High levels of soluble herpes virus entry mediator in sera of patients with allergic and autoimmune diseases

Herpes virus entry mediator (HVEM) is a newly discovered member of the tumor necrosis factor receptor (TNFR) superfamily that has a role in herpes simplex virus entry, in T cell activation and in tumor immunity. We generated mAb against HVEM and detected soluble HVEM (SHVEM) in the sera of patients with various autoimmune diseases. HVEM was constitutively expressed on CD4(+) and CD8(+) T cells, CD19(+) B cells, CD14(+) monocytes, neutrophils and dendritic cells. In three-way MLR, mAb 122 and 139 were agonists and mAb 108 had blocking activity. An ELISA was developed to detect sHVEM in patient sera. sHVEM levels were elevated in sera of patients with allergic asthma, atopic dermatitis and rheumatoid arthritis. The mAbs discussed here may be useful for studies of the role of HVEM in immune responses. Detection of soluble HVEM might have diagnostic and prognostic value in certain immunological disorders.     

H2/CO2 separations in multicomponent metal-adeninate MOFs with multiple chemically distinct pore environments

Metal–organic frameworks constructed from multiple (≥3) components often exhibit dramatically increased structural complexity compared to their 2 component (1 metal, 1 linker) counterparts, such as multiple chemically unique pore environments and a plurality of diverse molecular diffusion pathways. This inherent complexity can be advantageous for gas separation applications. Here, we report two isoreticular multicomponent MOFs, bMOF-200 (4 components; Cu, Zn, adeninate, pyrazolate) and bMOF-201 (3 components; Zn, adeninate, pyrazolate). We describe their structures, which contain 3 unique interconnected pore environments, and we use Kohn–Sham density functional theory (DFT) along with the climbing image nudged elastic band (CI-NEB) method to predict potential H₂/CO₂ separation ability of bMOF-200. We examine the H₂/CO₂ separation performance using both column breakthrough and membrane permeation studies. bMOF-200 membranes exhibit a H₂/CO₂ separation factor of 7.9. The pore space of bMOF-201 is significantly different than bMOF-200, and one molecular diffusion pathway is occluded by coordinating charge-balancing formate and acetate anions. A consequence of this structural difference is reduced permeability to both H₂ and CO₂ and a significantly improved H₂/CO₂ separation factor of 22.2 compared to bMOF-200, which makes bMOF-201 membranes competitive with some of the best performing MOF membranes in terms of H₂/CO₂ separations.

Tailorable multicomponent MOFs and MOF membranes for efficient H₂/CO₂ separation.     

Facile syntheses of all possible diastereomers of conduritol and various derivatives of inositol stereoisomers in high enantiopurity from myo-inositol

Phosphoinositide-based signaling processes are crucially important in intracellular signal transduction events. Inositol phosphate analogues have been useful in probing the structure-activity relationships between inositol phosphates and biomacromolecules, and in studying biological functions of newly found inositol phosphates. Thus, a systematic and ready access to inositol stereoisomers is highly desirable. And practical and convenient syntheses of conduritols and related compounds are also important because of their biological activities and their synthetic utilities in the preparation of other bioactive molecules. We herein report the first syntheses of all possible diastereomers of conduritol and various derivatives of eight inositol stereoisomers in high enantiopurity from myo-inositol, which involve efficient enzymatic resolution of the intermediates conduritol B and C derivatives, followed by oxidation-reduction or the Mitsunobu reaction, and cis-dihydroxylation in stereo- and regioselective manners.     

Insertion of a bis(phosphine)platinum group into the S-S bond of Mn(2)(CO)(7)(mu-S(2))

The reaction of Mn(2)(CO)(7)(mu-S(2)), 1, with Pt(PPh(3))(2)(PhC(2)Ph) yielded the new complex, Mn(2)(CO)(6)Pt(PPh(3))(2)(mu(3)-S)(2), 3, by loss of CO and insertion of a Pt(PPh(3))(2) group into the S-S bond of 1. Complex 3 was characterized crystallographically and was found to consist of an open Mn(2)Pt cluster with one Mn-Mn bond, 2.8154(14) A, one Mn-Pt bond, 2.9109(10) A, and two triply bridging sulfido ligands. Compound 3 reacts with CO to form adduct Mn(2)(CO)(6)(mu-CO)Pt(PPh(3))(2)(mu(3)-S)(2), 4. Compound 4 also contains an open Mn(2)Pt cluster with two triply bridging sulfido ligands but has only one metal-metal bond, Mn-Mn = 2.638(2) A. Under nitrogen, compound 4 readily loses CO and reverts back to 3.     

A serpentine laminating micromixer combining splitting/recombination and advection

Mixing enhancement has drawn great attention from designers of micromixers, since the flow in a microchannel is usually characterized by a low Reynolds number (Re) which makes the mixing quite a difficult task to accomplish. In this paper, a novel integrated efficient micromixer named serpentine laminating micromixer (SLM) has been designed, simulated, fabricated and fully characterized. In the SLM, a high level of efficient mixing can be achieved by combining two general chaotic mixing mechanisms: splitting/recombination and chaotic advection. The splitting and recombination (in other terms, lamination) mechanism is obtained by the successive arrangement of "F"-shape mixing units in two layers. The advection is induced by the overall three-dimensional serpentine path of the microchannel. The SLM was realized by SU-8 photolithography, nickel electroplating, injection molding and thermal bonding. Mixing performance of the SLM was fully characterized numerically and experimentally. The numerical mixing simulations show that the advection acts favorably to realize the ideal vertical lamination of fluid flow. The mixing experiments based on an average mixing color intensity change of phenolphthalein show a high level of mixing performance was obtained with the SLM. Numerical and experimental results confirm that efficient mixing is successfully achieved from the SLM over the wide range of Re. Due to the simple and mass producible geometry of the efficient micromixer, SLM proposed in this study, the SLM can be easily applied to integrated microfluidic systems, such as micro-total-analysis-systems or lab-on-a-chip systems.     

Phagocytosis of serum- and IgG-opsonized zymosan particles induces apoptosis through superoxide but not nitric oxide in macrophage J774A.1

Phagocytosis of serum- and IgG-opsonized zymosan (SOZ and IOZ, respectively) particles into J774A.1 macrophages induced apoptosis of the cells, accompanied by the expression of p21(WAF1), one of cyclin-dependent protein kinase (CDK) inhibitors. Furthermore, phagocytosis of SOZ and IOZ particles into macophages induced superoxide formation. Tat-superoxide dismutase (SOD), which is readily transduced into the cells using Tat-domain, protected the cells from the apoptosis induced by phagocytosis of SOZ and IOZ particles. lipopolysaccharide (LPS) /interferon-gamma (IFN-gamma) also caused the apoptosis of the cells. However, Tat-SOD could not protect the cells from LPS/IFN-gamma induced apoptosis, suggesting that apoptosis mechanisms involved are different from each other. In the present study, we determined the amounts of nitric oxide (NO) produced by SOZ, IOZ, and LPS/IFN-gamma, and found that SOZ and IOZ did not induce the generation of NO in macrophages, whereas LPS/ IFN-gamma did. The apoptosis due to phagocytosis was accompanied with the release of cytochrome c from mitochondrial membrane to cytosolic fraction. Furthermore, SOZ and IOZ induced the cleavage of procasapase-3 (35 kDa) to give rise to an active caspase-3 (20 kDa), which was blocked by Tat- SOD but not by 2-phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl 3-oxide (PTIO), a scavenger of NO. On the other hand, LPS/IFN-gamma caused the activation of procaspase-3, which was blocked by PTIO but not by Tat-SOD. Taken together, phagocytosis of SOZ and IOZ particles induced apoptosis through superoxide but not NO in macrophages, accompanied with the release of cytochrome c and the activation of caspase-3.     

Polymerizability,copolymerizability, and properties of cyanoacrylate‐telechelic polyisobutylenes I: three‐arm star cyanoacrylate‐telechelic polyisobutylene

This series of papers concern new materials for possible biological applications created by combining the chemistry of highly reactive cyanoacrylates (CAs) with polyisobutylene (PIB) rubbers. First, a new strategy for the synthesis of CA–telechelic PIBs is described. Subsequently, the strategy is employed for the synthesis of low viscosity (syringible) CA–telechelic three‐arm star PIB [Ø(PIB–CA)₃]. The intermediates of the synthesis route are characterized by ¹H NMR spectroscopy. Injecting liquid Ø(PIB–CA)₃ into living tissue (fresh chicken egg) produces a bolus of crosslinked PIB rubber. The spectacular oxidative resistance of this rubber is documented by its resistance to concentrated HNO₃. A structural model of the crosslinked rubber obtained upon contacting Ø(PIB–CA)₃ with proteinaceous tissue is proposed. Copyright © 2007 John Wiley & Sons, Ltd.     

Imidazole-based excited-state intramolecular proton-transfer materials: synthesis and amplified spontaneous emission from a large single crystal

We have synthesized a novel class of imidazole-based excited-state intramolecular proton-transfer (ESIPT) materials, i.e., hydroxy-substituted tetraphenylimidazole (HPI) and its derivative HPI-Ac, which formed large single crystals exhibiting intense blue fluorescence and amplified spontaneous emission (ASE). Transparent, clear, and well-defined fluorescent single crystals of HPI-Ac as large as 20 mm x 25 mm x 5 mm were easily grown from its dilute solution. From the X-ray crystallographic analysis and semiempirical molecular orbital calculation, it was deduced that the four phenyl groups substituted into the imidazole ring of HPI and HPI-Ac allowed the crystals free from concentration quenching of fluorescence by limiting the excessive tight-stacking responsible for intermolecular vibrational coupling and relevant nonradiative relaxation. Fluorescence spectral narrowing and efficient ASE were observed in the HPI-Ac single crystal even at low excitation levels attributed to the intrinsic four-level ESIPT photocycle.