Stimuli-responsive polypeptide materials prepared by ring-opening polymerization of α-amino acid N-carboxyanhydrides

Design and synthesis of biodegradable stimuli-responsive polypeptides are important areas considering their promising applications in biomedical fields. This article summarizes the most recent progresses in the development of stimuli-responsive polypeptide materials prepared via ring-opening polymerization of α-amino acid N-carboxyanhydrides. We discuss the design, synthesis and structure-property correlation of emerging materials including thermo-responsive, redox-responsive, photo-responsive and biomolecule responsive polypeptides. Considering the unique structural features of amino acids, we try to emphasize that the thermo-responsive properties not only depend on the amino acid structure but also rely on the secondary structures of polypeptides. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Reconstructing Hydrogen Bond Network Enables High Voltage Aqueous Zinc-Ion Supercapacitors

High-voltage aqueous rechargeable energy storage devices with safety and high specific energy are hopeful candidates for the future energy storage system. However, the electrochemical stability window of aqueous electrolytes is a great challenge. Herein, inspired by density functional theory (DFT), polyethylene glycol (PEG) can interact strongly with water molecules, effectively reconstructing the hydrogen bond network. In addition, N, N-dimethylformamide (DMF) can coordinate with Zn²⁺, assisting in the rapid desolvation of Zn²⁺ and stable plating/stripping process. Remarkably, by introducing PEG400 and DMF as co-solvents into the electrolyte, a wide electrochemical window of 4.27 V can be achieved. The shift in spectra indicate the transformation in the number and strength of hydrogen bonds, verifying the reconstruction of hydrogen bond network, which can largely inhibit the activity of water molecule, according well with the molecular dynamics simulations (MD) and online electrochemical mass spectroscopy (OEMS). Based on this electrolyte, symmetric Zn cells survived up to 5000 h at 1 mA cm⁻², and high voltage aqueous zinc ion supercapacitors assembled with Zn anode and activated carbon cathode achieved 800 cycles at 0.1 A g⁻¹. This work provides a feasible approach for constructing high-voltage alkali metal ion supercapacitors through reconstruction strategy of hydrogen bond network.     

Enhancing the Sensitivity of Aptameric Detection of Lysozyme with a “Feed‐Forward” Network of DNA‐Related Reaction Cycles

In this study, a network of DNA‐related reaction cycles was established to enhance the sensitivity of lysozyme detection with dual signal amplification, and aptamer‐based reactions were integrated into this system to provide high specificity. The network was organized in a feed‐forward manner: the “upstream cycles” recognized the lysozyme (the target) and released the “messenger strands” from probe A (a DNA construct); the “downstream cycles” received them and then released the “signal strands” from another DNA construct, probe B, in multiplied quantities to that of the original inputted lysozyme. The upstream cycles centered on “target‐displacement polymerization”, which circulates the lysozyme to provide primary amplification; the downstream cycles centered on “strand‐displacement polymerization”, which circulates the messenger strand to provide further amplification. There were also several “nicking–polymerization” cycles in both reaction groups that provide extra signal amplification. In total, the network enclosed eight interconnected and autonomic reaction cycles, with only two probes, two primers, and two enzymes needed as raw feeds, and the network can be operated simply in one‐pot mode. With this network, lysozyme could be quantified at lysozyme concentrations as low as 2.0×10^?14 M , with a detection limit of 3.6×10^?15 M (3σ rule), which was seven orders of magnitude lower than that obtained without any amplification(1.8×10^?8 M ). Detection of lysozyme in real serum samples confirmed the reliability and practicality of the assay based on this reported reaction network.     

An Autonomous Bio‐barcode DNA Machine for Exponential DNA Amplification and Its Application to the Electrochemical Determination of Adenosine Triphosphate

A novel autonomous bio‐barcode DNA machine that is driven by template‐dependent DNA replication is developed to exponentially amplify special DNA sequences. Combined with a DNA aptamer recognition element, the DNA machine can be further applied in the aptamer‐based, amplified analysis of small molecules. As a model analyte, adenosine triphosphate (ATP) is determined by using the DNA machine system in combination with a DNA aptamer recognition strategy and differential pulse anodic stripping voltammetry (DPASV). Under the optimum conditions, detection limits as low as 2.8×10^?17 M (3σ) for target DNA and 4.7×10^?9 M (3σ) for ATP are achieved. The satisfactory determination of ATP in K562 leukemia cell and Ramos Burkitt’s lymphoma cell reveal that this protocol possesses good selectivity and practicality. As a promising biomolecular device, this DNA machine may have an even broader application in the rapidly developing field of nanobiotechnology.     

以氧化锌为锌源的手性金属-有机骨架的合成及其用于联糠醛外消旋体的选择性吸附

通过使用氧化锌代替传统的金属无机盐为锌源,制备了手性金属-有机骨架(CMOF)[Zn(L-mal)(H₂O)₂]_n并对其手性分离性能进行了考察。将ZnO和L-苹果酸按物质的量之比1∶1溶于水中,在室温下静置24 h即可得到[Zn(L-mal)(H₂O)₂]_n。以100 mg [Zn(L-mal)(H₂O)₂]_n为吸附剂,将250μL 1 g/L的联糠醛外消旋体加入其中,并以4.5 mL异丙醇和1 mL甲醇为萃取剂和洗脱剂进行选择性吸附实验,最终滤液使用高效液相色谱仪(HPLC)进行分析。结果表明,[Zn(L-mal)(H₂O)₂]_n对R-联糠醛具有较好的选择性吸附,其对映体过量(ee)值为20%。该工作为CMOF的绿色制备提供了一定的方法和经验并拓展了其在手性分离领域的应用。     

超高效亲水色谱-串联质谱法快速检测鸡肉及其制品中的利巴韦林及其代谢物的总残留量

建立了鸡肉及其制品中利巴韦林和磷酸化利巴韦林代谢物总残留量的亲水作用色谱-串联质谱分析方法(HILIC-MS/MS)。样品采用含1%(v/v)乙酸的乙腈超声提取,于37 ℃条件下以酸性磷酸酶酶解,正己烷除脂后用C₁₈与PSA填料分散固相萃取净化。采用酰胺基超高效亲水作用色谱柱,在乙腈和0.1%甲酸组成的梯度洗脱流动相中分离,在电喷雾正离子电离多反应监测模式下监测,结果表明,样品中利巴韦林残留量在1~200 μg/kg之间时,线性相关系数大于0.999,方法检出限(LOD, S/N≥3)为1 μg/kg,定量限(LOQ, S/N≥10)为5 μg/kg,在3个添加水平下的回收率为67.8%~112.7%,相对标准偏差为6.1%~13.6%。经测定多种实际样品,证明该方法简便、快速、准确,可以满足日常鸡肉及其制品中利巴韦林及其代谢物总残留量的分析要求。     

The electrode modified with Langmuir–Blodgett film of p-tert-butylcalix[4]arene derivatives with sulfur-containing functionalities for the determination of silver

A new voltammetric sensor, based on a new p-tert-butylcalix[4]arene derivative (TCAD) modified glassy carbon electrode (GCE) using Langmuir–Blodgett (LB) technique, was designed successfully and used for recognition and determination of Ag⁺. The π?-?A isotherms suggested that the monolayer of TCAD can coordinate with Ag⁺ at the air–water surface. Under the optimum experimental conditions, this voltammetric sensor shows a linear voltammetric response for Ag⁺ in the range of 1.0?×?10^?8?～?6.0?×?10^?6?mol?L^?1 with detection limit 5.0?×?10^?9?mol?L^?1. The high sensitivity, selectivity, and stability of this LB film modified electrode also demonstrate its practical application for a simple, rapid and economical determination of Ag⁺ in water sample.     

多孔芳香骨架吸附剂-固相萃取-高效液相色谱法同时测定辣椒粉中4种偶氮类染料

建立了固相萃取-高效液相色谱同时测定辣椒粉中对位红、酸性橙Ⅱ、苏丹红Ⅰ和苏丹红Ⅱ 4种偶氮染料的方法。以多孔芳香骨架-6（PAF-6）材料作为固相萃取吸附剂，考察并获得了影响自制固相萃取柱的萃取效率和吸附容量等主要因素。在优化条件下，4种目标分析物的检出限（LOD）为1.5~7.0 μg/L（信噪比S/N=3），定量限（LOQ）为5.0~22.1 μg/L（S/N=10），加标回收率为76.5%~89.8%，相对标准偏差（RSD）均不大于5.3%（n=6）。此外，基于量子化学计算，考察了PAF-6与目标分析物之间的相互作用机制，结果表明，目标分析物可以稳定地吸附在PAF-6分子上。该方法准确可靠，具有良好的回收率和较高的灵敏度，可用于辣椒粉中4种偶氮类染料的检测。     

单纯形自动优化的顺序注射分析系统

报道了具有自动优化功能的微机控制的顺序注射光度分析系统的研制。系统主要由注射汞、十位选择阀和带流通池的分光光度检测器构成。操作参数设定、数据采集和处理通过微机完成。采用改进单纯形方法进行系统优化,其算法集成到ＳＩＡ系统控制程序中使优化过程在微机的控制下自动完成。系统研究了ＳＩＡ钼蓝法测磷的操作条件对结果的影响。