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Cyclodextrins are cyclic oligosaccharides that have received special attention due to their cavity-based structural architecture that imbues them with outstanding properties, primarily related to their capacity to host various guest molecules, from low-molecular-mass compounds to polymers. Cyclodextrin derivatization has been always accompanied by the development of characterization methods, able to unfold complicated structures with increasing precision. One of the important leaps forward is represented by mass spectrometry techniques with soft ionization, mainly matrix-assisted laser desorption/ionization (MALDI) and electrospray ionization (ESI). In this context, esterified cyclodextrins (ECDs) benefited also from the formidable input of structural knowledge, thus allowing the understanding of the structural impact of reaction parameters on the obtained products, especially for the ring-opening oligomerization of cyclic esters. The current review envisages the common mass spectrometry approaches such as direct MALDI MS or ESI MS analysis, hyphenated liquid chromatography-mass spectrometry, and tandem mass spectrometry, employed for unraveling the structural features and particular processes associated with ECDs. Thus, the accurate description of complex architectures, advances in the gas phase fragmentation processes, assessment of secondary reactions, and reaction kinetics are discussed in addition to typical molecular mass measurements.

The need for more advantageous and pharmaceutically active wound dressings is a pressing matter in the area of wound management. In this study, we explore the possibility of incorporating thymoquinone within bacterial cellulose, utilising cyclodextrins as a novel method of solubilising hydrophobic compounds. The thymoquinone was not soluble in water, so was incorporated within hydroxypropyl-β-cyclodextrin before use. Thymoquinone: hydroxypropyl-β-cyclodextrin inclusion complex produced was found to be soluble in water up to 7% ( w / v ) and was stable with no crystal formation for at least 7 days with the ability to be loaded within the bacterial cellulose matrix. The inclusion complex was found to be thermally stable up to 280 °C which is far greater than the production temperature of 80 °C and was stable in phosphate-buffered saline and extraction solvents in permeation and dose experiments. The adhesion properties of the Thymoquinone: hydroxypropyl-β-cyclodextrin loaded bacterial cellulose dressings were tested and found to be 2.09 N. Permeation studies on skin mimicking membrane Strat-M showed a total permeated amount (0-24 h) of 538.8 µg cm -2 and average flux after a 2 h lag of 22.4 µg h -1 cm -2 . To the best of our knowledge, the methods outlined in this study are the first instance of loading bacterial cellulose with thymoquinone inclusion complex with the aim of producing a pharmaceutically active wound dressing.

The application of mulch films for preserving soil moisture and preventing weed growth has been a part of agricultural practice for decades. Different materials have been used as mulch films, but polyethylene plastic has been considered most effective due to its excellent mechanical strength, low cost and ability to act as a barrier for sunlight and water. However, its use carries a risk of plastic pollution and health hazards, hence new laws have been passed to replace it completely with other materials over the next few years. Research to find out about new biodegradable polymers for this purpose has gained impetus in the past few years, driven by regulations and the United Nations Organization's Sustainable Development Goals. The primary requisite for these polymers is biodegradability under natural climatic conditions without the production of any toxic residual compounds. Therefore, biodegradable polymers developed from fossil fuels, microorganisms, animals and plants are viable options for using as mulching material. However, the solution is not as simple since each polymer has different mechanical properties and a compromise has to be made in terms of strength, cost and biodegradability of the polymer for its use as mulch film. This review discusses the history of mulching materials, the gradual evolution in the choice of materials, the process of biodegradation of mulch films, the regulations passed regarding material to be used, types of polymers that can be explored as potential mulch films and the future prospects in the area.

Environment-responsive-cum-site-specific delivery of therapeutic drugs into tumor cells is a foremost challenge for chemotherapy. In the present work, Moringa oleifera gum-based pH-responsive nanogel (MOGN) was functionalized as a doxorubicin (DOX) carrier. It was synthesized via free radical polymerization through the γ-irradiation method using acrylamide and N,N'-MBA followed by hydrolysis, sonication, and ultracentrifugation. The swelling behavior of MOGN as a function of pH was assessed using a gravimetric method that revealed its superabsorbent nature (365.0 g/g). Furthermore, MOGN showed a very high loading efficiency (98.35 %L) of DOX by MOGN. In vitro release studies revealed that DOX release from DOX-loaded MOGN was 91.92% at pH 5.5 and 12.18% at 7.4 pH, thus favorable to the tumor environment. The drug release from nanogel followed Korsmeyer-Peppas model at pH 5.5 and 6.8 and the Higuchi model at pH 7.4. Later, the efficient DOX release at the tumor site was also investigated by cytotoxicity study using Rhabdomyosarcoma cells. Thus, the synthesized nanogel having high drug loading capacity and excellent pH-triggered disintegration and DOX release performance in a simulated tumor environment could be a promising candidate drug delivery system for the targeted and controlled release of anticancer drugs.

This review article will discuss the ways in which various polymeric materials, such as polyethylene (PE), polypropylene (PP), polystyrene (PS), and poly(ethylene terephthalate) (PET) can potentially be used to produce bioplastics, such as polyhydroxyalkanoates (PHAs) through microbial cultivation. We will present up-to-date information regarding notable microbial strains that are actively used in the biodegradation of polyolefins. We will also review some of the metabolic pathways involved in the process of plastic depolymerization and discuss challenges relevant to the valorization of plastic waste. The aim of this review is also to showcase the importance of methods, including oxidative degradation and microbial-based processes, that are currently being used in the fields of microbiology and biotechnology to limit the environmental burden of waste plastics. It is our hope that this article will contribute to the concept of bio-upcycling plastic waste to value-added products via microbial routes for a more sustainable future.

Poly-γ-glutamic acid (γ-PGA) is a bio-derived water-soluble, edible, non-immunogenic nylon-like polymer with the biochemical characteristics of a polypeptide. This Bacillus-derived material has great potential for a wide range of applications, from bioremediation to tunable drug delivery systems. In the context of oral care, γ-PGA holds great promise in enamel demineralisation prevention. The salivary protein statherin has previously been shown to protect tooth enamel from acid dissolution and act as a reservoir for free calcium ions within oral cavities. Its superb enamel-binding capacity is attributed to the L-glutamic acid residues of this 5380 Da protein. In this study, γ-PGA was successfully synthesised from Bacillus subtilis natto cultivated on supplemented algae media and standard commercial media. The polymers obtained were tested for their potential to inhibit demineralisation of hydroxyapatite (HAp) when exposed to caries simulating acidic conditions. Formulations presenting 0.1, 0.25, 0.5, 0.75, 1, 2, 3 and 4% (w/v) γ-PGA concentration were assessed to determine the optimal conditions. Our data suggests that both the concentration and the molar mass of the γ-PGA were significant in enamel protection (p = 0.028 and p < 0.01 respectively). Ion Selective Electrode, combined with Fourier Transform Infra-Red studies, were employed to quantify enamel protection capacity of γ-PGA. All concentrations tested showed an inhibitory effect on the dissolution rate of calcium ions from hydroxyapatite, with 1% (wt) and 2% (wt) concentrations being the most effective. The impact of the average molar mass (M) on enamel dissolution was also investigated by employing commercial 66 kDa, 166 kDa, 440 kDa and 520 kDa γ-PGA fractions. All γ-PGA solutions adhered to the surface of HAp with evidence that this remained after 60 min of continuous acidic challenge. Inductively Coupled Plasma analysis showed a significant abundance of calcium ions associated with γ-PGA, which suggests that this material could also act as a responsive calcium delivery system. We have concluded that all γ-PGA samples tested (commercial and algae derived) display enamel protection capacity regardless of their concentration or average molar mass. However, we believe that γ-PGA D/L ratios might affect the binding more than its molar mass.

Presented herein are the results of a novel recycling method for waste Tetra Pak ® packaging materials. The polyethylene (PE-T) component of this packaging material, obtained via a separation process using a "solvents method", was used as a carbon source for the biosynthesis of polyhydroxyalkanoates (PHAs) by the bacterial strain Cupriavidus necator H16. Bacteria were grown for 48-72 h, at 30 °C, in TSB (nitrogen-rich) or BSM (nitrogen-limited) media supplemented with PE-T. Growth was monitored by viable counting. It was demonstrated that C. necator utilised PE-T in both growth media, but was only able to accumulate 40% w/w PHA in TSB supplemented with PE-T. Only 1.5% w/w PHA was accumulated in the TSB control, and no PHA was detected in the BSM control. Extracted biopolymers were characterised by nuclear magnetic resonance (NMR), Fourier-transform infrared (FTIR) spectroscopy, electrospray tandem mass spectrometry (ESI-MS/MS), gel permeation chromatography (GPC), and accelerator mass spectrometry (AMS). The characterisation of PHA by ESI-MS/MS revealed that PHA produced by C. necator in TSB supplemented with PE-T contained 3-hydroxybutyrate, 3-hydroxyvalerate, and 3-hydroxyhexanoate co-monomeric units. AMS analysis also confirmed the presence of 96.73% modern carbon and 3.27% old carbon in PHA derived from Tetra Pak ® . Thus, this study demonstrates the feasibility of our proposed recycling method for waste Tetra Pak ® packaging materials, alongside its potential for producing value-added PHA, and the ability of 14C analysis in validating this bioconversion process.

Poly( L -lactide) is capable of self-assembly into a nematic mesophase under the influence of temperature and mechanical stresses. Therefore, subsequent poly( L -lactide) films were obtained and characterized, showing nematic liquid crystal properties both before and after degradation. Herein, we present that, by introducing β-cyclodextrin into the polymer matrix, it is possible to obtain a chiral nematic mesophase during pressing, regardless of temperature and time. The obtained poly( L -lactide) films exhibiting liquid crystal properties were subjected to degradation tests and the influence of degradation on these properties was determined. Thermotropic phase behavior was investigated using polarized optical microscopy, X-ray diffraction, and differential scanning calorimetry. The degradation process demonstrated an influence on the liquid crystal properties of pressed polymer films. The colored planar texture of the chiral nematic mesophase, which was not observed prior to degradation in films without the addition of β-cyclodextrin, appeared after incubation in water as a result of the entrapment of degradation products in the polymer matrix. These unusual tailor-made properties, obtained in liquid crystals in (bio)degradable polymers using a simple method, demonstrate the potential for advanced photonic applications.

Antimicrobial and antiviral nanocomposites based on polylactic acid (PLA) and chitosan were synthesized by a thermochemical reduction method of Ag + ions in the PLA-Ag + -chitosan polymer films. Features of the structural, morphological, thermophysical, antimicrobial, antiviral, and cytotoxic properties of PLA-Ag-chitosan nanocomposites were studied by X-ray diffraction (XRD), transmission electron microscopy (TEM), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and antiviral, antimicrobial, and cytotoxic studies. The effects of temperature and the duration of reduction of Ag + ions on the structure of PLA-Ag-chitosan nanocomposites were established. During the thermochemical reduction ( T = 160 °C, t = 5 min) of silver palmitate ions in PLA-Ag + -chitosan polymer films, Ag nanoparticles with an average size of 4.2 nm were formed. PLA-Ag-chitosan polymer nanocomposites have strong antimicrobial activity against S. aureus and E. coli strains. In particular, for PLA-chitosan samples containing 4% Ag, the diameters of the S. aureus and E. coli growth inhibition zones were 25.8 and 25.0 mm, respectively. The antiviral activity of the nanocomposites against influenza A virus, herpes simplex virus type 1, and adenovirus serotype 2 was also revealed. The PLA-4%Ag-chitosan nanocomposites completely inhibited the cytopathic effect (CPE) of herpes virus type 1 by 5.12 log 10 TCID 50 /mL (high antiviral activity) and the development of the CPE of influenza virus and adenovirus by 0.60 and 1.07 log 10 TCID 50 /mL (relative antiviral activity). The obtained nanocomposites were not cytotoxic; they did not inhibit the viability of MDCK, BHK-21, and Hep-2 cell cultures.

Green synthesis of silver-containing nanocomposites based on polylactide (PLA) was carried out in two ways. With the use of green tea extract, Ag + ions were reduced to silver nanoparticles with their subsequent introduction into the PLA (mechanical method) and Ag + ions were reduced in the polymer matrix of PLA-AgPalmitate (PLA-AgPalm) (in situ method). Structure, morphology and thermophysical properties of nanocomposites PLA-Ag were studied by FTIR spectroscopy, wide-angle X-ray scattering (WAXS), transmission electron microscopy (TEM), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC) methods. The antimicrobial, antiviral, and cytotoxic properties were studied as well. It was found that the mechanical method provides the average size of silver nanoparticles in the PLA of about 16 nm, while in the formation of samples by the in situ method their average size was 3.7 nm. The strong influence of smaller silver nanoparticles (3.7 nm) on the properties of nanocomposites was revealed, as with increasing nanosilver concentration the heat resistance and glass transition temperature of the samples decreases, while the influence of larger particles (16 nm) on these parameters was not detected. It was shown that silver-containing nanocomposites formed in situ demonstrate antimicrobial activity against gram-positive bacterium S. aureus , gram-negative bacteria E. coli , P. aeruginosa , and the fungal pathogen of C. albicans , and the activity of the samples increases with increasing nanoparticle concentration. Silver-containing nanocomposites formed by the mechanical method have not shown antimicrobial activity. The relative antiviral activity of nanocomposites obtained by two methods against influenza A virus, and adenovirus serotype 2 was also revealed. The obtained nanocomposites were not-cytotoxic, and they did not inhibit the viability of MDCK or Hep-2 cell cultures.

A very important method of reducing the amount of polymer waste in the environment is the introduction to the market of polymers susceptible to degradation under the influence of environmental factors. This paper presents the results of testing the susceptibility to degradation in soil of branched polyesterurethane (PUR) based on poly([R,S]-3-hydroxybutyrate) (R,S-PHB), modified with poly([D,L]-lactide) (PLA) and starch (St). Weight losses of samples and changes in surface morphology (SEM, OM and contact angle system) with simultaneously only slight changes in molecular weight (GPC), chemical structure (FTIR and 1 HNMR) and thermal properties (DSC) indicate that these materials are subject to enzymatic degradation caused by the presence of microorganisms in the soil. Chemical modification of branched polyesterurethanes with R,S-PHB and their physical blending with small amounts of PLA and St resulted in a slow but progressive degradation of the samples.

The purpose of the current study is the experimental analysis of the dynamics and aerodynamic loads of a three-bladed rotor. The experimental tests focus on the rotation with three different angular velocities; for each angular speed, four different preset angles of beam have been studied. During the laboratory experiment, strain gauges, as well as high-speed cameras, have been used as the measurement system. The images from the high-speed cameras have been used to obtain aerodynamic loads in the form of polynomials, while the signals from strain gauges mounted on each beam allowed us to observe the synchronization phenomenon between beams.

Pectoralis major tendon ruptures are being reported with increasing frequency and primarily occur in young, high demand, male patients. The injury results from an eccentric contracture of the muscle most commonly while performing the bench press maneuver during weight training. In the setting of both acute and chronic injury, physical examination is critical for a timely and accurate diagnosis. During physical examination, comparison with the opposite side is imperative, and findings may include swelling, ecchymosis, loss of the anterior axillary fold, and a decreased pectoralis major index. Surgical treatment of acute ruptures is superior to nonsurgical treatment and results in improved functional outcomes and high levels of return to work and sport. Repair of chronic tears is more challenging and may require reconstruction with autograft or allograft tissue. Despite advances in surgical technique, tendon rerupture, persistent pain, and wound infection remain a concern., (Copyright © 2022 by the American Academy of Orthopaedic Surgeons.)

This paper presents the liquid crystal (LC) properties of poly(l-lactide) (PLLA). Mesophase behavior is investigated using polarized optical microscopy, X-ray diffraction, and differential scanning calorimetry. The performed analyses confirm that pressed PLLA films exhibit the unique capability of self-assembling into a nematic mesophase under the influence of mechanical pressure, temperature, and time. It was originally demonstrated that the chiral nematic mesophase can be obtained by introducing fine powders into the polymer. Based on the research conducted, it was proved that the pressed PLLA films have a chiral nematic mesophase with a nematic-to-isotropic phase transition and a large mesophase stability range overlapping the temperature of the human body, which can persist for years at ambient temperature. The obtained films show tailor-made properties toward a nematic mesophase with a specific texture, including colored planar texture of the chiral nematic mesophase and blue-phase (BP) LC texture. The BP, described for the first time in plain PLLA, occurred over a wider than usual temperature range of stability between isotropic and chiral nematic thermotropic phases (Δ T ≈ 9 °C), which is an advantage of the obtained polymer material, in addition to ease of preparation. This opens up new prospects for advanced photonic green applications., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

The feasibility of synthesis of functionalized poly(3-hydroxybutanoic acid) analogue and its copolymers via ring-opening polymerization of β-butyrolactone mediated by activated anionic initiators is presented. Using these new synthetic approaches, polyesters with a defined chemical structure of the end groups, as well as block, graft, and random copolymers, have been obtained and characterized by modern instrumental techniques, with special emphasis on ESI-MS. The relationship between the structure and properties of the prepared polymeric materials is also discussed.

The aim of this study was to determine the effect of a selected physical modifier with different granularity and mass percentage on the dynamics of aerospace polymer composites. The tests were carried out on samples made of certified aerospace materials used, among other purposes, for the manufacture of aircraft skin components. The hybrid composites were prepared from L285 resin, H286 hardener, GG 280T carbon fabric in twill 2/2 and alumina (Al 2 O 3 , designated as EA in this work). The manufactured composites contained alumina with grain sizes of F220, F240, F280, F320 and F360. The mass proportion of the modifier in the tested samples was 5% and 15%. The tested specimens, as cantilever beams fixed unilaterally, were subjected to kinematic excitation with defined parameters of amplitude and frequency excitation in the basic resonance zone of the structure. The results, obtained as dynamic responses, are presented in the form of amplitude-frequency characteristics. These relationships clearly indicate the variable nature of composite materials due to modifier density and grain size. The novelty of this study is the investigation of the influence of the alumina properties on system dynamics responses.

This perspective article summarizes the last decade's developments in the field of phthalocyanine (Pc)-polymeric nanoparticle (NP) delivery systems for cancer photodynamic therapy (PDT), including studies with at least in vitro data. Moreover, special attention will be paid to the various strategies for enhancing the behavior of Pc-polymeric NPs in PDT, underlining the great potential of this class of nanomaterials as advanced Pcs' nanocarriers for cancer PDT. This review shows that there is still a lot of research to be done, opening the door to new and interesting nanodelivery systems.

Following our previous studies on the molecular level structure of (co)oligoesters obtained via anionic homo- and co-polymerization of novel β-substituted β-lactones, prepared by the atmospheric pressure carbonylation reaction of respective epoxides, the boric acid biocatalyzed ring-opening (co)polymerization of δ-valerolactone has been studied. As a co-monomer the 6-methy-ε-caprolactone, prepared by the one-pot oxidation of respective alcohol, and ethylene glycol as polymerization initiator were used. The obtained copolymers were characterized by 1 H-NMR, GPC and ESI-MS, respectively in order to confirm their chemical structures and identity. Subsequently, tandem mass spectrometry (MS-MS studies) via collision-induced dissociation were utilized to characterize the fragmentation pattern. ESI-MS and NMR analyses confirmed the formation of random linear copolymer chains composed of different polyester repeat units. MS-MS experiments showed that fragmentation proceeds via ester bound cleavage along the (co)polyester chains. The innovative aspect of this contribution is related to the elaboration of the telechelic (co)polymers end-capped with hydroxyl end groups and well-defined molecular architectures, which could facilitate the development of new flexible macromolecular systems for potential biomedical applications.

The natural polysaccharides are promising compounds for applications in regenerative medicine. Gellan gum (GG) is the bacteria-derived polysaccharide widely used in food industry. Simple modifications of its chemical properties make GG superior for the development of biocompatible hydrogels. Beside reversible cationic integration of GG chains, more efficient binding is accomplished with 1-ethyl-3-[3-(dimethylamino)propyl]carbodiimide (EDC). However, the side-products of polymer cross-linking might affect viability and differentiation of stem cells introduced into the hydrogels. We found that O-acylisourea (EDU) stimulates autophagy-based vacuolation in both periodontal ligament and dental pulp stem cells. 24-h treatment of cells with GG extracts cross-linked with 15 mM EDC developed large cytoplasmic vacuoles. Freshly prepared EDU (2-6 mM) but not 15 mM EDC solutions initiated vacuole development with concomitant reduction of cell viability/metabolism. Most of the vacuoles stained with acridine orange displayed highly acidic environment further confirmed by flow cytometric analysis. Western blot of the LC3 autophagy marker followed by a transmission electron microscopy indicated the process is autophagy-dependent. We propose that the high reactivity of EDU with intracellular components initiates autophagy, although the targets of EDU remain unknown. Nevertheless, a burst release of EDU from GG hydrogels might modulate negatively cellular processes and final effectiveness of tissue regeneration., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

An increase in antifungal resistance has seen a surge in fungal wound infections in patients who are immunocompromised resulting from chemotherapy, disease, and burns. Human pathogenic fungi are increasingly becoming resistant to a sparse repertoire of existing antifungal drugs, which has given rise to the need to develop novel treatments for potentially lethal infections. Bacterial cellulose (BC) produced by Gluconacetobacter xylinus has been shown to possess many properties that make it innately useful as a next-generation biopolymer to be utilised as a wound dressing. The current study demonstrates the creation of a pharmacologically active wound dressing by loading antifungal agents into a biopolymer hydrogel to produce a novel wound dressing. Amphotericin B is known to be highly hepatotoxic, which reduces its appeal as an antifungal drug, especially in patients who are immunocompromised. This, coupled with an increase in antifungal resistance, has seen a surge in fungal wound infections in patients who are immunodeficient due to chemotherapy, disease, or injury. Antifungal activity was conducted via Clinical & Laboratory Standards Institute (CLSI) M27, M38, M44, and M51 against Candida auris , Candida albicans , Aspergillus fumigatus, and Aspergillus niger . This study showed that thymoquinone has a comparable antifungal activity to amphotericin B with mean zones of inhibition of 21.425 ± 0.925 mm and 22.53 ± 0.969 mm, respectively. However, the mean survival rate of HEp-2 cells when treated with 50 mg/L amphotericin B was 29.25 ± 0.854% compared to 71.25 ± 1.797% when treated with 50 mg/L thymoquinone. Following cytotoxicity assays against HEp-2 cells, thymoquinone showed a 71.25 ± 3.594% cell survival, whereas amphotericin B had a mean cell survival rate of 29.25 ± 1.708%. The purpose of this study was to compare the efficacy of thymoquinone, ocimene, and miramistin against amphotericin B in the application of novel antifungal dressings.

Background and Objective: The incidence of melanoma has increased significantly, and early diagnosis is the most effective way to reduce associated deaths. Dermoscopy increases diagnostic accuracy in melanoma and analysis of dermoscopic structures can help in the estimation of tumor thickness. The aim of this study was to analyze the influence of Breslow thickness on the dermoscopic characteristics of melanoma., Material and Methods: Observational, cross-sectional study of patients with histologically confirmed melanoma and dermoscopic images of the tumor. The patients were divided into three groups: melanoma in situ, thin melanoma (≥ 1 mm Breslow thickness), and thick melanoma (≥ 1 mm Breslow thickness). Age, sex, tumor location, and histologic and dermoscopic characteristics were analyzed in all cases., Results: We studied 215 patients: 88 with melanoma in situ, 73 with thin melanoma, and 54 with thick melanoma. The frequency of the following dermoscopic features increased with increasing Breslow thickness: the blue-white veil (p < 0.001), white shiny structures (p < 0.001), and milky-red areas (p < 0.003). Angulated lines, by contrast, became less common with increasing thickness (p < 0.002)., Conclusions: Dermoscopy not only improves diagnostic accuracy for pigmented lesions but also helps in the preoperative assessment of Breslow thickness in melanoma., (Copyright © 2020 AEDV. Publicado por Elsevier España, S.L.U. All rights reserved.)

One of the methods of making traditional polymers more environmentally friendly is to modify them with natural materials or their biodegradable, synthetic equivalents. It was assumed that blends with polylactide (PLA), polysaccharides: chitosan (Ch) and starch (St) of branched polyurethane (PUR) based on synthetic poly([R,S]-3-hydroxybutyrate) (R,S-PHB) would degrade faster in the processes of hydrolysis and oxidation than pure PUR. For the sake of simplicity in the publication, all three modifiers: commercial PLA, Ch created by chemical modification of chitin and St are called bioadditives. The samples were incubated in a hydrolytic and oxidizing environment for 36 weeks and 11 weeks, respectively. The degradation process was assessed by observation of the chemical structure as well as the change in the mass of the samples, their molecular weight, surface morphology and thermal properties. It was found that the PUR samples with the highest amount of R,S-PHB and the lowest amount of polycaprolactone triol (PCL triol ) were degraded the most. Moreover, blending with St had the greatest impact on the susceptibility to degradation of PUR. However, the rate of weight loss of the samples was low, and after 36 weeks of incubation in the hydrolytic solution, it did not exceed 7% by weight. The weight loss of Ch and PLA blends was even smaller. However, a significant reduction in molecular weight, changes in morphology and changes in thermal properties indicated that the degradation of the samples should occur quickly after this time. Therefore, when using these polyurethanes and their blends, it should be taken into account that they should decompose slowly in their initial life. In summary, this process can be modified by changing the amount of R,S-PHB, the degree of cross-linking, and the type and amount of second blend component added (bioadditives).

Bacterial cellulose (BC) is an extracellular polymer produced by Komagateibacter xylinus, which has been shown to possess a multitude of properties, which makes it innately useful as a next-generation biopolymer. The structure of BC is comprised of glucose monomer units polymerised by cellulose synthase in β-1-4 glucan chains which form uniaxially orientated BC fibril bundles which measure 3-8 nm in diameter. BC is chemically identical to vegetal cellulose. However, when BC is compared with other natural or synthetic analogues, it shows a much higher performance in biomedical applications, potable treatment, nano-filters and functional applications. The main reason for this superiority is due to the high level of chemical purity, nano-fibrillar matrix and crystallinity. Upon using BC as a carrier or scaffold with other materials, unique and novel characteristics can be observed, which are all relatable to the features of BC. These properties, which include high tensile strength, high water holding capabilities and microfibrillar matrices, coupled with the overall physicochemical assets of bacterial cellulose makes it an ideal candidate for further scientific research into biopolymer development. This review thoroughly explores several areas in which BC is being investigated, ranging from biomedical applications to electronic applications, with a focus on the use as a next-generation wound dressing. The purpose of this review is to consolidate and discuss the most recent advancements in the applications of bacterial cellulose, primarily in biomedicine, but also in biotechnology.

Background: The pectoralis major (PM) is made up of multilaminar muscle segments that form a complex insertion on the proximal humerus; it is composed of an anterior and a posterior tendon layer. The tear patterns and patient characteristics of operatively treated PM ruptures in the general population remain poorly understood., Purpose: To comprehensively report the demographic characteristics of patients who are clinically diagnosed with structurally significant PM ruptures and to describe PM tear patterns identified during surgery., Study Design: Case series; Level of evidence, 4., Methods: A retrospective analysis of surgically treated PM tears was performed for a single-surgeon case series between January 1, 2003, and November 1, 2017. Patient demographic characteristics, classification of tear pattern, and treatment (repair/reconstruction) were recorded., Results: A total of 104 surgical cases of PM tendon rupture were identified; 100 patients underwent primary repair and 4 underwent dermal allograft reconstruction. All patients were male, with a mean age of 36.5 ± 9.2 years. Chronic tears (>6 weeks old) accounted for 63.6% of surgical cases, and 96% (n = 100) of tears occurred at or between the musculotendinous junction and tendinous insertion. A partial-thickness, complete-width tear of the posterior tendon layer at this same location was the most common tear pattern identified., Conclusion: PM ruptures occurred almost exclusively at or between the musculotendinous junction and tendinous insertion, with predominant involvement of the posterior tendon layer. Chronic tears can be safely treated with primary repair in the vast majority of cases., Competing Interests: One or more of the authors has declared the following potential conflict of interest or source of funding: A.W.E. has received consulting fees and royalties from Arthrex. AOSSM checks author disclosures against the Open Payments Database (OPD). AOSSM has not conducted an independent investigation on the OPD and disclaims any liability or responsibility relating thereto., (© The Author(s) 2020.)

In this research, an analysis of polymer composite with the matrix of L285-cured hardener H286 and six reinforcement layers of carbon fabric GG 280 T was provided. It involved a comparison of the dynamical behavior responses for three cases of composite structures in the context of the presence of the mass share modifier. The samples with the addition of a physical modifier with varying mass percentages were investigated by being subjected to dynamic tests with specific parameters, i.e., constant excitation amplitude and vibration frequency in the vicinity of the base resonance zone. The analysis allowed for indicating the relationship between the composition of the prepared composites and their dynamic response via stiffness characteristics. In addition, the investigation resulted in determining the range of harmful dynamical operating conditions, which may contribute to damage to the composite structures.

Over thirty species of littoral marine Gammaridea occur along the coasts of the North Atlantic. From one to several species can coexist in a single region. There is an evident, inverse relationship between egg incubation time and temperature (from 14 to >120 days) and consequent trends in the size of the animals on reaching maturity (from 5 mm in warmer waters to 30 mm in the coldest ones) and in lifespan (from <6 months to >5 years). Littoral gammarids are a good example of the shrinking size effect of increasing temperatures and size-related species diversity. In large species, the annual cohorts of the population (3-5 annual size groups) functionally replace the adults of smaller species. The ongoing warming of the European Arctic seas may extend the distribution limits of boreal species so that more Gammarus species may appear on northern coasts hitherto occupied by just one or at most two species., Competing Interests: None declared., (© 2020 The Authors. Ecology and Evolution published by John Wiley & Sons Ltd.)

This article reports the studies on bioactive (co)oligoesters towards their use as controlled delivery systems of p-anisic acid. The objects of the study were oligo[3-hydroxy-3-(4-methoxybenzoyloxymethyl)propionate], (p-AA-CH 2 -HP) n oligoester, and oligo[(3-hydroxy-3-(4-methoxybenzoyloxymethyl)propionate)-co-(3-hydroxybutyrate)] [(p-AA-CH 2 -HP) x -co-(HB) y (co)oligoesters containing p-anisic acid moiety (p-AA, as the bioactive end and side groups) connected to the polymer backbone through the susceptible to hydrolysis ester bonds. A thorough insight into the hydrolysis process of the bioactive (co)oligoesters studied has allowed us to determine the release profile of p-AA as well as to identify polymer carrier degradation products. The p-AA release profiles determined on the basis of high-performance liquid chromatography (HPLC) measurements showed that the release of the bioactive compound from the developed (co)oligoester systems was regular and no burst effect occurred. Biological studies demonstrated that studied (homo)- and (co)oligoesters were well tolerated by HaCaT cells because none of them showed notable cytotoxicity. They promoted keratinocyte growth at moderate concentrations. Bioactive (co)oligoesters containing p-anisic acid moiety had somewhat decreased cell proliferation at the highest concentration (100 µg/mL). The important practical inference of the current study is that the (co)oligoesters developed have a relatively large load of the biologically active substance (p-AA) per polymer macromolecule, which unlocks their potential application in the cosmetic industry.

Periodontitis (PD) is a chronic inflammatory disease of periodontal tissues caused by pathogenic microorganisms and characterized by disruption of the tooth-supporting structures. Conventional drug administration pathways in periodontal disease treatment have many drawbacks such as poor biodistribution, low selectivity of the therapeutic effect, burst release of the drug, and damage to healthy cells. To overcome this limitation, controlled drug delivery systems have been developed as a potential method to address oral infectious disease ailments. The use of drug delivery devices proves to be an excellent auxiliary method in improving the quality and effectiveness in periodontitis treatment, which includes inaccessible periodontal pockets. This review explores the current state of knowledge regarding the applications of various polymer-based delivery systems such as hydrogels, liposomes, micro-, and nanoparticles in the treatment of chronic periodontal disease. Furthermore, to present a more comprehensive understanding of the difficulties concerning the treatment of PD, a brief description of the mechanism and development of the disease is outlined.

Welding technology may be considered as a promising processing method for the formation of packaging products from biopolymers. However, the welding processes used can change the properties of the polymer materials, especially in the region of the weld. In this contribution, the impact of the welding process on the structure and properties of biopolymer welds and their ability to undergo hydrolytic degradation will be discussed. Samples for the study were made from polylactide (PLA) and poly(3-hydroxyalkanoate) (PHA) biopolymers which were welded using two methods: ultrasonic and heated tool welding. Differential scanning calorimetry (DSC) analysis showed slight changes in the thermal properties of the samples resulting from the processing and welding method used. The results of hydrolytic degradation indicated that welds of selected biopolymers started to degrade faster than unwelded parts of the samples. The structure of degradation products at the molecular level was confirmed using mass spectrometry. It was found that hydrolysis of the PLA and PHA welds occurs via the random ester bond cleavage and leads to the formation of PLA and PHA oligomers terminated by hydroxyl and carboxyl end groups, similarly to as previously observed for unwelded PLA and PHA-based materials.

Chronic wounds are often recalcitrant to treatment because of high microbial bioburden and the problem of microbial resistance. Silver is a broad-spectrum natural antimicrobial agent with wide applications extending to proprietary wound dressings. Recently, silver nanoparticles have attracted attention in wound management. In the current study, the green synthesis of nanoparticles was accomplished using a natural reducing agent, curcumin, which is a natural polyphenolic compound that is well-known as a wound-healing agent. The hydrophobicity of curcumin was overcome by its microencapsulation in cyclodextrins. This study demonstrates the production, characterization of silver nanoparticles using aqueous curcumin:hydroxypropyl-β-cyclodextrin complex and loading them into bacterial cellulose hydrogel with moist wound-healing properties. These silver nanoparticle-loaded bacterial cellulose hydrogels were characterized for wound-management applications. In addition to high cytocompatibility, these novel dressings exhibited antimicrobial activity against three common wound-infecting pathogenic microbes Staphylococcus aureus , Pseudomonas aeruginosa , and Candida auris .

The number of cross-links in the non-linear polyurethane structure is the basic factor affecting its properties. Selected properties of aliphatic polyurethanes with soft segments made of different amounts of polycaprolactonetriol, polycaprolactonediol and synthetic, telechelic poly([R,S]-3-hydroxybutyrate) were determined. On the basis of changes in polyurethane properties, the correlation between these properties and the construction of soft segments was found. The structure of polyurethanes, their morphology, hydrophilicity, thermal and mechanical properties were examined. These properties were changed linearly up to 15% content of polycaprolactonetriol in soft segments. A further increase in the amount of triol causes that these properties are mainly determined by the high number of cross-links.

Biodegradable mulches are considered a promising alternative to polyethylene-based, nonbiodegradable mulch for sustainable agriculture. In the present study, a bioactive 2-methyl-4- cholorophenoxyacetic acid/poly(3-hydroxybutyrate- co -3-hydroxyvalerate) (MCPA-PHBV) conjugate blended with biodegradable poly(butylene adipate- co -terephthalate/polylactide (PBAT/PLA) was developed and used as mulch under controlled condition greenhouse pot experiment with fava bean ( Vicia faba ) as the nontarget crop species. The objectives were to examine the effectiveness of sustained-release of MCPA herbicide from biodegradable mulch for broadleaf weed suppression and to assess any adverse effects of the herbicide on the nontarget species (fava bean). The energy-dispersive X-ray spectroscopy analysis (EDS) suggests that a substantial quantity of the herbicide was released from the biodegradable mulch which effectively killed the broadleaf weed species even at 1% MCPA concentration. However, the higher concentrations of the herbicide adversely affected several physiological parameters of fava bean growth and development. Stomatal conductance decreased, while leaf temperature subsequently rose (at MCPA concentrations 5, 7.5, and 10%). The quantum yield of the Photosystem II (PSII) indicates that the photosynthetic efficiency was also restricted at concentrations 7.5% and 10%. Evidently, this slow-release herbicide system worked efficiently for broadleaf weed control but at higher concentrations, resulted in adverse physiological effects on the nontarget crop species. This study has demonstrated that biodegradable mulches containing MCPA herbicide are able to effectively inhibit the growth of broad leaf weed species and may be of potential importance in a wide variety of horticultural and agricultural applications., Competing Interests: The authors declare no competing financial interest.

Global warming is expected to cause reductions in organism body size, a fundamental biological unit important in determining biological processes. Possible effects of increasing temperature on biomass size spectra in coastal benthic communities were investigated. We hypothesized higher proportions of smaller size classes in warmer conditions. Soft bottom infauna samples were collected in six Norwegian and Svalbard fjords, spanning wide latitudinal (60-81°N) and bottom water temperature gradients (from -2 to 8 °C). Investigated fjords differed in terms of environmental settings (e.g., pigments or organic carbon in sediments). The slopes of normalised biomass size spectra (NBSS) did not differ among the fjords, while the benthic biomass and NBSS intercepts varied and were related to chlorophyll a and δ 13 C in sediments. The size spectra based on both abundance and biomass remained consistent, regardless of the strong variability in macrofauna taxonomic and functional trait composition. Variable relationships between temperature and body size were noted for particular taxa. Our results indicate that while benthic biomass depends on the nutritional quality of organic matter, its partitioning among size classes is consistent and independent of environmental and biological variability. The observed size structure remains a persistent feature of studied communities and may be resilient to major climatic changes.

In the investigation presented here the synthesis of new lariat ether derivative obtained from the modification of tetrapyrrolidinyl-PNP-crown ether macrocycle is described. The polyheterotopic molecular coreceptor consisted of the replacement of chlorine atoms with an optically active (S)-(1-benzylpyrrolidin-2-yl) methanamine. The structure was confirmed by using elemental analysis, mass spectrometry, and NMR spectroscopy. This work covers results concerning the complexing properties of the new ligand towards Ag + , Cu 2+, Co 2+, Ni 2+ , and Zn 2+ ions. The formation of non-covalent complexes of 1:1 stoichiometry with the Cu 2+, Co 2+, Ni 2+ , and Zn 2+ ions have been confirmed by mass spectrometry. Due to the previous work and application possibilities, a large emphasis was put on the investigation of the complexation ability of lariat ether with silver (I) cation to determine stability constants by direct potentiometric method. In this case, the formation of four different forms of complexes AgL, Ag 2 L, Ag 3 L, and Ag 4 L has been proved. The observed unusual binding through the nitrogen atoms from the exocyclic substituents may provide the structural unit to build a new coordination polymers.

The aim of this study is the analyze the structure of branched polyurethanes based on synthetic poly([R,S]-3-hydroxybutyrate) and their blends with biopolymers and montmorillonite. The properties which would predict the potential susceptibility of these materials to degradation are also estimated. Fourier-transform infrared spectroscopy with attenuated total reflection analysis shows that poly([d,l]-lactide) is on the surfaces of polyurethanes, whereas chitosan and starch are included inside the blend network. Atomic force microscopy images have shown that the surfaces of investigated samples are heterogenous with the formation of spherulites in case of pure polyurethanes. The presence of biopolymers in the blend reduced the crystallinity of polyurethanes. Thermal stability of blends of polyurethanes with poly([d,l]-lactide) and polysaccharides decreased in comparison to pure polyurethanes. Although the tensile strength is reduced after the blending of polyurethanes with biopolymers, the elongation at break increased, especially in the case of polyurethane/poly([d,l]-lactide) blends. The presence of polysaccharides in the obtained blends caused the significant reduction of contact angle after one minute from water drop immersion. This hydrophilizing effect is the highest when montmorillonite has been incorporated into the chitosan blend. The estimated properties of the obtained materials suggest their potential sensitivity on environmental conditions., Competing Interests: The authors declare no conflict of interest.

This study investigated the molecular structure of the polyhydroxyalkanoate (PHA) produced via a microbiological shake flask experiment utilizing oxidized polypropylene (PP) waste as an additional carbon source. The bacterial strain Cupriavidus necator H16 was selected as it is non-pathogenic, genetically stable, robust, and one of the best known producers of PHA. Making use of PHA oligomers, formed by controlled moderate-temperature degradation induced by carboxylate moieties, by examination of both the parent and fragmentation ions, the ESI-MS/MS analysis revealed the 3-hydroxybutyrate and randomly distributed 3-hydroxyvalerate as well as 3-hydroxyhexanoate repeat units. Thus, the bioconversion of PP solid waste to a value-added product such as PHA tert-polymer was demonstrated.

Malignant solid tumors are composed of tumor cells, stromal cells and the complex networks of the tumor microenvironment (TME), which is the underlying cause of the unsatisfactory outcome of conventional chemotherapy approaches only aimed at cancer cell killing. In this study, a novel TME-responsive polymeric micelle has been developed for the programmed site-specific delivery of the angiostatin sunitinib and chemotherapeutic paclitaxel (PTX). The pH-sensitive micelle core encapsulates PTX, while β-cyclodextrin molecules being conjugated to the micelle shell via matrix metalloproteinase 2 (MMP-2) sensitive peptides include sunitinib. Following the pH and MMP-2 dual sensitive structure design, the micelle may sequentially release sunitinib inside the tumor extracellular matrix and PTX into cancer cells through responding to enriched MMP-2 levels and decreased pH, respectively. Consequently, the anti-angiogenesis effect of sunitinib and tumor cell-killing effect of PTX synergize, resulting in highly efficient tumor treatment.

Knowledge of degradation and impairment phenomena of (bio)degradable polymeric materials under operating conditions, and thus the selection of test procedures and prediction of their behavior designates the scope and capabilities as well as possible limitations of both: the preparation of the final product and its durability. The main novelty and objective of this research was to determine the degradation pathways during testing of polylactide and polylactide/polyhydroxyalkanoate materials made with three-dimensional printing and the development of a new strategy for the comprehensive characterization of such complex systems including behavior during waste disposal. Prototype objects were subjected to tests for damage evolution performed under simulating operating conditions. The reference samples and the tested items were characterized by gel permeation chromatography and differential scanning calorimetry to determine changes in material properties. The studies showed that: polyhydroxyalkanoate component during accelerated aging and degradation in environments rich in microorganisms accelerated the degradation of the material; paraffin accelerates polylactide degradation and slows degradation of polyhydroxyalkanoate-based material; under the influence of an environment rich in enzymes, paraffin contamination accelerates biodegradation; under the influence of natural conditions, paraffin contamination slowed degradation; the processing conditions, in particular the printing orientation of individual parts of the container, influenced the material properties in its various regions, affecting the rate of degradation of individual parts.

In recent years, there has been an increasing interest in oncolytic adenoviral vectors as an alternative anticancer therapy. The induction of an immune response can be considered as a major limitation of this kind of application. Significant research efforts have been focused on the development of biodegradable polymer poly-gamma-glutamic acid (γ-PGA)-based nanoparticles used as a vector for effective and safe anticancer therapy, owing to their controlled and sustained-release properties, low toxicity, as well as biocompatibility with tissue and cells. This study aimed to introduce a specific destructive and antibody blind polymer-coated viral vector into cancer cells using γ-PGA and chitosan (CH). Adenovirus was successfully encapsulated into the biopolymer particles with an encapsulation efficiency of 92% and particle size of 485 nm using the ionic gelation method. Therapeutic agents or nanoparticles (NPs) that carry therapeutics can be directed specifically to cancerous cells by decorating their surfaces using targeting ligands. Moreover, in vitro neutralizing antibody response against viral capsid proteins can be somewhat reduced by encapsulating adenovirus into γ-PGA-CH NPs, as only 3.1% of the encapsulated adenovirus was detected by anti-adenovirus antibodies in the presented work compared to naked adenoviruses. The results obtained and the unique characteristics of the polymer established in this research could provide a reference for the coating and controlled release of viral vectors used in anticancer therapy.

Excessive levels of plastic waste in our oceans and landfills indicate that there is an abundance of potential carbon sources with huge economic value being neglected. These waste plastics, through biological fermentation, could offer alternatives to traditional petrol-based plastics. Polyhydroxyalkanoates (PHAs) are a group of plastics produced by some strains of bacteria that could be part of a new generation of polyester materials that are biodegradable, biocompatible, and, most importantly, non-toxic if discarded. This study introduces the use of prodegraded high impact and general polystyrene (PS0). Polystyrene is commonly used in disposable cutlery, CD cases, trays, and packaging. Despite these applications, some forms of polystyrene PS remain financially and environmentally expensive to send to landfills. The prodegraded PS0 waste plastics used were broken down at varied high temperatures while exposed to ozone. These variables produced PS flakes (PS1⁻3) and a powder (PS4) with individual acid numbers. Consequently, after fermentation, different PHAs and amounts of biomass were produced. The bacterial strain, Cupriavidus necator H16, was selected for this study due to its well-documented genetic profile, stability, robustness, and ability to produce PHAs at relatively low temperatures. The accumulation of PHAs varied from 39% for prodegraded PS0 in nitrogen rich media to 48% ( w / w ) of dry biomass with the treated PS. The polymers extracted from biomass were analyzed using nuclear magnetic resonance (NMR) and electrospray ionization tandem mass spectrometry (ESI-MS/MS) to assess their molecular structure and properties. In conclusion, the PS0⁻3 specimens were shown to be the most promising carbon sources for PHA biosynthesis; with 3-hydroxybutyrate and up to 12 mol % of 3-hydroxyvalerate and 3-hydroxyhexanoate co-monomeric units generated.

In this study, low molecular weight poly( δ -valerolactone) (PVL) was synthesized through bulk-ring openings polymerization of δ -valerolactone with boric acid (B(OH)₃) as a catalyst and benzyl alcohol (BnOH) as an initiator. The resulting homopolymer was characterized with the aid of nuclear magnetic resonance (NMR) and mass spectrometry (MS) techniques to gain further understanding of its molecular structure. The electrospray ionization mass spectrometry (ESI-MS) spectra of poly( δ -valerolactone) showed the presence of two types of homopolyester chains-one terminated by benzyl ester and hydroxyl end groups and one with carboxyl and hydroxyl end groups. Additionally, a small amount of cyclic PVL oligomers was identified. To confirm the structure of PVL oligomers obtained, fragmentation of sodium adducts of individual polyester molecules terminated by various end groups was explored in ESI-MS n by using collision induced dissociation (CID) techniques. The ESI-MS n analyses were conducted both in positive- and negative ion mode. The comparison of the fragmentation spectra obtained with proposed respective theoretical fragmentation pathways allowed the structure of the obtained oligomers to be established at the molecular level. Additionally, using matrix-assisted laser desorption ionization time-of-flight mass spectrometry (MALDI-TOF-MS), it was proven that regardless of the degree of oligomerization, the resulting PVL samples were a mixture of two types of linear PVL oligomers differing in end groups and containing just a small amount of cyclic oligomers that tended to be not visible at higher molar masses.

Application of new biodegradable polymer packaging based on polylactide (PLA), susceptible to organic recycling, can help in the waste reduction in landfills. In this paper, the results of the study on abiotic degradation of PLA and its blend containing 15 mol% of poly[(R,S)-3-hydroxybutyrate], as a model for the first step of organic recycling were presented. The samples used for this study have different shapes and thicknesses: rigid films and cuboid-bars. Particular emphasis was placed on determining the pattern of degradation products released into the medium. Originally, the results of present study revealed that the application of electrospray ionization mass spectrometry supported by high performance liquid chromatography allowed envisaging the differences in the degradation products pattern released from the studied PLA-based samples differing in thickness. The significant differences in degradation products pattern were predominately observed in the first steps of incubation process and are caused by an autocatalytic effect, which occurs mainly during degradation of the large size PLA samples. Although, the thickness of PLA-based packaging changes the degradation product patterns, however this does not increase the total amounts of acids released to the medium. Thus, it may be concluded that thickness should not affect significantly organic recycling of the packaging., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Background: Recurrent anterior instability following a failed Bankart repair in the shoulder represents a challenging clinical scenario. Few studies have examined the role of arthroscopic revision anterior stabilization as a treatment option in these cases. The purpose of this study was to evaluate the outcomes of arthroscopic revision anterior stabilization for patients with recurrent instability after a failed index procedure., Methods: Ninety-two patients underwent arthroscopic revision anterior stabilization after a failed index (open or arthroscopic) stabilization procedure. Sixty-five patients with a minimum of 2 years of follow-up were included in this study. The mean age at the time of revision surgery was 26 years (range, 15 to 57 years). The rate of recurrent instability and risk factors for failure were evaluated; the mean duration of follow-up was 4.7 years (range, 2 to 10.8 years). Glenoid and humeral bone loss were quantitatively assessed using preoperative T1-weighted magnetic resonance arthrograms to determine if the lesions were on-track or off-track., Results: Twenty-seven (42%) of the patients experienced recurrent instability at a mean of 2.3 years after arthroscopic revision anterior stabilization. On multivariate analysis, the presence of an off-track lesion, an age of <22 years, and ligamentous laxity were independent predictors of recurrence (p = 0.022, 0.028, and 0.031, respectively). Among a cohort with these risk factors excluded, the failure rate was 19%., Conclusions: Arthroscopic revision anterior stabilization is associated with a high rate of recurrent instability, and patient selection is of critical importance in order to minimize recurrence., Level of Evidence: Therapeutic Level IV. See Instructions for Authors for a complete description of levels of evidence.

Branched, aliphatic polyurethanes (PURs) were synthesized and compared to linear analogues. The influence of polycaprolactonetriol and synthetic poly([R,S]-3-hydroxybutyrate) (R,S-PHB) in soft segments on structure, thermal and sorptive properties of PURs was determined. Using FTIR and Raman spectroscopies it was found that increasing the R,S-PHB amount in the structure of branched PURs reduced a tendency of urethane groups to hydrogen bonding. Melting enthalpies (on DSC thermograms) of both soft and hard segments of linear PURs were higher than branched PURs, suggesting that linear PURs were more crystalline. Oil sorption by samples of linear and branched PURs, containing only polycaprolactone chains in soft segments, was higher than in the case of samples with R,S-PHB in their structure. Branched PUR without R,S-PHB absorbed the highest amount of oil. Introducing R,S-PHB into the PUR structure increased water sorption. Thus, by operating the number of branching and the amount of poly([R,S]-3-hydroxybutyrate) in soft segments thermal and sorptive properties of aliphatic PURs could be controlled.

An economically viable method to extract polyhydroxyalkanoates (PHAs) from cells is desirable for this biodegradable polymer of potential biomedical applications. In this work, two non-chlorinated solvents, cyclohexanone and γ-butyrolactone, were examined for extracting PHA produced by the bacterial strain Cupriavidus necator H16 cultivated on vegetable oil as a sole carbon source. The PHA produced was determined as a poly(3-hydroxybutyrate) (PHB) homopolyester. The extraction kinetics of the two solvents was determined using gel permeation chromatography (GPC). When cyclohexanone was used as the extraction solvent at 120 °C in 3 min, 95% of the PHB was recovered from the cells with a similar purity to that extracted using chloroform. With a decrease in temperature, the recovery yield decreased. At the same temperatures, the recovery yield of γ-butyrolactone was significantly lower. The effect of the two solvents on the quality of the extracted PHB was also examined using GPC and elemental analysis. The molar mass and dispersity of the obtained polymer were similar to that extracted using chloroform, while the nitrogen content of the PHB extracted using the two new solvents was slightly higher. In a nutshell, cyclohexanone in particular was identified as an expedient candidate to efficiently drive novel, sustainable PHA extraction processes.

Purpose: A deep lateral femoral notch (LFN) on lateral radiographs is indicative of ACL injury. Prior studies have suggested that a deep LFN may also be a sign of persistent rotatory instability and a concomitant lateral meniscus tear. Therefore, the purpose of this study was to evaluate the relationship between LFN depth and both quantitative measures of rotatory knee instability and the incidence of lateral meniscus tears. It was hypothesized that greater LFN depth would be correlated with increased rotatory instability, quantified by lateral compartment translation and tibial acceleration during a quantitative pivot shift test, and incidence of lateral meniscus tears., Methods: ACL-injured patients enrolled in a prospective ACL registry from 2014 to 2016 were analyzed. To limit confounders, patients were only included if they had primary ACL tears, no concurrent ligamentous or bony injuries requiring operative treatment, and no previous knee injuries or surgeries to either knee. Eighty-four patients were included in the final analysis. A standardized quantitative pivot shift test was performed pre-operatively under anesthesia in both knees, and rotatory instability, specifically lateral compartment translation and tibial acceleration, was quantified using tablet image analysis software and accelerometer sensors. Standard lateral radiographs and sagittal magnetic resonance images (MRI) of the injured knee were evaluated for LFN depth., Results: There were no significant correlations between LFN depth on either imaging modality and ipsilateral lateral compartment translation or tibial acceleration during a quantitative pivot shift test or side-to-side differences in these measurements. Patients with lateral meniscus tears were found to have significantly greater LFN depths than those without on conventional radiograph and MRI (1.0 vs. 0.6 mm, p < 0.05; 1.2 vs. 0.8 mm, p < 0.05, respectively)., Conclusion: There was no correlation between lateral femoral notch depth on conventional radiographs or MRI and quantitative measures of rotatory instability. Concomitant lateral meniscus injury was associated with significantly greater LFN depth. Based on these findings, LFN depth should not be used as an indicator of excessive rotatory instability, but may be an indicator of lateral meniscus injury in ACL-injured patients., Level of Evidence: Prognostic level IV.

Purpose: To investigate whether acute rupture of the proximal long head biceps is a harbinger of disease of the nearby supraspinatus and subscapularis tendons., Methods: A retrospective chart review from February 1, 2008, to August 31, 2016, was performed at our institution identifying patients who presented with an acute (<12-week) history of "Popeye" deformity of the distal biceps and a magnetic resonance imaging (MRI) of the affected shoulder. MRI images were then reviewed in duplicate to determine supraspinatus and subscapularis tendon tear incidence, size, chronicity, and depth. The association between rotator cuff status and acute long head biceps rupture as well as patient age, sex, smoking status, hand dominance, and history of diabetes mellitus or trauma was then evaluated., Results: A total of 116 patients were included in this study (mean age: 61.9 ± 10.9 years). A significant proportion (n = 99; incidence: 85%) were found to have some degree of supraspinatus or subscapularis tendon tearing on MRI (P < .001). These patients were also found to be significantly older compared with those with an intact rotator cuff (mean age 63.3 ± 10.7 vs 54.2 ± 9.2; P = .001). Full thickness rotator cuff tears were significantly more likely to involve the supraspinatus as opposed to the subscapularis (incidence: 44% and 21%; P = .002)., Conclusions: Despite the expected association of rotator cuff disease with increasing patient age, the results of this study also affirm the hypothesis that inflammation in the rotator cuff interval signaled by rupture of the long head of biceps is a harbinger of rotator cuff disease. Clinicians should have a high index of suspicion regarding concomitant anterosuperior rotator cuff pathology in patients presenting with acute long head of biceps rupture. Early evaluation with advanced imaging should be strongly considered., Level of Evidence: Level IV, case series., (Published by Elsevier Inc.)

The herbicide 2-methyl-4-chlorophenoxyacetic acid (MCPA) conjugated with poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) was prepared via a melt transesterification route. The resultant bioactive oligomer was then mixed with a blend of polylactide (PLA) and poly(butylene adipate-co-terephthalate) (PBAT) with different loadings to manufacture films to be used as a bioactive, biodegradable mulch to deliver the herbicide to target broadleaf weed species. The biological targeting of the MCPA-PHBV conjugate in the mulch film was investigated under glasshouse conditions using faba bean (Vicia faba) as a selective (nontarget) model crop species having broadleaf morphology. The presence of the MCPA-PHBV conjugate in the biodegradable PBTA/PLA blend was shown to completely suppress the growth of broadleaf weed species while displaying only a mild effect on the growth of the model crop. The degradation of the mulch film under glasshouse conditions was quite slow. The release of the MCPA-PHBV during this process was detected using NMR, GPC, EDS, and DSC analyses, indicating that the majority of the MCPA diffused out after MCPA-PHBV conjugate bond scission. These data provide a strong "proof of concept" and show that this biodegradable, bioactive film is a good candidate for future field applications and may be of wide agricultural applicability.