Aqueous Synthesis of Color-Tunable CuInS₂/ZnS Nanocrystals for the Detection of Human Interleukin 6

In this Article, we present a facile microwave-assisted synthesis route for the preparation of water-soluble and high-quality CuInS₂/ZnS nanocrystals (NCs) with glutathione as the stabilizer. The as-prepared CuInS₂/ZnS NCs exhibited small particle sizes (∼3.3 nm), long photoluminescence lifetimes, and color-tunable properties ranging from the visible to the near-infrared by varying the initial ratio of Cu/In in the precursors. The low-toxicity, highly luminescent and biocompatible CuInS₂/ZnS NCs were applied to cell imaging, showing that they could be used as promising fluorescent probes. Furthermore, the CuInS₂/ZnS NCs were used as the signal labels for a fluoroimmunoassay of the biomarker IL-6, showing their great potential for use as reliable point-of-care diagnostics for biomarkers of cancer and other diseases

Growing Crystalline Chalcogenidoarsenates in Surfactants: From Zero-Dimensional Cluster to Three-Dimensional Framework

Although surfactants have been widely used to tailor the size, shape, and surface properties of nanocrystals and control the pore size and phases of mesoporous frameworks, the use of surfactants as reaction media to grow chalcogenide crystals is unprecedented. In addition, compared with ionic liquids, surfactants are much cheaper and can have multifunctional properties such as acidic, basic, neutral, cationic, anionic, or even block. These features suggest that surfactants could be promising reaction platforms for the development of novel chalcogenide crystals. In this work, we used chalcogenidoarsenates as a model system to demonstrate our strategy. By using three different surfactants as reaction media, we obtained a series of novel thioarsenates ranging from a zero-dimensional (0D) cluster to a three-dimensional (3D) framework, namely, [NH₄]₈[Mn₂As₄S₁₆] (<b>1</b>), [Mn­(NH₃)₆]­[Mn₂As₂S₈(N₂H₄)₂] (<b>2</b>), [enH]­[Cu₃As₂S₅] (<b>3</b>), and [NH₄]­[MnAs₃S₆] (<b>4).</b> The band gaps (estimated from the steep absorption edges) were found to be 2.31 eV for <b>1</b> (0D), 2.46 eV for <b>2</b> (1D), 1.91 eV for <b>3</b> (2D), and 2.08 eV for <b>4</b> (3D). The magnetic study of <b>4</b> indicated weak antiferromagnetic behavior. Our strategy of growing crystalline materials in surfactants could offer exciting opportunities for preparing novel crystalline materials with diverse structures and interesting properties

Growing Crystalline Zinc-1,3,5-benzenetricarboxylate Metal–Organic Frameworks in Different Surfactants

Six new zinc-1,3,5-benzenetricarboxylate-based metal–organic frameworks (MOFs) have been successfully synthesized using three different surfactants (PEG 400, octanoic acid, and hexadecyltributylphosphonium bromide) as reaction media. These surfactants with different characteristics, such as being neutral, acidic, and cationic, have been demonstrated to show strong effects on directing the crystals’ growth and resulted in different secondary building units (SBUs) including an unusual SBU unit [Zn₄(μ₄-O)­(CO₂)₇]. Our results clearly indicated that the surfactant–thermal method could offer exciting opportunities for preparing novel MOFs or other inorganic crystalline materials with diverse structures and interesting properties

[4 + 2] Cycloaddition Reaction To Approach Diazatwistpentacenes: Synthesis, Structures, Physical Properties, and Self-assembly

Three novel diazatwistpentacenes (1,4,6,13-tetraphenyl-7:8,11:12-bisbenzo-2,3-diazatwistpentacene (<b>1</b>, IUPAC name: 9,11,14,16-tetraphenyl-1,6-dihydrobenzo­[8,9]­triphenyleno­[2,3-<i>g</i>]­phthalazine); 1,4-di­(pyridin-2-yl)-6,13-diphenyl-7:8,11:12-bisbenzo-2,3-diazatwistpentacene (<b>2</b>, IUPAC name: 9,16-diphenyl-11,14-di­(pyridin-2-yl)-1,6-dihydrobenzo­[8,9]­triphenyleno­[2,3-<i>g</i>]­phthalazine); and 1,4-di­(thien-2-yl)-6,13-diphenyl-7:8,11:12-bisbenzo-2,3-diazatwistpentacene (<b>3</b>, IUPAC name: 9,16-diphenyl-11,14-di­(thien-2-yl)-1,6-dihydrobenzo­[8,9]­triphenyleno­[2,3-<i>g</i>]­phthalazine)) have been successfully synthesized through [4 + 2] cycloaddition reaction involving <i>in situ</i> arynes as dienophiles and substituted 1,2,4,5-tetrazines as dienes. Their structures have been determined by single-crystal X-ray diffraction, confirming that all compounds have twisted configurations with torsion angles between the pyrene unit and the 2,3-diazaanthrance part as high as 21.52° (for <b>1</b>), 24.74° (for <b>2</b>), and 21.14° (for <b>3</b>). The optical bandgaps for all compounds corroborate the values derived from CV. The calculation done by DFT shows that the HOMO–LUMO bandgaps are in good agreement with experimental data. Interestingly, the substituted groups (phenyl, pyridyl, thienyl) in the 1,4-positions did affect their self-assembly and the optical properties of as-resulted nanostructures. Under the same conditions, compounds <b>1</b>–<b>3</b> could self-assemble into different morphologies such as microrods (for <b>1</b>), nanoprisms (for <b>2</b>), and nanobelts (for <b>3</b>). Moreover, the UV–vis absorption and emission spectra of as-prepared nanostructures were largely red-shifted, indicating J-type aggregation for all materials. Surprisingly, both <b>1</b> and <b>2</b> showed aggregation-induced emission (AIE) effect, while compound <b>3</b> showed aggregation-caused quenching (ACQ) effect. Our method to approach novel twisted azaacenes through [4 + 2] reaction could offer a new tool to develop unusual twisted conjugated materials for future optoelectronic applications

Exploring the Surfactant–Thermal Synthesis of Crystalline Functional Thioarsenates

Two new crystalline thioarsenate compounds, formulated as [pipH₂]­[Mn₂As₂S₆] (<b>1</b>) and [TMDPH₂]­[As₄S₆] (<b>2</b>) (pip = piperazine, TMDP = 1,3-bis­(4-piperidyl)­propane), have been surfactant–thermally synthesized with the utilization of octylamine and PEG-400 as the solvents. The crystal structure of <b>1</b> features [Mn₂As₂S₆]_<i>n</i>^2<i>n</i>– anionic layers which are separated by doubly protonated [pipH₂]²⁺ cations, while that of compound <b>2</b> is made of discrete [As₄S₆]^2– clusters and doubly protonated [TMDPH₂]²⁺ cations. Both compounds were characterized by powder X-ray diffraction analyses, solid-state optical diffuse reflectance spectroscopy, and thermogravimetric analyses. As estimated from the adsorption spectra, the band gaps of <b>1</b> and <b>2</b> are 2.32 and 2.49 eV, respectively. The electronic structure calculations based on density functional theory method confirm the indirect band gap of <b>2</b>. In addition, the magnetic investigation of <b>1</b> suggests antiferromagnetic behavior. Since compound <b>2</b> crystallizes in the space group <i>Imm</i>2, the nonlinear optical property of <b>2</b> was studied, and its second harmonic generation intensity was nearly twice as much as that of KDP. Furthermore, compounds <b>1</b> and <b>2</b> exhibited a photocurrent response with the photocurrent intensities of 17.5 μA/cm² and 2 μA/cm², respectively

Kinetically Controlling Phase Transformations of Crystalline Mercury Selenidostannates through Surfactant Media

Herein we report the surfactant-thermal method to prepare two novel one-dimensional mercury selenidostannates, [DBUH]₂[Hg₂Sn₂Se₆(Se₂)] (<b>1</b>) and [DBUH]₂[Hg₂Sn₂Se₇] (<b>2</b>), where DBU = 1,8-diazabicyclo[5.4.0]­undec-7-ene, by applying PEG-400 as the reaction medium. It is worth noting that <b>1</b> is kinetically stable and can be transformed into thermodynamically stable phase <b>2</b> under a longer reaction time. Our strategy “growing crystalline materials in surfactants” could open a new door to preparing novel crystals with diverse structures and interesting properties

1,5,9-Triaza-2,6,10-triphenyl­bora­coronene: BN-Embedded Analogue of Coronene

A novel BN-fused coronene derivative 1,5,9-triaza-2,6,10-triphenyl­bora­coronene (<b>1</b>) has been successfully synthesized in one step from 2,3,6,7,9,10-hexa­methoxy-1,5,9-triamino-triphenylene. Compound <b>1</b> has been investigated using photophysical, electrochemical, and molecular simulation methods. Interestingly, three phenyl groups at B centers in compound <b>1</b> can be replaced by hydroxyl units stepwise through hydroxylation in wet organic solvents, leading to changes in the packing and physical properties

Surfactant-Thermal Syntheses, Structures, and Magnetic Properties of Mn–Ge–Sulfides/Selenides

Although either surfactants or amines have been investigated to direct the crystal growth of metal chalcogenides, the synergic effect of organic amines and surfactants to control the crystal growth has not been explored. In this report, several organic bases (hydrazine monohydrate, ethylenediamine (<i>en</i>), 1,2-propanediamine (1,2-<i>dap</i>), and 1,3-propanediamine (1,3-<i>dap</i>)) have been employed as structure-directing agents (SDAs) to prepare four novel chalcogenides (Mn₃Ge₂S₇(NH₃)₄ (<b>1</b>), [Mn­(en)₂(H₂O)]­[Mn­(en)₂MnGe₃Se₉] (<b>2</b>), (1,2-dapH)₂­{[Mn­(1,2-dap)₂]­Ge₂Se₇} (<b>3</b>), and (1,3-dapH)­(puH)­MnGeSe₄(<b>4</b>) (pu = propyleneurea) under surfactant media (PEG-400). These as-prepared new crystalline materials provide diverse metal coordination geometries, including MnS₃N tetrahedra, MnGe₂Se₇ trimer, and MnGe₃Se₁₀ T2 cluster. Compounds <b>1</b>–<b>3</b> have been fully characterized by single-crystal X-ray diffraction (XRD), powder XRD, UV–vis spectra, Fourier transform infrared spectroscopy, and thermogravimetric analysis. Moreover, magnetic measurements for compound <b>1</b> showed an obvious antiferromagnetic transition at ∼9 K. Our research not only enriches the structural chemistry of the transitional-metal/14/16 chalcogenides but also allows us to better understand the synergic effect of organic amines and surfactants on the crystallization of metal chalcogenides

Surfactant-Thermal Syntheses, Structures, and Magnetic Properties of Mn–Ge–Sulfides/Selenides

Although either surfactants or amines have been investigated to direct the crystal growth of metal chalcogenides, the synergic effect of organic amines and surfactants to control the crystal growth has not been explored. In this report, several organic bases (hydrazine monohydrate, ethylenediamine (<i>en</i>), 1,2-propanediamine (1,2-<i>dap</i>), and 1,3-propanediamine (1,3-<i>dap</i>)) have been employed as structure-directing agents (SDAs) to prepare four novel chalcogenides (Mn₃Ge₂S₇(NH₃)₄ (<b>1</b>), [Mn­(en)₂(H₂O)]­[Mn­(en)₂MnGe₃Se₉] (<b>2</b>), (1,2-dapH)₂­{[Mn­(1,2-dap)₂]­Ge₂Se₇} (<b>3</b>), and (1,3-dapH)­(puH)­MnGeSe₄(<b>4</b>) (pu = propyleneurea) under surfactant media (PEG-400). These as-prepared new crystalline materials provide diverse metal coordination geometries, including MnS₃N tetrahedra, MnGe₂Se₇ trimer, and MnGe₃Se₁₀ T2 cluster. Compounds <b>1</b>–<b>3</b> have been fully characterized by single-crystal X-ray diffraction (XRD), powder XRD, UV–vis spectra, Fourier transform infrared spectroscopy, and thermogravimetric analysis. Moreover, magnetic measurements for compound <b>1</b> showed an obvious antiferromagnetic transition at ∼9 K. Our research not only enriches the structural chemistry of the transitional-metal/14/16 chalcogenides but also allows us to better understand the synergic effect of organic amines and surfactants on the crystallization of metal chalcogenides

Surfactant-Thermal Syntheses, Structures, and Magnetic Properties of Mn–Ge–Sulfides/Selenides

Although either surfactants or amines have been investigated to direct the crystal growth of metal chalcogenides, the synergic effect of organic amines and surfactants to control the crystal growth has not been explored. In this report, several organic bases (hydrazine monohydrate, ethylenediamine (<i>en</i>), 1,2-propanediamine (1,2-<i>dap</i>), and 1,3-propanediamine (1,3-<i>dap</i>)) have been employed as structure-directing agents (SDAs) to prepare four novel chalcogenides (Mn₃Ge₂S₇(NH₃)₄ (<b>1</b>), [Mn­(en)₂(H₂O)]­[Mn­(en)₂MnGe₃Se₉] (<b>2</b>), (1,2-dapH)₂­{[Mn­(1,2-dap)₂]­Ge₂Se₇} (<b>3</b>), and (1,3-dapH)­(puH)­MnGeSe₄(<b>4</b>) (pu = propyleneurea) under surfactant media (PEG-400). These as-prepared new crystalline materials provide diverse metal coordination geometries, including MnS₃N tetrahedra, MnGe₂Se₇ trimer, and MnGe₃Se₁₀ T2 cluster. Compounds <b>1</b>–<b>3</b> have been fully characterized by single-crystal X-ray diffraction (XRD), powder XRD, UV–vis spectra, Fourier transform infrared spectroscopy, and thermogravimetric analysis. Moreover, magnetic measurements for compound <b>1</b> showed an obvious antiferromagnetic transition at ∼9 K. Our research not only enriches the structural chemistry of the transitional-metal/14/16 chalcogenides but also allows us to better understand the synergic effect of organic amines and surfactants on the crystallization of metal chalcogenides