固相萃取结合高效液相色谱-三重四极杆质谱快速分离检测益气养血口服液中人参皂苷的新方法

以无机多孔材料作为固相萃取吸附剂,结合高效液相色谱-三重四极杆质谱(HPLC-QqQ/MS)建立了一种快速分离检测中药复方益气养血口服液中人参皂苷的新方法。考察了SAPO-34、SAPO-11、ZSM-5、Y型分子筛、SBA-15、多壁碳纳米管(MWCNTs) 6种无机多孔材料对4种主要人参皂苷Re、Rg1、Rb1、Ro的吸附活性。在优化条件下,MWCNTs的分离效果最好,可在2 min内分别达到吸附和脱附平衡,吸附率和脱附回收率分别达98.6%和96.8%以上。方法的检出限为0.01～0.05μg/mL,平均回收率为90.5%～99.7%,相对标准偏差为2.2%～4.9%。益气养血口服液中4种人参皂苷含量的分析结果显示,建立的方法对口服液中除皂苷外的其他成分吸附作用不明显,可以有效降低基质干扰并准确分析微量的人参皂苷。该方法在快速检测人参皂苷方面具有潜在的应用价值。     

Quantum Teleportation Schemes of an N-Particle State via Three-Particle General W States

Two schemes of teleporting an N-particle arbitrary and unknown state are proposed when N groups of three- particle general W states are utilized as quantum channels. In the first scheme, the quantum channels are shared by the sender and the recipient. After the sender＇s Bell-state measurements on his （her） particles, the recipient carries out unitary transformations on his （her） particles. And then, the recipient performs computational basis measurements to realize the teleportation. The recipient can recover the state on either of particle sequences with the equal maximal probability of successful teleportation if he （she） performs appropriate unitary transformations. In the second scheme, the quantum channels are shared by the sender, the recipient and the third ones. After the sender＇s Be11-state measurements and the third ones＇ computational basis measurements if they agree to cooperate, the recipient will introduce auxiliary particles and carry out appropriate unitary transformations. Finally, the recipient performs computational basis measurements to fulfill the teleportation. The second scheme can be realized if and only if the third ones agree to cooperate with the recipient.     

基于HPLC-HRMS/MS~n/QqQ技术的人参皂苷Rb_1化学转化产物的结构与途径分析

利用液相色谱-质谱联用技术分析了Keggin型12-磷钨酸化学转化人参皂苷Rb1产物的结构与转化途径.基于高效液相色谱对转化产物的快速分离,利用Q Exactive高分辨质谱的Full MS-AIF模式快速鉴定了产物结构,并利用多级串联质谱进行结构验证.进一步结合人参皂苷异构体在反向C18色谱柱上的相对保留时间,快速分析鉴定出Rb1的10种转化产物为20(S)-Rg3,20(R)-Rg3,20(S)-25-OH-Rg3,20(R)-25-OH-Rg3,25-OH-Rk1,25-OH-Rg5,Rg5,Rk1,(20S,25)-环氧-Rg3和(20R,25)-环氧-Rg3.根据转化产物的结构初步推断了人参皂苷的转化途径:在12-磷钨酸产生的酸性环境中,Rb1主要通过C20位去糖基化、差向异构化和烯烃链的水合、消除及环合反应转化为稀有皂苷.采用三重四极杆质谱的选择反应监测模式准确定量分析了Rb1的转化效率和稀有皂苷20(S)-Rg3,20(R)-Rg3,Rk1和Rg5的产率.定量分析结果显示,与生物转化相比,12-磷钨酸对Rb1有更高的转化效率,反应40 min后转化率达到100%.本文结果表明,HPLC-HRMS/MSn/Qq Q技术是人参皂苷等天然产物结构解析与定量分析的有效方法.     

恒温洗浴热水添加策略研究

用户和商家都期望有自动化程度高的浴缸加水系统出现,既能使浴缸中的水长时间保持恒定的舒适温度,又尽可能节约热水。综合考虑影响浴缸水温的各种因素,建立了浴缸加水的2个数学模型:热传输模型和微分方程模型。通过分析求解2个模型,分别给出包含加水时间和流速等信息的最优加水方案。最后对2个模型进行比较,推荐最优加水方案,从而为生产厂家制定智能加水系统提供理论支持。     

管式炉催化反应实验教学的改进

研究探讨了对管式炉催化反应教学实验的改进,包括反应体系的选择、催化剂的筛选和合成、反应操作参数及产物检测气相色谱条件的确定以及物料输送管路的改造,发展了基于"乙醇脱水制乙醚"反应的新型、绿色管式炉催化反应实验教学体系。该实验体系运转连续平稳,教学效果良好,环保绿色,节能减排,切合绿色化工技术的发展方向,适合高校化工专业教学实验使用。     

多约束条件下三状态复杂系统的优化分配

研究了三状态复杂系统在多约束条件下可靠度的问题.以串-并联系统为研究对象,利用选取重要度来提高系统可靠度的方法,获得了重要度对系统可靠度有着重要影响的结果,并通过算法、例题对实例进行了验证.     

Equivalent Conditions for Jacobian Nonsingularity in Linear Symmetric Cone Programming

In this paper we consider the linear symmetric cone programming (SCP). At a Karush-Kuhn-Tucker (KKT) point of SCP, we present the important conditions equivalent to the nonsingularity of Clarke’s generalized Jacobian of the KKT nonsmooth system, such as primal and dual constraint nondegeneracy, the strong regularity, and the nonsingularity of the B-subdifferential of the KKT system. This affirmatively answers an open question by Chan and Sun (SIAM J. Optim. 19:370–396, 2008).     

Microwave-assisted Solid-phase Synthesis,Biological Evaluation and Molecular Docking of Angiotensin I-converting Enzyme Inhibitors

Short peptides based on the tripeptides, Leu-Arg-Pro and Leu-Lys-Pro, were synthesized by microwaveassisted solid-phase synthesis method, in order to make a search for potential inhibitors for angiotensin I-converting enzyme(ACE) with minimum side effects in the treatment of hypertension. One peptide with the sequence Leu-Arg-Pro-Phe-Phe shows the strongest inhibition towards ACE with an IC50 value of 0.26 μmol/L in vitro. The study of structure-activity relationship shows that the introduction of a bulky group into the N-terminal of this series of inhibitors may enlarge steric hindrance, resulting in the poor inhibitory activity towards ACE. The inhibitory activity decreased in turn when L-Pro, D-Pro or Ac6c was at the C-terminal respectively. The binding interaction between each of these inhibitors and testicular ACE(tACE) was performed by molecular docking. The results suggest that Leu-Arg-Pro-Phe-Phe mainly occupied the S1 subsite of tACE, and made contact with tACE via seven H-bonds. It appeared that the site on the peptide that bound with tACE was influenced by the configuration of the amino acid, L- or D-form, at the C-terminal of the peptide.     

N’-苄基酰腙分子的氮-氮键旋转位阻及分子构象

采用动态核磁共振波谱(DNMR)和密度泛函理论(DFT)对N'-苄基酰腙化合物进行构象研究. 实验和理论计算表明, 1H NMR图谱中三组不同质子的双峰裂分是由N—N键旋转位阻造成的, 而这三个双峰裂分的化学位移差异随温度升高而减小. 通过模拟化学位移差异与温度的关系, 得到了交换速率常数, 采用Eyring方程计算出N—N键旋转位阻. 提出顺式和反式共存的模型来分析酰胺质子信号分裂的原因, 并利用DFT计算得出优化的异构体构象及其最低能量. 端甲基质子和次甲基质子信号裂分也来源于N—N键旋转受阻. N'-苄基酰腙通过缩合反应转变成1,3,4-二唑化合物, 消除了甲基空间取向的差异, 其信号变为单峰.