含手性原子硝基苯胺衍生的的合成及SHG效应

有机非线性光学材料具有ＳＨＧ活性高，响应时间快，分子结构可变性等优点。合成了２０个含不对称原子氨基酸取代的苯系化合物，测试了这些化合物的旋光度。紫外一可见吸收，ＳＨＧ效应，发现１７个化合物具有ＳＨＧ活性，初步探讨了影响ＳＨＧ效应的有关因素。     

查尔酮系化合物的合成及SHG效应

合成了２２个查尔酮系化合物，测试了它们的吸收光谱，其中１９个化合物的最高吸收λｍａｘ小于４００ｎｍ。采用固体粉末法测试了合成产品的ＳＨＧ效应，发现１３个品种具有ＳＨＧ活性。     

查尔酮系化合物的合成及SHG效应

合成了２２个查尔酮系化合物，测试了它们的吸收光谱，其中１９个化合物的最高吸收λｍａｘ小于４００ｎｍ。采用固体粉末法测试了合成产品的ＳＨＧ效应，发现１３个品种具有ＳＨＧ活性．     

对硝基苯胺衍生物的合成及SHG效应

合成了十个对硝基苯胺衍生物，其中４个化合物含有手性原子。测试了它们的旋光度、和吸收光谱，含手性原子的化合物均有旋光值，十个合成产品的最高吸收波长在３０７～３９０ｎｍ之间。采用固体粉末法测试了合成化合物的ＳＨＧ效应，其中五个品种具有ＳＨＧ活性。     

对硝基苯胺衍生物的合成及SHG效应

合成了十个对硝基苯胺衍生物，其中４个化合物含有手性原子。测试了它们的旋光度、和吸收光谱，含手性原子的化合物均有旋光值，十个合成产品的最高吸收波长在３０７￣３９０ｎｍ之间。采用固体粉末法测试了合成化合值的ＳＨＧ效应，其中五个品种具有ＳＨＧ活性。     

希夫碱的合成、提纯与倍频效应测试

芳胺与四种取代苯甲醛缩合，合成了２０个希夫碱化合物，进行重结晶提纯，讨论了希夫碱的分解与分解抑制。测试了希夫碱化合物的紫外 可见吸收曲线及ＳＨＧ效应，发现有７个化合物有倍频效应，其中两个倍频能力高于尿素，讨论了取代基对λｍａｘ、Δλ１／２ｍａｘ及ＳＨＧ效应的影响。     

芳醛与芳胺的缩合反应及产物的倍频效应

三种芳醛与芳胺缩合，合成了１４个希夫碱化合物，讨论了催化剂、空间效应对缩合反应的影响。测试了１４个希夫碱的紫外－可见吸收曲线及ＳＨＧ效应，发现有一个化合物有倍频效应，并讨论了取代基对λｍａｘ及Δλ１／２ｍａｘ的影响     

H2SO4石墨层间化合物稳定性分析研究

本文用日本理学转靶Ｘ射线分析仪Ｄ／ＭＡＸ／Ｂ首次制定了Ｈ２ＳＯ４－石墨层间化合物在各种条件下的Ｘ射线衍射图谱，根据各Ｘ射线衍射图，对Ｈ２ＳＯ４－ＧＩＣ的阶结构进行了详尽的分析，探讨了环境对Ｈ２ＳＯ４－ＧＩＣ隐定性的影响。在测试过程中采用特殊的样品制备方法，保证了Ｈ２ＳＯ４－ＧＩＣ衍射图谱的客观性．     

可膨胀石墨中有害硫的研究

通过ＧＩＣ合成工艺实验，对Ｈ２ＳＯ４－ＧＩＣ的有害元素Ｓ进行了分析研究，找出了影响含硫量的因素、提出了具有最低含硫量的工艺条件，并得出了Ｈ２ＳＯ４－ＧＩＣ中硫的分布情况。     

由原子转移自由基聚合制备具有预期结构的聚丙二醇—苯乙烯接枝共聚物

以氯甲基化苯氧基聚丙二醇（ＣＭＰＰＧ）为大分子引发剂，ＣｕＣｌ／ｂｐｙ为催化体系研究了ＣＭＰＰＧ－ｇ－ＰＳ共聚物的合成。结果表明，该聚合过程具有活性聚合特征，借助１Ｈ－ＮＭＲ表征确认了接枝共聚物具有预期结构。     

含二苯甲酮类高分子水溶性紫外线吸收剂的合成与表征

将具有较好紫外线吸收能力的2,4二-羟基二苯甲酮(UV-0)与丙烯酰氯反应合成2羟-基-4丙-烯酸酯基-二苯甲酮(HAB)中间体,而后利用HAB中的双键与二甲基氨基丙基丙烯酰胺(DMAPAA)进行共聚反应,合成了水溶性紫外线吸收剂共聚物。采用红外光谱(FTIR),核磁共振(1H-NMR),紫外光谱(UV)等表征手段对产物进行结构表征。通过紫外光谱表明,产物在351 nm处有强紫外吸收。     

Photobase‐generating new polyurethanes with oxime–urethane groups in the main chain

New polymeric photobase generators containing oxime–urethane groups were prepared by the polyaddition reaction of 2,4‐tolylene diisocyanate with terephthalaldehyde dioxime in the presence or absence of a polyol component to study the ability of these polymers to generate amines through the photolysis of oxime–urethane linkage. The amines induced the crosslinking of poly(glycidyl methacrylate), as proved by the variation of the amount of the insoluble fraction of polymer films with the heating temperature and/or irradiation time. UV and IR absorption spectra indicated that the thermal crosslinking of poly(glycidyl methacrylate) was catalyzed by the photogenerated amines. The photobehavior of the polymers was followed by a reduction of the absorption band at 290 nm, which was characteristic of oxime–urethane groups, as a function of the UV irradiation time. Blue fluorescence was visualized by the treatment of irradiated films with fluorescamine. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 2324–2332, 2004     

Covalent binding of peroxidized phospholipid to protein: III. Reaction of individual phospholipids with different proteins

Various peroxidized phospholipids were reacted with proteins under N₂. In all cases, phospholipid is bound covalently to the proteins whose molecular size is increased. Both the amount of bound phospholipid and the increase in molecular size of the protein depends on the nature of the phospholipid. Ultraviolet (UV) absorption of the proteins is increased in qualitatively similar ways. Their difference spectra, which show a gradual increase in absorption from 400 nm toward shorter wavelength, differ from that of malonaldehyde-protein complexes. The various complexes of proteins and peroxidized phospholipids have similar fluorescence spectra showing two excitation maxima at 310–320 nm and at 340–350 nm, respectively, and emission maximum at ca. 400 nm. This is different from both fluorescence spectra of malonaldehyde-protein complexes and fluorescence spectra reported for proteins after reaction with peroxidized polyunsaturated fatty acids. Amino groups of the proteins are consumed in the reaction with peroxidized phospholipids. Blocking the amino groups decreases the binding of phospholipid considerably. Besides amino groups, other structures of the protein molecule react with the peroxidized phospholipids. The similar features of UV absorption, fluorescence, decrease of amino groups, and covalently bound phospholipid phosphorus of the various complexes suggest that they are formed by common type of reactions. The reactions seem to be different from those generally believed important between peroxidized lipid and protein. Important reacting species are compounds other than malonaldehyde. Preliminary report of this work was presented at the ISF/AOCS World Congress, New York, 1980.     

脂质体催化其表面甘氨酸与磷酸吡哆醛形成希夫碱

利用脂质体的疏水微环境,完成了甘氨酸与磷酸吡哆醛的希夫碱反应.甘氨酸进行双烷基化修饰后,组装到脂质体中.利用肽脂质构建带正电荷的脂质体(pH=7.00),吸附带负电荷的磷酸吡哆醛,增强磷酸吡哆醛与脂质体上甘氨酸的伯胺基团作用,并通过脂质体疏水微环境促进脱水缩合过程.紫外光谱检测结果表明,单独的磷酸吡哆醛吸收峰为387 ...     

紫外可见光谱归一校正法检测2,4-二硝基苯酚

采用紫外可见光谱作为检测2,4-二硝基苯酚的方法,pH6或pH3时,2,4-二硝基苯酚的特征吸收峰分别为370 nm及260 nm处;在pH 3~6之间,两特征峰共存。文章提出一种简单的归一拟合方法,首先推导出260 nm处的吸收值与浓度的线性关系,再将pH不同的2,4-二硝基苯酚在370 nm处的吸收值校正到260 nm处。开发了一种简单快捷无需调节pH测定2,4-二硝基苯酚浓度的方法。     

Intercalation of 2,4-dihydroxybenzophenone-5-sulfonate anion into Zn/Al layered double hydroxides for UV absorption properties

Zn/Al-layered double hydroxides (LDHs) containing the organic anion of 2,4-dihydroxybenzophenone-5-sulfonate (DHBS) have been synthesized by co-precipitation method. Surface, structural, thermal and absorption properties of the ZnAl-DHBS-LDHs nanohybrids were characterized by BET analysis, scanning electron microscope, X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetry and differential thermal analysis and UV–visible spectroscopy. The results revealed that organic UV absorbent-DHBS has been intercalated into the interlayer spaces of ZnAl-LDHs and the intercalation of DHBS in LDHs interlayer galleries resulted to higher thermal stability and better UV absorption ability; these show that the hybrid ZnAl-DHBS-LDHs phase has potential applications as a UV absorber.     

1,4-二[2-(吡啶基)-1,3,4-(噁)二唑基]苯的合成及其光谱性质

利用双二酰肼的脱水化反应制备了两种新颖对称双二噁唑。通过IR、1HNMR、MS及元素分析等对化合物的结构进行表征。研究了此双噁二唑化合物在溶剂DMF中浓度为1×10-7mol/L时的紫外光谱和荧光光谱性质。结果表明:目标化合物在DMF溶液的最大紫外吸收波长在310 nm,最大荧光发射波长在364和383 nm。     

三嗪型紫外线吸收剂的合成及性能

用格氏试剂偶联法合成了4个有代表性的三嗪型紫外线吸收剂:2,4-双(2,4-二羟基苯基)-6-(4-甲氧基苯基)-1,3,5-三嗪、2,4-双(2,4-二羟基苯基)-6-苯基-1,3,5-三嗪、2-(2,4-二羟基苯基)-4,6-二苯基-1,3,5-三嗪和2,4,6-三(2,4-二羟基苯基)-1,3,5-三嗪,测定了它们的紫外光谱。其中,2,4-双(2,4-二羟基苯基)-6-(4-甲氧基苯基)-1,3,5-三嗪在UVB和UVA都有较强吸收,εmax=36000L/(mol.cm)(λmax=313nm),εmax=36333L/(mol.cm)(λmax=344nm),是其中最好的紫外线吸收剂。     

The Involvement of Xanthone and (E)-Cinnamoyl Chromophores for the Design and Synthesis of Novel Sunscreening Agents

Excessive UV exposure contributes to several pathological conditions like skin burns, erythema, premature skin aging, photodermatoses, immunosuppression, and skin carcinogenesis. Effective protection from UV radiation may be achieved with the use of sunscreens containing UV filters. Currently used UV filters are characterized by some limitations including systemic absorption, endocrine disruption, skin allergy induction, and cytotoxicity. In the research centers all over the world new molecules are developed to improve the safety, photostability, solubility, and absorption profile of new derivatives. In our study, we designed and synthesized seventeen novel molecules by combining in the structures two chromophores: xanthone and (E)-cinnamoyl moiety. The ultraviolet spectroscopic properties of the tested compounds were confirmed in chloroform solutions. They acted as UVB or UVA/UVB absorbers. The most promising compound 9 (6-methoxy-9-oxo-9H-xanthen-2-yl)methyl (E)-3-(2,4-dimethoxyphenyl)acrylate) absorbed UV radiation in the range 290–369 nm. Its photoprotective activity and functional photostability were further evaluated after wet milling and incorporation in the cream base. This tested formulation with compound 9 possessed very beneficial UV protection parameters (SPF_{in vitro} of 19.69 ± 0.46 and UVA PF of 12.64 ± 0.32) which were similar as broad-spectrum UV filter tris-biphenyl triazine. Additionally, compound 9 was characterized by high values of critical wavelength (381 nm) and UVA/UVB ratio (0.830) thus it was a good candidate for broad-spectrum UV filter and it might protect skin against UVA-induced photoaging. Compound 9 were also shown to be photostable, non-cytotoxic at concentrations up to 50 µM when tested on five cell lines, and non-mutagenic in Ames test. It also possessed no estrogenic activity, according to the results of MCF-7 breast cancer model. Additionally, its favorable lipophilicity (miLogP = 5.62) does not predispose it to penetrate across the skin after topical application.     

芒果叶提取物广谱防晒性能研究

基于树叶依靠诱导体内合成紫外吸收物质来抵御紫外伤害的生理特性,以树叶为原料提取紫外吸收物,比较不同树叶提取物的紫外吸收情况,结果发现:芒果叶提取物在280~400 nm的防晒区域紫外吸收能力强,强吸收覆盖波段宽,可实现广谱防晒。芒果叶质量浓度4倍于3种化学防晒剂时,其提取物紫外吸收强度高于化学防晒剂,且可在pH=3~7、强太阳光照4 h、80℃、室内存放1年保持稳定,产品化前景好。