热致可逆变色的聚二炔/稀土离子纳米复合物

将Dy⁺或Sm⁺掺杂到具有层状结构的10,12-二十五碳二炔酸(PCDA)纳米粒子中,得到二炔酸/稀土离子(PCDA-RE)纳米复合物．随后在稍微高于二炔酸熔点的温度下对PCDA-RE纳米复合物进行退火处理,退火后的PCDA-RE纳米复合物发生拓扑聚合反应得到聚二炔酸/稀土离子(PDA-RE)纳米复合物．虽然纯聚二炔酸的热致变色过程是不可逆的,但是PDA-Sm纳米复合物和PDA-Dy纳米复合物分别具有不完全和完全热致可逆变色的性能．研究表明,PDA-RE纳米复合     

卤素驱动石墨二炔带隙的打开以实现光催化全解水

本文通过杂化密度泛函理论研究了卤素(F、Cl和Br)功能化的石墨二炔的能带结构. 结果表明修饰的石墨二炔的带隙能随着卤素原子对的增加而增加;同时,价带顶的位置受卤素原子电负性大小的影响：当石墨二炔表面的卤素原子数目相同时,卤素原子的电负性越大,改性后石墨二炔的价带顶的位置越深. 另外,计算结果表明石墨二炔的带隙可以通过不同卤素原子的适当混合修饰来有效调节,不同卤素原子混合修饰的石墨二炔的价带底和导带顶跨越了水的氧化还原电位. 通过热力学分析进一步证明,不同卤素原子混合修饰的石墨二炔比单一卤素修饰的石墨二炔表现出更好的光催化水全解反应活性. 这项工作对于如何设计更高效的全解水光催化剂提供了洞见.     

卤素驱动石墨二炔带隙的打开以实现光催化全解水（英文）

本文通过杂化密度泛函理论研究了卤素(F、Cl和Br)功能化的石墨二炔的能带结构.结果表明修饰的石墨二炔的带隙能随着卤素原子对的增加而增加;同时,价带顶的位置受卤素原子电负性大小的影响;当石墨二炔表面的卤素原子数目相同时,卤素原子的电负性越大,改性后石墨二炔的价带顶的位置越深.另外,计算结果表明石墨二炔的带隙可以通过不同卤素原子的适当混合修饰来有效调节,不同卤素原子混合修饰的石墨二炔的价带底和导带顶跨越了水的氧化还原电位.通过热力学分析进一步证明,不同卤素原子混合修饰的石墨二炔比单一卤素修饰的石墨二炔表现出更好的光催化水全解反应活性.这项工作对于如何设计更高效的全解水光催化剂提供了洞见.     

聚乙烯醇中的紫外偏振线性聚炔分子（英文）

本文通过研究共轭线性碳链分子,聚炔H(C≡C)_nH(n=5～7)的电子吸收带,设计了适用于UV的光偏振膜.激光烧蚀的聚炔分子被分散在聚乙烯醇膜中.结构各向异性的性质使得多炔分子的UV吸收跃迁偶极子与分子轴平行,并且吸收仅发生在沿着分子轴具有电子矢量幅度的电磁波上.多炔分子在固体聚乙烯醇膜中作为特定波长入射光的偏振分量之一的选择性吸收剂.使用可旋转的偏振UV光研究包含聚炔分子的拉伸聚乙烯醇膜的吸收强度的角度依赖性,并根据线性二向色性理论中有序参数进行分析.     

聚乙烯醇中的紫外偏振线性聚炔分子

本文通过研究共轭线性碳链分子，聚炔H(C≡C)_nH (n=5∽7)的电子吸收带，设计了适用于UV的光偏振膜. 激光烧蚀的聚炔分子被分散在聚乙烯醇膜中. 结构各向异性的性质使得多炔分子的UV吸收跃迁偶极子与分子轴平行，并且吸收仅发生在沿着分子轴具有电子矢量幅度的电磁波上. 多炔分子在固体聚乙烯醇膜中作为特定波长入射光的偏振分量之一的选择性吸收剂. 使用可旋转的偏振UV光研究包含聚炔分子的拉伸聚乙烯醇膜的吸收强度的角度依赖性，并根据线性二向色性理论中有序参数进行分析.     

Theoretical Study of 1,3-Dipolar Cycloaddition of Hydrazoic Acid to Substituted Ynamines

采用高精度CBS-QB3方法对一系列取代炔胺与叠氮酸之间的1,3环加成反应进行了理论研究. 该反应生成两种区域选择性异构体,它们分别是4-取代和5-取代加成物,其中以5-取代加成物为优势产物. 此区域选择性由前线分子轨道理论给出了合理解释.该反应的活性和协同性随着取代炔胺的取代基吸电子能力增加而增加. 计算结果也表明,溶剂效应使叠氮酸与取代炔胺的1,3环加成反应的活化能垒增加,在极性溶剂下,该反应变得难以进行.     

银纳米粒子自组织二维有序阵列

采用液液二相转移方法合成出颗粒直径为(4.18±0.5)nm的银纳米粒子溶胶,并用紫外可见光谱对所制得的银纳米粒子溶胶的单分散性和稳定性进行了研究.结果表明,所得到的溶胶相为稳定的、粒径分布窄的单分散体系.红外光谱的分析结果表明,稳定剂1壬基硫醇包缚在银纳米粒子表面.并且,通过自组织方法获得了二维有序的银纳米粒子阵列 关键词： 银纳米粒子 液液二相转移方法 自组织 二维有序阵列     

一种含末端炔喹啉酮类化合物的波谱学研究

通过Cu(I)催化有机叠氮化物和端基炔之间的1,3-偶极Huisgen环加成反应,又称“点击化学”, 可快速、高效合成专一的1,4-二取代-1,2,3-三唑产物. 为得到含有末端炔的喹啉酮衍生物,以7,8-二氢-2,5(1H,6H)-二酮（1）为原料,通过烷基化反应将端基炔引入到化合物1中,合成了1-(2-炔丙基)-7,8-二氢喹啉-2,5(1H, 6H) 二酮（3）,并利用重结晶和硅胶柱分离两种化学手段,得到了该化合物的两种构型异构体. 采用DEPT、¹H NMR、¹³C NMR、¹H-¹H COSY、NOESY、HMQC多种NMR实验测试分析方法,对该化合物的构型异构体进行了验证和区分,并分别对其¹H NMR和¹³C NMR谱的信号进行了归属.     

DBU与全氟炔酸酯的迈克尔型加成及其产物的NMR谱学研究

1，8-二氮杂二环[5，4，0]十一碳-7-烯(DBU)与全氟炔酸酯反应生成成环化合物. 通过对成环产物的¹H NMR、¹H-¹H COSY、¹³C NMR和¹H-¹³C COSY的分析，归属了各NMR谱线，对相关化合物进行了结构确证，同时对反应机理进行了推测.     

N掺杂对α-石墨炔表面吸附H_2O,H,O和OH的电子性质和磁性的影响

石墨炔是一种新型的二维(2D)碳的同素异形体,炔键单元的高活性使其在小分子吸附方面相比石墨烯更具优势.本文基于密度泛函理论(DFT),研究了H_2O和H、O及OH分别在原始的和掺杂了N原子的α-石墨炔上的相互作用.研究结果表明,N掺杂和小分子吸附能够改变α-石墨炔的电子结构和磁性. N原子掺杂后α-石墨炔对小分子的吸附能力明显增强. H、O原子和OH吸附在N原子掺杂体系前后表现出明显的磁性差异:H原子和OH吸附在纯净的α-石墨炔上体系显示磁性,N原子掺杂后,磁性消失;而O原子则是吸附在纯净的α-石墨炔上未表现出磁性,N原子掺杂后,体系出现磁性.此外,α-石墨炔对水分子的吸附作用较弱,受范德瓦耳斯作用影响较大,属于物理吸附.本研究将为α-石墨炔中N杂质检测以及α-石墨炔基气体传感器的设计研究提供新的思路.     

Protein‐Affinitive Polydopamine Nanoparticles as an Efficient Surface Modification Strategy for Versatile Porous Scaffolds Enhancing Tissue Regeneration

Porous scaffolds for tissue regeneration are often functionalized with extracellular matrix proteins to enhance surface/cell interactions and tissue regeneration. However, continuous coatings produced by commonly used surface modification strategies may preclude cells from contacting and sensing the chemical and physical cues of the scaffold. Here, it is shown that polydopamine nanoparticles (PDA‐NPs) tightly adhere on various scaffolds to form nanostructures, and the coverage can be finely tuned. Furthermore, the PDA‐NPs have good affinity to a variety of proteins and peptides. Thus, the PDA‐NPs act as an anchor to immobilize signal biomolecules on scaffolds, and consequently promote cell activity and tissue regeneration. β‐Tricalcium phosphate (TCP) scaffolds decorated with PDA‐NPs demonstrate excellent osteoinductivity and bone‐regeneration performance due to the protein affinity of PDA‐NPs and the intrinsic bioactive characteristics of TCP scaffolds. In summary, PDA‐NPs with excellent affinity for protein adhesion represent a versatile platform to modify porous scaffolds while not compromising the biological functions of the scaffolds, and might have potential applications in tissue regeneration.     

Synthesis of highly stable silver colloids stabilized with water soluble sulfonated polyaniline

A simple technique was developed for the synthesis of silver nanoparticles (NPs) in an aqueous medium using water soluble sulfonated polyaniline as a new non-covalent effective stabilizer. The narrow size distribution of the NPs was achieved through the synthesis. In neutral and basic solutions the as-prepared silver NPs demonstrated resistance toward aggregation over several months and at least a few days at pH 1. The versatility of the procedure was demonstrated also for the preparation of gold nanoparticles. Transmission electron microscopy with electron microdiffraction, UV-vis spectroscopy, XRD, XPS and FTIR analyses were used to characterize the structure and chemical composition of as obtained silver NPs.     

1-Hexadecylamine as both reducing agent and stabilizer to synthesize Au and Ag nanoparticles and their SERS application

1-Hexadecylamine (HDA)-capped Au and Ag nanoparticles (NPs) have been successfully prepared by a one-pot solution growth method. The HDA is used as both reducing agent and stabilizer in the synthetic process is favorable for investigating the capping mechanism of Au and Ag NPs’ surface. The growth process and characterization of Au and Ag NPs are determined by Ultraviolet–visible (UV–vis) spectroscopy, transmission electron microscopy (TEM), and X-ray diffraction (XRD). Experimental results demonstrate that the HDA-capped Au and Ag NPs are highly crystalline and have good optical properties. Furthermore, surface-enhanced Raman scattering (SERS) spectra of 2-thionaphthol are obtained on the Au and Ag NPs modified glass surface, respectively, indicating that the as-synthesized noble metal NPs have potentially high sensitive optical detection application.     

Facile synthesis of SERS active Ag nanoparticles in the presence of tri-n-octylphosphine sulfide

A facile and novel way was reported here for the synthesis of hydrophobic Ag nanoparticles (NPs), using AgNO₃, tri-n-octylphosphine (TOP) and sulfur (S) powder in process. TOP was used as solvent, reducing agent and stabilizer. S could chelate with excessive TOP to form trioctylphosphine sulfide (TOPS), which served as second capping agent. The hydrophobic Ag NPs could be transformed into hydrophilic state through ligand exchange. Furthermore, surface-enhanced Raman scattering (SERS) spectra of 4-aminothiophenol (4-ATP) were obtained on the hydrophobic and hydrophilic Ag NPs modified substrates, indicating that the as-synthesized Ag NPs had great potential for high sensitive optical detection applications.     

PEGylated polyethylenimine-stabilized polypyrrole nanoparticles loaded with DOX for chemo-photothermal therapy of cancer cells

Combination of kinds of therapy modalities is promising for effective cancer treatment. Herein, a kind of multifunctional nanoparticles (NPs) was developed for cancer chemo-photothermal therapy applications. Polypyrrole (PPy) NPs were formed using a facile polymerization method using poly(ethyleneimine) (PEI) as stabilizer, followed by polyethylene glycol (PEG) modification and anticancer drug doxorubicin (DOX) loading. Showing obvious absorbance in the NIR range, the obtained PPy-PEI-PEG NPs displayed well photothermal ability with desirable photothermal stability. The release of the loaded DOX can be promoted by pH and laser stimulation. Compared with single therapy modality, the combination of chemotherapy and photothermal therapy showed higher cancer cell killing effect. The cellular internalization of the obtained NPs was proved to be effective. The developed multifunctional NPs are promising candidates for combined therapy of cancer cells.     

Understanding of Polydopamine Encapsulation of Hydrophobic Curcumin for Pleiotropic Drug Nanoformulation

Pleiotropic drug nanoformulation promises the enhanced efficacy of nanomedicines on the market. In this study, it is demonstrated that polydopamine (PDA)-based drug encapsulation is a potential strategy for such nanoformulation, yet its mechanism remains poorly investigated. This study elucidates the mechanism of PDA-encapsulated Curnanoformulations (CP NPs) using hydrophobic curcumin (Cur) as a model drug via local dopamine (DA) polymerization on self-assembled Cur NPs. The formation of PDA-based drug nanoformulations with the core–shell structure is comprehensively investigated by controlling the key synthetic parameters, deepening the understanding of DA polymerization in the context of drugs. An intriguing morphology evolution is proposed to be the key event in the formation of CP NPs, attributing to the Cur diffusion from the core to the shell of CP NPs. Moreover, the morphological data can be used to guide the optimization of the PDA-based nanoformulation. In addition, the verification of soluble DA polymers in CP NPs hints at the heterogeneous nature of the excipient (i.e., PDA) of CP NPs, providing a cautionary view on the long-term safety of PDA-formulated drugs. In sum, this study would enable the pharmaceutical development of PDA-encapsulated Cur nanomedicines and generalize the PDA-based nanoformulation approach for a wider range of hydrophobic drugs.     

A Curcumin-Based MOF Embedded Ag NPs and Modified with Polydopamine for Dual-Drug Delivery and Dual Biological Window Responsive Synergetic Cancer Therapy

A dual-drug delivery, pH-responsive composite nanoplatform (MAPD NPs) that can respond to two biological windows is developed to improve the efficacy of synergetic chemotherapic/photothermal/chemodynamic therapy (CDT) against tumors. This nanoplatform is surface-modified polydopamine (PDA) with excellent biocompatibility as the shell and Ag NPs as the catalyst for CDT. The curcumin (Cur) acts as an organic ligand to be encapsulated in metal−biomolecule frameworks (Bio-MOFs) by self-assembly, and Bio-MOF acts as a delivery carrier to deliver of DOX•HCl and then releases the Cur when it degrades in vivo. Moreover, Bio-MOF can be taken up by cells faster and accelerate cell death compared to free Cur. PDA modification enables MAP (PDA@MOF-Ag) to have photothermal properties under 808 and 1064 nm light irradiation, which not only improves the biocompatibility of MAP but also makes it produce high heat and abundant ·OH. The photothermal performance of MAP is stable after irradiation at 808 or 1064 nm, and the photothermal conversion efficiency reaches 63.57% and 26.25%. The survival rate of HeLa cells co-incubation with MAPD NPs after irradiation at 808 and 1064 nm decreases to 19.52 ± 0.69% and 30.48 ± 0.49%, respectively, providing a feasible scheme for the realization of deep tumor killing.     

Laser synthesis of aluminium nanoparticles in biocompatible polymer solutions

Pulsed laser ablation of Aluminium (Al) in pure water rapidly forms a thin alumina (Al₂O₃) layer which drastically modifies surface plasmon resonance (SPR) absorption characteristics in deep-UV region. Initially, pure aluminium nanoparticles (NPs) are generated in water without any stabilizers or surfactants at low laser fluence which gradually transform to stable Al-Al₂O₃ core-shell nanostructure with increasing either residency time or fluence. The role of laser wavelength and fluence on the SPR properties and oxidation characteristics of Al NPs has been investigated in detail. We also present a one-step in situ synthesis of oxide-free stable Al NPs in biocompatible polymer solutions using laser ablation in liquid method. We have used nonionic polymers (PVP, PVA and PEG) and anionic surfactant (SDS) stabilizer to suppress the Al₂O₃ formation and studied the effect of polymer functional group, polymeric chain length, polymer concentration and anionic surfactant on the incipient embryonic aluminium particles and their sizes. The different functional groups of polymers resulted in different oxidation states of Al. PVP and PVA polymers resulted in pure Al NPs; however, PEG and SDS resulted in alumina-modified Al NPs. The Al nanoparticles capped with PVP, PVA, and PEG show a good correlation between nanoparticle stability and monomeric length of the polymer chain.     

Mechanism study of Single-Step synthesis of Fe(core)@Pt(shell) nanoparticles by sonochemistry

Transition metal (TM) core-platinum (Pt) shell nanoparticles (TM@Pt NPs) are attracting a great deal of attention as highly active and durable oxygen reduction reaction (ORR) electrocatalysts of fuel cells and metal-air batteries. However, most of the reported synthesis methods of TM@Pt NPs are multistep in nature, a significant disadvantage for real applications. In this regard, our group has reported a single-step method to synthesize TM@Pt NPs for TM = Mn, Fe, Co, and Ni by using sonochemistry, namely the UPS (ultrasound-assisted polyol synthesis) method. Previously, we proposed the mechanism of the formation of these TM@Pt NPs by UPS method, but rather in a rough sense. Some details are missing and the optimal conditions have not been established. In the present work, we performed detailed studies on the formation mechanism of UPS reaction by using Fe@Pt NPs as the model system. Effects of synthesis parameters such as the nature of metal precursor, conditions of ultrasound, and temperature profile as a function of reaction time were assessed, along with the analyses of intermediates during the UPS reaction. As results, we verified our previously proposed mechanism that, under appropriate conditions, Fe core is formed through the cavitation and implosion of the solvent, induced by the ultrasound, and the Pt shell is formed by the chemical reaction between Fe core and Pt reagent, independent from the direct effect of ultrasound. In addition, we established the optimal conditions to obtain a high purity Fe@Pt NPs in a high yield (>90% based on Pt), which may enable the increase of synthesis scale of Fe@Pt NPs, a necessary step for the real application of TM@Pt NPs.     

Ultrafast dephasing of localized surface plasmons in colloidal silver nanoparticles: the influence of stabilizing agents

Localized surface plasmon dephasing times for aqueous colloidal silver nanoparticles (NPs) stabilized with three different capping agents (trisodium citrate??TSC, poly(vinylpyrrolidone)??PVP, and poly(vinylalcohol)?? PVA) were measured using the persistent spectral hole burning technique. The results obtained by fitting a theoretical curve to the experimental data show that the dephasing times are dependent on the chosen stabilizer (3.0, 2.3, and 1.8?fs for TSC, PVP, and PVA, respectively), and the differences are attributed to changes in the electronic density of states due to the interaction between the NPs and the capping agents. The results are supported by ab initio calculations for the chemisorbate and metallic cluster interaction.