Polyphosphoester‐based paclitaxel complexes

We demonstrated a feasible approach for the preparation of a biodegradable, water soluble polyphosphoester based paclitaxel complex. Applying poly(hydroxyoxyethylene phosphate) which contains both a strong proton accepting P?O group and a proton donating P? OH group, paclitaxel has been physically immobilized onto the polymer via H‐bonding. The water soluble complex contained 16.7 wt % paclitaxel and more than 4000 times increased drug solubility was achieved. The polymer‐drug complex formed nanosized aggregates that were characterized by dynamic light scattering. Intravenous injection of poly(hydroxyoxyethylene phosphate) in rats at a dose of 1000 mg/kg did not induce any clinical signs or body weight gain reduction. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42772.     

Camelina oil‐ and linseed oil‐based polymers with bisphosphonate crosslinks

Natural oils are the attractive biobased alternatives for petroleum derived chemicals in the production of polymers. A series of new biodegradable polymers based on epoxidized camelina oil was synthesized and investigated. The thermal, mechanical, swelling properties, hydrolysis, biodegradation, and bioresistance of the camelina oil‐based polymers with bisphosphonate crosslinks were studied and compared with those of the analogous polymers based on epoxidized linseed oil. The dependence of the polymer properties on the density of crosslinks was observed. The obtained results showed that the properties of the camelina oil‐based polymers are comparable with those of the linseed oil‐based polymers and that camelina oil is a promising starting material for the synthesis of polymers. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40683.     

Crosslinking of epoxidized natural oils with diepoxy reactive diluents

The different natural oils epoxidized with 3‐chloroperbenzoic acid were crosslinked with diepoxy reactive diluents, bisphenol A propoxylate diglycidyl ether, and 3,4‐epoxycyclohexylmethyl‐3,4‐epoxyclohexane‐carboxylate, using cationic initiator at 60°C and photoinitiators at the room temperature. The insoluble fraction of the polymeric products was 59–90%. The Young modulus of the crosslinked polymer films ranged from 2 to 861 MPa. The 10% weight loss temperatures of the crosslinked polymers estimated by thermogravimetric analysis were in the range from 250 to 420°C. The water vapor transmission rate of the crosslinked biopolymer films ranged from 6 to 49 g/m²/24 h. Biochemical oxygen demand and biodegradation in soil of the crosslinked polymers were studied. The crosslinked polymers showed higher biodegradation rate than cellulose, starch, and polyvinylalcohol. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Influence of Feeding and Oviposition by Phytophagous Pentatomids on Photosynthesis of Herbaceous Plants

Feeding by herbivorous insects may change photosynthetic activity of host plants. We studied how feeding and oviposition by herbivorous stink bugs, Murgantia histrionica and Nezara viridula (Heteroptera: Pentatomidae), affect photosynthetic parameters of Brassica oleracea (savoy cabbage) and Phaseolus vulgaris (French bean). First, we measured photosynthetic gas exchange, chlorophyll fluorescence imaging, and emission of induced volatile organic compounds (VOC) immediately after feeding and during a post-feeding period. Photosynthesis decreased rapidly and substantially in B. oleracea and P. vulgaris infested by feeding bugs. Stomatal conductance did not decrease proportionally with photosynthesis; instead, inhibition of photosynthesis likely was due to a reduced diffusion of CO₂ in the mesophyll. We also measured the impact of oviposition per se and oviposition associated with feeding on photosynthetic parameters. A surprisingly large inhibition of photosynthesis was detected in cabbage leaves in response to oviposition by M. histrionica, even when oviposition was not associated with feeding activity. High resolution chlorophyll fluorescence imaging revealed that the damage to photochemistry caused by feeding and oviposition was restricted to the attacked areas. By contrast, the photochemical yield increased temporarily in the unaffected areas of the attacked leaves, indicating the onset of a compensatory response. Measurement of volatile organic compounds (VOC) revealed that feeding-damaged plants did not emit detectable amounts of VOC, indicating cellular damage (methanol and green leaf volatiles). However, feeding by M. histrionica induced emission of mono- and sesquiterpenes in savoy cabbage leaves. The different time-course of the induction of these two classes of terpenes may reflect the induction of two different biosynthetic pathways and indicate different roles of these terpenoids in tritrophic interactions.     

Functionality dependent olefin activity in acyclic diene metathesis polymerization: mass spectrometry characterization of amino acid functionalized olefins

Mass spectrometry has become an essential tool in delineating the structural properties of a new series of amino acid functionalized acyclic diene metathesis (ADMET) polymers known as bioolefins. These measurements, coupled with the measurement of the polymers chemical and physical properties, assist in the determination of their utility as biomaterials. In the present study, a set of five polymers with different bulk size and electronic properties were chosen for structural analyses by MALDI-TOF, MALDI-FTICR, and DIOS-TOF. The obtained data show that due to the competing metathesis and isomerization during ADMET, depending on their structural properties, the olefins display different selectivity toward main metathesis or isomerized products.     

Effect of commercially available antioxidants over biodiesel/diesel blends stability

The main obstacle in biodiesel/conventional diesel blends acceptance worldwide seems to be its poor oxidative stability. Low resistance towards oxygenation is due to the fatty constituent in the blend. Even low concentrations of biodiesel (5%, 10% and 20%) can contribute to sticky, viscous and polymeric deposits formation after several months of storage. Two correlations were derived concerning insolubles formed in both stabilized and not stabilized blends, stressed under conditions of ASTM D2274.For treated with antioxidant additive:

Total insol.=0.6561+80.1213∗ΔTAN-114.27∗ΔPC-2.6073∗ΔIV     

Chemical bath deposition and characterization of electrochromic thin films of sodium vanadium bronzes

Thin yellow-orange films of sodium vanadium oxide bronzes have been prepared from a sodium–vanadium solution (1:1) at 75 °C and pH = 3. The composition, structure and morphology of the films have been studied by XRD, IR spectroscopy, TG and SEM–EDX analyses. It has been established that the prepared films are a phase mixture of hydrated NaV₆O₁₅ (predominant component) and Na_1.1V₃O_7.9 with total water content of 10.58%.The sodium vanadium bronze thin films exhibit two-step electrochromism followed by color change from yellow-orange to green, and then from green to blue. The cyclic voltammetry measurements on the as-deposited and annealed vanadium bronze films reveal the existence of different oxidation/reduction vanadium sites which make these films suitable for electrochromic devices. The annealing of the films at 400 °C changes the composition, optical and electrochemical properties     

Fluorescence Liquid Biopsy for Cancer Detection Is Improved by Using Cationic Dendronized Hyperbranched Polymer

(1) Background: Biophysical techniques applied to serum samples characterization could promote the development of new diagnostic tools. Fluorescence spectroscopy has been previously applied to biological samples from cancer patients and differences from healthy individuals were observed. Dendronized hyperbranched polymers (DHP) based on bis(hydroxymethyl)propionic acid (bis-MPA) were developed in our group and their potential biomedical applications explored. (2) Methods: A total of 94 serum samples from diagnosed cancer patients and healthy individuals were studied (20 pancreatic ductal adenocarcinoma, 25 blood donor, 24 ovarian cancer, and 25 benign ovarian cyst samples). (3) Results: Fluorescence spectra of serum samples (fluorescence liquid biopsy, FLB) in the presence and the absence of DHP-bMPA were recorded and two parameters from the signal curves obtained. A secondary parameter, the fluorescence spectrum score (FS_score), was calculated, and the diagnostic model assessed. For pancreatic ductal adenocarcinoma (PDAC) and ovarian cancer, the classification performance was improved when including DHP-bMPA, achieving high values of statistical sensitivity and specificity (over 85% for both pathologies). (4) Conclusions: We have applied FLB as a quick, simple, and minimally invasive promising technique in cancer diagnosis. The classification performance of the diagnostic method was further improved by using DHP-bMPA, which interacted differentially with serum samples from healthy and diseased subjects. These preliminary results set the basis for a larger study and move FLB closer to its clinical application, providing useful information for the oncologist during patient diagnosis.     

Finding an internal state of RC4 stream cipher

The RC4 is a stream cipher widely deployed in software applications due to its simplicity and efficiency. The paper presents a cryptanalytic attack that employs the tree representation of this cipher and introduces an abstraction in the form of general conditions for managing the information about its internal state. In order to find the initial state, the tree of general conditions is searched applying the hill-climbing strategy. The complexity of this attack is lower than that of an exhaustive search. The attack is derived from a general cryptanalytic approach for a class of table-shuffling ciphers, whose next-state function permutes the table entries. Incorporating the general conditions in the existing backtracking algorithm, the estimated complexity of the cryptanalytic attack is decreased below the best published result but the RC4 still remains a quite secure cipher in practice.