疏水性对溶胶-凝胶SiO2薄膜抗真空污染及抗激光损伤能力的影响

以正硅酸乙酯作为前驱体, 利用碱催化方式制备了SiO₂溶胶, 通过在溶胶中添加含疏水基团(-CH₃)的六甲基二硅氮烷(HMDS)对溶胶进行改性, 使用添加不同物质的量比HMDS改性后的溶胶用提拉法在K9基片上镀膜, 获得了具有疏水性能的SiO₂薄膜。采用自制接触角测量仪、紫外-可见-近红外分光光度计研究了薄膜的水接触角和透过率。测试了薄膜的激光损伤阈值, 并观察了激光辐照后薄膜的损伤形貌。通过真空污染实验对薄膜的抗污染能力及抗激光损伤能力进行了研究。实验结果表明:经疏水改性的溶胶所镀制的薄膜激光损伤阈值由未改性样品的24.3 J·cm^-2增加到37 J·cm^-2(1 064 nm, 10 ns), 且抗真空污染能力大大加强:在真空环境下保存168 h后, 未改性样品的峰值透过率下降了2%, 而疏水改性后的样品峰值透过率仅下降了0.25%, 并保持了较高的激光损伤阈值(30.8 J·cm^-2)。     

溶剂对镓Corrole光谱性质的影响

合成了一系列周边取代的Corrole(1, 2, 3, 4)及其镓配合物1-Ga(Py)、2-Ga(Py)、3-Ga(Py)、4-Ga(Py),通过核磁共振氢谱(¹H NMR), 紫外-可见光谱, 电喷雾离子质谱(ESI-MS)的方法对其进行了表征. 研究了不同溶剂对这一系列自由Corrole 及镓Corrole 的紫外-可见(UV-Vis)吸收光谱, 稳态荧光和时间分辨荧光光谱, 将获得的荧光衰减动力学曲线采用单指数拟合并进行解卷积处理获得荧光的寿命值. 非（弱)极性溶剂对镓Corrole 紫外光谱的影响服从Bayliss 方程, 且镓Corrole 非辐射能量损失hc(ν¹_A-ν_F)与F(n)呈线性相关.     

基于2，3-萘-18-冠-6单元的共轭高分子对金属离子的荧光传感器

能发射蓝绿色荧光的共轭高分子由单体1,4-二溴-2,3-萘-18-冠-6(M-2)与1,4-二乙烯基-2,5-二丁氧基苯(M-3)通过Pd催化的Heck偶联反应合成制得。通过荧光和紫外-可见光谱探讨了高分子对金属离子的响应性质,其中Hg²⁺能使高分子荧光淬灭、吸收增强,但As^Ⅲ、Pb²⁺和K⁺对高分子的荧光光谱改变很小。结果表明以2,3-萘-18-冠-6作为荧光团和识别位点的共轭高分子可作为有效识别Hg²⁺的荧光化学传感器。     

超声波激活纳米氧化锌损伤牛血清白蛋白的研究

利用紫外-可见(UV-Vis)光谱和荧光光谱研究了超声波照射激活纳米氧化锌(ZnO)粒子对牛血清白蛋白(BSA)的损伤,并考查了超声波照射时间、纳米ZnO粉末加入量、溶液酸度和照射功率等因素对BSA分子损伤的影响。结果表明,对于体系温度为37.0±0.2 ℃和浓度为1.0×10^-5 mol·L^-1的BSA溶液,BSA的损伤程度随着超声波照射时间,纳米ZnO粉末加入量,溶液pH值和照射功率的增加而增大。此外,还初步探讨了超声波照射激活纳米ZnO粒子损伤BSA分子的机理,认为是声致发光和高热激发使纳米ZnO粒子产生·OH自由基,进而损伤BSA分子。     

4-硝基咪唑A-带激发态结构动力学

通过共振拉曼光谱实验和量子化学计算的方法研究了4-硝基咪唑(4NI)A-带激发态衰变动力学. 对4NI的振动光谱、紫外电子吸收光谱、荧光光谱和共振拉曼光谱进行了指认. 在全活化空间自洽场法(CASSCF)/6-31G(d)计算水平下获得了单重激发态S₁(n_Oπ^*)和S₂(ππ^*)和势能面交叉点S₁(n_Oπ^*)/S₂(ππ^*)的优化几何结构和能量, 分析了A-带共振拉曼光谱的强度模式特征, 获得了短时结构动力学, 并结合全活化空间自洽场法(CASSCF)理论计算结果确定了4NI 在S₂(ππ^*)态衰变通道主要是S_{2, FC}→S_{2, min}(ππ^*)→S₀辐射弛豫.     

联吡啶[3,2-a：2’,3-c]-7-氮杂-吩嗪铜(I)配合物的合成、表征及其与DNA的相互作用

合成了邻菲罗啉衍生物联吡啶[3,2-a:2',3'-c]-7-氮杂-吩嗪(dpapz)及其铜(I)配合物[Cu(dpapz)₂]PF₆, 利用核磁共振氢谱(¹H NMR), 傅里叶变换红外(FTIR)光谱, 高分辨质谱(HR ESI-MS)等对合成的化合物进行了表征.采用紫外-可见吸收光谱,荧光光谱, DNA熔解温度实验和循环伏安方法研究了dpapz和[Cu(dpapz)₂]PF₆与小牛胸腺DNA(CT DNA)的相互作用. 配体dpapz与小牛胸腺DNA(CT DNA)作用时未观察到吸收峰红移并且减色效应较小(<30%), 且DNA熔解温度也上升较小(ΔT_m=7.8 ℃), 说明dpapz以沟槽结合的方式与CT DNA相互作用. 而[Cu(dpapz)₂]PF₆与CT DNA作用时, 可观测到较小的吸收峰红移(2-3 nm)和较大的减色效应(>50%), 同时DNA熔解温度上升较大(ΔT_m=11.1 ℃), 表明[Cu(dpapz)₂]PF₆以静电相互作用和部分扦插的方式与DNA结合. 溴乙锭(EB)荧光竞争实验和循环伏安实验进一步证实了这一结论. 配体dpapz和[Cu(dpapz)₂]PF₆与DNA的结合常数分别为2.88×10⁵和5.32×10⁵ mol·L^-1. 光照条件下, [Cu(dpapz)₂]PF₆产生单重态氧的能力与dpapz相当, 但产生超氧负离子自由基的能力要弱于dpapz. 活性氧猝灭实验表明, 超氧负离子自由基、单重态氧和羟基自由基均参与了dpapz和[Cu(dpapz)₂]PF₆对DNA的光损伤作用. [Cu(dpapz)₂]PF₆对DNA的亲和性要高于对dpapz的, 使得[Cu(dpapz)₂]PF₆对质粒DNA的光损伤效率明显强于dpapz.     

4',5,7-三羟基二氢黄酮与人血清白蛋白相互作用的光谱学研究

应用紫外吸收光谱、荧光光谱和红外光谱等方法对人血清白蛋白(HSA)与4',5,7-三羟基二氢黄酮(naringenin, NAR)相互作用的机理进行了研究. 紫外光谱显示, 在生理pH下NAR分子中A环7位的酚羟基发生部分解离, 7位酚羟基的解离使A环与B环上羰基形成的共轭体系的紫外吸收峰发生明显红移; 药物与蛋白质的相互作用使该谱带发生了进一步的红移, 说明该共轭体系参与了与蛋白质的相互作用. 在药物与蛋白质浓度比(c_NAR/c_HSA)为0.1～10 的范围内, NAR在HSA上只有一个结合位点(可能位于site I), 结合常数为1.27×10⁵ L•mol^－1 (n＝5, RSD小于5%). 研究了不同pH值条件下药物对蛋白质荧光猝灭的影响, 发现药物分子中的没有解离的活性基团在结合过程中发挥着主导作用. 在缓冲水溶液和重水溶液中分别测定了与药物作用前后蛋白质二级结构的变化. 随着药物浓度的增加, NAR和HSA之间的相互作用使HSA的α-螺旋结构的含量明显降低, 而β-折叠和β-转角结构的含量增加, 无轨结构在药物浓度较高时也有少量的增加. 结合紫外吸收光谱、荧光光谱和红外光谱结果, 探讨了HSA与NAR相互作用的模式.     

Tb3＋离子与植物辣根过氧化物酶的作用方式探讨

利用紫外可见吸收光谱、红外光谱、荧光光谱、原子吸收及酶分离方法, 首次研究了稀土离子Tb^3＋与植物辣根过氧化物酶(HRP)的相互作用方式. 结果表明, Tb^3＋与HRP作用方式包括: (1) Tb^3＋与肽链上的氨基酸残基作用, 影响酶活性中心的微结构; (2) Tb^3＋能部分取代酶中的Ca^2＋; (3) Tb^3＋能部分剪切肽链上的氨基酸残基, 改变酶的结构. 因此, Tb^3＋与HRP的相互作用可能以一种方式为主, 或几种作用方式同时存在.     

Inhibit化学逻辑门: 基于Al3＋和Fe3＋的β-二酮荧光开关的研究

合成了1,3-二苯基-4-苯乙酰-5-吡唑酮(HDPP-PA)与Al^3＋, Fe^3＋形成的配合物, 通过元素分析、质谱、红外光谱、紫外-可见吸收、荧光光谱等测试方法, 对其组成和结构进行了表征, 发现Fe^3＋能有效地减弱Al配合物的荧光, 为此将HDPP-PA与Al^3＋和Fe^3＋组成一个具有INHIBIT操作功能的化学逻辑门.     

新型蓝色上转换荧光分子的合成、表征与双光子吸收性能

设计并合成了3 个新的受体-给体-受体(A-D-A)构型上转换荧光分子,用傅里叶变换红外光谱、核磁共振氢谱、质谱和元素分析进行了表征. 测定了它们在不同溶剂中的线性吸收光谱、单光子荧光光谱和荧光量子产率. 以飞秒激光作为光源,研究了它们的双光子吸收和上转换荧光特性. 结果表明：该类化合物的荧光量子产率为0.20-0.68,双光子吸收截面为16×10^-50-101×10^-50 cm⁴·s·photon^-1,具有较强的蓝色上转换荧光发射.     

Ciprofloxacin photosensitized oxidation of 2'-deoxyguanosine-5'-monophosphate in neutral aqueous solution

Laser flash photolysis studies have been carried out to investigate the reactions of ciprofloxacin (CPX) with 2'-deoxyguanosine-5'-monophosphate (dGMP), N, N, N', N'-tetramethyl-p-phenylenediamine (TMPD) and ferulic acid (FCA) in neutral aqueous solutions, respectively. CPX triplet state ((3)CPX*) can be quenched by TMPD, FCA and dGMP, with rate constants of 1.8 × 10(9), 1.5 × 10(9) and 5.8 × 10(7) dm(3) mol(-1) s(-1), respectively. TMPD radical cation (TMPD(·+)) and FCA radical cation (FCA(·+)) were observed directly. The formation rate of CPX radical anion (CPX(·-)) was determined to be 1.5 × 10(9) dm(3) mol(-1) s(-1). Redox reaction of dGMP was investigated through competing reactions using TMPD and FCA as probe. The triplet energy of CPX was determined to be 262 kJ mol(-1). Electron transfer from TMPD, FCA and dGMP to (3)CPX* was proposed.     

Time resolve study on isopropyl-ether porphyrindiol

In the past years extensive studies have been conducted on porphyrin-type photosensitizers because of their photosensitive activity. With regard to their interaction with many important macromolecules such as nucleic acids, proteins and lipids, porphyrin-type photosensitizers are capable of damaging numerous cells. They damage DNA via oxidation of four bases, especially guanine and cytosine pairs[1], damage protein by oxidation of (at least) two amino acids——cysteine and tryptophan residues…     

A systematic capillary electrophoresis study on the effect of the buffer composition on the reactivity of the anticancer drug cisplatin to the DNA model 2′-deoxyguanosine 5′-monophosphate (dGMP)

The development of DNA-targeted next-generation platinum-based anticancer chemotherapeutics is often accompanied by studies on the reactivity to DNA models. However, the incubation conditions used in literature vary widely, and some of the buffer/salts used are known to form complexes with Pt. Such coordination can influence the binding process and also the adducts formed. In a systematic approach, studies on the binding of cisplatin (1 mM) to dGMP (2 mM) in a series of different incubation solutions of relevance to biological systems are reported, employing capillary zone electrophoresis (CZE) with UV/vis and electrospray ionization–mass spectrometric (ESI-MS) detectors. Kinetic experiments performed with CZE–UV showed a high reactivity of dGMP to cisplatin in pure water (τ _1/2?=?4.1?±?0.7 h) but a significantly slowed down in a solution containing a carbonate/phosphate buffer supplemented with NaCl, resulting in a half-life of dGMP of 25?±?3 h. Especially carbonate had a major impact on the binding, though no coordination to the metal center was detectable with the methods used. The only adducts containing buffer components were (phosphate)Pt and tris(ammine)Pt species, as identified by means of CZE–ESI-MS, in addition to the main adduct [Pt(NH₃)₂(dGMP)₂???4H⁺]^2? and other less abundant Pt-containing species.     

Oxidation of 2'-deoxyguanosine 5'-monophosphate photoinduced by pterin: type I versus type II mechanism

UV-A radiation (320-400 nm) induces damage to the DNA molecule and its components through different photosensitized reactions. Among these processes, photosensitized oxidations may occur through electron transfer or hydrogen abstraction (type I) and/or the production of singlet molecular oxygen ((1)O2) (type II). Pterins, heterocyclic compounds widespread in biological systems, participate in relevant biological processes and are able to act as photosensitizers. We have investigated the photosensitized oxidation of 2'-deoxyguanosine 5'-monophosphate (dGMP) by pterin (PT) in aqueous solution under UV-A irrradiation. Kinetic analysis was employed to evaluate the participation of both types of mechanism under different pH conditions. The rate constant of (1)O2 total quenching (k(t)) by dGMP was determined by steady-state analysis of the (1)O2 NIR luminescence, whereas the rate constant of the chemical reaction between (1)O2 and dGMP (k(r)) was evaluated from kinetic analysis of concentration profiles obtained by HPLC. The results show that the oxidation of dGMP photosensitized by PT occurs through two competing mechanisms that contribute in different proportions depending on the pH. The dominant mechanism in alkaline media involves the reaction of dGMP with (1)O2 produced by energy transfer from the PT triplet state to molecular oxygen (type II). In contrast, under acidic pH conditions, where PT and the guanine moiety of dGMP are not ionized, the main pathway for dGMP oxidation involves an initial electron transfer between dGMP and the PT triplet state (type I mechanism). The biological implications of the results obtained are also discussed.     

Photosensitizing properties of biopterin and its photoproducts using 2'-deoxyguanosine 5'-monophosphate as an oxidizable target

UV-A radiation (320-400 nm) induces damage to the DNA molecule and its components through photosensitized reactions. Biopterin (Bip) and its photoproducts 6-formylpterin (Fop) and 6-carboxypterin (Cap) accumulate in the skin of human beings suffering from vitiligo, a depigmentation disorder where the protection against UV radiation fails because of the lack of melanin. This study was aimed to evaluate the photosensitizing properties of oxidized pterins present in the skin and to elucidate the mechanisms involved in the photosensitized oxidation of purine nucleotides by pterins in vitro. For this purpose, steady-state and time-resolved experiments in acidic (pH 5.0-5.8) aqueous solution were performed using Bip, Fop and Cap as photosensitizers and the nucleotide 2'-deoxyguanosine 5'-monophosphate (dGMP) as an oxidizable target. The three pterin derivatives are able to photosensitize dGMP, being Fop the most efficient sensitizer. The reactions proceed through two competing pathways: (1) electron transfer from dGMP to triplet excited-state of pterins (type I mechanism) and (2) reaction of dGMP with (1)O(2) produced by pterins (type II mechanism). Kinetic analysis revealed that the electron transfer pathway is the main mechanism and the interaction of dGMP with the triplet excited-state of pterins and the formation of the corresponding dGMP radicals were demonstrated by laser flash photolysis experiments. The biological implications of the results obtained are also discussed.     

Comprehensive Analysis of DNA Strand Breaks at the Guanosine Site Induced by Low‐Energy Electron Attachment

To elucidate the role of guanosine in DNA strand breaks caused by low‐energy electrons (LEEs), theoretical investigations of the LEE attachment‐induced C? O σ‐bonds and N‐glycosidic bond breaking of 2′‐deoxyguanosine‐3′,5′‐diphosphate (3′,5′‐dGMP) were performed using the B3LYP/DZP++ approach. The results reveal possible reaction pathways in the gas phase and in aqueous solutions. In the gas phase LEEs could attach to the phosphate group adjacent to the guanosine to form a radical anion. However, the small vertical detachment energy (VDE) of the radical anion of guanosine 3′,5′‐diphosphate in the gas phase excludes either C? O bond cleavage or N‐glycosidic bond breaking. In the presence of the polarizable surroundings, the solvent effects dramatically increase the electron affinities of the 3′,5′‐dGDP and the VDE of 3′,5′‐dGDP^?. Furthermore, the solvent–solute interactions greatly reduce the activation barriers of the C? O bond cleavage to 1.06–3.56 kcal mol^?1. These low‐energy barriers ensure that either C_5′? O_5′ or C_3′? O_3′ bond rupture takes place at the guanosine site in DNA single strands. On the other hand, the comparatively high energy barrier of the N‐glycosidic bond rupture implies that this reaction pathway is inferior to C? O bond cleavage. Qualitative agreement was found between the theoretical sequence of the bond breaking reaction pathways in the PCM model and the ratio for the corresponding bond breaks observed in the experiment of LEE‐induced damage in oligonucleotide tetramer CGTA. This concord suggests that the influence of the surroundings in the thin solid film on the LEE‐induced DNA damage resembles that of the solvent.     

Study on the interactions between anti-tumor metal complexes and mononucleotides using trans -[en2Os(η2-H2)(CF3SO3)](CF3SO3) as a 1H NMR probe in a competitive mode

The interaction of several anti-tumor metal complexes with dGMP have been investigated using trans-[en₂Os(η²-H₂)]²⁺ as a ¹H NMR probe in a competitive mode. Me₂SnCl₂, Bu₂SnCl₂, Et₂Sn(phen)Cl₂ and Et₂SnCl₂can bind to dGMP mainly via phosphate; Cp₂TiCl₂ binds to dGMP mainly via phosphate and N₇. The binding constant for (CH₃)₂SnCl₂ binding to phosphate of dGMP exceeds 2.71×10⁴. The binding constant for Cp₂TiCl₂ to phosphate is even greater than that of Sn(IV). Cis-platin has high affinity for both N₇ and phosphate, but mainly for N₇. Binding of the probe to N₇ of dGMP reduces the binding affinity for phosphate of the same dGMP molecule by a factor of 5 to 6. Much the same factor is expected to apply to other metals containing agents interacting with dGMP.     

Reduction Process of Tetraplatin in the Presence of Deoxyguanosine Monophosphate (dGMP): A Computational DFT Study

The reduction mechanism of [Pt^IV(dach)Cl₄] (dach=diaminocyclohexyl) in the presence of dGMP was studied. The first step is substitution of a chloro ligand by dGMP, followed by nucleophilic attack of a phosphate or sugar oxygen atom to the C8‐position of guanine. Subsequent reduction forms the [Pt^II(dach)Cl₂] complex. The whole process is completed by a hydrolysis. Two different pathways for the substitution reaction were examined: a direct associative and a Basolo–Pearson autocatalytic mechanism. All the explored structures were optimized at the B3LYP‐D3/6‐31G(d) level and by using the COSMO solvation model with Klamt's radii. Single‐point energetics was determined at the B3LYP‐GD3BJ/6‐311++G(2df,2pd)/PCM/scaled‐UAKS level. Activation barriers were used for an estimation of the rate constants and these were compared with experimental values. It was found that the rate‐determining step is the nucleophilic attack with a slightly faster performance in the 3′‐dGMP branch than in the case of 5′‐dGMP with activation barriers of 21.1 and 20.4 kcal mol^?1 (experimental: 23.8 and 23.2 kcal mol^?1). The reduction reaction is connected with an electron flow from guanine. The product of the reduction reaction is a chelate structure, which dissociates within the last reaction step, that is, a hydrolysis reaction. The whole redox process (substitution, reduction, and hydrolysis) is exergonic by 34 and 28 kcal mol^?1 for 5′‐dGMP and 3′‐dGMP, respectively.     

Fast repair activities of quercetin and rutin toward dGMP hydroxyl radical adducts

The repair activities and mechanisms of both quercetin and rutin towards the oxidizing deoxyguanosine monophosphate (dGMP) hydroxyl radical adduct were investigated with pulse radiolytic technique. On pulse irradiation of nitrous oxide saturated 2 mM dGMP aqueous solution containing 0.1 mM quercetin, the transient absorption spectrum of the dGMP hydroxyl radical adduct decays with the formation of phenoxyl radical of quercetin within tens of microseconds. It indicates that there is a repair reaction between dGMP hydroxyl radical adduct and quercetin. The repair activity of rutin towards hydroxyl radical adducts of dGMP was also observed. The rate constants of the repair reactions were calculated to be 3.05×10⁸ and 1.31×10⁸ M⁻¹ s⁻¹ for quercetin and rutin, respectively. This result together with our previous studies demonstrated that non-enzymatic, fast repair is a universal repair mechanism of phenolic antioxidants.     

Evaluating the Removal of the Antibiotic Cephalexin from Aqueous Solutions Using an Adsorbent Obtained from Palm Oil Fiber

This study aimed to understand the adsorption process of cephalexin (CPX) from aqueous solution by a biochar produced from the fiber residue of palm oil. Scanning electron microscopy, Fourier transform infrared spectroscopy, Boehm titration, and the point of zero charge were used to characterize the morphology and surface functional groups of the adsorbent. Batch tests were carried out to evaluate the effects of the solution pH, temperature, and antibiotic structure. The adsorption behavior followed the Langmuir model and pseudo-second-order model with a maximum CPX adsorption capacity of 57.47 mg g⁻¹. Tests on the thermodynamic behavior suggested that chemisorption occurs with an activation energy of 91.6 kJ mol⁻¹ through a spontaneous endothermic process. Electrostatic interactions and hydrogen bonding represent the most likely adsorption mechanisms, although π–π interactions also appear to contribute. Finally, the CPX removal efficiency of the adsorbent was evaluated for synthetic matrices of municipal wastewater and urine. Promising results were obtained, indicating that this adsorbent can potentially be applied to purifying wastewater that contains trace antibiotics.