A cute intracerebral hemorrhage (ICH) is the most serious and least treatable form of acute stroke 1 for which established prognostic factors include clinical severity and location and volume of hematoma at presentation.2 Although stress hyperglycemia is associated with adverse outcomes in many medical conditions, including acute ischemic stroke, 3,4 traumatic brain injury, 5 and acute myocardial infarction, 6 evidence specifically related to the critical condition of ICH is varied and conflicting because of previous studies being limited to small single-center series 7,8 with short duration of follow-up. 9 Animal models have shown that elevated blood pressure (BP) exacerbates cerebral injury after ICH 10 and of an association between hyperglycemia and cerebral edema. There may be a supra-additive effect of hyperglycemia and Background and Purpose-We aimed to determine associations of baseline blood glucose and diabetes mellitus with clinical outcomes in participants of the Intensive Blood Pressure Reduction in Acute Cerebral Hemorrhage Trial (INTERACT2). Methods-INTERACT2 was an international prospective, open, blinded end point, randomized controlled trial of 2839 patients with spontaneous intracerebral hemorrhage (<6 hours) and elevated systolic blood pressure randomly assigned to intensive (target systolic blood pressure <140 mm Hg) or guideline-based (systolic blood pressure <180 mm Hg) BP management. Associations of hyperglycemia at presentation (>6.5 mmol/L) and combined and separate poor outcomes of death and major disability (scores of 3-6, 3-5, and 6, respectively, on the modified Rankin scale) at 90 days were determined in logistic regression models. Results-In 2653 patients with available data, there were 1348 (61%) with hyperglycemia and 292 (11%) with diabetes mellitus. Associations of baseline blood glucose and poor outcome were strong and near continuous. After adjustment for baseline variables, the highest fourth (7.9-25.0 mmol/L) of blood glucose was significantly associated with combined poor outcome (adjusted odds ratio 1. Materials and MethodsINTERACT2 was an international, multicenter, prospective, openlabel, assessor-blinded end point, randomized controlled trial, the details of which are described elsewhere. 11 In brief, 2839 patients with computed tomography-confirmed spontaneous ICH within 6 hours of onset and elevated systolic BP (150-220 mm Hg) were randomly assigned to receive intensive (target systolic BP <140 mm Hg within 1 hour) or guideline-recommended (target systolic BP <180 mm Hg) BP-lowering therapy using locally available agents according to standardized protocols. The study protocol was approved by the appropriate ethics committee at each participating site, and written informed consent was obtained from the patient or an appropriate surrogate.Demographic and clinical characteristics recorded at the time of enrollment included a history of diabetes mellitus and level of blood glucose. Stroke severity was measured using the Glasgow coma scale and National Institutes of He...
The present paper reports uniqueness of a simple, programmed design of disk-shaped homochiral nickel phthalocyanine (Pc) molecules bearing four enantiomerically pure 1-(p-tolyl)ethylaminocarbonyl groups at their peripheral positions, (Pc-(R) and Pc-(S)), and their controlled self-organization into mesoscopic supramolecular helical fibers with a preferential handedness in solution and onto solid surfaces. A combination of four fundamental intermolecular interactions, including quadruple hydrogen bonding, pi-pi stacking, homochiral interactions of the enantiopure bulky aralkyl entities, and noncoordinating nature of nickel ion of the Pc molecules afforded a high thermal stability of the Pc self-assembly in chloroform (CHCl(3)), tetrahydrofuran, and o-dichlorobenzene and onto hydrophilic mica and hydrophobic HOPG surfaces. A higher-ordered helical self-assembly of Pc disks was observed in these solutions (approximately 200 Pc molecules), while the self-assembly was completely dissociated into monomeric species in N,N-dimethylformamide due to a loss of hydrogen-bonding interactions between Pc molecules. Supramolecular chirality in the hierarchical self-assembly of Pc molecules originated from the presence of (R)- or (S)-chiral centers in the peripheral tails, which rotate noncovalently linked molecular building blocks to effectively form the helical architectures. The helical Pc nanofibers dissolved in CHCl(3), estimated to be ca. 70 nm from peak molecular weight obtained by SEC analysis, acts as a building block for higher-order helical fibers (ca. 1 microm) at single molecular level on the solid surfaces, as demonstrated by the dynamic force mode atomic force microscopy. Regardless of hydrophilic and hydrophobic substrates, the interaction between these Pc molecules and the solid surfaces could not affect the morphology of helical assemblies, indicating a unique robustness of these assemblies.
Novel helical poly(methyl-3,3,3-trifluoropropylsilane) (1) has been synthesized via Wurtz coupling by taking advantage of noncovalent Si···F−C intramolecular interactions. Such weak Si···F−C interactions make the conformation of the polysilane unique and controllable by proper choice of solvent and molecular weight. We have studied the conformation of polysilane by means of UV absorption, photoluminescence, NMR spectra, and viscosity measurements. Polysilane displayed a 73 helical rodlike conformation in noncoordinating solvents (e.g., toluene and decane) but a globule-like conformation in coordinating solvents (with N, O, or F as donor) at room temperature. The coordinating nature of solvents played an important role for solvatochromic transition rather than the solvent polarity, as such interactions are competitive in the presence of solvents with donor atoms. On the other hand, an analogous nonfluorinated polysilane, poly(n-propylmethylsilane) (2), revealed a disordered conformation in coordinating as well as in noncoordinating solvents. The unusual molecular weight dependent UV spectra of 1 showed an isosbestic point, suggesting the equilibrium between globule- and rodlike conformations at room temperature, which was further evident from the viscosity measurements. The proposed weak intramolecular interaction in 1 was supported by the 29Si NMR and 19F NMR in noncoordinating and coordinating solvents. The IR spectrum of cast film from a toluene solution of 1 showed an improper blue shift of 12 cm-1 in C−F stretching frequency compared to the IR spectrum cast from THF, suggesting very weak Si···F−C interaction in analogy with blue-shifted hydrogen bonds.
The present paper reports a new type of polymer-based chemosensor made of stiff fluoroalkylated polysilane, poly(3,3,3-trifluoropropylmethylsilane) (1), which showed a remarkable sensitivity for explosive nitroaromatic compounds (NACs), such as 2,4,6-trinitrophenol (picric acid), 1,3,5-trinitrobenzene (TNB), 2,4-dinitrotoluene (DNT), and m-dinitrobenzene (DNB), by a decrease in the photoluminescence (PL) intensity in the near-UV region with parts per million concentration of NACs in tetrahydrofuran (THF) solution and in the solid film in water. The PL intensity was completely reversible repeatedly after the removal of NACs from the thin film by rinsing with methanol (or water). A linear Stern−Volmer relationship was observed in all of the cases with high quenching constants. The PL quenching efficiency of 1 (M n = 3.12 × 104, PDI = 3.6, K = 4.15 × 104 M-1) for picric acid is 198 times better than that of nonfluoroalkylpolysilane, poly(n-propylmethylsilane) (2) (M n = 2.93 × 104, PDI = 2.1, K = 2.09 × 102 M-1). The weak noncovalent interaction between Si atoms of σ-conjugated polysilane and N and/or O atoms of electron-deficient NACs may be responsible for electron transfer from the excited state of the polysilane to the electron-deficient NACs, resulting in the PL quenching of 1 in solution and in the thin film by NACs.
The benefits and safety of intravenous recombinant tissue plasminogen activator (IV-tPA) for patients with mild ischaemic stroke (MIS) are still unclear. The objective of this meta-analysis was to evaluate the efficacy and safety of IV-tPA as treatment for patients with MIS. We performed a systematic literature search across MEDLINE, Embase, Central, Global Health and Cumulative Index to Nursing and Allied Health Literature (CINAHL), from inception to 10 November 2016, to identify all related studies. Where possible, data were pooled for meta-analysis with odds ratio (OR) and corresponding 95% confidence interval (CI) using the fixed-effects model. MIS was defined as having National Institutes of Health Stroke Scale score of ≤6. We included seven studies with a total of 1591 patients based on the prespecified inclusion and exclusion criteria. The meta-analysis indicated a high odds of excellent functional outcome based on the modified Rankin Scale or Oxfordshire Handicap Score 0–1 (OR=1.43; 95% CI 1.14 to 1.79; P=0.002, I2=35%) in patients treated with IV-tPA compared with those not treated with IV-tPA (74.8% vs 67.6%). There was a high risk of symptomatic intracranial haemorrhage (sICH) with IV-tPA treatment (OR=10.13; 95% CI 1.93 to 53.02; P=0.006, I2=0%) (1.9% vs 0.0%) but not mortality (OR=0.78; 95% CI 0.43 to 1.43; P=0.43, I2=0%) (2.4% vs 2.9%). Treatment with IV-tPA was associated with better functional outcome but not mortality among patients with MIS, although there was an increased risk of sICH. Randomised trials are warranted to confirm these findings.
Scheme 1. Structures of Poly(n-decyl-(S)-2-methylbutylsilane) (PS*), Poly(n-decyl-3-methylbutylsilane) (PS1), and Poly(n-decylisobutylsilane) (PS2)
Cooperative amplification of the C-F...Si weak interaction between side chains and the main chain was found to afford rigid rodlike helical polysilanes with a preferential screw sense.
Noncovalent interactions, such as hydrogen bonding, metal coordination, and p-p stacking, are increasingly being utilized to develop well-ordered and selforganized supramolecular materials. Recently, new types of nonclassical weak interactions, such as C-HÁÁÁp, C-HÁÁÁF-C, and C-HÁÁÁO, have been exploited in stabilizing the specific conformations of molecules and molecular assemblies in the solid state. These noncovalent interactions play an important role in materials comprised of polymer chains, because cooperative effects from a large number of weak interactions can lead to drastic changes in its conformation, several properties, and functionalities. The programmed design of synthetic helical polymer with well-defined molecular conformation has been the main subject in modern polymer science and engineering. Silicon-catenated polysilane is an ideal helical silicon quantum wire and polymers with unique photophysical properties. The present review highlights the spectroscopic evidences for through-space weak SiÁÁÁF-C interaction in poly(methyl-3,3,3-trifluoropropylsilane) (1) in noncoordinating and coordinating solvents by means of NMR ( 29 Si and 19 F) and IR spectroscopies, and viscometric measurement. It was found that 1 is applicable for chemosensors with an extremely high sensitivity and selectivity toward fluoride ions in tetrahydrofuran (THF) and with high sensitivity for nitroaromatic compounds, detected by a decrease in the photoluminescence intensity in THF and in thin solid film. V V C 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5060-5075, 2006
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