Cu掺杂对有序Sr3YCo4-xCuxO10.5+δ多晶的结构与物理性能的影响

采用固相反应法制备了四方Sr3YCo4-xCuxO10.5+δ(x=0~1.0)多晶。用热重-差示扫描量热分析,X射线衍射研究了多晶的有序化相变及结构。在固溶范围内(x=0~0.4),观察到有序峰(103)和(215),说明四方Sr3YCo4-xCuxO10.5+δ多晶为超结构,这是由于合成时在1000℃以上发生了吸氧(δ)有序化相变；当x=0.6~1.0时,978℃时在晶界处形成了单斜杂相,破坏了Sr3YCo4-xCuxO10.5+δ多晶的有序。当x=0~0.4时,多晶呈半导体输运行为。随着Cu掺杂量的增加,Co4+提供的空穴载流子浓度增大,电阻率明显下降；由于Cu的固溶,自旋熵增加,载流子浓度和自旋熵的共同作用使x=0~0.2多晶的热电势不变,x=0.4的热电势降低。并且Cu掺杂导致的晶格畸变使Co3+离子由高自旋态转变为高/低自旋混合态,磁化强度和铁磁转变温度(Tc)降低,磁结构由G-型反铁磁转变为铁磁。在进行二次烧结后,300K时电阻率明显降低,热电势为一次烧结的2倍,可能是二次烧结使多晶的有序化程度增大,提高了铁磁有序排列。     

子集模拟中马尔可夫链蒙特卡洛抽样算法比较

文章着重研究子集模拟中马尔可夫链蒙特卡洛(MCMC)抽样算法的抽样效率与计算精度。首先，阐述可靠度子集模拟的基本原理与中间状态样本生成的各种MCMC抽样算法，在稳态马尔可夫链构造基础上提出延迟拒绝MMH(Modified Metropolis Hasting)算法，通过在MMH算法上增加备选样本的延迟拒绝步提高MMH算法的抽样效率；阐述基于随机游走与基于扩散方程MCMC方法中建议分布的差异，进一步对备选样本接受率为1的preconditioned Crank-Nicolson(pCN)算法和条件抽样(Conditional sampling, CS)算法开展研究，证明两种算法的等价性；推导有效样本量的计算方法，提出采用有效样本量与总样本量的比值定义MCMC方法的抽样效率。通过复杂目标分布的样本生成研究不同MCMC抽样算法建议分布及其参数对备选样本接受率与抽样效率的影响，最后通过计算实例研究子集模拟过程采用不同MCMC抽样算法得到失效概率的相对误差及其变异性，揭示不同MCMC抽样算法对失效概率计算精度的影响。研究表明：不同MCMC抽样算法生成备选样本的接受率及其自相关性受建议分布及其参数影响较大，对于复杂的目标分布，pCN算法和CS算法的抽样效率较高，延迟拒绝MMH算法次之；采用CS算法和延迟拒绝MMH算法进行子集模拟得到的失效概率精度较高且变异性较低；增加子集模拟中间状态样本量可以提高失效概率计算精度并降低其变异性。     

Authenticity green coffee bean species and geographical origin using near-infrared spectroscopy combined with chemometrics

To prevent the adulteration of agricultural resources and provide a solution to enhance the green coffee bean supply chain, authentication using the near-infrared spectroscopy (NIRS) technique was investigated. Partial least square with discrimination analysis (PLS-DA) models combined with various preprocessing methods were built from NIR spectra of 153 Vietnamese green coffee samples. The model combined with the standard normal variate and the first order of derivative yielded excellent performance in predicting coffee species with the error cross-validation of 0.0261. PLS-DA model of mean centre and first-order derivative spectra also yielded good performance in verifying geographical indication of green coffee with the error of 0.0656. By contrast, the predicting abilities of post-harvest methods were poor. The overall results showed a high potential of the NIRS in online authentication practices.     

Adaptation to Endoplasmic Reticulum Stress Enhances Resistance of Oral Cancer Cells to Cisplatin by Up-Regulating Polymerase η and Increasing DNA Repair Efficiency

Endoplasmic reticulum (ER) stress response is an adaptive program to cope with cellular stress that disturbs the function and homeostasis of ER, which commonly occurs during cancer progression to late stage. Late-stage cancers, mostly requiring chemotherapy, often develop treatment resistance. Chemoresistance has been linked to ER stress response; however, most of the evidence has come from studies that correlate the expression of stress markers with poor prognosis or demonstrate proapoptosis by the knockdown of stress-responsive genes. Since ER stress in cancers usually persists and is essentially not induced by genetic manipulations, we used low doses of ER stress inducers at levels that allowed cell adaptation to occur in order to investigate the effect of stress response on chemoresistance. We found that prolonged tolerable ER stress promotes mesenchymal–epithelial transition, slows cell-cycle progression, and delays the S-phase exit. Consequently, cisplatin-induced apoptosis was significantly decreased in stress-adapted cells, implying their acquisition of cisplatin resistance. Molecularly, we found that proliferating cell nuclear antigen (PCNA) ubiquitination and the expression of polymerase η, the main polymerase responsible for translesion synthesis across cisplatin-DNA damage, were up-regulated in ER stress-adaptive cells, and their enhanced cisplatin resistance was abrogated by the knockout of polymerase η. We also found that a fraction of p53 in stress-adapted cells was translocated to the nucleus, and that these cells exhibited a significant decline in the level of cisplatin-DNA damage. Consistently, we showed that the nuclear p53 coincided with strong positivity of glucose-related protein 78 (GRP78) on immunostaining of clinical biopsies, and the cisplatin-based chemotherapy was less effective for patients with high levels of ER stress. Taken together, this study uncovers that adaptation to ER stress enhances DNA repair and damage tolerance, with which stressed cells gain resistance to chemotherapeutics.     

Dry Fractionation Approach in Concentrating Tocopherols and Tocotrienols from Palm Fatty Acid Distillate: A Green Pretreatment Process for Vitamin E Extraction

Palm fatty acid distillate (PFAD) is a rich source of vitamin E. As compared to other vegetable oil, PFAD has higher tocotrienol (70–80%) over tocopherol content, which makes it a valuable source for vitamin E extraction. Current vitamin E extraction methods are not sustainable due to the intensive usage of chemical and high operational cost. Hence, the present study investigated for the first time using dry fractionation process as a green and economical pretreatment method for separating solid fraction (stearin) and liquid fraction (olein) in order to concentrate vitamin E from PFAD in olein fraction. We examined the dry fractionation conditions: crystallization ending temperature (36–44 °C), cooling rate (0.3 and 1.5°C min⁻¹), stirring speed (20–125 rpm), and holding time (0–60 min) on the composition of unsaturated and saturated fatty acids as well as vitamin E content in liquid fraction (olein) and solid fraction (stearin) using gas chromatography and high performance liquid chromatography, respectively. In most of these conditions, vitamin E was ultimately higher in olein fraction as compared to stearin fraction, which is correlated with the high degree of unsaturation. Under a cooling rate of 0.3°C min⁻¹, 90 rpm stirring speed, and ending crystallization of 38 °C, the highest vitamin E rich olein fraction was attained with 1479 ± 10.51 ppm in 50 g olein fraction as compared to 1366 ± 7.94 ppm in 500 g of unfractionated PFAD.     

Two Methods,One Goal: Structural Differences between Cocrystallization and Crystal Soaking to Discover Ligand Binding Poses

In lead optimization, protein crystallography is an indispensable tool to analyze drug binding. Binding modes and non-covalent interaction inventories are essential to design follow-up synthesis candidates. Two protocols are commonly applied to produce protein–ligand complexes: cocrystallization and soaking. Because of its time and cost effectiveness, soaking is the more popular method. Taking eight ligand hinge binders of protein kinase A, we demonstrate that cocrystallization is superior. Particularly for flexible proteins, such as kinases, and larger ligands cocrystallization captures more reliable the correct binding pose and induced protein adaptations. The geometrical discrepancies between soaking and cocrystallization appear smaller for fragment-sized ligands. For larger flexible ligands that trigger conformational changes of the protein, soaking can be misleading and underestimates the number of possible polar interactions due to inadequate, highly impaired positions of protein amino-acid side and main chain atoms. Thus, if applicable cocrystallization should be the gold standard to study protein–ligand complexes.