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.

Characteristics and Comparative Study of Chlorophyll-protein Complexes from Siphonous Green Algae

By mild PAGE method, 11, 11, 7 and 9 chlorophyll_protein complexes were isolated from two species of siphonous green algae (Codium fragile (Sur.) Hariot and Bryopsis corticulans Setch.), green alga (Ulothrix flacca (Dillw.) Thur.), and spinach (Spinacia oleracea Mill.), respectively. Apparent molecular weights, Chl a/b ratios, distribution of chlorophyll, absorption spectra, low temperature fluorescence spectra of these complexes were determined, and compared with one another. PSⅠ complexes of two siphonous green algae are larger in apparent molecular weight because of the attachment of relative highly aggregated LHCⅠ. Four isolated light_harvesting complexes of PSⅡ are all siphonaxanthin_Chl a/b_protein complexes, and they are not monomers and oligomers like those in higher plants. Especially, the absence of 730 nm fluorescence in PSⅠ complexes indicates a distinct structure and energy transfer pattern.

Preparation and Physicochemical Characterization of Quercetin-HP-β-CD Inclusion Complexes

Aim To prepare and characterize the QURC-HP-β-CD inclusion complexes and investigate the thermodynamic parameters of the process. Methods QURC-HP-β-CD inclusion complexes were prepared by the grinding method. The equilibrium inclusion constants and thermodynamic parameters were determinated by phase solubility analysis. Dissolution tests were performed to study the dissolution rate of inclusion complexes. The formation of inclusion complexes was confirmed by differential scanning calorimetry （ DSC）, infrared spectroscopy （IR） , powder X-ray diffractometry （PXRD） and scanning electron microscopy （SEM）. Results The aqueous solubility of quercetin was greatly increased （ about 37 folds） by inclusion technique, and the initial dissolution rate was markedly improved （10 folds） in the first 5 min. The results of DSC and SEM photographs showed that quercetin crystal disappeared in inclusion complexes, which indicated the formation of new phase. FT-IR spectra showed that the carbonyl quercetin crystal grinding method. absorption band of quercetin was shifted. PXRD showed that the diffraction peak of disappeared. Conclusion QURC-HP-β-CD inclusion complexes are produced by the The solubility of quercetin is improved by the inclusion technique.

Electronic Structures, DNA-binding, SAR, and Spectral Properties of Ruthenium Methylimidazole Complexes [Ru（MeIm）4L]^2＋（L=iip,tip,2ntz）

Theoretical studies on the electronic and geometric structures, the trend in DNA-binding affinities as well as the the structure-activity relationship （SAR） of a series of water-soluble Ru（II） methylimidazole complexes, i.e. [Ru（Mehn）4iip]^2＋ （1） （MeIm=l-methylimidazole, iip=2-（1H-imidazo-4-group）-lH-imidazo[n,5-f][1,10]phenanthroline）, [Ru（MeIm）4tip]^2＋ （2） （tip=2-（thiophene-2-group）-lH-imidazo[4,5-f] [i,10]phenanthroline）, and [Ru（Melm）42ntz]^2＋ （3） （2ntz=2-（2-nitro-l,3-thiazole-5-group）-lH-imidazo[4,5-f][1,10]phenanthroline）, were car- ried out using the density functional theory （DFT）. The electronic structures of these Ru（II） complexes were analyzed on the basis of their geometric structures optimized in aqueous solution, and the trend in the DNA-binding constants （Kb） was reasonably explained. The results show that the replacement of imidazole ligand by thiophene ligand can effectively improve the DNA-binding affinity of the complex. Meanwhile, it was found that introduc- ing the stronger electronegative N atom and NO2 group on terminal loop of intercalative ligand can obviously reduce the complex＇s LUMO and HOMO-LUMO gap energies. Based on these findings, the designed complex [Ru（MeIm）42ntz]^2＋ （3） can be expected to have the greatest Kb value in complexes 1-3. In addition, the structure-activity relationships and antitumor mechanism were also carefully discussed, and the antimetastatic activity of the designed complex 3 was predicted. Finally, the electronic absorption spectra of this series of complexes in aqueous solution were calculated, simulated and assigned using DFT/TDDFT methods as well as conductor-like polarizable continuum model （CPCM）, and were in good agreement with the experimental results.

Resonance Raman Spectra of Purified PS Ⅱ Core Antenna Complexes CP43 and CP47

PSⅡ core antenna complexes, CP43 and CP47, were purified from spinach (Spinacia oleracea L.) by DEAE Fractogel TSK 650S anion exchange chromatography. Their normal temperature (298 K) resonance Raman spectra were measured. The results suggest that all β carotenoids bound to CP43 and CP47 are in all trans configuration and likely in twisted conformations.

Changes of Chorophyll protein Complexes and Photosynthetic Activities of Chloroplasts from Lotus (Nelumbo nucifera) Seeds Germinating in Light

The changes of chlorophyll_protein complexes and photosynthetic activities of chloroplast isolated from lotus ( Nelumbo nucifera Gaertn.) seeds germinating under illumination were studied. SDS PAGE analysis of chlorophyll_protein complexes showed that there was only the light harvesting chlorophyll a/b protein complex from PSⅡ (LHCⅡ) precursor in chloroplast from lotus seeds germinated for 2 to 6 days, while LHC Ⅱ 1, and the chlorophyll_protein complex of PSⅠ (CPⅠ) appeared on the 8th day of germination and PSⅡ reaction center complex appeared later. Studies on the polypeptides composition of the chloroplast revealed the following results: 1) Small amount of the 27 kD polypeptide was synthesized in invisible light; 2) The 30 kD polypeptide existed previously in the plumules of the dry seeds; 3) The amount of the 30 kD polypeptide was more than any other polypeptides before germination and decreased gradually throughout germination, while the 27 kD polypeptide changed in the opposite way; 4) In the process of germination, measurement of the electron transport rate and the fluorescence induction kinetics at room temperature showed that PSⅡ activities and efficiency of primary light energy transformation were only experimentally measurable after 7 days of germination and gradually increased afterwards. At the same time, the chl a/b ratio rose from the lower value to normal; 5) The changes of chloroplast membrane components and its functions are concomitant in concert with that of the ultrastructure of chloroplast membranes during germination, as shown in our earlier work . The results have proved again that a different developmental pathway of chloroplast is likely to exist in the lotus plumules, which might provide an important clue for N. nucifera in having an unique position in the phylogeny of the angiosperm.

The Possible Mechanism of Photoinhibition of Purified PSⅠ Complexes

The protecting effect of histidine on the photodamage of pigments and proteins of the isolated PSⅠ particles from the chloroplast of Spinacia oleracea L. during the strong illumination (2 300 μmol·m -2 ·s -1 ) was studied by spectroscopy and SDS_PAGE. The absorbance of PSⅠ particles decreased during the strong illumination treatment, but the decrease would be slowed down in the presence of externally added histidine after 30 min illumination. The decrease of CD (circular dichroism) signal intensities of PSⅠ particles also was slowed down by the added histidine after about 10 min illumination. The retarded protecting effect of the added histidine on the photobleaching of pigments of PSⅠ complexes implied that the mechanisms of photoinhibition of isolated PSⅠ complexes are different from early stage to later stage during the strong illumination treatment. In addition, the added histidine suppressed the decrease of 77 K fluorescence yield of PSⅠ particles during the illumination. SDS_PAGE showed that the added histidine not only protected the reaction center proteins of PSⅠ particles, but also protected other subunits of PSⅠ particles from degradation.

Investigation on Non-covalent Complexes of Cyclodextrins with Li＋ in Gas Phase by Mass Spectrometry

To investigate the non-covalent interaction between cyclodextrins （CD） and lithium ion, a stoichiometry of α-CD, β-CD, heptakis（2,6-di-O-methyl）-β-CD （DM-β-CD）, or heptakis（2,3,6-tri-O-methyl）-β-CD （TM-β-CD） was mixed with lithium salt, respectively, and then incubated at room temperature for 10 min to reach the equilibrium. In posi- tive mode, the electrospray ionization mass spectrometry （ESI-MS） results demonstrated that lithium ion can conjugate to α-, β-, DM-β- or TM-β-CD and form 1：1 stoichiometric non-covalent complexes. The binding of the complexes was further confirmed by collision- induced dissociation. The dissociation constants Kdl of four complexes （Li＋α-CD, Li＋β- CD, Li＋DM-β-CD, and Li＋TM-β-CD） were determined by mass spectrometric titration. The results showed Kdl were 18.7, 26.7, 33.6, 30.5 μmol/L for the complexes of Li＋ with α-CD, β-CD, DM-β-CD, and TM-β-CD, respectively. Kdl for the Li＋ complexes of/3-CD is smaller than that of DM-β-CD due to its steric effect of the partial substituted -CH3. The Kdl for the Li＋ complexes of DM-β-CD is nearly in agreement with that of TM-β-CD, indicating Li＋ is more likely to locate in the small rim of DM-β-CD＇s hydrophobic cavity. The DFT results showed through electrostatic interaction, one Li＋ can strongly conjugate to four neighboring oxygen atoms. For the （α-CD＋Li）＋ complex, one Li＋ may also situate the small rim of α-CD＇s hydrophobic cavity to form a non-specific host-guest complex.

Determination of Stability Constants of Cadmium-Glycine Complexes by a Unified Treatment for Potentiometric and Polarographic Data

The cadmium（Ⅱ）-glycine system was studied by the two experimental techniques, ion sensitive electrode （ISE） and differential pulse polarography （DPP）, and the experimental data obtained were used by a unified mathematical treatment to calculate the complex stability constants. The combination of the two techniques is of many advantages as ISE can be performed at low [LT]：[MT] ratios and significantly higher [MT], whereas DPP could be used well at large [LT]：[MT] ratios and much smaller [MT]. This makes it possible to study a metal-ligand system in a relatively broader range of experimental conditions that, in turn, provides more information about the metakligand system of interest. Applying the unified mathematical treatment to the cadmium-glycine system, two new complexes MHL and ML2（OH） as well as three complexes ML, ML2 and ML3, reported in literatures, could be modeled and all their stability constants have been refined.

Structural Analysis of Peptides of PSⅡ Light-harvesting Complexes in Siphonous Green Algae, Codium fragile

Peptide composition and arrangement of 4 major light-harvesting complexes LHCP 1-3 and LHCP 3′ isolated from siphonous green algae (Codium fragile (Sur.) Hariot.) were investigated. LHCP 1 showed five main peptides, 34.4, 31.5, 29.5, 28.2 and 26.5 kD in SDS-PAGE, the 34.4 and 31.5 kD peptides were never found in higher plants. LHCP 3 contained the other four kinds of LHCP 1 peptides except 34.4 kD, while LHCP 3′ consisted of only 28.2 and 26.5 kD peptides. We found that 34.4, 28.2 and 26.5 kD peptides were easy to decompose from LHCP 1 when subjected to SDS-PAGE without pretreatment. They might be located at the exterior of LHCP 1, while the 31.5 and 29.5 kD peptides were at the central part. The 28.2 and 26.5 kD peptides often occurred in CPa, the center complex of PSⅡ. They are possibly the LHCⅡ peptides tightly associated with CCⅡ. According to the results described above, a peptide map of LHCP 1 was sketched.

Spectral Properties and Characterization of the Modified PSⅡ Core Complexes

用组氨酸的特异性修饰剂 (DEPC)对PSⅡ核心复合物进行了化学修饰 ,并对其光谱性质进行了研究。研究结果表明 :修饰后的PSⅡ核心复合物的吸收光谱在红区发生了很大变化 ,随修饰时间的增加 ,6 80nm处的吸收逐渐下降。修饰后的PSⅡ核心复合物的荧光光谱在最初的 1min内出现荧光上升现象 ,然后逐渐下降 ,峰位蓝移。这些研究结果表明 ,组氨酸残基的修饰导致了原初电子供体P6 80结构的破坏 ,并对其功能产生了影响。

Theoretical Studies on Structures and Spectroscopic Properties of Highly Efficient Phosphorescent [Ru（terpy）（phen）X]＋ Complexes

The ground and the lowest-lying triplet excited state geometries, electronic structures, and spectroscopic properties of three mixed-ligand Ru（II） complexes [Ru（terpy）（phen）X]＋ （terpy=2,2＇,6＇,2″-terpyridine, phen=l,10-phenanthroline, and X=-C-=CH （1）, X=Cl （2）, X-CN （3）） were investigated theoretically using the density functional theory method. The ground and excited state geometries have been fully optimized at the B3LYP/LanL2DZ and UB3LYP/LanL2DZ levels, respectively. The absorption and emission spectra of the com- plexes in CHaCN solutions were calculated by time-dependent density functional theory with the PCM solvent model. The calculated bond lengths of Ru-C, Ru-N, and Ru-Cl in the ground state agree well with the corresponding experimental results. The highest occupied molecular orbital were dominantly localized on the Ru atom and monodentate X ligand for 1 and 2, Ru atom and terpy ligand for a, while the lowest unoccupied molecular orbital were π＊（terpy） type orbital. Therefore, the lowest-energy absorptions of 1 and 2 at 688 and 631 nln are attributed to a dyz （Ru）＋Tr/p（X）--π＊ （terpy） transition with MLCT/XLCT （metal-to-ligand charge transfer/X ligand to terpy ligand charge transfer） character, whereas that of 3 at 529 nm is related to a dyz （Ru）＋π（terpy）-π＊ （terpy） transition with MLCT and ILCT transition character. The calculated phosphorescence of three complexes at 1011 nm （1）, 913 nm （2）, and 838 nm （3） have similar transition properties to that of the lowest-lying absorption. It is shown that the lowest lying absorptions and emissions transition character of these Ru（II） complexes can be tuned by changing the electron-withdrawing ability of the monodentate ligand.

Purification and Spectral Characteristics of Cytochrome b-559 from Oxygen-evolving Photosystem Ⅱ Core Complexes of Spinach and Rice

Cytochrome b_559 in photosystem Ⅱ reaction center was purified from spinach ( Spinacia oleracea L.) and rice ( Oryza sativa L.) by a rapid and simple procedure. Their low temperature fluorescence emission and excitation spectra, ultraviolet fluorescence spectra and absolute absorption spectra were presented. The author's purification methods, which enhanced the yield of pure protein and shorted the time for isolation, have several advantages: 1. use of oxygen_evolving PSⅡ core complexes as the starting material in order to avoid disturbing from other cytochromes; 2. isocratic elution of cytochrome b_559 from a DEAE_Sephacel column for eliminating the impurity and yielding the protein in pure state; 3. a simple column procedure for removal of excess Triton X_100. Purified cytochromes b_559 from these species have similar optical spectra and mobility during gel electrophoresis under native conditions. From the results of novel electrophoresis (Tricine_SDS_PAGE), cytochrome b_559 from both spinach and rice reveal two polypeptide bands (apparent molecular weight 9 kD and 4 kD, respectively). By measuring of 77 K fluorescence spectra, it was shown that for the purified cytochrome b_559 there were two excitation peaks at 439 nm and 413 nm, and two emission peaks at 563 nm and 668 nm. This is the first indication that Cyt b_559 is able to emit fluorescence and also transfer excited electrons to chlorophyll. By the use of ultraviolet fluorescence spectra, it was demonstrated for the first time that the location of Trp residue could be in the hydrophobic transmembrane region of cytochrome b_559.

Long-Lived Coherence Originating from Electronic-Vibrational Couplings in Light-Harvesting Complexes

We theoretically investigate the evolutions of two-dimensional, third-order, nonlinear photon echo rephasing spectra with population time by using an exact numerical path integral method. It is shown that for the same system, the coherence time and relaxation time of excitonic states are short, however, if the couplings of electronic and intra-pigment vibrational modes are considered, the coherence time and relaxation time of this vibronic states are greatly extended. It means that the couplings between electronic and vibrational modes play important roles in keeping long-lived coherence in light-harvesting complexes. Particularly, by using the method we can fix the transition path of the energy transfer in bio-molecular systems.

Inhibition of cysteine protease papain by metal ions and polysulfide complexes,especially mercuric ion

Aim Cysteine proteases are closely associated with many human and non-human pathological processes and are potential targets for metal ions especially Hg^2＋ and the related species. In the present work, on the basis of to the general study on the effects of some metal ions on the activity of papain, a well-known representative of cysteine protease family, the inhibitory effects of Hg^2＋ and polysulfide complexes were studied. Results All the metal ions tested （Hg^2＋, Cu^2＋, Ag^＋, Au^3＋, Zn^2＋, Cd^2＋, Fe^3＋, Mn^2＋, Pb^2＋, Yb^3＋） inhibit the activity of papain anda good correlation between the inhibitory potency and softness-and-hardness was observed. Among the metals, Hg^2＋ was shown to be a potent inhibitor of papain with a Kiof 2 × 10^-7 mol·L^-1 among. Excessive amounts of glutathione and cysteine could reactivate the enzyme activity of papain deactivated by Hg^2＋. These evidences supported that Hg^2＋ might bind to the catalytic site of papain. Interestingly, Hg （Ⅱ） polysulfide complexes were for the first time found to inhibit papain with a Ki of 7 × 10^-6 mol·L^-1, whose potency is close to a well known mercury compound, thimerosal （Ki=2.7 × 10^-6）. In addition, Hg （Ⅱ） polysulfide complexes exhibit good permeability （ 1.9 × 10-5 cm· s^-1） to caco-2 monolayer. Conclusion These results suggested that mercury polysulfide complexes might be potential bioactive species in the interaction with cysteine proteases and other- SH-content proteins, providing a new clue to understand the mechanism of the toxicological and pharmacological actions of cinnabar and other insoluble mercury compounds.

Geochemistry,Nd Isotopic Characteristics of Metamorphic Complexes in Northern Hebei:Implications for Crustal Accretion

The middle segment of the northern margin of the North China Craton （NCC） consists mainly of metamorphosed Archean Dantazi Complex, Paleoproterozoic Hongqiyingzi Complex and unmetamorphosed gabbro-anorthosite-meta-alkaline granite, as well as metamorphosed Late Paleozoic mafic to granitoid rocks in the Damiao-Changshaoying area. The -2.49 Ga Dantazi Complex comprises dioritic-trondhjemitic-granodoritic-monzogranitic gneisses metamorphosed in amphibolite to granulite facies. Petrochemical characteristics reveal that most of the rocks belong to a medium- to high-potassium calc-alkaline series, and display Mg^# less than 40, right-declined REE patterns with no to obviously positive Eu anomalies, evidently negative Th, Nb, Ta and Ti anomalies in primitive mantlenormalized spider diagrams, εNd（t）=＋0.65 to -0.03, and depleted mantle model ages TDM=2.78-2.71 Ga. Study in petrogenesis indicates that the rocks were formed from magmatic mixing between mafic magma from the depleted mantle and granitoid magma from partial melting of recycled crustal mafic rocks in a continental margin setting. The 2.44-2.41 Ga Hongqiyingzi Complex is dominated by metamorphic mafic-granodioritic-monzogranitic gneisses, displaying similar petrochemical features to the Dantazi Complex, namely medium to high potassium calc-alkaline series, and the mafic rocks show evident change in LILEs, negative Th, Nb, Ta, Zr anomalies and positive P anomalies. And the other granitiod samples also exhibit negative Th, Nb, Ta, P and Ti anomalies. All rocks in the Hongqiyingzi Complex show right-declined REE patterns without Eu anomaly. The metamorphic mafic rocks with εNd（t） = -1.64 may not be an identical magmatic evolution series with granitoids that have εNd（t） values of ＋3.19 to ＋1.94 and TDM ages of 2.55-2.52 Ga. These granitic rocks originated from hybrid between mafic magma from the depleted mantle and magma from partial melting of juvenile crustal mafic rocks in an island arc setting. All the -311 Ma Late Paleozoic metamorphic mafic rocks and related granitic rocks show a medium-potassium calc-alkaline magmatic evolution series, characterized by high Mg^#, obviously negative Th, Nb, Ta anomalies and positive Sr anomalies, from no to strongly negative Ti anomalies and flat REE patterns with εNd（t） = ＋8.42, implying that the maflc magma was derived from the depleted mantle. However the other granitic rocks are characterized by right-declined REE patterns with no to evidently positive Eu anomalies, significantly low εNd（t） = -13.37 to -14.04, and TDM=1.97-1.96 Ga, revealing that the granitoid magma was derived from hybrid between maflc magma that came from -311 Ma depleted mantle and granitoid magma from Archean to Early Paleoproterozoic ancient crustal recycling. The geochemistry and Nd isotopic characteristics as well as the above geological and geochronological results indicate that the middle segment of the northern margin of the NCC mainly experienced four crustal growth episodes from Archean to Late Paleozoic, which were dominated by three continental marginal arc accretions （-2.49, -2.44 and 311 Ma）, except the 1.76-1.68 Ga episode related to post-collisional extension, revealing that the crustal accretion of this segment was chiefly generated from arc accretion and amalgamation to the NCC continental block.