Specifications for bituminous surface, open-graded aggregate type, subclass C-4 (Machine mix-asphalt and tar) : effective May 15, 1939 ...

Cover-title.

Novae Suetonii editionis specimen (Caes. C. 4-6)

On reel 78 beginning frame no. 1111.

中国北方草本植物及表土有机质碳同位素组成

Recently, more and more attention has been paid to stable isotope ratios in terrestrial depositional systems. Among them, δ~(13)C value is mainly determined by the surface vegetation, while vegetation is directly related to climate, therefore, carbon isotope ratio in soil organic matter and pedogenic carbonate has been employed as an important paleoecological indicator. In order to test the paleoecological information extracted from stable isotope ratios in terrestrial depositional systems, it is necessary to study the relationships between δ~(13)C value in standing terrestrial plants and today climate, as well as between δ~(13)C value in modern surface soil organic matter and standing vegetation. Thus, these relationships were studied in this paper by means of analysing δ~(13)C in standing plants and modem surface soil organic matter in North China. The main results and conclusions are presented as following: 1. According to their δ~(13)C values, 40 C-4 species represent about 16% of the 257 plant species sarnpled from the North China. C-4 photosynthesis mainly occurs in Poaceae, Cyperaceae and Chenopidaceae families, and percentage representation of C-4 photosynthesis is up to 56% in Poaceae family. 2. The δ~(13)C values of C-3 plant species in North China vary from -21.7‰ to -32.0‰ with an average of -27.1‰, and 93% focus on the range of -24.0‰ ～ -30.0‰; δ~(13)C values of C-4 plant species in North China are between -10.0‰ ～ -15.5‰ with an average of -12.9‰, and 90% concentrate on the range of -11.0‰ ～ -15.0‰. 3. The δ~(13)C composition of C-3 plant species collected from Beijing, a semi-moist district, mainly vary between -27.0‰ ～ -30.0‰, and the average is -28.7‰; the δ ~(13)C values of plants in the semi-arid district, east and west to the Liu Pan Moutain, focus on the range of-26.0‰ ～ -29.0‰ and -25.0‰ ～ -28.0‰, respectively, with the mean value of -27.6‰ and -26.6‰, respectively; the δ~(13)C composition in the arid district dominantly vary from -24.0‰ to -29.0‰, with the average of -26.2‰, and among them, the δ~(13)C values of C-3 plant species in deserts are often between - 22‰ ～ -24‰; the δ~(13)C values in the cold mountain district concentrate on the range of -24.0‰ to -29.0‰, with the average of -26.3‰. 4. The main range of δ~(13)C composition of C-4 plant species, derived from Beijing, a semi-moist district, are -13.0‰ ～ -15.5‰; the semi-arid district, -11.0‰ ～ -14.0‰; the arid district, -11.0‰ ～ -14.0‰. The mean values of them are -14.0‰, -12.4‰,-12.7‰, respectively. 5. From east to west in North China, δ~(13)C values of C-3 plant species increase with longitude. The correlation between δ~(13)C ratios of C-3 plant species and longitude is linear. Changing temperate and precipitation and changing atmosphere pressure are spossible explanations. 6. Almost all C-3 plant species have the trends that their δ~(13)C values gradually increase with decreasing precipitation, decreasing temperature and increasing altitude. Our results show the increases of the δ~(13)C value by 0.30 ～ 0.45‰, 0.19 ～ 0.27‰ and 1.1 ～ 1.2‰ per 100 mm, I℃ and 1000 m, respectively, for all C-3 plant species together. 7. The δ~(13)C values of all C-3 plant species together and a part of C-3 species show highly significant linear correlation with the mean annual temperature, the mean annual precipitation and the altitude, and the results suggest that they can be used as proxies of these environmental variables, while, those without highly significant correlation, may be not suitable as the proxies. 8. The extent, which of responses of δ~(13)C composition to environmental variables, is different for each C-3 plant specie. 9. The δ~(13)C variations along altitude and longitude may be non-linear for C-4 p1ant species in North China. The mean annual temperature may be not important influential factor, thus, it suggests that the δ~(13)C composition of C-4 plant species may be not suitable as the proxy of the mean annual temperature. The influences of summer temperature on δ~(13)C values are much bigger than that of annual temperature, among them, the influence of September temperature is biggest. The mean annual precipitation may be one of the dominant influential factors, and it shows a highly significant non-linear relationship with δ~(13)C values, and the result indicates that δ~(13) C composition of C-4 plant species can be employed as the proxy of the mean annual precipitation. 10. The variations of δ~(13)C ratios do not show systematic trends along longitude, latitude and altitude for modern surface soil organic in Northwest China. ll. The δ~(13)C ratios of modern surface soil organic do not exhibit systematic patterns with temperature and precipitation in Northwest China, it suggests that, unless soil organic is transferred from pure C-3 or C-4 vegetation, the δ~(13)C composition of soil organic may be not used as proxies of climatic variables. 12. The δ~(13)C values of modem surface soil organic are heavier than that of standing vegetation, and the difference ofrnean δ~(13)C between them is -2.18‰. 13. Without considering the δ~(13)C difference between vegetation and soil organic, as well as the δ~(13)C drift in various enviromnent, we may not obtain the valuable information of C-3, C-4 relative biomass in vegetation. 14. The C-4 biomass contribution in vegetation increase with decreasing latitude, increasing longitude and decreasing altitude in Northwest China. The C-4 biomass almost are zero in those regions north to 38 ° N, or west to 100°E, or above 2400 m. 15. The C-4 relative biomass in vegetation increase with growing temperature and precipitation. and, C-4 plants are rare at those regions where the mean annual temperature is less 4 ℃, or the mean annual precipitation is less 200 mm, and their biomass contribution in vegetation are almost zero. Both the mean annual temperature and the mean annual average precipitation may be the important influential factors of C-4 distribution, but the dominant factors.

Anatomical features of species of Cyperaceae from northeastern Brazil

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Regioselective Synthesis of 4-Substituted Indoles via C-H Activation: A Ruthenium Catalyzed Novel Directing Group Strategy

A highly regioselective functionalization of indole at the C-4 position by employing an aldehyde functional group as a directing group, and Ru as a catalyst, under mild reaction conditions (open flask) has been uncovered. This strategy to synthesize 4-substituted indoles is important, as this class of privileged molecules serves as a precursor for ergot alkaloids and related heterocyclic compounds.

Low-dimensional hydrogen-bonded structures in the 1:1 and 1:2 proton-transfer compounds of 4,5-dichlorophthalic acid with the aliphatic Lewis bases triethylamine, diethylamine, n-butylamine and piperidine

The structures of proton-transfer compounds of 4,5-dichlorophthalic acid (DCPA) with the aliphatic Lewis bases triethylamine, diethylamine, n-butylamine and piperidine, namely triethylaminium 2-carboxy-4,5-dichlorobenzoate C~6~H~16~N^+^ C~8~H~3~Cl~2~O~4~^-^ (I), diethylaminium 2-carboxy-4,5-dichlorobenzoate C~4~H~12~N^+^ C~8~H~3~Cl~2~O~4~^-^ (II), bis(n-butylaminium) 4,5-dichlorophthalate monohydrate 2(C~4~H~12~N^+^) C~8~H~2~Cl~2~O~4~^2-^ . H~2~O (III) and bis(piperidinium) 4,5-dichlorophthalate monohydrate 2(C~5~H~12~N^+^) C~8~H~2~Cl~2~O~4~^2-^ . H~2~O (IV)have been determined at 200 K. All compounds have hydrogen-bonding associations giving in (I) discrete cation-anion units, linear chains in (II) while (III) and (IV) both have two-dimensional structures. In (I) a discrete cation-anion unit is formed through an asymmetric R2/1(4) N+-H...O,O' hydrogen-bonding association whereas in (II), one-dimensional chains are formed through linear N-H...O associations by both aminium H donors. In compounds (III) and (IV) the primary N-H...O linked cation-anion units are extended into a two-dimensional sheet structure via amide N-H...O(carboxyl) and ...O(carbonyl) interactions. In the 1:1 salts [(I) and (II)], the hydrogen 4,5-dichlorophthalate anions are essentially planar with short intramolecular carboxylic acid O-H...O(carboxyl) hydrogen bonds [O...O, 2.4223(14) and 2.388(2)A respectively]. This work provides a further example of the uncommon zero-dimensional hydrogen-bonded DCPA-Lewis base salt and the one-dimensional chain structure type, while even with the hydrate structures of the 1:2 salts with the primary and secondary amines, the low dimensionality generally associated with 1:1 DCPA salts is also found.

Gas-phase reactions of aryl radicals with 2-butyne : an experimental and theoretical investigation employing the N-methyl-pyridinium-4-yl radical cation

Aromatic radicals form in a variety of reacting gas-phase systems, where their molecular weight growth reactions with unsaturated hydrocarbons are of considerable importance. We have investigated the ion-molecule reaction of the aromatic distonic N-methyl-pyridinium-4-yl (NMP) radical cation with 2-butyne (CH3C CCH3) using ion trap mass spectrometry. Comparison is made to high-level ab initio energy surfaces for the reaction of NMP and for the neutral phenyl radical system. The NMP radical cation reacts rapidly with 2-butyne at ambient temperature, due to the apparent absence of any barrier. The activated vinyl radical adduct predominantly dissociates via loss of a H atom, with lesser amounts of CH3 loss. High-resolution Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry allows us to identify small quantities of the collisionally deactivated reaction adduct. Statistical reaction rate theory calculations (master equation/RRKM theory) on the NMP + 2-butyne system support our experimental findings, and indicate a mechanism that predominantly involves an allylic resonance-stabilized radical formed via H atom shuttling between the aromatic ring and the C-4 side-chain, followed by cyclization and/or low-energy H atom beta-scission reactions. A similar mechanism is demonstrated for the neutral phenyl radical (Ph center dot)+2-butyne reaction, forming products that include 3-methylindene. The collisionally deactivated reaction adduct is predicted to be quenched in the form of a resonance-stabilized methylphenylallyl radical. Experiments using a 2,5-dichloro substituted methyl-pyridiniumyl radical cation revealed that in this case CH3 loss from the 2-butyne adduct is favoured over H atom loss, verifying the key role of ortho H atoms, and the shuttling mechanism, in the reactions of aromatic radicals with alkynes. As well as being useful phenyl radical analogues, pyridiniumyl radical cations may form in the ionosphere of Titan, where they could undergo rapid molecular weight growth reactions to yield polycyclic aromatic nitrogen hydrocarbons (PANHs).

Aromatic amines and their derivatives. Part 3. The synthesis and crystal structure of 4,4-NN-tetramethyl-NN-dinitroso-2,2-methylenedianiline

The synthesis of 4,4,N,N-tetramethyl-NN-dinitroso-2,2-methylenedianiline (1) by the route p-MeC6H4NH2+ HCHO + OH–(p-MeC6H4NMe)2CH2(7b); (7b)+ acid at 70 °C 4,N-dimethyl-6-(N-methyl-p-toluidinomethyl)aniline (4b); (4b)+ acid at 130 °C 4,4,NN-tetramethyl-2,2-methylenedianiline (3b); (3b)+ HNO2(1), is described. Aspects of the 1H n.m.r. spectra of the above and related compounds are discussed. A crystal-structure analysis of compound (1) shows one of the N-nitroso-groups to be disordered with the endo-form being in preponderance (4 : 1) over the exo-form. The other N-nitroso-group is exclusively exo in the solid state. There is little or no resonance between the benzene ring and the nitroso-group attached to the ring, the two groups being almost perpendicular to each other. In one of the N-nitroso-groups, the nitrogen atom deviates significantly from the plane of the benzene ring to which it is attached. Both amide nitrogen atoms show some pyramidal character.

Structural studies of analgesics and their interactions. Part 4. Crystal structures of phenylbutazone and a 2 : 1 complex between phenylbutazone and piperazine

The X-ray crystal structures of 4-butyl-1,2-diphenylpyrazolidine-3,5-dione (phenylbutazone)(I). and its 2 : 1 complex (II) with piperazine have been determined by direct methods and the structures refined to R 0.096 (2 300 observed reflections measured by diffractometer) and 0.074 (2 494 observed reflections visuallyestimated). Crystals are monoclinic, space group P21/c; for (I)a= 21.695(4), b= 5.823(2), c= 27.881(4)Å, = 108.06 (10)°, Z= 8, and for (II)a= 8.048(4), b= 15.081(4), c= 15.583(7)Å, = 95.9(3)°, Z= 2. The two crystallographically independant molecules in the structure of (I) are similar except for the conformation of the butyl group, which is disordered in one of the molecules. In the pyrazolidinedione group, the two C–C bonds are single and the two C–O bonds double. The two nitrogen atoms in the five-membered ring are pyramidal with the attached phenyl groups lying on the opposite sides of the mean plane of the ring. The phenylbutazone molecule in (II) exists as a negative ion owing to deprotonation of C-4. C-4 is therefore trigonal and the orientation of the Bu group with respect to the pyrazolidinedione group is considerably different from that in (I); there is also considerable electron delocalization along the C–O and C–C bonds. These changes in geometry and electronic structure may relate to biological activity. The doubly charged cationic piperazine molecule exists in the chair form with the nitrogen atoms at the apices. The crystal structure of (II) is stabilized by ionic interactions and N–H O hydrogen bonds.

Unusual Anisotropic Effects from 1,3-Dipolar Cycloadducts of 4-Azidomethyl Coumarins

4-Bromomethylcoumarins (1) reacted with sodium azide in aqueous acetone to give 4-azidomethyl-coumarins (2), which underwent 1,3-dipolar cycloaddition with acetylenic dipolarophiles to give triazoles (3). These triazoles (3) have been found to exhibit interesting variations in the chemical shifts of C-3-H and C-4-methylene protons. Protonation studies indicate that the shielding effect of the C-3-H of coumarin is due to pi-electrons of the triazole ring, further supported by diffraction and computational studies.

1-[2,4,6-Trimethyl-3,5-bis(4-oxopiperidin ylmethyl) benzyl ]piperidin- 4-one

In the structure of the title compound, C27H39N3O3, each of the (4-oxopiperidin-1-yl)methyl residues adopts a flattened chair conformation (with the N and carbonyl groups being oriented to either,side of the central C-4 plane) and they occupy positions approximatelym orthogonal to the central benzene ring [C-benzene-C-C-methylene-N torsion angles 103.4 (2), -104.4 (3) and 71.9 (3)degrees]; further, two of these residues are oriented to one side of the central benzene ring with the third to the other side. In the crystal packing, supramolecular layers in the ab plane are sustained by C-H center dotcenter dot center dot O interactions.

Self-assembly of Ru-4 and Ru-8 assemblies by coordination using organometallic Ru(II)(2) precursors: Synthesis, characterization and properties

Coordination-driven self-assembly of binuclear half-sandwich p-cymene ruthenium(II) complexes [Ru-2(mu-eta(4)-C2O4)(MeOH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1a) or [Ru-2(mu-eta(4)-N,N'-diphenyloxamidato)(MeOH)(2)(eta(6)-p-cymene)(2)]( O3SCF3)(2) (1b) separately with an imidazole-based tetratopic donor L in methanol affords two tetranuclear metallamacrocycles 2a and 2b, respectively. Conversely, the similar combination of L with 2,5-dihydroxy-1,4-benzoquinonato (dhbq) bridged binuclear complex [Ru-2(mu-eta(C6H2O4)-C-4)(MeOH)(2)(eta(6)-p-cymene)(2)](O3SCF3)(2) (1c) in 1:2 molar ratio resulted in an octanuclear macrocyclic cage 2c. All the self-assembled macrocycles 2a-2c were isolated as their triflate salts in high yields and were characterized fully by multinuclear (H-1, C-13 and F-19) NMR, infrared (IR) and electrospray ionization mass spectrometry (ESIMS). In addition, the molecular structure of macrocycle 2a was established unequivocally by single-crystal X-ray diffraction analysis and adopts a tetranuclear rectangular geometry with the dimensions of 5.53 angstrom x 12.39 angstrom. Furthermore, the photo-and electrochemical properties of these newly synthesized assemblies have been studied by using UV-vis absorption and cyclic voltammetry analysis.