906 resultados para Filosofía griega s.II-III
Resumo:
New metal complexes of the type M(nih)(L)](PF6)(n)center dot xAH(2)O and M(nih)(2)](PF6)center dot xH(2)O (where M = Co(III) or Ni(II), L = 1,10-phenanthroline (phen)/or 2,2' bipyridine (bpy), nih = 2-hydroxy-1-naphthaldehyde isonicotinoyl hydrazone, n = 2 or 1 and x = 3 or 2) have been synthesized and characterized by elemental analysis, magnetic, IR and H-1 NMR spectral data. The electronic and magnetic moment 2.97-3.07 B.M. data infers octahedral geometry for all the complexes. The IR data reveals that Schiff base (nih) form coordination bond with the metal ion through azomethine-nitrogen, phenolic-oxygen and carbonyl-oxygen in a tridentate fashion. In addition, DNA-binding properties of these six metal complexes were investigated using absorption spectroscopy, viscosity measurements and thermal denaturation methods. The results indicated that the nickel(II) complex strongly bind with calf-thymus DNA with intrinsic DNA binding constant K-b value of 4.9 x 10(4) M-1 for (3), 4.2 x 10(4) M-1 for (4), presumably via an intercalation mechanism compared to cobalt(III) complex with K-b value of 4.6 x 10(4) M-1 (1) and 4.1 x 10(4) M-1 (2). The DNA Photoclevage experiment shows that, the complexes act as effective DNA cleavage agent. (C) 2012 Elsevier B.V. All rights reserved.
Resumo:
En vista que en Nicaragua y principalmente en la capital Managua, existe una problemática en los establecimientos que se dedican a la venta de productos veterinarios y que brindan servicios directos a la ciudadanía para sus animales se propuso este estudio de tesis; que lleva por título: Evaluación de regencia en farmacias veterinarias de distritos I, II y III de Managua. Para lo cual se procedió a establecer objetivos tales como: Evaluar los tipos de farmacias veterinarias (Agroveterinarias, Farmacias Veterinarias, Farmacias Veterinarias con clínica Integrada y Farmacias Veterinarias Puras) de los distritos I, II, y III de Managua, para esto se efectuó dicho estudio en un periodo de 3 meses mediante visitas y recopilación de la información del 100% de los establecimientos encontrados en la guía telefónica del año 2007, por medio de información obtenida del Ministerio Agropecuario y Forestal (MAGFOR) y finalmente se tomaron en cuenta los establecimientos populares comprobados in situ, en total se evaluaron 20 establecimientos, en los cuales se aplicó una misma encuesta para la recolección de datos.. Los resultados obtenidos, demuestran que el alto porcentaje de las empresas que brindan servicio relacionado con la salud animal no esta siendo atendida por personal especializado, así el 80% de las Agroveterinarias equivalente a 4 establecimientos, actualmente son administradas 3 por comerciantes y una está a cargo de un Zootecnista. El 50% de las farmacias veterinarias son atendidas por Médicos Veterinarios y otro 50% por Comerciantes y Zootecnistas, no obstante aun en las farmacias veterinarias con clínica se encuentran regenciadas por Zootecnistas (9%) y el 91%(9), por Médicos Veterinarios. Se encontró que los 5 establecimientos agroveterinarios no están legalizados por las autoridades competentes del Ministerio Agropecuario y Forestal, 3 de las farmacias veterinarias (75%), laboran ilegalmente y 4 farmacias veterinarias con clínica (36%), brindan servicios a la población ilícitamente. Única y exclusivamente presentan permiso de la alcaldía de Managua. Concluyendo que la mayoría de los establecimientos son atendidos por no profesionales y /o profesionales que no son Médicos Veterinarios, no obstante se encontraron establecimientos atendidos por Médicos Veterinarios, por lo cual se recomienda que todo establecimiento de servicio Veterinario deben ser regenciados por un Médico Veterinario titulado, según citan los incisos 6.1.1 y 6.5.1 de la Norma Técnica Obligatoria Nicaragüense (NTON-20001-03.MAGFOR,2003).
Resumo:
Chapter I
Theories for organic donor-acceptor (DA) complexes in solution and in the solid state are reviewed, and compared with the available experimental data. As shown by McConnell et al. (Proc. Natl. Acad. Sci. U.S., 53, 46-50 (1965)), the DA crystals fall into two classes, the holoionic class with a fully or almost fully ionic ground state, and the nonionic class with little or no ionic character. If the total lattice binding energy 2ε1 (per DA pair) gained in ionizing a DA lattice exceeds the cost 2εo of ionizing each DA pair, ε1 + εo less than 0, then the lattice is holoionic. The charge-transfer (CT) band in crystals and in solution can be explained, following Mulliken, by a second-order mixing of states, or by any theory that makes the CT transition strongly allowed, and yet due to a small change in the ground state of the non-interacting components D and A (or D+ and A-). The magnetic properties of the DA crystals are discussed.
Chapter II
A computer program, EWALD, was written to calculate by the Ewald fast-convergence method the crystal Coulomb binding energy EC due to classical monopole-monopole interactions for crystals of any symmetry. The precision of EC values obtained is high: the uncertainties, estimated by the effect on EC of changing the Ewald convergence parameter η, ranged from ± 0.00002 eV to ± 0.01 eV in the worst case. The charge distribution for organic ions was idealized as fractional point charges localized at the crystallographic atomic positions: these charges were chosen from available theoretical and experimental estimates. The uncertainty in EC due to different charge distribution models is typically ± 0.1 eV (± 3%): thus, even the simple Hückel model can give decent results.
EC for Wurster's Blue Perchl orate is -4.1 eV/molecule: the crystal is stable under the binding provided by direct Coulomb interactions. EC for N-Methylphenazinium Tetracyanoquino- dimethanide is 0.1 eV: exchange Coulomb interactions, which cannot be estimated classically, must provide the necessary binding.
EWALD was also used to test the McConnell classification of DA crystals. For the holoionic (1:1)-(N,N,N',N'-Tetramethyl-para- phenylenediamine: 7,7,8,8-Tetracyanoquinodimethan) EC = -4.0 eV while 2εo = 4.65 eV: clearly, exchange forces must provide the balance. For the holoionic (1:1)-(N,N,N',N'-Tetramethyl-para- phenylenediamine:para-Chloranil) EC = -4.4 eV, while 2εo = 5.0 eV: again EC falls short of 2ε1. As a Gedankenexperiment, two nonionic crystals were assumed to be ionized: for (1:1)-(Hexamethyl- benzene:para-Chloranil) EC = -4.5 eV, 2εo = 6.6 eV; for (1:1)- (Napthalene:Tetracyanoethylene) EC = -4.3 eV, 2εo = 6.5 eV. Thus, exchange energies in these nonionic crystals must not exceed 1 eV.
Chapter III
A rapid-convergence quantum-mechanical formalism is derived to calculate the electronic energy of an arbitrary molecular (or molecular-ion) crystal: this provides estimates of crystal binding energies which include the exchange Coulomb inter- actions. Previously obtained LCAO-MO wavefunctions for the isolated molecule(s) ("unit cell spin-orbitals") provide the starting-point. Bloch's theorem is used to construct "crystal spin-orbitals". Overlap between the unit cell orbitals localized in different unit cells is neglected, or is eliminated by Löwdin orthogonalization. Then simple formulas for the total kinetic energy Q^(XT)_λ, nuclear attraction [λ/λ]XT, direct Coulomb [λλ/λ'λ']XT and exchange Coulomb [λλ'/λ'λ]XT integrals are obtained, and direct-space brute-force expansions in atomic wavefunctions are given. Fourier series are obtained for [λ/λ]XT, [λλ/λ'λ']XT, and [λλ/λ'λ]XT with the help of the convolution theorem; the Fourier coefficients require the evaluation of Silverstone's two-center Fourier transform integrals. If the short-range interactions are calculated by brute-force integrations in direct space, and the long-range effects are summed in Fourier space, then rapid convergence is possible for [λ/λ]XT, [λλ/λ'λ']XT and [λλ'/λ'λ]XT. This is achieved, as in the Ewald method, by modifying each atomic wavefunction by a "Gaussian convergence acceleration factor", and evaluating separately in direct and in Fourier space appropriate portions of [λ/λ]XT, etc., where some of the portions contain the Gaussian factor.
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I. Foehn winds of southern California.
An investigation of the hot, dry and dust laden winds
occurring in the late fall and early winter in the Los Angeles
Basin and attributed in the past to the influences of the desert
regions to the north revealed that these currents were of a
foehn nature. Their properties were found to be entirely due
to dynamical heating produced in the descent from the high level
areas in the interior to the lower Los Angeles Basin. Any dust
associated with the phenomenon was found to be acquired from the
Los Angeles area rather than transported from the desert. It was
found that the frequency of occurrence of a mild type foehn of this
nature during this season was sufficient to warrant its classification
as a winter monsoon. This results from the topography of
the Los Angeles region which allows an easy entrance to the air
from the interior by virtue of the low level mountain passes north
of the area. This monsoon provides the mild winter climate of
southern California since temperatures associated with the foehn
currents are far higher than those experienced when maritime air
from the adjacent Pacific Ocean occupies the region.
II. Foehn wind cyclo-genesis.
Intense anticyclones frequently build up over the high level
regions of the Great Basin and Columbia Plateau which lie between
the Sierra Nevada and Cascade Mountains to the west and the Rocky
Mountains to the east. The outflow from these anticyclones produce
extensive foehns east of the Rockies in the comparatively low
level areas of the middle west and the Canadian provinces of
Alberta and Saskatchewan. Normally at this season of the year very
cold polar continental air masses are present over this territory
and with the occurrence of these foehns marked discontinuity surfaces
arise between the warm foehn current, which is obliged to slide over
a colder mass, and the Pc air to the east. Cyclones are
easily produced from this phenomenon and take the form of unstable
waves which propagate along the discontinuity surface between the
two dissimilar masses. A continual series of such cyclones was
found to occur as long as the Great Basin anticyclone is maintained
with undiminished intensity.
III. Weather conditions associated with the Akron disaster.
This situation illustrates the speedy development and
propagation of young disturbances in the eastern United States
during the spring of the year under the influence of the conditionally
unstable tropical maritime air masses which characterise the
region. It also furnishes an excellent example of the superiority
of air mass and frontal methods of weather prediction for aircraft
operation over the older methods based upon pressure distribution.
IV. The Los Angeles storm of December 30, 1933 to January 1, 1934.
This discussion points out some of the fundamental interactions
occurring between air masses of the North Pacific Ocean in connection
with Pacific Coast storms and the value of topographic and
aerological considerations in predicting them. Estimates of rainfall
intensity and duration from analyses of this type may be made and
would prove very valuable in the Los Angeles area in connection with
flood control problems.
Resumo:
Part I
The spectrum of dissolved mercury atoms in simple liquids has been shown to be capable of revealing information concerning local structures in these liquids.
Part II
Infrared intensity perturbations in simple solutions have been shown to involve more detailed interaction than just dielectric polarization. No correlation has been found between frequency shifts and intensity enhancements.
Part III
Evidence for perturbed rotation of HCl in rare gas matrices has been found. The magnitude of the barrier to rotation is concluded to be of order of 30 cm^(-1).
Resumo:
I. The thermomagnetic behavior and infrared spectroscopic features of KFe3(SO4)2(OH)6 (jarosite), (H3O)Fe3(SO4)2 (OH)6 (hydronium jarosite), KFe3(CrO4)2 (OH)6, Fe(OH)SO4 (basic iron sulfate), and Fe(OH)CrO4 (basic iron chromate) are reported. Fe(OH)CrO4 and KFe3(CrO4)2 (OH)6 are shown to be weak ferro magnets with Curie temperatures of 73 and 71 °K, respectively. This unusual magnetic behavior is rationalized in terms of the ionic spin configurations of the phases. Exchange coupling through chromate bridging groups is shown to be weak.
II. The magnetic behavior and the influence of preparative history on the magnetic behavior of δFeO(OH) is reported. δFeO(OH) is shown to be a fine-particulate, uniaxial, magnetic species. Magnetization data for this species are shown to be consistent with the existence of magnetically inactive layers surrounding magnetic particles.
Resumo:
The determination of bi- and trivalent iron in proximity, in mineral waters has gained in significance, on biological and technical grounds. This short paper describes the procedure of the determination of bivalent iron and total iron in a water sample.
Resumo:
The structural specificity of α-chymotrypsin for polypeptides and denatured proteins has been examined. The primary specificity of the enzyme for these natural substrates is shown to closely correspond to that observed for model substrates. A pattern of secondary specificity is proposed.
A series of N-acetylated peptide esters of varying length have been evaluated as substrates of α-chymotrypsin. The results are interpreted in terms of proposed specificity theories.
The α-chymotrypsin-catalyzed hydrolyses of a number of N-acetylated dipeptide methyl esters were studied. The results are interpreted in terms of the available specificity theories and are compared with results obtained in the study of polypeptide substrates. The importance of non-productive binding in determining the kinetic parameters of these substrates is discussed. A partial model of the locus of the active site which interacts with the R’1CONH- group of a substrate of the form R’1CONHCHR2COR’3 is proposed.
Finally, some reactive esters of N-acetylated amino acids have been evaluated as substrates of α-chymotrypsin. Their reactivity and stereo-chemical behavior are discussed in terms of the specificity theories available. The importance of a binding interaction between the carboxyl function of the substrate and the enzyme is suggested by the results obtained.
Resumo:
Part I
Potassium bis-(tricyanovinyl) amine, K+N[C(CN)=C(CN)2]2-, crystallizes in the monoclinic system with the space group Cc and lattice constants, a = 13.346 ± 0.003 Å, c = 8.992 ± 0.003 Å, B = 114.42 ± 0.02°, and Z = 4. Three dimensional intensity data were collected by layers perpendicular to b* and c* axes. The crystal structure was refined by the least squares method with anisotropic temperature factor to an R value of 0.064.
The average carbon-carbon and carbon-nitrogen bond distances in –C-CΞN are 1.441 ± 0.016 Å and 1.146 ± 0.014 Å respectively. The bis-(tricyanovinyl) amine anion is approximately planar. The coordination number of the potassium ion is eight with bond distances from 2.890 Å to 3.408 Å. The bond angle C-N-C of the amine nitrogen is 132.4 ± 1.9°. Among six cyano groups in the molecule, two of them are bent by what appear to be significant amounts (5.0° and 7.2°). The remaining four are linear within the experimental error. The bending can probably be explained by molecular packing forces in the crystals.
Part II
The nuclear magnetic resonance of 81Br and 127I in aqueous solutions were studied. The cation-halide ion interactions were studied by studying the effect of the Li+, Na+, K+, Mg++, Cs+ upon the line width of the halide ions. The solvent-halide ion interactions were studied by studying the effects of methanol, acetonitrile, and acetone upon the line width of 81Br and 127I in the aqueous solutions. It was found that the viscosity plays a very important role upon the halide ions line width. There is no specific cation-halide ion interaction for those ions such as Mg++, Di+, Na+, and K+, whereas the Cs+ - halide ion interaction is strong. The effect of organic solvents upon the halide ion line width in aqueous solutions is in the order acetone ˃ acetonitrile ˃ methanol. It is suggested that halide ions do form some stable complex with the solvent molecules and the reason Cs+ can replace one of the ligands in the solvent-halide ion complex.
Part III
An unusually large isotope effect on the bridge hydrogen chemical shift of the enol form of pentanedione-2, 4(acetylacetone) and 3-methylpentanedione-2, 4 has been observed. An attempt has been made to interpret this effect. It is suggested from the deuterium isotope effect studies, temperature dependence of the bridge hydrogen chemical shift studies, IR studies in the OH, OD, and C=O stretch regions, and the HMO calculations, that there may probably be two structures for the enol form of acetylacetone. The difference between these two structures arises mainly from the electronic structure of the π-system. The relative population of these two structures at various temperatures for normal acetylacetone and at room temperature for the deuterated acetylacetone were calculated.
Resumo:
Part I
The physical phenomena which will ultimately limit the packing density of planar bipolar and MOS integrated circuits are examined. The maximum packing density is obtained by minimizing the supply voltage and the size of the devices. The minimum size of a bipolar transistor is determined by junction breakdown, punch-through and doping fluctuations. The minimum size of a MOS transistor is determined by gate oxide breakdown and drain-source punch-through. The packing density of fully active bipolar or static non-complementary MOS circuits becomes limited by power dissipation. The packing density of circuits which are not fully active such as read-only memories, becomes limited by the area occupied by the devices, and the frequency is limited by the circuit time constants and by metal migration. The packing density of fully active dynamic or complementary MOS circuits is limited by the area occupied by the devices, and the frequency is limited by power dissipation and metal migration. It is concluded that read-only memories will reach approximately the same performance and packing density with MOS and bipolar technologies, while fully active circuits will reach the highest levels of integration with dynamic MOS or complementary MOS technologies.
Part II
Because the Schottky diode is a one-carrier device, it has both advantages and disadvantages with respect to the junction diode which is a two-carrier device. The advantage is that there are practically no excess minority carriers which must be swept out before the diode blocks current in the reverse direction, i.e. a much faster recovery time. The disadvantage of the Schottky diode is that for a high voltage device it is not possible to use conductivity modulation as in the p i n diode; since charge carriers are of one sign, no charge cancellation can occur and current becomes space charge limited. The Schottky diode design is developed in Section 2 and the characteristics of an optimally designed silicon Schottky diode are summarized in Fig. 9. Design criteria and quantitative comparison of junction and Schottky diodes is given in Table 1 and Fig. 10. Although somewhat approximate, the treatment allows a systematic quantitative comparison of the devices for any given application.
Part III
We interpret measurements of permittivity of perovskite strontium titanate as a function of orientation, temperature, electric field and frequency performed by Dr. Richard Neville. The free energy of the crystal is calculated as a function of polarization. The Curie-Weiss law and the LST relation are verified. A generalized LST relation is used to calculate the permittivity of strontium titanate from zero to optic frequencies. Two active optic modes are important. The lower frequency mode is attributed mainly to motion of the strontium ions with respect to the rest of the lattice, while the higher frequency active mode is attributed to motion of the titanium ions with respect to the oxygen lattice. An anomalous resonance which multi-domain strontium titanate crystals exhibit below 65°K is described and a plausible mechanism which explains the phenomenon is presented.
Resumo:
No presente trabalho é descrita a obtenção de hidrazonas derivadas de isoniazida e de seus complexos de cobre(II) e gálio(III) candidatos a protótipos de fármacos antituberculose e antitumoral. Para investigar o efeito da modificação química sobre as bioatividades do fármaco isoniazida, foram preparados cinco derivados hidrazônicos: 2-piridinocarboxaldeído isonicotinoil hidrazona (HPCIH, 1), 2-acetilpiridina isonicotinoil hidrazona (HAPIH, 2), 2-benzoilpiridina isonicotinoil hidrazona (HBPIH, 3), 2-piridinoformamida isonicotinoil hidrazona (HPAmIH, 4) e 2-pirazinoformamida isonicotinoil hidrazona (HPzAmIH, 5), sendo o composto HPAmIH (4) inédito. Análises de ponto de fusão, espectroscopia de infravermelho (IV), espectrometria de massas, ressonância magnética nuclear (RMN), análise elementar e termogravimetria confirmaram a obtenção e pureza das hidrazonas. Foi determinada ainda a estrutura de HPCIH (1) por difração de raios X de monocristal. Essas moléculas foram efetivas em inibir o crescimento de cepas de micobactérias Mycobacterium tuberculosis H37Rv (ATCC 27294) nas concentrações testadas, com exceção de HPzAmIH (5). As hidrazonas HAPIH (2) e HBPIH (3) foram os compostos orgânicos mais ativos (concentração inibitória mínima, CIM = 0,625 g/mL), apresentando atividade antimicobacteriana apenas duas vezes inferior à do fármaco isoniazida.Quanto à ação contra células tumorais, as hidrazonas HAPIH (2) e HBPIH (3) foram as mais potentes contra as linhagens OVCAR-8 (tumor de ovário - humano), HCT-116 (tumor de cólon - humano) e SF-295 (glioblastoma humano), com inibições de 34,98 a 98,63% do crescimento celular, na concentração de 5 g/mL, enquanto que a isoniazida não foi efetiva contra as linhagens estudadas. Para avaliar o efeito da coordenação a metais sobre a atividade farmacológica das hidrazonas, foram sintetizados os complexos de cobre(II) e gálio(III), sendo todos inéditos: [Cu(HPCIH)Cl2]∙H2O (6), [Cu(HAPIH)Cl2]∙H2O (7), [Cu2(HBPIH)2Cl2]Cl2∙4H2O(8), [Cu(HPAmIH)Cl2]∙H2O (9), [Cu(HPzAmIH)Cl2]∙H2O (10), [Ga(HPCIH)2](NO3)32H2O (11), [Ga(HAPIH)(APIH)](NO3)22H2O (12), [Ga(HPAmIH)(PAmIH)](NO3)22H2O(13) e [Ga(HPzAmIH)(PzAmIH)](NO3)2H2O (14). Os complexos foram caracterizados por espectroscopia de IV, análise elementar, condutivimetria, RMN e espectroscopia eletrônica. Em geral, os complexos também demonstraram ação contra M. tuberculosis, sendo que apenas para 6, 9, 10 e 14 foi verificada melhor atividade em relação às hidrazonas livres. Os complexos metálicos foram tanto quanto ou mais ativos contra as células tumorais OVCAR-8, HCT-116 e SF-295 do que as hidrazonas livres. Merecem destaque os complexos 79 e 12, que apresentaram inibição de crescimento celular de 72,2100%, na concentração de 5 g/mL. Os resultados demonstram portanto que em geral os compostos 114 são menos ativos do que a isoniazida contra M. tuberculosis, enquanto que a modificação química do fármaco, formando-se hidrazonas com posterior complexação cobre(II) e gálio(III) constituíram uma estratégia interessante na obtenção de compostos mais potentes contra células tumorais
Resumo:
Using an all-electron band structure approach, we have systematically calculated the natural band offsets between all group IV, III-V, and II-VI semiconductor compounds, taking into account the deformation potential of the core states. This revised approach removes assumptions regarding the reference level volume deformation and offers a more reliable prediction of the "natural" unstrained offsets. Comparison is made to experimental work, where a noticeable improvement is found compared to previous methodologies.
Resumo:
自从1956年Blake等研究HDEHP萃取铀时发现协同效应以来,由于协同萃取具有可以显著地提高萃取效率,改变萃取选择性等优点,所以对协同萃取进行了大量研究工作,目前已广泛应用于核燃料稀有金属湿法冶金分离分析。但协同萃取研究领域十分广阔,新协萃体系,协萃机理和协萃配合物结构等许多方面还有待进一步研究。Fe~(3+)、Zn~(2+)和Cd~(2+)等过渡金属离子常与稀土离子在一起,成为高纯稀土产品的重要杂质元素,因此寻找Fe(III)、Zn(II)和Cd(II)与RE(III)的新协同萃取分离体系,不但具有理论意义,也有实际意义。本文研究了萃取分离中广泛使用的四种萑取剂,甲基膦酸二(1-甲基庚基)酯(P_(350), 以B表示)、仲碳伯胺N_(1923)(以RNH_2表示)、1-苯基-3-甲基-4-苯甲酰基吡唑酮-5(PMBP,以HL表示)和2-乙基基膦酸单(2-乙基已基)酯(P_(507),以HA表示)对盐酸介质中Fe(III)、Zn(II)、Cd(II)和Nd(III)等金属离子的协同萃取,得到了六个新协萃体系,并且对协萃机理和萃取平稀奇规律等进行了研究,得到了一些有意义的结果。
Resumo:
本论文新银盐分光光度法测定As(III)、As(V)、一甲基胂酸二甲基胂酸。包括三部分:(一)文献综述,对分光光度法测定形态砷的文献作了较为全面的评述,而且总结了其它仪器分析方法对形态砷的测定,并做了比较。(二)新银盐分光光度法测定As(III)、As(V)、一甲基胂酸和二甲基胂酸。该方法主要是在两种不同的酸条件下,分别两两发生四种形态的胂的氢化物,在两个不同波长下测量吸收,利用二元线性回归分析。得四种形态砷的含量。第一步在0.5M柠檬酸和柠檬酸钠的缓冲溶液中,用KBH_4还原片还原As(III)。二甲基胂酸为氢化物,用硝酸银一聚乙烯醇-乙醇吸收液吸收。在405nm和420nm波长处测量吸收;第二步在50%酒石酸介质中,用2片KBH_4发生As(V)、一甲基胂酸的氢化物,同上吸收,测量,二元线性回归分析结果,即得四种形态砷的含量。(三)新银盐分光光度法测定As(III)、As(V)、一甲基胂酸和二甲基胂酸-在实际样品中的应用。本文运用该种分析方法测定了水样、尿样、植扬样品和生物样品中形态砷的含量,取得了比较好的结果,回收率达95%以上。