Crystal chemistry and photomechanical behavior of 3,4-dimethoxycinnamic acid: correlation between maximum yield in the solid-state topochemical reaction and cooperative molecular motion

A new monoclinic polymorph, form II (P2(1)/c, Z = 4), has been isolated for 3,4-dimethoxycinnamic acid (DMCA). Its solid-state 2 + 2 photoreaction to the corresponding alpha-truxillic acid is different from that of the first polymorph, the triclinic form I (P (1) over bar, Z = 4) that was reported in 1984. The crystal structures of the two forms are rather different. The two polymorphs also exhibit different photomechanical properties. Form I exhibits photosalient behavior but this effect is absent in form II. These properties can be explained on the basis of the crystal packing in the two forms. The nanoindentation technique is used to shed further insights into these structure-property relationships. A faster photoreaction in form I and a higher yield in form II are rationalized on the basis of the mechanical properties of the individual crystal forms. It is suggested that both Schmidt-type and Kaupp-type topochemistry are applicable for the solid-state trans-cinnamic acid photodimerization reaction. Form I of DMCA is more plastic and seems to react under Kaupp-type conditions with maximum molecular movements. Form II is more brittle, and its interlocked structure seems to favor Schmidt-type topochemistry with minimum molecular movement.

Structure, chemistry, and energetics of organic and inorganic adsorbates on Ga-rich GaAs and GaP(001) surfaces

The work described in this dissertation includes fundamental investigations into three surface processes, namely inorganic film growth, water-induced oxidation, and organic functionalization/passivation, on the GaP and GaAs(001) surfaces. The techniques used to carry out this work include scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. Atomic structure, electronic structure, reaction mechanisms, and energetics related to these surface processes are discussed at atomic or molecular levels.

First, we investigate epitaxial Zn₃P₂ films grown on the Ga-rich GaAs(001)(6×6) surface. The film growth mechanism, electronic properties, and atomic structure of the Zn₃P₂/GaAs(001) system are discussed based on experimental and theoretical observations. We discover that a P-rich amorphous layer covers the crystalline Zn3P2 film during and after growth. We also propose more accurate picture of the GaP interfacial layer between Zn₃P₂ and GaAs, based on the atomic structure, chemical bonding, band diagram, and P-replacement energetics, than was previously anticipated.

Second, DFT calculations are carried out in order to understand water-induced oxidation mechanisms on the Ga-rich GaP(001)(2×4) surface. Structural and energetic information of every step in the gaseous water-induced GaP oxidation reactions are elucidated at the atomic level in great detail. We explore all reasonable ground states involved in most of the possible adsorption and decomposition pathways. We also investigate structures and energies of the transition states in the first hydrogen dissociation of a water molecule on the (2×4) surface.

Finally, adsorption structures and thermal decomposition reactions of 1-propanethiol on the Ga-rich GaP(001)(2×4) surface are investigated using high resolution STM, XPS, and DFT simulations. We elucidate adsorption locations and their associated atomic structures of a single 1-propanethiol molecule on the (2×4) surface as a function of annealing temperature. DFT calculations are carried out to optimize ground state structures and search transition states. XPS is used to investigate variations of the chemical bonding nature and coverage of the adsorbate species.

Water chemistry and osmoregulation in some arthropods, especially Malacostraca

This article briefly summarises some chief characteristics of osmoregulatory systems in malacostracan crustaceans, evolved to combat hydration, and the limitations thereby imposed on the salinity tolerance and distribution of these animals.

Design, Synthesis, and Study of Novel Platforms for Iron-N2 Chemistry and Photoinduced, Copper-mediated C-N Bond Formation

Several new ligand platforms designed to support iron dinitrogen chemistry have been developed. First, we report Fe complexes of a tris(phosphino)alkyl (CP^iPr₃) ligand featuring an axial carbon donor intended to conceptually model the interstitial carbide atom of the nitrogenase iron-molybdenum cofactor (FeMoco). It is established that in this scaffold, the iron center binds dinitrogen trans to the C_alkyl anchor in three structurally characterized oxidation states. Fe-C_alkyl lengthening is observed upon reduction, reflective of significant ionic character in the Fe-C_alkyl interaction. The anionic (CP^iPr₃)FeN₂^- species can be functionalized by a silyl electrophile to generate (CP^iPr₃)Fe-N₂SiR₃. This species also functions as a modest catalyst for the reduction of N₂ to NH₃. Next, we introduce a new binucleating ligand scaffold that supports an Fe(μ-SAr)Fe diiron subunit that coordinates dinitrogen (N₂-Fe(μ-SAr)Fe-N₂) across at least three oxidation states (Fe^IIFe^II, Fe^IIFe^I, and Fe^IFe^I). Despite the sulfur-rich coordination environment of iron in FeMoco, synthetic examples of transition metal model complexes that bind N₂ and also feature sulfur donor ligands remain scarce; these complexes thus represent an unusual series of low-valent diiron complexes featuring thiolate and dinitrogen ligands. The (N₂-Fe(μ-SAr)Fe-N₂) system undergoes reduction of the bound N₂ to produce NH₃ (~50% yield) and can efficiently catalyze the disproportionation of N₂H₄ to NH₃ and N₂. The present scaffold also supports dinitrogen binding concomitant with hydride as a co-ligand. Next, inspired by the importance of secondary-sphere interactions in many metalloenzymes, we present complexes of iron in two new ligand scaffolds ([SiP^NMe₃] and [SiP^iPr₂P^NMe]) that incorporate hydrogen-bond acceptors (tertiary amines) which engage in interactions with nitrogenous substrates bound to the iron center (NH₃ and N₂H₄). Cation binding is also facilitated in anionic Fe(0)-N₂ complexes. While Fe-N₂ complexes of a related ligand ([SiP^iPr₃]) lacking hydrogen-bond acceptors produce a substantial amount of ammonia when treated with acid and reductant, the presence of the pendant amines instead facilitates the formation of metal hydride species.

Additionally, we present the development and mechanistic study of copper-mediated and copper-catalyzed photoinduced C-N bond forming reactions. Irradiation of a copper-amido complex, ((m-tol)₃P)₂Cu(carbazolide), in the presence of aryl halides furnishes N-phenylcarbazole under mild conditions. The mechanism likely proceeds via single-electron transfer from an excited state of the copper complex to the aryl halide, generating an aryl radical. An array of experimental data are consistent with a radical intermediate, including a cyclization/stereochemical investigation and a reactivity study, providing the first substantial experimental support for the viability of a radical pathway for Ullmann C-N bond formation. The copper complex can also be used as a precatalyst for Ullmann C-N couplings. We also disclose further study of catalytic C_alkyl-N couplings using a CuI precatalyst, and discuss the likely role of [Cu(carbazolide)₂]^- and [Cu(carbazolide)₃]^- species as intermediates in these reactions.

Finally, we report a series of four-coordinate, pseudotetrahedral P₃Fe^II-X complexes supported by tris(phosphine)borate ([PhBP₃Fe^R]^-) and phosphiniminato X-type ligands (-N=PR'₃) that in combination tune the spin-crossover behavior of the system. Low-coordinate transition metal complexes such as these that undergo reversible spin-crossover remain rare, and the spin equilibria of these systems have been studied in detail by a suite of spectroscopic techniques.

Effect of high dietary starch levels on the growth performance, blood chemistry and body composition of gibel carp (Carassius auratus var. gibelio)

An 8-week growth trial was carried out in a semi-recirculation system to investigate the effect of high dietary starch levels on the growth performance, blood chemistry, starch utilization and body composition of gibel carp (Carassius auratus var. gibelio). Five isonitrogenous and isocarloric experimental diets were formulated to contain different starch levels (24%, 28%, 32%, 36% and 40% respectively). Triplicate groups of fish (24 fish per tank with an average body weight, of 8.5 g) were assigned to each diet. The results showed that dietary carbohydrate levels significantly affected the growth performance, hepatopancreatic lipid content, pyruvate kinase (PK) activity and whole-body lipid content. Growth performance, body crude lipid and plasma glucose concentrations showed a decreasing trend with an increase in dietary starch from 24% to 40%. Pyruvate kinase activities and hepatopancreatic lipid content showed an increasing trend with the dietary starch increasing from 24% to 32%, and then a decreasing trend with the dietary starch increasing from 32% to 40%. No significant difference in the hepatopancreatic hexokinase (HK) activity, plasma triglyceride contents, body crude protein, ash and calcium (Ca) and phosphorus (P) contents was observed between different treatments. In conclusion, higher dietary starch levels (32-40%) significantly (P < 0.05) decreased the growth of gibel carp in the present study.

PMo12-doped carbon ceramic composite electrode based on sol-gel chemistry and its electrocatalytic reduction of bromate

A conductive carbon ceramic composite electrode (CCE) comprised of cc-type 1:12 phosphomolybdic acid (PMo12) and carbon powder in an organically modified silicate matrix was fabricated using a sol-gel method and characterized by scanning electron microscopy, cyclic voltammetry, and Osteryoung square-wave voltammetry. Osteryoung square-wave voltammograms of the modified electrode immersed in different acidic aqueous solutions present the dependence of current and redox potential on pH. The PMo12-doped CCE shows more reversible reaction kinetics, good stability and reproducibility, especially the renewal repeatability by simple polishing in the event of surface fouling or dopant leaching. Moreover, the modified electrode shows good catalytic activity for the electrochemical reduction of bromate.

COORDINATION CHEMISTRY AND SUPERCONDUCTIVITY

Analysing the coordination state of copper ions in cuprate superconductors, it is found that the larger the energy splitting between d(x2-y2) and d(z2) orbitals of Cu or the higher the energy of the d(x2-y2) orbital, the higher the Tc. Thus, appropriate coordination structures and strong-field ligands must be chosen for expanding the energy splitting and increasing the energy of the d(x2-y2) orbital when searching for new high-Tc superconductors. Summarizing the experimental results of ESR and XPS, it is considered that the [Cu2+ - O open-square-box 2- - Cu3+] resonance exists in cuprate superconductors and the electron field breathing mode is present. Analysing the mechanism and the relationship between the coordination state of Cu and Tc, we consider that the two dimensional Cu-O planes are responsible for the superconductivity of YBa2Cu3O7-y.

Mineral chemistry and its genetic significance of olivine in Cenozoic basalts from the South China Sea

We dredged lots of Cenozoic basalts from areas covered from the northern sub-slope to the southern sub- slope of the South China Sea. Based on the study on mineral chemistry of clinopyroxenes in these Cenozoic hasalts, this paper indicates that pyroxenes are mostly enstatite and a few of augite, sahlite and Ca-rich pyroxene. Pyroxene microlite has higher content in, Ca, Ti and Fe than pyroxene phenocryst, it may reflect that the evolution trend of host magma of pyroxene is coincidence with that of alkali rock series. The depth of magma chambers which calculated from equilibrium temperatures and pressures between clinopyroxene and melt are as follows, that of magma of tephrite is about 49km, that of magma of trachybasalt is about 25km, and that of magma of basalt is about 15km. Correspondingly, Equilibrium temperatures( K) of three types rocks mentioned above gradually decrease from 1535 1498 to 1429 to 1369. By using discriminant plot which developed from pyroxene and alkali discriminant diagram of host rock, Cenozoic basalt from the South China Sea belongs to intraplate alkali basalt. The results suggest that alkali basalt series in the study area may be the products of continuous evolution of mantle plume, which result from some physical and chemistry process including partial melting and fractional crystallization of mantle plume during the course of its ascent to the surface.