Functionalization of bismuth sulfide nanomaterials for their application in cancer theranostics

Multifunctional bismuth sulfide (Bi₂S₃) nanomaterials exhibit significant potential as nanomedicines for the diagnosis and treatment of cancer. These nanomaterials act as excellent photothermal agents and radiation sensitizers for the treatment of tumors, and they can also act as contrast agents for computed tomography (CT) imaging, photoacoustic imaging (PA), and other forms of imaging to provide real-time tumor monitoring and testing guidance. Compared with other nanomaterials, Bi₂S₃ nanomaterials can readily adapt to different applications by virtue of the fact that they can be easily functionalized. However, these nanomaterials have some limitations that cannot be ignored and need to be addressed, such as poor biocompatibility, toxicity, and low chemical stability. It is widely believed that appropriate functionalization of Bi₂S₃ nanomaterials could remedy such defects and significantly improve performance. This review summarizes the ways in which Bi₂S₃ nanomaterials can be functionalized and discusses their applications in cancer theranostics over the last few years, focusing particularly on imaging and therapy. We also discuss issues relating to how Bi₂S₃ nanomaterials can be analyzed, including how we might be able to use these systems to inhibit and treat tumors and how current limitations might be overcome to improve treatment efficacy. Finally, we hope to provide inspiration and guidance as to how we might create a more optimized multifunctional nano-system for the diagnosis and treatment of tumors.     

Deep‐Level Defect Enhanced Photothermal Performance of Bismuth Sulfide–Gold Heterojunction Nanorods for Photothermal Therapy of Cancer Guided by Computed Tomography Imaging

Bismuth sulfide (Bi₂S₃) nanomaterials are emerging as a promising theranostic platform for computed tomography imaging and photothermal therapy of cancer. Herein, the photothermal properties of Bi₂S₃ nanorods (NRs) were unveiled to intensely correlate to their intrinsic deep‐level defects (DLDs) that potentially could work as electron–hole nonradiative recombination centers to promote phonon production, ultimately leading to photothermal performance. Bi₂S₃‐Au heterojunction NRs were designed to hold more significant DLD properties, exhibiting more potent photothermal performance than Bi₂S₃ NRs. Under 808 nm laser irradiation, Bi₂S₃‐Au NRs could trigger higher cellular heat shock protein 70 expression and more apoptotic cells than Bi₂S₃ NRs, and caused severe cell death and tumor growth inhibition, showing great potential for photothermal therapy of cancer guided by computed tomography imaging.     

Bi2S3量子点敏化TiO2纳米阵列结构的制备及光电性能

利用水热法制备一维TiO₂纳米棒阵列,并采用化学浴沉积法(CBD)结合自组装技术在TiO₂纳米棒上敏化Bi₂S₃量子点,形成TiO₂/Bi₂S₃复合纳米棒阵列。系统研究了复合结构的表面形貌、晶体结构、光学及光电性能。结果表明:在修饰有三氨丙基三乙氧基硅烷自组装单分子膜(APTS-SAMs)的TiO₂纳米棒表面形成一层致密的Bi₂S₃量子点敏化层,这一技术的关键是含-NH₂末端的APTS-SAMs可有效促进Bi₂S₃的异相成核作用;Bi₂S₃的沉积时间对复合结构的光吸收及光电响应性能有决定性的影响,薄膜的光电流随着沉积时间呈先增加后减小的趋势,在沉积时间为20min时,光电流密度最大。这是因为随着沉积时间的增加,TiO₂纳米棒表面Bi₂S₃量子点密度增大,光吸收增加;而当沉积时间进一步延长时,Bi₂S₃在TiO₂纳米棒表面的大量负载而形成堆积和团聚,导致表面缺陷增多,光生电子复合几率增大,从而使光电流密度减小。     

Bi2S3量子点敏化TiO2纳米阵列结构的制备及光电性能研究

利用水热法制备一维TiO₂纳米棒阵列,并采用化学浴沉积法(CBD)结合自组装技术在TiO₂纳米棒上敏化Bi₂S₃量子点,形成TiO₂/Bi₂S₃复合纳米棒阵列.系统研究了复合结构的表面形貌、晶体结构、光学及光电性能.结果表明:在修饰有三氨丙基三乙氧基硅烷自组装单分子膜(APTS-SAMs)的TiO₂纳米棒表面形成一层致密的Bi₂S₃量子点敏化层,这一技术的关键是含-NH₂末端的APTS-SAMs可有效促进Bi₂S₃的异相成核作用;Bi₂S₃的沉积时间对复合结构的光吸收及光电响应性能有决定性的影响,薄膜的光电流随着沉积时间呈先增加后减小的趋势,在沉积时间为20 min时,光电流密度最大.这是因为随着沉积时间的增加,TiO₂纳米棒表面Bi₂S₃量子点密度增大,光吸收增加;而当沉积时间进一步延长时,Bi₂S₃在TiO₂纳米棒表面的大量负载而形成堆积和团聚,导致表面缺陷增多,光生电子复合几率增大,从而使光电流密度减小.     

Facile Synthesis of Ultra‐wide Two Dimensional Bi2S3 Nanosheets: Characterizations,Properties and Applications in Hydrogen Peroxide Sensing and Hydrogen Storage

The ultra‐wide two dimensional Bi₂S₃ nanosheets (2D Bi₂S₃ Ns) as non‐toxic graphene‐like nanomaterials have been prepared through solvothermal decomposition of a single‐source precursor, Bi(S₂CNEt₂)₃, in ethylenediamine media for 2 h in 180 °C. The morphology, structure, properties and catalytic activity of prepared 2D Bi₂S₃ Ns were characterized with XRD, field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), UV‐Visible spectroscopy, cyclic voltammetry (CV), amperometry, electrochemical charge/discharge technique and electrochemical impedance spectroscopy (EIS). The SEM image showed the 2D Bi₂S₃ Ns with a thickness of 15±4 nm and lengths of several micrometers is synthesized. The UV−Vis spectrum of 2D Bi₂S₃ Ns showed high sensitivity to visible‐near infrared light with its direct energy band gap of ≈1.22 eV. These Bi₂S₃ Ns showed high electron transfer ability and good electrochemical behavior and also exhibited electro‐catalytic activity toward the reduction‐oxidation of hydrogen peroxide. It is found that Bi₂S₃ Ns could detect H₂O₂ at wide linear concentration range (50.0 μM–8.0 mM) with detection limit 8 μM, using amperometry as measuring technique. Also the synthesized Bi₂S₃ Ns exhibited excellent electrochemical H₂ storage properties. As a result, based on above properties, the Bi₂S₃ Ns can be used as a valuable and useful nanomaterial for H₂ storage, high‐energy batteries, electrocatalytic fields and electrochemical sensing.     

溶剂热法制备Bi2S3纳米材料

0引言纳米材料具有特殊的结构和性能,可广泛应用于化学、物理学、电子学、光学、机械和生物医药学等领域[1￣5]。其中一维或准一维纳米结构体系或纳米材料的研究既是研究其它低维材料的基础,又与纳米电子器件及微型传感器密切相关,是近年来国内外研究的前沿[6￣9]。近年来,人们虽然做了许多尝试来制备一维纳米结构材料,但合成这类材料特别是合成半导体一维纳米材料仍然是一个巨大的挑战。随着维数的减小,半导体材料的电子能态发生变化,其光、电、声、磁等方面性能与常规体材料相比有着显著的不同[10￣12]。Bi2S3是一种重要的半导体材料,受…     

One-pot synthesis of peony-like Bi2S3/BiVO4(040) with high photocatalytic activity for glyphosate degradation under visible light irradiation

In this work, samples consisting of BiVO₄ with exposed (040) facets coupled with Bi₂S₃ (Bi₂S₃/BiVO₄) were prepared through a one-pot hydrothermal method, using ethylenediaminetetraacetic acid as directing agent and L-cysteine as sulfur source and soft template. X-ray diffraction, field emission scanning electron microscopy, and high-resolution transmission electron microscopy measurements indicated that the Bi₂S₃ content had a significant influence on the growth of (040) and (121) facets as well as on the morphology of the Bi₂S₃/BiVO₄ samples. When the Bi₂S₃ content reached 1 mmol, the Bi₂S₃/BiVO₄ samples exhibited a peony-like morphology. The results of transient photocurrent tests and electrochemical impedance spectroscopy measurements confirmed that a more effective charge separation and a faster interfacial charge transfer occurred in Bi₂S₃/BiVO₄ than BiVO₄. The enhanced photocatalytic activity of the Bi₂S₃/BiVO₄ samples could be attributed to the improved absorption capability in the visible light region and the enhanced electron-hole pair separation efficiency due to the formation of the Bi₂S₃/BiVO₄ heterostructure. In addition, the Bi₂S₃/BiVO₄ samples showed relative stability and reusability. The simple method presented in this work could be used to fabricate composite photocatalysts with high activity for different applications, such as photocatalytic degradation of organic pollutants, photocatalytic splitting of water, and photocatalytic reduction of carbon dioxide.     

Enhanced Lithium‐Ion Storage Capability of a Bismuth Sulfide/Graphene Oxide/Poly(3,4‐ethylenedioxythiophene) Composite

A Bi₂S₃/graphene oxide (GO) composite enwrapped by a poly(3,4‐ethylenedioxythiophene) (PEDOT) coating was prepared for the first time for use as an anode in Li‐ion batteries. Pristine Bi₂S₃ nanoflowers and composites of Bi₂S₃/GO and Bi₂S₃/GO/PEDOT were assembled into half cells with Li metal as the counter electrode, and initial discharge capacities of 833, 1020, and 1300 mAh g^?1, respectively, were obtained. Composites of Bi₂S₃/GO/PEDOT and Bi₂S₃/GO showed superior cycling stability and better rate capability than pristine Bi₂S₃. GO provides highly conducting interconnections, which allow facile propagation of electrons during charge/discharge, and this improves the ion‐uptake capability of the Bi₂S₃ nanoflowers and also increases the rate capability. PEDOT furnishes a protective coating that prevents detachment of the material from the current collector during cycling, and it also imparts better cycling stability to the Bi₂S₃/GO/PEDOT composite.     

Structural and photoelectrochemical characterization of MWCNT-TiO2 matrices sensitized with Bi2S3

Structural and photoelectrochemical characterization of multiwall carbon nanotubes–titanium oxide (MWCNT-TiO₂) matrices, sensitized with bismuth sulfide (Bi₂S₃), are presented as a function of MWCNT-TiO₂ annealing temperature and Bi₂S₃ deposition time. Random matrices of multiwall carbon nanotubes were grown on stainless steel substrates by spray pyrolysis and then functionalized with a thin layer of TiO₂. Air annealing modifies the morphology and C/TiO₂ ratio in the hybrid materials, from MWCNT-TiO₂ core and shell structures at 400 °C to carbon-doped TiO₂ (C-TiO₂) at 550 °C. Both matrices increase the amount of Bi₂S₃ deposited by the chemical bath, but the best photoelectrochemical performance is observed in electrodes based on C-TiO₂. Electrodes based on core–shell structures of MWCNT-TiO₂ show large capacitive currents that interfere with photocurrent generation, demonstrating the storage potential of MWCNT and the critical role of MWCNT/TiO₂ ratio for photoelectrochemical applications. Regardless of the superior properties of C-TiO₂ photoanodes, the power conversion efficiency of Bi₂S₃-sensitized C-TiO₂ is limited by the appearance of an electron collection barrier at the substrate/film interface.     

Conversion Reactions of Solids: From a Surprising Three‐Step Mechanism towards Directed Product Formation

Directed conversion reactions from binary to multinary compounds are discovered from the reaction of Bi₂S₃ and Bi₂Se₃ with NiCl₂ ? 6 H₂O in polyol media under basic conditions. Control of the synthesis conditions allows the preparation of NiBiSe and superconducting Ni₃Bi₂S₂ and Ni₃Bi₂Se₂. The formation of Ni₃Bi₂S₂ from Bi₂S₃ is found from an unexpected three‐step reaction path with Bi and NiBi as intermediates. In the more complex Ni/Bi/Se system, the mechanism found can be used to selectively direct the reaction between the competing ternaries and to suppress side‐product formation. Contrary to solid‐state reactions (500–900 °C) control of product formation is reached at reaction temperatures and times between 166–300 °C and 0.5–10 h, respectively. The formation of different phases is discussed from results of DFT calculations.     

Preparation of bismuth sulfide nanoparticles as targeted biocompatible nano-radiosensitizer and carrier of methotrexate

In this study, Bi₂S₃@BSA–Bio–MTX nanoparticles (NPs) were synthesized for the first time by bovine serum albumin (BSA)-mediated biomineralization (Bi₂S₃@BSA NPs) followed by covalent bonding of biotin (Bio) and methotrexate (MTX) on the surface of the Bi₂S₃@BSA NPs via carbodiimide chemistry. The synthesized NPs were globular and exhibited uniform morphology with a hydrodynamic diameter of 107.6 ± 6.81 nm (mean ± standard deviation) and zeta potential of −20.9 ± 2.18 mV. Drug release from Bi₂S₃@BSA–Bio–MTX NPs indicated an enzyme-dependent release pattern. The in vitro biocompatibility of NPs was confirmed by investigating their cytotoxicity against the HEK-293 cell line and hemolysis assay test, whereas the in vivo biocompatibility of the NPs was evaluated and confirmed by the lethal dose 50 (LD₅₀) test. To evaluate the in vitro anticancer activity of the functionalized NPs and MTX, their cytotoxic effects was assessed against 4T1 cancer cells by 5-dimethylthiazol-z-yl)-2,5-diphenyltetrazolium bromide (MTT) assay with and without X-ray radiation. Results showed that Bi₂S₃@BSA–Bio–MTX NPs have excellent anticancer activity, especially following X-ray radiation.     

SiO2/PE/ Bi2S3核壳结构纳米颗粒的合成与性能(英)

以多层电解质作为微型反应器，制备了SiO₂/ Polyelectrolyte(PE) / Bi₂S₃核壳纳米粒子。XRD结果表明Bi₂S₃颗粒属于正交晶系。由透射电镜和场发射扫描电镜照片可知，在直径为640 nm左右的SiO₂表面覆盖了厚度35 nm的Bi₂S₃壳层。红外光谱分析结果表明硅烷网络在结构上发生了变化(SiO₂表面的硅烷醇键沉积在Bi₂S₃的表面)。SiO₂核和SiO₂ / PE / Bi₂S₃的紫外-可见吸收光谱显示在900 nm存在典型吸收边。     

Hydrothermal Synthesis of Bismuth Sulfide (Bi2S3) Nanorods: Bismuth(III) Monosalicylate Precursor in the Presence of Thioglycolic Acid

Well-segregated bismuth sulfide (Bi₂S₃) nanorods with a high order of crystallinity have been successfully prepared from bismuth(III) monosalicylate [BiO(C₇H₅O₃)] by a simple hydrothermal reaction in H₂O at 180 °C. Bismuth(III) monosalicylate and thioglycolic acid act as the starting materials. The products were characterized by powder X-ray diffraction, Ultraviolet–Visible (UV–Vis) spectroscopy, transmission electron microscopy photoluminescence spectroscopy, and Fourier transform infrared spectra. The powder X-ray diffraction pattern shows the product belongs to the orthorhombic Bi₂S₃ phase. Their UV–Vis spectrum shows the absorbance at 328 nm, with its direct energy band gap of 2.6 eV. Bismuth salicylate, which is known to be a complex, may play a critical role as a precursor and a template for the growth of linear bismuth sulfide nanorods. Finally the influences of the reaction conditions are discussed and a possible mechanism for the formation of Bi₂S₃ nanorods is proposed.     

Preparation of Bi<Subscript>2</Subscript>WO<Subscript>6</Subscript> by Electrospinning: Researching Their Synthesis Mechanism and Photocatalytic Activity

The novel Bi₂WO₆ nanomaterials, which consist of nanosheets and nanoparticles, were successfully synthesized by a combination of electrospinning and calcining processes. The Bi₂WO₆ with different morphologies and microstructures had been obtained in the same experimental conditions. The growth mechanism of such special nanostructures was investigated, and citric acid played an important role in the formation of Bi₂WO₆ nanostructures. The Bi₂WO₆ nanomaterials exhibited excellent photocatalytic property in the photodegradation of the pulping and papermaking wastewater under visible light irradiation. Besides, preparation of the photocatalyst using electrospinning was beneficial for separation and recycling. So, the Bi₂WO₆ nanomaterials have a great potential in application for wastewater treatment in the future.     

微波加热制备空心和锯齿形貌Bi_2Te_3晶体(英文)

Well-crystallized Bi₂Te₃ hollow spheres and nanosaws were prepared by microwave heating. Both the ionic liquid and the microwave heating play important role in the formation of the above nanostructures. Hollow spheres can not be obtained only by electronic stove heating, while the addition of ionic liquid leads to fast preparation of nanosaws structure under microwave heating conditions. The similar experimental results have been observed in the preparation of Bi₂S₃, Sb₂S₃ and Bi₂Se₃ nanostructures.     

Morphology Control of Bi2S3 Nanostructures and the Formation Mechanism

Bismuthinite (Bi₂S₃) nanostructures were prepared by a hydrothermal method with sodium ethylenediaminetetraacetate (EDTA‐Na₂). The morphology of Bi₂S₃ nanostructures was changed from a nanorod to a nanoplate by presence of the EDTA‐Na₂. The altered morphology was caused by the capping effect of EDTA‐Na₂ with Bi³⁺ ions, which induces the suboptimal growth direction due to partially blocking the preferential orientation direction. When the EDTA‐Na₂/Bi³⁺ molar ratio=1, the growth of Bi₂S₃ nanostructures was not allowed due to the chelating effect of EDTA‐Na₂. The obtained Bi₂S₃ nanorods, stacked nanorods, nanoplates and nanoparticles were characterized using X‐ray diffraction (XRD), transmission electron microscopy (TEM), high‐resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED) pattern. A possible formation mechanism of these morphologies was proposed. The successful synthesis of various morphologies of nanostructured Bi₂S₃ may open up new possibilities for thermoelectric, electronic and optoelectronic uses of nanodevices based on Bi₂S₃ nanostructure.     

In-situ construction of amorphous/crystalline contact Bi2S3/Bi4O7 heterostructures for enhanced visible-light photocatalysis

Constructing a heterojunction photocatalyst is a significant method to enhance photocatalytic activity because it can promote the separation of photogenerated carriers. Herein, amorphous/crystalline contact Bi₂S₃/Bi₄O₇ heterostructure was successfully synthesized by in-situ sulfidation of Bi₄O₇. The amorphous Bi₂S₃ is diffused on the surface of Bi₄O₇ rod, enhancing the visible light response and improving the transport of photogenerated carriers. Various characterizations confirm that the rapid separation of photogenerated carriers leads to increased photocatalytic performance. The optimized Bi₂S₃/Bi₄O₇ heterostructure photocatalyst (BiS-0.15) exhibits the highest Cr(VI) reduction (0.01350 min⁻¹) and RhB oxidation (0.08011 min⁻¹) activity, which is much higher than that of pure Bi₄O₇ and Bi₂S₃/Bi₄O₇ mixture under visible light irradiation. This work provides new insights into the construction of efficient novel photocatalysts.     

X-ray diffraction and electron microscope study of the Bi2S3PbBi2S4 system

An electron microscope and X-ray diffraction phase analytical study of the Bi₂S₃-galenobismutite (∼PbBi₂S₄) system has been made on samples rapidly quenched from the melt and samples prepared by sintering Bi₂S₃ and PbS at a temperature of 996 K, 10 K below the eutectic temperature. Five well-ordered phases were found, Bi₂S₃, galenobismutite, and three twinned phases, V-1, V-2, and V-3. The X-ray powder data of these materials are given as well as the refined lattice parameters. Electron microscope examination of the samples using a technique involving slight misalignment of the crystal fragments allowed the structures of disordered materials in the phase V region to be determined.     

Controlled synthesis of urchin-like Bi2S3 via hydrothermal method

The urchin-like Bi₂S₃ nanostructures have been grown by a facile environmentally friendly hydrothermal method. X-ray diffraction (XRD) and Raman spectrum demonstrate that the obtained samples are composed of pure orthorhombic phase Bi₂S₃. Scanning electron microscopy (SEM) images and transmission electron microscopy (TEM) images reveal that it is produced as uniform urchin-like pattern with spherical symmetry. High-resolution (HR) TEM and selected-area electron diffraction (SAED) demonstrate that the nanowires which grow radially from the center of the urchin-like nanostructures toward all directions are single-crystalline and grow along the [001]. It is found that the reaction time, reaction temperature and thiourea (Tu) play key roles for the formation of urchin-like Bi₂S₃ nanostructures. The formation mechanism is ascribed to self-assembly and the intrinsic splitting character of the Bi₂S₃ structure. The urchin-like Bi₂S₃ composed of porous nanorods, solid nanorods and nanowires could be found potential application in optical, catalysts and sensor devices.     

Dependence of the lone pair of bismuth on coordination environment and pressure: An ab initio study on Cu4Bi5S10 and Bi2S3

DFT calculations have been carried out for Cu₄Bi₅S₁₀ and Bi₂S₃ to provide an analysis of the relation between electronic structure, lone electron pairs and the local geometry. The effect of pressure is considered in Bi₂S₃ and the results are compared to published experimental data. Bi³⁺ in Cu₄Bi₅S₁₀ is found at both symmetrically and asymmetrically coordinated sites, whereas the coordination environments of Bi in Bi₂S₃ are asymmetric at room conditions and get more regular with increasing pressure. The charge density maps of the asymmetric sites show the lone pairs as lobes of non-shared charge. These lobes are related to an effective Bi s-Bi p hybridization resulting from coupling to S p orbitals, supporting the modern view of the origin of the stereochemically active lone pair. No effective Bi s-p hybridization is seen for the symmetric site in Cu₄Bi₅S₁₀, whereas Bi s-p hybridization coexists with a much reduced lone pair in Bi₂S₃ at high pressure.