Functional outcome and health-related quality of life after traumatic brain injury in the framework of the International Classification of Functioning, Disability and Health (ICF)

Traumatic brain injury (TBI) affects people of all ages and is a cause of long-term disability. In recent years, the epidemiological patterns of TBI have been changing. TBI is a heterogeneous disorder with different forms of presentation and highly individual outcome regarding functioning and health-related quality of life (HRQoL). The meaning of disability differs from person to person based on the individual s personality, value system, past experience, and the purpose he or she sees in life. Understanding of all these viewpoints is needed in comprehensive rehabilitation. This study examines the epidemiology of TBI in Finland as well as functioning and HRQoL after TBI, and compares the subjective and objective assessments of outcome. The frame of reference is the International Classification of Functioning, Disability and Health (ICF). The subjects of Study I represent the population of Finnish TBI patients who experienced their first TBI between 1991 and 2005. The 55 Finnish subjects of Studies II and IV participated in the first wave of the international Quality of life after brain injury (QOLIBRI) validation study. The 795 subjects from six language areas of Study III formed the second wave of the QOLIBRI validation study. The average annual incidence of Finnish hospitalised TBI patients during the years 1991-2005 was 101:100 000 in patients who had TBI as the primary diagnosis and did not have a previous TBI in their medical history. Males (59.2%) were at considerably higher risk of getting a TBI than females. The most common external cause of the injury was falls in all age groups. The number of TBI patients ≥ 70 years of age increased by 59.4% while the number of inhabitants older than 70 years increased by 30.3% in the population of Finland during the same time period. The functioning of a sample of 55 persons with TBI was assessed by extracting information from the patients medical documents using the ICF checklist. The most common problems were found in the ICF components of Body Functions (b) and Activities and Participation (d). HRQoL was assessed with the QOLIBRI which showed the highest level of satisfaction on the Emotions, Physical Problems and Daily Life and Autonomy scales. The highest scores were obtained by the youngest participants and participants living independently without the help of other people, and by people who were working. The relationship between the functional outcome and HRQoL was not straightforward. The procedure of linking the QOLIBRI and the GOSE to the ICF showed that these two outcome measures cover the relevant domains of TBI patients functioning. The QOLIBRI provides the patients subjective view, while the GOSE summarises the objective elements of functioning. Our study indicates that there are certain domains of functioning that are not traditionally sufficiently documented but are important for the HRQoL of persons with TBI. This was the finding especially in the domains of interpersonal relationships, social and leisure activities, self, and the environment. Rehabilitation aims to optimize functioning and to minimize the experience of disability among people with health conditions, and it needs to be based on a comprehensive understanding of human functioning. As an integrative model, the ICF may serve as a frame of reference in achieving such an understanding.

Influence of cerebral ischemia and post-ischemic reperfusion on mitochondrial oxidative phosphorylation

Unilateral ischemia in the right cerebral hemisphere of the rat was induced by ligation of the right common carotid artery coupled with controlled hemorrhage to produce hypotension (25±8 mm/Hg). Where indicated after 30 min of ischemia, the withdrawn blood was reinfused to restore arterial pressure to normal. Mitochondria isolated from the ipsilateral hemisphere after 30 min of ischemia showed significantly lower respiratory rates than the organelles isolated from the contralateral side. Oxidation of NAD+-linked substrates was more sensitive to inhibition in ischemia (30%) than was of ferrocytochromec (12%), succinate oxidation being intermediate. The activities of membrane-bound dehydrogenases (both NADH and succinate-linked) were also significantly lowered. Ischemia did not affect the cytochrome content of mitochondria. Respiratory activity (NAD+-linked) of mitochondria isolated from the ipsilateral hemisphere was twice as sensitive to inhibition by fatty acid as was of preparations from the contralateral side. Mitochondria isolated from cerebral cortex after 90 min of post-ischemic reperfusion showed no significant improvement in the rate of substrate oxidation. Adenine nucleotide translocase activity and energy-dependent Ca2+ uptake, both of which decreased significantly in mitochondria isolated from the ischemic brain, showed little recovery, on reperfusion. These observations suggested the strong possibility that the deleterious effects of ischemia on mitochondrial respiratory function might be mediated by free fatty acids that are known to accumulate in large amounts in ischemic tissues. The pattern of inhibition of ATPase activity was consistent with this view.

Oxidative copolymerization: microstructure analysis of the terpolymer of styrene, methyl methacrylate, and oxygen

This paper reports the first study of the microstructure of a copolyperoxide by nuclear magnetic resonance spectroscopy. The copolyperoxides of styrene and methyl methacrylate (MMA) of various compositions have been synthesized. An analysis of the resonance signal of the backbone methylene protons gave the diad sequence probabilities which led to the calculation of the oxidative copolymerization reactivity ratios for styrene and MMA and the microstructural parameters like average chain length of the repeat unit sequences, run number, etc. The results point to the tendency of the SO1 and MO:! units to alternate in the chain. Compared to poly(styrene peroxide), the aromatic C1 seems to be stereosensitive in the terpolymers.

A simplified kinetic model for oxidative dehydrogenation of ethylbenzene over Pd-NaBr/Al2O3 catalyst

The oxidative dehydrogenation of ethylbenzene is gaining considerable importance in recent years as a promising alternative for styrene production. This vapour phase reaction has been studied over Pd-NaBr/Al2O3 catalyst in the temperature range 623-793 K in a fixed bed reactor. Kinetic analysis of this reaction has been done using a recursion procedure developed in this work from first principles. The advantage of this method is the absence of any restriction on the conversion level as it uses an integrated rate equation. The rate of styrene formation was found to follow a linear relationship with concentration of ethylbenzene and shows a Langmuir type dependence on the concentration of oxygen.

Heterogeneous permanganate oxidations: Synthesis of medium ring keto-lactones via substituent directed oxidative cyclisation

Homoallyl alcohols 4a-b and 5a-b undergo smooth oxidative cyclisation to give the corresponding ring enlarged keto-lactones under heterogeneous permanganate oxidation conditions.

Towards the total synthesis of tashironin related allo-cedrane natural products: further exploitation of the oxidative dearomatization-IMDA-RCM triad based strategy

Synthetic studies directed towards allo-cedrane based, tashironin sibling natural products, involving some deft functional group manipulations on a preformed tetracyclic scaffold, are delineated. (C) 2011 Elsevier Ltd. All rights reserved.

Glutathione peroxidase3 of Saccharomyces cerevisiae protects phospholipids during cadmium-induced oxidative stress

The present study was undertaken to determine the role of glutathione peroxidase3 (gpx3) in phospholipid protection in cells. Wild-type (WT) cells showed an overall increase in phospholipids upon 50 mu M cadmium (Cd)-treatment, whereas an untreated gpx3 Delta strain showed a drastic reduction in overall phospholipids which was further reduced with 50 mu M Cd. In WT cells, Cd-exposure increased the short chain fatty acids and decreased the unsaturated fatty acids and the magnitude was high in Cd-treated gpx3 Delta cells. Purified recombinant gpx3p showed higher activity with phospholipid hydroperoxides than shorter hydroperoxides. An increase in gpx activity was observed in Cd-treated WT cells and no such alteration was observed in gpx3 Delta. WT cells treated with Cd showed an increase in MDA over untreated, while untreated gpx3 Delta cells themselves showed a higher level of MDA which was further enhanced with Cd-treatment. Iron, zinc and calcium levels were significantly altered in WT and gpx3 Delta cells during Cd-treatment.

Organometallic Chemistry of Diphosphazanes. 11. Reactions of fac-[Mo(CO)3(MeCN){.eta.2-Ph2PN(Pri)PPh(DMP)}] (DMP = 3,5-Dimethyl-1-Pyrazolyl) with Diphosphazanes and Diphosphinoalkanes and Oxidative Addition with Iodine

The use of fac-[Mo(CO)(3)(MeCN)(eta(2)-L(1))] (1a) {L(1) = Ph(2)PN(Pr-i)PPh(DMP)}(2) as a precursor to metalloligands and bimetallic, heterotrimetallic, and heptacoordinated complexes is reported. The reaction of 1a with diphosphazane, dppa, or a diphosphinoalkane such as dppm or dppe yields the fac-eta(1)-diphosphine substituted metalloligands, fac-[Mo(CO)(3)(eta(2)-L(1))(eta(1)-PXP)] {PXP = dppa (2), dppm (3), and dppe (4)}. These undergo isomerization to yield the corresponding mer-diphosphine complexes (5-7). Oxidation of the uncoordinated phosphorus atom of the mer-eta(1)-dppm-substituted complex eventually provides mer-[Mo(CO)(3)-(eta(2)-L(1)){eta(1)-Ph(2)PCH(2)P(O)Ph(2)}](8). The structure of the latter complex has been confirmed by single crystal X-ray diffraction {triclinic system, P ($) over bar 1; a = 11.994(3), b = 14.807(2), c = 15.855(3) Angstrom; alpha = 114.24(1), beta = 91.35(2), and gamma = 98.95(1)degrees; Z = 2, 4014 data (F-0 > 5 sigma(F-0)), R = 0.066, R(W) = 0.069}. Treatment of the dppe metalloligand 7 with [PtCl2(COD)] yields the heterotrimetallic complex cis-[PtCl2{mer-[Mo(CO)(3)(eta(2)-L(1))(eta(1)-dppe]}(2)] (9). Attempts to prepare a related trimetallic complex with the dppm-containing metalloligand were unsuccessful; only the tetracarbonyl complex cis-[Mo(CO)(4)(eta(2)-L(1))] (1b) and cis-[PtCl2(eta(2)-dppm)] were obtained. Reaction of la with dppe in the ratio 2:1 yields the mer-mer dinuclear complex [{mer-[Mo(CO)(3)(eta(2)-L(1))]}(2)(mu-dppe)] (10) bridged by dppe. Oxidation of 1a with iodine yields the Mo(II) heptacoordinated complex [MoI2(CO)(2)(eta(3)-L(1))] (11) with tridentate PPN coordination. The same Mo(II) complex 11 is also obtained by the direct oxidation of the tetracarbonyl complex cis-[Mo(CO)(4)(eta(2)-L(1))] (1b) with iodine. The structure of 11 has been confirmed by X-ray diffraction studies {monoclinic system, Cc; a = 10.471(2), b = 19.305(3), c = 17.325(3) Angstrom; beta = 95.47(2)degrees; Z = 4, 3153 data (F-0 > 5 sigma(F-0)), R = 0.049, R(W) = 0.051}. This complex exhibits an unusual capped-trigonal prismatic geometry around the metal. A similar heptacoordinated complex 12 with a chiral diphosphazane ligand {L(3) = (S,R)-P(h)2PN-(*CHMePh)*PPh(DMP)} has also been synthesized.

Mechanism of “Autoacceleration” in the Thermal Oxidative Polymerization of R-Methylstyrene

Thermal oxidative polymerization of alpha-methylstyrene (AMS) has been studied at various temperatures(45-70 degrees C) and pressures (50-400 psi). Due to its high electron dense double bond, it undergoes thermal oxidative polymerization even at low temperatures fairly easily. The major products are poly(alpha-methylstyrene peroxide) (PMSP), and its decomposition products are acetophenone and formaldehyde. Above 45 degrees C the rate of polymerization increases sharply at a particular instant showing an ''autoacceleration'' with the formation of a knee point. The ''autoacceleration'' is supported from the fact that the plot, of R-p vs T shows a rapid rise, and the plot of ln R-p vs 1/T is non-Arrhenius. The occurrence of autoacceleration is explained on the basis of acetophenone-induced cleavage of PMSP during polymerization, generating more initiating alkoxy radicals, which subsequently leads to the rapid rise in the rate of polymerization. The mechanism of autoacceleration is supported by the change in. order, activation energy, and activation volume before and after the knee point.

Oxidative addition of tetrachloro-1,2-benzoquinone to lambda(3)-cyclotriphosphazanes. An unusual ring contraction-rearrangement

The lambda(3)-cyclotriphosphazanes, [EtNP(OR)](3) [R = 2,6-Me2C6H3 (1), 4-BrC6H4 (2), or CH2CF3(3)], on treatment with tetrachloro-1,2-benzoquinone (TCB) give the lambda(5)-cyclodiphosphazanes, [EtNP(O2C6Cl4)(OR)][EtNP(O2C6Cl4){N(Et)P(OR)(2)}] (5-7) by an unusual ring contraction-rearrangement. The reaction of the mixed substituent lambda(3)-cyclotriphosphazane, [(EtN)(3)P-3(OR)(2)(OR')] [R = 2,6-Me2C6H3, R' = 4-BrC6H4] (4), with TCB gives the lambda(5)-cyclodiphosphazane, [EtNP(O2C6Cl4)(OR')][EtNP(O2C6Cl4){N(Et)P(OR)(2)}] (8), in which 4-bromophenoxide resides on one of the ring phosphorus atoms. The lambda(3)-bicyclic tetraphosphapentazane, (EtN)(5)P-4(OPh)(2), on treatment with TCB undergoes a double ring contraction-rearrangement to give the lambda(5)-cyclodiphosphazane, (EtN)[(EtN)(2)P-2(O2C6Cl4)(2)(OPh)](2) (9). Variable-temperature and high-field P-31 NMR studies indicate the presence of more than one isomer in solution for the rearranged products 5-9. The solid state structure of 8 reveals a trans arrangement of the substituents with respect to the P2N2 ring in contrast to the gauche arrangement observed for 5.

Catalytic oxidative polymerization of 1,1-diphenylethylene at ambient temperature and potential application of peroxide macroinitiator

The Co(II)TPP(Py) complex was used as an efficient dioxygen carrier for the radical polymerization of 1,1-diphenylethylene (DPE), which has a low ceiling temperature, at ambient temperature and low oxygen pressure. The mechanism of polymerization is discussed' on the basis of kinetic data, W-vis, ESR, and H-1 NMR studies. The rate of polymerization (RP) and number-average molecular weights (M) of poly(1,1-diphenylethylene peroxide) (PDPEP) are higher and the polydispersity is lower than in 2,2'-azobis(isobutyronitrile) (AIBN) initiated polymerization. PDPEP was further. used as a macroinitiator for the polymerization of MMA. The polymerization obeys classical kinetics. The K-2 value of the PDPEP has been determined from the slope of R-P(2) VS [M](2)[I], which reveals that it can also be used at higher temperature for the polymerization. An "active" PMMA was also synthesized, containing initiating segments in the polymer backbone.

Determination of the reactivity ratios for the oxidative copolymerizations of indene with methyl, ethyl and butyl acrylates

Full Paper: The copolyperoxides of various compositions of indene with methyl acrylate, ethyl acrylate and butyl acrylate have been synthesized by the free-radical-initiated oxidative copolymerization. The compositions of copolyperoxide obtained from H-1 and C-13 NMR spectra have been used to determine the reactivity ratios of the monomers. The copolyperoxides contain a greater proportion of the indene units in random placement. The NMR studies have shown irregularities in the copolyperoxide chain due to the cleavage reactions of the propagating peroxide radical. The thermal analysis by differential scanning calorimetry suggests alternating peroxide units in the copolyperoxide chain. From the activation energy for the thermal degradation, it was inferred that degradation occurs via the dissociation of the peroxide (O-O) bonds of the copolyperoxide chain. The flexibility of the polyperoxides in terms of glass transition temperature (T-g) has also been examined.

High-pressure kinetics of oxidative copolymerization of styrene with alpha-methyl styrene

This is the first report on the study carried out on high-pressure free-radical initiated oxidated copolymerization of styrene (STY) with alpha-methylstyrene (AMS) at various temperatures (45-65degreesC) at constant pressure (100 psi) and then at various pressures (50-300 psi) keeping the temperature (50degreesC) constant. The compositions of the copolyperoxides obtained from the H-1 NMT spectra were utilized to determine the reactivity ratios of the monomers. The reactivity ratios indicate that STY forms an ideal copolyperoxide with AMS and the copolyperoxide is richer in AMS. The effect of temperature and oxygen pressure in the reactivity ratios of the monomers was studied. The rates of copolymerization (R-p) were used to determine the overall activation energies (E-a) and activation volume (DeltaV(#)) of copolymerization. The unusually higher values of the DeltaV(#) may be due to the pressurizing fluid oxygen which itself is a reactant in the copolymerization, the side reactions, and the chain-transfer reactions occuring during copolymerizations.