森林流域单元水文模型的构建与应用

目前全球缺水、水污染、洪涝灾害以及水土流失仍然非常严重，尤其在我国北方地区。流域水文模型可用来进行不同需水管理的情景分析，为解决我国水问题提供科学依据。分布式水文模型是流域水文模型的发展方向，具有显著特点：1）应用前景广泛，不仅可以模拟流域水文过程，还可以协助模拟泥沙或污染物的运移过程，为水利工程设计、水土保持、环境保护等领域提供技术支持；2）能够预测流域土地利用或气候变化下的流域水文响应过程变化，为管理部门提供决策支持；3）模型所需要的参数全部具有物理意义，可通过实际测量确定，适合模拟实测系列较短或是无观测流域的水文过程；4）对于目前国际水文界的前沿问题—水文尺度转换提供了一种有效的解决途径。 然而分布式水文模型还不完善，如1)真实性问题。对一些水文过程和边界条件还不确定。2)尺度转换问题。目前很少考虑尺度对参数有效性的影响。3)检验问题。还无法判断对有些难以测量的水文状态变量的模拟正确与否。4)计算时间和数据存储的问题。有些分布式水文模型虽然具有很强的水文物理基础和完善的模型结构，但是计算时间过长和(或)数据存储过大，难以应用。上述问题的核心就是对分布式水文模型的核心—单元水文模型的研究不够，需要为进一步完善单元水文模型进行研究。 本文采用饱和入渗理论、Saint-Venant方程、Richards方程、Penman-Monteith方程等等构建了以有限差分法求解的适用于森林流域的单元水文模型，并通过实验室模拟试验和坡地径流场资料进行了验证，主要结论为： 通过不同坡度和不同雨强下的室内坡面产汇流实验模拟，表明：该模型模拟的坡面流和壤中流过程与实测过程基本一致，峰现时间、径流历时、峰值流量、出流总量模拟值与实测值的相对误差均较小，基本小于10%。模型的模拟精度较高，实用性较强，为深入研究壤中流机制和改进流域降雨-径流模型提供了理论依据。 通过坡地径流观测场实测资料的验证，表明：该模型模拟的坡面流过程精度较高，累计流量的精度更高于小时过程的精度，离差系数、效率系数、确定系数均较理想，具有应用价值，有助于改善分布式水文模型在森林流域的模拟效果。

Novel temperature- and pH-responsive graft copolymers composed of poly(L-glutamic acid) and poly(N-isopropylacrylamide)

A series of novel temperature- and pH-responsive graft copolymers, poly(L-glutamic acid)-g-poly(N-isopropylacrylamide), were synthesized by coupling amino-semitelechelic poly(N-isopropylacrylamide) with N-hydroxysuccinimide-activated poly(L-glutamic acid). The graft copolymers and their precursors were characterized, by ESI-FTICR Mass Spectrum, intrinsic viscosity measurements and proton nuclear magnetic resonance (H-1 NMR). The phase-transition and aggregation behaviors of the graft copolymers in aqueous solutions were investigated by the turbidity measurements and dynamic laser scattering.

Novel pH- and temperature-responsive block copolymers with tunable pH-responsive range

A series of novel pH- and temperature-responsive diblock copolymers composed of poly(N-isopropylacrylamide) (PNIPAM) and poly[(L-glutamic acid)-co-(gamma-benzyl L-glutamate)] [P(GA-co-BLG)] were prepared. The influence of hydrophobic benzyl groups on the phase transition of the copolymers was studied for the first time. With increasing BLG content in P(GA-co-BLG) block, the thermal phase transition of the diblock copolymer became sharper at a designated pH and the critical curve of phase diagram of the diblock copolymer shifted to a higher pH region.

Ion-Responsive Behavior of Ionic-Liquid Surfactant Aggregates with Applications in Controlled Release and Emulsification

We propose a simple but efficient, rapid, and quantitative ion-responsive micelle system based on counter-anion exchange of a surfactant with an imidazolium unit. The ion-exchange reaction results in the amphiphilic-to-hydrophobic transition of the imidazolium salt, leading to the destruction of the micelles, which has been successfully applied to control led release and emulsification.

Effect of block sequence and block length on the stimuli-responsive behavior of polyampholyte brushes: hydrogen bonding and electrostatic interaction as the driving force for surface rearrangement

Diblock polyampholyte brushes with different block sequences (Si/SiO2/poly(acrylic acid)-b-poly (2-vinylpyridine) (PAA-b-P2VP) brushes and Si/SiO2/P2VP-b-PAA brushes) and different block lengths were synthesized by sequent surface-initiated atom transfer radical polymerization (ATRP). The PAA block was obtained through hydrolysis from the corresponding poly(tert-butyl acrylate). The polyampholyte brushes demonstrated unique pH-responsive behavior. In the intermediate pH region, the brushes exhibited a less hydrophilic wetting behavior and a rougher surface morphology due to the formation of polyelectrolyte complex through electrostatic interaction between oppositely charged blocks. In the low pH and high pH regions, the rearrangement of polyampholyte brushes showed great dependence on the block sequence and block length. The polyampholyte brushes with P2VP-b-PAA sequence underwent rearrangement during alternative treatment by acidic aqueous solution (low pH value) and basic aqueous solution (high pH value).

Synthesis of biodegradable thermo- and pH-responsive hydrogels for controlled drug release

Novel intelligent hydrogels composed of biodegradable and pH-sensitive poly(L-glutamic acid) (PGA) and temperature sensitive poly(N-isopropylacrylamide-co-2-hydroxyethyl methacrylate) (PNH) were synthesized and characterized for controlled release of hydrophilic drug. The influence of pH on the equilibrium swelling ratios of the hydrogels was investigated. A higher PNH content resulted in lower equilibrium swelling ratios. Although temperature had little influence on the swelling behaviors of the hydrogels, the changes of optical transmittance of hydrogels as a function of temperature were marked, which showed that the PNH part of hydrogel exhibited hydrophobic property at temperature above the lower critical solution temperature (LCST). The biodegradation rate of the stimuli-sensitive hydrogels in the presence of enzyme was directly proportional to the PGA content. Lysozyme was chosen as a model drug and loaded into the hydrogels.

A Simple, Universal Colorimetric Assay for Endonuclease/Methyltransferase Activity and Inhibition Based on an Enzyme-Responsive Nanoparticle System

An enzyme responsive nanoparticle system that uses a DNA-gold nanoparticle (AuNP) assembly as the substrate has been developed for the simple, sensitive, and universal monitoring of restriction endonucleases in real time. This new assay takes advantage of the palindromic recognition sequence of the restriction nucleases and the unique optical properties of AuNPs and is simpler than the procedure previously described by by Xu et al. (Angew. Chem. Int. Ed. Engl. 2007, 46, 3468-3470). Because it involves only one type of ssDNA modified AuNPs, this assay can be directed toward most of the endonucleases by simply changing the recognition sequence found within the linker DNA. In addition, the endonuclease activity could be quantitatively analyzed by the value of the reciprocal of hydrolysis half time (t(1/2)(-1). Furthermore, our new design could also be applied to the assay of methyltransferase activity since the methylation of DNA inhibits its cleavage by the corresponding restriction endonuclease, and thus, this new methodology can be easily adapted to high-throughput screening of methyltransferase inhibitors.