Qualitative and quantitative analysis of the component variations of Raphani Semen during the stir-frying process and elucidation of transformation pathways of multiple components.

Raphani Semen (RS) encompasses two distinct application forms in Chinese clinical practice: raw RS (RRS) and stir-fried RS (SRS). They exhibit divergent drug properties and effects, as described in traditional Chinese medicine theory known as "Sheng shu yi zhi, sheng sheng shu jiang". The dissimilarity in RS's drug properties is intrinsically linked to alterations in its internal components during the stir-frying process. Previous studies have demonstrated that stir-frying renders myrosinase inactive, thereby preventing the enzymatic hydrolysis of glucosinolates in RS. However, the precise enzymatic hydrolysis pathway and products of glucosinolates remain unclear. Furthermore, it remains uncertain whether other components undergo changes influenced by endogenous enzymes. The objective of this study is to systematically analyze the chemical components disparities between RRS and SRS using high-performance liquid chromatography coupled with time-of-flight mass spectrometry (HPLC-TOF-MS). Additionally, it seeks to elucidate the potential transformation pathways of multiple components from an enzymatic hydrolysis perspective. We have developed a sensitive and efficient high-performance liquid chromatography coupled with triple quadrupole tandem mass spectrometry (HPLC-QQQ-MS) method for quantifying the content of 5 characteristic components, including glucoraphenin, sinapine thiocyanate, sulforaphene, sinapic acid, and 3',6-disinapoylsucrose. Based on retention time and MS spectra, we have identified 19 characteristic components in both SRS and RRS, encompassing glucosinolates and sulfur-containing derivatives, oligosaccharide esters, and small-molecule phenolic acids. Notably, 18 of these components undergo changes during the enzymatic hydrolysis process, leading to the identification of 4 transformation pathways: glucoraphenin, 6-sinapoylglucoraphenin, 3',6-disinapoylsucrose and ß-D-(3,4-disinapoyl) furanofructosyl-α-D-(6-sinapisoyl) glucoside, along with 3'-O-sinapoyl-6-O-feruloylsucrose. Quantitative analysis reveals significant differences, including lower levels of glucoraphenin in RRS compared to SRS, higher sulforaphene and sinapic acid levels in RRS, while sinapine thiocyanate and 3',6-disinapoylsucrose remain unchanged before and after stir-frying. The results of this study highlight distinct chemical compositions between RRS and SRS. Additionally, the method of characterization and content determination constructed in this paper has strong practical value and provides a useful approach for comprehensively evaluating the chemical composition and quality of RS.

High-Efficiency Intrinsic Yellow-Orange Emission in Hybrid Indium Bromide with Double Octahedral Configuration.

Zero-dimensional (0D) In-based organic-inorganic metal halides (OIMHs) have received growing interest in recent years as promising luminescent materials. However, the high efficiencies of 0D In-based OIMHs are all dependent on Sb doping in the existing literature. Here, we report a novel 0D In-based OIMH (C10H22N2)2In2Br10, which exhibits intrinsic broadband emission (610 nm), and the photoluminescence quantum yield (PLQY) can reach 70% without Sb doping. (C10H22N2)2In2Br10 shows a typical 0D structure with three different In-Br polyhedra (two octahedra and one tetrahedron) separated by large organic cations. Based on the optical property measurements and theoretical calculations, we demonstrate that (C10H22N2)2In2Br10 is an indirect semiconductor with a band gap of 3.74 eV, and the In-Br inorganic moiety is primarily responsible for the intense emission of (C10H22N2)2In2Br10. Interestingly, the unique double octahedral configuration in (C10H22N2)2In2Br10 may enhance the structural distortion and stimulate the self-trapped excitons (STEs), leading to the related high PLQY. Our work provides a novel 0D In-based OIMH with high-efficiency intrinsic emission, which is helpful for understanding the structure-PL relationships of hybrid halides.

Improving the Chemical Stability of Narrow-Band Green-Emitting Manganese(II) Hybrid by Zn-Doping.

Hybrid tetrahedral Mn(II)-based halides show great potential for narrow-band green emitters, which could be applied in the liquid crystal display field. However, the strategy to improve the chemical stability of tetrahedral Mn hybrids has not been fully investigated. Here, we demonstrate that Zn doping can be an effective route to significantly improve the stability of tetrahedral Mn hybrids under air conditions without compromising the luminous efficiency. A new bromide (ABI)2MnBr4 (ABI = 2-aminobenzimidazole) is synthesized, which exhibits a typical zero-dimensional structure with isolated [MnBr4]2- tetrahedra in the P1̅ space group. Under 450 nm excitation, a narrow-band green-emitting peak at 516 nm is observed with a full width at half maximum of 42 nm. It is indicated that spontaneous phase transition from the tetrahedral to octahedral motif occurs in this Mn hybrid driven by humidity, combined with the emission color change from green to red. Interestingly, this phase transition could be strongly suppressed by Zn doping with a very low doping amount (5%), leading to the significantly improved chemical stability of (ABI)2MnBr4 without reducing the photoluminescence quantum yield. Our work provides a simple and feasible strategy to enhance the chemical stability of the green-emitting (ABI)2MnBr4, and it may also be applicable for other tetrahedral Mn-based hybrids.

Zero-Dimensional Lead-Free Halide with Indirect Optical Gap and Enhanced Photoluminescence by Sb Doping.

Three new lead-free organic-inorganic metal halides (OIMHs) (C7H8N3)3InX6·H2O (X = Cl, Br) and (C7H8N3)2SbBr5 were synthesized. First-principles calculations indicate that the highest occupied molecular orbitals (HOMOs) of the two In-based OIMHs are constituted of π orbitals from [C7H8N3]+ spacers. (C7H8N3)3InX6·H2O (X = Cl, Br) shows an indirect optical gap, which may result from this organic-contributed band edge. Despite the indirect-gap nature with extra phonon process during absorption, the photoluminescence of (C7H8N3)3InBr6·H2O can still be significantly enhanced through Sb doping, with the internal photoluminescence quantum yields (PLQY) increased 10-fold from 5% to 52%. A white light-emitting diode (WLED) was fabricated based on (C7H8N3)3InBr6·H2O:Sb3+, exhibiting a high color-rendering index of 90. Our work provides new systems to deeply understand the principles for organic spacer choice to obtain the 0D metal OIMHs with specific band structure and also the significant enhancement of luminescence performance by chemical doping.

A Meta-Analysis of Concurrent Chemoradiotherapy for Advanced Esophageal Cancer.

BACKGROUND: Concurrent chemoradiotherapy is a standard treatment for local advanced esophageal cancer, but the outcomes are controversial. Our goals were to compare the therapeutic effects of concurrent chemoradiotherapy and radiotherapy alone in local advanced esophageal cancer using meta-analysis. METHODS: MEDLINE, EMBASE and the Cochrane library were searched for studies comparing chemoradiotherapy with radiotherapy alone for advanced esophageal cancer. Only randomized controlled trials were included, and extracted data were analyzed with Review Manager Version 5.2. The pooled relative risks (RR) and their 95% confidence intervals (CI) were calculated for statistical analysis. RESULTS: Nine studies were included. Of 1,135 cases, 612 received concurrent chemoradiotherapy and 523 were treated with radiotherapy alone. The overall response rate (complete remission and partial remission) was 93.4% for concurrent chemoradiotherapy and 83.7% for radiotherapy alone (P = 0.05). The RR values of 1-year, 3-year, and 5-year survival rates were 1.14 (95% CI: 1.04 - 1.24, P = 0.006), 1.66 (95% CI: 1.34 - 2.06, P < 0.001), and 2.43 (95% CI: 1.63 - 3.63, P < 0.001), respectively. The RR value of the merged occurrence rate of acute toxic effects was 2.34 (95% CI: 1.90 - 2.90, P <0.001). There was no difference in the incidence of late toxic effects, which had an RR value of 1.21 (95% CI: 0.96 - 1.54, P = 0.11). The RR level of persistence and recurrence was 0.71 (95% CI: 0.62 - 0.81, P <0.001), and for the distant metastasis rate, the RR value was 0.79 (95% CI: 0.61 - 1.02, P = 0.07). CONCLUSIONS: Concurrent chemoradiotherapy significantly improved overall survival rate, reduced the risk of persistence and recurrence, but had little effect on the primary tumor response, and increased the occurrence of acute toxic effects.