Theoretical study of static electric properties of benzothiazole containing push–pull systems as potential candidates for NLO materials

The dipole moments μ, static polarizabilities , and first hyperpolarizabilities β _vec of benzothiazole based push–pull chromophores have been theoretically investigated by means of SCF-HF and DFT (B3LYP, B3PW91) methods with cc-pVDZ basis sets at geometries optimized with 3-21G basis sets. The main attention has been paid to hyperpolarizability β _vec as a microscopic quantity directly linked with the nonlinear optical (NLO) response of materials with the aim to choose the most suitable candidate(s) for NLO materials from the set of 24 molecules. The 4-dimethylamino-4′-nitrostilbene (DANS) has also been included as a reference compound. The influence of various structural modifications of benzothiazole containing chromophores on μ,, and β _vec has been studied. These modifications involve the variation in unsaturated chain length connecting the aromatic units, different positions of electron withdrawing NO₂ and CN group attached to four possible positions in benzothiazole fragment, addition of the second NO₂ group, and the replacement of benzene by five-membered heteroaromatic rings (pyrrole, furan, thiophene) at N(CH₃)₂ site. The structural parameters, frontier orbitals and relative stabilities of these systems are also reported. The DFT scheme exaggerates the magnitude as well as the chain length dependence of β _vec with respect to the HF results. Both B3LYP and B3PW91 functionals give very close results. The DFT optimized structures are characterized by larger delocalization, planarity, and polarization of substituents. The best candidates for NLO materials have been identified from the studied series based on the β _vec values.     

Effects of the substituting groups and proton abstraction on the nonlinear optical properties of heteroleptic bis-tridentate Ru(II) complexes

The second-order nonlinear optical (NLO) properties have been carried out on a series of Ru(II) complexes with different 4′-substituted terpyridine derivatives and the tridentate ligand 2,6-bis(benzimidazole-2-yl)pyridine by using density functional theory (DFT). The introduction of different substituents enhances the static first hyperpolarizabilities in various degrees. Time-dependent density functional theory (TD-DFT) calculations indicate that the additional metal-to-ligand charge transfer (MLCT) transition, which is vectorially opposite to the intraligand charge transfer (ILCT) transition, could contribute to the smaller β_vec in species with electron-withdrawing groups compared to ones with electron-donating groups. The stepwise deprotonation brings about a change in electron density of the benzimidazole moiety and finally makes the moiety turn to be as donor, which subsequently leads to an efficient second-order NLO switching. For the species 3 with electron-donating group, the β_vec value of the mono-deprotonated system is 49.9 and 11.1 times as small as that of its diprotonated and fully deprotonated ones.     

Study of third-order nonlinear susceptibility of polySchiff base containing triphenylamine

PolySchiff base containing triphenylamine has been synthesized by polycondensation and character-ized by FT-IR,NMR,UV-visible spectrometer. Measurements of the third-order optical nonlinear sus-ceptibility χ(3) by Z-scan technique have shown that the large nonlinearity is dominated by the two-photon absorption in PSB. The sign and size of real part Reχ(3) ,nonlinear refractive index n2 have been measured with the condition of 532 nm,8 ns-duration pulses to be -1.23×10-10 esu,-3.06×10-12 esu;nonlinear absorption index β and size of image part Imχ(3) to be 3.63×10-10 m/W,1.15×10-11 esu,respec-tively,so the third-order nonlinear susceptibility χ(3) is 1.19×10-11 esu. The value is larger than other polymers reported. PSB is self-focusing material and has potential application in nonlinear optic field.     

DFT and TDDFT investigations on the ground and excited states for polynuclear platinum(II) complexes containing the rigid phenylacetylide ligand

We have studied the ground and excited states of the three dendritic polynuclear Pt(II) complexes 1-[Cl(PH3)2PtC≡≡ C]-3,5-[HC≡≡ C]C6H3 (1), 1,3-[Cl(PH3)2PtC≡≡ C]2-5-[HC≡≡ C]C6H3 (2), and 1,3,5-[Cl(PH3)2- PtC≡≡ C]3C6H3 (3), by using the B3LYP and UB3LYP methods, respectively. TDDFT approach with the PCM model was performed to predict the emission spectra properties of 1―3 in CH2Cl2 solution. We first predicted the excited-state geometries for the three complexes. With the change of the number of Pt(II) atom, 1―3 show the different geometry structures in both the ground and excited states; fur- thermore, the increase of the metal density from 1 to 3 results in the red shift of the lowest-energy emissions along the series. The luminescent properties of 1 are somewhat different from those of 2 and 3. The emission properties of 2 and 3 are richer than 1. Our conclusion can give a good support for designing the high efficient luminescent materials.     

Quantum chemical study of redox-switchable second-order optical nonlinearity in Keggin-type organoimido derivative [PW11O39(ReNC6H5)] n− (n = 2–4)

To analyze the effect of redox state changes on the second-order nonlinear optical (NLO) responses of organoimido-functionalized Keggin-type heteropolyanions, the excitation properties and static second-order polarizabilities of fully oxidized state, the first and second reduced states were calculated by means of the time-dependent density functional theory (TDDFT) method combined with the sum-over-states (SOS) formalism. The incorporation of extra electrons causes significant enhancement in the second-order NLO activity. The reduced complexes show more than three times the efficiency of fully oxidized state. Moreover, the NLO activities for PW₁₁Re^VNPh system can also be modified by controlling the spin multiplicity. The high spin state (³ 3) has twice larger β _vec value than the low spin state (¹ 3). The characteristic of the charge-transfer transition corresponding to the dominant contributions to the β _vec values indicates that metal-centered redox processes influence the intramolecular donor or acceptor character, which accordingly leads to the variations in the computed β values. Owing to the reversible and manipulable redox processes, these kinds of the POM-based hybrid complexes could comprise a promising family of three-state redox-switchable molecular device combining chromic, magnetic, and NLO output.     

Host-guest complexes of a water soluble cucurbit[6]uril derivative with some dications of 1,ω-alkyldipyridines: <Superscript>1</Superscript>H NMR and X-ray structures

Interactions between a symmetrical tetramethyl-substituted cucurbit[6]uril (host: TMeQ[6]) and 1,ω-alkylenedipyridine (ω = 2, 4, 6, 8, 10) dicationic guests were investigated using ¹H NMR spectroscopy and single crystal X-ray crystallography. In these inclusion complexes, combined cavity and portal binding in TMeQ[6] were observed, and the length of the bridged alkylene was found to play an important role not only in balancing the overall hydrophilic/hydrophobic interaction between the host and the guest, but also in defining the structure of the resulting inclusion complexes. For the guest 1,2-ethylenedipyridine (Edpy), TMeQ[6] includes a positively charged pyridine ring of Edpy to form an unsymmetrical inclusion complex; for the guest 1,4-butylenedipyridine (Bdpy), TMeQ[6] includes a positively charged pyridine ring of Bdpy, but the different competitive interactions in and between the related inclusion complexes could lead to a fast exchange between the hosts and guests. For the guests with longer bridge chains, such as 1,6-hexamethylenedipyridine (Hdpy) or 1,8-octylenedipyridine (Odpy), a stable pseudorotaxane inclusion complex is formed by combining the hydrophobic cavity and the outer portal dipole-ion interactions. However, for 1,10-decatylenedipyridine (Ddpy), the two TMeQ[6] host molecules include the two end pyridine rings of Ddpy and form a dumbbell inclusion complex. Supported by the National Natural Science Foundation of China (Grant Nos. 20662003 & 20767001), the International Collaborative Project of Guizhou Province (Grant No. 2007400108), the Science Technology Fund of Guizhou Province (Grant No. J-2008-2012) and the Natural Science Youth Foundation of Guizhou University (Grant No. 2007-005)     

Length-Dependent Direction-Tunable Charge-Transfer Behavior of Second-Order Optical Nonlinearity in Keggin-Type Organosilicone Derivative [PW<Subscript>11</Subscript>O<Subscript>39</Subscript>(RSi)<Subscript>2</Subscript>O]<Superscript>3−</Superscript>: A TDDFT Study

The second-order nonlinear optical (NLO) properties of Keggin-type organosilicone derivatives [PW₁₁O₃₉(RSi)₂O]³⁻ are investigated by time-dependent density functional theory (TDDFT). Our results indicated that the length of conjugated chain R has a crucial effect on the charge transfer (CT). The direction of CT alters with the end-cap-substituted electron donating or accepting moieties (NH₂ or NO₂), until the chain length reach a certain length, as the CT originates from the heteropolyanion to organosilicone moiety along the chain, further chain lengthening leaves this behavior invariant. The derivatives with long chain substitution and end-cap-substituted electron acceptor (NO₂) display excellent second-order NLO responses. The system 18 with the relevant long conjugated polyphenylethynyl chain and end-cap-substituted electron acceptor (NO₂) has the largest β ₀ value, 4538.1 × 10⁻³⁰ esu. The present investigation provides important insight into the characteristic of CT and NLO properties of Keggin-type organosilicone derivatives.     

Facile synthesis of small crystal ZSM-5 zeolite by acid-catalyzed hydrolysis of tetraethylorthosilicate

Small crystal zeolites ZSM-5 with sizes of 150–300 nm were synthesized using the colloidal silicate precursors as the silica source created by the acid-catalyzed hydrolysis of tetraethylorthosilicate with tetrapropylammonium bromide as the structure-directing agent within a short crystallization time of 20–35 h. The precursors and final products were detected by XRD, SEM, ICP and DLS. Supported by the National Natural Science Foundation of China (Grant No. 20776069), Key Natural Science Foundation for Universities of Jiangsu Province (Grant No. 06KJA53012), and Program for Changjiang Scholars and Innovative Research Team in University (Grant No. PCSIRT 0732)     

Thermal oxide synthesis and characterization of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> nanorods and Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> nanowires

Fe₃O₄ nanorods and Fe₂O₃ nanowires have been synthesized through a simple thermal oxide reaction of Fe with C₂H₂O₄ solution at 200–600°C for 1 h in the air. The morphology and structure of Fe₃O₄ nanorods and Fe₂O₃ nanowires were detected with powder X-ray diffraction, scanning electron microscopy and transmission electron microscopy. The influence of temperature on the morphology development was experimentally investigated. The results show that the polycrystals Fe₃O₄ nanorods with cubic structure and the average diameter of 0.5–0.8 μm grow after reaction at 200–500°C for 1 h in the air. When the temperature was 600°C, the samples completely became Fe₂O₃ nanowires with hexagonal structure. It was found that C₂H₂O₄ molecules had a significant effect on the formation of Fe₃O₄ nanorods. A possible mechanism was also proposed to account for the growth of these Fe₃O₄ nanorods. Supported by the Fund of Weinan Teacher’s University (Grant No. 08YKZ008), the National Natural Science Foundation of China (Grant No. 20573072) and the Doctoral Fund of Ministry of Education of China (Grant No. 20060718010)     

Assembly, crystal structure, and luminescent properties of three-dimensional (10,3)-a netted rare earth coordination polymers

Solid complexes [REL(NO3)3]n with novel (10,3)-a type three-dimensional networks structure have been assembled using rare earth nitrates and an amide type semirigid tripodal bridging ligand, 1,3,5-tris {[(2′-benzylaminoformyl)phenoxyl]methyl}benzene (L), as building blocks. The complexes were crys- tallized in the orthorhombic system with chiral space group P212121. The whole structure consists of an infinite array of trigonal RE(III) ions bridged by tridentate ligands, and a novel (10,3)-a net is formed, which is very uncommon in the rare earth complexes. At room temperature, the Sm(III), Eu(III), Tb(III), Dy(III) complexes all exhibited characteristic luminescence emissions of central metal ions under UV light excitation.     

X-ray fluorescent and EXAFS studies of the electronic and spatial structure of dialkyl sulfides and their PdCl2 complexes in extraction systems

SK_α, SK_β, ClK_β, ClK_β, and PdL_β2 X-ray fluorescent and PdK EXAFS spectra were obtained for some organic solutions of dialkyl sulfide complexes with palladium chloride. Solvent effects on the electronic and spatial structure of complexes in solution are discussed. In the benzene solution of [PdCl₂2(C₆H₁₃)₂S], complex molecules interact with solvent molecules along a coordinate that is perpendicular to the plane of the complex molecule. Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Translated fromZhurmal Strukturnoi Khimii, Vol. 35, No. 4, pp. 105c111, July–August, 1994. Translated by L. Smolina     

Enantiomer separation by CEC

Three chiral compounds were successfully separated in a short time with two enantiomer separation models on packed-capillary electrochromatography (CEC). (i) 75 μm I.D. capillaries were packed with 5 μm β-cyclodextrin (βCD) chiral stationary phase (CSP). Effects of voltage, pH and concentration of organic modifier on electroosmotic flow (EOF) and chiral separations were investigated systematically. Enantiomers of a neutral compound (benzoin) and a neutral drug (mephenytoin) were separated within a short time with high efficiency. Efficiency of 32 000 theoretical plates per meter and resolution (R8) of 1.42 were achieved for enantiomers of benzoin using a βCD packed column with 6.2crn packed length. Efficiency of 45 000 theoretical plates per meter andR8 of 3.40 were obtained for enantiomers of mephenytoin. Especially, the enantiomer separation of mephenytion was performed in just 3.4 min with R₈ of 2.60. (ii) 75 μm I.D. capillary was packed with octadecylsilica particles (ODs). Chiral separation of a basic drug, propranolol, was studied with chiral agent, via addition of the dimethyl-β-cyclodextrin (DM β-CD) directly into the mobile phase on this column. Baseline separation and efficiency of 81 000 theoretical plates per meter were achieved for propranolol. Project supported by the Natural Science Foundation of Liaoning Province, China, the National Natural Science Foundation of China (Grant No.29875030), and the Excellent Young Scientist Award from the National Natural Science Foundation of China. (Grant No.29725512).     

Photoelectrocatalytic oxidation of GMP on an ITO electrode modified with clay/[Ru(phen)<Subscript>2</Subscript>(dC18bpy)]<Superscript>2+</Superscript> hybrid film

An indium tin oxide (ITO) electrode modified with monolayer clay/[Ru(phen)₂(dC18bpy)]²⁺ (phen=1,10-phenanthroline, dC18bpy = 4,4′-dioctadecyl-2,2′ bipyridyl) hybrid film has been fabricated by the Langmuir-Blodgett (LB) method. Atomic force microscopy revealed that the single-layered hybrid film of clay/[Ru(phen)₂(dC18bpy)]²⁺ (denoted as Clay-Ru) was closely packed at a surface pressure of 25 mN·m⁻¹ and had a thickness of 3.4±0.5 nm. Cyclic voltammograms showed that the redox current of Ru(II) complex decreased when incorporated into the clay film, suggesting that the clay layer acts as a barrier against electron transfer. When applied to oxidizing the mononucleotide of guanosine 5′-monophosphate (GMP), a large catalytic oxidative current was achieved on the Clay-Ru(II) modified ITO electrode at the external potential above 900 mV (vs. Ag|AgCl|KCl) and, more significantly, this response was further enhanced by light irradiation (λ>360 nm), in which the photocurrent is increased about 11 times in comparison with that of a bare ITO. Mechanism of the photoelectrocatalytic effect was proposed in terms of the reduction of the photoelectrochemically generated Ru(III) complex in the Clay-Ru film by GMP. Supported by the National Natural Science Foundation of China (Grant Nos. 20471043 and 20843007), Zhejiang Provincial Natural Science Foundation (Grant Nos. Y404118 and Y408177), the “151” Distinguished Person Foundation of Zheji-ang Province of China, Zhejiang Technology Project Foundation (Grant No. 2007C21134) and Wenzhou Technology Project Foundation (Grant No. N2004B040)     

Metal-amyloid-β peptide interactions: a preliminary investigation of molecular mechanisms for Alzheimer''''s disease

Although humans have spent exactly 100 years combating Alzheimer's disease (AD), the molecular mechanisms of AD remain unclear. Owing to the rapid growth of the oldest age groups of the population and the continuous increase of the incidence of AD, it has become one of the crucial problems to modern sciences. It would be impossible to prevent or reverse AD at the root without elucidating its molecular mechanisms. From the point of view of metal-amyloid-β peptide (Aβ) interactions, we review the molecular mechanisms of AD, mainly including Cu2 and Zn2 inducing the aggregation of Aβ, catalysing the production of active oxygen species from Aβ, as well as interacting with the ion-channel-like structures of Aβ. Moreover, the development of therapeutic drugs on the basis of metal-Aβ interactions is also briefly introduced. With the increasingly rapid progress of the molecular mechanisms of AD, we are now entering a new dawn that promises the delivery of revolutionary developments for the control of dementias.     

Solid-state characterization and dissolution properties of ezetimibe–cyclodextrins inclusion complexes

The objectives of this research were to prepare and characterize inclusion complex of Ezetimibe (EZE) with cyclodextrins (β-cyclodextrin (β-CD) and hydroxypropyl-β-cyclodextrin (HPβ-CD)) and to study the effect of complexation on the dissolution rate of EZE, a water insoluble drug. Phase solubility curve was classified as A _P -type for both cyclodextrins, indicating the 2:1 stoichiometric ratio for β-CD–EZE and HPβ-CD – EZE inclusion complexes. The inclusion complexes in the molar ratio of 2:1 (β-CD–EZE and HPβ-CD–EZE) were prepared by various methods such as kneading, coevaporation and physical mixing. The molecular behaviors of drug in all samples were characterized by fourier-transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC) and powder X-ray diffraction (PXRD) studies. The results of these studies indicated that complex prepared by kneading and coevaporation methods showed inclusion of the EZE molecule into the cyclodextrins cavities. The highest improvement in in-vitro dissolution profiles was observed in complex prepared with hydroxypropyl-β-cyclodextrin using co-evaporation method. Mean dissolution time and similarity factor indicated significant difference between the release profiles of EZE from complexes and physical mixtures and from pure EZE.     

Properties of meso-tetrakis (4- n -alkanoyloxyphenyl) porphyrin liquid crystal Co and Ni complexes

Six series of meso-tetrakis (4-n-alkanoyloxyphenyl) porphyrin Co and Ni complexes (12 kinds) were reported. Nine of the compounds were found to exhibit liquid crystal properties and display a hexagonal columnar discotic columnar (Col_h) phase. Molecular structure of all synthesized compounds was confirmed by IR, UV, MS, ¹H NIVR, and elemental analysis. These liquid crystalline compounds have been studied by cyclic voltammetry, luminescence, and surface photovoltage spectroscopy. Supported by the National Natural Science Foundation of China (Grant No. 59783001), the Natural Science Foundation of Shandong Province (Grant No. Y2006B41), the Foundation of Shandong Provincial Education Department (Grant No. J06A53), the Natural Science Foundation of Shandong University of Technology (Grant No. 2004KJM15) and Doctor Foundation of Shandong University of Technology     

Direct electrochemistry and enzymatic activity of hemoglobin in positively charged colloid Au nanoparticles and hemoglobin layer-by-layer self-assembly films

Alternate adsorption of positively charged colloid-Au nanoparticles (nano-Au⊕) and negatively charged hemoglobin (Hb) on L-cysteine (L-cys) modified gold electrode resulted in the assembly of {Hb/nano-Au⊕}n layer-by-layer films/L-cys modified gold electrode. The nano-Au⊕ was characterized by transmission electron micrograph (TEM) and microelectrophoresis. The modified electrode interface morphology was characterized by electrochemical impedance spectroscopy (EIS), atomic force mi- croscopy (AFM), cyclic voltammograms (CV) and chronoamperometry. Direct electron transfer between hemoglobin and gold electrodes was studied, and the apparent Michaelis-Menten constant ( km app) of the modified electrode was evaluated to be 0.10 mmol·L?1. Moreover, the higher activity of proteins in the nano-Au⊕ films could be retained compared with the electropolymerization membrane, since the pro- teins in nano-Au⊕ films retained their near-native structure. Direct electron transfer between hemoglo- bin and electrode and electrochemically catalyzed reduction of hydrogen peroxide on a modified elec- trode was studied, and the linear range was from 2.1×10-8 to 1.2 ×10?3 mol·L-1 (r = 0.994) with a detection limit of 1.1×10-8 mol·L-1 H2O2.     

Multi-walled carbon nanotubes based catalyst plasmon resonance light scattering analysis of tetracycline hydrochloride

It was found that multi-walled carbon nanotubes (MWNTs) could catalyze the redox reaction between chlorauric acid (HAuCl4) and reductive drugs such as tetracycline hydrochloride (TC), producing gold nanoparticles (Au NPs). By measuring the plasmon resonance light scattering (PRLS) signals of the resulting Au NPs, tetracycline hydrochloride can be detected simply and rapidly with a linear range of 4―26 μmol/L, a correlated coefficient (r ) of 0.9955, and a limit of detection (3σ) of 6.0 nmol/L. This method has been successfully applied to the detection of tetracycline hydrochloride tablets in clinic with the recovery of 101.9% and that of fresh urine samples with the recovery of 98.3%―102.0%.     

Calculation of the molecular exchanging energy of binary surfactants system on the surface monolayer of aqueous solution

By using the binary anionic/cationic surfactants system CH3(CH2)nOSO_3/CH3(CH2)nN (CH3)3 as an ex-ample, the molecular exchanging energy (ε) of adsorption on the surface monolayer of aqueous solu-tion has been studied. ε can be obtained with two methods. One is from the relationship between ε and the molecule interaction parameter (β). This relationship is founded by considering that the adsorption of mixed surfactants on the surface monolayer of solution satisfies the dimensional crystal model condition under which β can be obtained by testing the surface tension of solution. The other is directly from the molecular structure of surfactants with the Lennard-Jones formula. The results for the studied system show that these two methods coincide well.     

Discussions about whether radioactive half life can be changed by mechanic motion

In this essay, some discussions and comments about the paper entitled “Can the decay rate of ³²P be changed by mechanic motion?” (Ding et al., Science in China Series B: Chemistry (Chinese version), 2008, 38(11):1035–1037) are given. It was strongly suggested that its experimental methods, data calculations and conclusion should be reconsidered. After the data were recalculated, the new results supported that the chiral mechanic motion could induce the changes of radioactive half life. Supported by the National Natural Science Foundation of China (Grant Nos. 20571085, and 20877099), Fund of the President of Chinese Academy of Sciences (Grant No. 0521021T04), 2005/2006 USA Li’s Foundation Merit Prize Fund, Fund of Graduate University of Chinese Academy of Sciences (Grant No. 065101HM03), and Fund of the Key Laboratory of Nuclear Analysis of the Institute of High Energy Physics of Chinese Academy of Sciences (Grant No. K129)