Macromolecules INDEX

A way to narrow the MWD and to approach the structure of dendrimers is the addition of a small fraction of a/-functional initiator, to inimers [40,71]. In this process the obtainable degree of polymerization is limited by the ratio of inimer to initiator. It can be conducted in two ways (i) inimer molecules can be added so slowly to the initiator solution that they can only react with the initiator molecules or with the already formed macromolecules, but not with each other (semi-batch process). Thus, each macromolecule generated in such a process will contain one initiator core but no vinyl group. Then, the polydispersity index is quite low and decreases with / M /Mn l-i-l//. (ii) Alternatively, initiator and monomer molecules can be mixed instantaneously (batch process). Here, the normal SCVP process and the process shown above compete and both kinds of macromolecules will be formed. For this process the polydispersity index also decreases with/,but is higher than for the semi-batch process, M /Mn=Pn//. ... 

In general the first reactant is immobilized on the surface, while the second one is applied in buffer solution. Enrichment of macromolecules (e. g., proteins) at the aqueous site of the sensor leads to an increase in refractive index of the corresponding phase and thereby to a change in resonance angle, which can be monitored directly in a time-resolved manner. 

The results summarized above were obtained by using fluorescence based assays employing phospholipid vesicles and fluorescent labeled lipopeptides. Recently, surface plasmon resonance (SPR) was developed as new a technique for the study of membrane association of lipidated peptides. Thus, artificial membranes on the surface of biosensors offered new tools for the study of lipopeptides. In SPR (surface plasmon resonance) systemsI713bl changes of the refractive index (RI) in the proximity of the sensor layer are monitored. In a commercial BIAcore system1341 the resonance signal is proportional to the mass of macromolecules bound to the membrane and allows analysis with a time resolution of seconds. Vesicles of defined size distribution were prepared from mixtures of lipids and biotinylated lipopeptides by extruder technique and fused with a alkane thiol surface of a hydrophobic SPR sensor. 

It is fortunate that theory has been extended to take into account selective interactions in multicomponent systems, and it is seen from Eq. (91) (which is the expression used for the plots in Fig. 42 b) that the intercept at infinite dilution of protein or other solute does give the reciprocal of its correct molecular weight M2. This procedure is a straightforward one whereby one specifies within the constant K [Eq. (24)] a specific refractive index increment (9n7dc2)TiM. The subscript (i (a shorter way of writing subscripts jUj and ju3) signifies that the increments are to be taken at constant chemical potential of all diffusible solutes, that is, the components other than the polymer. This constitutes the osmotic pressure condition whereby only the macromolecule (component-2) is non-diffusible through a semi-permeable membrane. The quantity... 

A copolymer is a macromolecule comprising two chemically distinct types of monometer unit, A and B, whilst a terpolymer is composed of units A, B and C. The analytically determined composition of a copolymer is expressed as the weight fractions WA and WB of its constituents. For LS studies on a copolymer solution it is necessary to know the value of the specific refractive index increment v, which can be either measured or calculated from ... 

The viscosity of the solution is significantly increased when macromolecules are dissolved in a solvent. The specific viscosity of a solution t sp=(ri-r o)lr o expected to increase proportionally to the concentration c. The reduced viscosity rjgp/c still increases with increasing concentration. The data, however, can be extrapolated to zero concentration and results in the intrinsic viscosity, or the viscosity number [77], sometimes also called the Staudinger index... 

Elementary probability theory shows [82] that on coupling f polydisperse arms onto a star center (this corresponds to an /-fold convolution of a most probable distribution) the polydispersity is reduced The polydispersity index of the star macromolecules (MJM is simply related to the polydispersity index of the arms as [80,82,83]... 

If one of the species is monomeric oxirane, then J = 1. Likewise, if one of the polymeric species supplied the oxirane, then J > 1. The molecule with the acid group is at degree of polymerization k. The degree of polymerization indexes the number of oxirane residuals within the macromolecule. Though the reaction sequence is simplified, it retains the essence of one molecule reacting with every other molecule. This step-growth mechanism (13) develops the thermoset resin microstructure. 

From a purely pragmatic perspective, it is clear that reactive metabolites are linked with toxicity and that a circumstantial link can be made to idiosyncratic toxicides. Consequently, even though the mechanism of this toxicity is not fully understood, since assays are available to measure the potential for bioactivation in an ideal world one would not carry this liability forward. Conversely, it is not an ideal world, all drug molecules have challenges and the definition of therapeutic index (i.e., the ratio between the toxic exposure and the therapeutic exposure) is critical. Covalent binding of reactive metabolites to macromolecules is a crude measure and not a full predictor of toxicity and it is well known that toxicity can be ameliorated by a lower dose. Furthermore, the so-called definitive assays require radiolabeled drug material which is expensive and generally slow to produce. 

Calibration can be eliminated by coupling the SEC or ThFFF system to a proper detection system such as MALS detector or MALS and refraction index, which yields molar mass information without reference to standards [45]. The advantage of this coupling method is that compositional and dimensional information can be obtained regardless of whether the thermophoretic properties are understood. A continuous two-dimensional ThFFF channel for semipreparative separations of macromolecules has also been developed [46]. 

With an approximate volume of 4 ml, the vitreous is the largest structure within the eye. It has a refractive index of 1.33 and consists of 98-99% water with a scaffold of collagen fibres and macromolecules of hyaluronic acid winding through the scaffold. The healthy human vitreous does not contain blood vessels and has a consistency comparable to that of egg white. 

Many macromolecules have been utilized as drug carriers in an attempt to decrease the toxicity and/or to increase the therapeutic index of a parent anticancer compound, and have been reviewed extensively [12-20]. 

Molecular weight and polydispersity determinations were obtained by GPC with THF as elution solvent with styragel columns (60, 100, 500, 10, 10, 10 and 3.10 A). Eluted macromolecule was observed simultaneously by refractive index and by ultraviolet absorption. 

Atom description in QSAR models development and use of an atom level index, 22, 1 Autoradiographic investigations of cholinergic and other receptors in the motor endplate, 3, 81 The Binding of drugs to blood plasma macromolecules Recent advances and therapeutic... 

The interaction between solvent components and the macromolecule is reflected also in the difference between the refractive index increments measured at constant concentration and those found at constant chemical... 

The most evident reason is that dilute solution measurements can preferably be compared directly with the unmodified dilute solution theory as reviewed in Chapter 3. As has already been pointed out in Section 2.6.1, the form birefringence in dilute solution can effectively be suppressed by the choice of a solvent of practically the same refractive index as the polymer. In such a "matching solvent the contrast between the coil of the macromolecule and its surrounding practically disappears. This means that, at the same time, the influence of the shape (form) of the coil disappears. Also the comparison with measurements on con-... 

As in Equation 14 for the density increment, the right side of Equation 13a is equal to (dn/dg2)T,m,ns, i-e., the refractive index increment measured by using a dialyzed macromolecule solution and the dialyzate as reference solvent.)... 

Methods used to obtain conformational information and establish secondary, tertiary, and quaternary structures involve electron microscopy, x-ray diffraction, refractive index, nuclear magnetic resonance, infrared radiation, optical rotation, and anisotropy, as well as a variety of rheological procedures and molecular weight measurements. Extrapolation of solid state conformations to likely solution conformations has also helped. The general principles of macromolecules in solution has been reviewed by Morawetz (17), and investigative methods are discussed by Bovey (18). Several workers have recently reexamined the conformations of the backbone chain of xylans (19, 20, 21). Evidence seems to favor a left-handed chain chirality with the chains entwined perhaps in a two fold screw axis. Solution conformations are more disordered than those in crystallites (22). However, even with the disorder-... 

When a monochromatic, coherent light is incident into a dilute macromolecule solution, if solvent molecules and macromolecules have different refractive index, the incident light is scattered by each illuminated macromolecule to all directions [9, 10]. The scattered light waves from different macromolecules mutually interfere, or combine, at a distant, fast photomultiplier tube detector and produce a net scattering intensity I(t) or photon counts n(t) which is not uniform on the detection plane. If all macromolecules are stationary, the scattered light intensity at each direction would be a constant, i.e. independent of time. 

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