Bioengineering seeks to replicate biological tissues exploiting scaffolds often based on polymeric biomaterials. Digital light processing (DLP) has emerged as a potent technique to fabricate tissue engineering (TE) scaffolds. However, the scarcity of suitable biomaterials with desired physico-chemical properties along with processing capabilities limits DLP\'s potential. Herein, we introduce acrylate-endcapped urethane-based polymers (AUPs) for precise physico-chemical tuning while ensuring optimal computer-aided design/computer-aided manufacturing (CAD/CAM) mimicry. Varying the polymer backbone (i.e. poly(ethylene glycol) (PEG) versus poly(propylene glycol) (PPG)) and photo-crosslinkable endcap (i.e. di-acrylate versus hexa-acrylate), we synthesized a series of photo-crosslinkable materials labeled as UPEG2, UPEG6, UPPG2 and UPPG6. Comprehensive material characterization including physico-chemical and biological evaluations, was followed by a DLP processing parametric study for each material. The impact of the number of acrylate groups per polymer (2 to 6) on the physico-chemical properties was pronounced, as reflected by a reduced swelling, lower water contact angles, accelerated crosslinking kinetics, and increased Young\'s moduli upon increasing the acrylate content. Furthermore, the different polymer backbones also exerted a substantial effect on the properties, including the absence of crystallinity, remarkably reduced swelling behaviors, a slight reduction in Young\'s modulus, and slower crosslinking kinetics for UPPG vs UPEG. The mechanical characteristics of DLP-printed samples showcased the ability to tailor the materials\' stiffness (ranging from 0.4 to 5.3 MPa) by varying endcap chemistry and/or backbone. The in vitro cell assays confirmed biocompatibility of the material as such and the DLP-printed discs. Furthermore, the structural integrity of 3D scaffolds was preserved both in dry and swollen state. By adjusting the backbone chemistry or acrylate content, the post-swelling dimensions could be customized towards the targeted application. This study showcases the potential of these materials offering tailorable properties to serve many biomedical applications such as cartilage TE.

This study investigates the nanoscale self-assembly from mixtures of two symmetrical poly(ethylene oxide)-poly(propylene oxide)-pol(ethylene oxide) (PEO-PPO-PEO) block copolymers (BCPs) with different lengths of PEO blocks and similar PPO blocks. The blended BCPs (commercially known as Pluronic F88 and L81, with 80 and 10% PEO, respectively) exhibited rich phase behavior in an aqueous solution. The relative viscosity (ηrel) indicated significant variations in the flow behavior, ranging from fluidic to viscous, thereby suggesting a possible micellar growth or morphological transition. The tensiometric experiments provided insight into the intermolecular hydrophobic interactions at the liquid-air interface favoring the surface activity of mixed-system micellization. Dynamic light scattering (DLS) and small-angle neutron scattering (SANS) revealed the varied structural morphologies of these core-shell mixed micelles and polymersomes formed under different conditions. At a concentration of ≤5% w/v, Pluronic F88 exists as molecularly dissolved unimers or Gaussian chains. However, the addition of the very hydrophobic Pluronic L81, even at a much lower (<0.2%) concentration, induced micellization and promoted micellar growth/transition. These results were further substantiated through molecular dynamics (MD) simulations, employing a readily transferable coarse-grained (CG) molecular model grounded in the MARTINI force field with density and solvent-accessible surface area (SASA) profiles. These findings proved that F88 underwent micellar growth/transition in the presence of L81. Furthermore, the potential use of these Pluronic mixed micelles as nanocarriers for the anticancer drug quercetin (QCT) was explored. The spectral analysis provided insight into the enhanced solubility of QCT through the assessment of the standard free energy of solubilization (ΔG°), drug-loading efficiency (DL%), encapsulation efficiency (EE%), and partition coefficient (P). A detailed optimization of the drug release kinetics was presented by employing various kinetic models. The [3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide] MTT assay, a frequently used technique for assessing cytotoxicity in anticancer research, was used to gauge the effectiveness of these QCT-loaded mixed nanoaggregates.

A reactor with silicone tubes as support medium was used for glycerol fermentation. The experimental set-up consisted of three phases. In P1, the applied glycerol loading rate (gly-LR) was in the range of 6-10 g.L-1.d-1 at an influent pH of 7.9 ± 0.4. In P2, gly-LR was kept constant (18.0 ± 1.8 g.L-1.d-1) with different doses of NaHCO3. Finally in P3, two different gly-LR (9 and 18 g.L-1.d-1) were evaluated, dosing 1 g-NaHCO3 per g-COD of glycerol. Glycerol consumption was close 90%. The main end-product was 1,3-propanediol (1,3-PDO) (0.40 mol.mol-gly-1), but ethanol was also generated, particularly at pH above 8 and low gly-LR (0.20 mol.mol-gly-1). After 1-year operation with glycerol as the only carbon source, a drastic shift in the bacterial community was observed. The 1,3-PDO producers Lacrimispora and Clostridium became dominant, although non-glycerol-degrading fermentative genera, e.g., Actinomyces and Eubacterium, thrived at the expense of cellular breakdown products.

Advancements in synthetic biology have facilitated the incorporation of heterologous metabolic pathways into various bacterial chassis, leading to the synthesis of targeted bioproducts. However, total output from heterologous production pathways can suffer from low flux, enzyme promiscuity, formation of toxic intermediates, or intermediate loss to competing reactions, which ultimately hinder their full potential. The self-assembling, easy-to-modify, protein-based bacterial microcompartments (BMCs) offer a sophisticated way to overcome these obstacles by acting as an autonomous catalytic module decoupled from the cell\'s regulatory and metabolic networks. More than a decade of fundamental research on various types of BMCs, particularly structural studies of shells and their self-assembly, the recruitment of enzymes to BMC shell scaffolds, and the involvement of ancillary proteins such as transporters, regulators, and activating enzymes in the integration of BMCs into the cell\'s metabolism, has significantly moved the field forward. These advances have enabled bioengineers to design synthetic multi-enzyme BMCs to promote ethanol or hydrogen production, increase cellular polyphosphate levels, and convert glycerol to propanediol or formate to pyruvate. These pioneering efforts demonstrate the enormous potential of synthetic BMCs to encapsulate non-native multi-enzyme biochemical pathways for the synthesis of high-value products.

This study investigated the effect of cooking on the levels of 3-chloro-1, 2-propanediol esters (3-MCPDEs), 2-chloro-1, 3-propanediol esters (2-MCPDEs) and glycidyl esters (GEs) in deep-fried rice cracker, fried potato, croquette, fish fillet, chicken fillet and cooking oils (rice bran oil and palm oil). The levels of 2-/3-MCPDE in rice cracker fried with rice bran oil and the used oil remained about the same, while the levels of GEs in them fell with frying time. The levels of 2-/3-MCPDEs in fried potato, croquette, fried fish and chicken cutlet fried with rice bran oil and palm oil respectively fell with frying time, while the level of GEs in them remained about the same. The levels of 2-/3-MCPDEs and GEs in fried rice cooked with rice bran oil were under the method limit of quantification. These results provide insights the cooking has no influence with the levels of 2-/3-MCPDEs and GEs in cooked foods.

OBJECTIVE: In previous studies, it was demonstrated that co-culturing Clostridium pasteurianum and Geobacter sulfurreducens triggers a metabolic shift in the former during glycerol fermentation. This shift, attributed to interspecies electron transfer and the exchange of other molecules, enhances the production of 1,3-propanediol at the expense of the butanol pathway. The aim of this investigation is to examine the impact of fumarate, a soluble compound usually used as an electron acceptor for G. sulfurreducens, in the metabolic shift previously described in C. pasteurianum.
RESULTS: Experiments were conducted by adding along with glycerol, acetate, and different quantities of fumarate in co-cultures of G. sulfurreducens and C. pasteurianum. A metabolic shift was exhibited in all the co-culture conditions. This shift was more pronounced at higher fumarate concentrations. Additionally, we observed G. sulfurreducens growing even in the absence of fumarate and utilizing small amounts of this compound as an electron donor rather than an electron acceptor in the co-cultures with high fumarate addition.
CONCLUSIONS: This study provided evidence that interspecies electron transfer continues to occur in the presence of a soluble electron acceptor, and the metabolic shift can be enhanced by promoting the growth of G. sulfurreducens.

Suppression of immune functions can be elicited by behavioural conditioning using drugs such as cyclosporin A or rapamycin. Nevertheless, little is known about the underlying mechanisms and generalisability of this phenomenon. Against this background, the present study investigated whether the pharmacological properties of fingolimod (FTY720), an immunosuppressive drug widely applied to treat multiple sclerosis, can be conditioned in rats by means of taste-immune associative learning. For this purpose, a conditioned taste avoidance paradigm was used, pairing the presentation of a novel sweet drinking solution (saccharin or sucrose) as conditioned stimulus (CS) with therapeutically effective doses of FTY720 as unconditioned stimulus (US). Subsequent re-exposure to the CS at a later time point revealed that conditioning with FTY720 induced a mild conditioned taste avoidance only when saccharin was employed as CS. However, on an immunological level, neither re-exposure with saccharin nor sucrose altered blood immune cell subsets or splenic cytokine production. Despite the fact that intraperitonally administered FTY720 could be detected in brain regions known to mediate neuro-immune interactions, the present findings show that the physiological action of FTY720 is not inducible by mere taste-immune associative learning. Whether conditioning generalises across all small-molecule drugs with immunosuppressive properties still needs to be investigated with modified paradigms probably using distinct sensory CS. Moreover, these findings emphasize the need to further investigate the underlying mechanisms of conditioned immunomodulation to assess the generalisability and usability of associative learning protocols as supportive therapies in clinical contexts.

Investigation of chiroptical polymers in the solution phase is paramount for designing supramolecular architectures for photonic or biomedical devices. This work is devoted to the case study of poly(propylene oxide) (PPO) optical activity in several solvents: benzonitrile, carbon disulfide, chloroform, ethyl acetate, and p-dioxane. To attain information on the interactions in these systems, rheological testing was undertaken, showing distinct variations of the rheological parameters as a function of the solvent type. These aspects are also reflected in the refractive index dispersive behavior, from which linear and non-linear optical properties are extracted. To determine the circular birefringence and specific rotation of the PPO solutions, the alternative method of the channeled spectra was employed. The spectral data were correlated with the molecular modeling of the PPO structural unit in the selected solvents. Density functional theory (DFT) computational data indicated that the torsional potential energy-related to the O1-C2-C3-O4 dihedral angle from the polymer repeating unit-was hindered in solvation environments characterized by high polarity and the ability to interact via hydrogen bonding. This was in agreement with the optical characterization of the samples, which indicated a lower circular birefringence and specific rotation for the solutions of PPO in ethyl acetate and p-dioxane. Also, the shape of optical rotatory dispersion curves was slightly modified for PPO in these solvents compared with the other ones.

Polyglycidol or polyglycerol (PG), a polyether widely used in biomedical applications, has not been extensively studied in its branched cyclic form (bcPG), despite extensive research on hyperbranched PG (HPG). This study explores the biomedical promise of bcPG, particularly its ability to cross the blood-brain barrier (BBB). We evaluate in vitro biocompatibility, endothelial permeability, and formation of branched linear PG (blPG) as topological impurities in the presence of water. Small angle X-ray scattering in solution revealed a fractal dimension of approximately two for bcPG and the mixture bc+blPG, suggesting random branching. Comparisons of cytotoxicity and endothelial permeability between bcPG, bc+blPG, and HPG in a BBB model using hCMEC/D3 cells showed different biocompatibility profiles and higher endothelial permeability for HPG. bcPG showed a tendency to accumulate around cell nuclei, in contrast to the behavior of HPG. This study contributes to the understanding of the influence of polymer topology on biological behavior.

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