Chemically tailorable colloidal particles from infinite coordination polymers

Micrometre- and nanometre-sized particles play important roles in many applications, including catalysis, optics, biosensing and data storage. Organic particles are usually prepared through polymerization of suitable monomers or precipitation methods. In the case of inorganic materials, particle fabrication tends to involve the reduction of a metal salt, or the controlled mixing of salt solutions supplying a metal cation and an elemental anion (for example, S2-, Se2-, O2-), respectively; in some instances, these methods even afford direct control over the shape of the particles produced. Another class of materials are metal-organic coordination polymers, which are based on metal ions coordinated by polydentate organic ligands and explored for potential use in catalysis, gas storage, nonlinear optics and molecular recognition and separations. In a subset of these materials, the use of organometallic complexes as ligands (so-called metalloligands) provides an additional level of tailorability, but these materials have so far not yet been fashioned into nano- or microparticles. Here we show that simple addition of an initiation solvent to a precursor solution of metal ions and metalloligands results in the spontaneous and fully reversible formation of a new class of metal-metalloligand particles. We observe initial formation of particles with diameters of a few hundred nanometres, which then coalesce and anneal into uniform and smooth microparticles. The ease with which these particles can be fabricated, and the ability to tailor their chemical and physical properties through the choice of metal and organic ligand used, should facilitate investigations of their scope for practical applications.     

有机碳源对氧化亚铁硫杆菌生长的影响

氧化亚铁硫杆菌为化能自养菌，嗜酸，通常生长于无机环境中。为了扩大其在有机环境中的应用，选择乙酸、丙酸和正丁酸三种低分子有机酸及葡萄糖作为氧化亚铁硫杆菌生之的有机环境，研究其在不同浓度不同有机物下的生长活性。实验结果显示：氧化亚铁硫杆菌在100mg／L低浓度的乙酸和400mg/L葡萄糖浓度范围内均能很好的生长，而在余下的几种有机物中生长则受到抑制。表明氧化亚铁硫杆菌并不是对所有的有机物都敏感，通过筛选和驯化能得到在有机环境中生长良好的菌株。     

Cementing mechanism of algal crusts from desert area

34-, 17-, 4-, 1.5-year old natural algal crusts were collected from Shapotou Scientific Station of the Chinese Academy of Sciences, 40-day old field and greenhouse artificial algal crusts were in situ developed in the same sandy soil and the same place (37°27′N, 104°57′E). Their different cohesions both against wind force and pressure were measured respectively by a sandy wind-tunnel experiment and a penetrometer. On the basis of these algal crusts, the cementing mechanism was revealed from many subjects and different levels. The results showed that in the indoor artificial crusts with the weakest cohesion bunchy algal filaments were distributed in the surface of the crusts, produced few extracellular polymers (EPS), the binding capacity of the crusts just accomplished by mechanical bundle of algal filaments. For field crusts, most filaments grew toward the deeper layers of algal crusts, secreted much more EPS, and when organic matter content was more than 2.4 times of chlorophyll a, overmuch organic matter (primarily is EPS) began to gather onto the surface of the crusts and formed an organic layer in the relatively lower micro-area, and this made the crust cohesion increase 2.5 times. When the organic layer adsorbed and intercepted amounts of dusts, soil particles and sand grains scattered down from wind, it changed gradually into an inorganic layer in which inorganic matter dominated, and this made the crusts cohesion further enhanced 2–6 times. For crust-building species Microcoleus vaginatus, 88.5% of EPS were the acidic components, 78% were the acidic proteglycan of 380 kD. The uronic acid content accounted for 8% of proteglycan, and their free carboxyls were important sites of binding with metal cations from surrounding matrix.     

聚合松香接枝功能基化合物的合成研究

采用常规加热法分别得到聚合松香接枝苏氨酸，酒石酸和柠檬酸的功能基化合物，并讨论了其合成条件．对软化点和红外进行了分析．聚合松香的接枝化舍物酸值增加，软化点降低，溶解度较大，还不适合做功能基高分子。需增大聚合松香接枝功能基化舍物的分子量和交联度．酸性强弱顺序与接枝的小分子酸酸性强弱相同，接枝酒石酸和柠檬酸化合物在有机溶剂中易溶，水中难溶．接枝苏氨酸化合物可以吸附铜铁钙三种金属离子．     

聚合松香接枝功能基化合物的合成研究

采用常规加热法分别得到聚合松香接枝苏氨酸,酒石酸和柠檬酸的功能基化合物,并讨论了其合成条件,对软化点和红外进行了分析.聚合松香的接枝化合物酸值增加,软化点降低,溶解度较大,还不适合做功能基高分子,需增大聚合松香接枝功能基化合物的分子量和交联度.酸性强弱顺序与接枝的小分子酸酸性强弱相同,接枝酒石酸和柠檬酸化合物在有机溶剂中易溶,水中难溶.接枝苏氨酸化合物可以吸附铜铁钙三种金属离子.     

北京市局部大气沉降颗粒表面成分分析

采用X射线光电子能谱（XPS）对大气沉降颗粒表面元素组成和元素的存在形式进行分析,发现其表面含有Al、Ca、Si等地壳元素和C、N、O等轻元素。Al、Si、Ca等地壳元素的原子数分数总和高达16.4%,表明大气颗粒物的沉降过程伴随着地壳元素的累积;元素S与N的原子数分数比值接近1,表明没有足够的碱性物质NH₃中和酸性物质SO₄^2-,沉降颗粒表面呈现酸性。结合高分辨率XPS图谱分析,发现沉降颗粒物表面的含碳物质以有机含碳化合物为主,同时存在少量的无定型碳;而氮元素则主要来源于以NO_x、NH₄⁺为主的无机氮和以吡啶氮为主的有机氮。     

小兴安岭松木醋液的生物活性及抑菌性能研究

为研究木醋液的综合利用技术,采用GC-MS法分析了小兴安岭松木醋液的有机成分,有机相中有机酸类占42.90%,酚类占26.68%。通过化学法分离木醋液分别得到活性组分有机酸类和[有机酸类+酚类],采用牛津杯法研究木醋液及分离活性组分对细菌的抑菌效果。结果表明,在较高浓度下对革兰氏性状不同的细菌均有明显的抑菌效果,活性组分[有机酸类+酚类]的抑菌效果普遍高于有机酸类,木醋液的抑菌活性组分是[有机酸类+酚类],以有机酸为主,酚类为辅,木醋液的抑菌效果优于市售化学品类消毒液,是一种很有应用前景的植物基抑菌剂。     

Effects of coagulation on submerged ultrafiltration membrane fouling caused by particles and natural organic matter （NOM）

Natural organic matter (NOM) and particles in source water are responsible for the majority of ultrafiltration (UF) membrane fouling that occurs during drinking water treatment. This study was conducted to (1) understand the UF membrane fouling phenomena caused by NOM and turbidity-causing particles and (2) investigate the effect of coagulation pretreatment on the alleviation of membrane fouling. In this study, kaolinite and humic acid (HA) were used to simulate the particles and NOM present in source water. The results revealed that the particles contributed to reversible fouling due to cake layer formation on the membrane surface, but that could be effectively reduced by increasing the frequency of physical backwashing. The results of the molecular weight (MW) distribution measurements, resin fractionation, SEM and FTIR analyses showed that HA primarily contributed to irreversible fouling. Taken together, the results of this study imply that the particles and NOM compounds present in source water may have different fouling behavior, and that particles may mitigate the irreversible fouling caused by HA. The addition of coagulant can lead to a higher rate of removal of large-sized hydrophobic compounds. Coagulation pretreatment can improve membrane performance and postpone membrane fouling development effectively, as well as retard the implementation of membrane chemical cleaning.     

电解法处理罗丹明B生产废水的工艺及机制研究

随着染料工业的不断发展,其生产过程中产生的废水已成为主要的工业水体污染源。采用电解法处理罗丹明B生产废水,首先研究了极板材料和电流密度对废水处理效果的影响,结果表明：分别以镍板和RuO₂-IrO₂-TiO₂/Ti钛网为阴、阳极,控制极间距3 cm,电流密度2.0 A/dm²,电解时间40 min,废水COD去除率可达44.3%,脱色率高达94.7%。然后通过H型电解槽实验和红外光谱对电解法处理罗丹明B生产废水的机制进行了探究,初步推断：阳极表面生成的氯气溶于水生成次氯酸,次氯酸氧化破坏废水中有机物分子的发色基团并促使其发生分解,生成的小分子有机物由于水溶性较差,被阳极表面生成的氯气以及阴极表面生成的氢气浮选出来,从而最终实现废水COD的降解和色度的去除。     

Complex organic matter in Titan's atmospheric aerosols from in situ pyrolysis and analysis

Aerosols in Titan's atmosphere play an important role in determining its thermal structure. They also serve as sinks for organic vapours and can act as condensation nuclei for the formation of clouds, where the condensation efficiency will depend on the chemical composition of the aerosols. So far, however, no direct information has been available on the chemical composition of these particles. Here we report an in situ chemical analysis of Titan's aerosols by pyrolysis at 600 degrees C. Ammonia (NH3) and hydrogen cyanide (HCN) have been identified as the main pyrolysis products. This clearly shows that the aerosol particles include a solid organic refractory core. NH3 and HCN are gaseous chemical fingerprints of the complex organics that constitute this core, and their presence demonstrates that carbon and nitrogen are in the aerosols.     

物理气相沉积法制备TP/TFA纳米薄膜与光致发光特性探究

为了探究有机荧光材料在微纳尺寸上的荧光特性，采用低真空物理气相沉积方法制备了茶碱（TP）和2，3，5，6-四氟对苯二甲酸（TFA）有机纳米薄膜。通过对TP和TFA薄膜的荧光性质进行表征发现：与TP粉末相比薄膜的荧光发射峰由1个增加到4个，发射波长范围拓宽了100 nm，TFA的荧光发射峰之间的相对荧光强度发生了变化，与原料粉末相比在408 nm处的荧光发射峰蓝移了7 nm，362 nm处的荧光发射峰红移了3 nm。另外随着纳米薄膜厚度的逐渐增加，其荧光效率也逐渐增大。通过对TP和TFA纳米薄膜的表面形貌表征发现：随着薄膜厚度的增加，颗粒的聚集形态尺寸逐渐增大，从而验证了荧光效率随膜厚增加而逐渐提升的特性。     

Atmospheric science: marine aerosols and iodine emissions

O'Dowd et al. describe the formation of marine aerosols from biogenic iodine and the growth of these aerosols into cloud-condensation nuclei (CCN). Based on chamber and modelling results, the authors suggest that biogenic organic iodine compounds emitted from macroalgae may be responsible for coastal particle bursts and that production of these compounds in the open ocean could increase CCN there too. It has since been shown that coastal particles are more likely to be produced from the photooxidation of molecular iodine. Moreover, I contend that open-ocean particle production and cloud enhancement do not result from emissions of organic iodine at atmospheric levels. For iodine particles to affect cloud properties over the remote ocean, an additional source of iodine is necessary as organic precursors cannot be responsible.     

Photochemical cycling of iron in the surface ocean mediated by microbial iron(III)-binding ligands

Iron is a limiting nutrient for primary production in large areas of the oceans. Dissolved iron(III) in the upper oceans occurs almost entirely in the form of complexes with strong organic ligands presumed to be of biological origin. Although the importance of organic ligands to aquatic iron cycling is becoming clear, the mechanism by which they are involved in this process remains uncertain. Here we report observations of photochemical reactions involving Fe(III) bound to siderophores--high-affinity iron(III) ligands produced by bacteria to facilitate iron acquisition. We show that photolysis of Fe(III)-siderophore complexes leads to the formation of lower-affinity Fe(III) ligands and the reduction of Fe(III), increasing the availability of siderophore-bound iron for uptake by planktonic assemblages. These photochemical reactions are mediated by the alpha-hydroxy acid moiety, a group which has generally been found to be present in the marine siderophores that have been characterized. We suggest that Fe(III)-binding ligands can enhance the photolytic production of reactive iron species in the euphotic zone and so influence iron availability in aquatic systems.     

生产废水清液和二次凝水回用对燃料乙醇发酵的影响

为研究燃料乙醇生产废水回用的可行性,以燃料乙醇生产发酵过程中产生的清液和二次凝水为研究对象,分析其有机酸组成,并研究单一有机酸和经D318离子交换树脂处理前后的清液和二次凝水对酿酒酵母Saccharomyce cerevisiae NJ-2019生长和发酵生产乙醇的影响。结果显示,乙酸、乳酸、丙酸和柠檬酸是清液中的主要有机酸,乙酸和乳酸是二次凝水中的主要有机酸;乳酸和丙酸对酿酒酵母Sc.erevisiae NJ-2019的生长和发酵过程表现出显著抑制作用,其最低抑制浓度分别为7.0g/L和1.0g/L;清液和二次凝水分别直接回用时,清液对乙醇发酵过程的抑制作用更强;去除或者部分去除有机酸能使清液和二次凝水回用时的乙醇产量分别提高10.11%和9.85%。燃料乙醇发酵过程产生的清液和二次凝水具有回用的潜力,有利于实现乙醇生产过程节能减排。     

催化降解水中有机污染物生成CO2的测定

设计了一套简易的装置和改进的方法来检测催化降解有机污染物过程中最终矿化所产生二氧化碳的量.利用四氮杂卟啉铁(FePz(dtn)4)负载在离子交换树脂上来活化分子氧降解了水中难降解的有机污染物--对硝基苯甲酸(NBA).采用饱和的氢氧化钡溶液来吸收有机物降解反应中所产生的二氧化碳,同时用沉淀分离滴定法来测定生成二氧化碳的量,即可计算出有机污染物降解的矿化率,其方法误差为4.2%.实验表明:在可见光光照7h后,对硝基苯甲酸碱性溶液中的矿化率可达到11.3%.     

聚环氧琥珀酸对纳米碳酸钙粒子的分散作用

采用自然沉降法和吸光光度法,研究了聚环氧琥珀酸（PESA）等高分子物质对粒径为60nm的碳酸钙粉体在水溶液中的分散行为,然后对它们进行复配,并对复配配方的分散性和稳定性进行了研究。研究结果表明PESA对纳米碳酸钙的分散性最好,其次为聚丙烯酸钠、丙烯酸-丙烯酸酯-膦酸-磺酸盐四元共聚物、丙烯酸-丙烯酸酯-磺酸盐和丙烯酸-2-甲基-丙烯酰胺基丙磺酸类共聚物。对PESA与其他几种分散剂进行复配,其中加入与碳酸钙的质量比为1.8%的ESA、0.7%的六偏磷酸钠和0.1%的十二烷基硫酸钠3元复配的分散性能和稳定性最佳。     

润滑油溶剂精制过程中有机酸分布的研究

用毛细管气相色谱－质谱联用的方法对润滑剂精制过程中回收循环溶剂Ｎ－甲基砒咯烷酮中残留的有机酸酯化物和直接从原油 分离出的有机酸的甲酯化物进行了研究；前者色谱分离出了２６个甲酯峰，ＧＣ／ＭＳ确定了其中的１７个主要成份，占有机酸甲酯总量的９０．８１％；后者色谱分离出了２９个甲酯峰，ＧＣ／ＭＳ确定了其中的２０个主要成份，占有机酸甲酯总量的９２．１１％；对前者色谱还分离出一个二重峰，占整个样品总量的９６．     

γ辐照后30% TRPO-煤油对钚的萃取与保留

研究了 6 0 Co源辐照剂量及辐照前预平衡硝酸浓度对 30 % TRPO-煤油对 Pu的萃取行为的影响。测定了用 0 .6mol/L草酸反萃后有机相中保留的 Pu的百分率。比较了辐照后 30 % TRPO-煤油分离得到的碱萃物、水萃物及中性物3种组分对 Pu的保留情况以及酸性辐解产物二烷基膦酸和一烷基膦酸对 Pu的萃取和保留的影响。结果表明 ,辐照剂量对 Pu分配比影响较大而预平衡酸度的影响较小 ;Pu保留随剂量的增加而增大。辐照后分成的 3种组分中中性聚合物引起的保留最多 ;一烷基膦酸及二烷基膦酸对 Pu的萃取与保留的影响都很小     

氢化物发生-原子荧光光谱法测定大气颗粒物中的砷形态

采用氢化物发生原子荧光法直接测定不同粒径大气颗粒物中As(Ⅲ)和As(Ⅴ)的含量.研究了还原剂用量、酸介质及其酸度、载气及屏蔽气流量和观测高度等对荧光强度的影响,探讨了共存离子对砷测定的干扰.在选定的最佳条件下,得到检出限为0.34μg/L,方法检出限为0.21μg/g,加标回收率为98.18%～102.54%,相对标...     

TiO2的有机改性及其电泳性能

以改性的TiO₂粒子为显色粒子，四氯乙烯为分散介质，油溶红为染料，加入分散剂制备了电泳显示液。选用不同类型的有机表面活性剂和硅烷偶联剂对纳米TiO₂粒子进行表面改性。用红外光谱（FT-IR）表征了改性粒子的表面组成和结构，并通过透射电镜（TEM）观察了粒子的形态、粒径及分散情况。采用静态沉降法考察了改性后的粒子在四氯乙烯中的分散稳定性，并利用自行设计的电泳仪对粒子的电场响应特性进行了测试。结果表明，用阴离子表面活性剂十二烷基苯磺酸钠(SDBS)改性的粒子其分散稳定性和带电性最好。随后探讨了SDBS用量和反应时间对粒子分散性和带电性的影响，得到改性的最佳工艺条件为：改性剂用量为TiO₂含量的15%，反应时间为1h。改性后的粒子分散性和带电性有明显的提高，粒子对电场有可逆响应且具备一定的双稳性。