Your browser doesn't support javascript.
loading
Mostrar: 20 | 50 | 100
Resultados 1 - 20 de 135
Filtrar
1.
J Plant Physiol ; 167(13): 1066-75, 2010 Sep 01.
Artigo em Inglês | MEDLINE | ID: mdl-20392520

RESUMO

Leaf growth is one of the first physiological processes affected by changes in plant water status under drought. A decrease in leaf expansion rate usually precedes any reduction in stomatal conductance or photosynthesis. Changes in leaf size and stomatal opening are potential adaptive mechanisms, which may help avoid drought by reducing transpiration rate, and can be used to improve rice genotypes in water-saving cultivation. The indica rice cultivar IR64 and four of its near-isogenic lines (NILs; BC(3)-derived lines) unique for leaf size traits, YTK 124 (long leaves), YTK 127 (broad leaves), YTK 205 (short leaves) and YTK 214 (narrow leaves), were compared in this study for changes in leaf growth and its water status. The plants were subjected to two soil water regimes, well-watered and progressive soil drying measured by the fraction of transpirable soil water (FTSW). Applied drought reduced leaf number, total leaf area, specific leaf area, plant biomass, tiller number, plant height, stomatal conductance, amount of water transpired, leaf relative water content, and leaf water potential more in IR64 and the NILs than in the respective controls; nonetheless, transpiration efficiency (TE) was slightly higher under drought than in the well-watered controls. NILs with broader leaves had higher biomass (and its individual components), less stomatal conductance, and higher TE under drought than NILs with narrow and shorter leaves. Under drought, leaf number was positively correlated with tiller number and plant height; nonetheless, root weight and total biomass, water transpired and TE, and plant height and TE were positively correlated with each other. However, a negative correlation was observed between stomatal conductance and the FTSW threshold at which normalized transpiration started to decline during soil drying. Overall, the IR64-derived lines with broader leaves performed better than NILs with narrow and short leaves under drought.


Assuntos
Secas , Oryza/anatomia & histologia , Oryza/fisiologia , Folhas de Planta/anatomia & histologia , Folhas de Planta/fisiologia , Estresse Fisiológico , Biomassa , Endogamia , Estômatos de Plantas/fisiologia , Transpiração Vegetal/fisiologia , Característica Quantitativa Herdável
2.
Proc Natl Acad Sci U S A ; 106(41): 17302-7, 2009 Oct 13.
Artigo em Inglês | MEDLINE | ID: mdl-19805171

RESUMO

Nitrification, a key process in the global nitrogen cycle that generates nitrate through microbial activity, may enhance losses of fertilizer nitrogen by leaching and denitrification. Certain plants can suppress soil-nitrification by releasing inhibitors from roots, a phenomenon termed biological nitrification inhibition (BNI). Here, we report the discovery of an effective nitrification inhibitor in the root-exudates of the tropical forage grass Brachiaria humidicola (Rendle) Schweick. Named "brachialactone," this inhibitor is a recently discovered cyclic diterpene with a unique 5-8-5-membered ring system and a gamma-lactone ring. It contributed 60-90% of the inhibitory activity released from the roots of this tropical grass. Unlike nitrapyrin (a synthetic nitrification inhibitor), which affects only the ammonia monooxygenase (AMO) pathway, brachialactone appears to block both AMO and hydroxylamine oxidoreductase enzymatic pathways in Nitrosomonas. Release of this inhibitor is a regulated plant function, triggered and sustained by the availability of ammonium (NH(4)(+)) in the root environment. Brachialactone release is restricted to those roots that are directly exposed to NH(4)(+). Within 3 years of establishment, Brachiaria pastures have suppressed soil nitrifier populations (determined as amoA genes; ammonia-oxidizing bacteria and ammonia-oxidizing archaea), along with nitrification and nitrous oxide emissions. These findings provide direct evidence for the existence and active regulation of a nitrification inhibitor (or inhibitors) release from tropical pasture root systems. Exploiting the BNI function could become a powerful strategy toward the development of low-nitrifying agronomic systems, benefiting both agriculture and the environment.


Assuntos
Brachiaria/fisiologia , Poaceae/fisiologia , Brachiaria/enzimologia , Diterpenos/metabolismo , Lactonas/metabolismo , Nitratos/metabolismo , Nitrogênio/metabolismo , Fixação de Nitrogênio/fisiologia , Nitrosomonas/metabolismo , Oxirredução , Oxirredutases/metabolismo , Raízes de Plantas/efeitos dos fármacos , Raízes de Plantas/fisiologia , Compostos de Amônio Quaternário/química , Compostos de Amônio Quaternário/farmacologia , Clima Tropical
3.
Neuroradiology ; 48(1): 50-3, 2006 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-16261335

RESUMO

We describe two patients with symptomatic vasospasms after aneurysmal subarachnoid hemorrhage who were successfully treated with intraarterial injection of colforsin daropate hydrochloride (HCl). Colforsin daropate HCl is capable of directly stimulating adenylate cyclase, which in turn causes vasorelaxation via elevated intracellular concentrations of cyclic adenosine monophosphate. We suggest that colforsin daropate HCl might be a useful therapeutic tool in treating cerebral vasospasm.


Assuntos
Colforsina/análogos & derivados , Hemorragia Subaracnóidea/tratamento farmacológico , Vasoespasmo Intracraniano/tratamento farmacológico , Angiografia Cerebral , Colforsina/administração & dosagem , Colforsina/uso terapêutico , Feminino , Humanos , Injeções Intra-Arteriais , Pessoa de Meia-Idade , Hemorragia Subaracnóidea/complicações , Hemorragia Subaracnóidea/diagnóstico , Tomografia Computadorizada de Emissão de Fóton Único , Vasoespasmo Intracraniano/diagnóstico , Vasoespasmo Intracraniano/etiologia
4.
Bioprocess Biosyst Eng ; 26(3): 141-5, 2004 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-14872334

RESUMO

To maximize nitrogen utilization rates during nitrification and denitrification in a simultaneous reaction for direct nitrogen removal from ammonia-nitrogen in a single reactor, two different carriers were applied that immobilized nitrifiers and denitrifiers separately. With the optimized DO concentration and mixing ratio of immobilization carriers, ammonium-nitrogen was successfully removed as designed until the middle phase of treatment where nitrogen removal rate was higher than 83% of the theoretical value, although an imbalance between nitrification and denitrification occurred at a later phase of treatment where residual nitrate-nitrogen concentration was less than 2 mg/l. The new approach using two different carriers to immobilize nitrifiers and denitrifiers separately was proved useful for controlling both nitrification and denitrification rates, enabling the utilization of maximum treatment ability of both nitrifiers and denitrifiers in a single reactor for direct nitrogen removal from ammonium-nitrogen.


Assuntos
Amônia/metabolismo , Bactérias Aeróbias/metabolismo , Reatores Biológicos/microbiologia , Nitrogênio/metabolismo , Oxigênio/metabolismo , Purificação da Água , Resinas Acrílicas , Aerobiose , Bactérias Aeróbias/crescimento & desenvolvimento , Células Imobilizadas/metabolismo , Eliminação de Resíduos Líquidos
5.
J Am Chem Soc ; 123(50): 12458-65, 2001 Dec 19.
Artigo em Inglês | MEDLINE | ID: mdl-11741408

RESUMO

In the presence of scandium triflate, an efficient photoinduced electron transfer from the triplet excited state of C(60) to p-chloranil occurs to produce C(60) radical cation which has a diagnostic NIR (near-infrared) absorption band at 980 nm, whereas no photoinduced electron transfer occurs from the triplet excited state of C(60) (3C(60)) to p-chloranil in the absence of scandium ion in benzonitrile. The electron-transfer rate obeys pseudo-first-order kinetics and the pseudo-first-order rate constant increases linearly with increasing p-chloranil concentration. The observed second-order rate constant of electron transfer (k(et)) increases linearly with increasing scandium ion concentration. In contrast to the case of the C(60)/p-chloranil/Sc(3+) system, the k(et) value for electron transfer from 3C(60) to p-benzoquinone increases with an increase in Sc(3+) concentration ([Sc(3+)]) to exhibit a first-order dependence on [Sc(3+)], changing to a second-order dependence at the high concentrations. Such a mixture of first-order and second-order dependence on [Sc(3+)] is also observed for a Sc(3+)-promoted electron transfer from CoTPP (TPP(2-) = tetraphenylporphyrin dianion) to p-benzoquinone. This is ascribed to formation of 1:1 and 1:2 complexes between the generated semiquinone radical anion and Sc(3+) at the low and high concentrations of Sc(3+), respectively. The transient absorption spectra of the radical cations of various fullerene derivatives were detected by laser flash photolysis of the fullerene/p-chloranil/Sc(3+) systems. The ESR spectra of the fullerene radical cations were also detected in frozen PhCN at 193 K under photoirradiation of the fullerene/p-chloranil/Sc(3+) systems. The Sc(3+)-promoted electron-transfer rate constants were determined for photoinduced electron transfer from the triplet excited states of C(60), C(70), and their derivatives to p-chloranil and the values are compared with the HOMO (highest occupied molecular orbital) levels of the fullerenes and their derivatives.

6.
Jpn Heart J ; 42(4): 393-408, 2001 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-11693276

RESUMO

Coronary dissection after plain old balloon angioplasty often shows regression during follow-up. This study sought to determine whether we can predict such phenomenon angiographically. We analyzed 64 patients with 71 type B-D coronary dissections determined by the National, Heart, Lung, and Blood Institute (NHLBI) criteria. Regression was considered present when minimal lumen diameter increased by more than 0.3 mm during follow-up. Dissections were divided into subgroups using the NHLBI criteria and our classification in which type a and b dissections were characterized by the width of a dissection lumen exceeding one quarter of the reference diameter with the outer edge of the dissection lumen within the boundary of reference in type a and beyond it in type b. In type c and type d dissections, the width of the dissection lumen was within one quarter of the reference with its outer edge within the boundary of reference in type c and beyond it in type d. Type e dissection had a protruding flap or spiral appearance. Regression was recognized in 23.9%. The distribution of dissection types was similar in the groups with and without regression by the NHLBI criteria, but type c dissection had regression more frequently than the other types of coronary dissections (p<0.001) using our classification.


Assuntos
Angioplastia Coronária com Balão/efeitos adversos , Angiografia Coronária , Doença das Coronárias/diagnóstico por imagem , Reestenose Coronária/diagnóstico por imagem , Vasos Coronários/lesões , Idoso , Doença das Coronárias/classificação , Vasos Coronários/patologia , Feminino , Seguimentos , Humanos , Masculino , Pessoa de Meia-Idade
7.
J Org Chem ; 66(24): 8026-9, 2001 Nov 30.
Artigo em Inglês | MEDLINE | ID: mdl-11722200

RESUMO

The photooxidation reactions of olefins sensitized by the excited triplet states of bisazafullerene (C(59)N)(2) and hydroazafullerene C(59)HN have been studied. Oxidation yields were compared with those of pristine C(60). The singlet oxygen yields are also determined directly from the emission intensities, which are in good agreement with the oxidation yields. The triplet states of (C(59)N)(2) and C(59)HN have been identified by the time-resolved spectroscopic method by observing the triplet-triplet absorption spectra, which decay in the presence of oxygen. It has been proven that (C(59)N)(2) and C(59)HN have the ability to sensitize the reactions via singlet oxygen in about half of the efficiency of that of pristine C(60). For both azafullerenes, the triplet lifetimes are shorter than that of pristine C(60), which may be related to the nitrogen atom embedded in the C(60) moiety.

8.
J Am Chem Soc ; 123(43): 10676-83, 2001 Oct 31.
Artigo em Inglês | MEDLINE | ID: mdl-11673999

RESUMO

The photochemical and electrochemical properties of four chlorin-C60 or porphyrin-C60 dyads having the same short spacer between the macrocycle and the fullerene are examined. In contrast with all the previous results on porphyrin-fullerene dyads, the photoexcitation of a zinc chlorin-C60 dyad results in an unusually long-lived radical ion pair which decays via first-order kinetics with a decay rate constant of 9.1 x 10(3) x s(-1). This value is 2-6 orders of magnitude smaller than values reported for all other porphyrin or chlorin donor-acceptor of the molecule dyad systems. The formation of radical cations of the donor part and the radical anion of the acceptor part was also confirmed by ESR measurements under photoirradiation at low temperature. The photoexcitation of other dyads (free-base chlorin-C60, zinc porphyrin-C60, and free-base porphyrin-C60 dyads) results in formation of the ion pairs which decay quickly to the triplet excited states of the chlorin or porphyrin moiety via the higher lying radical ion pair states as is expected from the redox potentials.


Assuntos
Carbono/química , Fulerenos , Metaloporfirinas/química , Porfirinas/química , Zinco/química , Eletroquímica , Espectroscopia de Ressonância de Spin Eletrônica , Radicais Livres/química , Cinética , Fotoquímica , Porfirinas/síntese química , Espectrometria de Fluorescência , Espectrofotometria Ultravioleta
9.
Hypertens Res ; 24(5): 551-7, 2001 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-11675950

RESUMO

Recent studies have demonstrated that cytochrome P450-dependent metabolites of arachidonic acid (CYP450-AA) play important roles in the control of renal vascular resistance (RVR). In the present study, we examined the possible involvement of CYP450-AA in the vasoconstrictor action of angiotensin II (Ang II) on the afferent arterioles (Af-Arts), a vascular segment crucial to the control of RVR. Rabbit Af-Arts were microperfused at 60 mmHg in vitro, and the vasoconstrictor action of Ang II (10(-11)-10(-8) M, added to both the bath and lumen) was examined with or without blocking the activity of CYP450 epoxygenase or hydroxylase. Ang II decreased the luminal diameter of Af-Arts in a dose-dependent manner (34+/-2% of control diameter at 10(-8) M, n=9, p<0.0001). Pretreatment with miconazole, an inhibitor of CYP450 epoxygenase, at 10(-6) M decreased the basal diameter by 14+/-1% (n=6, p<0.01) and augmented the vasoconstrictor action of Ang II (7+/-3% of control diameter at 10(-8) M, p<0.001 vs. without miconazole). This augmentation was abolished by blocking the Ang II type 2 (AT2) receptor with PD 123319 at 10(-7) M. In contrast, pretreatment with 17-octadecynoic acid (17-ODYA, 10(-6) M), which inhibits both epoxygenase and hydroxylase activity, had no effect on the basal diameter but attenuated the vasoconstrictor action of Ang 11(46+/-2% of control diameter at 10(-8) M, p<0.01 vs. without 17-ODYA). Our results demonstrate that in the Af-Art, endogenous CYP450-AA are involved not only in the control of basal tone but also in the action of Ang II. Further, it appears that the CYP450 epoxygenase pathway attenuates Ang II action via AT2 receptors.


Assuntos
Angiotensina II/farmacologia , Sistema Enzimático do Citocromo P-450/metabolismo , Circulação Renal/efeitos dos fármacos , Circulação Renal/fisiologia , Vasoconstritores/farmacologia , Antagonistas de Receptores de Angiotensina , Animais , Ácido Araquidônico/metabolismo , Arteríolas/efeitos dos fármacos , Arteríolas/metabolismo , Relação Dose-Resposta a Droga , Inibidores Enzimáticos/farmacologia , Ácidos Graxos Insaturados/farmacologia , Ácidos Hidroxieicosatetraenoicos/metabolismo , Masculino , Miconazol/farmacologia , Norepinefrina/metabolismo , Coelhos , Receptor Tipo 2 de Angiotensina , Receptores de Angiotensina/metabolismo , Resistência Vascular/efeitos dos fármacos , Resistência Vascular/fisiologia , Vasoconstrição/efeitos dos fármacos , Vasoconstrição/fisiologia
10.
J Am Chem Soc ; 123(32): 7756-66, 2001 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-11493049

RESUMO

The lowest excited state of aromatic carbonyl compounds (naphthaldehydes, acetonaphthones, and 10-methylacridone) is changed from the n,pi triplet to the pi,pi singlet which becomes lower in energy than the n,pi triplet by the complexation with metal ions such as Mg(ClO(4))(2) and Sc(OTf)(3) (OTf = triflate), which act as Lewis acids. Remarkable positive shifts of the one-electron reduction potentials of the singlet excited states of the Lewis acid-carbonyl complexes (e.g., 1.3 V for the 1-naphthaldehyde-Sc(OTf)(3) complex) as compared to those of the triplet excited states of uncomplexed carbonyl compounds result in a significant increase in the redox reactivity of the Lewis acid complexes vs uncomplexed carbonyl compounds in the photoinduced electron-transfer reactions. Such enhancement of the redox reactivity of the Lewis acid complexes leads to the efficient C-C bond formation between benzyltrimethylsilane and aromatic carbonyl compounds via the Lewis-acid-promoted photoinduced electron transfer. The quantum yield determinations, the fluorescence quenching, and direct detection of the reaction intermediates by means of laser flash photolysis experiments indicate that the Lewis acid-catalyzed photoaddition reactions proceed via photoinduced electron transfer from benzyltrimethylsilane to the singlet excited states of Lewis acid-carbonyl complexes.

11.
J Am Chem Soc ; 123(35): 8459-67, 2001 Sep 05.
Artigo em Inglês | MEDLINE | ID: mdl-11525652

RESUMO

A charge-shift type of photoinduced electron-transfer reactions from various electron donors to the singlet excited state of 10-decylacridinium cation (DeAcrH+) in a nonpolar solvent (benzene) is found to be as efficient as those of 10-methylacridinium cation (MeAcrH+) and DeAcrH+ in a polar solvent (acetonitrile). Irradiation of the absorption bands of MeAcrH+ in acetonitrile solution containing tetraalkyltin compounds (R(4)Sn) results in the efficient and selective reduction of MeAcrH+ to yield the 10-methyl-9-alkyl-9,10-dihydroacridine (AcrHR). The same type of reaction proceeds in benzene when MeAcrH+ is replaced by DeAcrH+ which is soluble in benzene. The photoalkylation of R'AcrH+ (R' = Me and De) also proceeds in acetonitrile and benzene using 4-tert-butyl-1-benzyl-1,4-dihydronicotinamide (Bu(t)BNAH) instead of R(4)Sn, yielding MeAcrHBu(t). The quantum yield determinations, the fluorescence quenching of R'AcrH+ by electron donors, and direct detection of the reaction intermediates by means of laser flash photolysis experiments indicate that the photoalkylation of R'AcrH+ in benzene as well as in acetonitrile proceeds via photoinduced electron transfer from the alkylating agents (R(4)Sn and Bu(t)BNAH) to the singlet excited states of R'AcrH+. The limiting quantum yields are determined by the competition between the back electron-transfer process and the bond-cleavage process in the radical pair produced by the photoinduced electron transfer. The rates of back electron transfer have been shown to be controlled by the solvent polarity which affects the solvent reorganization energy of the back electron transfer. When the free energy change of the back electron transfer (DeltaG(0)(bet)) in a polar solvent is in the Marcus inverted region, the rate of back electron transfer decreases with decreasing the solvent polarity, leading to the larger limiting quantum yield for the photoalkylation reaction. In contrast, the opposite trend is obtained when the DeltaG(0)(bet) value is in the normal region: the limiting quantum yield decreases with decreasing the solvent polarity.

12.
Photochem Photobiol ; 74(1): 22-30, 2001 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-11460533

RESUMO

Photoinduced electron-transfer processes in the systems of chlorophylls (Chl) (chlorophyll-a [Chl-a] and chlorophyll-b) and fullerenes (C60/C70) in both polar and non-polar solvents have been investigated with nanosecond laser photolysis technique, observing the transient spectra in the visible/near-IR regions. By the excitation of Chl in benzonitrile (BN) it has been proved that electron transfer takes place from the triplet excited states of Chl to the ground states of C60/C70. By the excitation of C70 in BN electron transfer takes place from the ground states of Chl to the triplet excited state of C70. In both Chl the rate constants and quantum yields for the electron-transfer processes are as high as those of zinc porphyrins and zinc phthalocyanines, indicating that the long alkyl chains of Chl play no role in retarding the electron transfer. The rate constant for the electron-mediating process from the radical anion of C70 to octylviologen dication yielding the octylviologen radical cation was evaluated. The back electron-transfer process from the viologen radical cation to the radical cation of Chl-a takes place in a longer time-scale, indicating that a photosensitized electron-transfer/electron-mediating cycle is achieved.


Assuntos
Carbono/efeitos da radiação , Clorofila/efeitos da radiação , Fulerenos , Carbono/química , Clorofila/química , Clorofila A , Transporte de Elétrons/efeitos da radiação , Lasers , Fotoquímica , Fotólise , Fármacos Fotossensibilizantes/química , Fármacos Fotossensibilizantes/efeitos da radiação
13.
J Am Chem Soc ; 123(4): 702-8, 2001 Jan 31.
Artigo em Inglês | MEDLINE | ID: mdl-11456584

RESUMO

The photophysical properties of tetra-tert-butylphthalocyaninatosilicon (SiPc) covalently linked to one or two 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) radicals (R1, R2) have been studied by fluorescence, transient absorption, and time-resolved electron paramagnetic resonance (TREPR) spectroscopies. It is found that the fluorescence quantum yields and lifetimes of R1 and R2 decrease compared with those of (dihydroxy)SiPc ((dihydroxy)SiPc = 6.8 ns, R1 = 4.7 ns and 42 ps, and R2 = 4.7 ns and <30 ps). Transient absorption measurements indicate that the lifetime of the excited triplet SiPc is markedly dependent on the number of linking TEMPO radicals ((dihydroxy)SiPc = 500 micros, R1 = 7.6 micros, and R2 = 3.7 micros). These short lifetimes of R1 and R2 in the excited states are explained as a result of the interaction with TEMPO changing the ISC between the singlet and triplet states to spin-allowed transitions. Quantitative TREPR investigations have been carried out for the radical-quartet pair mechanism of R1 and the photoinduced population transfer of R2. It is determined that the rise and decay times of these electron spin polarizations denote the spin-lattice relaxation time of the ground state and the lifetime of the excited multiplet state, respectively. This study contributes not only to an elucidation of radical-chromophore interactions but also to a novel approach for controlling magnetic properties by photoexcitation.

14.
J Am Chem Soc ; 123(11): 2571-5, 2001 Mar 21.
Artigo em Inglês | MEDLINE | ID: mdl-11456926

RESUMO

Dioxygen accelerates back electron transfer (BET) processes between a fullerene radical anion (C60) and a radical cation of zinc porphyrin (ZnP) in photolytically generated ZnP.+-C60.- and ZnP.+-H2P-C60.- radical ion pairs. The rate constant of BET increases linearly with increasing oxygen concentration without, however, forming reactive oxygen species, such as singlet oxygen or superoxide anion. When ferrocene (Fc) is used as a terminal electron donor moiety instead of ZnP (i.e., Fc-ZnP-C60), no catalytic effects of dioxygen were, however, observed for the BET in Fc+-ZnP-C60.-, that is, from C60.- to the ferricenium ion. In the case of ZnP-containing C60 systems, the partial coordination of O2 to ZnP.+ facilitates an intermolecular electron transfer (ET) from C60.- to O2. This rate-determining ET step is followed by a rapid intramolecular ET from O2.- to ZnP.+ in the corresponding O2.--ZnP.+ complex and hereby regenerating O2. In summary, O2 acts as a novel catalyst in accelerating the BET of the C60.--ZnP.+ radical ion pairs.


Assuntos
Metaloporfirinas/química , Oxigênio/farmacologia , Catálise , Elétrons
15.
J Am Chem Soc ; 123(11): 2607-17, 2001 Mar 21.
Artigo em Inglês | MEDLINE | ID: mdl-11456930

RESUMO

Photoinduced charge separation (CS) and charge recombination (CR) processes have been examined in various porphyrin-fullerene linked systems (i.e., dyads and triads) by means of time-resolved transient absorption spectroscopy and fluorescence lifetime measurements. The investigated compounds comprise a homologous series of rigidly linked, linear donor-acceptor arrays with different donor-acceptor separations and diversified donor strength: freebase porphyrin-C60 dyad (H2P-C60), zincporphyrin-C60 dyad (ZnP-C60), ferrocene-zincporphyrin-C60 triad (Fc-ZnP-C60), ferrocene-freebase porphyrin-C60 triad (Fc-H2P-C60), and zincporphyrin-freebase porphyrin-C60 triad (ZnP-H2P-C60). Most importantly, the lowest lying charge-separated state of all the investigated systems, namely, that of ferrocenium ion (Fc+) and the C60 radical anion (C60.-) pair in the Fc-ZnP-C60 triad, has been generated with the highest quantum yields (close to unity) and reveals a lifetime as long as 16 micros. Determination of CS and CR rate constants, together with the one-electron redox potentials of the donor and acceptor moieties in different solvents, has allowed us to examine the driving force dependence (-DeltaG0ET) of the electron-transfer rate constants (kET). Hereby, the semilogarithmic plots (i.e., log kET versus -DeltaG0ET) lead to the evaluation of the reorganization energy (lambda) and the electronic coupling matrix element (V) in light of the Marcus theory of electron-transfer reactions: lambda = 0.66 eV and V = 3.9 cm(-1) for ZnP-C60 dyad and lambda = 1.09 eV and V = 0.019 cm(-1) for Fc-ZnP-C60, Fc-H2P-C60, and ZnP-H2P-C60 triads. Interestingly, the Marcus plot in Fc-ZnP-C60, Fc-H2P-C60, and ZnP-H2P-C60 has provided clear evidence for intramolecular CR located in both the normal and inverted regions of the Marcus parabola. The coefficient for the distance dependence of V (damping factor: betaCR = 0.58 A(-1) is deduced which depends primarily on the nature of the bridging molecule.


Assuntos
Porfirinas/química
16.
J Am Chem Soc ; 123(22): 5277-84, 2001 Jun 06.
Artigo em Inglês | MEDLINE | ID: mdl-11457390

RESUMO

A new approach of probing proximity effects in porphyrin-fullerene dyads by using an axial ligand coordination controlled "tail-on" and "tail-off" binding mechanism is reported. In the newly synthesized porphyrin-fullerene dyads for this purpose, the donor-acceptor proximity is controlled either by temperature variation or by an axial ligand replacement method. In o-dichlorobenzene, 0.1 M (TBA)ClO(4), the synthesized zincporphyrin-fullerene dyads exhibit seven one-electron reversible redox reactions within the accessible potential window of the solvent and the measured electrochemical redox potentials and UV-visible absorption spectra reveal little or no ground-state interactions between the C(60) spheroid and porphyrin pi-system. The proximity effects on the photoinduced charge separation and charge recombination are probed by both steady-state and time-resolved fluorescence techniques. It is observed that in the "tail-off" form the charge-separation efficiency changes to some extent in comparison with the results obtained for the "tail-on" form, suggesting the presence of some through-space interactions between the singlet excited zinc porphyrin and the C(60) moiety in the "tail-off" form. The charge separation rates and efficiencies are evaluated from the fluorescence lifetime studies. The charge separation via the singlet excited states of zinc porphyrin in the studied dyads is also confirmed by the quick rise-decay of the anion radical of the C(60) moiety within 20 ns. Furthermore, a long-lived ion pair with lifetime of about 1000 ns is also observed in the investigated zinc porphyrin-C(60) dyads.

17.
Ann Rheum Dis ; 60(7): 685-9, 2001 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-11406523

RESUMO

OBJECTIVE: To examine the effect of transfection of oligodeoxynucleotides (ODNs) containing a CpG motif (CpG-ODN), of which the sequence was derived from circulating DNA in the sera of patients with systemic lupus erythematosus (SLE), on the expression of intercellular adhesion molecule-1 (ICAM-1) and synthesis of mRNA for proinflammatory cytokines and ICAM-1 in human umbilical vein endothelial cells (EC). METHODS: A CpG-ODN or a control analogue, GpC-ODN, was transfected into EC. ICAM-1 expression was examined by flow cytometry, and expression of mRNA in EC encoding interleukin 1 (IL1), IL6, IL8, tumour necrosis factor alpha (TNFalpha), interferon gamma (IFNgamma), and ICAM-1 was examined by semiquantitative reverse transcriptase-polymerase chain reaction. RESULTS: The CpG-ODN augmented the expression of ICAM-1 on EC determined by flow cytometry and increased mRNA levels of IL6, IL8, TNFalpha, IFNgamma, and ICAM-1, but the GpC-ODN did not. CONCLUSION: Synthesised DNA, with a sequence corresponding to that of the fragment containing the CpG motif, in sera of patients with SLE was found to enhance ICAM-1 expression on EC, suggesting the participation of circulating DNA fragments in the pathogenesis of vasculitis in SLE.


Assuntos
Ilhas de CpG , DNA/metabolismo , Endotélio Vascular/imunologia , Molécula 1 de Adesão Intercelular/metabolismo , Lúpus Eritematoso Sistêmico/genética , Células Cultivadas , Ácidos Graxos Monoinsaturados/farmacologia , Citometria de Fluxo , Corantes Fluorescentes/farmacologia , Humanos , Molécula 1 de Adesão Intercelular/genética , Interferon gama/genética , Interleucina-1/genética , Interleucina-6/genética , Interleucina-8/genética , Lúpus Eritematoso Sistêmico/imunologia , Compostos de Amônio Quaternário/farmacologia , RNA Mensageiro/análise , Reação em Cadeia da Polimerase Via Transcriptase Reversa , Fator de Necrose Tumoral alfa/genética
18.
Intern Med ; 40(5): 386-90, 2001 May.
Artigo em Inglês | MEDLINE | ID: mdl-11393407

RESUMO

We report a patient with insulinoma associated with Zollinger-Ellison syndrome. A 67-year-old woman was first admitted to our hospital for an abdominal mass. Abdominal computed tomography (CT) revealed a large pancreatic tumor, which was then diagnosed as an unresectable pancreatic adenocarcinoma. At the age of 71, she presented symptoms of hypoglycemia. Fasting blood glucose was 21 mg/dl and plasma immunoreactive insulin level was 846 microU/ ml. Plasma gastrin, glucagon, vasoactive intestinal polypeptide and somatostatin levels were all normal. At the age of 73, hypoglycemic attacks occurred more frequently and she was admitted to our hospital. Abdominal CT scan showed multiple liver metastases. Chemotherapy with 5-fluorouracil and doxorubicin was performed. Three months later, she had an emergency laparotomy because of a perforated duodenal ulcer. Plasma gastrin level was 1,960 pg/ml at that time. Gastric hypersecretion was well controlled with a proton pump inhibitor (lansoprazole) but she died of widespread cancer dissemination 8 years after her first admission. On autopsy, histologic examination revealed a mixed acinar-endocrine carcinoma of the pancreas. Immunohistochemical stains were positive for insulin, gastrin, and alpha1-antitrypsin.


Assuntos
Insulinoma/complicações , Neoplasias Pancreáticas/complicações , Síndrome de Zollinger-Ellison/complicações , Idoso , Colangiopancreatografia Retrógrada Endoscópica , Evolução Fatal , Feminino , Humanos , Insulinoma/diagnóstico por imagem , Insulinoma/patologia , Neoplasias Pancreáticas/diagnóstico por imagem , Neoplasias Pancreáticas/patologia , Tomografia Computadorizada por Raios X
19.
Environ Technol ; 22(3): 345-53, 2001 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-11346292

RESUMO

Nitrous oxide emission from the immobilized denitrification process was investigated under copper-added and copper-free conditions to realize high-speed denitrification with minimum nitrous oxide emission. Nitrous oxide emission was found to be smaller in culture using immobilized cells acclimatized under copper-added condition. Transient phenomena of nitrous oxide emission, nitrate reduction and nitrite accumulation were then investigated in repeated batch experiments by transferring immobilized cells acclimatized in copper-free conditions into copper-added medium. Nitrous oxide emission obviously decreased, and maximum nitrous oxide concentration of seventh batch culture was about 1/40,000 of that of first batch culture. Nitrate reduction gradually decreased from second batch to fourth batch culture and it turned to increase from fifth batch culture to seventh batch culture. At seventh batch culture, nitrate reduction rate was restored up to 80% of the initial speed. This repeated batch experiment clarified that nitrous oxide emission was repressed by copper sulfate addition. The effect of pH and temperature on nitrous oxide emission were also investigated in a continuous denitrification experiment under copper added conditions. Nitrous oxide emission was increased by lowering pH and lowering temperature. At optimum operating condition (pH8.0, 30 degrees C), nitrogen removal efficiency of 99.9%, nitrous-oxide concentration in the emitted gas of 3.1ppm(v/v) and conversion ratio to nitrous oxide of 0.000316% were obtained when 280mg-Nl(-1) nitrate containing medium was treated at 6 hours of hydraulic retention time.


Assuntos
Celulose , Sulfato de Cobre/química , Nitrogênio/química , Óxido Nitroso/química , Poluentes Químicos da Água , Células Cultivadas , Filtração , Humanos , Concentração de Íons de Hidrogênio
20.
Inorg Chem ; 40(6): 1213-9, 2001 Mar 12.
Artigo em Inglês | MEDLINE | ID: mdl-11300821

RESUMO

Irradiation of the absorption band of an NAD (nicotinamide adenine dinucleotide) dimer analogue, 1-benzyl-1,4-dihydronicotinamide dimer, (BNA)(2), in acetonitrile containing a cyclopentadienyliron dicarbonyl dimer, [CpFe(CO)(2)](2), results in generation of 2 equiv of the cyclopentadienyliron dicarbonyl anion, [CpFe(CO)(2)](-), accompanied by the oxidation of (BNA)(2) to yield 2 equiv of BNA(+). The studies on the quantum yields, the electrochemistry, and the transient absorption spectra have revealed that the photochemical generation of [CpFe(CO)(2)](-) by (BNA)(2) proceeds via photoinduced electron transfer from the triplet excited state of (BNA)(2) to [CpFe(CO)(2)](2).


Assuntos
Compostos Ferrosos/química , NAD/análogos & derivados , NAD/química , Niacinamida/química , Eletroquímica , Estrutura Molecular , NAD/efeitos da radiação , Niacinamida/análogos & derivados , Niacinamida/efeitos da radiação , Oxirredução , Fotoquímica , Espectrofotometria Atômica , Relação Estrutura-Atividade
SELEÇÃO DE REFERÊNCIAS
DETALHE DA PESQUISA
...