Biological and catalytic evaluation of Ru(II)‐p‐cymene complexes of Schiff base ligands: Impact of ligand appended moiety on photo‐induced DNA and protein cleavage,cytotoxicity and C‐H activation

Two organometallic Ru(II)‐p‐cymene complexes of the type [Ru(η⁶‐p‐cymene)(L)Cl]PF₆ 1 and 2 , where L is N,N‐bis(4‐isopropylbenzylidene)ethane‐1,2‐diamine (bien, L1 ) or N,N‐bis (pyren‐2‐ylmethylene)ethane‐1,2‐diamine (bpen, L2 ) have been prepared and characterized well. Because of appended pyrenyl groups in coordinated bpen ligand, the complex 2 exhibits higher DNA and protein binding than complex 1 in which isopropylbenzyl groups are incorporated. Interestingly, the luminescent characteristic complex 2 is unique in displaying DNA cleavage after light activation by UVA light at 365 nm through oxygen dependent mechanism. AFM analysis attests the photo‐induced DNA fragmentation ability of complex 2 . Also, the complex 2 cleaves the protein after light exposure in a non‐specific manner suggesting that it can act as a protein photo cleaving agent. In contrast to the trend of DNA and protein interaction of complexes, the complex 1 exhibits cytotoxic activity against human breast carcinoma ( MCF‐7 ) and liver carcinoma ( HepG2 ) with potency higher than that of complex 2 due to enhanced hydrophobicity of isopropyl groups present in p‐cymene and bien ligands. Indeed, complex 2 is inactive against MCF‐7 and HepG2 cancer cell lines even up to 200 μM concentration. The AO/EB staining assay reveals that the complex 1 is able to induce late apoptotic mode of cell death in breast cancer cells, which is further confirmed by inter‐nucleosomal DNA cleavage. Furthermore, the complexes 1 and 2 are evaluated for their catalytic activities and found to be working well for the β‐carboline directed C–H arylation to afford the desired products in good yield (40–47%).     

Tunable and highly sensitive temperature sensor based on graphene photonic crystal fiber

Optical fiber temperature sensors have been widely employed in enormous areas ranging from electric power industry, medical treatment, ocean dynamics to aerospace. Recently, graphene optical fiber temperature sensors attract tremendous attention for their merits of simple structure and direct power detecting ability. However, these sensors based on transfer techniques still have limitations in the relatively low sensitivity or distortion of the transmission characteristics, due to the unsuitable Fermi level of graphene and the destruction of fiber structure, respectively. Here, we propose a tunable and highly sensitive temperature sensor based on graphene photonic crystal fiber (Gr-PCF) with the non-destructive integration of graphene into the holes of PCF. This hybrid structure promises the intact fiber structure and transmission mode, which efficiently enhances the temperature detection ability of graphene. From our simulation, we find that the temperature sensitivity can be electrically tuned over four orders of magnitude and achieve up to ～ 3.34×10^-3 dB/(cm·℃) when the graphene Fermi level is ～ 35 meV higher than half the incident photon energy. Additionally, this sensitivity can be further improved by ～ 10 times through optimizing the PCF structure (such as the fiber hole diameter) to enhance the light-matter interaction. Our results provide a new way for the design of the highly sensitive temperature sensors and broaden applications in all-fiber optoelectronic devices.     

Rate sensitivity and deformation mechanism of semi-crystalline polymers during instrumented indentation

Instrumented indentation tests using both constant loading rate (CLR) and continuous stiffness measurement (CSM) operation modes were performed to investigate the deformation mechanism and their sensitivity to the deformation rate in semi-crystalline polymers through the quantitative analysis of load-depth loading and unloading curves. The strain rate was constant during the CSM tests, while the strain rate decreased with the increasing of loading time in CLR tests. The mechanical response mechanism of the semi-crystalline polymers to these tests was very complicated because of the combined effects of strain-hardening in the crystal phase and strain-softening in the amorphous phase. Results show that the loading index m reflects the strain-hardening or strain-softening response during indentation. When m > 2, the mechanical response was due to the strain-hardening, and when m < 2, the response was due to strain-softening. A method based on the measured contact hardness was proposed to obtain the unloading stiffness, and the other mechanical parameters could then be determined according to the unloading stiffness.     

Sensitivity improvement of aluminum-based far-ultraviolet nearly guided-wave surface plasmon resonance sensor

An aluminum (Al) based nearly guided-wave surface plasmon resonance (NGWSPR) sensor is investigated in the far-ultraviolet (FUV) region. By simultaneously optimizing the thickness of Al and dielectric films, the sensitivity of the optimized Al-based FUV-NGWSPR sensor increases from 183°/RIU to 309°/RIU, and its figure of merit rises from 26.47 RIU^-1 to 32.59 RIU^-1 when the refractive index of dielectric increases from 2 to 5. Compared with a traditional FUV-SPR sensor without dielectric, the optimized FUV-NGWSPR sensor can realize simultaneous improvement of sensitivity and figure of merit. In addition, the FUV-NGWSPR sensor with realistic materials (diamond, Ta₂O₅, and GaN) is also investigated, and 137.84%, 52.70%, and 41.89% sensitivity improvements are achieved respectively. This work proposes a method for performance improvement of FUV-SPR sensors by exciting nearly guided-wave, and could be helpful for the high-performance SPR sensor in the short-wavelength region.     

正电子冲击下氦电离三重微分截面的理论计算

我们发展了一种正电子碰撞原子电离的畸变波Born近似方法， 在这个方法中，正负电子偶素通道通过一个ab initio的光学势附加到入射粒子和靶的相互作用势上，且通道对电离作用被第一次被考虑在正电子碰撞原子电离的过程中. 应用这个方法计算了在50 eV入射能量范围氦的电离的三重微分截面，计算结果和实验数据很好的符合.     

Modeling and testing of snow penetration

Penetration by a cone into snow is commonly used to characterize snow properties. However, the effects of the diameter and half-angle of the cone on the mechanical properties of snow have not been systematically studied. In addition, no estimation of material parameters in a physically-based model has been made such that the results from penetration provide only an index of snow properties. In this paper, modeling and experimental methods are used to examine the effects of cone geometry on the maximum penetration force and associated hardness, with penetrometers ranging from 2.5 to 4 mm in diameter, 15° to 45° in cone half-angle, and testing both fine-grained and coarse-grained snows. The material point method, in conjunction with the Drucker–Prager cap plasticity model, was used to obtain the theoretical penetration force-distance relationship. Global sensitivity studies were conducted that indicate that the cohesion accounts for 86% of the penetration force, followed distantly by friction angle which accounts for 27%. A general trend, for the simulation results was established: for a given half-angle, the penetration force increases with the increase of diameter which holds for most of the test data as well; for a given diameter, the penetration force decreases with the increase of half-angle, which holds for some of the test data. In addition, for a given half-angle, the hardness decreases with the increase of diameter; for a given diameter, the hardness decreases with the increase of half-angle. To take into consideration the uncertainty of test data, a simple interval-based metric was used to compare test data with simulation results; the comparison was satisfactory. The material parameters from the simulations can thus be considered as calibrated ones for the snow studied.     

Facile synthesis of thermosensitive functional polyaspartamide derivatives by click chemistry

Biodegradable and thermosensitive polyaspartamide derivatives containing pendant azide groups P(Asp‐Az)_X‐HPAs were synthesized from poly(l ‐succinimide) via the ring‐opening reaction with 2‐azidoethylamine (Az) and 5‐hydroxypentylamine (HPA). Then hydrophobic phenethyl (PEA) and imidazole (IMZ) moieties were introduced successfully with very high reaction efficiency above 90% to the side chains of P(Asp‐Az)_X‐HPA by click reaction to obtain thermoresponsive polyaspartamide derivatives containing pendant aromatic rings P(Asp‐Az)_X‐HPA‐PEAs and the thermo/pH‐responsive polyaspartamide derivatives containing pendant imidazole rings P(Asp‐Az)_X‐HPA‐IMZs, respectively. The thermoresponsive behaviors of P(Asp‐Az)_X‐HPA‐PEAs and P(Asp‐Az)_X‐HPA‐IMZs were confirmed by dynamic light scattering (DLS) and transmittance measurements, and the cloud point can be tuned by designed amounts of azide groups and can be further adjusted by the grafting molar percentage of hydrophobic phenethyl or imidazole moieties to the side chains of P(Asp‐Az)_X‐HPA via click chemistry. The pH‐responsive behavior of P(Asp‐Az)_X‐HPA‐IMZs can also be tuned. These results indicate that the obtained polyaspartamide‐based functional polymers can be further functionalized with hydrophilic long PEG chain and/or targeted moieties via click chemistry for drug delivery. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 1296–1303     

不同抗凝比例对凝血四项检测结果的影响

目的观察并分析凝血四项检测结果与不同比例下的全血与抗凝剂之间的关系。方法研究对象取2015年6月来湖北省宜昌市第二人民医院参加体检的110例健康人员,抽取全血血液样本后按照不同比例与抗凝剂混匀,常规分离血浆并测定受试者凝血酶时间(TT)、凝血酶原时间(PT)、激活部分促凝血酶原激酶时间(APTT)以及纤维蛋白原(FIB),并对研究结果相关数据作统计学处理。结果当血液量与抗凝剂比例为1∶5时,标本TT、PT、APTT以及FIB各项指标较1∶9时差异显著而具有统计学意义(P0.05);抗凝比例1∶7的情况下,TT指标差异与1∶9抗凝比例标本相比差异具有统计学意义(P0.05),而PT、FIB以及APTT三项指标差异并无统计学意义(P0.05);抗凝比例为1∶11与1∶13的情况下,TT指标与1∶9抗凝比例标本相比差异具有统计学意义(P0.05),而PT、FIB以及APTT三项指标差异并无统计学意义(P0.05)。结论凝血四项检测工作中,标本质量检测控制最关键的环节在于准确采集血液量,倘若采集血量过多或过少,导致与抗凝剂比例失调往往会影响测定结果准确性,检验科工作人员应予以重视。     

航空导管弯曲试验的疲劳裂纹萌生寿命

飞行器液压导管受接头和卡箍等约束，在使用的振动环境中，会因弯曲应力而导致破裂，影响到飞行安全．本文对飞行器液压系统通用的不锈钢导管的裂纹萌生寿命进行了试验研究．首先在对8 mm、12 mm 无缺陷导管和含U 型缺口8 mm 导管的疲劳试验和有限元分析的基础上，得到了导管的最大拉应变-裂纹萌生寿命数据．然后采用基于强度极限和弹性模量估算法的Manson-Coffin 公式来预测导管裂纹萌生寿命．最后引入加载类型修正系数、表面质量修正系数、试样尺寸修正系数、应力集中敏感系数和有效应力集中系数，使修正后的公式对三种类型的导管均有较好的裂纹萌生寿命预测精度．     

Lossy mode resonance-based uniform core tapered fiber optic sensor for sensitivity enhancement

A lossy mode resonance (LMR)-supported fiber optic sensor in which a uniform fiber core is placed among two identical tapered regions, is investigated numerically. Indium tin oxide (ITO) and aluminum-doped zinc oxide (AZO) are considered as LMR active materials used to excite several lossy modes and gold and silver are used as surface plasmon resonance (SPR) active materials. In this probe design, a central uniform core coated with ITO/AZO is the active sensing region, whereas tapered regions are meant for bringing the incident angle close to the critical angle. The sensitivity of the present fiber optic bio-sensor is evaluated for first two LMRs utilizing both ITO and AZO separately, along with its variation with the taper ratio (TR). For ITO, the maximum sensitivity values are observed to be 18.425 μm RIU⁻¹ (refractive index unit) and 0.825 μm RIU⁻¹, corresponding to the first and second LMRs, respectively, at a TR of 1.6 and for AZO, equivalent values are 0.79 μm RIU⁻¹ and 0.35 μm RIU⁻¹, respectively, at a TR of 2.0. The results illustrate that the first LMR is more sensitive than the second LMR and the ITO-coated probe possesses greater sensitivity than the AZO-coated probe for both LMRs. Similarly, for the fiber optic SPR sensor, the maximum value of sensitivity is 5.6425 μm RIU⁻¹, in the case of gold and 5.0615 μm RIU⁻¹ in the case of silver, at a TR of 1.6. Hence, the result shows that the sensor with the present fiber optic probe design has around a 3-fold enhancement in sensitivity compared with conventional SPR sensors. This study will have applications in many sensing schemes where the requirement of large sensitivity is vital.