树状大分子接枝型聚合物色谱分离材料研究进展

随着色谱固定相制备技术和材料科学领域的不断发展,目前已经有大量修饰方法和新型材料被用于固相萃取、高效液相色谱以及离子色谱聚合物固定相填料的功能化修饰。其中聚酰胺-胺(PAMAM)树状大分子由于其独特的结构和性质,在色谱分离材料结构完善和性能提升中也发挥了重要的作用。该文主要综述了PAMAM树状大分子在以聚合物为基质的色谱分离材料修饰中的应用,并对其今后的发展进行了展望。     

Mass spectrometry imaging of latent fingerprints using titanium oxide development powder as an existing matrix

Recent research has focused on increasing the evidentiary value of latent fingerprints through chemical analysis. Although researchers have optimized the use of organic and metal matrices for matrix‐assisted laser desorption/ionization‐mass spectrometry imaging (MALDI‐MSI) of latent fingerprints, the use of development powders as matrices has not been fully investigated. Carbon forensic powder (CFP), a common nonporous development technique, was shown to be an efficient one‐step matrix; however, a high‐resolution mass spectrometer was required in the low mass range due to carbon clusters. Titanium oxide (TiO₂) is another commonly used development powder, especially for dark nonporous surfaces. Here, forensic TiO₂ powder is utilized as a single‐step development and matrix technique for chemical imaging of latent fingerprints without the requirement of a high‐resolution mass spectrometer. All studied compounds were successfully detected when TiO₂ was used as the matrix in positive mode, although, generally, the overall ion signals were lower than the previously studied CFP. TiO₂ provided quality mass spectrometry (MS) images of endogenous and exogenous latent fingerprint compounds. The subsequent addition of traditional matrices on top of the TiO₂ powder was ineffective for universal detection of latent fingerprint compounds. Forensic TiO₂ development powder works as an efficient single‐step development and matrix technique for MALDI‐MSI analysis of latent fingerprints in positive mode and does not require a high‐resolution mass spectrometer for analysis.     

TiC-MgO composite: an X-ray transparent and machinable heating element in a multi-anvil high pressure apparatus

ABSTRACT

TiC-MgO composite was developed as a heating element for X-ray study in the multi-anvil high pressure apparatus. We synthesized TiC-MgO blocks (50–70 wt.% of TiC) by compression in a cold isostatic press followed by baking in a gas flow furnace. Heaters of tubular shape were manufactured from the synthesized blocks either by lathe or numerically controlled milling machine. The so-produced heating elements have been proved to generate temperatures up to 2250?K at 10?GPa, condition where classical graphite heaters are not suitable anymore due to graphite-diamond transition. These new heaters have been successfully used for in situ X-ray radiography and diffraction measurements on liquid Fe alloys, exploiting excellent X-ray transparency.     

Ionic liquid gating control of magnetic anisotropy in Ni0.81Fe0.19 thin films

Voltage control magnetism is one of the most energy efficient pathway towards magnetoelectric (ME) device. Ionic liquid gating (ILG) method has already shown impressive manipulation power at the IL/electrode interface to influence the structure, orbital as well as spin of the electrode materials. As key material in anisotropy magnetoresistance sensor and spin valve heterostructure, the permalloy Ni_0.81Fe_0.19 was utilized as the electrode to investigate the ILG induced magnetic anisotropy change. In this work, we realized magnetic anisotropy control in Au/[DEME]⁺[TFSI]^-/Ni_0.81Fe_0.19 (2.5 nm)/Ta heterostructure via ILG caused electrostatic doping. This is evidenced in situ reversible ferromagnetic field (H_r) shift with electron spin resonance (ESR) spectrometer. Aiming at the question whether the charge accumulation at the ionic liquid interface is the main control mechanism at low voltage, we carefully tested the relationship between the change of resonance field and the amount of surface charge. It was found that these two had a good linear relationship between −1 V and +1 V. Defining the linear parameter as A whose value is 28.7 mT m²/Col. Unlike previously reported chemical regulation of Co, this article used ionic liquids to physically regulate NiFe, which has not been studied in the previous ionic liquid regulation. And NiFe has a narrower resonance line width for easy reference to microwave devices. In addition, It also has a stronger ferromagnetic signal than Co, which can be more easily detected as a sensor device. Therefore, this system is more promising. The ILG control NiFe may lead to a new kind of magnetoelectric sensor devices and path a new way to low energy consumption spintronics.     

Sparse Multicategory Generalized Distance Weighted Discrimination in Ultra-High Dimensions

Distance weighted discrimination (DWD) is an appealing classification method that is capable of overcoming data piling problems in high-dimensional settings. Especially when various sparsity structures are assumed in these settings, variable selection in multicategory classification poses great challenges. In this paper, we propose a multicategory generalized DWD (MgDWD) method that maintains intrinsic variable group structures during selection using a sparse group lasso penalty. Theoretically, we derive minimizer uniqueness for the penalized MgDWD loss function and consistency properties for the proposed classifier. We further develop an efficient algorithm based on the proximal operator to solve the optimization problem. The performance of MgDWD is evaluated using finite sample simulations and miRNA data from an HIV study.     

蓝宝石冲击消光晶向效应的第一性原理

蓝宝石的冲击消光现象是高压领域中的研究热点.低压段(86 GPa范围内)的实验研究表明蓝宝石的冲击消光与晶向相关,但在高压段(压力范围:131255 GPa)是否也具有晶向相关性目前尚不清楚.为此,利用第一性原理方法,分别计算了八个不同晶向的蓝宝石理想晶体和含氧离子空位缺陷晶体在高压段的光吸收性质,结果发现:1)蓝宝石在高压段的冲击消光表现出明显的晶向效应,且该效应还随压力增大而增强;一步的数据分析可以看出,在冲击实验采用的波段内,a晶向的消光最弱(透明性最好),c晶向的消光最强与c晶向的消光接近,g晶向的消光要弱于s晶向的消光.鉴于此,如果在高压段开展加窗冲击波实验,建议选择a晶向或m晶向的蓝宝石作为其光学窗口.本文结果不仅有助于深入地认识蓝宝石在极端条件下的光学性质,而且对未来的实验研究有重要的参考作用.     

The optimization of hydrothermal process of MoS_2 nanosheets and their good microwave absorption performances

In this study,flower-like MoS_2 constructed by nanosheets was synthesized by a simple hydrothermal method.The hydrothermal process was optimized and the effects of hydrothermal condition,including reaction temperature,reaction time and the ratio of Mo source to S source(Mo:S) in precursor,on microwave absorption performances and dielectric properties were investigated.Our results showed that when the reaction temperature was 180℃,the reaction time was 18 h,and the Mo:S was 1:3.5,the synthesized MoS_2 had the best performance:Its minimum reflection loss could reach-55.78 dB,and the corresponding matching thickness was 2.30 mm with a wide effective bandwidth of 5.17 GHz.Further researches on the microwave absorption mechanism revealed that in addition to the destructive interference of electromagnetic waves,various polarization phenomena such as defect dipole polarization were the main reasons for microwave loss.We believe that MoS_2 is a candidate for a practical microwave absorbent.     

Resolution and isolation of enantiomers of (±)‐isoxsuprine using thin silica gel layers impregnated with l‐glutamic acid,comparison of separation of its diastereomers prepared with chiral derivatizing reagents having l‐amino acids as chiral auxiliaries

Thin silica gel layers impregnated with optically pure l ‐glutamic acid were used for direct resolution of enantiomers of (±)‐isoxsuprine in their native form. Three chiral derivatizing reagents, based on DFDNB moiety, were synthesized having l ‐alanine, l ‐valine and S‐benzyl‐l ‐cysteine as chiral auxiliaries. These were used to prepare diastereomers under microwave irradiation and conventional heating. The diastereomers were separated by reversed‐phase high‐performance liquid chromatography on a C₁₈ column with detection at 340 nm using gradient elution with mobile phase containing aqueous trifluoroacetic acid and acetonitrile in different compositions and by thin‐layer chromatography (TLC) on reversed phase (RP) C₁₈ plates. Diastereomers prepared with enantiomerically pure (+)‐isoxsuprine were used as standards for the determination of the elution order of diastereomers of (±)‐isoxsuprine. The elution order in the experimental study of RP‐TLC and RP‐HPLC supported the developed optimized structures of diastereomers based on density functional theory. The limit of detection was 0.1–0.09 µg/mL in TLC while it was in the range of 22–23 pg/mL in HPLC and 11–13 ng/mL in RP‐TLC for each enantiomer. The conditions of derivatization and chromatographic separation were optimized. The method was validated for accuracy, precision, limit of detection and limit of quantification. Copyright © 2014 John Wiley & Sons, Ltd.     

Salt effect on molecular orientation at air/liquid methanol interface

The salt effects on molecular orientation at air/liquid methanol interface were investigated by the polarization-dependent sum frequency generation vibrational spectroscopy(SFG-VS). We clarified that the average tilting angle of the methyl group to be u = 308 58 at the air/pure methanol surface assuming a d-function orientational distribution. Upon the addition of 3 mol/L Na I, the methyl group tilts further away from the surface normal with a new u = 418 38. This orientational change does not explain the enhancement of the SFG-VS intensities when adding Na I, implying the number density of the methanol molecules with a net polar ordering in the surface region also changed with the Na I concentrations. These spectroscopic findings shed new light on the salt effects on the surfaces structures of the polar organic solutions. It was also shown that the accurate determination of the bulk refractive indices and Raman depolarization ratios for different salt concentrations is crucial to quantitatively interpret the SFG-VS data.