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Field-induced slow magnetic relaxation, molecular docking and antibacterial studies of quasi-isotropic copper (II) (S = ½) systems stabilised by tetradentate (ONNO) and tridentate (NNO)-donor ligands 四齿(ONNO)和三齿(NNO)供体配体稳定的准各向同性铜(II) (S = 1 / 2)体系的场致慢磁弛豫、分子对接和抗菌研究
IF 4 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-02-10 DOI: 10.1039/d6dt00119j
Amit Saha Roy, Sourav Ghosh, Indranil Nath, Sergio Caballero, Albert Escuer, Julia Mayans, Shasank Sekhar Swain
A series of penta-coordinate Cu(II) complexes were synthesised and structurally characterised to explore the relationship between coordinating environment, molecular magnetism, and antibacterial activities. A dinuclear complex, [Cu₂(L₁)₂] (1), derived from an ONNO-coordinated tetradentate ligand (H₂L₁ = N,N′-bis[(3-methoxy-2-hydroxybenzylidene)]ethane-1,2-diamine), and three paramagnetic Cu(II) complexes, [Cu₂(N₃)₂(L₂)₂] (2), [Cu(SCN)(L₂)]ₙ (3), and [Cu(CH₃COO)(L₂)]ₙ (4), stabilised by a tridentate NNO-donor ligand (HL₂ = (E)-1-(pyridin-2-yldiazenyl)naphthalen-2-ol), were isolated. Dinuclear complex 2 features an asymmetric end-on μ₁,₁-azido bridge, whereas 3 and 4 exhibit end-to-end μ₁,₃-thiocyanate/acetate bridges, forming one-dimensional polymeric architectures. Single-crystal X-ray diffraction confirmed their square-pyramidal molecular geometries. Complexes 1 and 4 exhibit field-induced single-molecule magnet (SMM) behaviour, consistent with quasi-isotropic S = ½ Cu(II) centres. All complexes show χMT ≈ 0.4 cm³•mol⁻¹•K⁻¹ with a slight decrease below 10 K. EPR parameters support the existence of mixed orbital character dz²/dx²–y² (gx = 2.23, gy = 2.06, gz = 1.90) (1) and dx²–y² (g∥ = 2.21, g⊥ = 2.06) (4) in the ground states. Molecular docking analyses demonstrated complex 3 has strong binding affinities against four biologically relevant targets: B-DNA (PDB ID: 1BNA), human DNA topoisomerase I (hTOPI, PDB ID: 1SC7), Escherichia coli MenB enzyme (EC-MenB, PDB ID: 3T88), and human serum albumin (HSA, PDB ID: 4LA0), indicating its potential for target-specific activity.
合成了一系列五配位Cu(II)配合物,并对其进行了结构表征,探讨了配合环境、分子磁性与抗菌活性之间的关系。从onno配位的四齿配体(H₂L₁= N,N′-双[(3-甲氧基-2-羟基苄基)]乙烷-1,2-二胺)衍生出的双核配合物[Cu₂(N₃)₂(L₂)₂](2)、[Cu(SCN)(L₂)]COO (L₂)]和三个顺磁性Cu(II)配合物(HL₂= (E)-1-(吡啶-2-基二氮基)萘-2-醇)进行了分离。双核配合物2具有端对μ₁、₁-叠氮桥,而3和4具有端对端μ₁、₃-硫氰酸酯/乙酸桥,形成一维聚合物结构。单晶x射线衍射证实了它们的方锥体分子几何形状。配合物1和4表现出场致单分子磁铁(SMM)行为,与准各向同性S =½Cu(II)中心一致。χMT≈0.4 cm³•mol⁻¹•K⁻¹,在10 K以下略有下降。EPR参数支持在基态中存在混合轨道特征dz²/dx²-y²(gx = 2.23, gy = 2.06, gz = 1.90)(1)和dx²-y²(g∥= 2.21,g⊥= 2.06)(4)。分子对接分析表明,复合物3与4个生物学相关靶标具有很强的结合亲和力:B-DNA (PDB ID: 1BNA)、人DNA拓扑异构酶I (hTOPI, PDB ID: 1SC7)、大肠杆菌MenB酶(EC-MenB, PDB ID: 3T88)和人血清白蛋白(HSA, PDB ID: 4LA0),表明其具有潜在的靶标特异性活性。
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引用次数: 0
DMRG/FQ: A Polarizable Embedding Approach Combining Density Matrix Renormalization Group and Fluctuating Charges. DMRG/FQ:一种结合密度矩阵重整化群和波动电荷的极化嵌入方法。
IF 5.5 1区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-02-10 DOI: 10.1021/acs.jctc.5c02116
Matteo Rinaldi, Chiara Sepali, Alicia M Kirk, Claudio Amovilli, Chiara Cappelli

We present an integrated multiscale framework that combines the Density Matrix Renormalization Group (DMRG) with a polarizable fluctuating-charge (FQ) force field for the simulation of electronic excited states in solution. The method exploits the capabilities of DMRG to accurately describe systems with strong static correlation, while the FQ model provides a self-consistent and physically grounded representation of solvent polarization within a QM/MM embedding. The DMRG/FQ approach is applied to representative solvated systems, using extensive molecular dynamics sampling. The method yields reliable excitation energies, solvatochromic shifts, and a close agreement with available experimental data. The results highlight the importance of mutual polarization for capturing specific solute-solvent interactions, particularly in systems where hydrogen bonding or directional interactions play a dominant role.

我们提出了一个集成的多尺度框架,该框架结合了密度矩阵重整化群(DMRG)和极化波动电荷力场(FQ),用于模拟溶液中的电子激发态。该方法利用DMRG的能力来准确描述具有强静态相关性的系统,而FQ模型在QM/MM嵌入中提供了自一致和物理接地的溶剂极化表示。DMRG/FQ方法应用于代表性溶剂化系统,使用广泛的分子动力学采样。该方法产生了可靠的激发能,溶剂变色位移,并与现有的实验数据密切一致。结果强调了互极化对于捕获特定溶质-溶剂相互作用的重要性,特别是在氢键或定向相互作用起主导作用的系统中。
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引用次数: 0
Uranium Chelation by Pyrazine-2-amidoxime: Speciation, Decorporation, and Computational Studies. 吡嗪-2-偕胺肟对铀的螯合作用:形态、修饰和计算研究。
IF 4.7 2区 化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-02-10 DOI: 10.1021/acs.inorgchem.5c04432
Ashutosh Srivastava, Manjoor Ali, Naman K Bharti, Shikha Sharma, Pranaw Kumar, Rama Mohana Rao Dumpala, Biswajit Sadhu, Amit Kumar

Uranium, being chemo-radiotoxic, requires confinement within a safe environment to prevent severe health consequences. Chelation therapy, utilizing multidentate ligands, is a widely accepted approach for developing effective uranium decorporation treatments. In this study, a systematic investigation of uranium complexation by pyrazine-2-amidoxime (PAM) was undertaken for the first time, employing chemical speciation, in vitro studies, and computational calculations. Potentiometric and spectrophotometric titrations, corroborated by electrospray ionization mass spectrometry (ESI-MS), revealed that PAM forms 1:1 (ML) and 1:2 (ML2) complexes with the uranyl ion (UO22+). PAM acts as a bidentate chelator, coordinating via the oxygen and nitrogen atoms of amidoxime, with high stability constants (log β) of 8.54 ± 0.04 for ML and 16.33 ± 0.07 for ML2 complexes. Density functional theory (DFT) calculations further elucidated the preferred coordination mode, donor-site contributions, and electronic factors governing the stability of the PAM-uranyl complexes. Ex vivo experiments with human erythrocytes (RBCs) confirmed that PAM is cytocompatible and significantly enhanced uranium decorporation from human RBCs, facilitating removal of 25-40% of uranium at 100-200 μM compared to uranium-treated controls. Additionally, PAM effectively reduced uranium content by 10-20% from physiologically relevant proteins such as human serum albumin and from native human blood plasma.

铀具有化学放射性毒性,需要将其隔离在安全的环境中,以防止严重的健康后果。利用多齿配体的螯合疗法是一种被广泛接受的开发有效铀去穿孔治疗的方法。在这项研究中,首次采用化学形态、体外研究和计算计算的方法对吡嗪-2-偕胺肟(PAM)对铀的络合作用进行了系统的研究。电喷雾电离质谱(ESI-MS)证实,电位滴定和分光光度滴定表明PAM与铀酰离子(UO22+)形成1:1 (ML)和1:2 (ML2)的配合物。PAM作为双齿螯合剂,通过偕胺肟的氧和氮原子配位,具有较高的稳定性常数(log β), ML为8.54±0.04,ML2为16.33±0.07。密度泛函理论(DFT)计算进一步阐明了pam -铀酰配合物的首选配位模式、供体-位点贡献以及控制其稳定性的电子因素。人红细胞的体外实验证实,PAM具有细胞相容性,可显著增强人红细胞的铀脱porporation,与铀处理对照组相比,在100-200 μM的条件下,PAM可去除25-40%的铀。此外,PAM有效地降低了生理相关蛋白(如人血清白蛋白)和天然人血浆中的铀含量10-20%。
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引用次数: 0
Tailoring porphyrinic MOF-545 performances for CO2 photocatalytic reduction through linker chlorination. 通过连接剂氯化裁剪卟啉MOF-545的CO2光催化还原性能。
IF 3.3 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Pub Date : 2026-02-10 DOI: 10.1039/d5dt02590g
Amanda Lyn Robinson, Sadiya Sadiya, Sandeep Kumar, Francesc Penas-Hidalgo, Khadija Talbi, Zakaria Halime, Mathieu Frégnaux, Damien Aureau, Maria Gomez-Mingot, Pierre Mialane, Albert Solé-Daura, Caroline Mellot-Draznieks, Anne Dolbecq

The development of technologies for CO2 sequestration and its conversion into value-added chemicals has received considerable and growing attention. However, achieving high conversion efficiency and product selectivity under mild conditions remains a major challenge. This study investigates the photocatalytic CO2 reduction activity of Zr-based porphyrinic MOF-545 derivatives synthesized by varying the percentages of two porphyrin linkers: tetrakis(4-carboxyphenyl)porphyrin (TCPP) and its β-pyrrolic chlorinated analogue (TCPPCl8). A comprehensive set of spectroscopic and analytical techniques was employed to characterize the materials, revealing the impact of linker chlorination on the optical band gap, particle size and crystallinity. The incorporation of chlorine-substituted linkers significantly enhanced the photocatalytic activity. Notably, under visible light irradiation and using triethanolamine (TEOA) as a sacrificial electron donor, the MOF-545 derivative containing 50% TCPPCl8 achieved the highest formate production, with a rate 2.6 times greater than that of pristine MOF-545, with a production rate of 625 μmol g-1 h-1 after 2 h. Density Functional Theory (DFT) calculations were also performed to gain insight into the electronic properties of the chlorinated porphyrinic materials. These calculations showed the stabilization of both the HOMO and LUMO energy levels upon chlorination of the porphyrin linkers, with a more pronounced stabilisation of the LUMO, leading to a smaller band gap, in line with optical measurements. Additionally, the stabilisation of the HOMO level is expected to increase the oxidizing power of the photogenerated holes, thus facilitating TEOA oxidation and enhancing the overall photocatalytic activity, and this rationalizes the experimental observations.

二氧化碳固存及其转化为增值化学品的技术的发展已受到相当大的关注。然而,在温和条件下实现高转化效率和产品选择性仍然是主要的挑战。本文研究了通过改变四(4-羧基苯基)卟啉(TCPP)及其β-吡咯氯化类似物(TCPPCl8)两种卟啉连接物的百分比合成的zr基卟啉MOF-545衍生物的光催化CO2还原活性。采用一套全面的光谱和分析技术来表征材料,揭示了连接剂氯化对光学带隙,粒度和结晶度的影响。氯代连接剂的加入显著提高了光催化活性。值得注意的是,在可见光照射下,以三乙醇胺(TEOA)作为牺牲电子供体,含50% TCPPCl8的MOF-545衍生物的甲酸酯生成率最高,是原始MOF-545衍生物的2.6倍,2 h后的生成率为625 μmol g-1 h-1。这些计算表明,卟啉连接物氯化后HOMO和LUMO能级稳定,LUMO稳定更明显,导致带隙更小,与光学测量一致。此外,HOMO水平的稳定有望增加光生成孔的氧化能力,从而促进TEOA氧化,提高整体光催化活性,这使实验观察结果更加合理。
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引用次数: 0
Direct synthesis of dehydroselenocysteine-containing peptides from cysteine derivatives. 半胱氨酸衍生物直接合成含硒脱氢半胱氨酸肽。
IF 2.7 3区 化学 Q1 CHEMISTRY, ORGANIC Pub Date : 2026-02-10 DOI: 10.1039/d5ob01967b
Sao Sumida, Taiki Mori, Seiji Shirakawa

Dehydroamino acids are valuable building blocks for the construction of artificially designed functional peptides. However, effective approaches for the preparation of dehydroselenocysteine derivatives remain largely unexplored. Herein, we disclose a concise and direct method for the synthesis of dehydroselenocysteine derivatives from cysteine derivatives using diphenyl diselenide.

脱氢氨基酸是构建人工设计的功能肽的重要组成部分。然而,制备脱氢硒半胱氨酸衍生物的有效方法在很大程度上仍未被探索。在此,我们公开了一种以二苯二烯为原料,由半胱氨酸衍生物合成脱氢硒代半胱氨酸衍生物的简洁直接的方法。
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引用次数: 0
Analytical Nuclear Gradients for the Multiconfigurational Self-Consistent Field Method Coupled with the Polarizable Fluctuating Charges Model. 耦合极化波动电荷模型的多构型自洽场法的解析核梯度。
IF 5.5 1区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-02-10 Epub Date: 2026-01-27 DOI: 10.1021/acs.jctc.5c01890
Francesco Mazza, Marco Trinari, Chiara Sepali, Chiara Cappelli

The multiscale model combining the multiconfigurational self-consistent field (MCSCF) method with the fully atomistic polarizable Fluctuating Charges (FQ) force field (Sepali, C.; et al. J. Chem. Theory Comput. 2024, 20, 9954-9967) is here extended to the calculation of analytical nuclear gradients. The gradients are derived from first-principles, implemented in the OpenMolcas package, and validated against numerical references. The resulting MCSCF/FQ nuclear gradients are employed to simulate vibronic absorption spectra of aromatic molecules in aqueous solution, namely benzene and phenol. By integrating this approach with molecular dynamics simulations, both solute conformational flexibility and the dynamical aspects of solvation are properly captured. The computed spectra reproduce experimental profiles and relative band intensities with remarkable accuracy, demonstrating the capability of the MCSCF/FQ model to simultaneously describe the multireference character of the solute and its interaction with the solvent environment.

将多构型自洽场(MCSCF)方法与全原子极化波动电荷(FQ)力场相结合的多尺度模型(Sepali, C.;等)。j .化学。理论计算。2024,20,9954-9967)在这里扩展到解析核梯度的计算。梯度是从第一性原理推导出来的,在OpenMolcas包中实现,并根据数值参考进行验证。利用所得的MCSCF/FQ核梯度模拟了水溶液中芳香族分子(即苯和苯酚)的振动吸收光谱。通过将这种方法与分子动力学模拟相结合,溶质构象灵活性和溶剂化的动力学方面都得到了适当的捕获。计算得到的光谱以极高的精度再现了实验剖面和相对波段强度,证明了MCSCF/FQ模型能够同时描述溶质的多参比特征及其与溶剂环境的相互作用。
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引用次数: 0
Benchmarking Density Functional Theory for Accurate Calculation of Nitride Band Gaps. 精确计算氮化物带隙的基准密度泛函理论。
IF 5.5 1区 化学 Q2 CHEMISTRY, PHYSICAL Pub Date : 2026-02-10 Epub Date: 2026-01-27 DOI: 10.1021/acs.jctc.5c01703
Chris E Mohn, Helmer Fjellvåg, Ponniah Vajeeston, Martin Valldor, Kristin Bergum

We benchmark exchange-correlation functionals for the calculation of fundamental band gaps of inorganic nitrides. These include conventional functionals such as the local density approximation (LDA), the generalized-gradient (Perdew-Burke-Ernzerhof) approximation (PBE), simple Slater exchange functionals (SLOC), specialized LDA/GGA-derived high local exchange (HLE16) and Armiento-Kümmel semilocal (AK13) functionals, meta-GGA functionals including TASK, the modified Becke-Johnson functional (mBJ), and Heyd-Scuseria-Ernzerhof (HSE06) hybrid functional, as well as quasiparticle GW theory. Since inorganic nitrides remain strongly under-represented in previous extensive benchmark studies, the current subdatabase contributes towards building a future large-scale balanced materials compilation of band gaps to benchmark theory. From a literature survey, we carefully collect 25 binary and 11 ternary nitrides with a focus on semiconductors spanning the periodic table, including ionic Li3N, antibixbyite-structured X3N2 (X = Be, Mg, Ca), early transition metals and lanthanides (e.g., ScN, YN, and LaN), ultrahard Th3P4-type structured M3N4 (M = Zr, Hf) compounds, promising photocatalysts Ta3N5, different polymorphs of III-V reference covalent nitrides (BN, AlN, GaN), and many M3N4 polymorphs (M = C, Si, and Ge) such as spinel-structured phases. Consistent with previous extensive benchmark tests, conventional LDA/PBE unsystematically largely underestimate band gaps with mean absolute errors (MAE) of >1.0 eV and mean absolute percentage errors (MAPE) of about 50%. Simple Slater exchange functional, SLOC, the GGA-derived AK13LDA and HLE16 functionals show improvement over LDA/PBE with MAE of 0.5-0.6 eV (MAPE ∼ 20-25%) with mBJ and HSE06 being the most accurate, with MAE = 0.30 and 0.28 eV (MAPE 12.1% and 11.1%), respectively. Strategies for the development of machine learning and the choice of appropriate exchange-correlation functionals for high-throughput large-scale material screening are discussed in light of these results.

我们将交换相关函数作为计算无机氮化物基本带隙的基准。这些包括传统的泛函,如局部密度近似(LDA)、广义梯度(Perdew-Burke-Ernzerhof)近似(PBE)、简单的Slater交换泛函(SLOC)、专门的LDA/ gga衍生的高局部交换(HLE16)和armiento - k mmel半局部(AK13)泛函、元gga泛函(包括TASK)、改进的Becke-Johnson泛函(mBJ)和Heyd-Scuseria-Ernzerhof (HSE06)混合泛函,以及准粒子GW理论。由于无机氮化物在以前广泛的基准研究中仍然严重不足,目前的子数据库有助于建立未来大规模平衡材料的带隙基准理论汇编。从文献调查中,我们仔细收集了25种二元和11种三元氮化物,重点关注半导体元素周期表,包括离子Li3N,抗碳素体结构的X3N2 (X = Be, Mg, Ca),早期过渡金属和镧系元素(例如,ScN, YN和LaN),超硬th3p4型结构的M3N4 (M = Zr, Hf)化合物,有前途的光催化剂Ta3N5, III-V参考共价氮化物(BN, AlN, GaN)的不同多晶型,以及许多M3N4多晶型(M = C, Si, Si)。和Ge),如尖晶石结构相。与之前广泛的基准测试一致,传统的LDA/PBE在很大程度上非系统地低估了带隙,平均绝对误差(MAE)为100 eV,平均绝对百分比误差(MAPE)约为50%。简单Slater交换功能,SLOC, gga衍生的AK13LDA和HLE16功能比LDA/PBE表现出改善,MAE为0.5-0.6 eV (MAPE ~ 20-25%),其中mBJ和HSE06最准确,MAE分别为0.30和0.28 eV (MAPE分别为12.1%和11.1%)。根据这些结果,讨论了机器学习发展策略和选择合适的交换相关函数进行高通量大规模材料筛选。
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引用次数: 0
Graphene-Oxide-Mediated Photothermal Ring-Closing Metathesis: A Gateway for Organelle Imaging Probes. 氧化石墨烯介导的光热闭合环复合:细胞器成像探针的一个门户。
IF 3.7 2区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY Pub Date : 2026-02-10 DOI: 10.1002/chem.202502947
Preeti, Ram Sewak, Tripti Mishra, Asima Sahu, Pratim Saha, Anirban Mondal, Sudipta Basu

Photothermal effect using mild light irradiation has emerged as an interesting strategy in modern synthetic chemistry due to its rapid reaction with high selectivity and spatiotemporal control over conventional heating. However, applying photothermal conversion to carry out organic reactions efficiently using carbon nanomaterials remained largely uncharted. To address this, herein, we report for the first time, graphene oxide (GO) as the photothermal agent to perform ring-closing metathesis (RCM) under 940 nm NIR LED light, as well as solar simulator and natural sunlight, using Grubbs-II catalyst to rapidly synthesize dihydro-pyrroles in high yield with excellent GO recyclability. Theoretical calculation unveiled that this photothermal RCM efficiency originated from the cumulative synergy between substrate-GO absorption energy, activation barrier, and nonradiative relaxation rate which emerged as the predominant contributor for the overall reaction outcome. The RCM product can be further functionalized through Pd-catalyzed Heck coupling to forge various fluorophores for efficient imaging of endoplasmic reticulum (ER), mitochondria, and Golgi apparatus (GA) in HCT-116 colon cancer cells. This GO-mediated photothermal RCM can open a new direction toward synthesizing complex organic molecules with ease and high yield for biomedical applications.

光热效应由于其反应速度快、选择性高、可控制时间和空间等优点,已成为现代合成化学中一种很有前途的方法。然而,应用光热转换来有效地利用碳纳米材料进行有机反应在很大程度上仍然是未知的。为了解决这一问题,本文首次报道了氧化石墨烯(GO)作为光热剂在940 nm近红外LED光、太阳模拟器和自然阳光下进行闭合环复分解(RCM),使用grubb - ii催化剂快速合成了二氢吡咯,收率高,且GO可回收性好。理论计算表明,这种光热RCM效率源于衬底-氧化石墨烯吸收能、激活势垒和非辐射弛豫率之间的累积协同作用,它们是整个反应结果的主要贡献者。RCM产品可以通过pd催化Heck偶联进一步功能化,形成各种荧光团,用于高效成像HCT-116结肠癌细胞的内质网(ER)、线粒体和高尔基体(GA)。这种氧化石墨烯介导的光热RCM可以为生物医学应用中简单、高效地合成复杂有机分子开辟新的方向。
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引用次数: 0
Cysteine carbon dots/Au3+ system for dual-mode detection of epinephrine and discrimination of different catecholamines with PCA. 半胱氨酸碳点/Au3+系统双模检测肾上腺素及不同儿茶酚胺的PCA鉴别。
IF 3.8 2区 化学 Q1 BIOCHEMICAL RESEARCH METHODS Pub Date : 2026-02-10 DOI: 10.1007/s00216-026-06371-y
Yi-Zhong Liang, Lina Bao, Li Xu, Xu Yu

Accurate and convenient detection of epinephrine (Ep) is critical for diagnosing neurological disorders and monitoring emergency medications. In this study, a ratiometric fluorescent platform was developed for Ep detection by integrating cysteine-functionalized carbon dots with gold ions (Cys-CDs/Au3+). The platform relied on Au3+-mediated oxidation of epinephrine to generate a fluorescence response, which is further enhanced by boric acid. Two detection modes were established: fluorescence assay and smartphone-assisted RGB analysis, demonstrating limits of detection (LOD) of 0.12 μM and 0.85 μM, respectively. The platform enabled accurate quantification of Ep in injections and artificial cerebrospinal fluid (aCSF). Furthermore, principal component analysis (PCA) facilitated discrimination among multiple catecholamines by reducing the dimensionality of fluorescence spectral data. This work provides a versatile platform for Ep detection and catecholamine discrimination.

准确、便捷地检测肾上腺素(Ep)对于诊断神经系统疾病和监测紧急药物至关重要。本研究通过将半胱氨酸功能化碳点与金离子(Cys-CDs/Au3+)结合,建立了一种比例荧光平台,用于Ep检测。该平台依靠Au3+介导的肾上腺素氧化产生荧光响应,硼酸进一步增强了荧光响应。建立了荧光法和智能手机辅助RGB法两种检测模式,检测限(LOD)分别为0.12 μM和0.85 μM。该平台能够准确定量注射剂和人工脑脊液(aCSF)中的Ep。此外,主成分分析(PCA)通过降低荧光光谱数据的维数,促进了多种儿茶酚胺的区分。这项工作为Ep检测和儿茶酚胺鉴别提供了一个通用的平台。
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引用次数: 0
Intriguing the significance of hydrophobic groove by the inhibitory mechanism of mineralocorticoid receptor bound with spironolactone through mutations using long-range molecular dynamics simulations in conjunction with statistical analysis. 利用远程分子动力学模拟与统计分析相结合的方法,探讨矿皮质激素受体通过突变与螺内酯结合的抑制机制对疏水沟的意义。
IF 2.5 4区 化学 Q4 BIOCHEMISTRY & MOLECULAR BIOLOGY Pub Date : 2026-02-10 DOI: 10.1007/s00894-026-06639-1
Seshan Gunalan, Kanagasabai Somarathinam, Sekar Kanagaraj, Jaimohan S M, Gugan Kothandan

Context: Elucidating the role of the hydrophobic groove in mineralocorticoid receptor (MR)-spironolactone interactions is important for structure-based drug design, receptor modulation, and the development of more selective MR antagonists. Despite the clinical importance of spironolactone, the contribution of the hydrophobic groove, particularly residues M807, F829, M845, C849, and M852, remains underexplored. Here, we demonstrate through molecular dynamic simulations that these hydrophobic residues, together with polar residue N770, stabilize the thioacetyl moiety of spironolactone. Binding free energy calculations of the hydrophobic groove, both with the complete binding site and with the groove alone, demonstrate the impact of the groove's hydrophobicity along with the polar residues N770, Q776, and R817. Simulation results, supported by statistical analysis, highlight the groove's structural and energetic significance. Site-directed mutagenesis targeting residues F829, M845, and C849 further clarifies their role in the binding mechanism, offering insights for rational drug design and biomarker development.

Methods: The crystal structure of the MR-spironolactone complex (PDB ID: 3VHU) was retrieved and mutated using COOT. Mutant complexes were constructed and subjected to 1 μs molecular dynamics simulations using GROMACS. Binding free energies were calculated via MM/PBSA. Residue-ligand interactions were analyzed from MD trajectories using LigPlot + and GROMACS tools. Statistical significance of residue contributions was assessed using ANOVA, comparing polar and hydrophobic residue mutations across simulated complexes.

背景:阐明疏水沟槽在矿物皮质激素受体(MR)-螺内酯相互作用中的作用,对于基于结构的药物设计、受体调节和开发更具选择性的MR拮抗剂具有重要意义。尽管螺内酯具有重要的临床意义,但疏水沟的作用,特别是残基M807、F829、M845、C849和M852,仍未得到充分的研究。在这里,我们通过分子动力学模拟证明了这些疏水残基与极性残基N770一起稳定了螺内酯的硫乙酰基部分。疏水沟槽的结合自由能计算,无论是完整结合位点还是单独结合沟槽,都证明了沟槽的疏水性以及极性残基N770、Q776和R817的影响。仿真结果在统计分析的支持下,突出了槽的结构和能量意义。靶向F829、M845和C849残基的定点突变进一步阐明了它们在结合机制中的作用,为合理的药物设计和生物标志物开发提供了见解。方法:采用COOT法对mr -螺内酯配合物(PDB ID: 3VHU)的晶体结构进行检索和突变。构建突变体复合物,并用GROMACS进行1 μs分子动力学模拟。结合自由能通过MM/PBSA计算。使用LigPlot +和GROMACS工具从MD轨迹分析残基-配体相互作用。使用方差分析(ANOVA)评估残基贡献的统计显著性,比较模拟复合物的极性和疏水性残基突变。
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