Biodegradable hybrid polymer films based on poly(vinyl alcohol) and collagen hydrolyzate

Hybrid blends of poly(vinyl alcohol) (PVA) and collagen hydrolyzate (CH), an added value waste from leather indutry, have been converted by blown molding extrusion, to environmentally degradable films. Blown extruded films comprising 5-15% of CH, were tested as sel fertilizing mulching films and analyzed for their propensity to enviromental degradation. PVA/CH films rapidly disintegrate when buried in soil, and resulted promising for application such as transplanting films, with additional fertilizing action of CH.     

Multifunctional polyesters as new candidate materials for biomedical applications. Synthesis and structural characterization

The present work was aimed at the development of functional polymeric materials to be used in the targeted delivery of proteic drug and tissue engineering fields. The adopted strategy was based on the design of special polymer classes whose structures and functionality could be easily modified by finely tuned synthetic procedures. Poly(ether ester)s containing H-bonding units were chosen as promising materials for the proposed applications. Commercially available precursors were successfully used for the synthesis of symmetrical diesters containing different H-bonding groups (amide, carbamate, and urea moieties). In all cases, pure products were obtained in good yields. Bulk polycondensation of the monomeric precursors with different mixtures of 1,4-butanediol and PEG 1000 diol afforded a variety of high molecular weight polymeric structures. Physical-chemical characterization of the polymers indicates that their thermal, mechanical, and swelling properties can be tailored by a proper selection of the H-bonding group and of the composition of the feed mixture.     

Biodegradation of PVA-based formulations

Investigation of the biodegradability of water soluble poly(vinyl alcohol) (PVA) based blown films was carried out under different lab-scale environmental conditions. In particular respirometric tests were utilized in order to evaluate the biodegradability of PVA films in composting, in modified Sturm test and in soil burial simulation tests. Several microbial inocula present in river water, mature compost, forest and farm soils as well as sewage sludge from municipal and paper mill wastewater treatments plants were utilized for the relevant tests. A mixed PVA-degrading microbial culture was obtained by a common enrichment procedure by using sewage sludge from paper mill as inoculum; this culture was tentatively utilized for the isolation of single PVA-degrading microorganisms. As a first result we can stress that significant biodegradation extent in fairly low incubation time can be obtained only in the presence of acclimated microbial populations such as those deriving from paper mill sewage sludge, in liquid cultures. Nevertheless separation of single degrading microbial species was impossible most likely due to the establishment of symbiotic or commensal interactions between the single components of the PVA-degrading mixed cultures. On the other hand, limited mineralization rates were recorded in solid cultures in the presence of soil or compost. Finally, a mechanism of degradation of polymer chains unlike random or unzipping was suggested in the presence of either PVA-degrading mixed culture and its filtrate by means of viscometric determinations of molecular weight within the time.     

Mesophase structure and alignment under different fields of liquid crystalline main-chain/side-group block copolymers

Liquid crystalline block copolymers are new materials in which multiple molecular interactions can provide the driving force for complex phase behaviors and states of order. Block copolymers containing both liquid crystalline main-chain polyester and side-group polymethacrylate blocks were investigated. They phase separated in the liquid crystalline state and their individual mesophases coexisted. The copolymers responded very differently when either a mechanical or a magnetic field was used for alignment. In the fibers the orientations of the side-group and main-chain smectic planes with respect to the fiber axis depended critically on the block lengths and on their distinct tendencies to align, whereas under a magnetic field the mesogens aligned collectively with their long molecular axis parallel to the field, independent of the copolymer structure.     

Congruence,similarity, and symmetries of geometric objects

We consider the problem of computing geometric transformations (rotation, translation, reflexion) that map a point setA exactly or approximately into a point setB. We derive efficient algorithms for various cases (Euclidean or maximum metric, translation or rotation, or general congruence).Part of this research was supported by the DFG under Grants Me 620/6-1 and Al 253/1-1.     

Structural characterization of the smectic polymorphism of chiral liquid crystalline polysiloxanes containing biphenyl mesogens

A structural characterization of chiral side chain siloxanes with different average degrees of polymerization, DP_n, was performed by X-ray diffraction experiments on powder and oriented fibre specimens. Polymers (DP_n = 35) and oligomers (DP_n = 4) contained the 4,4'-biphenylene unit with either an (S)-2-methylbutoxy (An, Bn) or an (S)-2-chloro-3-methylbutanoyloxy substituent (Cll). The spacer segment connected to the siloxane backbone had a variable number, n, of methylene groups (n = 5, 8, or 11). Independent of the spacer length and the chiral tail nature, the polysiloxanes underwent the same sequence of phases: C-S_F1 (or S_I1)-S_C1-S_A1-I, whereas in the oligosiloxanes the sequence C-S_B1-S_A1-I (B11) or C-S_F1-S_C1-I (B5) occurred. The influence of the structure of the polysiloxanes on the formation of the smectic (tilted or orthogonal) mesophases was elucidated. The rather large number of reflections (three or four) detected in the X-ray patterns at low angles, allowed a drawing of the projection of the electron density profiles along the layer normal, p(z), and deduction of the most physically acceptable electron density profiles from among the numerous possibilities for each smectic phase. The electron density profiles were in agreement with monolayer smectic phases presenting a microphase separation between the siloxane backbones and the side chains, so constraining the polymer backbones within a thin layer.     

Molecular structure refinement of a segmented thermotropic polyester containing an aromatic triad mesogen

The polymorphic behavior of a polyester consisting of an aromatic triad mesogen and a flexible spacer has been investigated. The effect of thermal and mechanical treatment on the appearance of two crystalline phases stable at room temperature is discussed. The molecular packing (triclinic cell, space group P1 ) and the morphological parameters of the crystalline phase stabilized by drawing process are evaluated and refined. The whole-pattern method, based on the analysis of the whole x-ray diffraction pattern from fiber samples of polymer, has been employed. The molecular packing resembles very much that of polyethylene terephthalate. ©1995 John Wiley & Sons, Inc.     

Combinatorial complexity bounds for arrangements of curves and spheres

We present upper and lower bounds for extremal problems defined for arrangements of lines, circles, spheres, and alike. For example, we prove that the maximum number of edges boundingm cells in an arrangement ofn lines is (m ^2/3 n ^2/3 +n), and that it isO(m ^2/3 n ^2/3 (n) +n) forn unit-circles, where(n) (and later(m, n)) is a function that depends on the inverse of Ackermann's function and grows extremely slowly. If we replace unit-circles by circles of arbitrary radii the upper bound goes up toO(m ^3/5 n ^4/5 (n) +n). The same bounds (without the(n)-terms) hold for the maximum sum of degrees ofm vertices. In the case of vertex degrees in arrangements of lines and of unit-circles our bounds match previous results, but our proofs are considerably simpler than the previous ones. The maximum sum of degrees ofm vertices in an arrangement ofn spheres in three dimensions isO(m ^4/7 n ^9/7 (m, n) +n ²), in general, andO(m ^3/4 n ^3/4 (m, n) +n) if no three spheres intersect in a common circle. The latter bound implies that the maximum number of unit-distances amongm points in three dimensions isO(m ^3/2 (m)) which improves the best previous upper bound on this problem. Applications of our results to other distance problems are also given.The research of the second author was supported by the National Science Foundation under Grant CCR-8714565. Work by the fourth author has been supported by Office of Naval Research Grant N00014-87-K-0129, by National Science Foundation Grant No. NSF-DCR-83-20085, by grants from the Digital Equipment Corporation and the IBM Corporation, and by a research grant from the NCRD, the Israeli National Council for Research and Development. A preliminary version of this paper has appeared in theProceedings of the 29th IEEE Symposium on Foundations of Computer Science, 1988.     

Quasi-optimal range searching in spaces of finite VC-dimension

The range-searching problems that allow efficient partition trees are characterized as those defined by range spaces of finite Vapnik-Chervonenkis dimension. More generally, these problems are shown to be the only ones that admit linear-size solutions with sublinear query time in the arithmetic model. The proof rests on a characterization of spanning trees with a low stabbing number. We use probabilistic arguments to treat the general case, but we are able to use geometric techniques to handle the most common range-searching problems, such as simplex and spherical range search. We prove that any set ofn points inE ^d admits a spanning tree which cannot be cut by any hyperplane (or hypersphere) through more than roughlyn ^1–1/d edges. This result yields quasi-optimal solutions to simplex range searching in the arithmetic model of computation. We also look at polygon, disk, and tetrahedron range searching on a random access machine. Givenn points inE ², we derive a data structure of sizeO(n logn) for counting how many points fall inside a query convexk-gon (for arbitrary values ofk). The query time isO(kn logn). Ifk is fixed once and for all (as in triangular range searching), then the storage requirement drops toO(n). We also describe anO(n logn)-size data structure for counting how many points fall inside a query circle inO(n log² n) query time. Finally, we present anO(n logn)-size data structure for counting how many points fall inside a query tetrahedron in 3-space inO(n ^2/3 log² n) query time. All the algorithms are optimal within polylogarithmic factors. In all cases, the preprocessing can be done in polynomial time. Furthermore, the algorithms can also handle reporting within the same complexity (adding the size of the output as a linear term to the query time).Portions of this work have appeared in preliminary form in Partition trees for triangle counting and other range searching problems (E. Welzl),Proc. 4th Ann. ACM Symp. Comput. Geom. (1988), 23–33, and Tight Bounds on the Stabbing Number of Spanning Trees in Euclidean Space (B. Chazelle), Comput. Sci. Techn. Rep. No. CS-TR-155-88, Princeton University, 1988. Bernard Chazelle acknowledges the National Science Foundation for supporting this research in part under Grant CCR-8700917. Emo Welzl acknowledges the Deutsche Forschungsgemeinschaft for supporting this research in part under Grant We 1265/1-1.