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1.
Eur J Trauma Emerg Surg ; 43(4): 451-459, 2017 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-28624992

RESUMO

PURPOSE: The main purpose of this systematic review was to investigate the effect of compression treatment on the perioperative course of ankle fractures and describe its effect on edema, pain, ankle joint mobility, wound healing complication, length of stay (LOS) and time to surgery (TTS). The aim was to suggest a recommendation to clinicians considering implementing compression therapy in the standard care of the ankle fracture patient, based on the existing literature. METHODS: We conducted a systematic search of literature including studies concerning adult patients with unstable ankle fractures undergoing surgery, testing either intermittent pneumatic compression, compression bandage and/or compression stocking and reporting its effect on edema, pain, ankle joint mobility, wound healing complication, LOS and TTS. To conclude on data a narrative synthesis was performed. RESULTS: The review included eight studies (451 patients). Seven studies found a significant effect on edema, two studies described a significant reduction in pain, one a positive effect on ankle movement, two a positive effect on wound healing, one a reduction in LOS and finally two studies reported reduction in TTS. A systematic bias assessment showed that the included studies had methodological limitations influencing the confidence in the effect estimate. CONCLUSIONS: Compression therapy has a beneficial effect on edema reduction and probably a positive effect on pain and ankle joint mobility, but with the methodological limitations in the included studies it is not possible to make a solid conclusion on the effect on wound healing, LOS and TTS.


Assuntos
Fraturas do Tornozelo/cirurgia , Bandagens Compressivas , Edema/prevenção & controle , Dispositivos de Compressão Pneumática Intermitente , Complicações Pós-Operatórias/prevenção & controle , Humanos , Tempo de Internação , Medição da Dor , Cicatrização
2.
Wounds ; 28(10): S1-S23, 2016 10.
Artigo em Inglês | MEDLINE | ID: mdl-28682298

RESUMO

Many wound care centers (WCCs) provide a specialized level of care using various wound care therapies and are managed by quali ed healthcare professionals (QHPs) from di erent specialty backgrounds such as family medicine, podiatry, and plastic surgery. However, these QHPs are sometimes challenged by reimbursement issues, limited therapy and dressing options, reduced access to multidisciplinary team members, and cost-driven factors unique to WCCs. To help address these issues, a meeting was convened by an expert panel of WCC physicians to discuss best practices for treating complex patients in a WCC. This publication presents an overview of WCC chal- lenges, describes a holistic approach to treating WCC patients, and provides clinical guidance on the decision-mak- ing process for selecting optimal treatment plans for the WCC patient. Clinical cases of atypical, surgical and chronic wounds seen in a WCC are also presented.


Assuntos
Antibacterianos/uso terapêutico , Biofilmes/efeitos dos fármacos , Infecção dos Ferimentos/microbiologia , Infecção dos Ferimentos/terapia , Ferimentos e Lesões/microbiologia , Ferimentos e Lesões/terapia , Desbridamento , Prestação Integrada de Cuidados de Saúde , Humanos , Guias de Prática Clínica como Assunto , Cicatrização/efeitos dos fármacos
3.
Plant Physiol Biochem ; 73: 420-6, 2013 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-24239614

RESUMO

Effect of salt stress was examined in in vitro shoot cultures of Myrtus communis L. a species of the Mediterranean maquis. To determine the effects of high salt concentrations on myrtle plantlets and contribute toward understanding the mechanisms adopted from this species to counteract soil salinity, in vitro rooted shoots were transferred to a liquid culture medium containing 0, 125 or 250 mM NaCl for 30 days. After 15 and 30 days of in vitro culture, shoot and root growth, chlorosis and necrosis extension, chlorophylls, carotenoids, proline, arginine, cysteine and total sugars content, as well as guaiacol peroxidase (G-POD, EC 1.11.1.7) and ascorbate peroxidase (APX, EC 1.11.1.11) activities were determined. In treated plants shoot and root growth, as well as chlorophyll content, significantly decreased, while carotenoids content was not affected by the NaCl treatment. Among osmolytes, proline did not significantly increase, arginine and cysteine decreased, while total sugars were found to be higher in the treated plants than in the control. Enhancement of G-POD and APX activities was positively related to increasing salt concentrations in the culture media, regardless of the exposure time. Salt-treated plants did not show significant changes in lipid peroxidation or DNA fragmentation after 30 days salt treatment, regardless of the NaCl concentrations applied. The results represent a contribution towards understanding the mechanisms adopted by this species to high salinity.


Assuntos
Ascorbato Peroxidases/metabolismo , Myrtus/fisiologia , Salinidade , Tolerância ao Sal , Cloreto de Sódio/farmacologia , Estresse Fisiológico , Arginina/metabolismo , Metabolismo dos Carboidratos/efeitos dos fármacos , Carotenoides/metabolismo , Clorofila/metabolismo , Meios de Cultura/química , Cisteína/metabolismo , Fragmentação do DNA/efeitos dos fármacos , Peroxidação de Lipídeos/efeitos dos fármacos , Myrtus/enzimologia , Myrtus/crescimento & desenvolvimento , Myrtus/metabolismo , Estresse Oxidativo , Peroxidase/metabolismo , Raízes de Plantas/efeitos dos fármacos , Raízes de Plantas/crescimento & desenvolvimento , Raízes de Plantas/metabolismo , Brotos de Planta/efeitos dos fármacos , Brotos de Planta/crescimento & desenvolvimento , Brotos de Planta/metabolismo , Prolina/metabolismo , Espécies Reativas de Oxigênio/metabolismo , Cloreto de Sódio/metabolismo , Superóxido Dismutase/metabolismo
4.
J Foot Ankle Surg ; 49(6): 517-22, 2010.
Artigo em Inglês | MEDLINE | ID: mdl-20864361

RESUMO

The goals of Charcot deformity correction are to restore osseous alignment, regain pedal stability, and prevent ulceration. Traditional reconstructive surgical approaches involve large, open incisions to remove bone and the use of internal fixation to attempt to fuse dislocated joints. Such operations can result in shortening of the foot and/or incomplete deformity correction, fixation failure, incision healing problems, infection, and the longterm use of casts or braces. We recommend a minimally invasive surgical technique for the treatment of Charcot deformity, which we performed on 11 feet in 8 patients. Osseous realignment was achieved through gradual distraction of the joints with external fixation, after which minimally invasive arthrodesis was performed with rigid internal fixation. Feet were operated on at various stages of Charcot deformity: Eichenholtz stage I (1 foot), Eichenholtz stage II (6 feet), and Eichenholtz stage III (4 feet). When comparing the average change in preoperative and postoperative radiographic angles, the transverse plane talar-first metatarsal angle (P = .02), sagittal plane talar-first metatarsal angle (P = .008), and calcaneal pitch angle (P = .001) were all found to be statistically significant. Complications included 3 operative adjustments of external or internal fixation, 4 broken wires or half-pins, 2 broken rings, and 11 pin tract infections. Most notably, no deep infection, no screw failure, and no recurrent ulcerations occurred and no amputations were necessary during an average follow-up of 22 months. Gradual Charcot foot correction with the Taylor spatial frame plus minimally invasive arthrodesis is an effective treatment.


Assuntos
Artrodese/métodos , Artropatia Neurogênica/cirurgia , Parafusos Ósseos , Pé Diabético/cirurgia , Fixadores Externos , Tendão do Calcâneo/cirurgia , Adulto , Idoso , Artropatia Neurogênica/diagnóstico por imagem , Pé Equino/cirurgia , Feminino , Fluoroscopia , Ossos do Pé/cirurgia , Articulações do Pé/diagnóstico por imagem , Articulações do Pé/cirurgia , Humanos , Masculino , Pessoa de Meia-Idade , Músculo Esquelético/cirurgia
5.
J Neuroendocrinol ; 19(7): 531-42, 2007 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-17532793

RESUMO

Intracerebroventricular (i.c.v.) administration of the opioid-like peptide, nociceptin/Orphanin (nociceptin), in conscious rats produces diuretic and antinatriuretic effects. The present study utilised changes in Fos and inducible cAMP early repressor (ICER) immunocytochemistry expression to examine the central nervous (CNS) sites activated or inhibited, respectively, by central administration of nociceptin. Urine samples were collected during control (15 min) and after i.c.v. vehicle (5 microl, n = 12) or nociceptin (10 microg/5 microl; n = 12). Four additional urine samples (15-min) were collected after the i.c.v. injection. The brain was processed for Fos using a commercially available antibody (Oncogene AB-5) and for ICER using a polyclonal anti-ICER antibody raised in rabbits. In vehicle-injected conscious rats, renal excretion of water or sodium was not altered. However, nociceptin produced a rapid and marked increase in urine flow (V) and a decrease in urinary sodium excretion rate. In addition, i.c.v. nociceptin produced a significant increase in Fos staining in the dorsomedial nucleus of the hypothalamus, the perinuclear zone of the supraoptic nucleus, the organum vasculosum of the lamina terminalis (OVLT), the lateral preoptic area and the lateral hypothalamic area compared to control. By contrast, Fos expression decreased in the area postrema and locus coeruleus compared to controls. Furthermore, ICER staining was significantly increased in the perinuclear zone of the supraoptic nucleus, supraoptic nucleus, median preoptic nucleus, OVLT, medial preoptic area, central nucleus of the amygdala, and medial nucleus of the solitary tract. Together, central opioid receptor-like type 1 activation in these CNS regions may participate in the neural pathways involved in the diuretic and antinatriuretic effects of nociceptin.


Assuntos
Sistema Nervoso Central/efeitos dos fármacos , AMP Cíclico/metabolismo , Diurese , Peptídeos Opioides/administração & dosagem , Proteínas Proto-Oncogênicas c-fos/metabolismo , Proteínas Repressoras/metabolismo , Animais , Sistema Nervoso Central/metabolismo , Imuno-Histoquímica , Microinjeções , Ratos , Nociceptina
7.
Phys Rev E Stat Nonlin Soft Matter Phys ; 68(1 Pt 2): 016702, 2003 Jul.
Artigo em Inglês | MEDLINE | ID: mdl-12935282

RESUMO

The isospectrality of a well-known pair of shapes constructed from two arrangements of seven congruent right isosceles triangles with the Neumann boundary condition is verified numerically to high precision. Equally strong numerical evidence for isospectrality is presented for the eigenvalues of this standard pair in new boundary configurations with alternating Dirichlet and Neumann boundary conditions along successive edges. Good agreement with theory is obtained for the corresponding spectral staircase functions. Strong numerical evidence is also presented for isospectrality in an example of a different pair of shapes whose basic building-block triangle is not isosceles. Some possible confirmatory experiments involving fluids are suggested.

8.
Phytochemistry ; 58(8): 1209-12, 2001 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-11738409

RESUMO

The presence of betacyanin pigments and their isoforms has been detected in the fruit of Hylocereus polyrhizus, a vine cactus native to South America. Along with the known betanin and phyllocactin (6'-O-malonylbetanin), a new betacyanin was structurally elucidated as betanidin 5-O-[6'-O-(3"-hydroxy-3"-methyl-glutaryl)-beta-D-glucopyranoside] (proposed trivial name hylocerenin) by means of electrospray MS/MS, HPLC, and NMR techniques.


Assuntos
Cactaceae/química , Indóis/química , Betacianinas , Frutas/química , Indóis/isolamento & purificação , Espectrometria de Massas
9.
Transgenic Res ; 10(5): 445-56, 2001 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-11708654

RESUMO

A beta-lactoglobulin (BLG)/luciferase gene vector (p907), composed of a luciferase intronless gene inserted between the second and sixth BLG exons was constructed. Stable transfections of CID-9 cells with this vector, as well as with a series of additional vectors, were performed to define regulatory regions within the BLG sequence, and the contribution of the SV40 polyadenylation (PA) site to luciferase expression. A relatively low level of luciferase activity was supported by vector p907. It was partially rescued by vector p906, in which the BLG 3' region, downstream of the luciferase cDNA, was replaced with the SV40 PA site. Flanking the SV40 region of vector p906, at its 3' end, with BLG sequences of exon 6/intron 6/exon 7 and the 3' region of the gene resulted in vector p904. This vector supported the highest luciferase activity, 10 times or 2.5 times higher than that measured in cells transfected with vectors p907 and p906, respectively. The induced activity supported by vector p904 is attributed to interaction between the SV40 PA site and elements of the distal part of the BLG 3' flanking sequences. The BLG 5' regulatory region of vector p904 encompasses a 3-kb promoter sequences. Deletion of 935 bp of its proximal end resulted in a 60% decrease in luciferase activity. Reduced activity was also seen with vector p915 lacking sequences of exon 1/intron 1/exon 2. This decrease could not be rescued with heterologous sequences of insulin intron 1, inserted upstream of the luciferase cDNA. Two sets of transgenic mice carrying vectors p907 and p904 were generated. Vector p907 supported only marginal luciferase activity in the mammary gland of all transgenic mice tested and luciferase RNA could not be detected by northern analysis. In contrast, 50% of the transgenic mice carrying vector p904 expressed luciferase RNA in the mammary gland and tissue-specific, hormonal-dependent activity was determined. However, the new p904 vector was not able to insulate the transgene from surrounding host DNA sequences, as reflected by its copy number-independent manner of expression. Nevertheless, vector p904 may represent a valuable tool for the expression of cDNAs in the mammary gland of transgenic animals.


Assuntos
Vetores Genéticos , Lactoglobulinas/genética , Luciferases/genética , Glândulas Mamárias Animais/fisiologia , Região 3'-Flanqueadora , Animais , Antígenos Transformantes de Poliomavirus/genética , Linhagem Celular , DNA Complementar , Feminino , Expressão Gênica , Humanos , Insulina/farmacologia , Luciferases/efeitos dos fármacos , Luciferases/metabolismo , Glândulas Mamárias Animais/efeitos dos fármacos , Camundongos , Camundongos Transgênicos , Prolactina/farmacologia , Albumina Sérica/genética , Albumina Sérica/metabolismo
10.
J Org Chem ; 66(20): 6711-8, 2001 Oct 05.
Artigo em Inglês | MEDLINE | ID: mdl-11578225

RESUMO

1,2,3,4,5,6,7,8-Octaethylanthracene (5), 1,2,3,4,6,7,8-heptaethylfluorene (7), and 1,2,3,4,5,6,7,8-octaethylfluorene (8) were synthesized by Friedel-Crafts ethylations of 9,10-dihydroanthracene and fluorene. MM3 calculations indicate that the two ethylated six-membered rings of 5 and 7 are conformationally independent. According to the calculations, two low-energy conformers of each compound are possible with the ethyl groups attached to the external aryl rings arranged in an alternated "up-down" orientation. MM3 calculations indicate that in the lowest energy conformation the central fluorene core of 8 adopts a twisted conformation to avoid repulsive steric interactions between the ethyls at the bay region. Two fully alternated up-down conformations are possible for 8, differing in the orientation ("in" or "out") of the ethyls in the bay region. MM3 calculations predict that the lowest energy conformer is the fully alternated "out" form of C(2)() symmetry. The rotational barriers of 5, 7, and 8 are in the 8.7-11.3 kcal mol(-1) range, the largest barrier corresponding to the more crowded octaethylfluorene 8. Anthracene 5 adopts in the crystal a conformation of approximate C(2)(h) symmetry with pairs of peri groups on the same edge of the molecule oriented syn. The conformations adopted in the crystal by 7 and 8 do not correspond to the calculated lowest energy form. In the conformation of 7 in the crystal the ethyl groups on the trisubstituted ring adopt the unusual all syn arrangement. Octaethylfluorene 8 adopts a conformation with a twisted central fluorene core but with a syn arrangement of a pair of vicinal ethyl groups.

11.
J Org Chem ; 66(16): 5463-81, 2001 Aug 10.
Artigo em Inglês | MEDLINE | ID: mdl-11485471

RESUMO

Since the nitrogens of nucleosides and nucleotides play an important role in the molecular recognition of these compounds, (15)N NMR became a method of choice in this field. Fully (15)N-labeled adenine, required in the latter studies, was obtained in four synthetic steps, in a good yield. Likewise, ((15)N(5))-2-hexylthioether-adenine and ((15)N(5))-8-Br-adenine were obtained in five synthetic steps from the relatively inexpensive (15)N sources: (15)N-NH(4)Cl, (15)N-NH(4)OH, (15)N-NaNO(2). Full (15)N labeling of these adenine prototypes enabled to obtain high-resolution (15)N NMR spectra of these bases at 60.8 MHz. Furthermore, the spectra suggested the existence of the N3-H species in the tautomeric mixtures of these compounds in solution, in addition to the well-reported N9-H (major) and N7-H (minor) tautomers. These observations were also supported by quantum mechanical calculations of the tautomeric equilibria in the gas phase and in solution of the above-mentioned adenine compounds. The gas-phase tautomeric equilibria were estimated using density functional theory and second-order perturbation theory methods. Solvent effects were included by means of both continuum and discrete solvation models. The observation of the existence of the N3-H tautomer has a clear impact on the possible H-bonding patterns of these adenine prototypes and on their molecular recognition by various biological macromolecules. The above(15)N-labeled analogues are expected to find use as (15)N NMR probes for numerous biochemical studies.


Assuntos
Adenina/síntese química , Adenina/análogos & derivados , Adenina/química , Espectroscopia de Ressonância Magnética/métodos , Modelos Teóricos , Isótopos de Nitrogênio
12.
Phytochemistry ; 58(1): 143-52, 2001 Sep.
Artigo em Inglês | MEDLINE | ID: mdl-11524124

RESUMO

In previous studies we have elucidated the presence of powerful, natural antioxidants (NAO) in water extracts of spinach leaves and demonstrated their biological activity in both in vitro and in vivo systems. In the present study, the chemical identity of several of these antioxidant components is presented. Spinach leaves were extracted with water and the 20,000 g supernatant which contained the antioxidant activity was extracted with a water:acetone (1:9) solution. The 20,000 g supernatant obtained was further purified on reverse phase HPLC using C-8 semi-preparative column. Elution with 0.1% TFA resulted in five hydrophilic peaks. Elution with acetonitrile in TFA resulted in seven additional hydrophobic peaks. All the peaks were detected at 250 nm. All the fractions obtained showed antioxidant activity when tested using three different assays. Based on 1H and 13C NMR spectroscopy four of the hydrophobic fractions were identified as glucuronic acid derivatives of flavonoids and three additional fractions as trans and cis isomers of p-coumaric acid and others as meso-tartarate derivatives of p-coumaric acid. The present study demonstrates for the first time the presence of both flavonoids and p-coumaric acid derivatives as antioxidant components of the aqueous extract of spinach leaves.


Assuntos
Antioxidantes/análise , Ácidos Cumáricos/química , Flavonoides/química , Extratos Vegetais/química , Spinacia oleracea/química , Acetona , Antioxidantes/química , Antioxidantes/isolamento & purificação , Isótopos de Carbono , Cromanos/análise , Cromanos/química , Cromatografia Líquida de Alta Pressão , Ácidos Cumáricos/análise , Flavonoides/análise , Hidrogênio , Espectroscopia de Ressonância Magnética , Modelos Moleculares , Conformação Molecular , Folhas de Planta/química , Soluções , Relação Estrutura-Atividade , Água
13.
Photochem Photobiol ; 73(5): 473-81, 2001 May.
Artigo em Inglês | MEDLINE | ID: mdl-11367567

RESUMO

A perfluorinated derivative of phthalocyanine was synthesized as the free base, hexadeca-(2,2,2-trifluoroethoxy) phthalocyanine (H2F48Pc), and as a zinc complex, hexadeca-(2,2,2-trifluoroethoxy)-phthalocyaninatozinc (ZnF48Pc), and their spectroscopic and photochemical properties were studied. The absorption bands are shifted bathochromically relative to simple phthalocyanines, exhibiting the longest wavelength band near 735 nm (H2F48Pc) and 705 (ZnF48Pc). The solvatochromism of both compounds was modeled by Reichardt's ET(30) parameter and Kamlet, Abboud and Taft multiparameter approach. The former, simpler, model was found to be adequate. We found that H2F48Pc undergoes unique basic and acidic titrations in organic solvents. These titration processes are accompanied by spectral changes that are explained on the basis of the chromophore's symmetry. Singular value decomposition was employed to resolve the spectra into the contributions of the species at various stages of protonation and to obtain the equilibrium constants. Nuclear magnetic resonance spectra (1H, 19F and 13C) for the free base were obtained in a tetrahydrofurand8 solution. The carbon spectrum, taken as a function of temperature, provided evidence for the presence of a tautomerization process, which switches the two internal hydrogens between the four central nitrogen atoms. As far as we know, this is the first report of the measurement of the free energy of activation for such process (delta G = 10.6-11.4 kcal mol-1 between 217 and 330 K) for a phthalocyanine, in solution. Like most other phthalocyanines these two compounds also act as photosensitizers and as generators of singlet molecular oxygen. The absolute quantum yields (phi delta) for ZnF48Pc was 0.58 +/- 0.01 in benzene and 0.35 +/- 0.01 in lipid vesicles. H2F48Pc had lower yields, 0.16 and 0.005, respectively. Either protonation or deprotonation of the pyrrole nitrogens in H2F48Pc lowered the phi delta.


Assuntos
Indóis/química , Fármacos Fotossensibilizantes/química , Concentração de Íons de Hidrogênio , Lipossomos , Espectroscopia de Ressonância Magnética , Fármacos Fotossensibilizantes/síntese química , Soluções , Espectrometria de Fluorescência
14.
Chemistry ; 7(21): 4715-22, 2001 Nov 05.
Artigo em Inglês | MEDLINE | ID: mdl-11757664

RESUMO

Conformational preferences in alkyl- as well as Ph-substituted 3-piperideines (1,2,3,6-tetrahydropyridines) have been characterized by ab initio and molecular mechanics calculations. A set of rules and subrules for estimation of the conformational equilibrium (in terms of preferred substituent orientation) in these systems. with differently positioned ring substituent (-s), is presented. Examples of the revision of some previous stereochemical assignments demonstrate the reliability of these rules.

15.
Steroids ; 65(1): 46-53, 2000 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-10624836

RESUMO

Cochliobolus lunatus 17beta-hydroxysteroid dehydrogenase (17beta-HSD) is pluripotent for several steroidal and nonsteroidal substrates. In the presence of NADPH the enzyme was found to reduce 3-keto groups of 4,5-dihydro steroids, 20-keto groups, and most efficiently, 17-keto groups of steroidal substrates. In addition, several quinones were accepted and found to be even better substrates as steroids due to their higher affinity for the enzyme-coenzyme complex and faster conversion of the enzyme-coenzyme-substrate complex into the corresponding products. As suggested by the competition studies quinones and 17-ketosteroids are converted by the same active center of the enzyme. For all tested substrates, the equilibrium ordered mechanism was established with NADPH binding first to the enzyme. According to our knowledge, the investigated 17beta-HSD is the first known fungal pluripotent enzyme of this type.


Assuntos
17-Hidroxiesteroide Desidrogenases/metabolismo , Ascomicetos/enzimologia , 17-Hidroxiesteroide Desidrogenases/antagonistas & inibidores , Inibidores Enzimáticos/farmacologia , Cinética , Especificidade por Substrato
16.
J Comb Chem ; 2(6): 732-5, 2000.
Artigo em Inglês | MEDLINE | ID: mdl-11126301

RESUMO

In the context of our high-throughput organic synthesis program, we have studied the reactivity of special beta-keto esters toward the Biginelli reaction. We have found that a cyclic beta-keto ester reacts with one molecule of urea and two molecules of aldehyde to give a new family of spiro heterobicyclic aliphatic rings in good yields. Interestingly, the Biginelli product was not detected. After analysis of products using HPLC, 1H NMR, and 13C NMR, we have found that the reaction is driven by a regio-specific condensation of two molecules of aldehyde with the other reagents to afford only products harboring substituents exclusively in cis configuration. Monte Carlo minimization studies using MM2 force field suggest that cis products are energetically more stable than the trans counterparts. Together with previously reported data, these results suggest that the trans products were not obtained as result of steric hindrance produced by the equatorial position of one of the ring substituents. This new reaction is useful for high-throughput organic synthesis. Indeed, the new scaffold can be used to introduce additional groups in the molecules through remaining functional groups by a "domino strategy".

17.
J Org Chem ; 65(25): 8621-8, 2000 Dec 15.
Artigo em Inglês | MEDLINE | ID: mdl-11112583

RESUMO

Dimerization of tetraethylbenzyne (generated by reaction of 1, 2-dibromo-3,4,5,6-tetraethylbenzene (8) with 1 equiv of BuLi) afforded in low yield octaethylbiphenylene (3), together with a major product which was characterized as 2,3,4,5,3',4', 5'-heptaethyl-2'-vinylbiphenyl (9). X-ray diffraction indicates that biphenylene 3 adopts in the crystal a conformation of approximate C(2)(h )()symmetry with the ethyl groups within each phenylene ring arranged in an alternated up-down fashion. Notably, pairs of vicinal ethyl groups located at peri positions are oriented in a syn arrangement in the crystal. Low temperature NMR spectroscopy is consistent with the presence in solution of either the crystal conformation or a fully alternated conformation lacking any syn interaction. Molecular mechanics (MM3), semiempirical (AM1, PM3), and ab initio calculations indicate that the crystal conformation is a high energy form, and that the lowest energy conformation is the fully alternated form. The topomerization barrier of the methylene protons of the ethyl groups of 3 is 9.4 +/- 0.1 kcal mol(-)(1), which is between the rotational barriers of 8 and 1,2,3, 4-tetraethylbenzene 7 (9.9 +/- 0.1 and 8.2 +/- 0.1 kcal mol(-)(1), respectively). The similarity in rotational barriers suggests that a given tetraethylphenylene subunit does not markedly affect the rotational barrier of the ethyl groups of the other subunit.

18.
Phytochemistry ; 55(7): 749-53, 2000 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-11190391

RESUMO

From the leaves of Renealmia chrysotrycha (Zingiberaceae), we isolated a sesquiterpene alcohol for which spectral data suggested the structure of a 10-aromadendranol. A meticulous NMR investigation, based mainly on vicinal proton-proton coupling constants and NOE interactions, and confirmed by a molecular mechanics calculation, established its relative stereochemistry as that of ledol. This finding resolves several recent literature ambiguities. Three known compounds (aromadendrene, cis-calamenene and palustrol) were also isolated.


Assuntos
Magnoliopsida/química , Sesquiterpenos/química , Espectroscopia de Ressonância Magnética , Modelos Moleculares , Sesquiterpenos/isolamento & purificação , Estereoisomerismo
20.
Compr Ther ; 24(3): 153-7, 1998 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-9559250

RESUMO

Widespread market consolidation, ongoing changes in Medicare and reimbursement schedules, the evolution of managed care. These megatrends have created a revolution in the eyecare industry with much instability in the marketplace. Practice consolidation on a local level allows practitioners to take charge of their destiny.


Assuntos
Marketing de Serviços de Saúde , Oftalmologia/economia , Optometria/economia , Reforma dos Serviços de Saúde , Humanos , Estados Unidos
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