氧化硅片表面配基疏水性及含量对蛋白质吸附行为的影响

采用双偏振极化干涉分析技术研究了氧化硅片表面配基疏水性及含量对蛋白质质吸附行为的影响,用3种不同疏水性配基3-(氨丙基)三乙氧基硅烷(APTES)、3-(N-甲氨基丙基)三甲氧基硅烷(MAPTMS)和3-(N,N-二乙基氨丙基)三甲氧基硅烷(DAPTMS)修饰氧化硅片,通过修饰时间控制硅片表面配基含量,研究了配基疏水性对牛血清白蛋白质(BSA)的影响和配基含量(N含量)对BSA、细胞色素C和糜蛋白酶吸附行为的影响. 结果表明,BSA在疏水性最强的DAPTMS修饰的氧化硅表面吸附量及吸附动力学常数最大,分别为1.371 ng/mm2和0.056 s?1; DAPTMS含量对3种蛋白质吸附的影响与蛋白质疏水性密切相关,疏水性中等的BSA和细胞色素C为单分子层吸附,吸附量随N含量增加先增大后减小,N含量2.1%时吸附量最大,分别为16.9和60.2 nmol/m2. 疏水性较强的糜蛋白酶为多分子层吸附,吸附量随N含量增大而减小,N含量1.1%时吸附量及吸附动力学常数分别为78.6 nmol/m2和0.040 s?1.     

Inhibition of Amyloid Protein Aggregation Using Selected Peptidomimetics

Aberrant protein aggregation leads to the formation of amyloid fibrils. This phenomenon is linked to the development of more than 40 irremediable diseases such as Alzheimer's disease, Parkinson's disease, type 2 diabetes, and cancer. Plenty of research efforts have been given to understanding the underlying mechanism of protein aggregation, associated toxicity, and the development of amyloid inhibitors. Recently, the peptidomimetic approach has emerged as a potential tool to modulate several protein-protein interactions (PPIs). In this review, we discussed selected peptidomimetic-based approaches for the modulation of important amyloid proteins (Islet Amyloid Polypeptide, Amyloid Beta, α-synuclein, mutant p53, and insulin) aggregation. This approach holds a powerful platform for creating an essential stepping stone for the vital development of anti-amyloid therapeutic agents.     

Hydrophobicity, solubility, and emulsifying properties of soy protein peptides prepared by papain modification and ultrafiltration

Peptide size control is important for obtaining desirable functional properties so that these peptides can be better utilized. Proteolytic enzymatic modification of soy protein isolates (SPI), followed by ultrafiltration, is an effective way to fractionate these proteins into peptides with controlled molecular size. SPI was predenatured by mild alkali at pH 10 and heated at 50°C for 1 h prior to partial hydrolysis by papain at pH 7.0 and 38°C for 10, 30, and 60 min (PMSPI10, PMSPI30, and PMSPI60). The hydrolysate PMSPI60 was further fractionated by ultrafiltration with a stirred cell and disc membranes (100-, 50-, and 20-kDa molecular weight cut-off) into one retentate (R100) and three permeates (P100, P50, and P20). Molecular weight distribution, surface hydrophobicity (S ₀), protein solubility (PS), emulsifying activity index (EAI), and emulsion stability index (ESI) of the control SPI (without added papain), hydrolysates, and ultrafiltrates were investigated. Significant increases (P<0.001) in S ₀, PS, EAI, and ESI were observed in the hydrolysates. Peptides in the permeates had higher PS and EAI but lower S ₀ than the peptides in the retentate and hydrolysate. Soy protein peptides that were prepared from SPI by papain modification and ultrafiltration had lower molecular weight, higher solubility, and higher emulsifying properties. They could find use in products that require these properties, especially in the cosmetic and health food industries.     

Explaining Ionic Liquid Water Solubility in Terms of Cation and Anion Hydrophobicity

The water solubility of salts is ordinarily dictated by lattice energy and ion solvation. However, in the case of low melting salts also known as ionic liquids, lattice energy is immaterial and differences in hydrophobicity largely account for differences in their water solubility. In this contribution, the activity coefficients of ionic liquids in water are split into cation and anion contributions by regression against cation hydrophobicity parameters that are experimentally determined by reversed phase liquid chromatography. In this way, anion hydrophobicity parameters are derived, as well as an equation to estimate water solubilities for cation-anion combinations for which the water solubility has not been measured. Thus, a new pathway to the quantification of aqueous ion solvation is shown, making use of the relative weakness of interactions between ionic liquid ions as compared to their hydrophobicities.     

A Fluorogenic AggTag Method Based on Halo- and SNAP-Tags to Simultaneously Detect Aggregation of Two Proteins in Live Cells

Protein aggregation involves the assembly of partially misfolded proteins into oligomeric and higher-order structures that have been associated with several neurodegenerative diseases. However, numerous questions relating to protein aggregation remain unanswered due to the lack of available tools for visualization of these species in living cells. We recently developed a fluorogenic method named aggregation tag (AggTag), and presented the AggTag probe P1 , based on a Halo-tag ligand, to report on the aggregation of a protein of interest (POI) in live cells. However, the Halo-tag-based AggTag method only detects the aggregation of one specific POI at a time. In this study, we have expanded the AggTag method by using SNAP-tag technology to enable fluorogenic and biorthogonal detection of the aggregation of two different POIs simultaneously in live cells. A new AggTag probe— P2 , based on a SNAP-tag ligand bearing a green solvatochromic fluorophore—was synthesized for this purpose. Using confocal imaging and chemical crosslinking experiments, we confirmed that P2 can also report both on soluble oligomers and on insoluble aggregates of a POI fused with SNAP-tag in live cells. Ultimately, we showed that the orthogonal fluorescence of P1 and P2 allows for simultaneous visualization of two different pathogenic protein aggregates in the same cell.     

Effects of Molecular Crowding and Betaine on HSPB5 Interactions,with Target Proteins Differing in the Quaternary Structure and Aggregation Mechanism

The aggregation of intracellular proteins may be enhanced under stress. The expression of heat-shock proteins (HSPs) and the accumulation of osmolytes are among the cellular protective mechanisms in these conditions. In addition, one should remember that the cell environment is highly crowded. The antiaggregation activity of HSPB5 and the effect on it of either a crowding agent (polyethylene glycol (PEG)) or an osmolyte (betaine), or their mixture, were tested on the aggregation of two target proteins that differ in the order of aggregation with respect to the protein: thermal aggregation of glutamate dehydrogenase and DTT-induced aggregation of lysozyme. The kinetic analysis of the dynamic light-scattering data indicates that crowding can decrease the chaperone-like activity of HSPB5. Nonetheless, the analytical ultracentrifugation shows the protective effect of HSPB5, which retains protein aggregates in a soluble state. Overall, various additives may either improve or impair the antiaggregation activity of HSPB5 against different protein targets. The mixed crowding arising from the presence of PEG and 1 M betaine demonstrates an extraordinary effect on the oligomeric state of protein aggregates. The shift in the equilibrium of HSPB5 dynamic ensembles allows for the regulation of its antiaggregation activity. Crowding can modulate HSPB5 activity by affecting protein–protein interactions.     

亲水/疏水性在宝石学中的应用探讨

亲水/疏水性在宝石领域中有一定的应用,但相关研究极少.本文总结了其在宝石学中的应用案例,分别通过表面自由能和分子结构两个方面直接和间接的分析固体表面润湿性的主要机理.从分子结构角度对钻石、合成立方氧化锆、蓝宝石进行分析,得出合成立方氧化锆和蓝宝石是极性分子所以表现为亲水性,而钻石是非极性分子所以表现为疏水性的结论.并对亲水/疏水性在宝石学中的应用提出展望.     

Aggregation Condition–Structure Relationship of Mouse Prion Protein Fibrils

Prion diseases are associated with conformational conversion of cellular prion protein into a misfolded pathogenic form, which resembles many properties of amyloid fibrils. The same prion protein sequence can misfold into different conformations, which are responsible for variations in prion disease phenotypes (prion strains). In this work, we use atomic force microscopy, FTIR spectroscopy and magic-angle spinning NMR to devise structural models of mouse prion protein fibrils prepared in three different denaturing conditions. We find that the fibril core region as well as the structure of its N- and C-terminal parts is almost identical between the three fibrils. In contrast, the central part differs in length of β-strands and the arrangement of charged residues. We propose that the denaturant ionic strength plays a major role in determining the structure of fibrils obtained in a particular condition by stabilizing fibril core interior-facing glutamic acid residues.     

有机氯硅烷修饰的介孔SBA-15及其疏水性

在非极性溶剂(甲苯)中,用三甲基氯硅烷和苯基二甲基氯硅烷对全硅介孔分子筛SBA-15进行了表面修饰.利用傅里叶变换红外光谱(FT IR)、X射线粉末衍射(XRD)和低温N2吸附-脱附等手段对样品进行了结构分析;并通过测定样品在水或正己烷饱和蒸汽中的吸附量,研究了它们的疏水性.结果表明,表面改性后的SBA-15仍保持完好...     

豆壳过氧化物酶的序列联配、二级结构预测及疏水性分析

利用生物大分子数据库和软件技术对豆壳过氧化物酶 (Soybeanhullperoxidase ,SHP ,EC 1 .1 1 .1 .7)进行了序列联配、二级结构预测及疏水性分析 ,通过与其它来源过氧化物酶的比较研究 ,分析了结构保守性与功能域的关系 ,从分子水平探讨了过氧化物酶活性位点结构特征。     

(De)stabilization of Alpha-Synuclein Fibrillary Aggregation by Charged and Uncharged Surfactants

Parkinson’s disease (PD) is the second most common neurodegenerative disorder. An important hallmark of PD involves the pathological aggregation of proteins in structures known as Lewy bodies. The major component of these proteinaceous inclusions is alpha (α)-synuclein. In different conditions, α-synuclein can assume conformations rich in either α-helix or β-sheets. The mechanisms of α-synuclein misfolding, aggregation, and fibrillation remain unknown, but it is thought that β-sheet conformation of α-synuclein is responsible for its associated toxic mechanisms. To gain fundamental insights into the process of α-synuclein misfolding and aggregation, the secondary structure of this protein in the presence of charged and non-charged surfactant solutions was characterized. The selected surfactants were (anionic) sodium dodecyl sulphate (SDS), (cationic) cetyltrimethylammonium chloride (CTAC), and (uncharged) octyl β-D-glucopyranoside (OG). The effect of surfactants in α-synuclein misfolding was assessed by ultra-structural analyses, in vitro aggregation assays, and secondary structure analyses. The α-synuclein aggregation in the presence of negatively charged SDS suggests that SDS-monomer complexes stimulate the aggregation process. A reduction in the electrostatic repulsion between N- and C-terminal and in the hydrophobic interactions between the NAC (non-amyloid beta component) region and the C-terminal seems to be important to undergo aggregation. Fourier transform infrared spectroscopy (FTIR) measurements show that β-sheet structures comprise the assembly of the fibrils.     

Influence of Glycerophosphate Salt Solubility on the Gelation Mechanism of Colloidal Chitosan Systems

Recently, thermosensitive chitosan systems have attracted the interest of many researchers due to their growing application potential. Nevertheless, the mechanism of the sol-gel phase transition is still being discussed, and the glycerophosphate salt role is ambiguous. The aim of the work is to analyze the possibility of the exclusive use of a non-sodium glycerophosphate salt and to determine its impact on the gelation conditions determined by rheological and turbidimetric measurements as well as the stability of the systems by measuring changes in the Zeta potential value. It was found that ensuring the same proportions of glycerophosphate ions differing in cation to amino groups present in chitosan chains, leads to obtaining systems significantly different in viscoelastic properties and phase transition conditions. It was clearly shown that the systems with the calcium glycerophosphate, the insoluble form of which may constitute additional aggregation nuclei, undergo the gelation the fastest. The use of magnesium glycerophosphate salt delays the gelation due to the heat-induced dissolution of the salt. Thus, it was unequivocally demonstrated that the formulation of the gelation mechanism of thermosensitive chitosan systems based solely on the concentration of glycerophosphate without discussing its type is incorrect.     

vGemini表面活性剂的聚集行为及应用的新进展

综述了已报道的几种新型Gemini表面活性剂的化学结构，并对它们在气／液、气／固界面及溶液中的聚集行为和应用做了讨论。     

Solubility of bacterial cellulose and its structural properties

Based on experiments conducted, it has been found that bacterial cellulose, like spruce cellulose, is soluble in an aqueous NaOH solution with the concentration of 8.5% at a temperature of −5°C if the polymerization degree of the cellulose does not exceed 400. When 1% of urea is added to the NaOH solution, the solubility of cellulose increases; and, in this solvent, bacterial cellulose may be dissolved so long as its polymerization degree is below 560. The results of these experiments are of great practical importance since they point to the possibility of the preparation of cellulose spinning solutions suitable for fiber formation. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 67:1871–1876, 1998     

Effect of Shear Rate Distribution on Particle Aggregation in a Stirred Vessel

The modeling of particle aggregation under a simple shear flow and the extension of the model to a stirred vessel is described. The model quantitatively demonstrates the change of the number of aggregates with time for each shear rate. This number increased with higher shear rate and, conversely, the aggregate size became small when raising the shear rate. This was because aggregates were broken by the stronger shear force. The number of aggregates for different impellers was determined. The shear rate was back‐calculated from the experimentally obtained aggregate size and the model equation. This shear rate was different from that estimated from the Metzner‐Otto method, consequently, some revisions of the Metzner‐Otto equation might be necessary for its application to particle aggregation.     

有机羧酸pKa和亲油性的定量结构-性质关系

化学萃取法是分离有机羧酸稀溶液的重要方法之一，羟酸的酸性(pKa)和亲油性(logP)是影响萃取平衡的关键参数。利用QSPR(Quantiative Structure-Property Relationship)的研究方法，对41种有机羧酸的各阶分子连接性指数及其价指数进行了计算。根据线性相关性分析，选择一阶分子连接性路径价指数^1Xp^v作为表征羧酸分子体积因素的参数，同时，将羧酸分子中氧原子的数目No以及Taft常数σ*作为表征羧酸分子电性因素的参数，分别建立了有机羧酸pKa和logP的QSPR数学模型。该模型具有参数少、拟合精度高、预测性好的优点。     

异氰酸酯对木塑力学性能与疏水性的影响

将木粉表面的羟基分别与异氟尔酮二异氰酸酯(IPDI)、甲苯二异氰酸酯(TDI)反应,再与聚乙烯(PE)通过挤出混合,挤出成型制备出了不同处理效果的木塑复合材料(WPC)。在不同种类和不同浓度的条件下,异氰酸酯改性木粉对木塑复合材料(WPC)的力学性能以及吸水率具有不同的影响。红外光谱(FTIR)和接触角测试表明,异氰酸酯成功接枝到木粉上。采用场发射扫描电子显微镜(FESEM)观察木粉与聚乙烯(PE)的相容性变化,通过微机控制电子万能试验机测试不同处理条件下的木塑复合材料力学性能,并参照GB/T 1462—2005计算了木塑吸水率。结果表明,在质量比为TDI∶木粉=5∶100条件下,木塑的力学性能和疏水效果最佳,拉伸强度达到27.8±0.7 MPa,浸入水中48 h吸水率达到0.45%。     

全硅介孔分子筛MCM-41的表面修饰及其疏水性

在极性溶剂(丙酮)或非极性溶剂(甲苯)中,用三甲基氯硅烷对全硅介孔分子筛MCM-41进行了表面修饰。利用IR、XRD和低温N2吸附-脱附等手段对样品进行了结构分析;并通过测定样品在水或正庚烷饱和蒸汽中的吸附量,研究了它们的疏水性。实验结果表明,表面改性后的MCM-41仍保持完好的介孔结构,由于有机官能团接枝在MCM-41的内表面,占据了孔道内部空间,使其比表面积、孔容和孔径都减小。样品的疏水性与其硅烷化程度成正关系,且在非极性溶剂中表面修饰的样品表现出更好的疏水性能。     

Predicting the Distribution Constants of Butane Extraction of Organic Pollutants from Aqueous Solubility

The n‐butane/water distribution constant is one of the key parameters in determining the extraction efficiency. Experimental results on 34 organic compounds illustrated that a fundamental linear relationship exists between the distribution constant and the aqueous solubility of the solute. The relationship can be broadly applied to many different classes of chemical compounds as well as to many different solvent extraction systems. The linear equation obtained by a regression method allows one to estimate the distribution constant and predict the result of butane extraction if the aqueous solubility of certain solute is available.     

β‐Cyclodextrin Improves Solubility and Enzymatic C‐Glucosylation of the Flavonoid Phloretin

Nothofagin is a prominent bioactive ingredient of rooibos tea. We recently reported its synthesis through a glucosyltransferase cascade reaction involving 3′‐C‐β‐D ‐glucosylation of the dihydrochalcone phloretin from uridine 5′‐diphosphate (UDP)‐glucose and in situ formation of UDP‐glucose from sucrose and catalytic amounts of UDP. Here we show that the limitation in process efficiency caused by the vanishingly low water solubility of phloretin – a major problem for biocatalytic modifications of hydrophobic natural products in general – was overcome effectively using phloretin inclusion complexation with β‐cyclodextrin. Unlike operating in a two‐phase system containing uncomplexed insoluble phloretin or using organic cosolvents, the addition of β‐cyclodextrin inclusion complexes was well tolerated regarding enzyme activity and stability. Besides enhancing the effective phloretin concentration in water (∼0.2 mM) to about 50 mM , inclusion complexation offered the additional advantage of overcoming the complex inhibition/inactivation effect of the free/microaggregated dihydrochalcone acceptor. Thus oversaturated phloretin solution was transformed in a single batch reaction in excellent conversion (99% in solution; 88% overall) and isolated yield (78%; 17.0 g L ⁻¹). The UDP‐glucose was regenerated up to ∼90 times and the nothofagin space‐time yield of 2.4 mM h⁻¹ presented an eight‐fold improvement compared to a reference reaction using 20% DMSO (dimethyl sulfoxide) and requiring controlled phloretin feed. We thus demonstrate the high potential of inclusion complexation by cyclodextrins for boosting the glycosylation of hydrophobic flavonoid‐like natural products.