Halogen bonding is an effective strategy for tuning supramolecular packing in molecular crystals, but its role in reinforcing polynuclear coordination lattices remains insufficiently quantified. In this work, the brominated dinuclear iron(III) Schiff base complex [Fe(35-Br-L1)(35-Br-L2)]2is directly compared with its non-halogenated analogue [Fe(L1)(L2)]2by combining single-crystal X-ray diffraction, FT-IR, UV-Vis, thermogravimetric analysis, and DFT/TD-DFT calculations. Bromination preserves the dinuclear Fe2O2 core while reorganizing the crystal packing into a denser three-dimensional network rich in Br & sdot;& sdot;& sdot;H, Br & sdot;& sdot;& sdot;C, and Br & sdot;& sdot;& sdot;Br contacts. Relative to the non-halogenated analogue, the brominated complex shows markedly improved thermal robustness: the onset of framework decomposition increases from ca. 150 to 300 degrees C, the mass loss at 230 degrees C decreases from 25.20% to about 5%, and complete framework collapse is delayed to 420 degrees C. The calculations further show a reduced HOMO-LUMO gap (2.64 vs 2.98 eV) and a stronger gas-phase dimer binding energy (-53.27 vs-37.80 kcal mol-1) for the brominated system. Hirshfeld, MEP, NCI/AIM, and IGMH analyses consistently indicate that bromine substitution strengthens a dense polarization-and dispersion-assisted noncovalent interaction network, providing the microscopic origin of the enhanced lattice rigidity and thermal stability.

Enhancing the thermal stability of molecular materials to ensure their structural and functional integrity at elevated temperatures is a critical challenge in materials design. To assess the influence of halogens on thermal stability in the absence of a classic halogen bond network, a brominated Co Schiff-base complex, [Co(L-3-Br(1)) (L-3-Br(2))], was selected as the study subject. A non-halogenated derivative, [Co(L-1)(L-2)], was introduced for systematic comparison. Thermogravimetric analysis (TGA) reveals a fundamental enhancement in thermal robustness upon bromination. After accounting for the initial loss of methyl substituents of the non-halogenated analogue, a comparative analysis demonstrates that bromination raises the main skeletal decomposition temperature by approximately 80 degrees C (from similar to 200 degrees C to 280 degrees C). Crucially, the degradation pattern transitions from a non-cooperative, multi-stage fragmentation to a highly synchronous, single-step collapse. Computational analysis indicates two contributions to this enhanced thermal robustness: (i) a denser supramolecular packing driven by bromine-induced polarizability; and (ii) the promotion of a pervasive network of weak intra- and intermolecular contacts (e.g., C-H center dot center dot center dot Br, dispersion forces). This study demonstrates that modulating the overall electronic structure and packing density via halogen atoms is a promising strategy for engineering molecular materials with exceptional thermal stability.

Using sulfinic acid as a sulfonyl source, we have developed a light-promoted photocatalyst-free alkene hydrosulfonylation reaction without any additives.

Correction for ‘Cytomembrane-mimicking nanocarriers with a scaffold consisting of a CD44-targeted endogenous component for effective asparaginase supramolecule delivery’ by Yongjia Huang et al., Nanoscale, 2020, 12, 12083–12097, https://doi.org/10.1039/D0NR02588G.

An efficient method for the construction of benzo[4,5]imidazo[1,2-a]pyrimidines using N,N-dimethylformamide as a one-carbon source and 2-aminobenzimidazoles and acetophenone as substrates through a one-pot, three-component cascade reaction is described. Spectra investigations indicated the fluorescent properties of selected products, exhibiting quantum yields 0.07-0.16 with maxima absorption at 266-294 nm and emission at 472-546 nm.

A simple, efficient and mild methodology for the synthesis of 1,3,2-benzodiazaborininones [R-B(aam)] from boronic acids and anthranilamides on ethyl acetate is described. A series of 1,3,2-benzodiazaborininones were prepared in moderate to excellent yields at room temperature without dehydrating agents, metal catalysts, corrosive acids or other additives. Meanwhile, a multi-gram scale reaction is also performed to ensure the scalability of the reaction, and the product can be conveniently isolated by simple filtration.

Course ideological and political education is an innovative means of practical teaching to enable professional knowledge to carry more social responsibility and value leading role. A teaching reform of Organic Chemistry experiment was proposed in Pharmacy specialty, which meant to improve teachers’ ideological and political consciousness, gather the strength of teaching team, explore the ideological and political elements in Organic Chemistry experiment, optimize teaching content, reform teaching methods and assessment methods. A system was built for curriculum ideological and political collaborative education and teaching with Organic Chemistry experiment as the carrier. The strategies of integrating political elements into the teaching process can realize the value guidance in the process of knowledge transmission.

This article reports an efficient method for the synthesis of amide derivatives by the direct reactions of aromatic amines with 1,3-diketones promoted by pyridine hydrochloride under metal-free and solvent-free conditions. This transformation was accomplished by cleavage of CC bond in the presence of pyridine hydrochloride as additive, which excludes the use of transition-metals and harsh reaction conditions. This method has a broad substrate scope and good tolerance for sensitive functional groups. A multi-gram scale reaction is also performed to ensure the scalability of the reaction.

A green and efficient method for the synthesis of oxadiazaborole, dioxazaborinine, and oxadiazaborinine from the reactions of phenylboronic acid with amidoxime, α-hydroxyl oxime and α-hydroxyl hydrazone, respectively, is described. The reactions were performed under catalyst-free and mild conditions. All products can be rapidly purified by filtration and washing. In addition, a set of iminoboronates were prepared following a one-pot multicomponent reaction procedure using α-hydroxyl hydrazone, salicylaldehyde and boronic acid derivatives as starting materials and their photophysical properties were assessed. Then, cross-coupling reactions can be carried out smoothly on some target compounds, which may help develop new boron masking strategies.

研究甾体化合物A环的C1,2-脱氢方法,并对其进行优化.采用正交设计实验方法考察了溶剂、氧气压力和催化剂对A环的C1,2-脱氢的影响.确定最佳在氧气存在条件下,乙酸做溶剂、DMSO、醋酸钯做催化剂进行脱氢效果最好,并通过底物扩展验证其适应性,制备路线具有反应条件温和,产率较高、后处理简单等优点,适合工业化生产.所有产物的结构经1H NMR、13 C NMR确证.

An environment-friendly methodology for the synthesis of R (alkyl or aryl)-B(dan) on water is described. 1,8-diamino naphthalene(danH2) was reacted with different types of organoboronic acids to furnish the products in moderate to excellent yields. A multi-gram scale reaction is also performed to ensure the scalability of the reaction.

A facile, universal and economical method was developed for the synthesis of polycyclic carbamyl pyridone analogues of Baloxavir marboxil from the cyclization of chloroacetaldehyde with o-aminoamide derivatives. In this method, without any other catalysts or additives, the polycyclic carbamoyl pyridone analogues can be obtained by ring closure of o-aminoamide derivatives and chloroacetaldehyde under the action of a base, and no harsh reaction conditions are required. The method operation is simple and suitable for industrial production. A series of polycyclic carbamyl pyridone analogues were prepared in moderate to excellent yields.

有机化学课程中的思政资源非常丰富.针对有机化学的课程特点,梳理"课程思政"的结合点,探索将"思政元素"融入课程教学的策略.采用结合知识点、借助信息技术、引入案例、联系社会热点、优化教学设计等方法,以培养学生的环保意识、正确人生观和价值观、科学发展观、严谨的科学态度以及辩证的思维品质,达到全方位育人的目的.

Evodiamine (EVO) was derivatized to a C10-amino derivative (EVA) using a two-step method suitable for industrializing production. This method has advantages such as a short reaction time, high yield, few byproducts and simple purification. The AUC and Cmax values of EVA were 7.02- and 4.62-fold, while the Tmax and Cl values were one-half and one-eighth that of EVO, respectively. EVA markedly improved the bioavailability, which might be ascribed to the serum albumin deposit effect. EVA was bound to albumin in the same hydrophobic pocket as EVO, but one more hydrogen bond was formed between Asp323 and the amino group at the C10 position. The amino derivative of natural alkaloids showed a substantial increase in antitumor activity on small cell lung cancer (SCLC) cells. The role of the PI3K/AKT signaling pathway in alkaloid/derivative-induced apoptosis in tumor cells was thoroughly described. p-AKT, its downstream effectors Bcl-2, Bax, caspase-3 and its upstream regulator PTEN were regulated by EVA. The interaction between EVO/EVA and the upstream protein PI3K p110 was first investigated with molecular docking. The apoptosis induced by EVA was abrogated after the PI3K/AKT signaling pathway was reactivated by IGF-1. The interaction between EVO/EVA and P-gp was also first studied using docking method. Their binding forces were weak. But EVA might reduce much expression of P-gp than EVO, and ultimately led to reduction of EVA efflux. Our study provides novel insights into a feasible and productive amino derivative of natural alkaloids for SCLC therapy.

为了认真贯彻"停课不停学"精神,文章从前期准备、在线课程教学活动的开展、通过监管和反馈保证教学质量三个方面论述了利用在线课堂实现医用有机化学"停课不停学"的实践.

Oral medication is the most acceptable therapy to treat chronic diseases. Natural drugs and excipients have unique advantages, such as low cost and high safety. We first investigated modified ethanol nanosomes for tumor treatment via oral administration. We loaded curcumin (CM) into small ethanol nanosomes coated with the natural alkaline polysaccharide chitosan (CCSET) for increased absorption and bioavailability and enhanced efficacy against small cell lung cancer (SCLC). Compared to CM and noncoated ethanol nanosomes, CCSETs exhibited superior physicochemical, in vitro-in vivo kinetic, and absorptive properties and treatment efficacy at the cellular and animal levels. The interaction of CM and serum albumin (the quantitative binding force) was analyzed. The bioavailability of CCSET increased by 11.84-fold and the tumor growth inhibition rate increased markedly compared to CM. We first confirmed the effect of CM on SCLC stem cells, and CCSET greatly enhanced this action. We first reported that CM had an antitumor effect on SCLC at the animal level and that CCSET enhanced this effect. Natural alkaline polysaccharide-coated small ethanol nanosomes delivering natural medicine may be a potential oral anticancer strategy.

文章首先阐述了医用化学教学的现状,然后论述了医用化学线上线下混合式教学模式的构建策略,接着分析了医用化学线上线下混合式教学模式的特色,最后提出了医用化学线上线下混合式教学模式构建需要注意的内容.

目的:研究吴茱萸碱丁酰基衍生物(evodiamine butyryl derivative,EAB)和吴茱萸碱丁酰基衍生物固体脂质纳米粒(evodiamine butyryl derivative-loaded lipid nanoparticles,EABLN)在大鼠体内的多功能性药效学行为.方法:采用薄膜超声法制备EABLN,对制剂的外观、粒径、电位和包封率进行检测.将32只SD雄性大鼠随机分为正常组、模型组、EAB治疗组、EABLN治疗组,每天监测大鼠的体质量变化.治疗组先连续口服灌胃给药治疗1周后,再口服灌胃次黄嘌呤并皮下注射氧嗪酸钾后成功造就了大鼠的高尿酸血症模型,检测血清中尿酸(uric acid,UA)、血肌酐(serum creatinine,CR)、尿素氮(usea nitrogen,BUN)、总胆固醇(total cholesterol,TC)、甘油三酯(triglyceride,TG)、低密度脂蛋白(low density lipoprotein,LDL)、高密度脂蛋白(high density lipoprotein,HDL)、谷丙转氨酶(alanine aminotransferase,ALT)、谷草转氨酶(aspartate aminotransferase,AST)水平,并进行心、肝、脾、肺、肾、脑组织病理学检查.结果:电镜结果显示,EABLN制备成功.体质量曲线结果显示不同组别对大鼠体质量影响未见不同,但4个组别在7个时间点上体质量有差异.生化指标结果显示,模型组UA、CR、BUN水平明显高于其他各组,差异有统计学意义(F=20.080,F=8.459,F=7.169;P=0.000,P=0.007,P=0.012);4组间的血清ALT、AST水平均无统计学差异(F=1.701,F=3.528;P=0.244,P=0.068).4组间的TC、TG、LDL和HDL水平均无统计学差异(F=3.069,F=0.398,F=0.191,F=3.291;P=0.091,P=0.758,P=0.899,P=0.079).病理组织学检查表明,模型组的肾单位完整性被严重破坏,而经EABLN治疗后,逆转了高尿酸血症对肾脏的损害,且EABLN不会对心、肝、脾、肺、脑造成病变.结论:EABLN首次被发现能用于治疗高尿酸血症及其所引发的并发症.

Highly effective and safe delivery of therapeutic enzymes is pivotal to the success of antitumor therapy. Herein, we report on a targeted enzyme delivery system based on cytomembrane-mimicking nanocarriers (CmN) and a supramolecular technique (SmT). Specifically, each CmN had a scaffold that mainly consisted of a CD44-targeted endogenous component conjugated with polyethylene glycol 2000 (HA-g-PEG) that self-assembled with α-cyclodextrin (ACD). The CmN acted as a microbioreactor with an inner hollow space with the capacity to confine the large molecule asparaginase (Asp) in an Asp/ACD-supramolecular complex conjugated to the inner region. The supramolecular Asp loaded into the CmN (A-S-CmN) exhibited superior stability, kinetic properties, catalytic activity and antitumor effects compared to free Asp due to the dual protection of the supramolecular complex and the nanovesicle, the CD44 targeting-homing ability, the prolonged effects of HA-g-PEG, and the favorable inner microenvironment of the constructed supramolecular CmN. The A-S-CmN also showed a decrease in in vivo toxicity and immunogenicity. CmN combined with SmT therapeutics are easy to implement and extend for use in the delivery of various enzymes and for many types of cancer treatment.

Natural phenolic drugs have good safety and various biological activities. However, poor bioavailability and inadequate bioactivity severely limit their application. A novel composite alkali polysaccharide nanovesicle was formed with supramolecule- and nano- technologies to efficiently deliver natural phenolic antitumor drugs. Alkali polysaccharide nanovesicles (ASDLM) containing supramolecular diferuloylmethane (DLM) had the additional effects of alkali polysaccharide nanovesicles and supramolecules of drug and high-molecular-weight polymers. DLM was isolated from the external environment when double loaded by cyclodextrin and nanovesicles; The nanosize, negative/positive charges and supramolecular structure were beneficial attributes that helped to increase the bioavailability and antitumor activity; supramolecular DLM-loaded nanovesicles made of natural biodegradable excipients showed good safety. Compared to free DLM, ASDLM exhibited superior physicochemical characteristics, favorable changes in the in vitro/in vivo kinetic performance, a possible in vitro-in vivo correlation, enhanced in situ gastrointestinal absorption, increased bioavailability, and an elevated anti-lung cancer efficiency. Composite alkali polysaccharide nanovesicles conjugated with supramolecular-/nano- technology may provide a valuable platform for the oral delivery of botanical drugs to meet clinical requirements.