Ultrasmall CuCo₂S₄ Nanocrystals: All‐in‐One Theragnosis Nanoplatform with Magnetic Resonance/Near‐Infrared Imaging for Efficiently Photothermal Therapy of Tumors

Abstract

Copper-based ternary bimetal chalcogenides have very promising potential as multifunctional theragnosis nanoplatform for photothermal treatment of tumors. However, the design and synthesis of such an effective platform remains challenging. Herein, hydrophilic CuCo2S4 nanocrystals (NCs) with a desirable size of ~10 nm were synthesized by a simple one-pot hydrothermal route. The as-prepared ultrasmall CuCo2S4 NCs show: 1) intense near-infrared (NIR) absorption, which is attributed to 3d-electronic transitions from the valence band (VB) to an intermediate band (IB), as identified by Density Functional Theory (DFT) calculations; 2) high photothermal performance with a photothermal conversion efficiency up to 73.4%; and 3) capability for magnetic resonance (MR) imaging, as a result of the unpaired 3d electrons of cobalt. Finally, we, for the first time, demonstrated that the CuCo2S4 NCs are a promising "all-in-one" photothermal theragnosis nanoplatform for photothermal cancer therapy under the irradiation of a 915 nm laser at a safe power density of 0.5 W cm-2 , guided by MR and infrared thermal imaging. Our work further promotes the potential applications of ternary bimetal chalcogenides for photothermal theragnosis therapy. B. Li, F. K. Yuan and G. J. He contributed equally to this work. The authors acknowledge our membership of the UK's HPC Materials Chemistry Consortium, which is funded by Engineering and Physical Sciences Research Council (EP/L000202). The authors would thank the use of the UCL Legion High Performance Computing Facility and associated support services, in the completion of this work.

Cu5FeS4 Nanoparticles With Tunable Plasmon Resonances for Efficient Photothermal Therapy of Cancers

“…The optical absorption spectrum of CFS nanoparticles, obtained from the reaction with a ratio of 20% for iron source to copper source, showed a peak around 1,100 nm. The NIR absorption may be attributed to 3d electronic transitions from the valence band to an intermediate band, similar to CuFeS 2 nanocrystals (Ghosh et al, 2016) and CuCo 2 S 4 nanocrystals (Li et al, 2017). The ratio of Cu to Fe was found to be 4.99, confirmed by ICP-AES.…”

One‐Pot Synthesis of CuCo2S4 Sub‐Microspheres for High‐Performance Lithium‐/Sodium‐Ion Batteries

“…[12] Yu's group employed a facile in-situ template removal process to receive NiCo 2 S 4 @C hollow nanospheres consisted of ultrathin nanosheets, which achieved a high capacity of 1137 mA h g À 1 for LIBs. [14][15][16][17][18][19][20] Additionally, the merits of high specific capacity, excellent electronic conductivity, rich redox action sites also endowed CuCo 2 S 4 with a promising prospective in application of energy-storage batteries. [14][15][16][17][18][19][20] Additionally, the merits of high specific capacity, excellent electronic conductivity, rich redox action sites also endowed CuCo 2 S 4 with a promising prospective in application of energy-storage batteries.…”

“…[13] Among numerous TMS, copper cobalt sulfide (CuCo 2 S 4 ) had wide applications in supercapacitors, water oxidation electrocatalysis and photothermal therapy because of its unique physical and chemical properties. [14][15][16][17][18][19][20] Additionally, the merits of high specific capacity, excellent electronic conductivity, rich redox action sites also endowed CuCo 2 S 4 with a promising prospective in application of energy-storage batteries. Up to now, a few attempts have been devoted to developing CuCo 2 S 4 and its nanocomposites with various morphologies and structures as LIBs/SIBs electrode materials.…”

Porous Core–Shell CuCo2S4 Nanospheres as Anode Material for Enhanced Lithium‐Ion Batteries

“…In the Co 2p region (Figure c), the binding energies located at 778.8 and 779.3 eV can be assigned to the presence of Co 3+ and Co 2+ , respectively, in the Co 2p 3/2 spectrum. Similarly, the peaks at 793.3 and 794.2 eV in the Co 2p 1/2 spectrum also suggest coexistence of Co 2+ and Co 3+ . According to the XPS spectra of S 2p in Figure d, two characteristic peaks at 161.3 and 162.3 eV are ascribed to S 2p 3/2 and S 2p 1/2 , respectively.…”

“…Similarly,t he peaks at 793.3 and 794.2 eV in the Co 2p 1/2 spectrum also suggest coexistence of Co 2 + and Co 3 + . [34,35] According to the XPS spectra of S2 pi nF igure 2d,t wo characteristic peaks at 161.3 and 162.3 eV are ascribed to S2 p 3/2 and S 2p 1/2 ,r espectively.F urthermore, the magnitude of the peak splitting is approximately 1.0 eV,a nd weak satellitep eaks are located at 168.4 eV,i ndicating the priority of S 2À in CuCo 2 S 4 . [36,37] The peak at 163.3 eV corresponds to the typical metal-sulfur (CuÀSa nd CoÀS) bonds for S2 p 1/2 .…”