Flavor Quality Analysis of Ten Actinidia arguta Fruits Based on High-Performance Liquid Chromatography and Headspace Gas Chromatography-Ion Mobility Spectrometry.

Actinidia arguta is a fruit crop with high nutritional and economic value. However, its flavor quality depends on various factors, such as variety, environment, and post-harvest handling. We analyzed the composition of total soluble sugars, titratable acids, organic acids, and flavor substances in the fruits of ten A. arguta varieties. The total soluble sugar content ranged from 4.22 g/L to 12.99 g/L, the titratable acid content ranged from 52.55 g/L to 89.9 g/L, and the sugar-acid ratio ranged from 5.39 to 14.17 at the soft ripe stage. High-performance liquid chromatography (HPLC) showed that citric, quinic, and malic acids were the main organic acids in the A. arguta fruits. Headspace gas chromatography-ion mobility spectrometry (HS-GC-IMS) detected 81 volatile compounds in 10 A. arguta varieties, including 24 esters, 17 alcohols, 23 aldehydes, 7 ketones, 5 terpenes, 2 acids, 1 Pyrazine, 1 furan, and 1 benzene. Esters and aldehydes had the highest relative content of total volatile compounds. An orthogonal partial least squares discriminant analysis (OPLS-DA) based on the odor activity value (OAV) revealed that myrcene, benzaldehyde, methyl isobutyrate, α-phellandrene, 3-methyl butanal, valeraldehyde, ethyl butyrate, acetoin, (E)-2-octenal, hexyl propanoate, terpinolene, 1-penten-3-one, and methyl butyrate were the main contributors to the differences in the aroma profiles of the fruits of different A. arguta varieties. Ten A. arguta varieties have different flavors. This study can clarify the differences between varieties and provide a reference for the evaluation of A. arguta fruit flavor, variety improvement and new variety selection.

Ardipusilloside-I Metabolites from Human Intestinal Bacteria and Their Antitumor Activity.

Ardipusilloside-I (ADS-I) is a triterpenoid saponin extracted from Ardisia pusilla DC, and has been demonstrated to have potent antitumor activity. However, ADS-I metabolism in humans has not been investigated. In this study, we studied the biotransformation of ADS-I in human intestinal bacteria, and examined the in vitro antitumor activity of the major metabolites. Ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) was used to detect ADS-I biotransformation products, and their chemical structures were identified by high performance liquid chromatography-nuclear magnetic resonance (HPLC-NMR). The antitumor activity of the major metabolites was determined by the MTT assay. Here, we show that main reaction seen in the metabolism of ADS-I in human intestinal bacteria was deglycosylation, which produced a total of four metabolites. The structures of the two major metabolites M1 and M2 were confirmed by using NMR. MTT assay showed that ADS-I metabolites M1 and M2 have the same levels of inhibitory activities as ADS-I in cultured SMMC-7721 cells and MCF-7 cells. In conclusion, this study demonstrates deglycosylation as a primary pathway of ADS-I metabolism in human intestinal bacteria, and suggests that the pharmacological activity of ADS-I may be mediated, at least in part, by its metabolites.

Study on the Effect of Different Concentrations of SO2 on the Volatile Aroma Components of 'Beibinghong' Ice Wine.

SO2 plays an important role in wine fermentation, and its effects on wine aroma are complex and diverse. In order to investigate the effects of different SO2 additions on the fermentation process, quality, and flavor of 'Beibinghong' ice wine, we fermented 'Beibinghong' picked in 2019. We examined the fermentation rate, basic physicochemical properties, and volatile aroma compound concentrations of 'Beibinghong' ice wine under different SO2 additions and constructed a fingerprint of volatile compounds in ice wine. The results showed that 44 typical volatile compounds in 'Beibinghong' ice wine were identified and quantified. The OAV and VIP values were calculated using the threshold values of each volatile compound, and t the effect of SO2 on the volatile compounds of 'Beibinghong' ice wine might be related to five aroma compounds: ethyl butyrate, ethyl propionate, ethyl 3-methyl butyrate-M, ethyl 3-methyl butyrate-D, and 3-methyl butyraldehyde. Tasting of 'Beibinghong' ice wine at different SO2 additions revealed that the overall flavor of 'Beibinghong' ice wine was the highest at an SO2 addition level of 30 mg/L. An SO2 addition level of 30 mg/L was the optimal addition level. The results of this study are of great significance for understanding the effect of SO2 on the fermentation of 'Beibinghong' ice wine.

Widely Targeted Metabolomics Was Used to Reveal the Differences between Non-Volatile Compounds in Different Wines and Their Associations with Sensory Properties.

In this study, metabolites from six varieties of wines, including 'Haasan' (A1), 'Zuoshaner' (A2), 'Beibinghong' (A3), 'Shuanghong' (A4), 'Zijingganlu' (A5), and 'Cabernet Sauvignon' (A6), were identified and quantified using widely targeted metabolomics analysis techniques. Based on the test results, 1172 metabolites were detected and classified into 18 categories. These include 62 amino acids, 178 alkaloids, 189 flavonoids, 106 phenols, 148 terpenoids, etc. Comparing the differential metabolites between the comparison groups of each variety, differences between varieties based on P-values and VIP values were shown. Among these differential metabolites, Trimethoprim and Crotonoside were screened out as core differential metabolites. Multiple comparisons also screened the biomarkers for each species. We used widely targeted metabolomics to reveal the differences between non-volatile compounds in different wines and their associations with sensory properties. We also used the simultaneous weighted gene co-expression network analysis (WGCNA) to correlate metabolites with sensory traits, including color difference values and taste characteristics. Two of the six key modules were screened by WGCNA for relevance to sensory traits (brown module and turquoise module). This study provides a high-throughput method for linking compounds to various sensory characteristics of food, opening up new avenues for explaining differences in different varieties of wine.

Thermally Activated Delayed Fluorescence Emitters Based on a Special Tetrahedral Silane Core.

Based on the tetraphenylsilane skeleton, a new class of thermally activated delayed fluorescence (TADF) molecules have been designed and synthesized. Benefiting from the unique tetrahedron architecture of tetraphenylsilane, the intermolecular distance between TADF units can be enlarged and thus weakened the aggregation-induced quenching of triplet excitons. By adjusting the numbers of TADF subunits, the spin-orbit coupling processes can be controlled, leading to efficient up-conversion processes. The related OLEDs are fabricated through the solution processing technology, and pure-blue and green electroluminescence were observed with maximum external quantum efficiencies (EQEmax) of 6.6 and 13.8% as well as Commission Internationale de l'Eclairage coordinates of (0.14, 0.15) and (0.25, 0.45), respectively. This study provides a new idea for designing color-tunable TADF emitters through spatial structure regulation.

Characterization of Key Compounds of Organic Acids and Aroma Volatiles in Fruits of Different Actinidia argute Resources Based on High-Performance Liquid Chromatography (HPLC) and Headspace Gas Chromatography-Ion Mobility Spectrometry (HS-GC-IMS).

Actinidia arguta, known for its distinctive flavor and high nutritional value, has seen an increase in cultivation and variety identification. However, the characterization of its volatile aroma compounds remains limited. This study aimed to understand the flavor quality and key volatile aroma compounds of different A. arguta fruits. We examined 35 A. arguta resource fruits for soluble sugars, titratable acids, and sugar-acid ratios. Their organic acids and volatile aroma compounds were analyzed using high-performance liquid chromatography (HPLC) and headspace gas chromatography-ion mobility spectrometry (HS-GC-IMS). The study found that among the 35 samples tested, S12 had a higher sugar-acid ratio due to its higher sugar content despite having a high titratable acid content, making its fruit flavor superior to other sources. The A. arguta resource fruits can be classified into two types: those dominated by citric acid and those dominated by quinic acid. The analysis identified a total of 76 volatile aroma substances in 35 A. arguta resource fruits. These included 18 esters, 14 alcohols, 16 ketones, 12 aldehydes, seven terpenes, three pyrazines, two furans, two acids, and two other compounds. Aldehydes had the highest relative content of total volatile compounds. Using the orthogonal partial least squares discriminant method (OPLS-DA) analysis, with the 76 volatile aroma substances as dependent variables and different soft date kiwifruit resources as independent variables, 33 volatile aroma substances with variable importance in projection (VIP) greater than 1 were identified as the main aroma substances of A. arguta resource fruits. The volatile aroma compounds with VIP values greater than 1 were analyzed for odor activity value (OAV). The OAV values of isoamyl acetate, 3-methyl-1-butanol, 1-hexanol, and butanal were significantly higher than those of the other compounds. This suggests that these four volatile compounds contribute more to the overall aroma of A. arguta. This study is significant for understanding the differences between the fruit aromas of different A. arguta resources and for scientifically recognizing the characteristic compounds of the fruit aromas of different A. arguta resources.

Comprehensive Evaluation of Ten Actinidia arguta Wines Based on Color, Organic Acids, Volatile Compounds, and Quantitative Descriptive Analysis.

Actinidia arguta wine is a low-alcoholic beverage brewed from A. arguta with a unique flavor and sweet taste. In this study, the basic physicochemical indicators, color, organic acid, and volatile aroma components of wines made from the A. arguta varieties 'Kuilv', 'Fenglv', 'Jialv', 'Wanlv', 'Xinlv', 'Pinglv', 'Lvbao', 'Cuiyu', 'Tianxinbao', and 'Longcheng No.2' were determined, and a sensory evaluation was performed. The findings show that 'Tianxinbao' produced the driest extract (49.59 g/L), 'Kuilv' produced the most Vitamin C (913.46 mg/L) and total phenols (816.10 mg/L), 'Jialv' produced the most total flavonoids (477.12 mg/L), and 'Cuiyu' produced the most tannins (4.63 g/L). We analyzed the color of the A. arguta wines based on CIEL*a*b* parameters and found that the 'Kuilv' and 'Longcheng No.2' wines had the largest L* value (31.65), the 'Pinglv' wines had the greatest a* value (2.88), and the 'Kuilv' wines had the largest b* value (5.08) and C*ab value (5.66) of the ten samples. A total of eight organic acids were tested in ten samples via high-performance liquid chromatography (HPLC), and we found that there were marked differences in the organic acid contents in different samples (p < 0.05). The main organic acids were citric acid, quinic acid, and malic acid. The aroma description of a wine is one of the keys to its quality. A total of 51 volatile compounds were identified and characterized in ten samples with headspace gas chromatography-ion mobility spectrometry, including 24 esters, 12 alcohols, 9 aldehydes, 3 aldehydes, 2 terpenes, and 1 acid, with the highest total volatile compound content in 'Fenglv'. There were no significant differences in the types of volatile compounds, but there were significant differences in the contents (p < 0.05). An orthogonal partial least squares discriminant analysis (OPLS-DA) based on the odor activity value (OAV) showed that ethyl butanoate, ethyl pentanoate, ethyl crotonate, ethyl isobutyrate, butyl butanoate, 2-methylbutanal, ethyl isovalerate, and ethyl hexanoate were the main odorant markers responsible for flavor differences between all the A. arguta wines. Sensory evaluation is the most subjective and effective way for consumers to judge A. arguta wine quality. A quantitative descriptive analysis (QDA) of the aroma profiles of ten grapes revealed that the 'fruity' and 'floral' descriptors are the main and most essential parts of the overall flavor of A. arguta wines. 'Tianxinbao' had the highest total aroma score. The flavor and quality of A. arguta wines greatly depend on the type and quality of the A. arguta raw material. Therefore, high-quality raw materials can improve the quality of A. arguta wines. The results of the study provide a theoretical basis for improving the quality of A. arguta wines and demonstrate the application prospects of HS-GC-IMS in detecting A. arguta wine flavors.

The Role of Housing Tenure Opportunities in the Social Integration of the Aging Pre-1970 Migrants in Beijing.

This study focuses on the social integration of the pre-1970 first-generation migrants in reformist China, who were born before the year 1970 while getting old in the destination cities. The pre-1970 first-generation migrants are not a homogeneous group but are composed of: (a) those over 45 years old and still working but facing age discrimination; and (b) the elderly granny as nanny assuming the domestic and child-care work for their sons or daughters in the destination cities. We conceptualized and re-defined the aging migrants' social integration into three dimensions (i.e., participation practices, communication contacts, and subjective perceptions), and used the 2017 Migrant Dynamics Monitoring Survey (MDMS) data from Beijing to measure and explain the varied integration levels among a total of 1267 aging migrant samples in the Beijing metropolis. It is proven that housing tenure matters and housing tenure entitlement would be conductive to beefing up aging migrants' integration. However, informal housing should not be "stigmatized" as a segregated world, since those dwelling in the informal housing have reported a higher probability of perceiving a fully integrated status (namely subjective well-being, SWB) than those living in the dormitory-like housing. Additionally, an employment-income paradox is found, which shows that higher economic achievement is NOT equivalent to a higher social integration status for the aging migrants.

[Effects of two implant systems on peri-implant soft tissue].

PURPOSE: To investigate the effect of different implant systems on peri-implant soft tissue. METHODS: Forty patients requiring single implant therapy in posterior teeth at Dental and Ophthalmic Clinic of Putuo District from December 2020 to February 2021 were selected. Ten patients were implanted with bone level implants and 30 patients with soft tissue level implants. Periodontal exploration was performed at the buccal side, lingual side, mesial and distal axial angle of the implants, and the gingival crevicular fluid of these locations were taken to detect the enzyme level. The probing depth, aspartate aminotransferase (AST) and alkaline phosphatase (ALP) level of the two groups were compared at the day, 3 months, 6 months and 12 months after crown restoration. Statistical analysis was completed by SPSS 17.0 software package. RESULTS: The probing depth and ALP level of soft tissue level implants were significantly lower than those of bone level implants at the day, 3 months, 6 months and 12 months after crown restoration(P＜0.05). At the day when crown restoration was accomplished, AST of soft tissue implant was significantly lower than that of bone level implant(P＜0.05). AST in gingival crevicular fluid of bone level implants decreased rapidly in the following three time periods, and close to that of the soft tissue level implants(P＞0.05) at last. CONCLUSIONS: Both bone level implants and soft tissue level implants have good clinical effects, but peri-implant soft tissues of the soft tissue level implants show better stability.

Using Green, Economical, Efficient Two-Dimensional (2D) Talc Nanosheets as Lubricant Additives under Harsh Conditions.

Two-dimensional (2D) nanomaterials have attracted much attention for lubrication enhancement of grease. It is difficult to disperse nanosheets in viscous grease and the lubrication performances of grease under harsh conditions urgently need to be improved. In this study, the 2D talc nanosheets are modified by a silane coupling agent with the assistance of high-energy ball milling, which can stably disperse in grease. The thickness and size of the talc nanosheet are about 20 nm and 2 µm. The silane coupling agent is successfully grafted on the surface of talc. Using the modified-talc nanosheet, the coefficient of friction and wear depth can be reduced by 40% and 66% under high temperature (150 °C) and high load (3.5 GPa), respectively. The enhancement of the lubrication and anti-wear performance is attributed to the boundary adsorbed tribofilm of talc achieving a repairing effect of the friction interfaces, the repairing effect of talc on the friction interfaces. This work provides green, economical guidance for developing natural lubricant additives and has great potential in sustainable lubrication.

[Comparative study on the accuracy of implant-borne single restoration by two production processes with Ti-base].

PURPOSE: To study on the accuracy of implant-borne single restoration by two production processes with Ti-base to provide experimental data for proper processes of single implant-borne restoration. METHODS: Thirty patients were selected with single posterior teeth missing from the Department of Oral Implantology of Shanghai Putuo District Eye Disease and Dental Disease Prevention and Treatment Institute. The patients were taken 2 traditional impressions clinically for two plaster model equipped with implant analogue. These models were then divided into 2 groups according to different production processes. The experimental group was scanned with the scan body installed in the model implant analogue, while the control group was scanned directly on the Ti-base abutment installed in the model implant analogue. The implant-borne single restorations of the two groups were cut along the buccal-lingual side and the distance between the measuring point to the Ti-Base abutment was observed by electron microscopy. In addition, the breaking limit of zirconia crown was observed, universal test machine was used to load direct force to the crown. SPSS 22.0 software package was used for data analysis. RESULTS: The gap between the implant-borne single restoration to the Ti-base abutment of the experimental group was significantly smaller than that of the control group. The difference between the two groups was statistically significant (P<0.05). However, by testing the breaking limit of zirconia crown, there was no significant difference(P>0.05). CONCLUSIONS: Using scan body to transfer the implant position and Ti-base abutment data information to the digital dental design software is more accurate and reliable than directly scanning the Ti-base on the model analogue. Using scan body is recommended for processing and manufacture of implant-borne singe restoration.

Characterization of the Key Aroma Volatile Compounds in Nine Different Grape Varieties Wine by Headspace Gas Chromatography-Ion Mobility Spectrometry (HS-GC-IMS), Odor Activity Values (OAV) and Sensory Analysis.

During this study, the physicochemical properties, color, and volatile aroma compounds of the original wines produced from the grape varieties 'Hassan', 'Zuoshaner', 'Beibinghong', 'Zuoyouhong', 'Beta', 'Shuanghong', 'Zijingganlu', 'Cabernet Sauvignon', and 'Syrah' were determined and sensory evaluation was performed. Results indicated that 'Hassan' contained the most solids, 'Zuoshaner' produced the most total acid, residual sugar, total anthocyanin, and total phenol, and 'Shuanghong' produced the most tannin. Calculation of the chroma and hue of the wines according to the CIEL*a*b* parameters revealed that the 'Cabernet Sauvignon' wines were the brightest of the nine varieties and that the 'Zuoshaner' wines had the greatest red hue and yellow hue and the greatest saturation'. A total of 52 volatile compounds were identified and quantified in nine wine samples by HS-GC-IMS analysis, with the most significant number of species detected being 20 esters, followed by 16 alcohols, 8 aldehydes, four ketones, one terpene, and one furan, with the highest total volatile compound content being 'Beta'. A total of 14 volatile components with OAV (odor activity value) >1 were calculated using the odor activity value (OAV) of the threshold of the aromatic compound, and the OPLS-DA analysis was performed by orthogonal partial least squares discriminant analysis (OPLS-DA) using the OAV values of the compounds with OAV values >1 as the Y variable. The VIP (Variable Importance in Projection) values of six compounds, ethyl isobutyrate, ethyl hexanoate-D, 2-methylpropanal, ethyl octanoate, ethyl butanoate-D, and Isoamyl acetate-D, were calculated to be higher than one between groups, indicating that these six compounds may influence aroma differences. It is essential to recognize that the results of this study have implications for understanding the quality differences between different varieties of wines and for developing wines that have the characteristics of those varieties.

[Clinical effectiveness evaluation of gingival recession by using perioscope as an adjunct to non-surgical periodontal therapy].

PURPOSE: To investigate the effects of ultrasonic scaling and root planning(SRP) assisted by perioscope on gingival recession of maxillary lateral incisor. METHODS: Thirty-six outpatients with moderate to advanced chronic periodontitis from the Department of Periodontology at Dental and Ophthalmic Clinic of Putuo District from June 2020 to December 2020 were collected as research objects. Periodontal treatment was carried out according to a single-blind split-mouth self-control design randomly with(experimental group, namely perioscope group) or without(control group, namely SRP group) periodontal endoscope．The labial periodontal probing depth (PD), labial attachment loss (AL) and gingival recession(GR) in the maxillary lateral incisors were recorded at baseline, 3 and 6 months, and compared among groups by SPSS 22.0 software package. RESULTS: There was no significant difference between perioscope group and SRP group at baseline. ΔGR (the recession extent of gum within two observation time) in perioscope group was significantly smaller than that in SRP group at 3 months（P<0.05）. There was no significant difference in other periodontal indicators at 3 and 6 months between the 2 groups after treatment, but it can be found that the degree of PD reduction and AL improvement in perioscope group was more than those in SRP group, this trend was most obvious at 3 months. PD and AL were significantly different between baseline and 3 months or 6 months in the two groups. There were significant differences in ΔGR at 3 months and 6 months between the two groups. CONCLUSIONS: Compared with routine SRP, the extent of root surface debridement with perioscope-assisted SRP is thorough and less invasive, and the reduction of gingival recession of labial surface of maxillary lateral incisor at 3 months is significantly less; thus, the aesthetic effect is prominent.

Effect of Polyacrylonitrile Precursor Orientation on the Structures and Properties of Thermally Stabilized Carbon Fiber.

The thermal stabilization process of polyacrylonitrile (PAN) precursor fiber was the key step to prepare high-performance carbon fiber. During the thermal stabilization process, the aggregation structure and the reactivity of molecular chains have significant effects on the microstructures and mechanical properties of carbon fiber. In the present paper, the effects of the orientation structure of PAN precursor fiber on the thermal stabilization reaction and the mechanical properties of carbon fiber were experimentally studied. Using multi-dimensional structural and mechanical properties tests, such as XRD, DSC, 13C NMR and Instron machine testing, the crystalline and skeleton structure, exothermic behavior, and tensile properties of PAN precursor fiber with different orientations in the process of thermal stabilization were characterized to reveal the relationship between microstructure evolution and tensile properties. The results showed that the orientation structure of PAN precursor fiber had an obvious effect on the thermal stabilization process and the tensile stress-strain characteristic. When the heat treatment temperature was lower than 200 °C, the crystallinity and crystallite size of PAN fibers with higher orientation degrees increased significantly. After sufficient thermal stabilization, the original PAN precursor fiber with a higher orientation degree could form more aromatic lamellar structures and showed better regularity. Furthermore, the yield strength and initial modulus of the fibers with a higher orientation degree increased due to the formation of more aromatic rings. The maximum increase in the percentages of yield strength and tensile modulus of the PAN fibers were achieved when the heat-treated temperature was 200 °C, and the percentage values were 138.4% and 158.7% compared to the precursor without heat-treatment. In addition, the elongation at break of the fibers with a higher orientation degree was also relatively larger.

Formation and Evolution of sp2 Hybrid Conjugate Structure of Polyacrylonitrile Precursor during Stabilization.

The generated sp2 hybrid conjugate structure of a C atom, which resulted from the chemical reaction affected by temperature and time, is an effective six-membered ring planar structure of the final carbon fiber. This kind of hybrid conjugate structure determined the formation of the final structure and mechanical properties of carbon fiber. In this paper, the formation and evolution of sp2 hybrid conjugated structures of PAN precursor during thermal stabilization were investigated by Raman, UV-vis and 13C-NMR methods. The results indicated that with the increase of stabilization temperature, the degree of the sp2 hybrid conjugated structure of stabilized PAN fiber increases "linearly", while the content of the sp2 hybrid carbon atoms increases with "S-type". The final sp2 hybrid conjugated ring structure is mainly composed of single-ring, double-ring, triple-ring, and double-bond structures. Compared with the time factor, the temperature effect plays a decisive role in the formation of the sp2 hybrid conjugate structure.

Phase Transition and Melt-Recrystallization Behavior of Poly(Butylene Adipate) Investigated by Simultaneous Measurements of Wide-Angle X-Ray Diffraction (WAXD) and Differential Scanning Calorimetry (DSC).

Simultaneous measurements of wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC) were carried out to investigate the phase transition and melting behaviors of poly(butylene adipate) (PBA). Thermal expansion changes along the a and b axes of the ß form unit cell are different from each other during the heating process. At the beginning of the ß to αH (high-temperature α phase) phase transition, the ß phase melts very fast, while the recrystallization of the αH phase is delayed and slowed. With the further increment of the temperature, the melting rate of the ß phase slows down, while the recrystallization of the αH phase accelerates. The diffraction peak intensity ratios of the ß(020):ß(110) and αH(020):αH(110) diffraction peaks during the first heating process have similar value. However, the above value is different from the value of α(020):α(110) during the following melt-crystallization process. This difference comes from the different orientations of the crystal lattices of the α and αH(ß) crystals to the substrate plane, which indicates that the αH phase inherits the orientation of the ß phase during phase transition and the orientation of αH form crystals is different from the α form crystals that crystallized from the melt.

Synchrotron study on the evolution of the radial structural distribution of carbon fiber monofilaments during heat treatment process.

Evolution of the radial distribution of a micro-crystalline structure within polyacrylonitrile monofilaments at various temperatures during carbonization was investigated via the method of synchrotron wide-angle X-ray diffraction (S-WAXD) and micro-scanning Raman spectroscopy. The result indicated that in the core region of the carbon fiber monofilaments, the L c is lower while the interplanar spacing (d 002) is higher compared with those in the skin region at 1300 °C. The difference between the skin and core regions in L c and d 002 constantly decreases as the heat treatment temperature increases. The results of micro-scanning Raman indicated that the micro-crystallites grow faster along the L a direction, and the graphite degree is higher in the skin region than that in the core region. This is attributed to the fact that the removal of nitrogen element is the domain factor on the growth of a pseudo-graphite crystallite at relatively lower heat treatment temperatures. As the temperature rises, L c is developed mainly in the core region with the closed packing of a graphite layer, while the crystallites in the skin region grow in both L a and L c directions, which are mainly affected by the disordered and boundary graphite structure.

Relationship between morphological change and crystalline phase transitions of polyethylene-poly(ethylene oxide) diblock copolymers. 3. Dependence of morphological transition phenomena on the PE/PEO segmental lengths and its possible origins.

By measurement of the small-angle and wide-angle X-ray scatterings and infrared and Raman spectra and thermal data, microphase separation phenomena have been investigated for a series of polyethylene-poly(ethylene oxide) diblock copolymer (PE-b-PEO) in both the heating and cooling processes and compared with the structural changes occurring inside the PE and PEO domains. The complicated morphological changes between lamella, perforated lamella, gyroid, cylinder, and sphere phases were detected for the copolymer with relatively short PE segments. The orthorhombic crystalline structure of PE was kept unchanged in the lamella-to-gyroid transition. When the PE orthorhombic phase transformed to the pseudohexagonal or rotator phase, the gyroid morphology changed to the cylinder. On the other hand, the diblock copolymer with relatively long PE segment was found to show only the lamellar morphology, in which the order-disorder structural transition between the orthorhombic and pseudohexagonal phases occurred in the PE crystal region. As a possibility, the large difference in morphological change between the copolymers with short and long PE segments has been ascribed to the difference in thermal mobility of PE segments, which is controlled by the conformation of chains and their packing mode, i.e., an extended chain or a folded chain. The extended chains may move thermally and actively along the interfacial boundary in addition to the librational motion around the chain axis, resulting in a variety of morphological changes, whereas the thermal motion of the folded chains may be suppressed because of the geometrical constraint and does not cause such a large-scale morphological change from the lamellar structure. This concept, a thermal activity and geometrical constraint, is considered to be quite important in the interpretation of complicated morphological changes observed for many crystalline-amorphous and crystalline-crystalline diblock copolymers when viewed from the molecular level.

Formation Mechanism of Skin-Core Chemical Structure within Stabilized Polyacrylonitrile Monofilaments.

Although it has been half a century since polyacrylonitrile (PAN)-based carbon fibers were first developed, the exact formation mechanism of skin-core structure of PAN-based carbon fibers, especially the stabilized PAN fibers, was still not well clarified from the viewpoint of the chemical structure. In order to address this aforementioned challenge, a powerful tool with nanoscale resolution named photo-induced force microscopy was applied to map the chemical group distribution in the cross section of stabilized PAN fibers and reveal the evolution mechanism of skin-core structure throughout the whole stabilization process. The results indicated that the formation of skin-core structure of stabilized PAN fiber was attributed to the complex and overlapped chemical reactions caused by gradient of oxygen along radial direction and the formation of dense crystal layer at the interface between the skin and core part. Finally, the crystal layer was destroyed and the monofilaments tended to be homogeneous with further oxidation.

Hierarchical radial structure of polyacrylonitrile precursor formed during the wet-spinning process.

Electron probe micro-analysis (EPMA), micro-beam wide angle X-ray diffraction (Micro-beam WAXD), micro-Raman and nano-infrared (nano-IR) spectroscopy were performed to characterize the hierarchical radial structure within polyacrylonitrile (PAN) fibre which was obtained by the wet-spinning method, including morphology, aggregation structure and molecular chain conformation. The results indicated that along the radial direction of the PAN fibre, the skin layer reflects denser morphology compared to the core region. The crystallinity, d-spacing of the (100) Miller plane and crystalline orientation in PAN fibres were gradually decreased from the skin layer to the central part, while the crystalline size shows opposite distribution tendency which was affected by the diffusion depending on the coagulation environment. As to the molecular chain structure, PAN chains tend to keep the helical conformation rather than planar zigzag conformation and packed more orderly in the skin layer of fibres.