Synthesis of a new macrocyclic compound and its self-assembly

A new macrocyclic compound has been synthesized by condensation of pyridine-1-oxide-2,6-dialdehyde with diethylenetria-mine. The self-assemly behaviours were studied by X-ray diffraction. The results show that the self-assembly were controlled by intermolecular hydrogen bonds and π-π stacking effects.     

Physical and chemical properties of a durably efficacious ammonium bicarbonate as a fertilizer and its yield-increasing mechanism

A new fertilizer of cocrystal type,known as durably efficacious ammonium bicarbonate (DEAB),has been developed by adding a certain amount of dicyandiamide (DCD) as an ammonia-stabilizing agent to ammonium bearbenate(AB)during the process of its production.As compared with AB,DEAB was found to have a reduction of direct volatilization loss by 53%,a fertilizer availability period prolonged from 35-45 to 90-110 d,and an increase in the rate of nitrogen in fertilizer being utilized by 5.9%-10.2%,and a saving of the amount of fertilizer to be ap-phed by 20%-30% for the same level of yield,or an increase of the crop yield by over 10% for the same level of ni-tregen fertilization;in addition,it was found to show usually a function of promoting the crop to early mature.It can be apptied as basal dressing all in one time to soil and thus also used as a labour-saving and crop yield-increasing fertil-izer for is non-mtertillage,plastics film covering and water-saving agriculture     

Study on the Total Synthesis of Et 743 and its Analogues： Synthesis of a Tricyclic Intermediate and its 11-Epimer

The tricyclic compound 1, a key intermediate of the pentacyclic core of Et 743 and its analogues, was synthesized. Its 11-epimer was found as the product of racemization when BOP was used as the coupling agen4 but not when BOP-Cl used in the same reaction. The stereochemistry of both isomers was confirmed on basis of the ^1H NMR and NOE-difference spectra.     

Hysteretic spin crossover between a bisdithiazolyl radical and its hypervalent σ-dimer

The bisdithiazolyl radical 1a is dimorphic, existing in two distinct molecular and crystal modifications. The α-phase crystallizes in the tetragonal space group P4?2(1)m and consists of π-stacked radicals, tightly clustered about 4? points and running parallel to c. The β-phase belongs to the monoclinic space group P2(1)/c and, at ambient temperature and pressure, is composed of π-stacked dimers in which the radicals are linked laterally by hypervalent four-center six-electron S···S-S···S σ-bonds. Variable-temperature magnetic susceptibility χ measurements confirm that α-1a behaves as a Curie-Weiss paramagnet; the low-temperature variations in χ can be modeled in terms of a 1D Heisenberg chain of weakly coupled AFM S = (1)/(2) centers. The dimeric phase β-1a is essentially diamagnetic up to 380 K. Above this temperature there is a sharp hysteretic (T↑= 380 K, T↓ = 375 K) increase in χ and χT. Powder X-ray diffraction analysis of β-1a at 393 K has established that the phase transition corresponds to a dimer-to-radical conversion in which the hypervalent S···S-S···S σ-bond is cleaved. Variable-temperature and -pressure conductivity measurements indicate that α-1a behaves as a Mott insulator, but the ambient-temperature conductivity σ(RT) increases from near 10(-7) S cm(-1) at 0.5 GPa to near 10(-4) S cm(-1) at 5 GPa. The value of σ(RT) for β-1a (near 10(-4) S cm(-1) at 0.5 GPa) initially decreases with pressure as the phase change takes place, but beyond 1.5 GPa this trend reverses, and σ(RT) increases in a manner which parallels the behavior of α-1a. These changes in conductivity of β-1a are interpreted in terms of a pressure-induced dimer-to-radical phase change. High-pressure, ambient-temperature powder diffraction analysis of β-1a confirms such a transition between 0.65 and 0.98 GPa and establishes that the structural change involves rupture of the dimer in a manner akin to that observed at high temperature and ambient pressure. The response of the S···S-S···S σ-bond in β-1a to heat and pressure is compared to that of related dimers possessing S···Se-Se···S σ-bonds.     

An investigation on a novel PDLC film's fabrication and its electro-optical properties

A polymer dispersed liquid crystal (PDLC) film that has good electro-optical properties is produced by the method of polymerized-induced phase separation. Based on the application foreground, its capability parameters, such as contrast ratio, work voltage, and visual angle, are characterized for the first time by a white light but not a fixed wavelength light. The results show the PDLC film has a low work-voltage of 20 V, more than 150° visual angle, high stability, and long lifetime. The differences between plastic and glass ITO-coated substrates of PDLC films are also studied in this paper. The plastic substrate has better property and will have a wider perspective especially in the portable, tender and folded display devices. Due to adjustable properties of film by electric field, PDLC has the potential application for display device, sensor, switch, grating, and new generation analytical apparatus.     

Studies on the Synthesis of a Natural Product—Piceatannol and its Analogs

Piceatannol,(E)-3,3′,4,5′-tetrahydroxy stilbene, a natural polyhydroxy stibene, possesses many biological activities, its synthesis has been reported. We designed another route of its synthesis, which can be controlled more easily. The synthetic product was characterized by elemental analysis,IR,MS and ^1H-NMR. Its analogs were synthesized by the similar method.     

Synthesis of a Polymer—bound Sensitizer and its Application in the Photoisomeriz

A polymer-bound photosensitizer was synthesized by the reaetion of Merritield resin with 9-anthraeenemethanol in the presence of potassium hydride.The photoisomerization of trans-vitamin D3 to cis-vitamin D3 was earried out with this polymer-bound photosensitizer in ethanol and toluene solutions.The experiment results demonstrate that this solid photosensitizer is efficient for the photoismerization and easy for separation from the reaetion mixtures.     

Synthesis of a New Cobalt （Ⅱ） Complex and its Interaction with DNA

A new complex of bis(N-benzyl benzotriazole-N^3) dichloro Co(Ⅱ) (Co(Ⅱ)L2Cl2) was synthesized and its crystal was characterized. The interaction of this new complex with fs-DNA was studied by electrochemical and UV spectrophotometric method. In 0.01 mol/L pH 4.2 Tris-HCl buffer solution Co(Ⅱ)L2Cl2 has two reductive peaks with peak potentials at 0.38 V and 0.27 V, respectively, and an oxidative peak at 1.05 V. After the addition of DNA, the peak currents decrease and the peak potential at 0.27 V shifts negatively. The UV spectrophotometric experiment indicates that the maximum absorbance of Co(Ⅱ)L2Cl2 at 204 nm decreases and exhibits bathochromic shift after the addition of DNA. All the results reveal that Co(Ⅱ)L2Cl2binds with DNA by intercalation as well as electrostatic interaction.     

Synthesis of a New Cobalt (II) Complex and its Interaction with DNA

The interaction of metal complexes with DNA has been widely studied by differentmethods such as spectrophotometry, light scattering technique, fluorometry1-3. Manycomplexes such as Co(phen)2 ,Co(en)2 ,Fe(EDTA)2- etc.4,5 have been synthesized and 3+ 3+their effect on DNA has been studied in order to further explain the mechanism of genemutation, anti-cancer or cancer-induced reason and DNA targeted drugs. In this paper,a new cobalt complex was synth…     

p-Phenylenecarbenonitrene and its halogen derivatives: how does resonance interaction between a nitrene and a carbene center affect the overall electronic configuration?

A series of para-conjugatively coupled phenylenecarbenonitrenes [(4-nitrenophenyl)methylene (3a), (4-nitrenophenyl)fluoromethylene (3b), (4-nitrenophenyl)chloromethylene (3c), and (4-nitrenophenyl)bromomethylene (3d)] were generated in argon matrix at low temperature (10 or 13 K) and characterized by IR and UV/vis spectroscopy. Density functional theory (B3LYP/6-31G(d)) and ab initio (MCSCF, CASPT2) methods were used to study the ground- and some low-lying excited states of 3a-d. The experimental and computational data suggest that 3a-d have singlet ground states (S0) and can be thought of as quinonoidal biradicals. In all cases, the lowest triplet (T1) and quintet (Q1) states lie about 2 kcal mol(-1) and 28-29 kcal mol(-1), respectively, higher in energy than S0. On the other hand the substituent is found to have a significant effect on the relative energy of the second excited triplet (T2) state. This state tends to become relatively more stable as the ability of the substituent to enforce a closed-shell configuration at the carbene subunit increases. Interestingly, the energy difference between the T2 and S0 states in 3a-d is found to depend linearly on the S-T gap of the corresponding phenylcarbenes 7a-d. This relationship is helpful in predicting when a substituted p-phenylenecarbenonitrene may have a triplet ground state instead of a singlet one.     

The relationship between the eigenvalues and eigenvectors of a similarity matrix and its associated Carbó index matrix

The eigenvalues and eigenvectors of a quantum similarity matrix are also generalized eigenvalues and eigenvectors of the associated matrix of Carbó indices. This establishes bounds on the spectrum of the Carbó index matrix; for example, a quantum similarity matrix is positive semidefinite if and only if the associated Carbó index matrix is also positive semidefinite. The generalized eigenvalue problem for the Carbó index matrix has a diagonal metric matrix on the right-hand-side. Every generalized eigenvalue problem can be written in this diagonal form (i.e., this form is not special to this application). This diagonally structure generalized eigenvalue problem is especially convenient because it can be converted to a conventional eigenvalue problem by a particularly simple partial Löwdin transformation.     

Preparation and characterization of a water resistance flame retardant and its enhancement on charring–forming for polycarbonate

Hexakis(4-nitrophenoxy) cyclotriphosphazene (HNTP) was synthesized and was added into polycarbonate (PC) functioned as intumescent flame retardant and charring agent. The chemical structure of HNTP was confirmed by hydrogen and phosphorus nuclear magnetic resonance (¹H-NMR, ³¹P-NMR), energy-dispersive spectroscopy and Fourier transform infrared (FTIR). Flame retardancy and charring–forming behaviors of HNTP- and PC-based composites were extensively investigated with the limiting oxygen index, UL-94 vertical burning test, microscale combustion calorimeter (MCC) and thermogravimetric analysis. The water resistance of PC-based composites was studied by stationary water contact angle measurements. Furthermore, TG/FTIR was used to research their gaseous products and their releasing intensity during the decomposition. The morphology and chemical structure of residual char were used to study scanning electron microscopy (SEM) analyses and FTIR spectroscopy. The mechanical properties of samples were compared by tensile and impact tests.     

Identification of a novel cannabimimetic phenylacetylindole, cannabipiperidiethanone, as a designer drug in a herbal product and its affinity for cannabinoid CB₁ and CB₂ receptors

A new cannabimimetic phenylacetylindole (cannabipiperidiethanone, 1) has been found as an adulterant in a herbal product which contains two other known synthetic cannabinoids, JWH-122 and JWH-081, and which is distributed illegally in Japan. The identification was based on analyses using GC-MS, LC-MS, high-resolution MS and NMR. Accurate mass spectrum measurement showed the protonated molecular ion peak of 1 at m/z 377.2233 [M+H]? and the molecular formula of 1 was C??H??N?O?. Both mass and NMR spectrometric data revealed that 1 was 2-(2-methoxyphenyl)-1-{1-[(1-methylpiperidin-2-yl)methyl]-1H-indol-3-yl}ethanone. Compound 1 has a mixed structure of known cannabimimetic compounds: JWH-250 and AM-2233. Namely, the moiety of phenylacetyl indole and N-methylpiperidin-2-yl-methyl correspond to the structure of JWH-250 and AM-2233, respectively. However, no synthetic, chemical or biological information about 1 has been reported. A binding assay of compound 1 to cannabinoid receptors revealed that 1 has affinity for the CB? and CB? (IC??=591, 968 nM, respectively) receptors, and shows 2.3- and 9.4-fold lower affinities than those of JWH-250. This is the first report to identify cannabimimetic compound (1) as a designer drug and to show its binding affinity to cannabinoid receptors.     

Synthesis and characterization of a novel organic–inorganic hybrid supramolecular recognition material and its selective adsorption for cesium

To separate Cs(I) from highly active liquid waste, a macroporous silica-based 25, 27-bis(iso-propyloxy)calix[4]arene-26,28-crown-6 (BiPCalix[4]C6) supramolecular recognition material, BiPCalix[4]C6/SiO₂–P, was synthesized and characterized by SEM, FT-IR, and TG-DSC. The adsorption properties of BiPCalix[4]C6/SiO₂–P and a macroporous polymer-based supramolecular recognition composite, BiPCalix[4]C6/XAD-7, were compared. It was found that BiPCalix[4]C6/SiO₂–P exhibited better adsorption ability and faster adsorption dynamics than BiPCalix[4]C6/XAD-7. The adsorption isotherm of Cs(I) onto BiPCalix[4]C6/SiO₂–P was studied at 298 K and it was well described by Langmuir isotherm model. The complex composition between BiPCalix[4]C6/SiO₂–P and Cs(I) was determined as 1:1 type by investigating the effect of the concentrations of BiPCalix[4]C6, Cs(I), and H⁺ on the adsorption. Meanwhile, the selectivity of BiPCalix[4]C6/SiO₂–P towards Na(I), K(I), Rb(I), Cs(I), Sr(II), Ba(II), Ru(III), Mo(VI), La(III), and Y(III) was investigated.     

Transient species and its properties of melatonin

Reactive oxygen species (ROS) are generated dur- ing radiation, respiratory burst, normal metabolic processes and so on. There are enzymatic and non-enzymatic antioxidants such as superoxide dis- mutase (SOD), glutathione peroxidase (GSH-Px), vi- tamin E (VE) and carotenoids that can either inhibit or repair the ROS-induced damage. ROS is essential to maintain physiological homeostasis. However, exces- sive ROS give rise to oxidative damage to proteins, lipids and DNA which related t…     

Synthesis of γ-benzyltert-butoxycarbonyl-L-alanyl-D-glutamate and its derivatives

A convenient method of obtaining Boc-L-Ala-D-iGln-OBzl and its amide analogs by condensing the N-hydroxysuccinimidyl ester of Boc-L-Ala with the -benzyl ester ofD-Glu in the presence of NaHCO₃, followed by amidation of the resulting Boc-L-Ala-D-Glu--OBzl, is proposed. The use of l-adamantylamine and octadecylamine as amino components has enabled the corresponding -adamantylamide and octadecylamide of the dipeptide to be obtained.Simferopol' State University, 4 Yaltinskaya ul., Simferopol', Crimea, Ukraine 333036. Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 101–103, January–February, 1998.     

Total synthesis and cytotoxicity of (−)-jorumycin and its analogues

(?)-Jorumycin and its 15 C-22 analogues were prepared employing l-tyrosine as the chiral starting material via 21 steps. These analogues, along with (?)-jorumycin itself, were evaluated in vitro for cytotoxicity against HCT-8, BEL-7402, Ketr3, A2780, MCF-7, A549, BGC-823, Hela, HELF, and KB cells. The IC₅₀ values of the cytotoxicity of most of these analogs were at the level of nM, which was similar to that of (?)-jorumycin. Among these analogs including (?)-jorumycin, hippuric acid ester derivative 23 exhibited the most potent and broad-spectrum cytotoxic activity against the ten cell lines with an average IC₅₀ of 2.12 nM.     

Synthesis and Application of a New Acrylic Ester Resin for Recycling SIPA from its Water Solution

A new acrylic ester polymer YWB-7 resin was prepared and characterized. The properties of YWB-7 resin were compared with those of the commercial Amberlite XAD-7, Diaion HP2MG and hypercrosslinked macroporous polymer NDA-150 resins. Both surface area and micropore area of YWB-7 resin were bigger than those of XAD-7 resin and HP2MG resin. The YWB-7 resin was successfully employed to recycle 5-sodiosulfoisophthalic acids （SIPA） from its solutions with and without methanol.