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1.
Dalton Trans ; 48(45): 16943-16951, 2019 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-31687709

RESUMO

1,2-Propanediaminetetraacetic acid (H4pdta = C11H18O8N2) is degraded selectively to 1-methyl-1,2-propanediaminetriacetic acid (H3pd3a = C9H16O6N2) with a yield of 75% at room temperature, while N-(2-hydroxyethyl) ethylenediaminetriacetic acid (H4eed3a = C10H18O7N2) is converted with difficulty to ethylenediaminetriacetic acid (H3ed3a = C8H14O6N2) on peroxotitanates(iv), showing the influence of the uncoordinated leaving group. Various species in the reaction sequence are isolated and fully characterized, including (NH4)[Ti(O2)(Hpdta)]·H2O (1), (NH4)3[Ti(O2)(pdta)H(pdta)(O2)Ti]·7H2O (2), (NH4)[Ti(O2)(pd3a)]·H2O (3) and (NH4)[Ti(O2)(Heed3a)]·H2O (5). Peroxo dimer 2 forms a strong intramolecular hydrogen bond [2.451(3) Å] as an intermediate in the peroxo Ti-pdta system, which results in the absence of a fully deprotonated species of peroxo pdta titanate. A catalytic reaction of the peroxo titanate (NH4)3[Ti(O2)(pdta)H(pdta)(O2)Ti]·7H2O (2) for the conversion of pyridine to pyridine N-oxide shows 94% conversion at 80 °C.

2.
Soft Matter ; 15(33): 6725-6731, 2019 Aug 21.
Artigo em Inglês | MEDLINE | ID: mdl-31389469

RESUMO

The adsorption of xylyl-substituted biquaternary ammonium salt Gemini surfactants with different spacer (C3 and C6) at polytetrafluoroethylene (PTFE) and polymethylmethacrylate (PMMA) surfaces has been investigated and the different adsorption parameters such as surface tension, contact angle, adhesional tension, solid-water interfacial tension and work of adhesion have been estimated. The results show that C3 and C6 have similar adsorption behaviors at PTFE and PMMA surfaces. C3 and C6 adsorb gradually at a PFTE-water interface via hydrophobic interactions and the adsorption amounts at the water-air interface are almost three times higher than those at the PTFE-water interface due to the steric hindrance effect. However, the contact angle keeps constant throughout the experimental concentration range because the decrease in surface tension just counterbalances the decrease in PFTE-water interfacial tension. On the other hand, C3 and C6 adsorb at the PMMA surface via polar interactions between xylyl and functional groups of PMMA before CMC. Similar to PTFE, the increase in PMMA-water interfacial tension compensates the decrease in surface tension and the contact angle also shows a stationary value before the CMC. A bi-layer structure of C3 and C6 will be formed at the PMMA-water interface via hydrophobic interaction and PMMA-water interfacial tension decreases consequently after the CMC, which results in the decrease in contact angle.

3.
Dalton Trans ; 48(35): 13388-13395, 2019 Sep 21.
Artigo em Inglês | MEDLINE | ID: mdl-31432836

RESUMO

N-Oxido copper(ii) ethylenediaminetetraacetate Na4n[Cu2(edtaO2)2(H2O)4]n·13nH2O (2) (H4edta = ethylenediaminetetraacetic acid, C10H16O8N2) and N-oxido copper(ii) 1,3-propanediaminetetraacetate Na5nOn[Cu2(HpdtaO2)2Cl]n·12.5nH2O (4) (H4pdta = 1,3-propanediaminetetraacetic acid, C11H18O8N2) were obtained from the reactions of copper(ii) edta and pdta respectively with hydrogen peroxide. The copper ions in 2 and 4 are hexa-coordinated by edtaO2 or pdtaO2 ligands, forming 1D chain structures. Further reactions of 2 and 4 at lower pH values result in the isolation of copper(ii) iminodiacetate K[Cu(ida)(H2O)2Cl] (3) (H2ida = iminodiacetate acid, C4H7O4N) and copper(ii) propanediaminediacetate [Cu2(pdda)2]n·nH2O (5) (H2pdda = propanediaminediacetic acid, C7H10O4N2), respectively, which show the selective degradation of ethylenediaminetetraacetate and propanediaminetetraacetate.

4.
Dalton Trans ; 48(9): 2959-2966, 2019 Feb 26.
Artigo em Inglês | MEDLINE | ID: mdl-30741287

RESUMO

Novel additives of lanthanum aminopolycarboxylates with inorganic anions, Na12n[La(edta)L]4n·8nNaCl·4nH2O (1: L = HPO32-; 2: L = CO32-) and K12n[La(cdta)(CO3)]4n·35nH2O (3) (H4edta = ethylenediaminetetraacetic acid; H4cdta = cyclohexanediaminetetraacetic acid), were obtained in alkaline solution. Structural analyses reveal that 1 and 2 are isomorphous and contain interesting square structures. HPO32- (CO32-) was encaged in the constructed tetranuclear frameworks. Tetranuclear lanthanum ethylenediaminetetraacetate was further encaged in superstructures of sodium chloride. 3 has a similar square structure, in which edta is replaced by cdta. All complexes are fully characterized via elemental, FT-IR, NMR, thermogravimetric and structural analyses. Solution 13C NMR spectra show that 1 and 2 dissociate into mononuclear units in water. Interestingly, 2 possesses 3.7 Å diameter holes inside its crystals, which can adsorb a small amount of O2 or CO2 selectively. The amounts of O2 and CO2 adsorbed increase gradually from 0.32 and 0.38 mg g-1 at 0.4 bar to 15.90 and 10.54 mg g-1 at 29.9 bar, respectively.

5.
Inorg Chem ; 58(4): 2523-2532, 2019 Feb 18.
Artigo em Inglês | MEDLINE | ID: mdl-30726074

RESUMO

A similar pair of protonated and deprotonated mononuclear oxidovanadium glycolates [VO(Hglyc)(phen)(H2O)]Cl·2H2O (1) and [VO(glyc)(bpy)(H2O)] (2) and a mixed-(de)protonated oxidovanadium triglycolate (NH4)2[VO(Hglyc)2(glyc)]·H2O (3) were isolated and examined. The ≡C-O(H) (≡C-OH or ≡C-O) groups coordinated to vanadium were spectroscopically and structurally identified. The glycolate in 1 features a bidentate chelation through protonated α-hydroxy and α-carboxy groups, whereas the glycolate in 2 coordinates through deprotonated α-alkoxy and α-carboxy groups. The glycolates in 3 coordinate to vanadium through α-alkoxy or α-hydroxy and α-carboxy groups and thus have both protonated ≡C-OH and deprotonated ≡C-O bonds simultaneously. Structural investigations revealed that the longer protonated V-Oα-hydroxy bonds [2.234(2) Å and 2.244(2) Å] in 1 and 3 are close to those of FeV-cofactor (FeV-co) 2.17 Å1 (FeMo-co 2.17 Å2), while deprotonated V-Oα-alkoxy bonds [2, 1.930(2); 3, 1.927(2) Å] were obviously shorter. This shows a similar elongated trend as the Mo-O distances in the previously reported deprotonated vs protonated molybdenum lactates (Wang, S. Y. et al. Dalton Trans. 2018, 47, 7412-7421) and these vanadium and molybdenum complexes have the same local V/Mo-homocitrate structures as those of FeV/Mo-cos of nitrogenases. The IR spectra of these oxidovanadium and the previously synthesized molybdenum complexes including different substituted ≡C-O(H) model compounds show red-shifts for ≡C-OH vs ≡C-O alternation, which further assign the two IR bands of extracted FeMo-co at 1084 and 1031 cm-1 to ≡C-O and ≡C-OH vibrations, respectively. Although the structural data or IR spectra for some of the previously synthesized Mo/V complexes and extracted FeMo-co were measured earlier, this is the first time that the ≡C-O(H) coordinated peaks are assigned. The overall structural and IR results well suggest the coexistence of homocitrates coordinated with α-alkoxy (deprotonated) and α-hydroxy (protonated) groups in the extracted FeMo-co.

6.
Inorg Chem ; 57(22): 14116-14122, 2018 Nov 19.
Artigo em Inglês | MEDLINE | ID: mdl-30376302

RESUMO

Water-soluble wheel-like icosanuclear peroxotitanate K16[Ti20(µ-O)8(HO2)8(O2)12( R, R-tart)12]·52H2O (1) chelated by tartrate has been successfully isolated. As the largest peroxotitanate reported, {Ti20} features 20 (hydro)peroxo groups with three kinds of coordination modes in µ-η1:η2, µ-η2:η2, and η2 fashions. The cluster is stable in solution and solid states. It has been tested for the catalytic oxidations of methyl phenyl sulfide and pyridine with hydrogen peroxide, respectively, which shows reversible elimination and the addition of peroxo groups. This provides a rare example of well-characterized titanium peroxide for homogeneous catalysis and mechanism research.

7.
Dalton Trans ; 47(22): 7412-7421, 2018 Jun 05.
Artigo em Inglês | MEDLINE | ID: mdl-29786717

RESUMO

Glycolato and R,S-lactato imidazole molybdenum(iv) complexes [Mo3SO3(glyc)2(im)5]·im·H2O (1), Na2[Mo3SO3(R,S-lact)3(im)3]·10H2O (2), and [Mo6O10(R,S-lact)2(im)10]·16H2O (3) have been isolated and characterized (H2glyc = glycolic acid, H2lact = lactic acid, im = imidazole). α-Alkoxy coordination with molybdenum [Mo-Oα-alkoxy 1.993(7)av Å] in 1 and 2 showed obvious differences to their counterpart with α-hydroxy coordination [MoIV3S4(PPh3)3(Hlact)2(lact)] [2.204(4)av Å] as shown in M. N. Sokolov, S. A. Adonin, A. V. Virovets, P. A. Abramov, C. Vicent, R. Llusar and V. P. Fedin, Inorg. Chim. Acta, 2013, 395, 11-18. This was also true for the 36 reported structures of FeMo-cofactors in the RCSB protein data bank (Mo-Oav 2.272 Å), which can serve as indirect evidence for the protonation of homocitrate in FeMo-co. The C-OHα-hydroxy bonds were longer than the short C-Oα-alkoxy bonds. Trinuclear Mo3SO3 cores were stabilized by imidazoles and/or α-hydroxycarboxylates, whereas only two glycolates were present in 1. α-Hydroxycarboxylates in 1 and 2 acted as bidentate ligands of Mo(iv) atoms through α-alkoxy and α-carboxy groups, while the imidazoles coordinated monodentately with nitrogen atoms. The lactates in 3 coordinated with Mo(iv) atoms through two oxygen atoms of α-carboxy groups, leaving the α-hydroxy group free. Furthermore, novel hexanuclear oxomolybdenum(v) malate Na6[(Mo2O4)3(mal)4]·5H2O (4) was also isolated (H3mal = malic acid). Solid-state and solution 13C NMR resonances of carbon atoms in α-alkoxy groups appeared in a high-field region (71.6, 77.4 ppm), indicating that α-alkoxy groups were easy to protonate.


Assuntos
Carbonatos/química , Imidazóis/química , Molibdênio/química , Molibdoferredoxina/química , Nitrogenase/química , Glicolatos/química , Ferro/metabolismo , Ácido Láctico/química , Ligantes , Malatos/química , Nitrogênio/metabolismo , Conformação Proteica , Prótons , Ácidos Tricarboxílicos/química
8.
Langmuir ; 34(1): 291-301, 2018 01 09.
Artigo em Inglês | MEDLINE | ID: mdl-29228778

RESUMO

Effects of calcium ions (Ca2+) on the solubility, aggregate structure, and rheological behavior of a C22-tailed zwitterionic surfactant, erucyl dimethyl amidopropyl hydroxyl sulfobetaine (EHSB), have been investigated in aqueous solution. In comparison with sodium ions (Na+), Ca2+ ions exhibit a much higher efficiency in decreasing the Krafft temperature (TK) of EHSB. Specifically, contrary to Na+ ions which have no obvious effect on the rheological properties of the EHSB solution, Ca2+ ions increase the viscosity of the EHSB solution at lower EHSB concentration, and enhance its elasticity at higher EHSB concentration. Moreover, Ca2+ ions raise the temperature needed for the elastic-to-viscous transition of the EHSB solution at higher concentration. At lower EHSB concentration, the hydrophobic interaction between the ultralong hydrocarbon chains induces a tighter packing of the hydrophobic chains by forming a more stretched configuration, while at higher EHSB concentration, the electrostatic attraction between Ca2+ ions and the sulfonate groups of EHSB induces a tighter packing of the headgroups by forming Ca2+-mediated bridges among the EHSB headgroups. Besides, the above interactions may strengthen the hydrogen bonding of OH groups and/or of C═O amide groups, which in turn facilitates the compact packing of the surfactant molecules in aggregates and promotes the growth and entanglement of wormlike micelles. Thus, the EHSB solution shows Ca2+-dependent rheological behaviors. The solubility and rheological properties of the ultralong chain surfactant solution can be simultaneously improved with the addition of divalent Ca2+ ions.

9.
Org Biomol Chem ; 15(25): 5395-5401, 2017 Jun 27.
Artigo em Inglês | MEDLINE | ID: mdl-28621782

RESUMO

Chiral amino alcohol-copper(ii) catalysts Cu-L1c and Cu-ent-L1c were utilized to promote the diastereoselective nitroaldol reactions of chiral aldehydes (S)-3 or (R)-3 with nitromethane, which respectively led to the preferential formation of certain stereoisomer for nitro diol derivatives 4. Using this catalytic protocol, all the four stereoisomers of the antidepressant reboxetine were divergently prepared. The highest overall yield of this synthetic route reached up to 30.5% from aldehyde (S)-3.


Assuntos
Antidepressivos/química , Antidepressivos/síntese química , Morfolinas/química , Morfolinas/síntese química , Estrutura Molecular , Reboxetina , Estereoisomerismo
10.
Org Biomol Chem ; 15(6): 1530-1536, 2017 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-28116376

RESUMO

Chiral ß-amino alcohol ligands were found effective for the copper(ii)-catalyzed asymmetric Henry reaction of benzofuran-2-carbaldehydes with nitromethane, which led to the formation of (S)-enriched benzofuryl ß-nitro alcohols with satisfactory enantioselectivities (up to 98% ee). Using this catalytic protocol, bioactive (S)-benzofuryl ß-amino alcohols could be conveniently prepared in short steps.

11.
Dalton Trans ; 46(4): 1290-1296, 2017 Jan 24.
Artigo em Inglês | MEDLINE | ID: mdl-28067375

RESUMO

Unlike the usual formations of peroxo and superoxo cobalt products as oxygen carriers, N-oxido cobalt(ii) ethylenediaminetetraacetates K4[Co2(edtaO2)2]·nH2O [n = 6.5 (1), 10 (2), H4edta = ethylenediaminetetraacetic acid, C10H16O8N2] and their aggregate [Co2(edtaO2)(H2O)6]n·2nH2O (3) were obtained as dioxygen insertion products. The cobalt ions in dimers 1 and 2 are hexa-coordinated by two edtaO2 ligands in different configurations respectively, which is attributed to the packing of an interesting (H2O)12 water cluster in 2. Further reaction of K4[Co2(edtaO2)2]·nH2O with hydrogen peroxide results in the final trivalent cobalt ethylenediaminetetraacetate K[Co(edta)]·2H2O (4). A water-soluble coordination polymer Na2n[Co(edta)]n·4nH2O (5) was also obtained with a one dimensional zigzag structure. Bond valence calculation is consistent with the products 1-5.

12.
Zhongguo Gu Shang ; 30(4): 318-321, 2017 Apr 25.
Artigo em Chinês | MEDLINE | ID: mdl-29349980

RESUMO

OBJECTIVE: To compare the clinical effects of arthroscopic debridement versus open debridement on controlling and treatment of infection after total knee replacement. METHODS: From October 2009 to September 2016 in three hospitals, 11 patients with 11 joints which were infected after total knee replacement were randomly divided into two groups:5 cases in arthroscopy group and 6 cases in routine group. Patients in arthroscopy group were treated with arthroscopic debridement to remove the necrotic tissues, then closed-type irrigation with sensitive antibiotics by using two sebific ducts were performed continuously for 2 or 3 weeks until the flushing fluid became clear for 3 or 5 days;other 6 patients in routine group were treated with open surgical debridement and the following procedures in keeping with those in the arthroscopy group. Operation time, blood loss and incision length were recorded during the operation, and pain scores were recorded on the 1st, 3rd and 7th day after the operation. The curative effects were evaluated according to the Hospital for Special Surgery score system. RESULTS: The local and general symptoms of the 11 patients disappeared, and the test outcomes of biochemistry, blood and synovial fluid were normal. All patients were followed up, and the duration ranged from 6 to 18 months. Infection recurrences were observed in 1 case of arthroscopy group and 2 cases of routine group 3 months later after operation, and all these patients who underwent the second time operation with arthroscopic debridement were cured. According to the Hospital for Special Surgery score system, 3 cases obtained excellent result, 2 good, no poor and bad cases in arthroscopy group;3 cases obtained excellent result, 1 good, 1 poor and 1 bad in routine group. CONCLUSIONS: If the sensitive antibiotics can be found for the infected joints without obvious destruction of bone and no prosthesis loosening, it has a better therapeutic effect by using arthroscopic debridement combined with continuous drainage and irrigation. The method has a better curative effect with smaller trauma.


Assuntos
Artroplastia do Joelho , Artroscopia , Infecções Bacterianas/cirurgia , Desbridamento/métodos , Complicações Pós-Operatórias/cirurgia , Artroplastia do Joelho/efeitos adversos , Humanos , Irrigação Terapêutica , Resultado do Tratamento
13.
Dalton Trans ; 45(12): 5388-94, 2016 Mar 28.
Artigo em Inglês | MEDLINE | ID: mdl-26906409

RESUMO

Direct reactions of the MRI contrast agent K2[Gd(DTPA)(H2O)]·5H2O (1) (H5DTPA = diethylenetriaminepentaacetic acid) with dipotassium hydrogen phosphate (K2HPO4) or phosphite (K2HPO3) result in the isolation of well-defined Gd-DTPA phosphite K6[Gd2(DTPA)2(HPO3)]·7H2O (2) or phosphate K6[Gd2(DTPA)2(HPO4)]·10H2O (3), respectively. Their lanthanum analogs K4[La2(DTPA)2(H2O)]·8H2O (4), K6[La2(DTPA)2(HPO3)]·7H2O (5) and K6[La2(DTPA)2(HPO4)]·10H2O (6) are used for comparison. The phosphate and phosphite groups are able to substitute the coordinated water molecules in 1 and 4 in a close physiological aqueous solution, and act as bridging ligands to link adjacent Ln(DTPA)(2-) (Ln = Gd and La) into dimeric structures. Solid state and solution (13)C NMR spectra of dimer 4 show complete dissociation into its monomeric species in solution, while no dissociation is observed for lanthanum phosphite 5 and phosphate 6 in solution, which show only one set of (13)C spectra with the largest downfield shifts at 182.0 and 182.3 ppm respectively. Comparisons of the bond distances and spectral data indicate that the interaction between DTPA and central Ln(3+) cations are weakened after the substitutions, which support phosphate substituted Gd-DTPA as an initial intermediate in nephrogenic systemic fibrosis.


Assuntos
Meios de Contraste/química , Gadolínio DTPA/química , Fosfatos/química , Fosfitos/química , Cristalografia por Raios X , Dimerização , Lantânio/química , Imagem por Ressonância Magnética , Espectroscopia de Ressonância Magnética , Conformação Molecular , Compostos de Potássio/química
14.
Soft Matter ; 11(40): 7960-8, 2015 Oct 28.
Artigo em Inglês | MEDLINE | ID: mdl-26323459

RESUMO

The contact angle measurements for the aqueous solutions of two pairs of zwitterions on quartz surfaces have been investigated by the sessile drop analysis. The different physicochemical parameters such as the critical micelle concentration (CMC), surface tension, contact angle, surface excess on air-liquid and solid-liquid interfaces and work of adhesion have been estimated. The obtained results show that the contact angle of surfactants such as alkyl carboxylbetaine (ACB) and ditolyl substituted alkyl carboxylbetaine (BCB) remains almost constant in a wide range of surfactant concentration and increases gradually above CMC, which are quite different from traditional surfactants reported in the literature. Surfactants with bigger polar groups have a more steric effect on the quartz surface and the contact angle remains relatively unchanged. Moreover, an increase in quartz-liquid interfacial tension (γSL) has been observed due to the adsorption of four zwitterionic surfactants. Especially for ACB and BCB, at the surfactant concentrations higher than 5 × 10(-5) mol L(-1), a moderate increase in the interfacial tension of the quartz-liquid is observed, which suggests that ACB and BCB can form a saturated adsorption film briefly on the quartz surface and then adsorb again. However, the addition of alkyl sulfobetaine (ASB) and ditolyl substituted alkyl sulfobetaine (BSB) after CMC cannot adsorb on the quartz surface again due to the steric effect of bigger polar groups.

15.
J Inorg Biochem ; 141: 114-120, 2014 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-25240212

RESUMO

Unlike the most of α-alkoxy coordination in α-hydroxycarboxylates to vanadium, novel α-hydroxy coordination to vanadium(IV) has been observed for a series of chiral and achiral monomeric α-hydroxycarboxylato vanadyl complexes [VO(H2cit)(bpy)]·2H2O (1), [VO(Hmal)(bpy)]·H2O (2), [VO(H2cit)(phen)]·1.5H2O (3), [VO(Hmal)(phen)]·H2O (4), and [(Δ)VO(S-Hcitmal)(bpy)]·2H2O (5), [VO(H2cit)(phen)]2·6.5H2O (6), which were isolated from the reactions of vanadyl sulfate with α-hydroxycarboxylates and N-heterocycle ligands in acidic solution. The complexes feature a tridentate citrate, malate or citramalate that chelates to vanadium atom through their α-hydroxy, α-carboxy and ß-carboxy groups; while the other ß-carboxylic acidic group of citrate is free to participate strong hydrogen bonds with lattice water molecule. The neutral α-hydroxy group also forms strong intermolecular hydrogen bonds with water molecule and the negatively-charged α-carboxy group in the environment. The inclusion of a hydrogen ion in α-alkoxy group results in the formation of a series of neutral complexes with one less positive charge. There are two different configurations of citrate with respect to the trans-position of axial oxo group, where the complex with trans-hydroxy configuration seems more stable with less hindrance. The average bond distances of V-Ohydroxy and V-Oα-carboxy are 2.196 and 2.003Å respectively, which are comparable to the VO distance (2.15Å) of homocitrate in FeV-cofactor of V-nitrogenase. A new structural model is suggested for R-homocitrato iron vanadium cofactor as VFe7S9C(R-Hhomocit) (H4homocit=homocitric acid) with one more proton in homocitrate ligand.


Assuntos
Complexos de Coordenação/química , Malatos/química , Metaloproteínas/química , Nitrogenase/química , Compostos Organometálicos/química , Prótons , Proteínas de Algas/química , Proteínas de Bactérias/química , Ácidos Carboxílicos/química , Cristalografia por Raios X , Ligações de Hidrogênio , Concentração de Íons de Hidrogênio , Ligantes , Estrutura Molecular , Soluções , Eletricidade Estática , Estereoisomerismo
16.
Zhongguo Zhen Jiu ; 34(7): 636-40, 2014 Jul.
Artigo em Chinês | MEDLINE | ID: mdl-25233646

RESUMO

OBJECTIVE: To compare the clinical efficacy in the treatment of post-stroke shoulder-hand syndrome between floating-needle therapy and conventional acupuncture on the basis of rehabilitation training. METHODS: One hundred cases of post-stroke shoulder-hand syndrome were randomized into a floating-needle group and an acupuncture group, 50 cases in each one. The passive and positive rehabilitation training was adopted in the two groups. Additionally, in the floating-needle group, the floating-needle therapy was used. The needle was inserted at the site 5 to 10 cm away from myofasical trigger point (MTrP), manipulated and scattered subcutaneously, for 2 min continuously. In the acupuncture group, the conventional acupuncture was applied at Jianqian (EX-UE), Jianyu (LI 15), Jianliao (TE 14), etc. The treatment was given once every two days, 3 times a week, and 14 days of treatment were required. The shoulder hand syndrome scale (SHSS), the short form McGill pain scale (SF-MPQ) and the modified Fugl-Meyer motor function scale (FMA) were used to evaluate the damage severity, pain and motor function of the upper limbs before and after treatment in the two groups. The clinical efficacy was compared between the two groups. RESULTS: SHSS score, SF-MPQ score and FMA score were improved significantly after treatment in the two groups (all P < 0.01), and the improvements in the floating-needle group were superior to those in the acupuncture group (all P < 0.05). The total effective rate was 94.0% (47/50) in the floating-needle group, which was better than 90.0% (45/50) in the acupuncture group (P < 0.05). CONCLUSION: The floating-needle therapy combined with rehabilitation training achieves a satisfactory efficacy on post-stroke shoulder-hand syndrome, which is better than the combined therapy of conventional acupuncture and rehabilitation training.


Assuntos
Terapia por Acupuntura , Distrofia Simpática Reflexa/reabilitação , Distrofia Simpática Reflexa/terapia , Acidente Vascular Cerebral/complicações , Terapia por Acupuntura/instrumentação , Terapia por Acupuntura/métodos , Adulto , Idoso , Idoso de 80 Anos ou mais , Feminino , Humanos , Masculino , Pessoa de Meia-Idade , Distrofia Simpática Reflexa/etiologia , Resultado do Tratamento , Adulto Jovem
17.
Dalton Trans ; 43(23): 8690-7, 2014 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-24769659

RESUMO

From neutral solutions, dimeric 1,3-propanediaminetetraacetato lanthanides (NH4)2[Ln2(1,3-pdta)2(H2O)4]·8H2O [Ln = La, 1; Ce, 2] and K2[Ln2(1,3-pdta)2(H2O)4]·11H2O [Ln = La, 3; Ce, 4] (1,3-H4pdta = 1,3-propanediaminetetraacetic acid, C11H18N2O8) were isolated in high yields. The reaction of excess strontium nitrate with 1 resulted in the formation of a two dimensional coordination polymer [La2(1,3-pdta)2(H2O)4]n·[Sr2(H2O)6]n·[La2(1,3-pdta)2(H2O)2]n·18nH2O (5) at 70 °C. Complexes 1-4 show a similar central molecular structure. The lanthanide ions are coordinated by two nitrogen atoms, four carboxy oxygen atoms from one 1,3-pdta ligand, two from the neighboring 1,3-pdta ligand forming a four-membered ring and two water molecules. Complex 5 has two kinds of dimeric lanthanum unit and extends into a 2D coordination polymer through strontium ions and bridged oxygen atoms, and forms a fourteen membered ring linked by oxygen atoms from carboxy groups of pdta. Complexes 1-4 are soluble in water. The (13)C{(1)H} NMR experiments for complex 1 were tested in solution. Thermal products from 1 and 5 show good catalytic activities towards the oxidative coupling reaction of methane (OCM). The conversion of methane and selectivity to C2 reached 29.7% and 51.7% at 750 °C for the product of 5. From TGA, XRD and SEM analyses, the thermal products from 1 and 5 are rod- and poly-shaped, which are assigned as lanthanum oxocarbonate and a mixture of La2O3, SrCO3 and La2O2CO3 for 1 and 5, respectively. The precursor method is favorable for the formation of regular shaped mixed oxides.

18.
Dalton Trans ; 43(16): 6026-31, 2014 Apr 28.
Artigo em Inglês | MEDLINE | ID: mdl-24382489

RESUMO

A new type of thermally stable chelate {La(H2O)4[La(1,3-pdta)(H2O)]3}n · 12nH2O (1) [1,3-H4pdtaCH2[CH2N(CH2CO2H)2]2] with an open-channel shows significant and unusual solvent transport properties and demonstrates a use for low-pressure desalination, which is constructed by cheap and available lanthanum salt and 1,3-propanediaminetetraacetate. The chelate could be converted reversibly to its trihydrate {La(H2O)4[La(1,3-pdta)(H2O)]3}n · 3nH2O (1a), dehydrated product {La(H2O)4[La(1,3-pdta)(H2O)]3}n (1b) and ethanol adduct {La(H2O)4[La(1,3-pdta)(H2O)]3}n · 3nH2O · 3nEtOH (1c). The latter nano-confined ethanol shows a remarkable downfield shift (Δδ = 6.0 ppm) for the methylene group in the solid 13C NMR spectrum compared with that of the free EtOH. Crystal 1 with a regular hexagonal appearance can be used directly for saline water desalination on a small-scale at an ambient temperature, demonstrating a low energy consumption and environmentally friendly method. This is attributed to the 10.0 Å hydrophobic open-channel containing water nanotubes (WNTs, Φ = 4.2 Å). The nano-confined WNTs can be removed at a low temperature (45 °C).

19.
Dalton Trans ; 43(2): 639-45, 2014 Jan 14.
Artigo em Inglês | MEDLINE | ID: mdl-24132302

RESUMO

In neutral media, reactions of gadolinium ethylenediaminetetraacetates with phosphorous acid result in the formation of the mixed-ligand polymeric complex K3n[Gd(EDTA)(HPO3)]n·7nH2O () and dimeric complex Na6[Gd2(EDTA)2(HPO3)2]·2.5NaCl·21H2O () (H4EDTA = ethylenediaminetetraacetic acid) in warm solution. Further substitution with citric acid gives the monomeric gadolinium citrate with EDTA (NH4)2Na[Gd(EDTA)(H2cit)]·4H2O (). The compounds were characterized by elemental analysis, single crystal X-ray diffraction, FT-IR, ESI-MS and thermogravimetric analysis. Structural analysis indicates that three coordinated water molecules in the gadolinium ethylenediaminetetraacetate trihydrates are replaced by phosphite ions (HPO3(2-)) in the compounds and . Gadolinium atoms are octa-coordinated by EDTA and the phosphite ion, the latter links adjacent Gd-EDTA units to generate an infinite one-dimensional chain in compound and a dimeric octatomic ring in . In complex , coordinated water molecules were substituted by the α-hydroxy, α-carboxy and ß-carboxy groups of citrate. Citrate is favourable for inhibiting the formation of Gd-EDTA phosphite. All the complexes are very easily soluble in water. The solution behavior of the isostructural lanthanum complexes was probed with (13)C and (31)P NMR spectra in D2O for comparison. ESI-MS analysis and recrystallization proved that complexes and dissociate to the monomeric unit of Gd-EDTA and free HPO3(2-) in aqueous solution. Substitutions of gadolinium ethylenediaminetetraacetates to and are attributed to be the cause of nephrogenic systemic fibrosis in some way.


Assuntos
Meios de Contraste/química , Ácido Edético/química , Gadolínio/química , Dermopatia Fibrosante Nefrogênica/diagnóstico , Compostos Organometálicos/química , Fosfitos/química , Cristalografia por Raios X , Humanos
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