Host-Guest System

主机 - 客户机系统
  • 文章类型: Journal Article
    Buprofezin(BUP)是一种广泛用于农业控制半翅目害虫的昆虫生长调节剂,尤其是甜瓜蚜虫,山雀,由于其效率和低毒性。虽然得到了中国政府的批准,其在食品中的最大残留限量(MRL)受到严格管制,和用于检测BUP的常规技术具有若干限制。我们的研究报告了使用超分子荧光探针DP@ALB成功检测BUP,以查尔酮基荧光染料DP和白蛋白为宿主构建。该探头具有成本低等优点,具有高荧光颜色变化的视觉信号输出,快速反应,和高灵敏度。此外,便携式测试条可以方便地进行现场BUP检测,并简化了实际样品的现场监测。该研究实现了葡萄果实BUP的精确定性和定量分析,地下水和土壤,回收率令人满意。Further,证明了传感器在体外检测L929活细胞中BUP的生物学适用性。这一研究突破了传统分析方法的局限性,为食品和环境监测和农药残留检测提供了有效和可靠的方法。
    Buprofezin (BUP) is an insect growth regulator widely used in agriculture to control hemipteran pests, particularly the melon aphid, Aphis gossypii, due to its efficiency and low toxicity. Although approved by the Chinese government, its maximum residue limit (MRL) in food is strictly regulated, and conventional techniques for detecting BUP have several limitations. Our study reports successful BUP detection using a supramolecular fluorescent probe DP@ALB, constructed with chalcone-based fluorescent dye DP and albumin as the host. The probe offers advantages such as low cost, visual signal output with high fluorescence color variation, rapid response, and high sensitivity. Additionally, portable test strips enable convenient on-site BUP detection and simplifying field monitoring of spiked real samples. The study achieves precise qualitative and quantitative BUP analysis in grape fruit, groundwater, and soil with satisfactory recoveries. Further, the biological applicability of sensor for the in vitro detection of BUP in L929 living cells was demonstrated. This research breakthrough overcomes the limitations of traditional analytical methods, offering an efficient and reliable approach for food and environmental monitoring and pesticide residue detection.
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  • 文章类型: Journal Article
    聚合物膜中周期性微/纳米结构的操纵对于反卫星的学术和工业应用非常重要。然而,随着信息安全需求的不断增长,迫切需要具有时间依赖性特征的材料,尤其是相同信息在时间尺度上可以不止一次出现的材料。这里,提出了一种基于主客系统实现时间依赖的反伪造和“双锁”信息加密的简洁策略,以一种光敏偶氮聚合物为主体,以一种液晶分子为客体。通过调整偶氮基团的顺式到反式回收过程和介晶反式异构体的组装,该系统在预先设计的周期性微/纳米结构中表现出可调的质量传输,导致薄膜的动态结构颜色。利用这个非凡的功能,已经实现了时间依赖的动态防伪。更重要的是,在整个过程中每个状态出现的时间可以通过改变主客比来调节。将传质的可操作过程与独特的解码方法相结合,电影中存储的信息可以正确解密。这项工作为先进的防伪技术提供了前所未有的动态方法,具有更高的安全性和信息加密中的高端应用。
    Manipulation of periodic micro/nanostructures in polymer film is of great importance for academics and industrial applications in anticounterfeiting. However, with the increasing demand on information security, materials with time-dependent features are urgently required, especially the material where the same information can appear more than once on the time scale. Here, one concise strategy to realize time-dependent anticounterfeiting and \"double-lock\" information encryption based on a host-guest system is proposed, with one photoresponsive azopolymer as the host and one liquid-crystalline molecule as the guest. The system exhibits a tunable mass transport in pre-designed periodic micro/nanostructures by tailoring the process of cis-to-trans recovery of azo groups and assembly of mesogenic trans-isomers, resulting in a dynamic structural color in film. Taking advantage of this extraordinary feature, time-dependent dynamic anticounterfeiting has been achieved. More importantly, the time of each state\'s appearance in the whole process can be modulated by changing the host-guest ratio. Combining the manipulatable process of mass transport with the unique decoding method, the stored information in film can be decrypted correctly. This work provides an unprecedented dynamic approach for advanced anticounterfeiting technology with a higher level of security and high-end applications in information encryption.
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  • 文章类型: Journal Article
    不小心,发现来自商业来源的三苯胺(TPA)像商业咔唑一样显示超黄绿色室温磷光(RTP),然而,对于具有高纯度的实验室合成的TPA,其消失。在这里,我们首次确定了导致商业TPARTP的杂质类型,是两个N,N-二苯基-萘胺异构体。由于相似的分子极性和非常微量(≈0.8‰,摩尔比),这些萘基取代的杂质很容易被忽视。我们进一步表明,即使在极低的杂质量(1000000:1,质量比),RTP发射仍然产生,归因于三重态到三重态的能量转移机制。值得注意的是,这种掺杂策略也适用于三苯基膦和二苯甲酮主体系统,其中强RTP发射可以通过简单地将相应的萘基取代的类似物掺杂到它们中来激活。因此,这项工作为高性能和多样化的有机RTP材料提供了一种通用且有效的主机/客户策略。
    Accidentally, it was found that triphenylamine (TPA) from commercial sources shows ultralong yellow-green room temperature phosphorescence (RTP) like commercial carbazole, which however disappears for lab-synthesized TPA with high purity. Herein, we for the first time identify the impurity types that cause RTP of commercial TPA, which are two N, N-diphenyl-naphthylamine isomers. Due to similar molecular polarity and very trace amount (≈0.8 ‰, molar ratio), these naphthyl substituted impurities can be easily overlooked. We further show that even at an extremely low amount (1000000 : 1, mass ratio) of impurities, RTP emission is still generated, attributed to the triplet-to-triplet energy transfer mechanism. Notably, this doping strategy is also applicable to the triphenylphosphine and benzophenone host systems, of which strong RTP emission can be activated by simply doping the corresponding naphthyl substituted analogues into them. This work therefore provides a general and efficient host/guest strategy toward high performance and diverse organic RTP materials.
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  • 文章类型: Journal Article
    促进系统间交叉(ISC)对于从有机材料获得高效的长持久性发光(LPL)至关重要。然而,过渡金属络合物用于LPL材料还没有被探索,因为它还可以通过加速磷光衰减来缩短发射寿命。这里,我们通过将一价Au-卡宾络合物掺杂到嵌入硼的分子主体中,报告了一类新的LPL材料。供体-受体系统表现出具有高效率(>57%)和长寿命(约40ms)在室温下。结果表明,Au原子促进了主体聚集体(T1*)的低位三重态激发态的种群,可以将其转换为电荷转移(CT)态,导致余辉发光。此外,在客体分子上使用手性单元使LPL圆极化。这项工作表明,通过对激发态机制的精细控制,过渡金属配合物可用于开发有机余辉体系。
    The promotion of intersystem crossing (ISC) is critical for achieving a high-efficiency long-persistent luminescence (LPL) from organic materials. However, the use of a transition-metal complex for LPL materials has not been explored because it can also shorten the emission lifetime by accelerating the phosphorescence decay. Here, we report a new class of LPL materials by doping a monovalent Au-carbene complex into a boron-embedded molecular host. The donor-acceptor systems exhibit photoluminescence with both high efficiencies (>57 %) and long lifetimes (ca. 40 ms) at room temperature. It is revealed that the Au atom promotes the population of low-lying triplet excited states of the host aggregate (T1 *) which can be converted into the charge-transfer (CT) state, thereby resulting in afterglow luminescence. Moreover, the use of a chirality unit on the guest molecule results in the LPL being circularly polarized. This work illustrates that transition-metal complexes can be used for developing organic afterglow systems by exquisite control over the excited state mechanism.
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  • 文章类型: Journal Article
    巴比妥酸衍生物(TDPT)是一种非手性分子,并且其在表面上的吸附导致两个相反的对映异构体取向基序,即TDPT-Sp和Rp。可以形成两种类型的结构单元;嵌段I是对映体纯的,并且由相同的基序(格式为SpSp或RpRp)构成,而嵌段II是对映体混合的,并且组成两个基序(格式为SpRp)。分别。构建块的组织决定了不同纳米结构的形成,这些纳米结构在液体/HOPG界面处使用扫描隧道显微镜进行研究。复杂的,高度对称的“纳米孔”首先由I和II两个结构单元形成,并且是异手性的。“纳米孔”是亚稳态的,并逐步演变成更紧密堆积的“纳米线”,它们由对映体纯的结构单元I形成,并且是同手性的。在单分子水平上证明了动态的异向同向转化和同时的多尺度相变。我们的工作提供了新的见解,手性组装和手性转变的控制和起源,揭示了对映体选择和手性竞争的各种作用,驱动力,稳定性和分子覆盖率。
    Barbituric acid derivative (TDPT) is an achiral molecule, and its adsorption on a surface results in two opposite enantiomerically oriented motifs, namely TDPT-Sp and Rp. Two types of building blocks can be formed; block I is enantiomer-pure and is built up of the same motifs (format SpSp or RpRp) whereas block II is enantiomer-mixed and composes both motifs (format SpRp), respectively. The organization of the building blocks determines the formation of different nanoarchitectures which are investigated using scanning tunneling microscopy at a liquid/HOPG interface. Sophisticated, highly symmetric \"nanowaves\" are first formed from both building blocks I and II and are heterochiral. The \"nanowaves\" are metastable and evolve stepwisely into more close-packed \"nanowires\" which are formed from enantiomer-pure building block I and are homochiral. A dynamic hetero- to homochiral transformation and simultaneous multi-scale phase transitions are demonstrated at the single-molecule level. Our work provides novel insights into the control and the origin of chiral assemblies and chiral transitions, revealing the various roles of enantiomeric selection and chiral competition, driving forces, stability and molecular coverage.
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  • 文章类型: Journal Article
    多面体分子因其引人注目的结构和独特的化学而吸引人。这样的全氟化,通常会产生很大的应变,是一个重大挑战。它极大地改变了电子分布,结构和属性。值得注意的是,小型高对称性全氟多面体的特征是位于中央,星形低能未占据的分子轨道,可以在多面体框架内承载一个额外的电子,从而产生自由基阴离子,不失去对称性。这种预测的电子托管能力肯定是为全氟卡布确定的,第一个被分离纯的全氟化柏拉图式多面体。承载原子,这种“笼子”结构中的分子或离子是,然而,除了直率,当不是虚幻的时候,提供不容易获得超分子结构。虽然金刚烷和古巴在材料科学中促进了许多应用,医学和生物学,其全氟对应物的具体用途仍有待确定。高氟化碳同素异形体的某些方面,如富勒烯或石墨,简要提及上下文。
    Polyhedral molecules are appealing for their eye-catching architecture and distinctive chemistry. Perfluorination of such, often greatly strained, compounds is a momentous challenge. It drastically changes the electron distribution, structure and properties. Notably, small high-symmetry perfluoropolyhedranes feature a centrally located, star-shaped low-energy unoccupied molecular orbital that can host an extra electron within the polyhedral frame, thus producing a radical anion, without loss of symmetry. This predicted electron-hosting capacity was definitively established for perfluorocubane, the first perfluorinated Platonic polyhedrane to be isolated pure. Hosting atoms, molecules, or ions in such \"cage\" structures is, however, all but forthright, if not illusionary, offering no easy access to supramolecular constructs. While adamantane and cubane have fostered numerous applications in materials science, medicine, and biology, specific uses for their perfluorinated counterparts remain to be established. Some aspects of highly fluorinated carbon allotropes, such as fullerenes and graphite, are briefly mentioned for context.
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  • 文章类型: Journal Article
    探索了笼形水合物包裹气态分子的内在能力。除了物理参数外,封装能力还取决于腔的大小和客体气态物质的类型,温度和压力。这里我们报道了结构,不同客体占据sH水合物腔中相互作用的稳定性和性质。双原子气体分子和小的多原子烃被认为是客人。sH水合物的不规则二十面体(512一68)腔是宿主。使用三种不同的混合DFT功能计算了客体分子封装的不同热力学参数,B3LYP,M05-2X,M06,并且此外使用色散校正(PBE0-D3)。考虑到大型H键合系统,将6-31G*和cc-pVTZ基集用于两组计算。为了公开主体-客体系统之间的相互作用的性质以及主体内部客体分子之间的相互作用,进行了非共价相互作用(NCI)指数和能量分解分析(EDA)。讨论了主客和宾客互动的影响。
    The intrinsic ability of clathrate hydrates to encage gaseous molecules is explored. Encapsulation ability depends on the cavity size and the type of guest gaseous species in addition to the physical parameters, temperature and pressure. Here we have reported the structure, stability and nature of interaction in dissimilar guest occupied sH hydrate cavity. Diatomic gas molecules and small polyatomic hydrocarbons are considered as guests. The irregular icosahedron (512 68 ) cavity of sH hydrate is the host. Different thermodynamic parameters for the guest molecules encapsulation were calculated using three different hybrid DFT functionals, B3LYP, M05-2X, M06, and moreover using dispersion correction (PBE0-D3). With the consideration of large H-bonded systems the 6-31G* and cc-pVTZ basis sets were used for two set of computations. To disclose the nature of interaction between the host-guest systems as well as the interaction between the guest molecules inside the host the non-covalent interaction (NCI) indices and energy decomposition analysis (EDA) were done. Impact of host-guest and guest-guest interactions are discussed.
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  • 文章类型: Journal Article
    具有优异柔性行为和独特光学性质的有机单晶(OSC)由于其在光学/光电器件和传感器中的广泛适用性而非常重要。然而,制造具有室温磷光(RTP)的柔性OSC仍然是一个巨大的挑战。在这里,我们提出了一种主客体掺杂策略来实现OSC的RTP和柔性特性。单链晶体在外力作用下高度可弯曲,并且在消除应力后能够立即恢复其原始的直线形状,令人印象深刻地发出明亮的深红色磷光。理论和实验结果表明,明亮的RTP源于从三亚苯分子到掺杂剂的Förster共振能量转移(FRET)。该策略在概念上和合成上都很简单,并且为使用RTP制备灵活的OSC提供了通用方法。
    Organic single crystals (OSCs) with excellent flexibility and unique optical properties are of great importance due to their broad applicability in optical/optoelectronic devices and sensors. Nevertheless, fabricating flexible OSCs with room-temperature phosphorescence (RTP) remains a great challenge. Herein, we propose a host-guest doping strategy to achieve both RTP and flexibility of OSCs. The single-stranded crystal is highly bendable upon external force application and can immediately return to its original straight shape after removal of the stress, impressively emitting bright deep-red phosphorescence. The theoretical and experimental results demonstrate that the bright RTP arises from Förster resonance energy transfer (FRET) from the triphenylene molecules to the dopants. This strategy is both conceptually and synthetically simple and offers a universal approach for the preparation of flexible OSCs with RTP.
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  • 文章类型: Journal Article
    合成了由二芳基蒽和三烯单元组成的大环笼型化合物的三种衍生物。这些纳米笼与C60和其他富勒烯客体形成主体-客体配合物,如1HNMR和荧光光谱所证实的。经测定,共三苯甲基和2,4,6-三氧基苯基衍生物与C60的缔合常数为2.2×104Lmol-1,大于五氟苯基衍生物。通过X射线衍射分析获得了络合的直接实验证据:客体C60分子通过多点CH····π相互作用被包含在腔中。在变温X射线分析中包含的C60分子的动态紊乱表明单轴运动,如陀螺运动。由笼形定子通过晶体中的CH·····π相互作用锚定的球形C60转子的独特动态行为,以及取代基对缔合性质的影响,在DFT计算的帮助下进行了讨论。
    Three derivatives of macrocyclic cage compounds consisting of diarylanthracene and triptycene units were synthesized. These nanocages formed host-guest complexes with C60 and other fullerene guests as confirmed by 1 H NMR and fluorescence spectroscopy. The association constant of the mesityl and 2,4,6-tributoxyphenyl derivatives with C60 was determined to be 2.2 × 104  L mol-1 , which was larger than that of the pentafluorophenyl derivative. Direct experimental evidence of the complexation was obtained by X-ray diffraction analysis: the guest C60 molecule was included in the cavity via multipoint CH⋅⋅⋅π interactions. Dynamic disorders of the included C60 molecule in variable-temperature X-ray analysis indicated uniaxial motion, such as gyroscopic motion. The unique dynamic behavior of the spherical C60 rotor anchored by the cage stator via CH⋅⋅⋅π interactions in the crystal, as well as substituent effects on the association properties, are discussed with the aid of DFT calculations.
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  • 文章类型: Journal Article
    具有多功能和永久孔的氢键有机骨架(HOFs)由于其在气体吸附/分离中的潜在应用而受到广泛关注。药物输送,光催化,质子传导,和其他领域。在这里,我们通过π-π堆叠和氢键相互作用自组装,利用带有卟啉核活性中心和氮原子开放位点的双官能四唑基卟啉配体,构建了具有1D正方形通道的三维(3D)HOF。该结构同时具有耐溶剂性和热稳定性,尤其是,在转化为纳米粒子后保持这些。同时,暴露在孔内壁上的活性位点可以与光敏阳离子染料分子很好地相互作用,形成有效的主客体(H-G)系统,可以实现在红光照射下增强光敏单线态氧(1O2)的产生和对金黄色葡萄球菌的协同灭菌(S.金黄色葡萄球菌)的抑制率高达99.9%。这项工作为追求提升的光活性的HOF相关系统提供了有价值的设计概念。
    Hydrogen-bonded organic frameworks (HOFs) with multiple functions and permanent pores have received widespread attention due to their potential applications in gas adsorption/separation, drug delivery, photocatalysis, proton conduction, and other fields. Herein, we constructed a three-dimensional (3D) HOF with 1D square channels by utilizing a dual-functional tetrazolyl porphyrin ligand bearing an active center of the porphyrin core and open sites of nitrogen atoms through π-π stacking and hydrogen-bonding interaction self-assembly. The structure exhibits both solvent resistance and thermal stability, and especially, maintains these after being transformed into nanoparticles. Meanwhile, the active sites exposed on the inner wall of the pores can interact well with the photoactive cationic dye molecules to form an effective host-guest (H-G) system, which can realize boosted photosensitized singlet oxygen (1O2) production under red light irradiation and synergistic sterilization toward Staphylococcus aureus (S. aureus) with an inhibition ratio as high as 99.9%. This work provides a valuable design concept for HOF-related systems in pursuit of promoted photoactivity.
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