Hydrolysis of cisplatin, the most widely used anticancer drug in the world, is believed to be the key activation step before the drug reaching its intracellular target DNA. To obtain an accurate hydrolysis theory for this important class of square-planar Pt(II) complexes, three typical reactions, i.e., the first and second hydrolyses of cisplatin and the hydrolysis of [Pt(dien)Cl](+) (dien = diethylenetriamine), were studied at the experimental temperature with the solvent effect using mPW1PW91/SDD from a comprehensive methodological study on the Hartree-Fock (HF) ab initio method, electron correlation methods, pure density functional theory (DFT) methods, and hybrid HF-DFT methods with several basis sets. The true five stationary states in the second-order nucleophilic substitution (S(N)2) pathway for the hydrolysis process, namely, reactant (R) --> intermediate 1 (I1) --> TS --> intermediate 2 (I2) --> product (P) were obtained and characterized theoretically for the first time. The most remarkable structural variations and the associated atomic charge variations in the hydrolysis process were found to occur in the equatorial plane of the five-coordinate trigonal-bipyramidal (TBP)-like structures of I1, TS, and I2. The reaction with the TS structure of smaller L-M-E angle and more lengthened M-L and M-E bonds was found to have a smaller Gibbs free energy change and accordingly the better hydrolysis yield. It is found that the sum of the three concentric angles in the TBP's equator is near 360 degrees in I1 and I2 and is almost 360 degrees in TS in each reaction. The associated energy profiles again demonstrated a typical S(N)2 reaction curve. The computed forward and backward reaction enthalpy (Delta H(++)) and reaction entropy (Delta S(++)) in the rate-determining step I1 --> TS --> I2 are in good agreement with the experiments. Natural bonding orbital population analysis shows that the charge-separating extent follows the same order of Delta G in studied reactions. Comparing with the computational results of gas-phase reactions, it can be concluded that the solvent effect should be considered to obtain an accurate hydrolysis picture. The most affected structural parameters after solvation are related to the equatorial plane of the TBP-like geometry. The results provide theoretical guidance on detailed understanding on the mechanism of the hydrolysis of cisplatin, which could be useful in the design of novel Pt-based anticancer agents.

Graphene field effect transistor sensitized by a layer of semiconductor (sensitizer/GFET) is a device structure that is investigated extensively for ultrasensitive photodetection. Among others, organometallic perovskite semiconductor sensitizer has the advantages of long carrier lifetime and solution processable. A further step to improve the responsivity is to design a structure that can promote electron-hole separation and selective carrier trapping in the sensitizer. Here, the use of a hybrid perovskite-organic bulk heterojunction (BHJ) as the light sensitizer to achieve this goal is demonstrated. Our spectroscopy and device measurements show that the CH 3 NH 3 PbI 3 -PCBM BHJ/GFET device has improved charge separation yield and carrier lifetime as compared to a reference device with a CH 3 NH 3 PbI 3 sensitizer only. The key to these enhancement is the presence of [6,6]-phenyl-C 61 -butyric acid methyl ester (PCBM), which acts as charge separation and electron trapping sites, resulting in a 30-fold increase in the photoresponsivity. This work shows that the use of a small amount of electron or hole acceptors in the sensitizer layer can be an effective strategy for improving and tuning the photoresponsivity of sensitizer/GFET photodetectors.

No abstract

Millimeter-sized CsPbBr3 single crystals were prepared via a facile solvent-evaporation method in ambient environment. The heterojunction between p-type CuI and n-type CsPbBr3 was formed by a simple immersion process. The as-integrated CsPbBr3/CuI device exhibits a good rectifying behavior (ratio of 250 at ±2 V). In particular, the photodetector shows excellent self-powered characteristics under 540 nm light illumination, including high photocurrent (near 100 nA); high photosensitivity (on/off ratio of 1.5 × 103); fast response speed (0.04/2.96 ms); and good wavelength selectivity (565–525 nm), responsivity (1.4 mA W–1), and detectivity (6.2 × 1010 Jones). This work provides a simple, low-cost, and effective method for preparing millimeter-level CsPbBr3 single crystals. The simple device architecture further provides a promising approach for fabricating high-performance self-powered photodetectors.