DSpace community: 應用科學博士班

Flavones and Aminoflavones Increase the Cytotoxicity of NK Cells in Human Non-Small Cell Lung Cancer

title: Flavones and Aminoflavones Increase the Cytotoxicity of NK Cells in Human Non-Small Cell Lung Cancer abstract: Natural flavonoids (flavones) and synthetic aminoflavones are known for their anti‐cancer properties; however, their immunomodulation ability has been largely unexplored. This study determined that synthetic flavones and aminoflavones modulate the cytotoxicity of natural killer (NK) cells against lung cancer cells. Notably, flavones 2, 3, and 6 and aminoflavone 8 were shown to increase the cytotoxicity of NK‐92MI cells against A549 lung cancer cells without adversely affecting MRC5 normal cells. Aminoflavone 8 enhanced NK‐92MI cell cytotoxicity, as evidenced by the elevated expression of cytotoxic effectors, such as IFN‐γ, perforin, and granzyme B. Aminoflavone 8 also inhibited STAT3 phosphorylation in A549 lung cancer and NK‐92MI cells under co‐culture conditions. Moreover, aminoflavone 8 exhibited anti‐tumour effects in a lung cancer xenograft mouse model. Combined therapy with aminoflavone 8 and NK‐92MI cells had synergistic anti‐tumour effects without liver or kidney toxicity. Our analysis revealed that the amino group in the C6 position of aminoflavone 8 was crucial to the enhanced cytotoxicity of NK cells. These findings suggest that aminoflavone 8 can potentiate NK cell cytotoxicity against lung cancer cells, highlighting its potential as a novel therapeutic agent for the treatment of lung cancer.

Photodynamic Agents of Synthetic Curcuminoids with Antibacterial and Anticancer Activities

title: Photodynamic Agents of Synthetic Curcuminoids with Antibacterial and Anticancer Activities abstract: Our previous study demonstrated that thiophene-substituted synthetic curcumin analogs possessed better antibacterial activity and stability than natural curcumin, demethoxycurcumin, or bisdemethoxycurcumin in antibacterial photodynamic therapy (aPDT). In addition, the activity of the furan-substituted analogs was weaker than that of the thiophene-substituted compounds. As oxygen, sulfur, and selenium belong to the same group in the periodic table, the antibacterial and anticancer activities of these three different elemental analogs were compared and investigated. The thiophene-substituted analog (compound 3) exhibited the most potent antibacterial activity in aPDT experiments. However, the furan-substituted analog (compound 1) exhibited the most potent anticancer activity. These results indicate that the differences in atomic radii or energy levels in these compounds produce different cell-attack results on generated free radicals. Ruthenium(II) complexes have a good reputation for use in PDT for cancer treatment. Our results show that complexation of ruthenium(II) with thiophene-substituted curcumin analogs does not enhance their antibacterial or anticancer activity.

Determine of pH-dependent diketo and keto-enol tautomers of curcumin analogs by ultraperformance liquid chromatography-mass spectrometry

title: Determine of pH-dependent diketo and keto-enol tautomers of curcumin analogs by ultraperformance liquid chromatography-mass spectrometry

Design and synthesis of unsymmetric benzils, quinoxalines, and evaluations of their anticancer activities against human non-small lung cancer cells

title: Design and synthesis of unsymmetric benzils, quinoxalines, and evaluations of their anticancer activities against human non-small lung cancer cells abstract: Quinoxaline and its derivatives exhibit a broad spectrum of biological activity, making them valuable for various therapeutic applications. However, most quinoxalines are synthetically produced due to their scarcity in nature. In this article, a series of unsymmetric benzils were synthesized and subsequently condensed with 1,2-diaminobenzene to produce unsymmetric quinoxalines. The novel synthetic benzils and quinoxalines were evaluated for their anticancer activities against human non-small-cell lung cancer (NSCLC) cells harboring different gene mutations, to explore their potential as anticancer agents. Among these synthesized molecules, compound 5 g demonstrated inhibitory effects comparable to those of cisplatin.

硒吩基查爾酮衍生物及其用途

title: 硒吩基查爾酮衍生物及其用途 abstract: 本發明揭示具有下列化學式(I)之硒吩基查爾酮衍生物(selenophene-based chalcone derivatives)或者它們的一藥學上可接受的鹽類可被用於治療肺癌 (I) 其中各個取代基的定義是如說明書與申請專利範圍中所界定者。本發明亦揭示一具有化學式(I)之新穎的硒吩基查爾酮衍生物或者它的一藥學上可接受的鹽類，其中，R 1、R 3以及R 5為氫；以及R 2以及R 4為羥基。
description: 專利證號：I896052

硒吩基色原酮衍生物及其用途

title: 硒吩基色原酮衍生物及其用途 abstract: 本發明揭示具有下列化學式(I)之新穎的硒吩基色原酮衍生物(selenophene-based chromone derivatives)： (I) 或者它們的一藥學上可接受的鹽類，其中各個取代基的定義是如說明書與申請專利範圍中所界定者。本發明亦揭示該等衍生物可被用於治療肺癌。
description: 專利證號：I873001

有機化學基礎與進階

title: 有機化學基礎與進階 abstract: 與前一本「理解有機化學」的內容相比較，此本書加入了較多反應機制的推導元素，並將章節的安排上做了重新調整。本書另外的特色是將一些生活周遭有關有機化學的故事加入每一個章節的後段，目的是讓各位在學習有機化學時能夠了解，有機化學的發生是無所不在的，它是一個很有趣但不是全部都是枯燥記憶的科學。也希望藉由這本書讓有志於學習化學者知道有機化學之美，而有機化學家是可以創造分子的藝術家。在第十一章中，為了尋求與「理解有機化學」的翻譯一致性，一律將“free radical”翻譯成游離基，雖然也有人翻譯成自由基；“chiral center”以掌性中心取代手性中心的翻譯。所有英文化學術語的翻譯，均參考國家教育研究院的樂詞網 (https://terms.naer.edu.tw/) 或網路上最接近正確的翻譯。有機化學的反應就是親核劑尋找親電子劑的反應，這個道理永遠不會改變，如果能了解反應的機制就更容易學習。本書盡力做到正確的勘誤，如果有未盡事宜，請不吝指教

A naphthalimide derivative exerts potent antiplatelet and antithrombotic activities without a bleeding tendency

title: A naphthalimide derivative exerts potent antiplatelet and antithrombotic activities without a bleeding tendency abstract: Background: Bleeding is the inherent adverse effect of antiplatelet drugs that has limited their use in the prevention of secondary heart attack and stroke. Thus, finding a novel antiplatelet drug with antithrombotic activities while preserving hemostatic function remains a crucial issue. Here, we screened naphthalimide derivatives that we previously synthesized and identified a novel derivative compound 6, which has a more potent antithrombotic effect and has no effect on bleeding cessation. This study is aimed to determine the antiplatelet mechanism of compound 6 and further test whether compound 6 is a safer and more potent antithrombotic agent. Methods: Platelet aggregation, flow cytometry and immunoblotting were used to determine the in vitro antiplatelet effect of compound 6. The study of thrombus formation of mesenteric venules in mice was used to evaluate the antithrombotic effect of compound 6. Results: Compound 6 selectively inhibited collagen-mediated platelet aggregation and markedly prevented thrombus formation without bleeding tendency. Compound 6 also inhibited glycoprotein VI (GPVI) downstream signaling, such as Fyn and Lyn, phospholipase C gamma 2, protein kinase C. Moreover, a surface plasmon resonance assay indicated that compound 6 may directly bind to GPVI, thereby interrupting the interaction of collagen and GPVI. Compound 6 also effectively attenuates collagen-induced granule release, calcium mobilization, and GPIIbIIIa activation. Conclusion: These findings indicate that compound 6 can selectively inhibit GPVI, eventually suppressing platelet activation and thrombus formation while preserving hemostasis. Compound 6 is a GPVI antagonist and safe antiplatelet agent. Compound 6 also has therapeutic potential for treating cardiovascular diseases.

Giant X-ray circular dichroism in a time-reversal invariant antiferromagnet

title: Giant X-ray circular dichroism in a time-reversal invariant antiferromagnet abstract: X-ray circular dichroism, arising from the contrast in X-ray absorption between opposite photon helicities, serves as a spectroscopic tool to measure the magnetization of ferromagnetic materials and identify the handedness of chiral crystals. Antiferromagnets with crystallographic chirality typically lack X-ray magnetic circular dichroism because of time-reversal symmetry, yet exhibit weak X-ray natural circular dichroism. Here, the observation of giant natural circular dichroism in the Ni L3-edge X-ray absorption of Ni3TeO6 is reported, a polar and chiral antiferromagnet with effective time-reversal symmetry. To unravel this intriguing phenomenon, a phenomenological model is proposed that classifies the movement of photons in a chiral crystal within the same symmetry class as that of a magnetic field. The coupling of X-ray polarization with the induced magnetization yields giant X-ray natural circular dichroism, revealing typical ferromagnetic behaviors allowed by the symmetry in an antiferromagnet, i.e., the altermagnetism of Ni3TeO6. The findings provide evidence for the interplay between magnetism and crystal chirality in natural optical activity. Additionally, the first example of a new class of magnetic materials exhibiting circular dichroism is established with time-reversal symmetry.

Single-Crystal X-ray Analysis of the Diketo form of Asymmetric Curcuminoids and Coupled with NMR Insights into Its β-Keto-enol Tautomerization at Ambient Temperature

title: Single-Crystal X-ray Analysis of the Diketo form of Asymmetric Curcuminoids and Coupled with NMR Insights into Its β-Keto-enol Tautomerization at Ambient Temperature abstract: In this study, we present a detailed analysis of the structural forms of asymmetric curcuminoids through single-crystal X-ray diffraction and nuclear magnetic resonance (NMR) spectroscopy. Curcuminoids substituted with electron-withdrawing groups (Cl and Br) predominantly adopt the β-keto-enol form, whereas those with an OMe group exhibit both diketo and β-keto-enol forms. Variable-temperature X-ray diffraction studies confirm that the structural state of curcuminoids is influenced by temperature. Our findings also reveal that the β-keto-enol form is favored in acidic and neutral conditions, while the diketo form is more prevalent in basic environments. The theoretical Density Functional Theory (DFT) calculations further elucidate the energy differences between the diketo and β-keto-enol forms, emphasizing the significance of electronic effects and temperature on tautomeric distributions. These insights enhance our understanding of the structural dynamics of curcuminoids, with implications for their biological activity and pharmacological applications.

Synthesis of quinoxalines and assessment of their inhibitory effects against human non-small-cell lung cancer cells

title: Synthesis of quinoxalines and assessment of their inhibitory effects against human non-small-cell lung cancer cells abstract: Twenty-six quinoxalin derivatives were synthesized to assess their biological activities against human non-small-cell lung cancer cells (A549 cells). Compound 4b (IC50 = 11.98 ± 2.59 μM) and compound 4m (IC50 = 9.32 ± 1.56 μM) possess anticancer activity comparable to 5-fluorouracil (clinical anticancer drug) (IC50 = 4.89 ± 0.20 μM). Western blot tests further confirmed that compound 4m effectively induced apoptosis of A549 cells through mitochondrial- and caspase-3-dependent pathways. The introduction of bromo groups instead of nitro groups into the quinoxaline skeleton has been shown to provide better inhibition against lung cancer cells in this article. This modification in the molecular structure could enhance the biological activity and effectiveness of quinoxaline derivatives in the design and synthesis of anticancer drugs, making bromo-substituted quinoxalines a promising avenue for further research and development in anticancer therapeutics.

Metabolic engineering of the borneol and camphor degradation pathways in Pseudomonas to produce optically pure bicyclic monoterpenes

title: Metabolic engineering of the borneol and camphor degradation pathways in Pseudomonas to produce optically pure bicyclic monoterpenes abstract: Borneol, a medicinally important bicyclic monoterpene, facilitates drug transport across mucous membranes and the blood-brain barrier. Derivatives of borneol and camphor also have numerous biomedical applications. Borneol is currently industrially synthesized via the conversion of turpentine and α-pinene. However, the major product is racemic isoborneol rather than racemic borneol. Both borneol and isoborneol are degraded by the soil bacterium Pseudomonas via a well-established degradation pathway. Two indigenous Pseudomonas strains were used to convert racemic isoborneol to other optically pure bicyclic monoterpenes here. Our results showed that deletion of the camE2,5 gene alone from the strain TCU-HL1 genome led to the complete loss of borneol and camphor degradation ability. Knockout of both camE2,5 and bdh1 (TCU-HL1Δbdh1ΔcamE2,5) restored the degradation capability as the role of Bdh1 was replaced by that of Bdh2. This mutant converted racemic isoborneol into an optically pure bicyclic monoterpene, 2,5-diketocamphane, with a 45 % recovery yield. RT-qPCR results suggested that camE2,5 expression plays a pivotal role in regulating the borneol/camphor degradation cluster. While (+)-borneol, (–)-borneol and (+)-camphor can be obtained from plants for mass production purposes, (–)-camphor cannot be obtained in the same manner. P. monteilii TCU-CK1 converted racemic isoborneol into (–)-camphor and 3,6-diketocamphane, with 15 % and 10 % recovery yields, respectively. In conclusion, we report the role of camE2,5 in regulating the borneol/camphor degradation operon and biotransformation methods to produce several optically pure bicyclic monoterpenes.

含硒元素的查爾酮化合物及其製備方法、包含其的醫藥組合物、以及用於製備預防或治療大腸癌之醫藥組合物的用途

title: 含硒元素的查爾酮化合物及其製備方法、包含其的醫藥組合物、以及用於製備預防或治療大腸癌之醫藥組合物的用途 abstract: 一種含硒元素的查爾酮化合物及其製備方法、包含其的醫藥組合物、以及用於製備預防或治療大腸癌之醫藥組合物的用途，其中含硒元素的查爾酮化合物由式(I)或其醫藥上可接受的鹽所表示；本發明利用簡單的合成方法合成四種含硒元素的查爾酮化合物，相較於習知的化療藥5-FU對於大腸癌的治療效果更佳。
description: 專利證號：I811116

Flavonol-ruthenium complexes as antioxidant and anticancer agents

title: Flavonol-ruthenium complexes as antioxidant and anticancer agents abstract: Flavonol-metal complexes can enhance the biological activity of flavonols. Inspired by the potential of ruthenium-based drugs in pharmaceutical applications, seven flavonol-Ru (II) complexes were synthesized to evaluate their biological activities. Among these compounds, compounds 8, 11, and 12 showed potent antioxidant activities. Compound 12 exhibited superior anti-inflammatory activity to natural quercetin, which served as a positive control. This study is the first to report the free radical scavenging abilities and antioxidant activity of flavonol-Ru (II) complexes. Furthermore, compound 12 demonstrated comparable efficacy to 5-FU against human non-small-cell lung cancer cells (A549). These results strongly support the potential of flavonol-Ru (II) agents.

Novel 1,8-Naphthalimide Derivatives Inhibit Growth and Induce Apoptosis in Human Glioblastoma

title: Novel 1,8-Naphthalimide Derivatives Inhibit Growth and Induce Apoptosis in Human Glioblastoma abstract: Given the rapid advancement of functional 1,8-Naphthalimide derivatives in anticancer research, we synthesized these two novel naphthalimide derivatives with diverse substituents and investigated the effect on glioblastoma multiforme (GBM) cells. Cytotoxicity, apoptosis, cell cycle, topoisomerase II and Western blotting assays were evaluated for these compounds against GBM in vitro. A human GBM xenograft mouse model established by subcutaneously injecting U87-MG cells and the treatment responses were assessed. Both compounds 3 and 4 exhibited significant antiproliferative activities, inducing apoptosis and cell death. Only compound 3 notably induced G2/M phase cell cycle arrest in the U87-MG GBM cells. Both compounds inhibited DNA topoisomerase II activity, resulting in DNA damage. The in vivo antiproliferative potential of compound 3 was further validated in a U87-MG GBM xenograft mouse model, without any discernible loss of body weight or kidney toxicity noted. This study presents novel findings demonstrating that 1,8-Naphthalimide derivatives exhibited significant GBM cell suppression in vitro and in vivo without causing adverse effects on body weight or kidney function. Further experiments, including investigations into mechanisms and pathways, as well as preclinical studies on the pharmacokinetics and pharmacodynamics, may be instrumental to the development of a new anti-GBM compound.

Synthesis of Flavonols and Assessment of Their Biological Activity as Anticancer Agents

title: Synthesis of Flavonols and Assessment of Their Biological Activity as Anticancer Agents abstract: A series of flavanols were synthesized to assess their biological activity against human non-small cell lung cancer cells (A549). Among the sixteen synthesized compounds, it was observed that compounds 6k (3.14 ± 0.29 µM) and 6l (0.46 ± 0.02 µM) exhibited higher potency compared to 5-fluorouracil (5-Fu, 4.98 ± 0.41 µM), a clinical anticancer drug which was used as a positive control. Moreover, compound 6l (4’-bromoflavonol) markedly induced apoptosis of A549 cells through the mitochondrial- and caspase-3-dependent pathways. Consequently, compound 6l might be developed as a candidate for treating or preventing lung cancer.

Synthesis of selenophene-containing flavonols and 2-styrylchromones: Evaluation of their activities compared with selenophene-containing chalcones as potential anticancer agents

title: Synthesis of selenophene-containing flavonols and 2-styrylchromones: Evaluation of their activities compared with selenophene-containing chalcones as potential anticancer agents abstract: Previously, we documented the synthesis and assessed the biological effects of chalcones containing selenium against HT-29 human colorectal adenocarcinoma cells, demonstrating their significant potential. As research on selenium-containing flavonoids remains limited, this article outlines our design and synthesis of three selenium-based flavonols and three 2-styrylchromones. We conducted evaluations of these compounds to determine their impact on human lung cancer cells (A549, H1975, CL1-0, and CL1-5) and their influence on normal lung fibroblast MRC5 cells. Additionally, we included selenium-based chalcones in our testing for comparative purposes. Our findings highlight that the simplest compound, designated as compound 1, exhibited the most promising performance among the tested molecules.

Dissolution of Nanoprecipitate on Aluminum-Alloy Anode for High Discharging Performance in Al Battery Applications

title: Dissolution of Nanoprecipitate on Aluminum-Alloy Anode for High Discharging Performance in Al Battery Applications abstract: Use of aluminum alloy anodes as metal fuel in electrochemical batteries has specific advantages in numerous applications. In this paper, we report novel Al alloy anodes obtained by adding In and Bi to a reported Al ternary-element alloy, Al-Zn-Sn. An electron probe microanalyzer is used to obtain the elemental composition of Al-5Zn-0.1Sn, Al-5Z-0.1Sn-0.1In, and Al-5Zn-0.1Sn-0.1In-0.1Bi. Tafel analysis, electrochemical impedance spectroscopy, and constant-current chronopotentiometry are performed for electrochemical analysis. In addition, the self-corrosion of the alloys is examined to determine the hydrogen evolution and anode discharge stability. These results indicate that Al-5Zn-0.1Sn-0.1In-0.1Bi has the highest anode performance. On the basis of the scanning electron microscopy and transmission electron microscopy microstructure analysis, we propose that the dissolution and sedimentation process induced by Bi nanoprecipitates may activate a passive Al surface, significantly enhancing the discharge efficiency.

Synthesis of 2‐(pyridylvinyl)chromen‐4‐ones and their N‐oxide analogs for assessment of their biological activities as anticancer agents

title: Synthesis of 2‐(pyridylvinyl)chromen‐4‐ones and their N‐oxide analogs for assessment of their biological activities as anticancer agents abstract: 2-Styrylchromones have been shown to possess a broad spectrum of biological activities. Replacing the carbon atom in 2-styrylchromones with a nitrogen atom in the benzene rings forms 2-(pyridylvinyl)chromen-4-ones (aza-2-styrylchromones). We have synthesized a series of novel 2-(pyridylvinyl)chromen-4-ones and their pyridine N-oxides to evaluate them as potential anticancer agents against human non-small-cell lung cancer cells (A549). Among the 18 synthesized molecules, compounds 18 and 8a exhibited comparable inhibitory effects to 5-fluorouracil and showed no toxicity against normal cells.

Klein(3rd)有機化學課本重點整理

title: Klein(3rd)有機化學課本重點整理

理解有機化學

title: 理解有機化學 abstract: 有機化學的反應即是親核劑尋找親電子劑的反應，本書會提及部分的反應機制讓學生有初步的了解，但不會鉅細靡遺，本書淺顯易懂，希望能夠對莘莘學子對於有心理解有機化學能有所助益。本書包含二十章節，書寫本書的目的是想把有機化學之美介紹給一般有機會學習有機化學的學子們。有機化學給人們的印象是需要"死記”，然而它是一個非常有邏輯的學科，只要掌握一些基本的命名規則，對於往後"看懂"分子才能夠奠定基礎。另外學習有機化學時需要掌握立體效應、電子效應以及親核劑尋找親電子劑的原則。藥物化學、材料化學和生物化學等皆與有機化學息息相關，希望藉由這本書，在各位接觸有機化學時不再畏懼並且愛上它。 -作者施增廉

Design, synthesis, and evaluation of 1,2,3-triazole-based benzenesulfonamide and flavonol hybrid molecules as anticancer agents

title: Design, synthesis, and evaluation of 1,2,3-triazole-based benzenesulfonamide and flavonol hybrid molecules as anticancer agents abstract: Background The design and synthesis of hybrid molecules will explore finding new drugs. Objectives The synthesized hybrid molecules to evaluate their biological properties. Methods Apply click chemistry to tether flavonols and benzenesulfonamide. Results Two drug candidates show potential against lung cancer. Conclusions Two drug candidates did not affect the normal cells and provided a new drug design route.

Synthesis and Evaluation of 6‐Amino‐2‐styrylchromones as Anticancer Agents

title: Synthesis and Evaluation of 6‐Amino‐2‐styrylchromones as Anticancer Agents abstract: 2-Styrylchromones, a C-2 styrene derivative of chromones, possess a broad spectrum of biological activity. However, 2-styrylchromones are scarce in nature but not to mention the amino-substituted styrylchromones. We have synthesized fourteen 6-amino-2-styrylchromones and evaluated their anti-cancer activity on human caucasian colon adenocarcinoma cells (HT-29). 6-Amino-2-styrylchromones and related derivatives have never been revealed their pharmacology profiles. Among the novel fourteen compounds, we reported that compound 9 h exhibited its potential with the comparable activity with 5-flurouracil (5-FU) as a referenced drug.

己二烯-3,4二酮類或喹㗁啉類化合物或其醫藥學上可接受之鹽用於製備抑制胰臟癌之藥物的用途

title: 己二烯-3,4二酮類或喹㗁啉類化合物或其醫藥學上可接受之鹽用於製備抑制胰臟癌之藥物的用途 abstract: 本發明提供一種式(I)之化合物或其醫藥學上可接受之鹽用於製備抑制胰臟癌之藥物的用途，其中，R1為選自由苯基、對氟苯基、呋喃基及2-噻吩基所組成之群組。本發明還提供一種式(II)之化合物或其醫藥學上可接受之鹽用於製備抑制胰臟癌之藥物的用途，其中，R2為選自由對乙醯胺苯基、呋喃基及2-噻吩基所組成之群組。
description: 專利證號：I776736

Synthesis of selenophene‐based chalcone analogs and assessment of their biological activity as anticancer agents

title: Synthesis of selenophene‐based chalcone analogs and assessment of their biological activity as anticancer agents abstract: Selenium is an essential micronutrient that is beneficial to human health. Selenium-containing drugs have been developed as antioxidants, anti-inflammatory, and anticancer agents. However, the synthesis of selenium-containing chalcones has not been fully explored. Therefore, we report the synthesis of novel selenophene-based chalcone analogs and reveal their biological activities as anticancer agents. Among the seven synthesized molecules, compounds 6, 8, and 10 exhibited anticancer activity with IC50 values of 19.98 ± 3.38, 38.23 ± 3.30, and 46.95 ± 5.68 μM, respectively, against human colorectal adenocarcinoma (HT-29) cells. Clonogenic assays and Western blot analysis tests further confirmed that compound 6 effectively induced apoptosis in HT-29 cells through mitochondrial- and caspase-3-dependent pathways.

Synthesis of cinnamils and quinoxalines and their biological evaluation as anticancer agents

title: Synthesis of cinnamils and quinoxalines and their biological evaluation as anticancer agents abstract: We synthesized multiple cinnamils and quinoxalines to evaluate their anticancer activity. Cinnamils were used as precursors for quinoxalines via condensation with 1,2-diaminobenzene. Among the 26 synthesized compounds reported in this article, we found that cinnamil 3l exhibited its inhibitory effect with an IC50 value of 1.45 ± 0.98 μM, significantly higher than doxorubicin (8.5 ± 0.85 μM) against pancreatic cancer cells (PANC-1). Additionally, cinnamil 3l (IC50 10.98 ± 3.63 μM) showed less cytotoxicity than doxorubicin to Hs68 cells (0.92 ± 1.11 μM). The colony formation assay demonstrated that 3l obviously decreased the PANC-1 cell viability, and Western blot assays confirmed that 3l markedly induced apoptosis of PANC-1 cells through Bax, Bcl-2, and caspase 3 signaling cascades. These results demonstrate that cinnamil 3l has great potential to be further developed as a promising chemotherapeutic agent for pancreatic cancer.

Improved Synthesis of Asymmetric Curcuminoids and Their Assessment as Antioxidants

title: Improved Synthesis of Asymmetric Curcuminoids and Their Assessment as Antioxidants abstract: In this paper, the syntheses of twelve asymmetric curcumin analogs using Pabon’s method are reported. Generally, the previously reported yields of asymmetric curcuminoids, such as 9a (53%), 9c (38%), and 9k (38%), have been moderate or low. Herein, we propose that the low yields were due to the presence of water and n-BuNH2 in the reaction media. To prove this formulated hypothesis, we have demonstrated that the yields can be improved by adding molecular sieves (MS) (4 Å) to the reaction mixture, thus reducing the interference of water. Therefore, improved yields (41–76%) were obtained, except for 9b (36.7%), 9g (34%), and 9l (39.5%). Furthermore, compounds 9b, 9d, 9e, 9f, 9g, 9h, 9i, 9j, and 9l are reported herein for the first time. The structures of these synthetic compounds were determined by spectroscopic and mass spectrometry analyses. The free radical scavenging ability of these synthetic asymmetric curcuminoids was evaluated and compared to that of the positive control butylated hydroxytoluene (BHT). Among the synthesized asymmetric curcuminoids, compounds 9a (IC50 = 37.57 ± 0.89 µM) and 9e (IC50 = 37.17 ± 1.76 µM) possessed effective 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical scavenging abilities, and compounds 9h (IC50 = 11.36 ± 0.65 µM) and 9i (IC50 = 10.91 ± 0.77 µM) displayed potent 2,2’-azinobis-(3- ethylbenzthiazoline-6-sulphonate) (ABTS) radical scavenging abilities comparable to that of curcumin (IC50 = 10.14 ± 1.04 µM). Furthermore, all the synthetic asymmetric curcuminoids were more active than BHT.

Magnetic structures and spin reorientation in the B-site disordered perovskite PrFe0.5Cr0.5O3

title: Magnetic structures and spin reorientation in the B-site disordered perovskite PrFe0.5Cr0.5O3 abstract: Through the detailed studies utilizing x-ray and neutron powder diffraction and magnetometry measurements, we report the magnetic phase transitions in the B-site disorder perovskite oxide PrFe0.5Cr0.5O3. The Fe3+/Cr3+ sublattice was observed to form a long-range magnetic order with the GxFz configuration below TN = 270 K from neutron powder diffraction. It then undergoes the second-order phase transition to FxGz spin configuration below 210 K and the transition ends at ~170 K. On the other hand, long range magnetic ordering with FxCy configuration at Pr3+ sublattice can be identified at base temperature. The magnetic phase diagram is derived with spontaneous spin ordering and reorientation at A- and B-sublattices.

Bandgap Shrinkage and Charge Transfer in 2D Layered SnS2 Doped with V for Photocatalytic Efficiency Improvement

title: Bandgap Shrinkage and Charge Transfer in 2D Layered SnS2 Doped with V for Photocatalytic Efficiency Improvement abstract: Effects of electronic and atomic structures of V-doped 2D layered SnS2 are studied using X-ray spectroscopy for the development of photocatalytic/photovoltaic applications. Extended X-ray absorption fine structure measurements at V K-edge reveal the presence of VO and VS bonds which form the intercalation of tetrahedral OVS sites in the van der Waals (vdW) gap of SnS2 layers. X-ray absorption near-edge structure (XANES) reveals not only valence state of V dopant in SnS2 is ≈4+ but also the charge transfer (CT) from V to ligands, supported by V Lα,β resonant inelastic X-ray scattering. These results suggest V doping produces extra interlayer covalent interactions and additional conducting channels, which increase the electronic conductivity and CT. This gives rapid transport of photo-excited electrons and effective carrier separation in layered SnS2. Additionally, valence-band photoemission spectra and S K-edge XANES indicate that the density of states near/at valence-band maximum is shifted to lower binding energy in V-doped SnS2 compare to pristine SnS2 and exhibits band gap shrinkage. These findings support first-principles density functional theory calculations of the interstitially tetrahedral OVS site intercalated in the vdW gap, highlighting the CT from V to ligands in V-doped SnS2.

Role of Interfacial Defects in Photoelectrochemical Properties of BiVO4 Coated on ZnO Nanodendrites: X-ray Spectroscopic and Microscopic Investigation

title: Role of Interfacial Defects in Photoelectrochemical Properties of BiVO4 Coated on ZnO Nanodendrites: X-ray Spectroscopic and Microscopic Investigation abstract: Synchrotron-based X-ray spectroscopic and microscopic techniques are used to identify the origin of enhancement of the photoelectrochemical (PEC) properties of BiVO4 (BVO) that is coated on ZnO nanodendrites (hereafter referred to as BVO/ZnO). The atomic and electronic structures of core–shell BVO/ZnO nanodendrites have been well-characterized, and the heterojunction has been determined to favor the migration of charge carriers under the PEC condition. The variation of charge density between ZnO and BVO in core–shell BVO/ZnO nanodendrites with many unpaired O 2p-derived states at the interface forms interfacial oxygen defects and yields a band gap of approximately 2.6 eV in BVO/ZnO nanocomposites. Atomic structural distortions at the interface of BVO/ZnO nanodendrites, which support the fact that there are many interfacial oxygen defects, affect the O 2p–V 3d hybridization and reduce the crystal field energy 10Dq ∼2.1 eV. Such an interfacial atomic/electronic structure and band gap modulation increase the efficiency of absorption of solar light and electron–hole separation. This study provides evidence that the interfacial oxygen defects act as a trapping center and are critical for the charge transfer, retarding electron–hole recombination, and high absorption of visible light, which can result in favorable PEC properties of a nanostructured core–shell BVO/ZnO heterojunction. Insights into the local atomic and electronic structures of the BVO/ZnO heterojunction support the fabrication of semiconductor heterojunctions with optimal compositions and an optimal interface, which are sought to maximize solar light utilization and the transportation of charge carriers for PEC water splitting and related applications.

Anomalous boron isotope effects on electronic structure and lattice dynamics of CuB2O4

title: Anomalous boron isotope effects on electronic structure and lattice dynamics of CuB2O4 abstract: Copper metaborate had a unique crystal structure and exhibited noteworthy magnetic phase transitions at 21 and 10 K. The electronic structure and lattice dynamics of copper metaborate Cu11B2O4 single crystals were investigated and compared with the optical properties of CuB2O4, to assess the boron isotope effect. The optical absorption spectrum at room temperature revealed two charge-transfer bands at approximately 4.30 and 5.21 eV with an extrapolated direct optical band gap of 3.16 ± 0.07 eV. Compared with the data on CuB2O4, the electronic transitions were shifted to lower energies upon the replacement of a heavier boron isotope. The band gap was also determined to be lower in Cu11B2O4. Anomalies in the temperature dependence of the optical band gap were observed below 21 K. Furthermore, 38 Raman-active phonon modes were identified in the room-temperature Raman scattering spectrum of Cu11B2O4, which were also observed in CuB2O4 with a shift to lower frequencies. No broadening caused by isotopic changes was observed. As the temperature decreased, phonon frequencies shifted to higher wavenumbers and the linewidth decreased. Anomalous softening in the Raman peaks below 21 K was also revealed.

Efficient Photodynamic Killing of Gram-Positive Bacteria by Synthetic Curcuminoids

title: Efficient Photodynamic Killing of Gram-Positive Bacteria by Synthetic Curcuminoids abstract: In our previous study, we have demonstrated that curcumin can efficiently kill the anaerobic bacterium Propionibacterium acnes by irradiation with low-dose blue light. The curcuminoids present in natural plant turmeric mainly include curcumin, demethoxycurcumin, and bisdemethoxycurcumin. However, only curcumin is commercially available. Eighteen different curcumin analogs, including demethoxycurcumin and bisdemethoxycurcumin, were synthesized in this study. Their antibacterial activity against Gram-positive aerobic bacteria Staphylococcus aureus and Staphylococcus epidermidis was investigated using the photodynamic inactivation method. Among the three compounds in turmeric, curcumin activity is the weakest, and bisdemethoxycurcumin possesses the strongest activity. However, two synthetic compounds, (1E,6E)-1,7-bis(4-bromophenyl)hepta-1,6-diene-3,5-dione and (1E,6E)-1,7-bis(3-bromophenyl)hepta -1,6-diene-3,5-dione, possess the best antibacterial activity among all compounds examined in this study. Their chemical stability is also better than that of bisdemethoxycurcumin, and thus has potential for future clinical applications.

A novel naphthalimide derivative reduces platelet activation and thrombus formation via suppressing GPVI

title: A novel naphthalimide derivative reduces platelet activation and thrombus formation via suppressing GPVI abstract: Naphthalimide derivatives have multiple biological activities, including antitumour and anti-inflammatory activities. We previously synthesized several naphthalimide derivatives; of them, compound 5 was found to exert the strongest inhibitory effect on human DNA topoisomerase II activity. However, the effects of naphthalimide derivatives on platelet activation have not yet been investigated. Therefore, the mechanism underlying the antiplatelet activity of compound 5 was determined in this study. The data revealed that compound 5 (5–10 μM) inhibited collagen- and convulxin- but not thrombin- or U46619-mediated platelet aggregation, suggesting that compound 5 is more sensitive to the inhibition of glycoprotein VI (GPVI) signalling. Indeed, compound 5 could inhibit the phosphorylation of signalling molecules downstream of GPVI, followed by the inhibition of calcium mobilization, granule release and GPIIb/IIIa activation. Moreover, compound 5 prevented pulmonary embolism and prolonged the occlusion time, but tended to prolong the bleeding time, indicating that it can prevent thrombus formation but may increase bleeding risk. This study is the first to demonstrate that the naphthalimide derivative compound 5 exerts antiplatelet and antithrombotic effects. Future studies should modify compound 5 to synthesize more potent and efficient antiplatelet agents while minimizing bleeding risk, which may offer a therapeutic potential for cardiovascular diseases.

A case study of the iodine-mediated cyclization of C2'-OH- and C2-OH-chalcones toward the synthesis of flavones:Reinvestigation of the mechanisms

title: A case study of the iodine-mediated cyclization of C2'-OH- and C2-OH-chalcones toward the synthesis of flavones:Reinvestigation of the mechanisms abstract: Synthesis of flavones from chalcones via the iodine-mediated cyclization required at least one hydroxy group at their C2′-positions. On the contrary, the ring oxidative cyclization from C2-OH-chalcones under the same condition was unusual and reported only once. We evaluated the aforementioned method and found different results. The mechanisms in detail were discussed.

Probing charge order and hidden topology at the atomic scale by cryogenic scanning transmission electron microscopy and spectroscopy

title: Probing charge order and hidden topology at the atomic scale by cryogenic scanning transmission electron microscopy and spectroscopy abstract: Charge orders (COs) and entangled topology denote the fundamentals of correlated electron systems at low temperatures, and their profound revelation at atomic scale awaits experimental advances. Here, we report such a spatially resolved investigation using cryogenic atomic-scale electron microscopy and spectroscopy at 100 K, with the CO insulator of HgMn7O12 below 240 K as an exemplification. By the cryogenic technique, we can resolve the charge and lattice characteristics of the insulating CO phase at atomic resolution and identify the order parameters (OPs) at play as charge-density-modulated (∼31.4 Å, modulation length) and antiphase (∼10.5 Å) OPs. Both OPs are largely unaddressed forms of COs in correlated oxides and display the emergent topology of intertwining mesoscopic stripes of 10–40 nm in width and ≥500 nm in length, distinctly different from the atomically narrow CO stripes conventional to correlated systems and depicting the unique electronic contour of the phase. This preliminary demonstration of the cryogenic unveiling of the OPs and topological landscape paves the way to disentangling the multifarious COs and hidden topology in condensed matters and, meanwhile, calls for further developments in the atomic-scale cryogenic spectral probing at an enhanced speed.

Spectroscopic signature of spin-charge-lattice coupling in CuB2O4

title: Spectroscopic signature of spin-charge-lattice coupling in CuB2O4 abstract: CuB2O4 has attracted considerable attention because of its unique chemical and physical properties and potential practical applications. In this paper, we investigated the optical properties of CuB2O4 single crystals through spectroscopic ellipsometry and Raman scattering spectroscopy. The optical absorption spectrum at room temperature revealed a direct band gap at approximately 3.88 ± 0.01 eV and two bands near 4.49 and 5.90 eV. The observed bands were related to charge transfer of electrons from the 2p states of the oxygen ions to the 3d states of the copper ions. The band gap exhibited unusual redshift with a decrease in temperature. Upon cooling across 21 K, which is the canted antiferromagnetic ordering temperature, the band gap, peak energy, and normalized intensity of charge-transfer bands presented anomalies. Furthermore, 38 phonon modes were identified in the room-temperature Raman scattering spectrum of CuB2O4. The phonon modes at approximately 335, 393, 403, 445, 473, 598, 706, 787, and 900 cm–1 exhibited softening below 21 K. The spin–phonon coupling constants were estimated to be 0.02–0.03 cm–1. These findings highlight a complex nature of spin–charge–lattice interactions in CuB2O4.

Discovery of a more potent anticancer agent than C4-benzazole 1,8-naphthalimide derivatives against murine melanoma

title: Discovery of a more potent anticancer agent than C4-benzazole 1,8-naphthalimide derivatives against murine melanoma abstract: Three novel naphthalimide‐based derivatives were synthesized and tested in vitro as anticancer agents. Our previous report of the C4‐benzazole 1,8‐naphthalimide derivatives showed good inhibition against murine melanoma. We aimed to synthesize more potent agents and found that compound 5 reported in this article behaved 5‐ to 10‐fold potency than our previous best results. The unique structure of compound 5 consisted of a naphthalimide framework in which C4 position was linked with an ethylenediamine group where the amino group was coupled with a 2‐piconic acid moiety. Compound 5 exhibited the most potent inhibitory activity toward human DNA topoisomerase II proteins with IC50 value (2.6 ± 0.1 μM) against murine B16F10 melanoma cells among the three target compounds synthesized in this study. In accordance with this finding, the results of molecular docking also revealed that compound 5 has the highest affinity with human DNA topoisomerase II among the selected compounds. Compound 5 , therefore, has high potential for becoming a lead compound.

Conformational analysis of a seven-membered ring azasugar, (3R,4R,6S)-trihydroxyazepane: Comparison of GIAO calculation and experimental NMR spectra on 13C chemical shifts

title: Conformational analysis of a seven-membered ring azasugar, (3R,4R,6S)-trihydroxyazepane: Comparison of GIAO calculation and experimental NMR spectra on 13C chemical shifts abstract: DFT/B3LYP/6-311++G(d,p) calculation of the relative stable conformations of (3R,4R,6S)-trihydroxyazepane are presented. The GIAO/DFT/OPBE, GIAO/DFT/B3LYP and GIAO/HF single point calculations with 6-311++G(d,p), 6-311+G(2d,p), cc-pVDZ and cc-pVTZ basis sets of (3R,4R,6S)-trihydroxyazepane were conducted to generate their 13C NMR chemical shifts. According to calculation results, 14 (3R,4R,6S)-trihydroxyazepane with optimized structure were generated. There were three conformers which contain the intramolecular hydrogen bonding exhibit a lowest electronic energies and TCN1(eq) was the most stable conformer than others. Boltzmann weighting factor analysis exhibits that TCN1(eq), TCN3(eq) and TCN5(eq) dominate a major contribution among the 14 conformers. The individual calculated NMR results of TCN1(eq), TCN3(eq) and TCN5(eq) represents a quite close correlation with experimental data. Moreover, the experimental 13C NMR chemical shifts gave only the average contribution of all conformers. In our investigation, the calculated 13C NMR chemical shifts of mixture (3R,4R,6S)-trihydroxyazepane exhibit a good agreement with the experimental NMR data. Calculated NMR results of mixture (3R,4R,6S)-trihydroxyazepane conformers display a remarkable MAE and RMS improvement over that of each individual conformer. A good calculation method and basis set choice to evaluate the theoretical chemical shifts for these conformers is HF/cc-pVTZ.