hexanoic acid and heptanoic acid content, contributing to a lower sensory score in PO20. CONCLUSION: The FFs' flavor became undesirable when TPC was above 19.5% due to significant influences of some off-flavor compounds. It is therefore essential to prevent the generation of rancid substances to prolong the optimum stage during frying. © 2021 Society of Chemical Industry.


Assuntos
Odorantes , Compostos Orgânicos Voláteis , Cromatografia Gasosa-Espectrometria de Massas , Odorantes/análise , Óleos , Olfatometria , Óleo de Palmeira , Compostos Orgânicos Voláteis/química
13.
Food Chem ; 368: 130581, 2022 Jan 30.
Artigo em Inglês | MEDLINE | ID: mdl-34399180

RESUMO

Flavor is a significant factor determining the popularity of French fries (FFs). The frying process of soybean oil (SO) showed three obvious stages-break-in, optimum, and degrading. Further, in order to distinguish the key aroma compounds in each stage, the FFs prepared in SO with total polar compounds (TPC) of 6.5% (FF7), 16.37% (FF16), and 26.5% (FF27), and their corresponding oils (SO7, SO16, SO27) were chosen for sensory-directed analysis. In the break-in stage (6.50-13.50% of TPC), the flavor of the FFs was light and undesirable due to the lower content of (E,E)-2,4-decadienal. Then at the optimum stage (15.43-22.70% of TPC), the FFs obtained a higher sensory score, mainly owing to the increase of (E,E)-2,4-decadienal with a strong, deep-fried odor. However, in the degrading stage (over 22.70% of TPC), high level of four acids (hexanoic, heptanoic, octanoic, and nonanoic acid), benzeneacetaldehyde and trans-4,5-epoxy-(E)-2-decenal resulted in flavor deterioration in FF27.


Assuntos
Odorantes , Solanum tuberosum , Culinária , Odorantes/análise , Óleos de Plantas/análise , Paladar
14.
Inorg Chem ; 60(24): 18924-18937, 2021 Dec 20.
Artigo em Inglês | MEDLINE | ID: mdl-34878759

RESUMO

The influence of the pincer platform composition and substitution on the reactivity and physical properties of pincer complexes can be easily explored through different experimental techniques. However, the influence of these factors on the molecular structures and thermodynamic stability of pincer complexes is usually very subtle and cannot always be unambiguously established. To rationalize this subtle influence, a survey of crystallographic data from 130 group 10 metal pincer complexes supported by benzene-based PYCYP pincer ligands, [2,6-(R2PY)2C6H3-nR'n]MX (Y = CH2, NH, O, S; M = Ni, Pd, Pt; R = tBu, iPr, Ph, Cy, Me; R' = CO2Me, tBu, CF3, Ac; n = 0-2; X = F, Cl, Br, I, H, SH, SPh, SBn, Ph, Me, N3, NCS), was carried out. Theoretical calculations for some selected complexes were performed to evaluate the relative bond strength. It was found that the M-Cipso bond length decreases following the linker series of CH2 > NH > O and that the relative M-Cipso bond strength increases following the linker series of CH2 < NH < O. In most cases, the M-P bond length decreases following the linker series of NH > CH2 > O. The relative M-P bond strength increases following the linker series of CH2 < NH < O. A comparison of the thermochemical balance for the isodesmic displacement of the side-arm interactions with PH3 as a probe ligand indicated that the Ni-P bond in a PCCCP-type pincer complex is far less difficult to break compared with that in a POCOP-type complex. As a result, with the same donor substituents and the same auxiliary ligand, the POCOP-type pincer complexes are thermodynamically more stable than the PCCCP complexes. The influence of other backbone and donor substitutions as well as the pincer platform composition on the M-Cipso, M-P, and M-X bond lengths, relative bond strengths, and P-M-P bite angles was also discussed.

15.
J Oleo Sci ; 70(10): 1373-1380, 2021 Oct 05.
Artigo em Inglês | MEDLINE | ID: mdl-34497175

RESUMO

Fourier transform infrared (FTIR) spectroscopy combined with backpropagation artificial neural network (BP-ANN) were utilized for rapid and simultaneous assessment of the lipid oxidation indices in French fries. The conventional indexes (i.e. total polar compounds, oxidized triacylglycerol polymerized products, oxidized triacylglycerol monomers, triacylglycerol hydrolysis products, and acid value), and FTIR absorbance intensity in French fries were determined during the deep-frying process, and the results showed the French fries had better quality in palm oil, followed by sunflower oil, rapeseed oil and soybean oil. The FTIR spectra of oil extracted from French fries were correlated to the reference oxidation indexes determined by AOCS standard methods. The results of BP-ANN prediction showed that the model based on FTIR fitted well (R2 > 0.926, RMSEC < 0.481) compared with partial least-squares model (R2 > 0.876). This facile strategy with excellent performance has great potential for rapid characterization quality of French fries during frying.


Assuntos
Culinária/métodos , Análise de Alimentos/métodos , Qualidade dos Alimentos , Temperatura Alta , Redes Neurais de Computação , Óleo de Palmeira/química , Óleo de Brassica napus/química , Solanum tuberosum/química , Óleo de Soja/química , Espectroscopia de Infravermelho com Transformada de Fourier/métodos , Óleo de Girassol/química , Oxirredução
16.
PLoS One ; 16(3): e0248064, 2021.
Artigo em Inglês | MEDLINE | ID: mdl-33735244

RESUMO

Taxi order demand prediction is of tremendous importance for continuous upgrading of an intelligent transportation system to realise city-scale and personalised services. An accurate short-term taxi demand prediction model in both spatial and temporal relations can assist a city pre-allocate its resources and facilitate city-scale taxi operation management in a megacity. To address problems similar to the above, in this study, we proposed a multi-zone order demand prediction model to predict short-term taxi order demand in different zones at city-scale. A two-step methodology was developed, including order zone division and multi-zone order prediction. For the zone division step, the K-means++ spatial clustering algorithm was used, and its parameter k was estimated by the between-within proportion index. For the prediction step, six methods (backpropagation neural network, support vector regression, random forest, average fusion-based method, weighted fusion-based method, and k-nearest neighbour fusion-based method) were used for comparison. To demonstrate the performance, three multi-zone weighted accuracy indictors were proposed to evaluate the order prediction ability at city-scale. These models were implemented and validated on real-world taxi order demand data from a three-month consecutive collection in Shenzhen, China. Experiment on the city-scale taxi demand data demonstrated the superior prediction performance of the multi-zone order demand prediction model with the k-nearest neighbour fusion-based method based on the proposed accuracy indicator.


Assuntos
Automóveis , Planejamento de Cidades , Modelos Teóricos , Meios de Transporte/métodos , Viagem , China , Cidades , Análise Espacial
17.
Dalton Trans ; 48(36): 13760-13768, 2019 Sep 17.
Artigo em Inglês | MEDLINE | ID: mdl-31475715

RESUMO

Organometallic chemists usually like to use the word robust to describe pincer ligand frameworks in metal pincer complexes. Although most transition metal pincer complexes are thermally stable, the pincer backbone frameworks can still decompose under certain circumstances. In order to explore the stability of the bis(phosphinite) (POCOP) pincer backbone in transition metal pincer complexes, group 10 metal POCOP pincer complexes were exposed to different nucleophilic and electrophilic conditions, respectively. It was found that the POCOP pincer backbone is stable under intermolecular nucleophilic conditions but cannot survive intramolecular nucleophilic attack; the POCOP pincer backbone is also stable under weak electrophilic conditions but the backbone can be completely destroyed by strong Lewis acids such as AlCl3. Possible decomposition/reconstruction pathways of the POCOP pincer ligand framework were proposed.

18.
Soft Matter ; 15(21): 4363-4370, 2019 May 29.
Artigo em Inglês | MEDLINE | ID: mdl-31086876

RESUMO

With the combination of a low-temperature extension rheometer and in situ synchrotron radiation wide-angle X-ray diffraction (SR-WAXD), the strain-induced crystallization (SIC) of poly(isobutylene-isoprene) rubber (IIR) was studied in the low-temperature region (-60 °C → 25 °C). The detailed structural evolution of IIR during the SIC is summarized in the strain-temperature space, where three distinct temperature zones are defined. The absence of the SIC in zone I (T > 0 °C) results in the poorest drawability of IIR among all measured temperatures. And with respect to the lowest temperature zone III (-60 °C < T < -50 °C), the SIC still occurs with low ultimate crystallinity (ca. 0.9%). More complicated structural evolution induced by the strain occurs in the intermediate-temperature zone II (-50 °C ≤ T ≤ 0 °C). The orientation ratio of the amorphous part Oa increases monotonically with the increment of the strain, but reaches a platform with Hencky strain ε > ca. 1.8. Meanwhile, the strain-induced crystal growth of IIR is evidenced by the dramatic increment of the lateral crystallite size of (110) and (113) planes. Moreover, the retraction experiment further reveals the network evolutions of IIR: suffering from low ultimate crystallinity (

19.
Soft Matter ; 15(4): 734-743, 2019 Jan 28.
Artigo em Inglês | MEDLINE | ID: mdl-30633295

RESUMO

Strain-induced crystallization (SIC) of natural rubber (NR) at descending temperatures as low as -60 °C is systematically investigated by in situ synchrotron radiation wide-angle X-ray diffraction (SR-WAXD) measurement. The detailed structural evolution of NR during SIC is studied in the strain-temperature space, where up to four regions are defined depending on the SR-WAXD results. In region I, the molecular chains begin to be oriented under tensile loading. The onset of crystallization happens in the very beginning of region II, and the NR crystal acts as a new physical cross-linking point to form a crystal network, namely the series model. The further increment of crystallinity (> ca. 8%) leads to the transition of the crystal network from the series model to the parallel model in region III. The crystal network is finally accomplished in region IV, where the crystallinity remains almost constant. Interestingly, regions III and IV exist only in the intermediate-temperature zone II (-40 °C to -10 °C), which are missing in zones I (-10 °C to 25 °C) and III (-60 °C to -40 °C). This suggests that sufficient crystallinity (χII-III > ca. 8%) is required to form the parallel model. The new crystal network provides a deep understanding of SIC of NR considering the microscopic features, i.e. oriented amorphous component, the onset of crystallization and crystallinity evolution and its correlation with the macroscopic stress-strain curve.

20.
Chem Asian J ; 13(21): 3231-3238, 2018 Nov 02.
Artigo em Inglês | MEDLINE | ID: mdl-30129168

RESUMO

Several pincer ligated nickel mercapto complexes, [2,6-(R2 PCH2 )2 C6 H3 ]NiSH (R=tBu, 1 a; iPr, 1 b), [2,6-(R2 PO)2 C6 H3 ]NiSH (R=tBu, 2 a; iPr, 2 b) and [4-MeOCO-2,6-(tBu2 PO)2 C6 H2 ]NiSH (3 a), were synthesized and fully characterized. The reactivity of the mercapto groups against boron hydrides and organic bases was investigated. It was found that the mercapto groups are difficult to be deprotonated by boron hydrides or organic bases. The treatment of complex 2 a or 2 b with an excess amount of catecholborane (HBcat) afforded the corresponding pincer ligated nickel borohydride complexes and the HBcat degradation product. The treatment of complex 1 a, 2 a or 2 b with an excess amount of BH3 ⋅THF produced the corresponding nickel borohydride species and the S-bridged triborane species THF⋅BH2 -µ2 -S(B2 H5 ) (5). No reactions between these complexes and organic bases were observed. DFT calculations were carried out to understand this reactivity and get mechanistic insights into the reactions.

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