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.

CHARACTERIZATION OF MOLECULAR MASS OF SIX WATER-SOLUBLE POLYSACCHARIDE -PROTEIN COMPLEXES FROM GANODERMA TSUGAE MYCELIUM

Six water-soluble polysaccharide-protein complexes coded as GM1, GM2, GM3, GM4, GM5 and GM6 wereisolated from the mycelium of Ganoderma tsugae by extracting with 0.2 mol/L phosphate buffer solution at 25, 40 and80℃, water at 120℃, 0.5 mol/L aqueous NaOH solution at 25 and 65℃, consecutively. Their chemical components wereanalyzed by using IR, GC, HPLC and ^(13)C-NMR, and some new results were obtained. The four samples GM1, GM2, GM3and GM4 are heteropolysaccharide-prote in complexes, in which, α- (1→3) linked D-glucose is the major monosaccharidewhile galactose, mannose and ribose are the secondary ones. GM5 and GM6 are β-(1→3)-D-glucan-protein complexes. Theprotein content increased from 32% to 69% with the progress of isolation. Weight-average molecu1ar mass M_w and theintrinsic viscosity [η] of the GM samples in 0.5 mol/L aqueous NaCl solution at 25℃ were measured systematically by laserlight scartering (LLS), size exclusion chromatography (SEC) combined with LLS, and viscometry. The M_w of GM1 to GM6are 35.5, 46.8, 58.9, 41.6, 3.3 and 22.0×10~4, respectively. The conformation and molecular mass of the two fractions of sample GM5 were characterized satisfactorily by SEC-LLS without further fractionation.

SCIENTIFIC PRINCIPLES FOR MODIFICATION OF WATER-SOLUBLE POLYMERS. FORMATION OF MACROMOLECULAR COMPLEXES

The study of nanosecond dynamics of macromolecules with the lumines-cent methods make it possible to investigate the formation and functioning of polymericcomplexes, polymeric conjugates and macromolecular metal complexes, which are widelyused for solving many practical tasks. The nanosecond dynamics of macromolecules are ahighly sensitive indicator of interpolymer complexes (IPC) formation. It enables us to solvethe problems of studying IPC formation and stability and to investigate the interpolymerreactions of exchange and substitution. The investigation of changes in the rotational mo-bility of globular protein molecules as a whole makes it possible to determine the complexcomposition and its stability, and to control the course of polymer-protein conjugate forma-tion reaction. The nanosecond dynamics of polymers interacting with surfacants' ions (S)are the sensitive indicator of the S-polymer complex formation. A method for determin-ing the equilibrium constants of the S-polymer complex formation was developed on thebasis of the study of polymer chains mobility. It is established that nanosecond dynamicsinfluences the course of chemical reactions in polymer chains. Moreover, the marked effectof the nanosecond dynamics is also revealed in the study of photophysical processes (theformation of excimers and energy migration of electron excitation) in polymers with pho-toactive groups. It was found that the efficiency of both processes increases with increasingthe mobility of side chains, the carriers of photoactive groups.

Preparation and characterization of complexes of RE^(3+) with furfural modified water-soluble chitosan

Degraded chitosan, with highly water-solubility, was obtained by the oxidation of chitosan with H2O2, and then reacted with furrural. The final product coordinated with the rare earth ions （RE^3＋ = Sm^3＋, Eu^3＋）, which led to the formation of the complexes. The prepared complexes were characterized with Infrared Spectroscopy （IR）, Ultra Violet （UV）, fluorescence, X-Ray Diffraction （XRD）, and Thermogravimetric-Differential Scanning Calorimetry （TG-DSC） measurements.

Flocculating Properties of Water-Soluble Polymer-Colloid Complexes of Aluminoxane Particles with Weakly Charged Cationic Polyelectrolytes

The flocculating properties of polymer-colloid complexes (PCCs) formed via noncovalent interactions of positively charged aluminoxane particles (APs) with macromolecules of weakly charged cationic acrylamide copolymers from the Praestol and Organopol series have been studied. The PCCs that spontaneously formed during mixing of sols of a high-basicity aluminum polyhydroxochloride (APHC) with aqueous solutions of the copolymers exhibit high flocculating ability under the conditions of gravity sedimentation of the model kaolin dispersion with Сd = 8 g/dm3, and their efficiency exceeds both that of the copolymers and the earlier obtained PCCs with nonionogenic polyacrylamide (PAA). In contrast to weakly charged polycationites, the fully charged KF-99 polyelectrolyte does not form PCCs and the products of its mixing with APHC do not reveal an increased flocculating effect.

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.

Structure, properties and application to water-soluble coatings of complex antimicrobial agent Ag-carboxymethyl chitosan-thiabendazole

The structure, properties and application to water-soluble coatings of a new complex antimicrobial agent Ag-carboxylmethyl citosan-thiabendazole （Ag-CMCTS-TBZ） prepared from different materiel ratios were reported. The silver ions were preferably coordinated with the free-NH2 groups and the -OH groups of secondary alcohol and carboxyl in CMCTS. TBZ preferably bonded to carboxyl group in CMCTS by electrostatic force and hydrogen bonding. Increase in silver ions content in the complex agent improved to some limited extent the antibacterial activity, but enhanced coloring and cost of the complex agent. Increase in TBZ content resulted in increase of antifungal activity, but decrease of water solubility of the complex agent. The antimicrobial MICs of the complex agent to Esherichia coil, Staphylococcus aureus, Candida albicans, Aspergillus niger, Mucor sp. were 20 -80, 15 -60, 20 - 55, 40 - 250, and 400 - 1700 mg/kg, respectively. Addition of 0.1% of this complex agent to acrylic emulsion paint made the paint without substantial change in color, luster, viscosity, odor or pH value, but with an excellent and chronically persisting broad-spectra antimicrobial activity.

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.

Hydroaminomethylation of 1-Dodecene Catalyzed by Water-soluble Rhodium Complex

The hydroaminomethylation of 1-dodecene catalyzed by water soluble rhodium complex RhCl(CO)(TPPTS)2 in the presence of surfactant CTAB was investigated. High reactivity and selectivity for tertiary amine were achieved under relatively mild conditions.

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.