1-萘甲酰苯胺和2-萘甲酰苯胺的分子内电荷转移研究

A series of 1-naphthanilides (1) and 2-naphthanilides (2) with varied substituents at the para- or meta-position of anilino phenyl ring were prepared and their absorption and fluorescence spectra in a nonpolar solvent cyclohexane were investigated. An abnormal long wavelength emission assigned to the charge transfer (CT) state was found for all of the prepared naphthanilides in cyclohexane. A linear free energy correlation between the CT emission energies and the Hammett constants of the substituent was found within series 1 and 2. The value of the linear slope with 1 (0.42 eV) was higher than that with 2 (0.32 eV) being close to that of the substituted benzanilides 3 (0.31 eV) The higher slope value suggested higher charge separation extent in the CT state of 1 than that of 2. It was found that the corresponding linear slope of anilino-substituted benzanilides remained unchanged when para-, meta-, ortho-, or ortho, ortho-methyls were introduced into the anilino moiety, which ruled out the possible contribution of the difference in the steric effect and the electron accepting ability of the naphthoyl acceptor in 1 and 2. Compared with the early reported N-substituted-benzoyl-aminonaphthalene derivatives 4 and 5, it was considered that 1-naphthoyl enhanced the charge transfer in 1 and the proximity of its ^1La and ^1Lb states was suggested to be responsible. It was shown that 1- and/or 2-substituted naphthalene cores acting as either electron acceptor (naphthoyl) or electron donor (aminonaphthalene) were different in not only electron accepting (donating) ability but also shaping the charge transfer pathway.     

Molecular Design of Trypsin Towards High Substrate Selectivity

Molecular design of trypsin mutants towards higher substrate specificity for arginine or ly-sine type substrates was studied. The difference in side chain pKa of arginine and lysine was utilized in redesigning trypsin. If the enzyme could react effectively at a pH higher than lysine's pKa but lower than that of arginine, it would react more selectively with arginine-type substrates, since in that pH range, the side chain of arginie remain protonated, while that of lysine is deprotonated. For trypsin. the change of histidine (57)'s pKa reflects the shift in reaction optimum pH. Electrostatic calculations showed that when surface positive residues were mutated into neutral or negative ones, the pKa of histidine(57) would be raised and those surface charges within a cone of 70 degree around histidine(57) have strong influence on its pKa. Several sites were suggested in rat trypsin which might serve as potential mutation locations to make trypsin active at a higher pH, thus more selective towards arginine t     

LaCl3提高菠菜光系统Ⅱ活性的作用机制

The effect of LaCl3 on the K3Fe(CN)6 (FeCy) reduction rate and the oxygen-evolving rate of PSU particles of spinach, and the spectral characterization of the D1/D2/Cytb559 of a PSII reaction center complex consisting of three polypeptides from spinach were studied. The experimental results showed that LaCl3 could significantly accelerate the transformation from light energy to electric energy, the electron transport, water photolysis and oxygen evolution of PSII of spinach, which was related to the spectral characterization of the D1/D2/Cytb559 complex.Soret band and Q band of Chl-a of UV-vis spectrum of D1/D2/Cytb559 complex were blue shifted, and the fluorescence emission peak was blue shifted in LaCl3 treated spinach compared with that in the control. The EXAFS (extended X-ray absorption fine structure spectroscopy) revealed that La^3 was coordinated with 8 nitrogen or oxygen atoms in the first coordination shell with La-N or La-O bond length of 0.254 nm, and with 6 nitrogen or oxygen atoms in the second coordination shell with La-N or La-O bond length of 0.321 nm in the D1/D2/Cytb559 complex. The CD suggested that the secondary structure of D1/D2/Cytb559 complex have been litfie affected by the treatment of LaCl3.     

High-selective removal of ultra-low level mercury ions from aqueous solution using oligothymonucleic acid functionalized polyethylene film

We prepare oligothymonucleic acid (OTA) functionalized polyethylene (PE) film and evaluate its selective removal ability of mercury ions at ultra-low levels in aqueous solution. The selective binding of OTA with mercury ions is confirmed by fluorescence in situ hybridization (FISH). The quantitative results via cold-vapor atomic fluorescence spectrometry (CVAFS) indicate that OTA-functionalized PE film is able to remove mercury ions at the sub-ppb level selectively from aqueous solution, even with the coexistence of other metal ions at concentrations 250-fold or higher than that of mercury.     

Syntheses,Crystal Structures and Antibacterial Activities of Schiff Base Ligand and Its Nickel(Ⅱ) Complex

A complex [NiL2] was synthesized, in which L, or to be exact, a Schiff base ligand(HL), was derived from the condensation of 1-phenyl-3-methyl-4-phenylacetyl-5-pyrazolone(PMPAP) with L-phenylalanine methyl ester. They were characterized by IR and single-crystal X-ray diffraction. Green block crystals of both ligand and its complex were grown at room temperature. The ligand, which consists of two individual fragments, crystalizes in the P1 space group(a = 5.6268(5), b = 10.6892(11) and c = 19.4869(18) ). The complex crystalizes in the P21 space group(a = 21.4076(18), b = 9.4792(8) and c = 25.287(2) ), which consists of a nickel six-coordinated compound. Every fragment is a distorted octahedron with four oxygen and two nitrogen atoms. The Schiff base ligand(HL) and its complex have been tested in vitro to evaluate their antibacterial activity against bacteria Escherichia Coli and Bacillus subtilis. It is found that the complex has higher activity than the corresponding free Schiff base ligand(HL) against the same bacterial.     

The specific detection of Cu(Ⅱ) using an AIE-active alanine ester

Cu(Ⅱ) detection is important because it plays crucial role in several biological processes and ecological systems.Fluorescent techniques have attracted more and more attention in Cu(Ⅱ) detection.In this report,we contribute a novel strategy to use fluorescence spectroscopy for Cu(Ⅱ) specific detection.The specificity relies on the fact that,of the many metal cations,only Cu(Ⅱ) can catalyze the hydrolyzation of a-amino acid ester.The novelty originates from the unique aggregation-induced emission(AIE) property of the fluorescent label.We designed a model a-amino acid ester(TPE-Ala) constructed with alanine and tetraphenylethene-functionalized methanol(TPE-methanol).In comparison with the precursor TPE-Ala, TPE-methanol has lower solubility and is easy to form aggregates in water,thereby displaying a higher fluorescent response.Thus,the Cu(Ⅱ) catalyzed hydrolyzation can be monitored by recording the fluorescence enhancement and fluorescent detection Cu(Ⅱ) is rationally achieved.     

APPLICATION OF THE SULFONATE ESTER GROUP AS A LINKER FOR SOLID PHASE ORGANIC SYNTHESIS

1. INTRODUCTIONIn recent years, solid phase organic synthesis (SPOS) has been increasingly used in the synthesis of small organic molecules [1]. The rapid development of SPOS brings with it the need for expanding a variety of linkers in order to accommodate new synthesis methods[2], and especially in the case of combinatorial chemistry, to allow additional diversity elements.Recently, Rueter and coworkers reported the use of a sulfonate ester as a linker in SPOS [3,4] and the compati…     

Molecular modeling and spectroscopic studies on the binding of guaiacol to human immunoglobulin

The fluorogenic property of guaiacol was exploited for the first time to analyze the interaction with target protein as a probe by molecular modeling, fluorescence, circular dichroism (CD) and Fourier transform infrared (FT-IR) spectroscopy. Molecular docking was performed to reveal the possible binding mode or mechanism and suggested that guaiacol can strongly bind to human immu- noglobulin (HIgG). It is considered that guaiacol binds to HIgG mainly by a hydrophobic interaction and there are two hydrogen bond interactions between the drug and the residues LEU 80 and ASP 65, which is in good agreement with the results from the experimental thermodynamic parameters (the enthalpy change △H0 and the entropy change △S0 were calculated to be 65.55 kJ·mol-1 and 132.95 J·mol-1·K-1 according to the Vant’ Hoff equation). Data obtained by the fluorescence spectroscopy indicated that binding of guaiacol with HIgG leads to dramatic enhancement in the fluorescence emission intensity along with significant occurrence of efficient Frster resonance energy transfer (FRET) from the residue of HIgG to the protein bound guaiacol. From the low value of fluorescence anisotropy (r = 0.06), it is argued that the probe molecule is located in the motionally unrestricted environment of the protein. The alterations of protein’s secondary structure in the presence of guaiacol in aqueous solution were quantitatively calculated by the evidences from FT-IR and CD spectroscopes.     

Crystal Structures of 2-Aminobenzothiazole-based Inhibitors in Complexes with Urokinase-type Plasminogen Activator

Urokinase-type plasminogen activator （uPA） plays a crucial role in the regulation of plasminogen activation, tumor cell adhesion and migration. The inhibition of uPA activity is a promising mechanism for anti-cancer therapy. Most current uPA inhibitors employ a highly basic group （either amidine or guanidine group） to target the S1 pocket of uPA active site, which leads to poor oral bioavailability. Here we study the possibility of using less basic 2-aminobenzothiazole （ABT） as S1 pocket binding group. We report the crystal structures of uPA complexes with ABT or 2-amino-benzothiazole-6-carboxylic acid ethyl ester （ABTCE）. The inhibitory constants of these two inhibitors were measured by a chromogenic competitive assay, and it was found that ABTCE is a better inhibitor for uPA （Ki = 656 μM） than ABT （Ki = 5.03 mM）. This work shows that 2-amniobenzothiazole can be used as P1 group which may have better oral bioavailability than the commonly used amidine or guanidine group. We also found the ethyl ester group occupies the characteristic oxyanion hole and contacts to uPA 37- and 60-loops. Such work provides structural information for further improvements of potency and selectivity of this new class of uPA inhibitor.     

Computer simulation on kinetics of primary process in photosynthesis of algae (V) --Excitation energy transfer in phycoerythrocyanins

Excitation energy transfer in phycoerythrocyanins (PEC) was studied by use of computer simulation. The results observed from the simulation are as follows: (i) The α84 is a more efficient sensitizing chromophore than β155 and donates the excitation energy into β84 and β155 while it scarcely emits fluorescence itself, (ii) Only the 1α84 →2β84 is the sub-picosecond process in a PEC trimer, therefore it is readily to obtain the time constant from fs-level time-resolved spectral measurement. (iii) The β84 and β155 chromophores in PEC behave quite differently from those in C-PC because of the changes in α84. It is observed that 1β156→6β155 is the dominant pathway linking two trimers and both of the chromophores possess much higher fluorescence fractions, and about 80% of the total fluorescence is emitted from the β84 chromophore. (iv) A far less mean number of transfer times is observed through the fast-transfer pairs in PEC compared with that in C-PC because of slow transfer rate for the path     

Study on the second-order non-linear optical properties of 10-hydrocarbylacridones

Twenty 10-hydrocarbylacridones and 2-methylacridone, 1-hydroxyacridone were synthesized from acridone and characterized by mp, IR, UV, 1H NMR and MS. Using Nd:YAG as a laser source, the second-order harmonic generation (SHG) values of the acridone derivatives were measured in powder state as compared with urea powder. The results showed that the SHG values of some of 10-hydrocarbylacridones were higher than that of urea, while others were lower. Although the hydrocarbyl substituents (R) attached to nitrogen atom of acridone were different in size and electronegativity, they had a little effect on the SHG values of 10-hydrocarbylacridones. Substituents, such as methyl or hydroxy group connected to the phenyl ring, caused a little effect on the SHG values, too, compared with acridone. The ability of R to push electron toward the nitrogen atom or to pull electron from the nitrogen atom play an important role on the maximum wavelengthes of UV-visible absorption of acridone derivatives.     

Crystal Structure and Anticancer Properties of Cinobufagin 3-Hemisuberate Methyl Ester

The title compound cinobufagin 3-hemisuberate methyl ester(1) was isolated from the venom of Bufo bufo gargarizans CANTOR. The crystal structure of 1, C35H48O9, was determined by single-crystal X-ray diffraction analysis. It belongs to orthorhombic, space group P212121 with a = 8.9338(3), b = 16.2970(4), c = 22.4019(6) , V = 3261.59(16) 3, Mr = 612.73, Z = 4, Dc = 1.248 g/cm3, μ = 0.725 mm-1, F(000) = 1320, S = 1.040, the final R = 0.0374 and wR = 0.0412 for 4458 unique reflections, of which 4088 were observed(I 2σ(I)). In the solid state, short intermolecular C-H...O interactions involving a methine and the ester carbonyl group in cinobufagin moiety and a methyl in the suberate moiety linked adjacent molecules into a three-dimensional network. Detailed analysis of the 1H-NMR data showed that X-ray structure of 1 would be expected to closely resemble the solution conformation in chloroform. Compound 1 was inactive for the inhibition of PC3 and HepG2 cancer cells, but the parent compound cinobufagin showed potent inhibition with IC50 values of 0.145 and 5.48 μM, respectively, indicating that esterification at C(3) decreased the cytotoxic effect of 1.     

NIR photosensitizers activated by γ-glutamyl transpeptidase for precise tumor fluorescence imaging and photodynamic therapy

Photodynamic therapy(PDT), a light triggered therapeutic mode, has been recognized as an attractive treatment for oncotherapy.The phototoxicity to normal tissues during treatment limited the development of PDT owing to the always "on" properties of photosensitizers. Activatable photosensitizers are of great importance for improving the selectivity of PDT. Herein, we regarded the overexpressed GGT(γ-Glutamyl transpeptidase) enzyme in tumor cells as a biomarker and developed an activatable photosensitizer Cy-GGT by decorating a specific recognition moiety of GGT, L-glutamic acid, to a hemicyanine dye based on photosensitizer Cy-NH_2. Cy-GGT was in the "off" state with negligible fluorescence and suppressed singlet oxygen generation,but it could be specifically hydrolyzed to Cy-NH_2 in the presence of GGT, accompanied with significant fluorescence recovery and singlet oxygen generation increase under light irradiation. The in vitro and in vivo studies indicated that Cy-GGT was suitable for precise tumor imaging and could work as an efficient photosensitizer for inhibiting tumor growth.     

Synthesis of a fluorescent probe based on naphthalimide derivative for simultaneous detecting of NO and pH in bioimagingEI北大核心CSCD

A new type of fluorescent probe Na-pHNO was synthesized for the simultaneous detection of NO and pH based on naphthalimide derivative. The probe had good fluorescence property in mixture solution of 99% phosphate buffer solution（PBS）and 1% dimethyl sulfoxide（DMSO）solution. It can produce a yellow-green emission peak at 544 nm,and the fluorescence intensity can be enhanced with the increase of NO concentration or the decrease of pH. The probe Na-pHNO displayed good selectivity,high sensitivity,and strong anti-interference towards NO,exhibiting good fluorescence reversibility at pH 5.5-8.5. The spectral studies showed that the probe Na-pHNO exhibited weak fluorescence due to a dual photoinduced electron transfer（PET）effect. After interacting with NO or pH,the dual PET inhibitory effect occurred,and the fluorescence intensity was significantly enhanced. The fluorescence imaging of probe Na-pHNO in HeLa cells showed that it could realize the visual monitoring of the changes of intracellular pH and NO concentration. The probe has been successfully applied to fluorescence imaging of Caenorhabditis elegans. © 2023, Youke Publishing Co.,Ltd. All rights reserved.     

Synthesis,DNA binding and topoisomerase inhibition of mononaphthalimide homospermidine derivatives

Two novel mononaphthalimide homospermidine derivatives （2a, 2b） with three or four methylene unit as linkages were synthesized and evaluated for cytotoxicity against human leukemia K562, murine melanoma B 16 and Chinese hamster ovary CHO cell lines. The presence of homospermidine motif could greatly elevate the potency of 1,8-naphthalimide. Conjugate 2b with longer spacer exhibited higher in vitro cytotoxicity than 2a. The DNA binding experiments indicated that conjugates 2b could bind to herring sperm DNA. The topoisomerase Ⅱ poison trials revealed that 2b could inhibit the activity of top. Ⅱ.     

Corrosion Inhibition of a Green Scale Inhibitor Polyepoxysuccinic Acid

The corrosion inhibition of a green scale inhibitor, polyepoxysuccinic acid (PESA) was studied based on dynamic tests. It is found that when PESA is used alone, it had good corrosion inhibition. So, PESA should be included in the category of corrosion inhibitors. It is not only a kind of green scale inhibitor, but also a green corrosion inhibitor. The synergistic effect betweenPESA and Zn2 or sodium gluconate is poor. However, the synergistic effect among PESA, Zn2 and sodium gluconate is excellent, and the corrosion inhibition efficiency for carbon steel is higher than 99%. Further study of corrosion inhibition mechanism reveals that corrosion inhibition of PESA is not affected by carboxyl group, but by the oxygen atom inserted. The existence of oxygen atom in PESA molecular structure makes it easy to form stable chelate with pentacyclic     

KINETICS AND MECHANISM OF PHOTOINDUCED POLYMERIZATION BY α,α-DIMETHOXY-α-PHENYL ACETOPHENONE

α,α-dimethoxy-α-Phenyl acetophenone (DMPA) is an efficient and thermally stable photoinitiator. Here its spectral characteristics in the transient state were shown. The transient species were identified as a benzoyl radical and a dimethoxyi benzyl radical that played a primary initiation role in polymerization. The kinetics and mechanism of the bulk polymerization of MMA were investigated. The exponent of DMPA concentration and k_p/k_1~(1/2) value were found to be 0.5 and 0.066 mol(-1/2)l~(1/2)s~(-1/2), respectively. The existence of oxygen led to obtain the polymer with higher molecular weight, which can be attributed to the occurrence of the subsequent polymerization induced by active polymer end group. In the photocrosslinking reaction, the dependence of DMPA content on initial rate has been found. A principal reason is that the sample contained higher percentage of DMPA has higher light-absorbed efficiency. In solid film, higher concentration of DMPA is permitted to be used because there is little excited state self-quenching effect in the rigid medium.     

Low-bandgap polymers with quinoid unit as π bridge for high-performance solar cells

To construct efficient low band gap polymers, increasing the Quinone structure of the polymer backbone could be one desirable strategy. In this work, two D–Q–A–Q polymers P1 and P2 were designed and synthesized with thiophenopyrrole diketone(TPD) and benzothiadiazole(BT) unit as the core and ester linked thieno[3,4-b]thiophene(TT) segment as π-bridging, and the main focus is to make a comparative analysis of different cores in the influence of the optical, electrochemical, photochemical and morphological properties. Compared with the reported PBDTT_(EH–)TBTT_(HD-i), P1 exhibited the decreased HOMO energy level of-5.38 e V and lower bandgap of 1.48 e V. Furthermore, when replaced with BT core, P2 showed a red-shifted absorption profile of polymer but with up-shifted HOMO energy level. When fabricated the photovoltaic devices in conventional structure, just as expected, the introduction of ester substituent made an obvious increase of V_(OC) from 0.63 to 0.74 V for P1. Besides, due to the deep HOMO energy level,higher hole mobility and excellent phase separation with PC_(71) BM, a superior photovoltaic performance(PCE = 7.13%) was obtained with a short-circuit current density(J_(SC)) of 14.9 m A/cm~2, significantly higher than that of P2(PCE = 2.23%). Generally, this study highlights that the strategy of inserting quinoid moieties into D–A polymers could be optional in LBG-polymers design and presents the importance and comparison of potentially competent core groups.     

Photochemical fixation and reduction of sulfur dioxide to sulfide by tetraphenylporphyrin magnesium: Spectroscopic and kinetic studies

The photochemical reaction of sulfur dioxide(SO2) with tetraphenylporphyrin magnesium(MgTPP) has been investigated in dichloromethane(CH2Cl2) solution at room temperature with illumination by visible light.Conventional fluorescence,UV-vis,and MS spectral analyses showed that under these conditions,SO2 was initially photochemically fixed by MgTPP to form a 1:1 molecular adduct.On continued irradiation and maintaining the flow of SO2,MS and XRD results showed that MgTPP is remarkably effective in the photochemical reduction of SO2 to sulfide(S2).The kinetics of the photochemical reaction of MgTPP with SO2 was studied in a SO2-saturated solution.Under irradiation,the reaction follows pseudo first order kinetics for MgTPP,having a half-life decreasing from 106 to 57 min as the illumination intensity is increased from 350 to 600 Lm.This investigation of the photochemical fixation and reduction of SO2 by MgTPP is of key interest in elucidating fundamental photochemical reaction mechanisms associated with porphyrins in the presence of SO2 ;furthermore,the analysis of the photochemical reaction may offer new opportunities for the fixation and reduction of SO2 to less harmful species.     

The synthesis of porphyrin-anthraquinone dyad via an azo-rearrangement

One novel porphyrin P-Q2 is planned to be synthesized by condensation between ATPP and Q1.However,after separation by chromatography and characterization with IR,~1H NMR,HR-MS and X-ray,P-Q1 is obtained unexpectedly.Compared the structure of P-Q1 with that of P-Q2,it is realized that an intramolecular cyclization rearrangement takes place when the azo group is situated in the O-position to the amido group.This rearrangement offers a new way to prepare indazole heterocycle.In addition,the spectral properties of P-Q1 have been studied by UV-vis and steady state fluorescence spectroscopy.Strong fluorescence quenching is observed in the preliminary emission spectrum due to the proposed electron transfer from the excited porphyrin to the anthraquinone moieties.