Reversible Local Protonation-Deprotonation: Tuning Stimuli-Responsive Circularly Polarized Luminescence in Chiral Hybrid Zinc Halides for Anti-Counterfeiting and Encryption.

Precise control over the organic composition is crucial for tailoring the distinctive structures and properties of hybrid metal halides. However, this approach is seldom utilized to develop materials that exhibit stimuli-responsive circularly polarized luminescence (CPL). Herein, we present the synthesis and characterization of enantiomeric hybrid zinc bromides: biprotonated ((R/S)-C12H16N2)ZnBr4 ((R/S-LH2)ZnBr4) and monoprotonated ((R/S)-C12H15N2)2ZnBr4 ((R/S-LH1)2ZnBr4), derived from the chiral organic amine (R/S)-2,3,4,9-Tetrahydro-1H-carbazol-3-amine ((R/S)-C12H14N2). These compounds showcase luminescent properties; the zero-dimensional biprotonated form emits green light at 505 nm, while the monoprotonated form, with a pseudo-layered structure, displays red luminescence at 599 and 649 nm. Remarkably, the reversible local protonation-deprotonation behavior of the organic cations allows for exposure to polar solvents and heating to induce reversible structural and luminescent transformations between the two forms. Theoretical calculations reveal that the lower energy barrier associated with the deprotonation process within the pyrrole ring is responsible for the local protonation-deprotonation behavior observed. These enantiomorphic hybrid zinc bromides also exhibit switchable circular dichroism (CD) and CPL properties. Furthermore, their chloride counterparts were successfully obtained by adjusting the halogen ions. Importantly, the unique stimuli-responsive CPL characteristics position these hybrid zinc halides as promising candidates for applications information storage, anti-counterfeiting, and information encryption.

Multiple Stimuli-Responsive Luminescent Chiral Hybrid Antimony Chlorides for Anti-Counterfeiting and Encryption Applications.

Stimuli-responsive circularly polarized luminescence (CPL) materials are ideal for information anti-countering applications, but the best-performing materials have not yet been identified. This work presents enantiomorphic hybrid antimony halides R-(C5 H12 NO)2 SbCl5 (1) and S-(C5 H12 NO)2 SbCl5 (2) showing mirror-imaged CPL activity with a dissymmetry factor of 1.2×10-3 . Interestingly, the DMF-induced structural transformation is realized to obtain non-emissive R-(C5 H12 NO)2 SbCl5 ⋅ DMF (3) and S-(C5 H12 NO)2 SbCl5 ⋅ DMF (4) upon exposure to DMF vapor. The transformation process is reversed upon heating. DFT calculations showed that the DMF-induced-quenched-luminescence is attributed to the intersection of the ground and excited state curves on the configuration coordinates. Unexpectedly, the nanocrystals of the chiral antimony halides 1 and 2 were prepared and indicate the excellent solution process performance. The reversible PL and CPL switching gives the system applications in information technology, anti-counterfeiting, encryption-decryption, and logic gates.

Regulating structural asymmetry via fluorination engineering in hybrid lead bromide perovskites.

Here, we synthesized a pair of chiral two-dimensional lead bromide perovskites R-/S-(C3H7NF3)2PbBr4 (1R/2S) using a H/F substitution strategy, which exhibit circular dichroism (CD) and circularly polarized luminescence (CPL) activity. Compared with one-dimensional non-centrosymmetric (C3H10N)3PbBr5 with local asymmetry obtained by isopropylamine, 1R/2S show a centrosymmetric inorganic layer despite the global chiral space group. Density functional theory calculations show that the formation energy of 1R/2S is lower than that of (C3H10N)3PbBr5, which implies the improved moisture stability in photophysical properties and CPL activity.

A multi-responsive indium-viologen hybrid with ultrafast-response photochromism and electrochromism.

A novel 0D organic-inorganic metal halide hybrid (C13H16N2O2)2InCl6·Cl (1) has been obtained by integrating the mono-viologen derivative with InCl3. Compound 1 exhibits reversible and ultrafast UV/sunlight/X-ray induced photochromic properties, as well as excellent electrochromic performance, which is the first example of an indium-based organic-inorganic chromic hybrid.

Clinical Characteristics and Survival Outcomes for Non-Small-Cell Lung Cancer Patients with Epidermal Growth Factor Receptor Double Mutations.

Multiple randomized clinical trials have demonstrated that epidermal growth factor receptor (EGFR) exon 19 deletion (19Del) and exon 21 L858R mutation (L858R) are highly correlated with sensitivity to epidermal growth factor receptor tyrosine kinase inhibitor (EGFR-TKI) treatment in non-small-cell lung cancer (NSCLC). A mutation in exon 20 (T790M) is reportedly associated with resistance to EGFR-TKIs. However, few studies have focused on patients harboring double mutations in these 3 mutation sites. In this retrospective study, forty-five patients (45/2546, 1.7%) harbored double mutations of 19Del, L858R, and T790M. Twenty-four patients with EGFR double mutations received EGFR-TKI therapy. Clinical characteristics of these patients, including the response to EGFR-TKIs and progression-free survival outcome for EGFR-TKI treatment (PFS-TKI), were analyzed. Patients with EGFR double mutations were more likely to be nonsmokers, have an Eastern Cooperative Oncology Group Performance Status (ECOG PS) of 0-1, have adenocarcinoma, and be at stage III-IV. The ORR, DCR, and median PFS-TKI in patients harboring EGFR double mutations were lower than in patients with a single EGFR-activating mutation. The differences in ORR and DCR were statistically insignificant between the 3 groups. Patients with double mutations of 19Del and T790M had longer PFS-TKIs than patients in the other 2 groups.

Efficacy of EGFR tyrosine kinase inhibitors in non-small cell lung cancer patients harboring different types of EGFR mutations: A retrospective analysis.

With the development of molecular pathology, many types of epidermal growth factor receptor (EGFR) mutations have been identified. The efficacy of EGFR tyrosine kinase inhibitors (EGFR-TKIs) in non-small cell lung cancer (NSCLC) patients with different types of EGFR mutations, especially in patients with single rare mutations or complex mutations (co-occurrence of two or more different mutations), has not been fully understood. This study aimed to examine the efficacy of EGFR-TKIs in NSCLC patients with different types of EGFR mutations. Clinical data of 809 NSCLC patients who harbored different types of EGFR mutations and treated from January 2012 to October 2016 at Renmin Hospital and Zhongnan Hospital, Wuhan, were retrospectively reviewed. The clinical characteristics of these patients and the efficacy of EGFR-TKIs were analyzed. Among these patients, 377 patients had only the EGFR del-19 mutation, 362 patients the EGFR L858R mutation in exon 21, 33 patients single rare mutations and 37 patients complex mutations. Among these 809 patients, 239 patients were treated with EGFR-TKIs. In all the 239 patients, the disease control rate (DCR) was 93.7% with two patients (0.2%) achieving complete response (CR), the median progression free survival (PFS) was 13.0 months (95% confidence interval [CI], 11.6-14.4 months), and the median overall survival (OS) was 55.0 months (95% CI, 26.3-83.7 months). Subgroup analysis revealed that the DCR in patients harboring single rare or complex mutations of EGFR was significantly lower than in those with del-19 or L858R mutation (P<0.001). Patients with classic mutations (del-19 and/or L858R mutations) demonstrated longer PFS (P<0.001) and OS (P=0.017) than those with uncommon mutations (single rare and/or complex mutations). Furthermore, the patients with single rare mutations had shorter median OS than in those with other mutations. Multivariate Cox regression analysis identified that the type of EGFR mutations was an independent risk factor for PFS (hazard ratio [HR]=0.308, 95% CI, 0.191-0.494, P<0.001) and OS (HR=0.221, 95% CI, 0.101-0.480, P<0.001). The results suggest that the single rare or complex EGFR mutations confer inferior efficacy of EGFR-TKIs treatment to the classic mutations. The prognosis of the single rare EGFR mutations is depressing. EGFR-TKIs may be not a good choice for NSCLC patients with single rare mutations of EGFR. Further studies in these patients with uncommon mutations (especially for the patients with single rare mutations) are needed to determine a better precision treatment.