有机化学实验教学资源的建设与实践

教学资源建设是高校教学改革的一项重要工作。以提高实验教学质量和培养创新能力为目标,探索了我校有机化学实验教学资源的建设内容,并通过网络平台用于辅助教学。视频资源,有效地提高了课前预习效果;课件资源,培养了学生的实验设计思想和创新能力;拓展资源,开拓了学生的视野,提高了化学实验兴趣;在线测试题库资源,有效准确地检验了学生的理论水平。教学资源通过实践应用,教学效果明显,切实提高了教学质量。     

QuEChERS/超高效液相色谱-串联质谱法同时测定水产品中四溴双酚A与六溴环十二烷

建立了同时测定水产品中四溴双酚A(TBBPA)和六溴环十二烷(HBCD)的超高效液相色谱-串联质谱方法。样品前处理采用QuEChERS方法,均质生物样品用水分散后加乙腈提取,经C_(18)分散固相萃取净化。采用CORTECS~?C_(18)色谱柱(4.6 mm×100 mm×2.7μm)分离,以甲醇-水为流动相进行梯度洗脱,流速为0.7 mL/min。采用电喷雾离子源,在负离子模式下以多反应监测(MRM)方式检测。结果表明,TBBPA和3种HBCD单体在0.5～500μg/L范围内线性良好,相关系数(r)大于0.998,检出限(LOD,S/N=3)和定量下限(LOQ,S/N=10)分别为0.04～0.16μg/kg和0.12～0.55μg/kg。在5、20、50μg/kg加标水平下的平均回收率为74.0%～121%,相对标准偏差(RSD)为0.20%～23%。该方法操作简单、快速、重现性好,适用于水产品中TBBPA和HBCD的快速检测。     

柱前衍生毛细管电泳-电致化学发光法测定瓜瓤组织中的瓜氨酸含量

以甲醛和硼氢化钠为主要衍生反应试剂,对瓜氨酸分子中的α-氨基进行N-甲基化得到具有强电致化学发光信号的单一衍生产物。据此建立了一种用毛细管电泳-电致化学发光法(CE-ECL)高选择性测定瓜瓤组织中瓜氨酸含量的新方法。在优化的实验条件下,瓜氨酸的衍生物可在5 min内达到电泳分离,且瓜氨酸浓度在9.0～250μmol/L范围内时,其衍生物的电泳峰强度值与待测浓度间呈良好的线性关系(r~2=0.999 6),检出限(S/N=3)为3.2μmol/L。对同一标准样品平行进样6次,测得其电泳峰强度值和迁移时间值的相对标准偏差分别为2.6%和0.92%。此外,采用标准加入法对4种鲜瓜瓤组织中的瓜氨酸进行了定量测定,结果表明西瓜、甜瓜、籽瓜、哈密瓜的鲜瓜瓤组织中瓜氨酸的含量分别为2.75、0.95、1.26、1.19 mg/g,对实际样品的加标回收率为91.4%～106%。     

酸洗脱灰处理对新疆和丰低阶煤结构和萃取性能的影响

对新疆和丰低阶煤样进行酸洗脱灰处理,通过相关表征,分析了脱灰处理对煤样主体结构、石油醚和CS₂萃取性能的影响。FT-IR表征表明,煤样经酸洗脱灰处理,结构仅发生了微弱改变,酸洗煤样（AC）仅在1712 cm^-1处出现了较弱的原煤样（RC）所没有的羧酸类C=O吸收峰。由TG-DTG表征可知,酸洗使得煤中小分子键断裂,但并未破坏煤样的大分子网络主体结构。以石油醚（PE）和CS₂为溶剂对RC和AC两煤样进行常温两级超声萃取的研究表明,AC煤样的PE和CS₂萃取率均高于RC煤样,分别从0.16%和0.53%（RC煤样）增加到0.17%和0.64%,且萃取速率也更大,显著降低了煤样的溶剂萃取次数。萃取物的FT-IR和GC-MS分析表明,酸洗处理不仅能有效脱除煤样中的杂原子,且使得煤样CS₂萃取物的种类增加。另外,由萃余物TG-DTG结果可知,超声萃取主要是一个物理溶胀过程,并没有破坏煤样的大分子主体结构。     

QuEChERS-气相色谱-串联质谱法测定枸杞中农药残留

建立了QuEChERS-气相色谱-串联质谱法测定枸杞中农药残留的分析方法。样品经乙腈提取，采用乙二胺-N-丙基硅烷（PSA）、C18和石墨化炭黑（GCB）3种吸附剂净化，在多反应监测模式（MRM）下进行检测，基质外标法定量。结果显示，检测项目在5~500 μg/L范围内呈良好线性（R²>0.99），在3个添加水平下测得回收率为71.5%~109.7%，相对标准偏差（RSD）为1.94%~9.87%（n=6）。该方法灵敏度高、净化效果好，可同时快速检测有机磷类、有机氯类农药。     

Synthesis of chiral γ-lactones via a RuPHOX-Ru catalyzed asymmetric hydrogenation of aroylacrylic acids

An asymmetric hydrogenation of aroylacrylic acids catalyzed by RuPHOX-Ru catalyst has been developed, affording the corresponding chiral γ-lactones in high yields and with up to 93% ee. The methodology has the advantage of utilizing easily accessible substrates and has therefore expand the scope of the resulting chiral γ-lactones. Furthermore, high catalytic efficiency was achieved in that the reduction of both the CC and CO double bonds was achieved in one step. The current work provides an alternative and convenient pathway for the synthesis of a wide range of chiral γ-lactones.     

Strain‐Induced Isomerization in One‐Dimensional Metal–Organic Chains

The ability to use mechanical strain to steer chemical reactions creates completely new opportunities for solution‐ and solid‐phase synthesis of functional molecules and materials. However, this strategy is not readily applied in the bottom‐up on‐surface synthesis of well‐defined nanostructures. We report an internal strain‐induced skeletal rearrangement of one‐dimensional (1D) metal–organic chains (MOCs) via a concurrent atom shift and bond cleavage on Cu(111) at room temperature. The process involves Cu‐catalyzed debromination of organic monomers to generate 1,5‐dimethylnaphthalene diradicals that coordinate to Cu adatoms, forming MOCs with both homochiral and heterochiral naphthalene backbone arrangements. Bond‐resolved non‐contact atomic force microscopy imaging combined with density functional theory calculations showed that the relief of substrate‐induced internal strain drives the skeletal rearrangement of MOCs via 1,3‐H shifts and shift of Cu adatoms that enable migration of the monomer backbone toward an energetically favorable registry with the Cu(111) substrate. Our findings on this strain‐induced structural rearrangement in 1D systems will enrich the toolbox for on‐surface synthesis of novel functional materials and quantum nanostructures.     

A Diruthenium‐Based Mixed Spin Complex Ru25+(S=1/2)‐CN‐Ru25+(S=3/2)

An unusual tetra‐nuclear linear cyanido‐bridged complex [Ru₂(μ‐ap)₄‐CN‐Ru₂(μ‐ap)₄](BPh₄) ( 1 ) (ap=2‐anilinopyridinate) has been synthesized and well characterized. The crystallographic data, magnetic measurement, IR, EPR and theoretical calculation results demonstrate that complex 1 is the first example of mixed spin Ru₂⁵⁺‐based complex with uncommon electronic configurations of S=1/2 for the cyanido‐C bound Ru₂⁵⁺ and S=3/2 for the cyanido‐N bound Ru₂⁵⁺. This phenomenon can be understood by the theoretical calculation results that from the precursor Ru₂(μ‐ap)₄(CN) (S=3/2) to complex 1 the energy gap between π* and δ* orbitals of the cyanido‐C bound Ru₂⁵⁺ core increases from 0.57 to 1.61 eV due to the enhancement of asymmetrical π back‐bonding effect, but that of the cyanido‐N bound Ru₂⁵⁺ core is essential identical (0.56 eV). Besides, the analysis of UV/Vis‐NIR spectra suggests that there exists metal to metal charge transfer (MMCT) from the cyanido‐N bound Ru₂⁵⁺ (S=3/2) to the cyanido‐C bound Ru₂⁵⁺ (S=1/2), supported by the TDDFT calculations.     

Thermal Efficiency of Solar Steam Generation Approaching 100 % through Capillary Water Transport

Solar‐driven interfacial water evaporation yield is severely limited by the low efficiency of solar thermal energy. Herein, the injection control technique (ICT) achieves a capillary water state in rGO foam and effectively adjusts the water motion mode therein. Forming an appropriate amount of capillary water in the 3D graphene foam can greatly increase the vapor escape channel, by ensuring that the micrometer‐sized pore channels do not become completely blocked by water and by exposing as much evaporation area as possible while preventing solar heat from being used to heat excess water. The rate of solar steam generation can reach up to 2.40 kg m^?2 h^?1 under solar illumination of 1 kW m^?2, among the best values reported. In addition, solar thermal efficiency approaching 100 % is achieved. This work enhances solar water‐evaporation performance and promotes the application of solar‐driven evaporation systems made of carbon‐based materials.