不同尺寸COM、COD对阳离子表面活性剂CTAB的吸附性质差异

为比较研究不同纳微米尺寸的一水草酸钙(COM)和二水草酸钙(COD)晶体对阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)的吸附差异, 探讨抑制剂对结石形成的抑制机理, 本研究测定了各浓度CTAB下不同尺寸COM或COD对CTAB的吸附量; 采用XRD和FT-IR表征吸附前后晶体是否发生晶相改变; 采用Zeta电位仪测定吸附后晶体表面的Zeta电位随CTAB浓度的变化。结果发现, 随着c(CTAB)浓度升高, 3 μm和10 μm的COM、COD晶体的吸附曲线由上升段和平台段组成, 而小尺寸的50 nm、100 nm、1 μm的COM、COD晶体的吸附曲线为直线型。随着晶体尺寸的增大, COM和COD晶体的吸附量依次降低。当尺寸相同时, COM对CTAB的吸附量要大于COD, 归因于CTAB更容易选择吸附在COM表面负电荷的区域。上述结果表明, 草酸钙晶体对阳离子表面活性剂的吸附量与比表面积和晶体的晶面结构有关。晶体尺寸越小, 比表面积越大, 晶面暴露的草酸根密度越大, CTAB的吸附量越大, 导致晶体表面Zeta电位绝对值增大, 静电排斥力增强, 从而抑制尿微晶的聚集, 有利于抑制草酸钙结石的形成。     

凝胶体系中混合羧酸钾对草酸钙结晶的调控作用

酒石酸钾(K₂tart)、柠檬酸钾(K₃cit)和乙二胺四乙酸钾(K₂edta)均可用于防治草酸钙(CaOxa) 结石, 但它们各有其优缺点. 本文采用双扩散法比较研究了这3种羧酸钾以不同比例两两混合时对CaOxa结晶的影响, 结果表明, 混合剂或者能够诱导更多的二水草酸钙(COD)和三水草酸钙(COT)晶体, 或者减小一水草酸钙(COM)的尺寸, K₂edta-K₃cit混合剂还能诱导(100)晶面减小、螺旋式生长的COD晶体, 该COD与肾小管细胞膜的粘附力较弱. 这些均有利于抑制草酸钙结石形成, 表明混合剂的防石效果优于单一钾盐.     

聚丙烯酰胺/聚甲基丙烯酸(2-甲基氨基)乙酯高强度双网络水凝胶的制备及pH响应性

利用两步法合成了聚丙烯酰胺(PAM)/聚甲基丙烯酸(2-甲基氨基)乙酯(PDMAEMA)双网络水凝胶,第一网络为锂藻土(Laponite)物理交联的PAM纳米复合水凝胶,第二网络为化学交联剂N,N-亚甲基双丙烯酰胺(BIS)交联PDMAEMA。研究了2种网络相对含量、纳米黏土Laponite用量、化学交联剂BIS用量对水凝胶强度和pH响应性的影响。研究结果表明,PAM/PDMAEMA双网络水凝胶具有高强度,改变单体AM和DMAEMA的配比、交联剂的用量,其拉伸强度在36～91.9 kPa范围内可调。PAM/PDMAEMA双网络水凝胶还具有灵敏的pH刺激响应性,在pH=4时双网络水凝胶溶胀度急剧下降。     

氨羧钾调控草酸钙晶体生长及其与分子结构的关系

采用扫描电子显微镜(SEM)和X射线衍射(XRD)在凝胶体系中研究了不同结构氨羧钾对草酸钙(CaOxa)结晶的影响,这些氨羧钾包括氨基乙酸钾(KGLY)、乙二醇二乙醚二胺四乙酸二钾(K2EGTA)、氨基三乙酸二钾(K2NTA)、二乙三胺五乙酸二钾(K2DTPA)、乙二胺四乙酸二钾(K2EDTA)和环已二胺四乙酸二钾(K2CDTA).这些物质均能诱导二水草酸钙(COD)形成,抑制一水草酸钙(COM)聚集和减小COM的比表面积,其诱导COD能力依次为:K2DTPA(55wt%)K2EDTA≈K2CDTA(50wt%)K2NTA(43wt%)K2EGTA(4wt%)KGLY(2wt%),抑制COM聚集的能力依次为:K2DTPAK2NTAK2CDTA≈K2EDTAK2EGTAKGLY.从氨羧盐的分子结构、羧基的相对含量、羧基的空间位置、与钙离子的配位能力及其配位方式等角度讨论了其抑制COM聚集和诱导COD形成的化学基础.结果表明K2NTA和K2DTPA有可能成为防止草酸钙结石形成的潜在药物.     

低温等离子体高效净化含PAM废水工艺研究

采用低温等离子体技术处理含聚丙烯酰胺(PAM)废水,研究了放电电压、放电时间、溶液pH对不同浓度PAM溶液化学需氧量(COD)降解率的影响规律,同时还研究了不放电条件下PAM溶液pH以及放电条件下放电时间对不同浓度PAM溶液黏度去除率的影响,考察了放电条件下pH对质量浓度1.0g/L PAM溶液黏度去除率的影响规律。通过正交试验确定影响PAM溶液COD降解率的主次顺序为:放电时间>放电电压>溶液浓度>溶液pH。在放电时间5h、放电电压40kV、PAM溶液质量浓度1.0g/L、pH=1.5时,COD降解率最佳,可达85.74%。     

EDTA对α半水脱硫石膏晶体形貌的影响及调晶机理研究

采用SEM研究了乙二胺四乙酸(EDTA)对α半水脱硫石膏晶体形貌的影响、EDTA在α半水石膏表面的吸附作用,分析了EDTA的调晶机理。结果表明,EDTA能显著改变α半水石膏晶体形貌,使其从长棒状转变为短柱状,且晶体尺寸增大;EDTA调晶效果对pH值比较敏感,在中性范围内EDTA有最佳调晶效果;Al 3+会影响ED-TA的调晶效果,为了得到最佳的调晶效果,要控制溶液中的杂质金属离子含量;EDTA通过与Ca2+的络合反应吸附于α半水石膏晶体(111)晶面上,抑制晶体在C轴方向的生长,从而改变各个晶面的相对生长速率,使α半水石膏晶体形貌发生变化。     

铅酸蓄电池废水反渗透处理浓水的沉淀去除工艺开发

采用调节pH值、依次加入硫化钠、硫酸亚铁、聚合氯化铝、聚丙烯酰胺工艺,对铅酸电池厂反渗透处理浓水进行铅离子、镉离子的有效去除,进行了详细深入的研究.结果表明,浓水pH调节为9.5,依次加入200mg/L Na2S、50mg/L FeSO4、10mg/L聚合氯化铝(PAC)、5mg/L聚丙烯酰胺(PAM)时,浓水中Pb2+、Cd2+被沉淀剂去除效率达最高,分别为98.2%、95.8%.反渗透浓水处理后的水质,达到地表水三级排放标准.该浓水处理方法具有操作简便、成本低廉、处理工艺稳定可靠的特点,解决了反渗透浓水难以处理的难题.反渗透浓水处理成本为4元/m3.     

分子间相互作用调控丝素蛋白/聚丙烯酰胺水凝胶的网络形貌和β片结晶，赋予水凝胶优异的黏附、应变和传感性能（英文）

丝素蛋白(SF)作为一种特殊的天然聚合物,具有优异的生物相容性、生物降解性和双亲性,是制备柔性传感器的良好候选者.然而,丝素蛋白的高结晶度和结晶不可控性使获得这种出色的仿生水凝胶传感器具有挑战性.纯SF水凝胶是脆性的,没有黏性.在此,我们通过引入聚丙烯酰胺(PAM)到SF水凝胶中来解决这一问题.由于SF/PAM水凝胶具有较强的分子间相互作用,其网络形貌由欧几里得孔改变为非欧几里得孔.同时,其β片结晶很容易被抑制到纳米尺度.这些演变不仅使SF/PAM水凝胶具有优异的机械性能,而且具有出色的黏附性能.与纯PAM水凝胶相比,SF8/PAM水凝胶的拉伸强度、拉伸破坏应变、抗压强度(80%应变下)和黏附性能(在猪皮上)分别提高了133.1%、120.9%、610.8%和104.8%.此外,SF的双亲性可以使碳纳米管(CNTs)在水凝胶中分散良好.制备的CNT0.3/SF8/PAM水凝胶继承并进一步改善了上述性能.除此之外,它还表现出优异的自黏附传感性能,最大灵敏度因子高达10.13,工作应变范围超过1000%,大应变下稳定循环拉伸达500次以上.同时,六种人类活动的精确检测也得到了验证.本工作为...     

聚丙烯酸钠/纳米纤维素晶体-g-聚丙烯酰胺复合高吸水性树脂的制备与表征EI北大核心CSCD

先用铈(Ⅳ)盐引发丙烯酰胺(AM)在纳米纤维素晶体(NCC)表面接枝聚合,接枝产物NCC-g-PAM可稳定地分散在丙烯酸钠/丙烯酸混合单体水溶液中,然后以N,N-亚甲基双丙烯酰胺作交联剂通过原位光聚合制得聚丙烯酸钠(PAANa)/NCC-g-PAM复合高吸水性树脂。用红外光谱、X射线衍射、元素分析等方法对NCC-g-PAM进行了表征,通过红外光谱、扫描电镜、溶胀实验考察了NCC-g-PAM的添加对高吸水性树脂结构、形貌和吸水性能的影响。结果表明,NCC-g-PAM中NCC的晶态结构未改变,聚丙烯酰胺(PAM)的含量为59.54%。PAANa/NCC-g-PAM复合高吸水性树脂具有丰富的网孔结构,NCC-g-PAM中的PAM链与PAANa基体间形成了氢键。与PAANa高吸水性树脂相比,PAANa/NCC-g-PAM复合高吸水性树脂的吸水倍率和吸水速率均有所增加,吸水倍率最高可达3000 g/g,是PAANa的3.2倍,吸生理盐水倍率最高可达139 g/g,是PAANa的2.5倍。     

一种新的制膜方法

诱导成膜聚合反应是一种新型的、不同于局部化学聚合的固态晶相光聚合反应。它的特点是一般乙烯基单体在其它无定型聚合物的诱导下成膜,结晶、并在紫外光照射下聚合而成为晶态聚合物薄膜。用这种方法,可以制得晶态聚合物与无定型聚合物的交叉复合膜。PAM—G 膜就是用这种方法制得的晶态聚丙烯酰胺与明胶的复合膜,这是一联一次成型的新颖的非对称膜。在渗透蒸发分离技术中,用它分离乙醇—水混合液时,可获得十分满意的分离效果。文中,对丙烯酰胺的聚合反应和复合膜PAM—G 的结构也分别进行了红外光谱检定和光学显微镜、电子显微镜的观测。还对诱导成膜聚合的可能机理以及PAH—G 膜的高效分离作用进行了初步的分析与讨论。     

Elucidating the role of hyaluronic acid in the structure and morphology of calcium oxalate crystals

Recent surge in reports describing new additives that inhibiting the growth and nucleation of calcium oxalate (CaOx), the most common component of renal calculi or kidney stones, have rekindled interest in CaOx crystallization. In this in vitro study, the effect of hyaluronic acid (HA), a protein commonly found in urine, on the morphology and phase of the CaOx crystals is investigated. CaOx crystals were crystallized at pH 5.8 and 37 °C with a [Ca²⁺]:[C₂O₄^2-] ratio of 20:1, which is close to physiological conditions, in aqueous solution and artificial urine media. The obtained crystals were characterized structurally, morphologically and in terms of their surface charge. The crystals precipitated in aqueous solution without the HA additive were pure phase calcium oxalate monohydrate (COM) crystals with typical hexagonal morphology. The addition of HA partially promotes the transformation of COM into calcium oxalate dihydrate (COD) in aqueous solution. However, the only solid phase to form in artificial urine media with and without HA was identified as COD with tetragonal bipyramidal morphology. The results of this investigation will contribute to the understanding of the role HA plays on the morphology, structure, and thermal characteristics of CaOx and ultimately facilitate the development of effective treatments for kidney stones.     

Effects of temperature on growth and aggregation of calcium oxalate in presence of various carboxylic acids in silica gel systems

The effect of monocarboxylic acetic acid (HAc), dicarboxylic tartaric acid (H₂tart), and tricarboxylic citric acid (H₃cit) on growth and aggregation of calcium oxalate (CaOxa) crystals was investigated in gel at different temperature. Calcium oxalate dihydrate (COD) crystals were induced under the conditions of low temperature and in the presence of di- and tricarboxylic acids. The calcium oxalate monohydrate (COM) crystals were more rounded and blunt in the presence of H₃cit and H₂tart. If more COD or more COM crystals with round tips and edges can be induced, CaOxa stones can be inhibited.     

Circular patterns of calcium oxalate monohydrate induced by defective Langmuir–Blodgett film on quartz substrates

The defective Langmuir–Blodgett (LB) film of dipalmitoylphosphatidylcholine (DPPC) on quartz injured by potassium oxalate (K₂C₂O₄) was used as a model system to induce growth of calcium oxalate crystals. Atomic force microscopy (AFM) indicated that circular defective domains with a diameter of 1–200 μm existed in the LB film. Scanning electron microscopy (SEM) showed circular patterns of aggregated calcium oxalate monohydrate (COM) crystallites were induced by these defective domains. It was ascribed to that the interaction between the negatively-charged oxalate ions and the phosphatidyl groups in DPPC headgroups makes the phospholipid molecules rearranged and exist in an out-of-order state in the LB film, especially at the boundaries of liquid-condensed (LC)/liquid-expanded (LE) phases, which provide much more nucleating sites for COM crystals.     

Crystallization rules of calcium oxalate crystals in lithogenic urine and in healthy urine in vitro

Crystallization of calcium oxalate (CaOxa) was comparatively studied in vitro in diluted lithogenic urine and in diluted healthy urine by means of scanning electron microscopy (SEM), X-ray diffraction (XRD), and Fourier transform infrared (FT-IR) spectroscopy. In healthy urine, the crystallization was a growth-controlled process in the early stage of crystallization and a nucleation-controlled process in the middle and late stage. However, the crystallization of CaOxa was always a growth-controlled process in the lithogenic urine. That is, the size of CaOxa particles grow gradually and at last large size of CaOxa stones formed. Comparing the CaOxa crystals grown in lithogenic urine and in healthy urine, three differentiations were observed. First, the average particle size of CaOxa crystals precipitated in lithogenic urine is larger than that in healthy urine. Second, the morphology of calcium oxalate monohydrate (COM) crystals changes from sharp hexagonal in lithogenic urine to round and blunt in healthy urine. Third, calcium oxalate dihydrate (COD) crystals were induced in healthy urine. The results in this study may provide important clues to cure urinary stones.     

Degradation of sulfated polysaccharide extracted from algal Laminaria japonica and its modulation on calcium oxalate crystallization

Sulfated polysaccharide (LPS) extracted from alga Laminaria japonica was degraded by hydrogen peroxide (H₂O₂). The average molecular weight of LPS was apparently decreased from 172,000 to 9550 after degradation, while the proportion of sulfate groups (–OSO₃^?) and carboxylic groups (–COO^?) in the molecular chains of LPS were slightly decreased from 4.5% and 5.20% to 3.9% and 4.64%, respectively. The effects of degraded and natural LPS on formation of calcium oxalate (CaOxa) crystals were investigated in vitro using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), zeta-potential, and atomic absorption spectroscopy. LPS could increase the concentration of soluble Ca²⁺ ions in the solution, decrease the weight of precipitated CaOxa, and increase the negative value of zeta-potential of CaOxa crystals. LPS also inhibits the formation of thermodynamically stable calcium oxalate monohydrate (COM) crystals, while inducing and stabilizing metastable calcium oxalate dihydrate (COD) crystals. These results suggested that both degraded and natural LPS could decrease CaOxa crystallization, but the inhibition efficiency of the degraded LPS was clearly superior to that of the natural LPS. We expected this investigation would provide encouragement for further exploration into new drugs for the prevention and treatment of urolithiasis.     

Comparative investigations of ultrafine crystals in urine of healthy human and lithogenic patients

The ultrafine crystals in urine of lithogenic patients and healthy human were investigated by transmission electron microscopy (TEM), selected-area electron diffraction (SAED), X-ray diffraction (XRD) and Fourier transform infrared (FT-IR) spectroscopy. Phosphates and calcium oxalate monohydrate (COM) were present in urine of both healthy human and lithogenic patients. In urine of healthy human, the ultrafine crystals were well dispersed and more rounded, their size was smaller. However, the ultrafine crystals in lithogenic urine were highly aggregated. These results were explained by the difference of the concentration and activity of urinary inhibitors. The inhibitors in healthy urine have strong ability to inhibit the growth and aggregation of urinary crystals, making the edges and tips of these crystals more rounded.     

Mediation of calcium oxalate crystal growth on human kidney epithelial cells with different degrees of injury

The current study examined the role of injured human kidney tubular epithelial cell (HKC) in the mediation of formation of calcium oxalate (CaOxa) crystals by means of scanning electronic microscopy and X-ray diffraction. HKC was injured using different concentrations of H₂O₂. Cell injury resulted in a significant decrease in cell viability and superoxide dismutase (SOD) concentration and an increase in the level of malondialdehyde (MDA) and expression of osteopontin (OPN). Injured cells not only promote nucleation and aggregation of CaOxa crystals, but also induce the formation of calcium oxalate monohydrate (COM) crystals that strongly adhere to cells. These results imply that injured HKCs promote stone formation by providing more nucleating sites for crystals, promoting the aggregation of crystals, and inducing the formation of COM crystals.