Black Phosphorous Nanosheets Research Articles

Bio-synthesized copper nanoparticle anchored ultrathin petal-shaped black phosphorous nanosheets and 3D graphene decorated nanocomposite for electrochemical sensing of methotrexate and paracetamol in diverse matrices

Creating a sensor that can concurrently monitor multiple therapeutic drugs in complex media is a challenging yet essential endeavor. This study presents a novel biomolecule-free electrochemical platform for simultaneous and highly selective detection of methotrexate (MTR) and paracetamol (PRC) in various matrices, including pharmaceutical formulations, simulated blood samples, and water samples. The platform utilizes a multi-layered petal-shaped black phosphorous structure supported on 3D graphene, along with bio-synthesized copper nanoparticles (BP-3DGp@BCuN). Prior to the sensing study, the as-prepared BP-3DGp@BCuN nanocomposite was characterized using FESEM, EDX, FTIR, UV, XPS, Raman spectroscopy, BET, and XRD. Electrochemical studies of BP-3DGp@BCuN nanocomposite reveal a considerable enhancement of the current compared to pure BP or 3DGp. The petal-shaped black phosphorous comprising of 3DGp and BCuN provides a larger surface area, effective mass transport, and more active sites for the attachment of the target analytes that amplified the current signals and detection sensitivity. Furthermore, computational analysis proves that the BP-3DGp@BCuN nanocomposite has strong interaction with the target MTR and PRC compared to other modifiers. Under optimized conditions, the proposed sensing method shows a linear detection range of 0.05–70 µM and 0.5–210 µM with limit of detection (LOD) values of 0.045 nM and 0.36 nM, with high sensitivity of 37.40 and 14.94 μA μM−1 cm−2 for PRC and MTR respectively. The real-life application of the present sensor was examined in pharmaceutical formulations, simulated blood, and water samples.

A win-win platform: Stabilized black phosphorous nanosheets loading gallium ions for enhancing the healing of bacterial-infected wounds through synergistic antibacterial approaches.

Bacterial infection is the most common complication in wound healing, highlighting an urgent need for the development of innovative antibacterial technologies and treatments to address the growing threats posed by bacterial infections. Black phosphorus nanosheets (BPNSs), as a promising two-dimensional nanomaterial, have been utilized in treating infected wounds. However, BP's limited stability restricts its application. In this study, we enhance BP's stability and its antibacterial properties by anchoring gallium ions (Ga3+) onto BP's surface, creating a novel antibacterial platform. This modification reduces BP's electron density and enhances its antibacterial capabilities through a synergistic effect. Under near-infrared (NIR) irradiation, the BP/Ga3+ combination exerts antibacterial effects via photothermal therapy (PTT) and photodynamic therapy (PDT), while also releasing Ga3+. The Ga3+ employ a 'Trojan horse strategy' to disrupt iron metabolism, significantly boosting the antibacterial efficacy of the complex. This innovative material offers a viable alternative to antibiotics and holds significant promise for treating infected wounds and aiding skin reconstruction.

Biomimetic MDSCs membrane coated black phosphorus nanosheets system for photothermal therapy/photodynamic therapy synergized chemotherapy of cancer

Photothermal therapy is favored by cancer researchers due to its advantages such as controllable initiation, direct killing and immune promotion. However, the low enrichment efficiency of photosensitizer in tumor site and the limited effect of single use limits the further development of photothermal therapy. Herein, a photo-responsive multifunctional nanosystem was designed for cancer therapy, in which myeloid-derived suppressor cell (MDSC) membrane vesicle encapsulated decitabine-loaded black phosphorous (BP) nanosheets (BP@ Decitabine @MDSCs, named BDM). The BDM demonstrated excellent biosafety and biochemical characteristics, providing a suitable microenvironment for cancer cell killing. First, the BDM achieves the ability to be highly enriched at tumor sites by inheriting the ability of MDSCs to actively target tumor microenvironment. And then, BP nanosheets achieves hyperthermia and induces mitochondrial damage by its photothermal and photodynamic properties, which enhancing anti-tumor immunity mediated by immunogenic cell death (ICD). Meanwhile, intra-tumoral release of decitabine induced G2/M cell cycle arrest, further promoting tumor cell apoptosis. In vivo, the BMD showed significant inhibition of tumor growth with down-regulation of PCNA expression and increased expression of high mobility group B1 (HMGB1), calreticulin (CRT) and caspase 3. Flow cytometry revealed significantly decreased infiltration of MDSCs and M2-macrophages along with an increased proportion of CD4+, CD8+ T cells as well as CD103+ DCs, suggesting a potentiated anti-tumor immune response. In summary, BDM realizes photothermal therapy/photodynamic therapy synergized chemotherapy for cancer.

Bimetallic metal organic framework anchored multi-layer black phosphorous nanosheets with enhanced electrochemical activity for paracetamol detection

Bimetallic metal organic framework anchored multi-layer black phosphorous nanosheets with enhanced electrochemical activity for paracetamol detection

Rational Utilization of Black Phosphorus Nanosheets to Enhance Palladium-Mediated Bioorthogonal Catalytic Activity for Activation of Therapeutics.

Pd-catalyzed chemistry has played a significant role in the growing subfield of bioorthogonal catalysis. However, rationally designing Pd nanocatalysts that show outstanding catalytic activity and good biocompatibility poses a great challenge. Herein, we propose an innovative strategy through exploiting black phosphorous nanosheets (BPNSs) to enhance Pd-mediated bioorthogonal catalytic activity. Firstly, the electron-donor properties of BPNSs enable in situ growth of Pd nanoparticles (PdNPs) on it. Meanwhile, due to the superb capability of reducing PdII , BPNSs can act as hard nucleophiles to accelerate the transmetallation in the decaging reaction process. Secondly, the lone pair electrons of BPNSs can firmly anchor PdNPs on their surface via Pd-P bonds. This design endows Pd/BP with the capability to retard tumor growth by activating prodrugs. This work proposes new insights into the design of heterogeneous transition-metal catalysts (TMCs) for bioorthogonal catalysis.

Rational Utilization of Black Phosphorus Nanosheets to Enhance Palladium‐Mediated Bioorthogonal Catalytic Activity for Activation of Therapeutics

AbstractPd‐catalyzed chemistry has played a significant role in the growing subfield of bioorthogonal catalysis. However, rationally designing Pd nanocatalysts that show outstanding catalytic activity and good biocompatibility poses a great challenge. Herein, we propose an innovative strategy through exploiting black phosphorous nanosheets (BPNSs) to enhance Pd‐mediated bioorthogonal catalytic activity. Firstly, the electron‐donor properties of BPNSs enable in situ growth of Pd nanoparticles (PdNPs) on it. Meanwhile, due to the superb capability of reducing PdII, BPNSs can act as hard nucleophiles to accelerate the transmetallation in the decaging reaction process. Secondly, the lone pair electrons of BPNSs can firmly anchor PdNPs on their surface via Pd−P bonds. This design endows Pd/BP with the capability to retard tumor growth by activating prodrugs. This work proposes new insights into the design of heterogeneous transition‐metal catalysts (TMCs) for bioorthogonal catalysis.

Cu(II) harmonize g-C3N4 and black phosphorous together under the interaction of surface charges to form unconventional type-II photocatalyst BPs/Cu/CNs with attractive performance

Rational utilization of the surface charge property of components is an effective method to prepare heterojunction. The surface of g-C3N4 nanosheets (CNs) and black phosphorous nanosheets (BPs) both exhibit negative charge, which would produce repulsive force to hinder them from approaching each other. Herein, non-noble and low-toxic Cu(II) was selected to harmonize the CNs and BPs together under the interaction of surface charges, and the Cu(II) was reduced in situ to Cu with good conductivity, obtaining the sandwich-like product BPs/Cu/CNs with tight interface and high separation efficiency of photogenerated carriers. The composites exhibited attractive degradation performance for various pollutants under visible light, especially, 95.3 % of ciprofloxacin (10 mg/L, 200 mL) was removed in 60 min with 50 mg of 6BPs/4Cu/CNs as photocatalyst, and the removal ratio can still reach 87.4 % after the fifth reuse with negligible leaching of Cu ions. An unconventional type-II band structure was built in the BPs/Cu/CNs under the drive of internal electric field and mutual attraction of opposite charges, in which the e- from CB of BPs transferred to Cu and then combined with the h+ from VB of CNs, leaving the e- from CB of CNs and h+ from VB of BPs still work. Despite the same result to that of typical type-II band structure of BPs/CNs, the flow of photogenerated carriers in the BPs/Cu/CNs was more favorable in thermodynamics.

Calcium Phosphate Bone Cements Incorporated with Black Phosphorus Nanosheets Enhanced Osteogenesis.

For decades, calcium phosphate bone cements (CPCs) showed impressive advantages for their good biocompatibility, injectability, and osteoconductivity in the bone repair field. However, it is still difficult to prepare CPCs with outstanding antibacterial and self-curing properties, sufficient phosphorus release, and osteoinductivity for clinical application. Herein, we used partially crystallized calcium phosphate and dicalcium phosphate anhydrate particles incorporated with black phosphorous nanosheets to prepare calcium phosphate bone cements (CPCs). The curing time, compressive strength, photothermal properties, and degradation performance of BP/CPC were investigated. In addition, the cytocompatibility and osteoinductivity of BP/CPC were evaluated by cell adhesion, cytotoxicity, alkaline phosphatase detection, alizarin red staining, and western blot assay. The results indicated that BP/CPC showed adjustable curing time, good cytocompatibility, outstanding photothermal properties, and osteoinductivity, suggesting their potential application for bone regeneration.

Covalent Functionalization of Black Phosphorus Nanosheets with Photochromic Polymer for Transient Optoelectronic Memory Devices

AbstractHow to erase sensitive data stored on memory devices quickly in an emergency has become a critical issue that needs to be addressed. Using BP‐BIBB as a key template for atom transfer radical polymerization, which is prepared by the reaction of p‐hydroxyphenyl‐functionalized black phosphorous nanosheets (C6H4OH‐BP) with 2‐bromoisobutyryl bromide (BIBB), a highly soluble poly[4‐(4‐(3,3,4,4,5,5‐hexafluoro‐2‐(2‐methyl‐5‐phenylthiophen‐3‐yl)cyclopent‐1‐en‐1‐yl)‐5‐methylthiophen‐2‐yl)phenyl methacrylate] (PHPM)‐covalently grafted BP derivative, hereafter abbreviated as PHPM‐g‐BP, is synthesized in situ. PHPM is a typical photochromic polymer that emits blue light under UV irradiation, while showing pale yellow under visible light illumination. By using PHPM‐g‐BP as an active layer, an as‐fabricated transient optoelectronic memory device exhibits a nonvolatile rewritable memory effect under UV irradiation, with an ON/OFF current ratio of 3.6 × 103, a turn‐on voltage of 1.60 V, and a turn‐off voltage of −1.41 V. Upon visible light illumination for 10 s, all the information stored in the device is erased quickly. The observed device current drops down from 10−3 to 10−8 A rapidly.

A versatile diketopyrrolopyrrole-based photosensitizing nanoplatform with high photostability and photoactivity for metastatic breast cancer treatment

Owing to the merits of acceptable biocompatibility, excellent efficacy and minimal invasiveness, photodynamic therapy (PDT) represents a promising alternative approach for fighting against malignant tumor. However, the photobleaching, photodegradation and dark toxicity of traditional photosensitizers limit the therapeutic efficacy and clinical use of PDT. In present work, we synthesized a diketopyrrolopyrrole-based photosensitizer, AN(DPP)2, with excellent fluorescence emission, photodynamic performance and photostability. We then fabricated a versatile photosensitizing nanoplatform composed of AN(DPP)2-loaded PEGylated black phosphorous nanosheets (named AN/pBPN), for synergetic photodynamic-photothermal therapy (PDT/PTT) against metastatic breast cancer. AN/pBPN exhibited a multitude of notable superiorities in terms of superior optical characters, favorable photodynamic and photothermal performance in physiological environment, and excellent internalization efficiency toward tumor cells. Upon light irradiation, abundant singlet oxygen and hyperthermia were generated by AN/pBPN, resulting in a remarkable antitumor effect toward 4T1 cells. In vivo studies verified that AN/pBPN showed potent light-triggered suppression of tumor growth as well as distant pulmonary metastasis, accompanied by minimal safety concern in metastatic breast cancer mouse model. Collectively, multifunctional diketopyrrolopyrrole-based photosensitizing nanoplatform with prominent photoactivity, acceptable biosafety, powerful antitumor and anti-metastasis activity, such as AN/pBPN, might be a promising nanomedicine for combating malignant tumor via synergetic phototherapy.

An ultrasensitive electrochemical self-signal circulating tumor DNA recognition strategy employing black phosphorous nanosheets assembled with flavin adenine dinucleotide

A self-signal electrochemical sensing platform was constructed for direct recognition of circulating tumor DNA (ctDNA) employing black phosphorous nanosheets (BPNS) assembled with flavin adenine dinucleotide (FAD) prepared by ultrasonication approach. FAD provided a highly efficient and stable dispersing medium for acquiring highly dispersed BPNS in aqueous phase. The obtained FAD/BPNS nanocomposite exhibited favorable electrochemical redox activity and was utilized as the interface for the immobilization and hybridization of DNA. The amine-terminated probe ssDNA was covalently assembled onto the FAD/BPNS nanocomposite with plentiful phosphonate groups accompanied by the decrease of the self-signal. The self-redox signal of the nanointerface regenerated after the probe hybridized with the complementary sequence as a result of DNA transformation. Electrochemical response enhanced with complementary DNA concentration from 1.0 × 10-18 to 1.0 × 10-8 mol/L with a detection limit of 2.6 × 10-19 mol/L. The DNA determination platform revealed outstanding sensitivity, specificity and stableness, and was successfully employed in the detection of ctDNA associated with colorectal cancer. The developed biosensing strategy is simple to accomplish and has the potency for the application for diverse morbific gene without sophisticated label procedure.

All-cellulose gel electrolyte with black phosphorus based lithium ion conductors toward advanced lithium-sulfurized polyacrylonitrile batteries

Sulfurized polyacrylonitrile (SPAN) have been regarded as a promising cathode in high-energy-density lithium-sulfur batteries. However, severe safety issues derived from the electrolyte leakage and the uncontrollable lithium dendrite growth have seriously hindered the practical usage of Li-SPAN batteries. To address these issues, an eco-friendly and porous cellulose gel electrolyte (GE) was designed and prepared by UV photopolymerization and phase inversion methods. Also, covalent functional black phosphorous nanosheets (denoted as BP-Li) were fabricated and chosen as superior Li+ conductors in cellulose GE, ensuring the rapid ion transmission and suppressing the growth of lithium dendrites. As expected, the cellulose/BP-Li GE exhibited satisfactory ionic conductivity up to 5.21 × 10−3 S cm−1 with the high lithium ion transference number of 0.72. The Li-SPAN battery assembled with cellulose/BP-Li GE delivered high capacity of 938.8 mAh g−1 after 500 cycles with the capacity retention of 72.8 %. Hence, the cellulose/BP-Li GE displayed its promising usage in Li-SPAN batteries.

Enhanced hydrogen evolution via in situ generated 2D black phosphorous nanocomposites at the liquid/liquid interfaces

The mimicry of bio-membrane with a liquid/liquid interface between two immiscible electrolyte solutions is intrinsically defect-free to study catalysis of energy conversion reactions i.e., CO2 reduction, oxygen reduction, and hydrogen evolution. Herein, we report the in-situ generation of electrodeposited black phosphorous (BP) based nanocomposites at the liquid/liquid interface for the first time and their catalysis in hydrogen evolution reaction (HER). The catalytic HER activities of these catalysts have been investigated electrochemically and also chemically by two-phase reactions. The BP/MoSx, BP/Cu, and BP/Pt nanocomposites were formed by reducing the catalyst precursors such as (NH4)2MoS4, (NH4)2PtCl4, and CuCl2 salts, respectively on the BP nanosheets by decamethylferrocene (DMFc) electron donor during the catalytic HER. The electrodeposited nanocomposites were collected from the interface and characterized by using advanced analytical techniques. Among them, the BP/MoSx nanocomposites showed the highest HER activity with a reaction rate constant of 0.202 min−1 was about 230- and 7-times greater than the ones obtained by non-catalytic reaction and the free-MoSx catalyst. Moreover, the nucleation of the catalysts and the HER mechanisms were also explained in detail. The BP/MoSx also showed higher HER activity compared to that of carbon nanotubes CNTMoSx and reduced graphene oxide rGOMoSx nanocomposites.

Enzyme-free sandwich-type electrochemical immunosensor based on high catalytic binary PdCu mesoporous metal nanoparticles and conductive black phosphorous nanosheets for ultrasensitive detection of pro-SFTPB in non-small cell lung cancer

Pro-surfactant protein B (pro-SFTPB) has been proven to be a powerful biomarker for the early diagnosis of non-small-cell lung cancer (NSCLC). In this study, a novel enzyme-free electrochemical immunosensor is developed for the ultrasensitive detection of pro-SFTPB using binary PdCu mesoporous metal nanoparticles (MMNs) and few-layer black phosphorous (BP nanosheets). Concretely, PdCu MMNs, as novel essential signal labels, were successfully synthesized, offering excellent outstanding peroxidase-like catalytic activity toward hydrogen peroxide (H2O2). Meanwhile, the combination of BP nanosheets with biocompatible gold nanoparticles (AuNPs) served as the substrate on the electrode. With the aid of binary PdCu MMNs nanozymes and BP nanosheets, the enzyme-free electrochemical immunosensor revealed ultrasensitivity detection of pro-SFTPB ranging from 10 pg/mL to 100 ng/mL with an ultralow limit of detection of 5.3 pg/mL. In addition, the immunosensor enables accurate detection of pro-SFTPB in serum samples. Altogether, the developed electrochemical immunosensor provides an enzyme-free platform for pro-SFTPB detection, providing a new method for the early diagnosis of NSCLC.

S-scheme heterojunction BP/WO3 with tight interface firstly prepared in magnetic stirring reactor for enhanced photocatalytic degradation of hazardous contaminants under visible light

Black phosphorous (BP) has attracted extensive attention because of its unique properties, but the unstable structure restricts its practical application. Herein, exfoliated tungsten trioxide (WO3) was innovatively chosen to couple with BP nanosheets to form a novel 2D/2D heterojunction BP/WO3 through self-assembly process. Instead of conventional hydrothermal reactor without the stirring function or just simple mixing at room temperature and pressure, the magnetic stirring reactor was adopted to provide an inert gas atmosphere (N2) with high temperature and pressure (120 °C and 0.4 MPa), where the contact chance of BP and WO3 nanosheets would be improved greatly and then be pushed towards each other to form tighter interface. The establishment of S-scheme band structure was proved by the abundant existence of ·OH and ·O2– detected by radical scavenging experiments and EPR test. Besides, the electron injection from WO3 to BP under irradiation confirmed by XPS test can improve the chemical stability of BP much, and it further indicated the construction of S-scheme charge migration pathway between BP and WO3, which can achieve effective spatial separation of photogenerated e--h+ pairs without sacrifice of weakening the redox power of useful electrons and holes. As a result, the 6BP/WO3 showed enhanced photocatalytic performance with a removal ratio of 98.6% for tetracycline hydrochloride (TCH) and 93.2% for Cr(VI) within 60 min, respectively. This study provides new strategy to the design and preparation of efficient 2D/2D S-scheme photocatalyst with visible light responsive ability.

Ultrasensitive Flexible Memory Phototransistor with Detectivity of 1.8×1013 Jones for Artificial Visual Nociceptor

Emerging intelligent devices that can simulate an artificial intelligence vision system are of great interest for the development of modern information technology. Nociceptor is a crucial sensory neuron that recognizes harmful inputs and sends pain signals to the central nervous system to avoid injury; however, visual nociceptors, considered to be a key bionic function to protect eyesight based on optoelectronic devices, have yet to be developed. Herein this study, a three‐terminal flexible memory phototransistor (MPT) is first fabricated, which simulates the visual nociceptive behavior by adjusting light stimulation. The CsPbBr3 quantum‐dots (QDs)‐few‐layered black phosphorous nanosheets (FLBP NSs) heterojunction MPT demonstrates high responsivity of 7.2 × 103 AW−1 and high detectivity of 1.8 × 1013 Jones due to the high absorption coefficient of CsPbBr3 QDs materials and a high carrier transport property of FLBP NSs. Moreover, the proposed device can be used to emulate ultraviolet‐stimuli‐induced characteristics of visual nociceptors such as a threshold, no adaption, relaxation, allodynia, and hyperalgesia. It provides a new avenue for the realization of next‐generation neural‐integrated devices via its visual pain sense‐perception abilities.

Ag Decoration-Enabled Sensitization Enhancement of Black Phosphorous Nanosheets for Trace No2 Detection at Room Temperature

Ag Decoration-Enabled Sensitization Enhancement of Black Phosphorous Nanosheets for Trace No2 Detection at Room Temperature

Dual-Light-Triggered In Situ Structure and Function Regulation of Injectable Hydrogels for High-Efficient Anti-Infective Wound Therapy.

Most injectable hydrogels used in biomedical engineering have unsatisfactory and untunable mechanical properties, making it difficult to match them with the mechanical strengths of different tissues and organs, which can cause a series of adverse consequences such as immune rejection and soft tissue contusion. In this contribution, dopamine-modified hyaluronic acid (HA-DA) is developed as the backbone for an injectable hydrogel using a catechol-Fe3+ coordination crosslinking strategy. Due to dynamic physical crosslinking, the hydrogel can be easily injected through a single syringe. Into the hydrogel, black phosphorous nanosheets loaded with a Zr-based porphyrinic metal-organic framework (PCN@BP) are introduced that could generate reactive oxygen species (ROS) under 660nm laser irradiation, this promotes the oxidative coupling of dopamine in the presence of the ROS, introducing in situ chemical crosslinking into the hydrogel. A physical/chemical double-crosslinked hydrogel is obtained, effectively improving the hydrogel's mechanical properties, which are tuned in situ by adjusting the irradiation time to match the mechanical modulus of different biological tissues. Combining the excellent photothermal properties and photodynamic performance of the PCN@BP nanosheets yields effective sterilization under mild conditions (below 50 °C, low ROS production). The results show that this hydrogel is an excellent multifunctional wound dressing.

Black phosphorous nanosheets–gold nanoparticles–cisplatin for photothermal/photodynamic treatment of oral squamous cell carcinoma

To improve five-year survival rate of oral squamous cell carcinoma (OSCC), the development of a novel composite material of black phosphorus nanosheets (BPNSs) and gold nanoparticles (AuNPs) for tumor treatment was carried out. The purpose of this study is to evaluate the cytostatic effects of BPNSs, AuNPs loaded with cisplatin (CDDP) on human tongue squamous cell carcinoma cells lines (SCC-9), and 7,12-dimethylbenz anthracene induced cheek squamous cell carcinoma was validated in golden hamsters animal models. The results showed that BPNSs could efficiently inhibit the metastasis and growth of OSCC compared with CDDP and AuNPs. And a combination composite of AuNPs–BPNSs loaded with CDDP could more effectively inhibit the metastasis and growth of OSCC, which might be due to the high drug-loading capacity, excellent photothermal properties and the combination of photodynamic and photothermal therapy of BPNSs and AuNPs, as well as the synergistic effects of AuNPs, BPNSs and CDDP.

Air stable conductivity of black phosphorous/graphitic carbon nitride blends

Black phosphorous nanosheets are combined with carbon nitride to fabricate 2-terminal devices featuring high environmental stability lasting for over four months of storage in air when the devices contained at least 50% carbon nitride.