In this study, two types of ionic liquids (ILs) based on 1-butyl-3-methylimidazolium [Bmim] + and butyltrimethylammonium [Btma] + cations, paired to tetrafluoroborate [BF 4 ] − , hexafluorophosphate [PF 6 ] − , dicyanamide [DCA] − , and bis(trifluoromethylsilfonyl)imide [Tf 2 N] − anions, were chosen as adsorbates to investigate the influence of cation and anion type on the adsorption of ILs on the graphene surface. The adsorption process on the graphene surface (circumcoronene) was studied using M06-2X/cc-pVDZ level of theory. Empirical dispersion correction (D3) was also added to the M06-2X functional to investigate the effects of dispersion on the binding energy values. The graphene•••IL configurations, binding energies, and thermochemistry of IL adsorption on the graphene surface were investigated. Orbital energies, charge transfer behavior, the influence of adsorption on the hydrogen bond strength between cation and anion of ILs, and the significance of noncovalent interactions on the adsorption of ILs on the graphene surface were also considered. ChelpG analysis indicated that upon adsorption of ILs on the graphene surface the overall charge on the cation, anion, and graphene surface changes, enabled by the charge transfer that occurs between ILs and graphene surface. Orbital energy and density of states calculations also show that the HOMO−LUMO energy gap of ILs decreases upon adsorption on the graphene surface. Quantum theory of atoms in molecules analysis indicates that the hydrogen-bond strength between cation and anion in ILs decreases upon adsorption on the graphene surface. Plotting the noncovalent interactions between ILs and graphene surface shows the role and significance of cooperative π•••π, C−H•••π, and X•••π (X = N, O, F atoms from anions) interactions in the adsorption of ILs on the graphene surface. The thermochemical analysis also indicates that the free energy of adsorption (ΔG ads ) of ILs on the graphene surface is negative, and thus the adsorption occurs spontaneously.
Quantitative humoral profiling of recent samples from a human immunodeficiency virus (HIV)-infected adult who was cured following a delta32/delta32 CCR5 stem cell transplant in 2007 revealed no antibodies against p24, matrix, nucleocapsid, integrase, protease, and gp120, but low levels of antibodies against reverse transcriptase, tat, and gp41. Antibody levels to these HIV proteins persisted at high and stable levels in most noncontrollers, elite controllers, and antiretroviral-treated subjects, but a rare subset of controllers had low levels of antibodies against matrix, reverse transcriptase, integrase, and/or protease. Comprehensive HIV antibody profiles may prove useful for monitoring curative interventions.
Type I diabetes (T1D) is an autoimmune disease characterized by destruction of insulin-producing β-cells in the pancreas. Although several islet cell autoantigens are known, the breadth and spectrum of autoantibody targets has not been fully explored. Here the luciferase immunoprecipitation systems (LIPS) antibody profiling technology was used to study islet and other organ-specific autoantibody responses in parallel. Examination of an initial cohort of 93 controls and 50 T1D subjects revealed that 16% of the diabetic subjects showed anti-gastric ATPase autoantibodies which did not correlate with autoantibodies against GAD65, IA2, or IA2-β. A more detailed study of a second cohort with 18 potential autoantibody targets revealed marked heterogeneity in autoantibody responses against islet cell autoantigens including two polymorphic variants of ZnT8. A subset of T1D subjects exhibited autoantibodies against several organ-specific targets including gastric ATPase (11%), thyroid peroxidase (14%), and anti-IgA autoantibodies against tissue transglutaminase (12%). Although a few T1D subjects showed autoantibodies against a lung-associated protein KCNRG (6%) and S100-β (8%), no statistically significant autoantibodies were detected against several cytokines. Analysis of the overall autoantibody profiles using a heatmap revealed two major subgroups of approximately similar numbers, consisting of T1D subjects with and without organ-specific autoantibodies. Within the organ-specific subgroup, there was minimal overlap among anti-gastric ATPase, anti-thyroid peroxidase, and anti-transglutaminase seropositivity, and these autoantibodies did not correlate with islet cell autoantibodies. Examination of a third cohort, comprising prospectively collected longitudinal samples from high-risk individuals, revealed that anti-gastric ATPase autoantibodies were present in several individuals prior to detection of islet autoantibodies and before clinical onset of T1D. Taken together, these results suggest that autoantibody portraits derived from islet and organ-specific targets will likely be useful for enhancing the clinical management of T1D.
The oxidant-free dehydrogenation of alcohols to corresponding carbonyl compounds has been performed by using silver (0) nanoparticles supported on silica-coated ferrite as an efficient and recyclable heterogeneous catalyst.
Standard care of burn wounds consists of cleaning and debridement (removing devitalized tissue), followed by daily dressing changes. Children with burns undergo multiple, painful and anxiety-provoking procedures during wound care and rehabilitation. The goal of procedural sedation is safe and efficacious management of pain and emotional distress, requiring a careful and systematic approach. Achieving the best results needs understanding of the mechanisms of pain and the physiologic changes in burn patients, frequent evaluation and assessment of pain and anxiety, and administration of suitable pharmacological and nonpharmacological therapies. Pharmacological therapies provide the backbone of analgesia and sedation for procedural pain management. Opioids provide excellent pain control, but they must be administered judiciously due to their side effects. Sedative drugs, such as benzodiazepines and propofol, provide excellent sedation, but they must not be used as a substitute for analgesic drugs. Ketamine is increasingly used for analgesia and sedation in children as a single agent or an adjuvant. Nonpharmacological therapies such as virtual reality, relaxation, cartoon viewing, music, massage and hypnosis are necessary components of procedural sedation and analgesia for children. These can be combined with pharmacological techniques and are used to limit the use of drugs (and hence side effects), as well as to improve patient participation and satisfaction. In this article, we review the pathophysiologic changes associated with major thermal injury in children, the options available for sedation and analgesia for wound care procedures in these children and our institutional guidelines for procedural sedation.
BackgroundThe mechanisms by which varicella zoster virus (VZV) reactivation causes postherpetic neuralgia (PHN), a debilitating chronic pain condition, have not been fully elucidated. Based on previous studies identifying a causative role for anti-cytokine autoantibodies in patients with opportunistic infections, we explored this possibility in PHN.MethodsSera from herpes zoster (HZ) patients without and with PHN (N = 115 and 83, respectively) were examined for the presence of autoantibodies against multiple cytokines, and other known autoantigens. In addition, a cohort of patients with complex regional pain syndrome or neuropathic pain was tested for autoantibodies against selected cytokines. Antibody levels against VZV, Epstein Barr virus, and herpes simplex virus-2 were also measured in the HZ and PHN patients. Patient sera with high levels of anti-cytokine autoantibodies were functionally tested for in vitro neutralizing activity.ResultsSix PHN subjects demonstrated markedly elevated levels of single, autoantibodies against interferon-α, interferon-γ, GM-CSF, or interleukin-6. In contrast, the HZ and the pain control group showed low or no autoantibodies, respectively, against these four cytokines. Further analysis revealed that one PHN patient with high levels of anti-interleukin-6 autoantibodies had a markedly depressed antibody level to VZV, potentially reflecting poor T cell immunity against VZV. In vitro functional testing revealed that three of the five anti-cytokine autoantibody positive PHN subjects had neutralizing autoantibodies against interferon-α, GM-CSF or interleukin-6. In contrast, none of the HZ patients without PHN had neutralizing autoantibodies.ConclusionsThese results suggest the possibility that sporadic anti-cytokine autoantibodies in some subjects may cause an autoimmune immunodeficiency syndrome leading to uncontrolled VZV reactivation, nerve damage and subsequent PHN.
BackgroundThere is an urgent need for a simple and accurate test for the diagnosis of human Mycobacterium tuberculosis, the infectious agent causing tuberculosis (TB). Here we describe a serological test based on light emitting recombinant proteins for the diagnosis of pulmonary Mycobacterium tuberculosis infection.MethodsLuciferase Immunoprecipitation Systems (LIPS), a fluid-phase immunoassay, was used to examine antibody responses against a panel of 24 different M. tuberculosis proteins. Three different strategies were used for generating the constructs expressing the recombinant fusion M. tuberculosis proteins with luciferase: synthetic gene synthesis, Gateway recombination cloning, and custom PCR synthesis. A pilot cohort of African pulmonary TB patients was used for initial antibody screening and confirmatory studies with selected antigens were performed with a cohort from Thailand and healthy US blood donors. In addition to testing M. tuberculosis antigens separately, a mixture that tested seven antigens simultaneously was evaluated for diagnostic performance.ResultsLIPS testing of a pilot set of serum samples from African pulmonary TB patients identified a potential subset of diagnostically useful M. tuberculosis antigens. Evaluation of a second independent cohort from Thailand validated highly significant antibody responses against seven antigens (PstS1, Rv0831c, FbpA, EspB, bfrB, HspX and ssb), which often showed robust antibody levels up to 50- to 1000-fold higher than local community controls. Marked heterogeneity of antibody responses was observed in the patients and the combined results demonstrated 73.5 % sensitivity and 100 % specificity for detection of pulmonary TB. A LIPS test simultaneously employing the seven M. tuberculosis antigen as a mixture matched the combined diagnostic performance of the separate tests, but showed an even higher diagnostic sensitivity (90 %) when a cut-off based on healthy US blood donors was used.ConclusionA LIPS immunoassay employing multiple M. tuberculosis antigens shows promise for the rapid and quantitative serological detection of pulmonary TB.Electronic supplementary materialThe online version of this article (doi:10.1186/s12866-015-0545-y) contains supplementary material, which is available to authorized users.
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