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991.
Top7 is a de novo designed protein with atomic level accuracy and shows a folded structure not found in nature. Previous studies showed that the folding of Top7 is not cooperative and involves various folding intermediate states. In addition, various fragments of Top7 were found to fold on their own in isolation. These features displayed by Top7 are distinct from those of naturally occurring proteins of a similar size and suggest a rough folding energy landscape. However, it remains unknown if and how the intra-polypeptide chain interactions among the neighboring sequences of Top7 affect the folding of these Top7 fragments. Here we used single-molecule optical tweezers to investigate the folding–unfolding pathways of full length Top7 as well as its C-terminal fragment (CFr) in different sequence environments. Our results showed that the mechanical folding of Top7 involves an intermediate state that likely involves non-native interactions/structure. More importantly, we found that the folding of CFr is entirely dependent upon its sequence context in which it is located. When in isolation, CFr indeed folds into a cooperative structure showing near-equilibrium unfolding–folding transitions at ∼6.5 pN in OT experiments. However, CFr loses its autonomous cooperative folding ability and displays a folding pathway that is dependent on its interactions with its neighboring sequence/structure. This context-dependent folding dynamics and pathway of CFr are distinct from those of naturally occurring proteins and highlight the critical importance of intra-chain interactions in shaping the overall energy landscape and the folding pathway of Top7. These new insights may have important implications on the de novo design of proteins.Optical tweezers experiments reveal that the folding of the C-terminal fragment of Top7 (cFr) is context-dependent. Depending on its neighboring sequence, cFr shows very different folding pathways and folding kinetics. 相似文献
992.
Jun Liu Kelton A. Schleyer Tyrel L. Bryan Changjian Xie Gustavo Seabra Yongmei Xu Arjun Kafle Chao Cui Ying Wang Kunlun Yin Benjamin Fetrow Paul K. P. Henderson Peter Z. Fatland Jian Liu Chenglong Li Hua Guo Lina Cui 《Chemical science》2021,12(1):239
Heparanase (HPA) is a critical enzyme involved in the remodeling of the extracellular matrix (ECM), and its elevated expression has been linked with diseases such as various types of cancer and inflammation. The detection of heparanase enzymatic activity holds tremendous value in the study of the cellular microenvironment, and search of molecular therapeutics targeting heparanase, however, no structurally defined probes are available for the detection of heparanase activity. Here we present the development of the first ultrasensitive fluorogenic small-molecule probe for heparanase enzymatic activity via tuning the electronic effect of the substrate. The probe exhibits a 756-fold fluorescence turn-on response in the presence of human heparanase, allowing one-step detection of heparanase activity in real-time with a picomolar detection limit. The high sensitivity and robustness of the probe are exemplified in a high-throughput screening assay for heparanase inhibitors.Heparanase, a critical enzyme involved in the remodeling of the extracellular matrix, activates a disaccharide probe HADP to give a strong fluorescence signal. 相似文献
993.
本文采用以ASED-MO(含原子对排斥的EHMO法)为基础的结构自动优化的EHTOPT法及Monte-Carlo法, 对甲醇羰基化制乙酸催化剂的共聚物配体交替结构进行了理论研究。计算了AA, AB, BB, BA二聚反应的反应途径, 找出了过渡态, 并确定了反应活化势垒。在假设两反应频率因子相同的前提下, 求出竞聚率, 采用Monte-Carlo法模拟共聚物结构, 计算出共聚物配体中起催化活性的AB交替结构所占比率。比较不同共聚物配体的活性, 并研究了温度及单体配比对共聚物配体交替结构的影响。 相似文献
994.
有机-无机纳米复合材料的研究在当前纳米科学技术的发展中占有重要地位,开创了材料与催化科学研究的新纪元。自从10年前首次合成纳米孔无机材料MCM-41至今,该领域研究不断深入,已展现出广阔的应用前景。当客体有机分子分散于纳米孔道内部时,其分子性质将产生明显变化。本文结合作者近期研究成果,力图从实验与理论两方面阐明在纳米复合体系中客体分子性质变化的原因。 相似文献
995.
纳秒强激光场中苯电离产生高价离子的研究 总被引:2,自引:0,他引:2
用25 ns脉冲Nd-YAG 532 nm的激光,在1010~1011 W•cm-2的光场强度下,利用飞行时间质谱对He、 N2、Ar载气条件下苯的激光电离过程进行了研究.发现当利用氩作为载气时,除观察到C2+、C2H2+、C3H3+、C6H6+离子外,还观察到很强的Cq+(q=1~3)高价离子.这些离子都有很高的平动能, C2+的最可几平动能为12.9 eV, C3+为37.5 eV.通过改变载气种类和压力及在不同光场强度条件下的实验,可以认为这些高价离子来源于含苯团簇的库仑爆炸过程. 相似文献
996.
In this paper, pressurized CEC was used for the separation and determination of seven fluoroquinolones (FQs). The effect of different experimental conditions, such as the concentration and pH of the buffer, the organic modifier concentration, the surfactant and ion-paring agents added to the electrolyte, and applied voltage were studied. All the seven FQs were baseline separated using mobile phase containing 27% v/v ACN, 5 mmol/L Na2HPO4 buffer (pH 4.0 adjusted using citric acid), 11 mmol/L SDS, and 0.01% TEA v/v at detection wavelength of 287 nm and at an applied voltage of -10 kV. The calibration curves were linear (r>0.9991) over a concentration range of 1.0-50.0 mg/L for norfloxacin (NFLX); 2.5-50.0 mg/L for fleroxacin (FLX), ciprofloxacin (CPFX), and lomefloxacin (LMX); and 5.0-50.0 mg/L for enoxacin (ENX), ofloxacin (OFLX), and gatifloxacin (GFLX). The detection limits (S/N = 3) for ENX, OFLX, FLX, NFLX, CPFX, LMX, and GFLX were 0.5, 0.8, 0.4, 0.2, 0.4, 0.5, and 1.0 mg/L, respectively. The method is simple, rapid, and reproducible. It was successfully applied to the analysis of fish muscle samples spiked with FQs. Mean recoveries ranged from 81.6 to 97.6%. 相似文献
997.
998.
直链醇链长对层状液晶结构与稳定性的影响 总被引:8,自引:4,他引:8
作为助表面活性剂,直链醇在层状溶致液晶的制备中是非常重要的。本文以层状液晶的相行为和小角度X射线衍射测量,研究了直链醇链长对层状液晶结构与稳定的影响。 相似文献
999.
Ming‐Lin Guo Hong‐Xia Cao 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(9):m431-m433
The title complex, [Ba2Ni(C3H2O4)2(NO3)2(H2O)10]n, has a two‐dimensional layer structure. The Ni atom lies on a crystallographic centre of symmetry in an octahedral NiO6 environment, and is coordinated by four malonate O atoms in a planar arrangement and by two water molecules in axial positions. The coordination of the unique Ba atom involves two nitrate O atoms, five water molecules and three malonate O atoms. 相似文献
1000.
High performance liquid chromatography (HPLC) and electrospray ionization mass spectrometry (ESI-MS) have been utilized to analyze the synthesized 2-(2-arylaminomethylphenoxy)pyrimidine derivatives, which are a new kind of environmentally benign herbicides and have passed the temporary pesticide registration. The identification of main product and impurities has been achieved according to the UV and mass spectra. Moreover, one impurity, introduced by the raw material in the last step of the synthetic route, was identified by GC-MS analysis. It can be concluded that the combination of chromatography and mass spectrometry, including LC-MS and GC-MS, provided a vital tool of the pesticide science. 相似文献