- 标题
- 摘要
- 关键词
- 实验方案
- 产品
-
Fluorescence and absorption studies of DNA-Pd(II) complex interaction: Synthesis, spectroanalytical investigations and biological activities
摘要： Novel palladium(II) complexes (7a–7e) of substituted quinoline derivatives were synthesized. The complexes were characterized using various techniques such as thermogravimetric analysis (TGA), elemental analysis, conductance measurement, mass, absorption, infra‐red (IR), 1H NMR, 13C NMR and energy‐dispersive X‐ray spectroscopy (EDX). Complexes for herring sperm DNA (HS DNA) binding were explored and absorption titration and the binding constant (Kb) as well as Gibb's free energy were evaluated. Complex 7d exhibited the highest binding constant, therefore the thermodynamic parameters of 7d at different temperatures were evaluated. To support the results of the absorption titration, fluorescence titration, viscosity measurement and molecular docking studies were performed. The fluorescence quenching data as evaluated from Stern–Volmer equation were used to calculate KSV, K f and the number of binding sites. The results of all these studies were in good agreement with the absorption study. DNA electrophoretic mobility was performed to explore the possible application of metal complexes as artificial metallonucleases. The antibacterial activity of the complexes was accessed against different pathogenic bacteria and cytotoxicity was measured using brine shrimp and S. pombe.
关键词： Stern–Volmer equation,absorption titration,thermodynamic parameters,cytotoxicity,fluorescence quenching,artificial metallonuclease
更新于2025-09-23 15:23:52
-
Hypoxia-Irrelevant Photonic Thermodynamic Cancer Nanomedicine
摘要： The hypoxic tumor microenvironment severely lowers the therapeutic efficacy of oxygen-dependent anticancer modalities because tumor hypoxia hinders the generation of toxic reactive oxygen species. Here we report a thermodynamic cancer-therapeutic modality that employs oxygen-irrelevant free radicals generated from thermo-labile initiators for inducing cancer-cell death. Free radical nanogenerator was engineered via direct growth of mesoporous silica layer onto the surface of two-dimensional Nb2C MXene nanosheets towards multifunctionality, where the mesopore provided the reservoirs for initiators and MXene core acted as the photonic-thermal trigger at near infrared-II biowindow (NIR-II). Upon illumination by a 1064 nm NIR-II laser, the photothermal-conversion effect of Nb2C MXene induced the fast release and quick decomposition of the encapsulated initiators (AIPH) to produce free radicals, which promoted cancer-cell apoptosis in both normoxic and hypoxic microenvironment. Systematic in vitro and in vivo evaluations have demonstrated the synergistic-therapeutic outcome of this intriguing photonic nanoplatform-enabled thermodynamic cancer therapy for completely eradicating the tumors without recurrence by NIR-II laser irradiation. This work pioneers the thermodynamic therapy for oxygen-independent cancer treatment by photonic triggering at NIR-II biowindow.
关键词： nanomedicine,thermodynamic therapy,photothermal effect,tumor hypoxia,free radicals
更新于2025-09-23 15:23:52
-
H-complexes in the “4-n-alkoxybenzoic acid: 4-pyridyl 4′-n-alkoxybenzoate” system. IR spectroscopy and quantum chemical calculations
摘要： IR spectra of individual 4-n-dodecyloxybenzoic acid (A) and 4-pyridyl 4'-n-dodecyloxybenzoate (B) compounds as well as IR spectra of 2A:1B and 1A:1B systems were recorded. For the assignment of the experimental vibrational spectra a series of quantum chemical calculations of DFT(B97-D)/6-311++G** level was carried out. Hydrogen-bonded complexes of types A···A, A···B, as well as various trimers that can be formed at different component ratios in system A-B were simulated. The geometric structure of these complexes was optimized and the vibrational frequencies were calculated. The conclusions on the molecular organization of system A-B for different ratios of the components A and B were based on the interpretation of IR spectra and the analysis of calculated thermodynamic characteristics of self-assembly processes. Thus, it is determined that the system A consists of cyclic A···Acycl dimers; in 1A:1B system the H-complexes of A···B type are formed. In the 2A:1B system in the process of self-assembly, instead of the complexes A···A···B and A···B···A of stoichiometric composition, the complexes A···B and A···Acycl are formed in the ratio 2:1. These results are confirmed by the dilatometric method data.
关键词： thermodynamic characteristics,4-pyridyl 4'-n-alkoxybenzoate,DFT,IR spectra,self-assembly,4-n-alkoxybenzoic acid,hydrogen bonded complexes
更新于2025-09-23 15:23:52
-
Molecular interactions and mutational impact upon rhodopsin (G90→D90) for hindering dark adaptation of eye: A comparative structural level outlook for signaling mechanism in night blindness
摘要： For night blindness, a detailed structural exploration of the interactions among G-protein receptor rhodopsin, transducin and arrestin was performed. Rhodopsin is responsible for dim light vision while a point mutation (G90→D90) results in an adverse change in its photo-transduction. The validated 3D models of the three proteins were utilized, and upon mutation and interactions, rhodopsin attained higher stability (evaluated through thermodynamic energy calculations, electrostatic surface potential and solvent accessible area), thereby participating strongly with transducin. Conformational switches in mutated rhodopsin also depicted a firm conformation with few 310 helices accompanied by increased percentage of pure α-helices and sheets. All evaluations were corroborated through paired T-tests. Glu33 (glycosylated unit in the N-terminal zone) of rhodopsin plays a chief role in the overall interaction pattern. Arg69 and Glu33 from wild-type rhodopsin participated in ionic interactions, while the latter set of ionic interaction remained preserved even after mutation. Cys323 (C-terminal residue) and Arg69 formed H-bonds from the wild-type rhodopsin. Cys323 exceptionally supports cellular signaling pattern in the non-mutated situation and for the non-sufferers of night-blindness. Ser297 and Tyr43 from mutated rhodopsin reside in helices and interact with Thr32 of transducin, preserving the steady conformation in activated interacted state, even in the dark. Ser297 lies adjoined to Lys296 (retinal attachment site), which resides in NPXXY motif (an 'activation switch' for signal transduction). Thus, the molecular facet for involvement of photo-transduction, which holds a paramount zone in ophthalmology, was dealt with. This might instigate the future prospect for drug discovery to prevent such mutations.
关键词： Rhodopsin,Thermodynamic Stabilities,Conformational Fluctuations,Mutational Impact
更新于2025-09-23 15:23:52
-
Structural investigation of oxygen stoichiometry during thermocycles in PMN-28PT
摘要： The current research focuses on the role of oxygen partial pressure on structure and phase transitions of (1-x)Pb(Mg1/3Nb2/3)O3-xPbTiO3 with x ? 0.28 (PMN-28PT). The changes in oxygen content have been traced through weight gain/loss during 160 cycles between 250 and 300 (cid:2)C. The structural phase transitions have been investigated by in-situ high temperature powder X-ray diffraction and high temperature Raman spectroscopy. The variations in oxygen content in PMN-28PT result in structural changes and have a signi?cant effect on electrical impedance. It is suggested that bonding between oxygen and Ti and Pb atoms in the perovskite structure of PMN-28PT can be controlled by low oxygen partial pressure heat treatment.
关键词： Crystal structure,Phase transitions,Oxide materials,Thermodynamic properties,Thermal analysis
更新于2025-09-23 15:22:29
-
A thermodynamic potential for barium zirconate titanate solid solutions
摘要： Barium zirconate titanate [Ba(ZrxTi1?x)O3] solid solutions are promising lead-free ferroelectric materials that have received substantial interest. Thermodynamic analysis based on phenomenological Landau–Devonshire theory is a powerful method for theoretical investigation of ferroelectric materials, but cannot be applied to Ba(ZrxTi1?x)O3 because there is no thermodynamic potential. In this paper, a thermodynamic potential for Ba(ZrxTi1?x)O3 (0 ≤ x ≤ 0.3) solid solutions is constructed, and then a thermodynamic analysis carried out. The results accurately reproduce known phase structures and their transition temperatures, with good agreement with experimentally measured polarization, dielectric, and piezoelectric constants. It is found that Ba(ZrxTi1?x)O3 solid solutions at room temperature have three phase boundaries, including a tetragonal–orthorhombic phase boundary at x = 0.013, an orthorhombic–rhombohedral phase boundary at x = 0.0798, and a rhombohedral–paraelectric phase boundary at x = 0.2135. The results also indicate that the chemical composition-induced ferroelectric–paraelectric phase boundary has superior electromechanical properties, suggesting a new way to enhance electromechanical coupling in Ba(ZrxTi1?x)O3 solid solutions.
关键词： Landau–Devonshire theory,electromechanical properties,solid solutions,lead-free ferroelectric materials,Barium zirconate titanate,phase boundaries,thermodynamic potential
更新于2025-09-23 15:21:21
-
Thermodynamic stability, half-metallic and optical nature of graphene-like Mn <sub/>2</sub> Zr <i>Z</i> ( <i>Z</i> = Ge, Si): <i>Ab initio</i> study
摘要： Half-metallic, optical and thermodynamic phase diagrams of two-dimensional Mn2ZrZ (Z = Ge, Si) have been calculated by density functional theory (DFT) framework with full-potential linear augmented plane-wave (FP-LAPW) method. The spin-polarized electronic computations show that these layers have metallic behavior with a spin polarization less than 100%. It is observed that with increasing thickness of the layers, both the thermodynamic and energy stabilities increased, and the graphene-like layers of Mn2ZrGe with a thickness of 7.6955 ?A and Mn2ZrSi with a thickness of 7.551 ?A are completely stable thermodynamically. The optical responses of Mn2ZrZ (Z = Ge, Si) have anisotropy at infrared region versus the optical direction and have high metallic nature in this optical range. The plasmonic frequencies have occurred after the visible edge and the refraction index becomes lower than one after the ultra-violet edge.
关键词： optical property,half-metal,thermodynamic phase diagram,DFT,Graphene-like Mn2ZrZ (Z = Ge, Si)
更新于2025-09-23 15:21:21
-
Mechanism of Liquid-Phase Reductive Thin-Film Deposition under Quasiballistic Electron Incidence
摘要： Highly reducing activity of quasiballistic hot electrons emitted from a nanocrystalline silicon (nc-Si) diode is veri?ed in terms of liquid-phase thin ?lm deposition. Incident electrons reduce positive ions in salt solutions coated on a target substrate, and then result in deposition of thin metal (Cu) and semiconducting (Si, Ge, and SiGe) ?lms. This mechanism is investigated here throughout the process from electron incidence to thin ?lm deposition. Thermodynamic criterion deduced from classical nucleation theory suggests that the output electron energy of the nc-Si emitter is suitable for promoting preferential reduction of target ions in solutions leading to the nuclei formation. In accordance with mass-transport analyses on generated nanoclusters, the most primary factor of thin ?lm growth is the dose of incident electron. The formulated deposition rate rapidly increases and reaches a stationary value within 0.1 s after electron incidence. The theoretical dependency of the thin ?lm thickness on the electron incidence time is consistent with the experimental results. Speci?c features of this scheme as an alternative approach for thin ?lm deposition are discussed in comparison with the conventional dry and wet processes.
关键词： nanocrystalline silicon diode,quasiballistic hot electrons,mass-transport analyses,thermodynamic criterion,liquid-phase thin film deposition
更新于2025-09-23 15:21:21
-
Diarylethene moiety as an enthalpy-entropy switch: photoisomerizable stapled peptides for modulating p53/MDM2 interaction
摘要： Analogs of the known inhibitor (peptide pDI) of the p53/MDM2 protein–protein interaction are reported, which are stapled by linkers bearing a photoisomerizable diarylethene moiety. The corresponding photoisomers possess significantly different affinities to the p53-interacting domain of the human MDM2. Apparent dissociation constants are in the picomolar-to-low nanomolar range for those isomers with diarylethene in the 'open' configuration, but up to eight times larger for the corresponding 'closed' isomers. Spectroscopic, structural, and computational studies showed that the stapling linkers of the peptides contribute to their binding. Calorimetry revealed that the binding of the 'closed' isomers is mostly enthalpy-driven, whereas the 'open' photoforms bind to the protein stronger due to their increased binding entropy. The results suggest that conformational dynamics of the protein-peptide complexes may explain the differences in the thermodynamic profiles of the binding.
关键词： Photoisomerizable stapled peptides,Thermodynamic profiles,p53/MDM2 interaction,Diarylethene,Conformational dynamics
更新于2025-09-23 15:21:01
-
Prediction of solidification cracking by an empirical-statistical analysis for laser cladding of Inconel 718 powder on a non-weldable substrate
摘要： This paper presents an empirical-statistical approach to predict solidification cracking during laser cladding of Inconel 718 powder on A-286 Fe-based superalloy. This approach is based on a linear regression analysis and empirical-statistical correlations between the key processing parameters (laser power, P; powder feed rate, F; and scanning speed, V) and the geometrical attributes of single laser cladding tracks. These correlations were used for the development of a processing map which assesses the effects of the geometrical characteristics on the solidification cracking and the required conditions to obtain crack-free clads. Scanning electron microscopy was used for microstructural characterization. Thermodynamic calculations using the non-equilibrium Scheil solidification model were also employed. The empirical-statistical analysis showed that the processing parameters directly associated with the height and angle of single laser cladding tracks are and, respectively. The processing map revealed that the dilution ratio is the governing macrostructural attribute required to avoid solidification cracking. Indeed, a substrate dilution ratio lower than 25% shifts the cladding composition to an alloy regime, which has lower susceptibility to solidification cracking. The role of this macrostructural feature in reducing the susceptibility of the fusion zone to solidification cracking is thoroughly discussed.
关键词： Thermodynamic simulation,Inconel 718,Processing map,Solidification cracking,Laser cladding,Dilution ratio
更新于2025-09-23 15:21:01