Dipyrido[24]crown-8 (DP24C8) has been synthesized and shown to form [2]pseudorotaxanes spontaneously with dibenzylammonium ions. These complexes, which have been demonstrated by (1)H NMR spectroscopy to form faster in solution than when the macrocyclic polyether is dibenzo[24]crown-8 (DB24C8), are also stronger than their DB24C8 counterparts. One of the [2]pseudorotaxanes has been used to construct a [2]rotaxane (see above) comprising a dumbbell-shaped component based on a dibenzylammonium ion which is encircled by a DP24C8 macrocycle and terminated by (triphenylphosphonium)methyl stoppers.
Chronic, repetitive stress in the wrists of adolescent gymnasts results in a localized growth disturbance of the distal radius with resultant ulnar-plus variance. Stress injuries of the physis may lead to permanent sequelae, even in asymptomatic individuals.
A gradient-driven methodology has been developed to manipulate the movement of dendritic macromolecules. Poly(propyleneimine) dendrimers, labeled with rhodamine B, are attached to glass substrates via multiple imine bonds. The dendrimers are able to move on the surface by the hydrolysis and re-formation of these imine bonds. In the absence of an external stimulus, this random movement results in a two-dimensional diffusion on the substrate. We are able to bias the movement of these nanoparticles by means of an aldehyde gradient on the glass substrate.
Cell cycle regulation by differentiation signals is critical for eukaryote development. We investigated the roles of bone morphogenetic protein (BMP)-4, an important stimulator of osteoblast differentiation and bone formation, in regulating cell cycle distribution in four osteoblast-like cell lines and mouse primary osteoblasts, and the underlying mechanisms. In all cells used, BMP-4 induced G(0)/G(1) arrest. The molecular basis of the BMP-4 effect was analyzed, and the presentation on molecular mechanism is focused on human MG63 cells. BMP-4 induced p21(CIP1) and p27(KIP1) expressions and hence cell differentiation but had no effects on the expressions of cyclins A, B1, D1, and E, cyclin-dependent protein kinase-2, -4, and -6. Using specific small interfering RNA (siRNA), we found that BMP-4-induced G(0)/G(1) arrest, and p21(CIP1) and p27(KIP1) expressions were mediated by BMP receptor type IA (BMPRIA)-specific Sma- and Mad-related protein (Smad)1/5. BMP-4 induced transient phosphorylations of ERK; transfection of MG63 cells with ERK2, but not ERK1, -specific siRNA inhibited the BMP-4-induced responses in MG63 cells. Pretreatment of MG63 cells with Arg-Gly-Asp-Ser, which blocks the cell-extracellular matrix interaction, or transfection with beta(3) integrin-specific siRNA inhibited BMP-4-induced ERK and Smad1/5 phosphorylations. BMP-4 induced transient increases in associations of beta(3)-integrin with focal adhesion kinase and Shc, the dominant-negative mutants of which inhibited BMP-4-induced ERK and Smad1/5 phosphorylations. Our results indicate that BMP-4 induces G(0)/G(1) arrest and hence differentiation in osteoblast-like cells through increased expressions of p21(CIP1) and p27(KIP1), which are mediated by BMPRIA-specific Smad1/5. The extracellular matrix/beta(3) integrin/ focal adhesion kinase/Shc/ERK2 signaling pathway is involved in these BMP-4-induced responses in osteoblast-like cells.
Direct transorbital puncture through the superior orbital fissure is an alternate treatment for CCF, especially when the ipsilateral ICA has been occluded.
The making of mechanically interlocked molecular compounds [1] has evolved from a statistical beginning [2] to the use of molecular-recognition-driven, self-assembly protocols [3] that rely upon the operation of covalent, [4] metal, [5] or noncovalent [6] templates, [7] prior to the formation of the mechanical bond(s) by either kinetically or thermodynamically controlled processes, involving either dative [8] or covalent [9] bond formation. Previously, we have speculated [10] about the existence of another class of interlocked molecule beyond the archetypal catenanes [11] and rotaxanes, [12] which are not all that dissimilar from carceplexes [13] and yet are distinguishable from them. [14] In searching for some simple term for this class of mechanically interlocked molecule (Figure 1), which consists of two separate components-a body with two or more limbs that are rigid and protrude outwards, the torso of which carries a close-fitting, all-in-one suit, such that it encompasses the torso of the body-we have come up with the term suitane, in which a number is inserted between "suit" and "ane" to indicate the number of protruding limbs. Thus, the simplest member of the series would be suit Let us consider the specific example (Scheme 1) of a linear body template [15] LBT-H 2 2+ carrying two -CH 2 -NH 2 + CH 2 -recognition sites separated from each other by a bulky midriff [16] such that the double linking up of two matching [24]crown-8 rings in the shape of (CHO) 2 -DP24C8 units [17] can be achieved reversibly by forming four imine bonds with a diaminobenzene spacer, such as p-phenylenediamine (PPD). The virtue of employing reversible imine bond formation [18] to clothe the LBT-H 2 2+ dication with two (CHO) 2 -DP24C8 units and two PPD spacers is that errors can be corrected [19] before the final structure is fixed by
Der Nicht‐Häm‐Eisen(III)‐Komplex [(PaPy3)Fe(NO2)](ClO4) (1) überträgt in Acetonitril bei 45–65 °C Sauerstoff auf PPh3 unter Bildung von OPPh3. Das Produkt, [(PaPy3)Fe(NO)](ClO4), eine {Fe‐NO}7‐Spezies, bildet in Gegenwart von Disauerstoff rasch wieder den ursprünglichen Komplex 1, was dem System katalytischen Charakter verleiht (siehe Schema). Durch Bildung einer Oxo‐verbrückten Spezies wird der Sauerstoff‐Transfer abgebrochen. PaPy3H=N‐[N,N‐Bis(2‐pyridylmethyl)aminoethyl]‐2‐pyridincarboxamid.
A prospective evaluation of the coexistence of calcific tendinitis and tear of the rotator cuff demonstrated by arthrography was made in patients presenting with shoulder pain. Patients were X-rayed using conventional views and impingement views. Eighty-one patients (mean age 61.2 years) with calcific tendinitis underwent arthrography. Arthrography showed 22 partial or complete tears of the rotator cuff. A small rather than a large amount of calcification was more likely to be associated with a rotator cuff tear (p = 0.005). The coexistence of calcific tendinitis with rotator cuff tear is not uncommon, especially in older age groups.
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