Synthesis and Physico-Chemical Characterizations of Novel Hydrazone Ligands and Their Metal Complexes against Hormone-Dependent and Independent Cancers

This work deals with the synthesis and physicochemical characterizations of a new group of novel retinoidal ligands and their metal complexes. Their in vitro anti-proliferative activities have shown that ligand L1 is effective against human breast cancer BT-20 and MCF-7 cell lines. At the same time, compound L2 exerts its effect on human prostate cancer PC-3 and human breast cancer MDA-MB-231 and MCF-7 cell lines respectively. The retinoid ligands exert their pleiotropic action toward retinoic acid receptors (RARs) than their metal complexes but all compounds exhibit concentration-dependent.

Structures and magnetism of dinuclear Co complexes based on imine derivatives

This study presents the synthesis of three dinuclear cobalt complexes based on three imine derivatives:bis-[4-(2-pyridylmethyleneamino)-phenyl]thioether(L1),bis-[4-(2-pyridylmethyleneamino)-phenyl]ether(L2),and bis-[4-(2-pyridylmethyleneamino)-phenyl]methane(L3).Single-crystal X-ray diffraction analysis reveals that the complexes[Co_(2)(L1)3](ClO_(4))4·2CH_(3)CN(1),[Co_(2)(L2)3](ClO_(4))4·2CH_(3)OH(2),and[Co_(2)(L3)3](ClO_(4))4·2CH_(3)OH(3)all exhibit a dinuclear structure.Magnetic test results show that complex 3 exhibited irreversible SCO behavior induced by loss of solvent at 300 K,with the average Co-N bond length increasing from 0.2139(3)to 0.2153(3)nm.Meanwhile,the desolvated complex 3 exhibited paramagnetic behavior similar to that of complexes 1 and 2.Variable-temperature UV-Vis spectroscopic studies also indicate that complex 3 undergoes a solvent-loss-induced spin-state transition.CCDC:2347354,1(120 K);2347355,2(120 K);2347356,3(120 K);2347357,3(400 K).

3,6-Bis-β-Dicarbonylsubstituted Carbazoles Bearing N-Spacers and Their Eu(III) Complexes as Immunofluorescent Labelling Agents

New reagents for immunofluorescence analysis of carbazole series containing fluorinated β-dicarbonyl fragments and carboxylic substituent groups separated by spacers of different lengths from the light-gathering carbazole scaffold have been developed. The markers in complex with Eu3+ ions possess stability in the aqueous phase, intense and prolonged luminescence (τ 550 - 570 μs) with characteristic emission maxima in the region of 615 nm and excitation wavelengths in the region of 380 - 390 nm, which distinguishes them from most of the analogs used. In the study of marker conjugation with streptavidin, a reagent containing 4 - 5 europium labeling complexes based on spacer-containing carbazole tetraketone was obtained. The marker-doped silicate nanoparticles exhibit intense and long-lived luminescence in the characteristic region.

Catalytic Effect of Transition Metal Complexes of Triaminoguanidine on the Thermolysis of Energetic NC/DEGDN Composite

The transition metal complexes of triaminoguanidine(TAG-M,where M=Cobalt(Co)or Iron(Fe))have been prepared.The catalytic effect of these complexes on the thermolysis of energetic composite based on nitrocellulose and diethylene glycol dinitrate,has been investigated.Extensive characterization of the resulting energetic composites was carried out using scanning electron microscopy(SEM),X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),and differential scanning calorimetry(DSC).Isoconversional kinetic analysis was performed to determine the Arrhenius parameters associated with the thermolysis of the elaborated energetic formulations.It is found that TAG-M complexes have strong catalytic effect on the thermo-kinetic decomposition of NC/DEGDN by decreasing the apparent activation energy and significantly increased the total heat release.The models that govern the decomposition processes are also studied,and it is revealed that different reaction processes are accomplished by introduction metal complexes of triaminoguanidine.Overall,this study serves as a valuable reference for future research focused on the investigation of catalytic combustion features of solid propellants.

Subtraction of liposome signals in cryo-EM structural determination of protein-liposome complexes

Reconstituting membrane proteins in liposomes and determining their structure is a common method for determining membrane protein structures using single-particle cryo-electron microscopy(cryo-EM).However,the strong signal of liposomes under cryo-EM imaging conditions often interferes with the structural determination of the embedded membrane proteins.Here,we propose a liposome signal subtraction method based on single-particle two-dimensional(2D)classification average images,aimed at enhancing the reconstruction resolution of membrane proteins.We analyzed the signal distribution characteristics of liposomes and proteins within the 2D classification average images of protein–liposome complexes in the frequency domain.Based on this analysis,we designed a method to subtract the liposome signals from the original particle images.After the subtraction,the accuracy of single-particle three-dimensional(3D)alignment was improved,enhancing the resolution of the final 3D reconstruction.We demonstrated this method using a PIEZO1-proteoliposome dataset by improving the resolution of the PIEZO1 protein.

Two novel Cu(Ⅰ)complexes based on diimide and bisphosphine ligands:synthesis,crystal structure and spectroscopic properties

Two Cu(Ⅰ)complexes[Cu(Bphen)(dppBz)]ClO_(4)·2CH_(3)OH(1)and[Cu_(2)(Bphen)_(2)(dpppda)]BF_(4)(2){Bphen=4,7-diphenyl-1,10-phenanthroline,dppBz=1,2-Bis(diphenylphosphino)benzene,dpppda=N1,N1,N4,N4-tetrakis[(diphenylphosphino)methyl]-1,4-benzenediamin}were synthesized using a one-pot method.X-ray crystallography was used to elucidate their crystal structures and photophysical properties.A series of characterization tests including elemental analysis,NMR,FT-IR,UV-Vis absorption spectroscopy,fluorescence spectroscopy,thermal gravimetric analysis and terahertz time-domain spectroscopy(THz-TDS)were used to further investigate their properties.The results show that complex 1 structure is mononuclear containing two solvent molecules per unit cell,while complex 2 structure is binuclear containing two metal centers per unit cell.According to photophysical properties and density functional theory(DFT)calculations,their luminescence properties can be attributed to metal-to-ligand charge transfer(MLCT).Both complexes have a unique stability,which is confirmed by thermal gravimetric analysis.

DNA-free genome editing in grapevine using CRISPR/Cas9 ribonucleoprotein complexes followed by protoplast regeneration

CRISPR/Cas9 genome editing technology can overcome many limitations of traditional breeding,offering enormous potential for crop improvement and food production.Although the direct delivery of Cas9-single guide RNA(sgRNA)ribonucleoprotein(RNP)complexes to grapevine(Vitis vinifera)protoplasts has been shown before,the regeneration of edited protoplasts into whole plants has not been reported.Here,we describe an efficient approach to obtain transgene-free edited grapevine plants by the transfection and subsequent regeneration of protoplasts isolated from embryogenic callus.As proof of concept,a single-copy green f luorescent protein reporter gene(GFP)in the grapevine cultivar Thompson Seedless was targeted and knocked out by the direct delivery of RNPs to protoplasts.CRISPR/Cas9 activity,guided by two independent sgRNAs,was confirmed by the loss of GFP f luorescence.The regeneration of GFP−protoplasts into whole plants was monitored throughout development,confirming that the edited grapevine plants were comparable in morphology and growth habit to wild-type controls.We report the first highly efficient protocol for DNA-free genome editing in grapevine by the direct delivery of preassembled Cas9-sgRNA RNP complexes into protoplasts,helping to address the regulatory concerns related to genetically modified plants.This technology could encourage the application of genome editing for the genetic improvement of grapevine and other woody crop plants.

Synergistic Optimization of Buried Interface by Multifunctional Organic-Inorganic Complexes for Highly Efficient Planar Perovskite Solar Cells

For the further improvement of the power conversion efficiency(PCE)and stability of perovskite solar cells(PSCs),the buried interface between the perovskite and the electron transport layer is crucial.However,it is challenging to effectively optimize this interface as it is buried beneath the perovskite film.Herein,we have designed and synthesized a series of multifunctional organic-inorganic(OI)complexes as buried interfacial material to promote electron extraction,as well as the crystal growth of the perovskite.The OI complex with BF4−group not only eliminates oxygen vacancies on the SnO_(2) surface but also balances energy level alignment between SnO_(2) and perovskite,providing a favorable environment for charge carrier extraction.Moreover,OI complex with amine(−NH_(2))functional group can regulate the crystallization of the perovskite film via interaction with PbI2,resulting in highly crystallized perovskite film with large grains and low defect density.Consequently,with rational molecular design,the PSCs with optimal OI complex buried interface layer which contains both BF4−and−NH_(2) functional groups yield a champion device efficiency of 23.69%.More importantly,the resulting unencapsulated device performs excellent ambient stability,maintaining over 90%of its initial efficiency after 2000 h storage,and excellent light stability of 91.5%remaining PCE in the maximum power point tracking measurement(under continuous 100 mW cm−2 light illumination in N2 atmosphere)after 500 h.

Encapsulation of Ru(II) Polypyridine Complexes for Tumor-Targeted Anticancer Therapy

Ru(II)polypyridine complexes have attracted much attention as anticancer agents because of their unique photophysical,photochemical,and biological properties.Despite their promising therapeutic profile,the vast majority of compounds are associated with poor water solubility and poor cancer selectivity.Among the different strategies employed to overcome these pharmacological limitations,many research efforts have been devoted to the physical or covalent encapsulation of the Ru(II)polypyridine complexes into nanoparticles.This article highlights recent developments in the design,preparation,and physicochemical properties of Ru(II)polypyridine complex-loaded nanoparticles for their potential application in anticancer therapy.

Pathfinder-Based Simulation and Optimization of Evacuation of Large Commercial Complexes

Large commercial complexes are large in scale, complex in function, and located in densely populated areas that are prone to casualties due to unfavorable evacuation. To comprehend the safety evacuation of large commercial complex buildings in China, investigate the safety evacuation problems encountered during the evacuation process and the evacuation optimization design strategy, the paper uses Pathfinder to build a simulation model based on literature research and study to simulate the evacuation of personnel in a large commercial complex in Dalian and explore its problems during the evacuation process. The results show that the type of personnel has an effect on the large commercial complex’s evacuation simulation results;the total number of evacuees is non-linearly correlated with the time change curve;some staircases take a long time to evacuate and have a low utilization rate. To improve evacuation efficiency, optimization suggestions for safety exits, evacuation stairs, and evacuation channels are made based on the results.

Modeling time-dependent mechanical behavior of hard rock considering excavation-induced damage and complex 3D stress states

To investigate the long-term stability of deep rocks,a three-dimensional(3D)time-dependent model that accounts for excavation-induced damage and complex stress state is developed.This model comprises three main components:a 3D viscoplastic isotropic constitutive relation that considers excavation damage and complex stress state,a quantitative relationship between critical irreversible deformation and complex stress state,and evolution characteristics of strength parameters.The proposed model is implemented in a self-developed numerical code,i.e.CASRock.The reliability of the model is validated through experiments.It is indicated that the time-dependent fracturing potential index(xTFPI)at a given time during the attenuation creep stage shows a negative correlation with the extent of excavationinduced damage.The time-dependent fracturing process of rock demonstrates a distinct interval effect of the intermediate principal stress,thereby highlighting the 3D stress-dependent characteristic of the model.Finally,the influence of excavation-induced damage and intermediate principal stress on the time-dependent fracturing characteristics of the surrounding rocks around the tunnel is discussed.

Synthesis and Characterisation of Cr(III) and Co(II) Schiff Base Complexes

Co(II) and Cr(III) metal complexes of Schiff bases were synthesized from the condensation reaction between 4-(dimethylamino)benzaldehyde and 4-amino-3-hydroxy-naphthalene-1-sulfonic acid. Their structures were investigated by elemental analysis, molar conductance measurements, infrared spectroscopy, electronic spectroscopy, and 1HNMR spectroscopy. The elemental analysis data suggested a 1:1 [M:L] ratio for the complexes. The molar conductance measurements of the complexes indicate their electrolytic nature in DMSO as a solvent. The absorption bands in the electronic spectra verified an octahedral environment around the metal ions in the complexes.

Saturation Estimation with Complex Electrical Conductivity for Hydrate-Bearing Clayey Sediments:An Experimental Study

Clays have considerable influence on the electrical properties of hydrate-bearing sediments.It is desirable to understand the electrical properties of hydrate-bearing clayey sediments and to build hydrate saturation(S_(h))models for reservoir evaluation and monitoring.The electrical properties of tetrahydrofuran-hydrate-bearing sediments with montmorillonite are characterized by complex conductivity at frequencies from 0.01 Hz to 1 kHz.The effects of clay and Sh on the complex conductivity were analyzed.A decrease and increase in electrical conductance result from the clay-swelling-induced blockage and ion migration in the electrical double layer(EDL),respectively.The quadrature conductivity increases with the clay content up to 10%because of the increased surface site density of counterions in EDL.Both the in-phase conductivity and quadrature conductivity decrease consistently with increasing Sh from 0.50 to 0.90.Three sets of models for Sh evaluation were developed.The model based on the Simandoux equation outperforms Archie’s formula,with a root-mean-square error(E_(RMS))of 1.8%and 3.9%,respectively,highlighting the clay effects on the in-phase conductivity.The fre-quency effect correlations based on in-phase and quadrature conductivities exhibit inferior performance(E_(RMS)=11.6%and 13.2%,re-spectively)due to the challenge of choosing an appropriate pair of frequencies and intrinsic uncertainties from two measurements.The second-order Cole-Cole formula can be used to fit the complex-conductivity spectra.One pair of inverted Cole-Cole parameters,i.e.,characteristic time and chargeability,is employed to predict S_(h) with an E_(RMS) of 5.05%and 9.05%,respectively.

2,4-Dinitrophenyl Ether of Polyvinyl Alcohol and Polymer Bound Anionic SIGMA Complexes

A new electrophilic polymer, 2,4-dinitrophenyl ether of polyvinyl alcohol (PVA-DNP), having a degree of substitution of 0.5 was prepared from polyvinyl alcohol (PVA) and 1-fluro-2,4-dinitrobenzene (DNFB). The PVA-DNP polymer was characterized by NMR, IR, and UV-visible spectroscopy. The reaction of PVA-DNP with sodium methoxide was followed by NMR and UV-visible spectroscopy. Evidence of polymer bound spirocyclic SIGMA complex, C-1 and C-3 polymer bound DNP-methoxy SIGMA complexes and the formation and C-1 methoxy complex of 2,4-dinitroanisole was observed.

A Theoretical Study of Tris-(o-benzoquinonediimine)-First-Row Divalent Transition Metal Complexes

The ligand o-phenylenediamine (opda) and its oxidized form, o-benzoquinonediimine (bqdi), act as a fascinating candidate coordinating toward transition metal ions leading to the photochemical hydrogen production in absence of photosensitizers. Herein, we report the systematic study of the interaction between the oxidized form bqdi ligand, tris-(o-benzoquinonediimine) with divalent first-row transition metal series using DFT calculations. The lowest energy structures, bond length, binding energies, frontier molecular orbital analysis, natural bond orbitals, and global reactivity descriptor were calculated using B3LYP/6-311G(d,P) level of theory. The time dependent-DFT at the CAM-B3LYP/6-311+G(d,p) level of theory was applied to determine the electronic structures and the optical spectra. The theoretical binding trend of the divalent first-row transition metal series is decreasing as follows: Cu >Ti > V > Co > Ni > Fe > Cr > Zn >Mn. Among them, the binding potency of iron (II) by the bqdi ligand was not predominantly sturdy as compared to other first-row divalent transition metal ions. The origin of strong coordination with Fe(II) is attributed to its extra capability to induce covalent coordination of bqdi ligands. The complex exhibited two strong peaks at 370 nm and 452 nm, due to the HOMO-3 to LUMO+1 and HOMO-1 to LUMO transitions, respectively. Natural bond orbital analysis showed that the major interaction happens between the N lone pair electrons of the ligand with an anti-bonding orbital of metal ions, in which Ti showed the highest interaction energy than other metal ions. The present systemic DFT study of bqdi ligands with the first-row transition metals strongly encourages the future establishment of photochemical hydrogen production in absence of photosensitizers.

Probing electronic structures of transition metal complexes using electron paramagnetic resonance spectroscopy

Electron paramagnetic resonance(EPR)or electron spin resonance(ESR)has been widely employed to characterize transition metal complexes.However,because of the high degree of complexity of transition metal EPR spectra,how to extract the underlying electronicstructure information inevitably poses a major challenge to beginners,in particular for systems with S>1/2.In fact,the physical principles of transition metal EPR have long been well-established and since 1970s a series of dedicated voluminous monographs have been published already.Not surprisingly,they are not appropriate stating points for novices to grasp a panorama of the profound theory prior to scrutinizing in-depth references.The present review aims to fill this gap to provide a perspective of transition metal EPR and unveil some peculiar subtleties thereof on the basis of our recent work.

A novel complex-high-order graph convolutional network paradigm:ChyGCN

In recent years,there has been a growing interest in graph convolutional networks(GCN).However,existing GCN and variants are predominantly based on simple graph or hypergraph structures,which restricts their ability to handle complex data correlations in practical applications.These limitations stem from the difficulty in establishing multiple hierarchies and acquiring adaptive weights for each of them.To address this issue,this paper introduces the latest concept of complex hypergraphs and constructs a versatile high-order multi-level data correlation model.This model is realized by establishing a three-tier structure of complexes-hypergraphs-vertices.Specifically,we start by establishing hyperedge clusters on a foundational network,utilizing a second-order hypergraph structure to depict potential correlations.For this second-order structure,truncation methods are used to assess and generate a three-layer composite structure.During the construction of the composite structure,an adaptive learning strategy is implemented to merge correlations across different levels.We evaluate this model on several popular datasets and compare it with recent state-of-the-art methods.The comprehensive assessment results demonstrate that the proposed model surpasses the existing methods,particularly in modeling implicit data correlations(the classification accuracy of nodes on five public datasets Cora,Citeseer,Pubmed,Github Web ML,and Facebook are 86.1±0.33,79.2±0.35,83.1±0.46,83.8±0.23,and 80.1±0.37,respectively).This indicates that our approach possesses advantages in handling datasets with implicit multi-level structures.

Discovery of nano organo-clay complex pore-fractures in shale and its scientific significance:A case study of Cretaceous Qingshankou Formation shale,Songliao Basin,NE China

A new pore type,nano-scale organo-clay complex pore-fracture was first discovered based on argon ion polishing-field emission scanning electron microscopy,energy dispersive spectroscopy and three-dimensional reconstruction by focused ion-scanning electron in combination with analysis of TOC,R_(o)values,X-ray diffraction etc.in the Cretaceous Qingshankou Formation shale in the Songliao Basin,NE China.Such pore characteristics and evolution study show that:(1)Organo-clay complex pore-fractures are developed in the shale matrix and in the form of spongy and reticular aggregates.Different from circular or oval organic pores discovered in other shales,a single organo-clay complex pore is square,rectangular,rhombic or slaty,with the pore diameter generally less than 200 nm.(2)With thermal maturity increasing,the elements(C,Si,Al,O,Mg,Fe,etc.)in organo-clay complex change accordingly,showing that organic matter shrinkage due to hydrocarbon generation and clay mineral transformation both affect organo-clay complex pore-fracture formation.(3)At high thermal maturity,the Qingshankou Formation shale is dominated by nano-scale organo-clay complex pore-fractures with the percentage reaching more than 70%of total pore space.The spatial connectivity of organo-clay complex pore-fractures is significantly better than that of organic pores.It is suggested that organo-complex pore-fractures are the main pore space of laminar shale at high thermal maturity and are the main oil and gas accumulation space in the core area of continental shale oil.The discovery of nano-scale organo-clay complex pore-fractures changes the conventional view that inorganic pores are the main reservoir space and has scientific significance for the study of shale oil formation and accumulation laws.

Complexity Considerations in the Heisenberg Uncertainty Principle

This work introduces a modification to the Heisenberg Uncertainty Principle (HUP) by incorporating quantum complexity, including potential nonlinear effects. Our theoretical framework extends the traditional HUP to consider the complexity of quantum states, offering a more nuanced understanding of measurement precision. By adding a complexity term to the uncertainty relation, we explore nonlinear modifications such as polynomial, exponential, and logarithmic functions. Rigorous mathematical derivations demonstrate the consistency of the modified principle with classical quantum mechanics and quantum information theory. We investigate the implications of this modified HUP for various aspects of quantum mechanics, including quantum metrology, quantum algorithms, quantum error correction, and quantum chaos. Additionally, we propose experimental protocols to test the validity of the modified HUP, evaluating their feasibility with current and near-term quantum technologies. This work highlights the importance of quantum complexity in quantum mechanics and provides a refined perspective on the interplay between complexity, entanglement, and uncertainty in quantum systems. The modified HUP has the potential to stimulate interdisciplinary research at the intersection of quantum physics, information theory, and complexity theory, with significant implications for the development of quantum technologies and the understanding of the quantum-to-classical transition.

Three-dimensional magnetic reconnection in complex multiple X-point configurations in an ancient solar-lunar terrestrial system

Magnetic reconnection processes in three-dimensional(3D)complex field configurations have been investigated in different magneto-plasma systems in space,laboratory,and astrophysical systems.Two-dimensional(2D)features of magnetic reconnection have been well developed and applied successfully to systems with symmetrical property,such as toroidal fusion plasmas and laboratory experiments with an axial symmetry.But in asymmetric systems,the 3D features are inevitably different from those in the 2D case.Magnetic reconnection structures in multiple celestial body systems,particularly star-planet-Moon systems,bring fresh insights to the understanding of the 3D geometry of reconnection.Thus,we take magnetic reconnection in an ancient solar-lunar terrestrial magneto-plasma system as an example by using its crucial parameters approximately estimated already and also some specific applications in pathways for energy and matter transports among Earth,ancient Moon,and the interplanetary magnetic field(IMF).Then,magnetic reconnection of the ancient lunar-terrestrial magnetospheres with the IMF is investigated numerically in this work.In a 3D simulation for the Earth-Moon-IMF system,topological features of complex magnetic reconnection configurations and dynamical characteristics of magnetic reconnection processes are studied.It is found that a coupled lunar-terrestrial magnetosphere is formed,and under various IMF orientations,multiple X-points emerge at distinct locations,showing three typical magnetic reconnection structures in such a geometry,i.e.,the X-line,the triple current sheets,and the A-B null pairs.The results can conduce to further understanding of reconnection physics in 3D for plasmas in complex magnetic configurations,and also a possible mechanism for energy and matters transport in evolutions of similar astrophysical systems.