Synthesis and G-quadruplex binding studies of new 4-N-methylpyridinium porphyrins

A series of cationic porphyrins carrying 1-3 meso-N-pyridinium groups has been synthesised, and their binding to G-quadruplex DNA has been explored by surface plasmon resonance (SPR) and circular dichroism spectroscopy. Two trans substituents appear to be sufficient for tight binding; preferential binding to the anti-parallel intramolecular human telomeric DNA was observed for the A2trans and A3 porphyrins. The A2trans is able to induce the formation of an anti-parallel G-quadruplex in a K+ free solution, mimicking the effect of a molecular chaperone.     

Reversible Stereoselective Folding/Unfolding Fueled by the Interplay of Photoisomerism and Hydrogen Bonding

A linear molecular architecture equipped with complementary three‐fold hydrogen‐bonding units embedded with a photoswitchable trans ‐tetrafluoroazobenzene moiety was synthesized. The trans to cis photoisomerism of the azobenzene unit induced drastic changes in the molecular architecture as a result of intramolecular hydrogen bonding as evidenced by NMR spectroscopy and size exclusion chromatography. A minute stereogenic element in the linear trans state enabled stereoselective folding into the cis state, thus producing a globular architecture with enhanced chiroptical property.     

Light-driven molecular hinge: a new molecular machine showing a light-intensity-dependent photoresponse that utilizes the trans-cis isomerization of azobenzene

[reaction: see text] A new class of molecular machine exhibits a hingelike motion upon photoirradiation. The motion (close and open) can be operated by alternate irradiation with UV and visible light. The trans/trans and cis/cis isomers are thermally stable at 40 degrees C, and the photochemical closure reaction (from trans/trans to cis/cis isomer) is dependent on the intensity of the light used because of the short-lived intermediate (trans/cis isomer).     

Possible conformations of the seven-membered rings and relative stabilities of the C10 epimers oftrans,trans-,trans,cis-, andcis,trans-linked pseudoguai-11(13)-EN-8,12-olides

A calculation has been made by the molecular mechanics method of the CIO-epimers of trans,trans-, trans,cis-, and cis,trans-linked pseudoguai-11(13)-en-8,12-olides. Possible conformations in these compounds and probabilities of their realization have been determined.     

Crystallinity and thermal properties of polyamides containing cis- and trans-1,3-cyclohexane rings

The cyclohexane ring-containing polyamide 1,3-CBMA-6 was synthesized from 1,3-cyclohexane-bismethylamine (1,3-CBMA) and adipic acid (6), and effects of cis/trans isomers of the ring on crystallinity and thermal properties were studied. Polymers with high cis and high trans contents, respectively, were made by polymerizing the 1,3-CBMA-6 salts of 98% cis and 93% trans derived from the salt of 75/25 (cis/trans) by fractional crystallization. A polymer with 97% cis content was highly crystalline, with a melting temperature of 253°C, while one with 93% trans contents was amorphous. In contrast to this, little difference was found in the glass transition temperature of 97 and 84°C. These results indicate that the isomers affect the conformation of the molecular chains, which determines the crystallinity and melting temperature, but they do not much affect the mobility of the chains as manifested by the glass transition.     

假1,2-二苯乙烯型偶氮苯合成、表征及其光致异构性能

合成系列假1,2-二苯乙烯型偶氮苯,利用FT-IR、NMR、ESI-MS和元素分析等技术手段确定目标化合物结构,并通过UV-Vis光谱研究其光致变色性能,测定其溶液态光致顺反异构速率常数,同时考察其在聚甲基丙烯酸甲酯掺杂薄膜中抗疲劳性能,结果表明,目标化合物在乙酸乙酯中π-π^*能级低于n-π^*能级,且两个能级出现重叠,异构转变速率常数数量级10^-1~10⁰ s^-1,反→顺异构转变速率常数k_t受到偶极-偶极作用力和空间位阻效应影响,偶极-偶极作用力对单溴代物的k_t影响比二溴代物大,空间位阻效应对二溴代物的k_t影响比单溴代物大,顺→反异构转变速率常数k_c与k_t大小顺序相反,在聚甲基丙烯酸甲酯掺杂薄膜中有良好的抗疲劳性能。     

Syntheses of bisazo‐containing polymethacrylates using atom transfer radical polymerization and the photoalignment behavior

Three kinds of photoresponsive polymethacrylates containing different bisazo chromophores were prepared with atom transfer radical polymerization and characterized with proton nuclear magnetic resonance, gel permeation chromatography, and ultraviolet–visible spectra. These polymers had similar molecular weights, molecular weight distributions, glass‐transition temperatures, and absorption coefficients. The irradiation of these polymer films with a linearly polarized laser could induce birefringence because of the reorientation of the bisazo chromophores through trans–cis–trans isomerization cycles of double azo bonds, and the corresponding mechanism was also examined. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4237–4247, 2004     

新的钌环丙烷化催化体系的探索(Ⅱ) 氮膦配体立体化学结构控制顺反比选择性的初步研究

本文研究了一个新的钌催化的苯乙烯环丙烷化反应催化体系。当该催化体系用三氟甲磺酸银预处理后其催化的环丙烷化反应产物的顺反比接近1：1,且顺式产物略微占优。这在环丙烷化反应中是不多见的。我们用分子力学／动力学对该催化体系进行了模拟。结果表明键能并非是决定产物顺反比的主要因素,但是对于非键能来说,由于中间体M1与苯乙烯作用生成顺式产物时的范德华作用非常强,它弥补了由静电能所引起的能量上的不利因素。所以总能量对生成顺式产物较为有利。但是由于生成顺式产物与反式产物的总能量差别不大（2．5kcal.mol^-1),所以环丙烷化产物的顺反比接近1：1。这是氮膦配体立体化学结构控制产物选择性的结果。     

1-萘酚的紫外共振双光子电离光谱

利用脉冲分子束技术, 在305-322 nm范围内研究了1-萘酚(1NP)的共振双光子电离(R2PI)光谱. 1NP分子存在cis和trans两种旋转异构体, 但实验中仅观测到trans异构体的电子振动跃迁光谱, 其S1←S0跃迁的(0-0)带头出现在317.90 nm(即31456 cm-1)位置. 利用光谱选律及ab initio和密度泛函(DFT)计算, 对trans异构体在S1态的振动模进行标识, 得出主要对应于对称性为a'的平面内振动模. 计算显示, cis异构体在电子基态S0的能量较trans异构体高出439 cm-1, 而第一激发能却比trans异构体的低1216 cm-1, 与之相应的实验值分别是220和274 cm-1. 计算数值与实验结果在能量变化趋势上完全一致. 共振双光子电离谱中没有观测到cis异构体的光谱信号, 其原因可归结为分子束的有效冷却效应使得处于基态的cis异构体的布居数密度相对trans异构体极低, 导致cis光谱信号太小而未能被探测到.     

Pt碘乙二胺配合物的DFT和DV-Xα研究

利用密度泛函DFT/LANL2DZ和DV-Xα，对两种Pt(IV)碘配合物trans，cis-[Pt (OAc)_2I_2(en)] (A)，trans，cis-[Pt(OH)_2I_2(en)] (B)及它们的光照产物 [Pt(OAc)_2(OH)I(en)] (C)，[Pt(OH)_3I(en)] (D)完成了几何优化；计算了配合 物能级、光谱、前线轨道组成、电荷布居等性质。计算结果能解释有关的实验现象 。     

Porphyrins 27. Synthesis of metal complexes of cis-1,2-bis(octaethyl-5-porphyrinyl)ethylene and their transformation into the trans isomers

The synthesis of the Cu, Ni, and Zn complexes of cis-1,2-bis(octaethyl-5-porphyrinyl)ethylene has been carried out and their transformation into the corresponding trans isomers has been investigated under various conditions. The crystal and molecular structure of the Ni complex of trans-1,2-bis(octaethyl-5-porphyrinyl)ethylene was determined by x-ray structural analysis. It was shown that the Zn and Ni complexes of the cis isomer were readily converted into the trans isomers in chloroform. A stepwise introduction of Ni atoms into the trans dimer was discovered on heating it with Ni(OAc)₂ in DMF. The conversion of the Zn complex of the cis dimer into the trans dimer was facilitated on adding pyridine.For Communication 26 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1339–1344, October, 1993.The author is sincerely grateful to Professor Y. Sakata for making this investigation possible, to Professor Y. Kai for the XSA of complex (Ib), to Dr. Y. Takai for plotting the PMR spectra, and to Professor K. M. Smith for his interest in the work.     

The observation of cis residues in poly(L-proline) in aqueous solution.

Proton Fourier transform NMR spectra at 270 MHz were obtained for three different molecular weight samples of poly(L-proline) in D2O. A weak, but clearly discernable, resonance at 4.3 ppm was observed in each case with an integrated intensity about 2-3% of the Calpha trans proton resonance. Based on the Torchia-Bovey assignment this resonance is attributed to the Calpha cis proton. The presence of cis residues, even in this small concentration, necessitates a reexamination of the conformational properties of this polymer. Definite conclusions cannot be reached from spectra obtained in organic solvents because of the much smaller separation between the cis and trans resonances.     

Conformations of the rings and relative stabilities of isomers of trans,trans- and trans,cis-eudesman-8,12-olides

A series of isomers of trans,trans- and trans,cis-eudesman-8,12-olides has been investigated by the method of molecular mechanics (MMM). Questions of the energetic suitability of particular isomers, of the influence of the orientation of substituents attached to the basic skeleton on their conformation, and of the relative stabilities of the conformers with different methods of linking the rings are considered. A. N. Nesmeyanov Institute of Heteroorganic Compounds, USSR Academy of Sciences, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 334–338, May–June, 1990.     

Conformations of the rings and relative stabilities of isomers of trans,trans- and trans,cis-eudesman-8,12-olides

A series of isomers of trans,trans- and trans,cis-eudesman-8,12-olides has been investigated by the method of molecular mechanics (MMM). Questions of the energetic suitability of particular isomers, of the influence of the orientation of substituents attached to the basic skeleton on their conformation, and of the relative stabilities of the conformers with different methods of linking the rings are considered.A. N. Nesmeyanov Institute of Heteroorganic Compounds, USSR Academy of Sciences, Moscow. Translated from Khimiya Prirodnykh Soedinenii, No. 3, pp. 334–338, May–June, 1990.     

Molecular structure of the trans and cis isomers of metal-free phthalocyanine studied by gas-phase electron diffraction and high-level quantum chemical calculations: NH tautomerization and calculated vibrational frequencies

The molecular structure of the trans isomer of metal-free phthalocyanine (H2Pc) is determined using the gas electron diffraction (GED) method and high-level quantum chemical calculations. B3LYP calculations employing the basis sets 6-31G**, 6-311++G**, and cc-pVTZ give two tautomeric isomers for the inner H atoms, a trans isomer having D2h symmetry and a cis isomer having C2v symmetry. The trans isomer is calculated to be 41.6 (B3LYP/6-311++G**, zero-point corrected) and 37.3 kJ/mol (B3LYP/cc-pVTZ, not zero-point corrected) more stable than the cis isomer. However, Hartree-Fock (HF) calculations using different basis sets predict that cis is preferred and that trans does not exist as a stable form of the molecule. The equilibrium composition in the gas phase at 471 degrees C (the temperature of the GED experiment) calculated at the B3LYP/6-311++G** level is 99.8% trans and 0.2% cis. This is in very good agreement with the GED data, which indicate that the mole fraction of the cis isomer is close to zero. The transition states for two mechanisms of the NH tautomerization have been characterized. A concerted mechanism where the two H atoms move simultaneously yields a transition state of D2h symmetry and an energy barrier of 95.8 kJ/mol. A two-step mechanism where a trans isomer is converted to a cis isomer, which is converted into another trans isomer, proceeds via two transition states of C(s) symmetry and an energy barrier of 64.2 kJ/mol according to the B3LYP/6-311++G** calculation. The molecular geometry determined from GED is in very good agreement with the geometry obtained from the quantum chemical calculations. Vibrational frequencies, IR, and Raman intensities have been calculated using B3LYP/6-311++G**. These calculations indicate that the molecule is rather flexible with six vibrational frequencies in the range of 20-84 cm(-1) for the trans isomer. The cis isomer might be detected by infrared matrix spectroscopy since the N-H stretching frequencies are very different for the two isomers.     

Stereochemistry of cyclic compounds Communication 66. Stereochemistry of the oxidation of the maleic anhydride adduct of trans-6-acetoxy-8a-methyl-1-vinyl-δ-1-octalin with peracetic acid

Conclusions A study was made of the stereochemistry of the oxidation by peracetic acid of 7-acetoxy-⁴(12)-dodecahydro-13-methyl-1,2-phenanthrenedicarboxylic acid, its diester, and its anhydride, which have trans annellation of the A and B rings and a trans disposition of the carboxy groups relative to the angular methyl group. On the basis of an examination of molecular models the configurations of the isomeric epoxy anhydrides are discussed, and their behavior on hydrolysis is studied.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1203–1209, July, 1966.     

EXCITED STATES AND PHOTOBIOLOGICAL PROPERTIES OF POTENTIAL DNA CROSS-LINKING AGENTS, THE BENZODIPYRONES

Abstract —Potential DNA cross-linking agents, benzo{1,2-b:4,5-b'}dipyran-2,8-dione ( cis -benzodipyrone) and benzo{1,2-b:4,5-b'}dipyran-2,7-dione ( trans -benzodipyrone), have been synthesized. The excited triplet states of these reagents resemble those of other coumaryl derivatives in their spectroscopic assignments and characteristics and thus their reactivites. In particular, trans -benzodipyrone is significantly more reactive toward pyrimidine bases in solution than the other coumaryl derivatives examined, by virtue of its possessing two reactive pyrone C=C bonds within the molecular framework. The unique reactivity of trans -benzodipyrone, with its two reactive pyrone bonds across the long molecular axis, appears to be reflected in its ability to photoinduce mutation in certain Bacillus subtilis strains. This preliminary study provides data that will be useful in designing experiments to elucidate the molecular mechanisms for the biological activities of these compounds.     

Crystallographic and chiroptical studies on tetraarylferrocenes for use as chiral rotary modules for molecular machines

A crystal structure of the racemic form of chiral molecular scissors 1 with a trans configuration at the azobenzene unit (rac-trans-1), in which the scissors adopt a closed geometry with two blade phenyl groups that overlap each other, was successfully determined. X-ray crystallographic determination of the structure of (1S,1'S)-10, which is a derivative of the key precursor of trans-1, was also successful. On the basis of the crystal structure of (1S,1'S)-10, the absolute configuration of 1 and related molecular machines, such as molecular pedal 2, and self-locking rotor 3, which all contain a chiral tetrasubstituted ferrocene module, were determined. A correlation between the absolute configuration and the circular dichroism properties of these molecular machines and their synthetic precursors was also determined.     

Properties of Polyurethanes Based on Mesogenic Diol and 4,4'-methylenebis(cyclohexyl Isocyanate)

New polyurethanes with mesogenic units in the main chain due to the use of a liquid crystalline chain extender were synthesized from 4,4'-methylenebis(cyclohexyl isocyanate) (HMDI)using diisocyanates of different trans, trans isomer content, a low molecular diol4,4'-bis(6-hydroxyhexoxy)biphenyl (BHHBP) and a high molecular poly(hexyleneadipate)diol (PHA). The growth of trans, trans isomer content in HMDI used to syntheses of PU induces monotonic growth of melting point, rectilinear growth of crystallization temperatures and the growth of crystallization enthalpy, both for hard segment polyurethanes and block polyurethanes. The increase of trans, trans isomer content in HMDI increases also glass transition temperatures and dynamic storage modulus of the polyurethanes. This revised version was published online in August 2006 with corrections to the Cover Date.