A comprehensive review on surface modifications of black phosphorus using biological macromolecules
Chaiqiong Guo1, Xuhong He1, Xuanyu Liu1, Yuhui Wang1, Yan Wei1,2(), Ziwei Liang1,2, Di Huang1,2()
1. Department of Biomedical Engineering, Research Center for Nano-biomaterials & Regenerative Medicine, College of Biomedical Engineering, Taiyuan University of Technology, Taiyuan 030024, China 2. Shanxi-Zheda Institute of Advanced Materials and Chemical Engineering, Taiyuan 030032, China
Black phosphorus (BP), a novel two-dimensional material, exhibits remarkable photoelectric characteristics, ultrahigh photothermal conversion efficiency, substantial specific surface area, high carrier mobility, and tunable band gap properties. These attributes have positioned it as a promising candidate in domains such as energy, medicine, and the environment. Nonetheless, its vulnerability to light, oxygen, and water can lead to rapid degradation and loss of crystallinity, thereby limiting its synthesis, preservation, and application. Moreover, BP has demonstrated cytotoxic tendencies, substantially constraining its viability in the realm of biomedicine. Consequently, the imperative for surface modification arises to bolster its stability and biocompatibility, while concurrently expanding its utility spectrum. Biological macromolecules, integral components of living organisms, proffer innate advantages over chemical agents and polymers for the purpose of the BP modifications. This review comprehensively surveys the advancements in utilizing biological macromolecules for the modifications of BP. In doing so, it aims to pave the way for enhanced stability, biocompatibility, and diversified applications of this material.
The optical absorption range of BP covers the ultraviolet?visible band to the mid-infrared band, and its linear optical absorption is anisotropic. The extinction coefficient along the AC direction is several times larger than that along the ZZ direction.
[16–17]
Electrical property
The electrical conductivity of BP is anisotropic both inside and outside the plane, and the conductivity along the AC direction is larger than that along the ZZ direction. The difference in the electrical conductivity between the BP plane and the edge also leads to different electromagnetic differences.
[8,18]
Thermal conductivity
The thermal conductivity of BP is related to the number of layers and the crystal orientation, and the thermal conductivity in the ZZ direction is usually greater than that in the AC direction.
[19]
Mechanical property
The mechanical resistance of BP is anisotropic both in and out of the plane. The transverse deformation along the ZZ direction is smaller than that along the AC direction, and the friction in the AC direction is higher than that in the ZZ direction.
[20]
Photo-thermal property
Under laser irradiation, BP can convert light energy into heat energy (with a very high conversion rate), causing rapid temperature rise in the fixed point area, and local excessive heat leads to the inactivation of protein molecules such as intracellular enzymes.
[21–22]
Photodynamic property
Under photon irradiation, BP can activate oxygen molecules into singlet oxygen, resulting in the inactivation of living cell mitochondria, biological enzymes, and so on.
[6,23]
Tab.1
Fig.3
Fig.4
Fig.5
Fig.6
Fig.7
Nanomaterial
Surface modification material
Compound
Size/nm
Surface charge/mV
Application
Ref.
Type
Modifier
BPQDs
Nucleic acid
DNA
OPC B2/PBCD
55–60
6.9
Regeneration of diabetic infected wound
[38]
BPNSs
VEGF-BP/DNA
277 ± 12
?2 ± 2
Bone repair
[39]
BPNSs
Protein
Plasma protein
BPNS-corona
365.3 ± 5.9
?8.4
Innate immunity and inflammation
[40]
BPNSs
Serum protein
BP-HSA-PTX
300
?
Chemical photothermal combined anti-tumor
[41]
BPQDs
Cas9
CRISPR/Cas9
100
?17.8
Genome editing and gene silencing
[42]
BPQDs
Zein NP
BP-GEM@NPs
116.8 ± 9.6
?13.5
Pancreatic tumor
[43]
BPQDs
Cys
BPQD/Cys-PDSA
?
?
Cancer diagnosis and treatment
[44]
BPQDs
FKF
FKF-OVAp@BP
?
?
Checkpoint blocking in melanoma
[45]
BPQDs
KKF
BP@FKK
?
?
?
[46]
BPQDs
Homing peptide
iRGD-RM@BPQDs
50
?16
Photothermal catalytic synergistic antitumor
[47]
BPQDs
RGD
BPQDs@RGD-EXO
105
?
Angiogenesis
[48]
BPQDs
RGD
BPQDs@PEI + RGD-PEG + DMMA
93.45
13.1
Photodynamic targeted combination therapy
[49]
BPNSs
Gelatin
BPNS-gelatin
?
?
Photothermal treatment of breast cancer
[50]
BPNSs
BP/Gel
350
?10.0 ± 0.5
Osteanagenesis
[51]
BPNSs
BP/GT-MP
280
?
Lupus erythematosus
[52]
BPNSs
MNBC
?
?
Angiocardiopathy
[53]
BPNSs
Polysaccharide
Agarose
BP@hydrogel
160.3
?12.3
Oncotherapy
[54]
BPNSs
Hydrogel/BP/emetine
?
?
Photothermal therapy
[55]
BPQDs
Chitosan
PEG@CS/BPQDs AM NPs
200
7.8 ± 2.5
Chronic obstructive pulmonary disease
[56]
BPNSs
CS@BPNSs@CuNPs
?
?
Cancer therapy
[57]
BPNSs
C&BP
?
?
Skin wound healing
[58]
BPNSs
Polylactic acid
ZnO-BP/PLA
?
?
Antibacterial
[59]
BPNSs
Hyaluronic acid
Cy@HBPN
187 ± 7.4
?40.2 ± 3.3
Breast cancer
[60]
BPNSs
BPNS-PAMAM@DOX-HA
254.0 ± 3.45
22.1 ± 5.42
Chemical photothermal combined anti-tumor
[61]
BPQDs
EMP
EMP-BP
?
?
Antisepsis
[62]
BPNSs
Sodium alginate
M-ALG-BP
?
?
Bone repair
[63]
BPNSs
Cellulose
Cellulose/BPNS
?
?
Cancer therapy
[64]
BPQDs
Liposome
Lipidosome
BPQDs@Lipo
105.6 ± 6.8
0.5 ± 0.1
Chemical photothermal combined anti-tumor
[65]
BPNSs
Multifunctional liposome
RV/CAT-BP@MFL
256 ± 83
30.4
Chemical/photothermal/photodynamic synergistic treatment of cancer
[66]
BPQDs
Thermosensitive liposome
BPQDs-vanco@liposome
?
?
Subcutaneous abscess infected with drug-resistant bacteria
[67]
BPQDs
Cell membrane
Tumor cell membrane
BPQD-CCNV
230
?27
Cancer therapy
[68]
BPNSs
M-RP/BP@ZnFe2O4
122
?
Cancer therapy
[69]
BPQDs
Erythrocyte membrane
BPQD-RMNV
100
?13
Breast cancer
[70]
BPQDs
RBC@BPQDs-DOX/KIR
63.0 ± 1.6
?27.2 ± 0.9
Chemical photothermal targeted combined anti-tumor
[71]
BPQDs
Platelet membrane
PLT@BPQDs-HED
145 ± 5.0
?30.5 ± 2.5
Cancer therapy
[72]
BPNSs
Exosome
Gel-BP-Exo
?
?
Bone repair
[73]
BPQDs
EVs
Apt
100
?
Osteanagenesis
[74]
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