Cu3BiS3 Composites with Enhanced

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Urchin-Shaped BiS/CuS/CuBiS Composites with Enhanced Photothermal and CT Imaging Performance Guodong Yu, Aili Liu, Huile Jin, Yangzong Chen, Dewu Yin, Rui Huo, Shun Wang, and Jichang Wang J. Phys. Chem. C, Just Accepted Manuscript • DOI: 10.1021/acs.jpcc.7b12505 • Publication Date (Web): 25 Jan 2018 Downloaded from http://pubs.acs.org on January 30, 2018

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The Journal of Physical Chemistry C is published by the American Chemical Society. 1155 Sixteenth Street N.W., Washington, DC 20036 Published by American Chemical Society. Copyright © American Chemical Society. However, no copyright claim is made to original U.S. Government works, or works produced by employees of any Commonwealth realm Crown government in the course of their duties.

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The Journal of Physical Chemistry

Urchin-Shaped

Bi2S3/Cu2S/Cu3BiS3

Composites

with

Enhanced

Photothermal and CT Imaging Performance Guodong Yu,a Aili Liu,a* Huile Jin, a Yangzong Chen,b Dewu Yin,a Rui Huo,a Shun Wang,a* and Jichang Wang c* a

College of Chemistry and Materials Engineering, Wenzhou University, Wenzhou, Zhejiang,

China 325035. b

The First Affiliated Hospital of Wenzhou Medical University, Wenzhou, Zhejiang, China

325000. c

Department of Chemistry and Biochemistry, University of Windsor, Windsor, ON, Canada

N9B 3P4.

1

ACS Paragon Plus Environment

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ABSTACT Urchin-shaped Bi2S3/Cu2S/Cu3BiS3 nanocomposites were successfully prepared in this study through one-pot synthesis, which involved microwave-assisted simultaneous pyrolysis of two precursors. The as-prepared Bi2S3/Cu2S/Cu3BiS3 hybrids exhibit stronger absorption in near infrared regime than the individual component, i.e., Bi2S3, Cu2S and Cu3BiS3, The photothermal conversion efficiency (η) of Bi2S3/Cu2S/Cu3BiS3 composites can even reach to 43.8%, which is significantly higher than that seen with most of the transition metal chalcogenide materials. The excellent photothermal performance of Bi2S3/Cu2S/Cu3BiS3 hybrids is likely arising from its unique urchin-like structure, in which needle-like Bi2S3/Cu2S nanocomposites grows from the core of Cu3BiS3. The co-presence of Bi2S3 and Cu2S also leads this newly synthesized composites produce high contrast for X-ray computer tomography imaging, an important property required for a great potential application in theranostic cancer treatment.

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1. INTRODUCTION The near infrared (NIR) laser-driven photothermal therapy (PTT) has recently attracted increasing attention due to its low side effects,1-3 when compared with those traditional clinical treatments of cancer.4-8 However, PTT has strict requirements on the properties of the photothermal reagents, such as good biocompatibility and stability, strong NIR absorption, high photothermal conversion efficiency, etc.9 In the last decade, various materials such as noble metals (Au, Pt, Au-Ag),10-12 carbon,13,14 polymer nanoparticles15,16 and semiconductors (Cu1.75S, WSe2, CuFeS2)17-19 have been explored as the PTT substances. To overcome the low photostability of polymer particles and the low efficiency of inorganic nanomaterials20, copper sulfides had been intensively investigated as the future ideal PTT agent, due to its low cost, biodegradability, high stability and no obvious side effects.21 However, the low photothermal conversion efficiency hindered it from a broad range of applications.22 Some methods such as incorporation of bismuth sulfide (Bi2S3) into copper sulfide-based nanoparticles have been employed to enhance their photothermal conversion. Due to the intrinsic nature of Bi element in absorbing X-ray with a very high efficiency, bismuth sulfides have also been used as CT contrast agents and a sensitizing agent for enhancing the efficacy of radiation therapy (RT). 23 The great benefits of integrating Bi and Cu sulfides have been seen in a plenty of studies reported in the last three years, in which Cu3BiS3 has been synthesized as an example of integrating/combining the advantages of bismuth sulfides and copper chalcogenides.24,38 The substance does exhibit promising properties and functions for both as the photothermal and the CT image contrast agent.25-27 Unfortunately, the synthetic method of Cu3BiS3 has so far 3



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been complicated and the overall photothermal (PT) conversion efficiency of Cu3BiS3 compound is still not high. In this study, we developed a one-step microwave-assisted synthetic procedure, leading to the production of chalcogenides with distinct morphologies. By simply adjusting the proportion of copper and bismuth precursors, cuboid shaped Cu3BiS3 and urchin-like Bi2S3/Cu2S/Cu3BiS3 composites were prepared. Both composite materials exhibit strong optical absorption spanning from ultraviolet (UV) to near infrared wavelength. The PT conversion efficiency of Cu3BiS3 cuboids and urchin-like Bi2S3/Cu2S/Cu3BiS3 composites reaches 27.6% and 43.8% respectively, which are higher than most of the copper and bismuth sulfide-based PTT agents reported.28-30 The as-prepared urchin-like Bi2S3/Cu2S/Cu3BiS3 also showed great performance as a CT imaging agent due to the large X-ray attenuation coefficient of bismuth. 2. EXPERIMENTAL SECTION Chemicals All reagents were analytical grade and used without further purification. Copper (II) nitrate trihydrate (Cu(NO3)2·3H2O), bismuth nitrate pentahydrate (Bi(NO3)3·5H2O) were obtained from Macklin Chemical Reagents Shanghai Co. Sodium dimethyl dithiocarbamate was obtained from Zhejiang Ultrafine Powders & Chemicals Co. Ethylene glycol (>98%) were purchased from Aladdin Chemical Reagent Shanghai Co. Deionized water was prepared with a Elix5-Milli-Q Water System (18.2 MΩ·cm).

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Synthesis of Bi2S3 and Cu2S precursors Copper dimethyl dithiocarbamate (Cu(DMDC)2)31 was prepared by adding 0.1 mmol of copper nitrate trihydrate (Cu(NO3)2·3H2O), 0.2 mmol of sodium dimethyl dithiocarbamate and 400.0 mL deionized water into a 500.0 mL beaker. The mixture was ultrasounded for 20.0 min and kept at room temperature for 12.0 h. The solids were collected through filtration and then washed with ethanol several times. Finally, the products were dried in vacuum at 60.0 °C for 12.0 h. The bismuth dimethyl dithiocarbamate (Bi(DMDC)3) was prepared by mixing 0.1 mmol bismuth nitrate pentahydrate (Bi(NO3)3·5H2O), 0.3 mmol of sodium dimethyl dithiocarbamate and 400.0 mL deionized water, while all other steps were the same as the preparation of Cu(DMDC)2. Synthesis of metal chalcogenide products The Bi2S3/Cu2S/Cu3BiS3 hybrids were prepared by adding 0.06 mmol copper dimethyl dithiocarbamate (Cu(DMDC)2), 0.06 mmol bismuth dimethyl dithiocarbamate (Bi(DMDC)3) and 50.0 mL ethylene glycol to a 100.0 mL round bottom flask with double necks. The flask was then placed in an ultrasonic cleaning machine to ultrasound for 10.0 min with the water bath being kept at 50.0 °C. The reaction solution was subsequently microwave-heated to 90.0 °C in 3.0 min, and the solution temperature was then raised to 180.0 °C in 9.0 min with a heating rate of 10.0 °C/min. The solution was let to cool down to room temperature naturally after being kept at 180.0 °C for a total of 5.0 min. The resultant solid products were collected by centrifugation at 15000 rpm/min for 5.0 min and washed with deionized water and ethanol several times. The solid was finally dried at 60.0 °C in vacuum for 6.0 h. When 5



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the ratio of copper dimethyl dithiocarbamate (Cu(DMDC)2) and bismuth dimethyl dithiocarbamate (Bi(DMDC)3) was adjusted from the values used above, other forms of composites, such as Cu3BiS3 was prepared. Measurement of photothermal conversion efficiency In order to determine the photothermal conversion efficiency, a solution that contains the target products Cu3BiS3 or Bi2S3/Cu2S/Cu3BiS3 hybrids at a concentration of 50.0 µg/mL was put under the irradiation of 808 nm laser which is equipped with a tunable power from 0 to 10.0 W. The output power of the laser source was determined with an optical power meter (Newport model 1918-C, CA, U.S.A.) and was fixed at a safe power density of 0.75 W·cm-2 throughout this study. The temperature change was recorded at every 30.0 s interval using a thermocouple thermometer with an accuracy of ± 0.1 °C (DT-8891E, Shenzhen Everbest Machinery Industry Co. Ltd). The photothermal conversion efficiency (η) is calculated with the following equation:32

where h is heat transfer coefficient, s is the surface area of container, (Tmax - Tsurr) is temperature difference between the system and ambient, Qdis is the heat dissipation of the container, which is calculated independently with pure water measured at the same conditions, I is the laser power density and Aλ is the absorbance of the sample at wavelength of λ. The hs can be calculated using equation: 6


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where mw is the mass of water (1.0 g), Cw is the heat capacity of water (4.2 J/g), and τs is a time constant of the studied system. τs can be obtained from the plot of the cooling time versus –ln(θ) obtained from the cooling stage, where θ = (Tt –Tsurr)/(Tmax –Tsurr).The value of Qdis was measured to be 26.6 mW in this study. In vitro CT imaging study CT images were recorded by Philips GEMINI TF 64 PET/CT (positron emission tomography/computed tomography, Philips). The imaging parameters were set as follows: voltage, 120.0 kV; current, 120.0 mA. The Bi2S3/Cu2S/Cu3BiS3 urchin-like nanoparticles was dispersed in deionized water with concentrations ranging from 0 to 30.0 mg/mL. 3. RESULTS AND DISCUSSION A

series

of

solvothermal

reactions

with

different

mole

ratios

of

Cu(DMDC)2/Bi(DMDC)3 have been conducted and SEM images of the as-obtained solid materials are presented in Figure 1. Cu2S crystals appear to have the irregular cubic structure as seen in Figure 1a, whereas pure Bi2S3 crystals show tubular structure in Figure 1f. Notably, there is a dramatic change in the morphology of the solid products when the ratio of Cu(DMDC)2/Bi(DMDC)3 was adjusted from 3:1 to 1:1. Nearly uniform cuboids were obtained at the Cu(DMDC)2/Bi(DMDC)3 ratio of 3:1 (see Figure 1c). Urchin-like solid is seen in Figure 1d. As the Cu(DMDC)2/Bi(DMDC)3 ratio is reduced further, the core of urchin shrinks greatly, making it look like a bundle of rods being 7



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jointed together at one end (Figure 1e). Specific surface area of the above solid products were measured with the nitrogen adsorption/desorption isotherm, yielding the following values (a) 3.92 m2/g, (b) 3.04 m2/g, (c) 2.85 m2/g, (d) 10.68 m2/g, (e) 12.91 m2/g , and (f) 14.59 m2/g . It shows that solids with an urchin-like or tubular structure have larger specific surface area.

Figure 1. SEM images of the solid products prepared at different mole ratios of Cu(DMDC)2/Bi(DMDC)3: (a) 1:0, (b) 5:1, (c) 3:1, (d) 1:1, (e) 1:2, and (f) 0:1. The solid products synthesized at the 1:1 mole ratio of Cu(DMDC)2 and Bi(DMDC)3 are thoroughly characterized in Figure 2, where SEM image in Figure 2a illustrates that it has a unique urchin-like morphology TEM image in Figure 2b reveals that the centre of this urchin structure has a spherical shape with a diameter of 200 to 250 nm and those tubular structures, which grow out of the center, are solid rods instead of tubes with a length between 200 and 300 nm. Figure 2c presents a HRTEM image taken from the area marked with a red circle in Figure 2b. It shows a lattice spacing of 0.28 nm and 0.19 nm, which matches (220) plane of cubic Cu2S and (221) plane of orthorhombic Bi2S3, suggesting that the rods are made up by Cu2S and Bi2S3 hybrids. Figure 2d shows another HRTEM image of the nanorod, in which 8


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the lattice spacing can be well indexed to the (021) and (310) planes of Bi2S3. The two planes intersect at an angle of 78°, which is the same as that calculated for the orthorhombic Bi2S3. The high-resolution XPS spectrum of Bi 4f orbital region is displayed in Figure 2f, where Bi 4f characteristic peaks at 157.1 eV and 162.4 eV are found, and the peak fitting suggests the existence of Bi3+.33,34 Figure 2e shows two characteristic peaks of Cu 2p 3/2 and Cu 2p 1/2 at 931.8 and 950.9 eV. The splitting energy of 19.1 eV between Cu 2p 3/2 and Cu 2p 1/2 is a signature of Cu+. As seen in Figure 2f, the S 2p 3/2 and S 2p 1/2 electrons are manifested by two peaks at 160.1 eV and 161.2 eV, which are in good agreement with the reference values of S2−.35 The above XPS analysis confirms that valence states of Bi, Cu, and S in those rods are +3, +1 and −2, respectively. The EDX elemental mapping of an individual urchin-like structure in Figure 2g illustrates that Cu (red), Bi (green) and S (blue) elements are uniformly distributed across the whole sample. To the best of our knowledge, the as-prepared urchin-like Bi2S3/Cu2S/Cu3BiS3 composites have not been synthesized before. Solid products that were obtained at a mole ratio of Cu(DMDC)2/Bi(DMDC)3 = 3:1 were systematically characterized in Figure S2, which include measurements of TEM, XRD, XPS and EDS. These characterizations illustrate that the cuboid solids is pure Cu3BiS3 compound.

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Figure 2. The urchin-like Bi2S3/Cu2S/Cu3BiS3 composites characterized by (a)SEM, (b) TEM, (c, d) HRTEM of the areas marked with a red circle in (b), (e) high-resolution XPS of Cu 2p, (f) XPS spectra of S 2p and Bi 4f, and (g) STEM-EDX elemental mapping. To determine chemical compositions of the core of urchin-like solids presented in Figure 10


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3, reaction was stopped at the time when only cores have been formed. TEM image in Figure 3a indicates that those spherical cores are solid. Lattice spacing of the spherical solids was measured in Figure 3b as 0.33 nm, which corresponds to the (201) plane of orthorhombic-phase Cu3BiS3. Elemental mapping, presented in Figure 3c, demonstrates that Cu, Bi and S are uniformly distributed across the spherical solid. Figure 3d shows X-ray diffraction (XRD) patterns, in which diffraction peaks of the samples can be exclusively indexed to orthorhombic-phase Cu3BiS3 (JCPDS no: 73-1185). Results presented in this figure suggest that the central portion of each urchin is made up mainly by Cu3BiS3. In other words, Cu3BiS3 will form first and grow into nanoparticles in this synthetic process. Results presented in Figures 2 and 3 suggests that the urchin shaped solid composites are Bi2S3/Cu2S/Cu3BiS3 hybrids.

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Figure 3. Characterization of the solids samples prepared with mole ratios of Cu(DMDC)2/Bi(DMDC)3=1:1: (a) TEM, (b) HRTEM of the areas marked with red circle in (a), (c) STEM-EDX elemental map, and (d) XRD patterns. To shed light on the formation mechanism of urchin-shaped Bi2S3/Cu2S/Cu3BiS3 composites, the solvothermal reaction was stopped at various reaction times and the solid products were collected and analyzed. According to the experiment procedure developed in this study, temperature of the reaction solution reached 140.0 ℃,145.0 ℃, 150.0 ℃, 12


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160.0 ℃, 170.0 ℃, and 180.0 ℃ at the time when these reactions were stopped. As shown in Figure 4a, at temperature of 140.0 ℃, the reaction solution contains many particles with various sizes and the bulky materials in the sample are likely the undissolved strating reagents Cu(DMDC)2 and Bi(DMDC)3. After the temperature of reaction solution was increased to 145.0 ℃ (Figure 4b), most of the bulky materials have disappeared and the solid products are dominated by spherical particles with rough surfaces. Chemical compositions of those spheres are determined to be Cu3BiS3, suggesting that Cu3BiS3 is formed first. At 150.0 ℃ (Figure 4c), many small and irregular particles appeared on the surface of these spherical particles. SEM image in Figure 4d illustrates that when the reaction has progressed for a total of 10.0 min. (i.e., 160.0 ℃), those spheres got covered by many short rods attached vertically to the sphere core. As the reaction progressed further, those rods continue to grow in length (Figure 4e) and eventually form urchin-like microstructures (Figure 4f). These nanorods have a length between 200 and 300 nm. Based on the above observation, a possible growth model has been proposed in Figure 4g, in which these Cu3BiS3 spheres were formed first through the simultaneous decomposition of Cu(DMDC)2 and Bi(DMDC)3. As Cu(DMDC)2 was gradually consumed, the formation of Cu3BiS3 became more and more difficult. As a result, small particles of Cu2S and Bi2S3 were formed, which together led to the formation of nanorods on these Cu3BiS3 sphere. This hypothesis was confirmed by XRD patterns shown in Figure 4h, in which XRD patterns of solids collected at different reaction stages are presented. The high diffraction peak of 2-theta at 45.4° is accord with Cu2S of (220) planes, which has also been identified 13



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from the HRTEM in Figure 2c. XRD peaks of Cu2S and Bi2S3 become visible and more and more obvious as the reaction time is increased (i.e., solution temperature reaches 160 ℃). Overall, diffraction peaks in Figure 4h can be indexed as Cu2S (JCPDS No:65-2980), Bi2S3 (JCPDS No:75-1306) and Cu3BiS3 (JCPDS No:73-1185). The conclusion that nanorods of the urchin-like microstructure mainly consist of Cu2S and Bi2S3 is consistent with the TEM characterization of the rods presented in Figures 2c and 2d, where the crystal lattices belong to orthorhombic Bi2S3 and Cu2S. The formation mechanism of Cuboid shape Cu3BiS3 also was analyzed through the same procedure and the related experimental results are presented in Figures S3.

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Figure 4. (a-f) SEM images of urchin-like Bi2S3/Cu2S/Cu3BiS3 prepared at a terminal reaction temperature of (a) 140.0 ℃, (b) 145.0 ℃, (c) 150.0 ℃, (d) 160.0 ℃, (e) 170.0 ℃, and (f) 180.0 ℃. (g) Growth scheme for the urchin-like Bi2S3/Cu2S/Cu3BiS3, (h) XRD patterns of the samples obtained at temperature of 140.0 ℃, 150.0 ℃, 160.0 ℃, 170.0 ℃ and 180.0 ℃ respectively. The above temperature is the solution temperature at the time when the reaction was stopped.

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Photothermal properties of the urchin-like Bi2S3/Cu2S/Cu3BiS3 were investigated and was compared with the control experiment using pure Cu3BiS3 composite as the photothermal agent. Temperature changes of the aqueous solution containing different amounts of Bi2S3/Cu2S/Cu3BiS3 or Cu3BiS3 (0, 10.0, 25.0, 50.0, 100.0, 200.0 µg·mL−1) under the irradiation of a 808 nm NIR laser (0.75 W·cm−2) was recorded. As shown in Figure 5a, after 600 s irradiation, temperature of the pure water only exhibited a small increase of 4.0℃, while the solution containing 50.0 µg·mL−1 of Cu3BiS3 has increased by 18.1℃. On the other hand, when urchin-like Bi2S3/Cu2S/Cu3BiS3 composites were studied at the same conditions, temperature of the sample solution increased by 24.0 ℃ after 600 s (Figure 5b). Temperature change (∆T) of aqueous solution containing different amounts of Cu3BiS3 and Bi2S3/Cu2S/Cu3BiS3 composites are compared in Figure 5c, where the solution was irradiated for 600 s at the power of 0.75 W·cm−2. The temperature change presented here deducted the value of pure water. It shows that Bi2S3/Cu2S/Cu3BiS3 outperforms Cu3BiS3 at all concentrations. Figure 5d summarizes the photothermal performance of the solid products that were prepared at different mole ratios of Cu(DMDC)2 and Bi(DMDC)3. In this series of experiments, temperature change of 1.0 mL water containing 50.0 µg·mL−1 or 100.0 µg·mL−1 solids was investigated. The results show that Cu2S outperforms Bi2S3 at the same mass. However, as the content of Bi2S3 in the compound increases while the total mass is kept constant, the thermal conversion efficiency increases until a maximum point is reached. Beyond the optimum combination, the thermal conversion efficiency decreases as the Bi2S3 content is increased further. Such a behavior suggests that there may exist synergetic interactions between Cu2S and Bi2S3. In addition, the urchin-like Bi2S3/Cu2S/Cu3BiS3 16


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composites have the best photothermal performance, implicating that morphology of the thermal reagents also plays an important role. To fully understand the importance of morphology and the contribution of each individual components in the above observed photothermal performance, more systematic exploration will be needed.

Figure 5. (a) Photothermal profiles of pure water and aqueous dispersion of cuboid Cu3BiS3 at different concentrations, (b) photothermal profiles of pure water and aqueous dispersion of urchin-like Bi2S3/Cu2S/Cu3BiS3 composites at different concentrations, (c) plot of the temperature change (∆T) of aqueous solution over a period of 600 s versus the concentration of Cu3BiS3 and Bi2S3/Cu2S/Cu3BiS3, (d) Temperature change of water containing 50.0 µg and 100.0 µg of solids that were prepared under different ratios of Cu(DMDC)2 and Bi(DMDC)3: (a) 1:0; (b) 5:1; (c) 3:1; (d) 1:1;(e) 1:2; and (f) 0:1. The irradiation in (d) lasted for 600 s and used 808 nm laser with a power density of 0.75 W·cm−2. 17



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Using the data presented in Figure 6a, (Tmax-Tsurr) and τs of the cuboid Cu3BiS3 are calculated to be 20.6 ℃ and 502 s, respectively. (Tmax-Tsurr) and τs of the urchin Bi2S3/Cu2S/Cu3BiS3 composites are calculated from Figure 6b to be 27.2 ℃ and 400 s. The value of Qdis is measured to be 26.6 mW in this study. The photothermal conversion efficiency of cuboid Cu3BiS3 and urchin-like Bi2S3/Cu2S/Cu3BiS3 composites was calculated to be 27.6% and 43.8%, respectively. Such a result is superior to many well-known photothermal agents, such as WSe2-BSA nanosheets (35.07%),36 MoS2 hollow spheres (34.46%),37 Cu3BiS3 hollow nanospheres (27.5%),38 Cu9S5 nanocrystals (25.7%)39and PEG-Bi2S3 nano-urchins.40 Temperature variation of Cu3BiS3 and Bi2S3/Cu2S/Cu3BiS3 containing water under on-off cycles are presented in Figures 6c and 6d. There is nearly no attenuation in their photothermal performance, demonstrating excellent photostability. Morphologies of Cu3BiS3 and Bi2S3/Cu2S/Cu3BiS3 solids prior and after these irradiation cycles do not exhibit any obvious difference, lending further support on their photostability. The slight decrease of temperature peak as seen in Figure 6c is mainly due to the precipitation of Cu3BiS3 particles on to the bottom of the container.

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Figure 6. Plot of the cooling time versus –ln(θ) obtained from deionized water containing (a) Cu3BiS3 and (b) Bi2S3/Cu2S/Cu3BiS3; (c) Temperature change during on-off irradiation of the solution containing (c) Cu3BiS3 and (d) Bi2S3/Cu2S/Cu3BiS3. The amounts of solids used is 50.0 µg·mL−1. 808 nm laser with a power of 0.75 W·cm−2 was used for irradiation. Figure 7 presents the UV-Vis-NIR absorption spectra of solutions containing 50.0 µg·mL−1 of the solids that have been synthesized at different mole ratios of Cu(DMDC)2/Bi(DMDC)3.

The

measurements

indicate

that

composites

of

Bi2S3/Cu2S/Cu3BiS3 (curves c and d) have optical absorption from ultraviolet all the way to near infrared regime, due to the synergistic interactions between Bi2S3 and Cu2S. More importantly, the composites exhibit the highest absorption at 808 nm. Results of the above absorption spectra are consistent with their photothermal performance. In this study, it is found that when the amounts of solids in water is less than 50.0 µg·mL−1, the solid could be well dispersed in solution and stay dispersed for a longer time. 19



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Figure 7. UV-Vis-NIR absorption spectrum of water containing 50.0 µg of the solids that were synthesized at different mole ratios of Cu(DMDC)2/Bi(DMDC)3: (a) 1:0, (b) 5:1, (c) 3:1, (d) 1:1, (e) 1:2, and (f) 0:1.

Computed Tomography (CT) is an auxiliary examination method for biological treatment, in which CT contrast agents are injected into a body to highlight the tissue with a low density. Because Bi possesses a low toxicity and large X-ray attenuation coefficient,41 Bi-based materials, such as Bi2Se and Bi2S3, have been exploited as CT contrast agents. An in vitro CT imaging test was carried out to evaluate the CT contrast performance of our Bi2S3/Cu2S/Cu3BiS3 hybrids, which have shown improved PT performance and dispersion stability in water. Figure 8a shows that the Hounsfield unit (HU) value, which is an important parameter for measuring CT contrast performance, increases linearly with the concentration of Bi2S3/Cu2S/Cu3BiS3. The slop of the HU value is determined to be about 16.7, which is slightly higher than that of the commercial Ultravist 300 (14.48).42 Figure 8b, 20


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the CT signal intensity was gradually enhanced with the increase of Bi2S3/Cu2S/Cu3BiS3 concentration. The result suggests that Bi2S3/Cu2S/Cu3BiS3 hybrids can be potentially applied as a CT contrast agent.

Figure 8. (a) CT value (HU) and (b) In vitro CT images as a function of the concentration. The solid is urchin-like Bi2S3/Cu2S/Cu3BiS3. 4. CONCLUSION A series of copper and bismuth chalcoginides with distinct morphologies, such as cuboid and urchin-like, have been prepared in this study. The fabrication was achieved through a one-pot microwave-assisted pyrolysis reaction. The facilely-synthesized urchin-like Bi2S3/Cu2S/Cu3BiS3 composites exhibit excellent photothermal efficiency. Specifically, the photothermal conversion efficiency of Bi2S3/Cu2S/Cu3BiS3 composites is about 43.8%. Such an outstanding performance can be attributed to the improved absorption within NIR range. 21



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In addition, the Bi2S3/Cu2S/Cu3BiS3 composites remain very stable in water (Figure 6c and 6d). Significantly, Bi2S3/Cu2S/Cu3BiS3 composites show a very good X-ray computer tomography (CT) imaging capability, making it promising candidates as multi-functional PTT agents for a variety of photothermal applications. AUTHOR INFORMATION Corresponding Authors *E-mail: [email protected] (W.S.) . *E-mail: [email protected] (W.J.C.) *E-mail: [email protected] (L.A.L.) Notes The authors declare no competing financial interest. ACKNOWLEDGEMENTS We are grateful for financial support from the National Natural Science Foundation of China (21471116, 21601138, 21628102 and 51641210), the Zhejiang Provincial Natural Science Foundation of China (LY17E020003, LZ15E020002 and LZ17E020002). ASSOCIATED CONTENT Supporting Information Additional data and text related to synthesis, TEM, SEM, XRD and XPS characterizations and photothermal activities of Bi2S3/Cu2S/Cu3BiS3.

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Table of Contents Graphic

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Cu3BiS3 Composites with Enhanced

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