The Attenuated Secretion of Hyaluronan by UVA-Exposed Human Fibroblasts Is Associated with Up- and Downregulation of HYBID and HAS2 Expression via Activated and Inactivated Signaling of the p38/ATF2 and JAK2/STAT3 Cascades

Little is known about the effects on hyaluronan (HA) metabolism of UVA radiation. This study demonstrates that the secretion of HA by human dermal fibroblasts (HDFs) is downregulated by UVA, accompanied by the down- and upregulation of mRNA and protein levels of the HA-synthesizing enzyme (HAS2) and the HA-degrading protein, HYaluronan Binding protein Involved in HA Depolymerization(HYBID), respectively. Signaling analysis revealed that the exposure distinctly elicits activation of the p38/MSK1/CREB/c-Fos/AP-1 axis, the JNK/c-Jun axis, and the p38/ATF-2 axis, but downregulates the phosphorylation of NF-kB and JAK/STAT3. A signal inhibition study demonstrated that the inhibition of p38 significantly abrogates the UVA-accentuated mRNA level of HYBID. Furthermore, the inhibition of STAT3 significantly downregulates the level of HAS2 mRNA in non-UVA exposed HDFs. Analysis using siRNAs demonstrated that transfection of ATF-2 siRNA but not c-Fos siRNA abrogates the increased protein level of HYBID in UVA-exposed HDFs. An inhibitor of protein tyrosine phosphatase but not of protein serine/threonine phosphatase restored the diminished phosphorylation level of STAT3 at Tyr 705, accompanied by a significant abolishing effect on the decreased mRNA expression level of HAS2. Silencing with a protein tyrosine phosphatase PTP-Meg2 siRNA revealed that it abrogates the decreased phosphorylation of STAT3 at Tyr 705 in UVA-exposed HDFs. These findings suggest that the UVA-induced decrease in HA secretion by HDFs is attributable to the down- and upregulation of HAS2 and HYBID expression, respectively, changes that are mainly ascribed to the inactivated signaling of the STAT3 axis due to the activated tyrosine protein phosphatase PTP-Meg2 and the activated signaling of the p38/ATF2 axis, respectively.     

由双环戊二烯制备环戊烷

对以双环戊二烯为原料,经解聚、加氢制备环戊烷的工艺进行了研究,重点考察了环戊二烯加氢条件。结果表明:在Raney镍催化剂加入量为0.5％～2％,加氢压力为0.5～3.0MPa,加氢温度为30～50℃时,环戊二烯的加氢转化率约为100％,加氢选择性也在99％以上,由双环戊二烯制备环戊烷的总收率>60％,产品的纯度在99％以上。     

Influence of pectin properties and processing conditions on thermal pectin degradation

Texture degradation of fruits and vegetables during thermal processing is partly due to pectin depolymerization. In this contribution we investigate the influence of pectin properties (degree and pattern of methoxylation) and processing conditions (pH 2.0, 3.0, 5.0 and 7.0; temperatures of 80 up to 110 °C) on pectin degradation rate constants. Pectins with different degrees and patterns of methoxylation were prepared and heated, the extent of acid hydrolysis, β-elimination and demethoxylation was assayed as a function of treatment time. As the degree of methoxylation and pH decreased, β-elimination rate constants decreased while acid hydrolysis rate constants increased. Demethoxylation rate constants were minimal at pH 3.0 and increased both at lower and higher pH. Reaction rate constants were not considerably influenced by the pattern of methoxylation. All reaction rate constants increased with increasing temperature. As β-elimination rates are reduced by competing demethoxylation, both rate constants were compared. The ratio of these reaction rate constants showed no trend with pH. However, an increase in degree of methoxylation or temperature resulted in a more pronounced increase in β-elimination rate constants than in demethoxylation rate constants.     

Heat Transfer Studies in an Agitated Vessel During Aqueous Alkaline Depolymerization of Poly(Ethylene Terephthalate) (PET) Waste

Depolymerization reactions of poly(ethylene terephthalate) (PET) waste in aqueous sodium hydroxide solution were carried out in a batch reactor at 150°C at atmospheric pressure. Disodium terephthalate (terephthalic acid salt) and ethylene glycol (EG) remain in the liquid phase. Terephthalic acid (TPA) salt was converted into TPA. The produced monomeric products (TPA and EG) were recovered. Various design parameters were estimated. Design of a batch reactor was undertaken for depolymerization of PET waste in aqueous sodium hydroxide solution. As expected, the Reynolds numbers, Prandtl numbers, Nusselt numbers, coil-side heat transfer coefficients, and overall heat transfer coefficients were consistent with the fluid velocities. It shows excellent potential for commercialization of the depolymerization of PET waste.     

Effect of reaction pH on the photodegradation of model melanoidins

The effect was studied of the pH of the amino-carbonyl reaction on the photodegradation of model melanoidins. Nondialyzable model melanoidins were prepared from glucose and lysine with or without initial pH control to 7.0.: 2 mol/l phosphate buffer (buffer-melanoidin) and pH adjustment at the reaction start with NaHCO₃ (NaHCO₃-melanoidin). Melanoidin was also prepared from glucose and the lysine-Cu²⁺complex to investigate the difference of complexes between melanoidin and Cu²⁺ (Cu²⁺-melanoidin). Each melanoidin solution was irradiated with a Xe or tungsten-halogen lamp under dissolved oxygen or by the continuous supply of oxygen in a Cu²⁺/O₂ or ascorbic acid/Cu²⁺/O₂ system. The effects of the concentrations of Cu²⁺ and melanoidin, reaction pH value, and metal ion species on the decolorization rate in the Cu²⁺/O₂ system were investigated. The most effective factor for decolorization was found to be the melanoidin concentration. The decolorization rate was negligible when 14 g/l of Cu²⁺-melanoidin was photodegraded in the ascorbic acid/Cu²⁺/O₂ system under dissolved oxygen, although depolymerization was observed. Photodegradation of NaHCO₃-melanoidins in the Cu²⁺/O₂ system by the continuous supply of oxygen resulted in an increased decolorization rate, decreased molecular mass, production of low-molecular-weight compounds, release of free lysine, and pI change. The buffer- and Cu²⁺-melanoidins did not show changes in chemical characteristics similar to those of the NaHCO₃-melanoidin.     

Synthesis and characterization of new polymethacrylate bearing cyclopropane ring as side group

A cyclopropanation reaction of allylmethacrylate (1) with ethyldiazoacetate (2) lead to the formation of 2-(2-methyl-acryloyloxymethyl)-cyclopropanecarboxylic acid ethyl ester (3) as a mixture of cis/trans isomers in molar ratio 2:1. The cis isomer could be selectively hydrolyzed by use of Pig liver esterase (PLE). An isolated cis-2-(2-methyl-acryloyloxymethyl)-cyclopropanecarboxylic acid (4) exhibited optical activity. The monomer 3 was easily polymerized using AIBN and benzopinacol as free radical initiators at 65 and 130 °C, respectively. ¹H NMR and FT-IR analyses confirmed the presence of the chemically stable cyclopropane ring in both monomer and polymers. The obtained polymers were also characterized by GPC and DSC measurements. A depolymerization behaviour was observed heating the polymers at 200-250 °C. The regeneration of starting cis/trans isomers of 3 can be taken as a proof of the high thermal stability of the cyclopropane ring.     

塑料解聚技术

塑料采用解聚技术可还原成单体,从而获得了循环利用。介绍了ＰＥＴ、ＰＡ６、ＰＭＭＡ的解聚技术。     

Preparation of water‐soluble starch oligomers from variable starch species in 1‐allyl‐3‐methylimidazolium chloride

Native wheat, barley, rice, maize, wx maize, and potato starch species were modified by depolymerization in 1‐allyl‐3‐methylimidazolium chloride ([AMIM]Cl) ionic liquid (IL) using oil bath or microwave heating. Reactions were catalyzed with p‐toluenesulfonic acid (p‐TsOH). Reaction times varied depending on the starch species and its concentration, the heating method, and volume of the reaction mixture. Depolymerization products were analyzed with HPLC‐ELSD. All starch species mostly degraded into water‐soluble 1500–2000 Da‐sized starch oligomers. Glucose and other short‐chained sugars did not precipitate along with starch oligomers due to their high solubility in IL. This property was utilized in the purification of commercial maltodextrins. Produced water‐soluble, low MW starch oligomers might be used, e.g., in bacterial cultivations as a glucose source.     

脂肪酶解聚壳聚糖及其衍生物的研究

壳聚糖及其衍生物能很容易被脂肪酶解聚。当壳聚糖乳酸盐溶液与脂肪酶在２５℃下作用１０ｍｉｎ后，其溶液粘度被降低到初始值的３５％，分子量从约７００ｋＤａ减少到１３ｋＤａ（还原糖滴定法测定）。脂肪酶浓度在４．５×１０－３～９×１０－１ｇ／Ｌ范围内，解聚初速度与酶浓度成对数线性关系。Ｎ－羧甲基壳聚糖比壳聚糖更容易被脂肪酶解聚。     

Lignin Depolymerization and Conversion: A Review of Thermochemical Methods

The structure of lignin suggests that it can be a valuable source of chemicals, particularly phenolics. However, lignin depolymerization with selective bond cleavage is the major challenge for converting it into value‐added chemicals. Pyrolysis (thermolysis), gasification, hydrogenolysis, chemical oxidation, and hydrolysis under supercritical conditions are the major thermochemical methods studied with regard to lignin depolymerization. Pyrolytic oil and syngases are the primary products obtained from pyrolysis and gasification. A significant amount of char is also produced during pyrolysis. Thermal treatment in a hydrogen environment seems very promising for converting lignin to liquid fuel and chemicals like phenols, while oxidation can produce phenolic aldehydes. Reaction severity, solvents, and catalysts are the factors of prime importance that control yield and composition of the product.