Chemically Separable Co(II) Spin-State Isomers.

The phenomenon of spin crossover involves coordination complexes with switchable spin states. This spin state change is accompanied by significant geometric changes such that low and high spin forms of a complex are distinct isomers that exist in equilibrium with one another. Typically, spin-state isomers interconvert rapidly and are similar enough in polarity to prevent their independent separation and isolation.

Magnetic-Field Dependence of LC-Photo-CIDNP in the Presence of Target Molecules Carrying a Quasi-Isolated Spin Pair.

NMR spectroscopy is well known for its superb resolution, especially at high applied magnetic field. However, the sensitivity of this technique is very low. Liquid-state low-concentration photo-chemically-induced dynamic nuclear polarization (LC-photo-CIDNP) is a promising emerging methodology capable of enhancing NMR sensitivity in solution.

Variable Temperature LED-NMR: Rapid Insights into a Photocatalytic Mechanism from Reaction Progress Kinetic Analysis.

A multitude of techniques are available to obtain a useful understanding of photocatalytic mechanisms. The combination of LED illumination with nuclear magnetic resonance spectroscopy (LED-NMR) provides a rapid, convenient means to directly monitor a photocatalytic reaction in situ. Herein, we describe a study of the mechanism of an enantioselective intermolecular [2 + 2] photocycloaddition catalyzed by a chiral Ir photocatalyst using LED-NMR.

LED-NMR Monitoring of an Enantioselective Catalytic [2+2] Photocycloaddition.

We report that an NMR spectrometer equipped with a high-power LED light source can be used to study a fast enantioselective photocatalytic [2+2] cycloaddition. While traditional applications of NMR provide considerable information on reaction mechanisms, they are often ineffective for observing fast reactions. Recently, motivated by renewed interest in organic photochemistry, several approaches have been reported for monitoring of photochemical reactions.

Structural and biophysical characterization of the Burkholderia pseudomallei IspF inhibitor L-tryptophan hydroxamate.

The enzyme 2-methylerythritol 2,4-cyclodiphosphate synthase, IspF, is essential for the biosynthesis of isoprenoids in most bacteria, some eukaryotic parasites, and the plastids of plant cells. The development of inhibitors that target IspF may lead to novel classes of anti-infective agents or herbicides. Enantiomers of tryptophan hydroxamate were synthesized and evaluated for binding to Burkholderia pseudomallei (Bp) IspF.

Stepwise genetic engineering of Pseudomonas putida enables robust heterologous production of prodigiosin and glidobactin A.

Polyketide synthases (PKS) and nonribosomal peptide synthetases (NRPS) comprise biosynthetic pathways that provide access to diverse, often bioactive natural products. Metabolic engineering can improve production metrics to support characterization and drug-development studies, but often native hosts are difficult to genetically manipulate and/or culture. For this reason, heterologous expression is a common strategy for natural product discovery and characterization.

Physical activity, sports participation and exercise-related constraints in adult women with primary hypothyroidism treated with thyroid hormone replacement therapy.

Awareness of physical activity (PA) constraints in patients with primary hypothyroidism on thyroid hormone replacement therapy (THR) is important. Hence, this cross-sectional matched case-control study aimed to determine PA and sports participation (SP) in patients with hypothyroidism on THR in comparison to control subjects. Accordingly, survey questions were selected from the National Survey on Injuries and Physical Activity in the Netherlands (IPAN), supplemented with questions related to self-reported clinical characteristics and exercise-related constraints (ERC) of patients.

No Self Without Salience: Affective and Self-relevance Ratings of 552 Emotionally Valenced and Neutral Dutch Words.

It is unknown how self-relevance is dependent on emotional salience. Emotional salience encompasses an individual's degree of attraction or aversion to emotionally-valenced information. The current study investigated the interconnection between self and salience through the evaluation of emotional valence and self-relevance.

Fast-pulsing LED-enhanced NMR: A convenient and inexpensive approach to increase NMR sensitivity.

Low-concentration photochemically induced dynamic nuclear polarization (LC-photo-CIDNP) has recently emerged as a powerful technology for the detection of aromatic amino acids and proteins in solution in the low-micromolar to nanomolar concentration range. LC-photo-CIDNP is typically carried out in the presence of high-power lasers, which are costly and maintenance-heavy. Here, we show that LC-photo-CIDNP can be performed with light-emitting diodes (LEDs), which are inexpensive and much less cumbersome than lasers, laser diodes, flash lamps, or other light sources.

The conversion of azo-quenchers to fluorophores.

In this short note we describe the conversion of the widely used fluorescence quenching azo-dyes DABCYL and HABA to fluorophores. The dyes were conjugated to the proteins RNase and human serum albumin (HSA) and subsequently reduced using sodium dithionite (NaSO), thus forming amine-containing fluorophores. Since this chemical reaction can be applied to any azo-containing quencher compound, a great variety of substances can be readily obtained synthetically.

Geminal Diol of Dihydrolevoglucosenone as a Switchable Hydrotrope: A Continuum of Green Nanostructured Solvents.

The addition of water to dihydrolevoglucosenone (Cyrene) creates a solvent mixture with highly unusual properties and the ability to specifically and efficiently solubilize a wide range of organic compounds, notably, aspirin, ibuprofen, salicylic acid, ferulic acid, caffeine, and mandelic acid. The observed solubility enhancement (up to 100-fold) can be explained only by the existence of microenvironments mainly centered on Cyrene's geminal diol. Surprisingly, the latter acts as a reversible hydrotrope and regulates the polarity of the created complex mixture.

The effectiveness of functional task exercise and physical therapy as prevention of functional decline in community dwelling older people with complex health problems.

Background: A physically active lifestyle in older people contributes to the preservation of good health. We assessed the influence of physiotherapy on daily functioning among community dwelling older people (75+) with complex health problems identified with screening, versus usual care. We also compared functional task exercise (FTE), with problems prioritized by older people, trained in the home environment, versus usual preventive physical therapy (PPT).

High Permeation Rates in Liposome Systems Explain Rapid Glyphosate Biodegradation Associated with Strong Isotope Fractionation.

Bacterial uptake of charged organic pollutants such as the widely used herbicide glyphosate is typically attributed to active transporters, whereas passive membrane permeation as an uptake pathway is usually neglected. For 1-palmitoyl-2-oleoyl- sn-glycero-3-phosphocholine (POPC) liposomes, the pH-dependent apparent membrane permeation coefficients ( P) of glyphosate, determined by nuclear magnetic resonance (NMR) spectroscopy, varied from P (pH 7.0) = 3.

Modeling Caries Experience: Advantages of the Use of the Hurdle Model.

In dental epidemiology, the decayed (D), missing (M), and filled (F) teeth or surfaces index (DFM index) is a frequently used measure. The DMF index is characterized by a strongly positive skewed distribution with a large stack of zero counts for those individuals without caries experience. Therefore, standard generalized linear models often lead to a poor fit.

Alteration of the cytokine signature by various TLR ligands in different T cell populations in MOG37-50 and MOG35-55-induced EAE in C57BL/6 mice.

Interleukin 17 (IL-17), produced by T cells, plays an important role in Multiple Sclerosis (MS) and its animal model, Experimental Autoimmune Encephalomyelitis (EAE). In contrast to IL-17-producing CD4+ T cells, the contribution of IL-17-producing CD8+ T cells (Tc17) in CNS autoimmunity has been investigated less intensively. Here we investigate the role of TC17 in EAE.

Effectiveness of a Multilevel Workplace Health Promotion Program on Vitality, Health, and Work-Related Outcomes.

Objective: Evaluation of the effectiveness of a workplace health promotion program on employees' vitality, health, and work-related outcomes, and exploring the influence of organizational support and the supervisors' role on these outcomes.

Methods: The 5-month intervention included activities at management, team, and individual level targeting self-management to perform healthy behaviors: a kick-off session, vitality training sessions, workshops, individual coaching, and intervision. Outcome measures were collected using questionnaires, health checks, and sickness absence data at baseline, after the intervention and at 10 months follow-up.

Decreased physical activity, reduced QoL and presence of debilitating fatigue in patients with Addison's disease.

Background: Health-related quality of life in patients with Addison's disease has been assessed in various European countries, indicating a reduced quality of life. However, no studies have addressed the impact of Addison's disease on physical activity.

Objective: The aim of this study was to investigate the quality of life in Dutch patients with Addison's disease particularly regarding the presence of fatigue and the ability to be physically active.

Pseudomonas aeruginosa and Its Bacterial Components Influence the Cytokine Response in Thymocytes and Splenocytes.

Infections with Pseudomonas aeruginosa may cause many different diseases. The spectrum of such infections in general includes inflammation and bacterial sepsis. Hospital-acquired pneumonia, naturally resistant to a wide range of antibiotics, is associated with a particularly high mortality rate in mechanically ventilated patients.

Site-directed immobilization of a genetically engineered anti-methotrexate antibody via an enzymatically introduced biotin label significantly increases the binding capacity of immunoaffinity columns.

In this study, the effect of random vs. site-directed immobilization techniques on the performance of antibody-based HPLC columns was investigated using a single-domain camelid antibody (VHH) directed against methotrexate (MTX) as a model system. First, the high flow-through support material POROS-OH was activated with disuccinimidyl carbonate (DSC), and the VHH was bound in a random manner via amines located on the protein's surface.

BAX inhibitor-1 is a Ca(2+) channel critically important for immune cell function and survival.

The endoplasmic reticulum (ER) serves as the major intracellular Ca(2+) store and has a role in the synthesis and folding of proteins. BAX (BCL2-associated X protein) inhibitor-1 (BI-1) is a Ca(2+) leak channel also implicated in the response against protein misfolding, thereby connecting the Ca(2+) store and protein-folding functions of the ER. We found that BI-1-deficient mice suffer from leukopenia and erythrocytosis, have an increased number of splenic marginal zone B cells and higher abundance and nuclear translocation of NF-κB (nuclear factor-κ light-chain enhancer of activated B cells) proteins, correlating with increased cytosolic and ER Ca(2+) levels.

A primer on the use of cluster analysis or factor analysis to assess co-occurrence of risk behaviors.

Objective: The aim of this paper is to provide a guideline to a universal understanding of the analysis of co-occurrence of risk behaviors. The use of cluster analysis and factor analysis was clarified.

Method: A theoretical introduction to cluster analysis and factor analysis and examples from literature were provided.

Bacteria and their cell wall components uniformly co-activate interleukin-17-producing thymocytes.

Interleukin (IL)-17-producing T cells play a critical role in the immune response against microbial pathogens. Traditionally, experimental studies have focused upon understanding the activity of IL-17-producing T cells which differentiate from naive T cells in the peripheral immune system. However, we have demonstrated previously that IL-17-producing T cells are also present in the thymus of naive wild-type mice and can be co-activated there by microbial stimuli.

Bacterial flagellin and diphtheria toxin co-stimulate IL-17-producing thymocytes.

IL-17-producing thymocytes have been recently described and are believed to play a role as an immune cell population which is able to react against microbial components rapidly. For this reason, we here investigated the ability of two microbial stimulants, bacterial flagellin (a ligand for TLR5) and diphtheria toxin from Corynebacterium diphtheriae, to activate or co-activate (together with α-CD3 stimulation) thymocyte cytokine production. We find that both bacterial molecules do not induce cytokine-production by themselves, but co-activate IL-17-producing thymocytes together with α-CD3.

Citalopram suppresses thymocyte cytokine production.

Antidepressant drugs, in particular those targeting the serotonin (5-HT)-reuptake system via the serotonin transporter (5-HTT), are known to exhibit antiinflammatory properties and have demonstrated therapeutic efficacy in rodent models of autoimmune disease like experimental autoimmune encephalomyelitis or experimental rheumatoid arthritis. A crucial difference between animal models and the actual human autoimmune disease is the fact that in animals predominantly induced T cells are studied after sensitization with autoantigen. In humans, however, naturally occurring cytokine-producing T cells might play a significant role as well.

Induction of pro-inflammatory cytokine production in thymocytes by the immune response modifiers Imiquimod and Gardiquimod™.

An emerging role is postulated for IL-17-producing thymocytes, which in their majority consist of IL-17-producing CD4(+) cells. For these, a specific role in the immediate defense against infectious pathogens is suggested, independent from the development of an adaptive immune response in the immune periphery. Immune response modifiers, like the TLR7 ligands Imiquimod and Gardiquimod™ are effective pharmacological therapeutics applied topically against dermal tumors and virus infections and have been demonstrated to activate immune cells.