PEGylated AdipoRon derivatives improve glucose and lipid metabolism under insulinopenic and high-fat diet conditions.

The pleiotropic actions of adiponectin in improving cell survival and metabolism have motivated the development of small-molecule therapeutic agents for treating diabetes and lipotoxicity. AdipoRon is a synthetic agonist of the adiponectin receptors, yet is limited by its poor solubility and bioavailability. In this work, we expand on the protective effects of AdipoRon in pancreatic ß-cells and examine how structural modifications could affect the activity, pharmacokinetics, and bioavailability of this small molecule. We describe a series of AdipoRon analogs containing amphiphilic ethylene glycol (PEG) chains. Among these, AdipoRonPEG5 induced pleiotropic effects in mice under insulinopenic and high-fat diet (HFD) conditions. While both AdipoRon and AdipoRonPEG5 substantially attenuate palmitate-induced lipotoxicity in INS-1 cells, only AdipoRonPEG5 treatment is accompanied by a significant reduction in cytotoxic ceramides. In vivo, AdipoRonPEG5 can substantially reduce pancreatic, hepatic, and serum ceramide species, with a concomitant increase in the corresponding sphingoid bases and improves insulin sensitivity of mice under HFD feeding conditions. Furthermore, hyperglycemia in streptozotocin (STZ)-induced insulinopenic adiponectin-null mice is also attenuated upon AdipoRonPEG5 treatment. Our results suggest that AdipoRonPEG5 is more effective in reducing ceramides and dihydroceramides in the liver of HFD-fed mice than AdipoRon, consistent with its potent activity in activating ceramidase in vitro in INS-1 cells. Additionally, these results indicate that the beneficial effects of AdipoRonPEG5 can be partially attributed to improved pharmacokinetics as compared with AdipoRon, thus suggesting that further derivatization may improve affinity and tissue-specific targeting.

Comparative effectiveness of PEEK rods versus titanium alloy rods in cervical fusion in a new sheep model.

BACKGROUND: Pedicle screw and rod instrumentation based on titanium can produce satisfying strength and stiffness for spinal fusion. However, excessive stiffness produced by titanium rods may cause stress shielding. Thus, polyetheretherketone (PEEK) rods with a low modulus of elasticity were introduced as substitutes for titanium rods. The purpose of this paper is to compare the effectiveness of PEEK rods versus titanium alloy rods in anterior spinal fusion with a new sheep model. METHODS: Sheep models of anterior-posterior cervical fusion were innovatively adopted in our study. Twenty-four sheep were randomly divided into a control group and a treatment group that received anterior-posterior cervical fixation with titanium rods or PEEK rods, respectively. Then, surgical segments were harvested and assessed by X-ray, micro-CT and histological examination to evaluate the efficiency of bone fusion. RESULTS: No complications related to fixation were found during the research process. The results of the X-ray showed a stronger spinal fusion in the PEEK rod groups than in the titanium rod group at 12 weeks postoperatively, and both groups underwent bone fusion at 24 weeks postoperatively. The results of micro-CT showed that fixation with PEEK rods achieved better bone ingrowth at an early postoperative stage (12 weeks) compared to fixation with titanium rods (bone volume fraction (BVF): 20.26 ± 4.36% vs 14.48 ± 3.49%, p < 0.05). The same trend was detected in the histological analysis, where the mineralized bone fraction in the experiment group (21.01 ± 3.48%) was significantly higher than that in the control group (16.73 ± 2.95%). In addition, better osseointegration was found in the experiment group at the early postoperative stage at 12 weeks (bone apposition (BA): 16.22 ± 3.24% vs 11.67 ± 3.63%, p < 0.05). However, there were no significant differences at 24 weeks postoperatively. CONCLUSION: PEEK rods can be used safely in a sheep model of anterior-posterior cervical fixation. Compared to traditional titanium rods, earlier and more evident bone fusion was found in the PEEK rods group. These slides can be retrieved under Electronic Supplementary Material.

Microstructure, mechanical properties, and in vitro behavior of biodegradable Zn-1Mg-0.1Ca and Zn-1Mg-0.5Ca.

In the present study, the microstructure, mechanical properties, corrosion behavior, wettability, haemocompatibility, and cytocompatibility of the as-cast and as-rolled biodegradable Zn-1Mg-0.1Ca and Zn-1Mg-0.5Ca have been systematically investigated to evaluate their feasibility as potential biodegradable materials. The results demonstrated that the Zn-1Mg-0.1Ca have significantly improved mechanical properties, with the yield strength (YS), ultimate tensile strength (UTS), and elongation of as-rolled Zn-1Mg-0.1Ca are (209.04 ± 28.31) MPa, (331.51 ± 40.06) MPa, and (35.43 ± 3.53)%, respectively. Wettability test results demonstrated that the Zn-1Mg-0.1Ca and Zn-1Mg-0.5Ca have hydrophilic surfaces that can enhance cell responses and tissue-implant interactions. The haemocompatibility evaluation showed that the hemolysis ratio of Zn-1Mg-0.1Ca have a low hemolysis ratio of 0.6%; the platelets remain sphere morphology and are not activated. High cell viability indicates the cytocompatibility of the as-rolled Zn-1Mg-0.1Ca alloy. The Zn-1Mg-0.1Ca alloy can be considered as new suitable biodegradable Zn-based alloys for further biomedical applications.

Insight into the Structure and Activity of Surface-Engineered Lipase Biofluids.

Despite a successful application of solvent-free liquid protein (biofluids) concept to a number of commercial enzymes, the technical advantages of enzyme biofluids as hyperthermal stable biocatalysts cannot be fully utilized as up to 90-99% of native activities are lost when enzymes were made into biofluids. With a two-step strategy (site-directed mutagenesis and synthesis of variant biofluids) on Bacillus subtilis lipase A (BsLA), we elucidated a strong dependency of structure and activity on the number and distribution of polymer surfactant binding sites on BsLA surface. Here, it is demonstrated that improved BsLA variants can be engineered via site-mutagenesis by a rational design, either with enhanced activity in aqueous solution in native form, or with improved physical property and increased activity in solvent-free system in the form of a protein liquid. This work answered some fundamental questions about the surface characteristics for construction of biofluids, useful for identifying new strategies for developing advantageous biocatalysts.

Single-dose local administration of parathyroid hormone (1-34, PTH) with ß-tricalcium phosphate/collagen (ß-TCP/COL) enhances bone defect healing in ovariectomized rats.

Parathyroid hormone (1-34, PTH) combined ß-tricalcium phosphate (ß-TCP) achieves stable bone regeneration without cell transplantation in previous studies. Recently, with the development of tissue engineering slow release technology, PTH used locally to promote bone defect healing become possible. This study by virtue of collagen with a combination of drugs and has a slow release properties, and investigated bone regeneration by ß-TCP/collagen (ß-TCP/COL) with the single local administration of PTH. After the creation of a rodent critical-sized femoral metaphyseal bone defect, ß-TCP/COL was prepared by mixing sieved granules of ß-TCP and atelocollagen for medical use, then ß-TCP/COL with dripped PTH solution (1.0 µg) was implanted into the defect of OVX rats until death at 4 and 8 weeks. The defected area in distal femurs of rats was harvested for evaluation by histology, micro-CT, and biomechanics. The results of our study show that single-dose local administration of PTH combined local usage of ß-TCP/COL can increase the healing of defects in OVX rats. Furthermore, treatments with single-dose local administration of PTH and ß-TCP/COL showed a stronger effect on accelerating the local bone formation than ß-TCP/COL used alone. The results from our study demonstrate that combination of single-dose local administration of PTH and ß-TCP/COL had an additive effect on local bone formation in osteoporosis rats.

A 3D Printed Porous Titanium Alloy Rod with Diamond Crystal Lattice for Treatment of the Early-Stage Femoral Head Osteonecrosis in Sheep.

Instruments made of porous titanium alloy and fabricated with a 3D printed technique are increasingly used in experimental and clinical research. To date, however, few studies have assessed their use in early-stage osteonecrosis of the femoral head (ONFH). In this study, porous titanium alloy rods (Ti-Rod) with diamond crystal lattice, fabricated using an electron beam melting (EBM) technique, were implanted into sheep models (n=9) of early-stage ONFH for 6 months. Bone ingrowth and integration were investigated and compared with those of sheep (n=9) undergoing core decompression (CD) alone. Following Ti-Rod implantation, femoral heads showed fine osteointegration, with X-ray evaluation showing compact integration between peripheral bone and rods without radiolucent lines encircling the rods, as well as new bone growth along the metal trabeculae without the intervention of fibrous tissue. The regions of interest (ROIs) of femoral heads showed fine bone ingrowth after Ti-Rod implantation than CD alone. By micro-CT evaluation, the ratios of bone volume to total volume (BV/TV) of ROIs in Rod group was 930 % and 452 % higher than CD group after 3 (0.206 ± 0.0095 vs. 0.020 ± 0.0058, p < 0.05, n=3) and 6 (0.232 ± 0.0161 vs. 0.042 ± 0.0061, p < 0.05, n=3) months respectively. By histological evaluation, the BV/TV of ROIs in Rod group was 647 % and 422 % higher than CD group after 3 (0.157 ± 0.0061 vs. 0.021 ± 0.0061, p < 0.05, n=3) and 6 (0.235 ± 0.0145 vs. 0.045 ± 0.0059, p < 0.05, n=3) months respectively. The new bone grew along metal trabeculae into the center of the rod with a rapid bone ingrowth in Rod gorup. Whereas in CD group, new bone grew mainly at the periphery of the decompressive channel with a slow bone ingrowth. Mechanical analysis showed that maximum load on the femoral head-necks was 31 % greater 6 months after Ti-Rod implantation than after CD alone when the vertical press reached the apex (3751.75 ± 391.96 vs. 2858.25 ± 512.91 N, p < 0.05, n=3). The association of rod implantation with fine bone ingrowth, osteointegration, and favorable mechanical properties suggests that implantation of the porous titanium alloy rod with the diamond crystal lattice may be a beneficial intervention for patients with early-stage ONFH.

Influences of Schneiderian membrane conditions on the early outcomes of osteotome sinus floor elevation technique: a prospective cohort study in the healing period.

OBJECTIVES: To radiographically investigate early outcomes of osteotome sinus floor elevation in the healing phase utilizing cone beam computed tomography and evaluate influences of Schneiderian membrane conditions. MATERIAL AND METHODS: One hundred patients were consecutively recruited for osteotome sinus floor elevation (OSFE) surgery using deproteinized bone mineral. CBCT was taken prior to (T0), immediately post-operatively (T1), and after the healing period (T2). Linear and volumetric measurements of the elevated region from T0 to T1 were performed for evaluation on computed tomography (CT). RESULTS: Osteotome sinus floor elevation were performed in 100 patients. One implant of each patient was selected. Mean residual bone height (RH) was 7.21 ± 1.12 mm. Mean sinus floor elevation height (SE) was 4.81 ± 0.75 mm. The mean endo-sinus bone gain after the healing period was 3.25 ± 0.83 mm. Pre-opterative CBCT scans revealed that 72 patients had a normal sinus membrane in osteotome region, 13 patients presented with flat thickened mucosa and 15 patients with antral pseudocysts. There is no significant difference in sinus mucosa elevation height, bone graft volume and new bone formation in group of Thickening membrane and Antral pseudocysts compared with normal. CONCLUSIONS: The radiographical results show that OSFE is a safe and predictable surgical procedure in residual bone height of 7.21 ± 1.12 mm. Mild flat thickening (>2 and <5 mm) and antral pseudocysts in a small size without clinical symptoms may not be contraindications to OSFE surgery.

Developmental changes in digestive enzyme activity in American shad, Alosa sapidissima, during early ontogeny.

In order to assess the digestive physiological capacity of the American shad Alosa sapidissima and to establish feeding protocols that match larval nutritional requirements, we investigated the ontogenesis of digestive enzymes (trypsin, amylase, lipase, pepsin, alkaline phosphatase, and leucine aminopeptidase) in larvae, from hatching to 45 days after hatching (DAH). We found that all of the target enzymes were present at hatching, except pepsin, which indicated an initial ability to digest nutrients and precocious digestive system development. Trypsin rapidly increased to a maximum at 14 DAH. Amylase sharply increased until 10 DAH and exhibited a second increase at 33 DAH, which coincided with the introduction of microdiet at 30 DAH, thereby suggesting that the increase was associated with the microdiet carbohydrate content. Lipase increased until 14 DAH, decreased until 27 DAH, and then increased until 45 DAH. Pepsin was first detected at 27 DAH and then sharply increased until 45 DAH, which suggested the formation of a functional stomach. Both alkaline phosphatase and leucine aminopeptidase markedly increased until 18 DAH, which indicated intestinal maturation. According to our results, we conclude that American shad larvae possess the functional digestive system before mouth opening, and the significant increases in lipase, amylase, pepsin, and intestinal enzyme activities between 27 and 33 DAH suggest that larvae can be successfully weaned onto microdiets around this age.

Longitudinal response of membrane thickness and ostium patency following sinus floor elevation: a prospective cohort study.

OBJECTIVES: To investigate the influence of sinus floor elevation (SFE) on sinus physiology, including Schneiderian membrane thickness (MT) and ostium patency, using cone beam computed tomography (CBCT). MATERIALS AND METHODS: Based on pre-established selection criteria, 53 patients in combination with 53 sinuses were referred for SFE with a lateral approach using deproteinized bone mineral. CBCT was performed prior to, immediately after surgery and before staged implant placement. The Schneiderian MT of the elevated region, ostium patency, and other clinical data was evaluated. RESULTS: The two-stage sinus augmentation technique was applied in 33 males and 20 females. Four membrane perforations were observed during the surgical procedure. The Schneiderian membrane exhibited significant swelling immediately after augmentation (P < 0.0001), but this difference disappeared after a mean healing period of 7.51 months. The corresponding changes were also observed for ostium patency with a tendency of transient obstruction after surgery. Sinuses with flat mucosal thickening or pseudocysts did not present a liability of perforation compared to the normal cases, and the augmentation procedure was not likely to deteriorate the pathology of mucosal thickening or pseudocysts. CONCLUSIONS: The results show that SFE with a lateral approach has no significant influence on MT and ostium patency after the healing period except for postoperative transient swelling and obstruction. Thickened membranes and antral pseudocysts in a small size might not be contraindications to SFE from the standpoint of the surgical impact on the Schneiderian membrane.

Improving the osteointegration of Ti6Al4V by zeolite MFI coating.

Osteointegration is crucial for success in orthopedic implantation. In recent decades, there have been numerous studies aiming to modify titanium alloys, which are the most widely used materials in orthopedics. Zeolites are solid aluminosilicates whose application in the biomedical field has recently been explored. To this end, MFI zeolites have been developed as titanium alloy coatings and tested in vitro. Nevertheless, the effect of the MFI coating of biomaterials in vivo has not yet been addressed. The aim of the present work is to evaluate the effects of MFI-coated Ti6Al4V implants in vitro and in vivo. After surface modification, the surface was investigated using field emission scanning electron microscopy (FE-SEM) and energy dispersive spectroscopy (EDS). No difference was observed regarding the proliferation of MC3T3-E1 cells on the Ti6Al4V (Ti) and MFI-coated Ti6Al4V (M-Ti) (p > 0.05). However, the attachment of MC3T3-E1 cells was found to be better in the M-Ti group. Additionally, ALP staining and activity assays and quantitative real-time RT-PCR indicated that MC3T3-E1 cells grown on the M-Ti displayed high levels of osteogenic differentiation markers. Moreover, Van-Gieson staining of histological sections demonstrated that the MFI coating on Ti6Al4V scaffolds significantly enhanced osteointegration and promoted bone regeneration after implantation in rabbit femoral condylar defects at 4 and 12 weeks. Therefore, this study provides a method for modifying Ti6Al4V to achieve improved osteointegration and osteogenesis.

Giant cell tumor of axial vertebra: surgical experience of five cases and a review of the literature.

BACKGROUND: Due to the complex anatomy of the upper cervical spinal column region and the variable aggressiveness of giant cell tumors (GCTs), there exists no standard treatment for GCTs of axial vertebra. To the best of our knowledge, there are only a few case reports in the literature and no large sum numbers of clinical trials about the treatment of, or research into, axial vertebra GCTs. METHODS: Between 2009 and 2013, five patients pathologically diagnosed with axial vertebra GCTs were treated at our hospital. We performed intralesional excision and odontoid process reconstructive surgery to preserve the odontoid process, followed with adjuvant radiation therapy after surgery. RESULTS: For those with an intact bone shell, part of the ß-TCP (beta tricalcium phosphate) artificial bone could be seen clearly after surgery and became blurred three months after surgery, as seen on a radiograph. One year later, the part of ß-TCP artificial bone was fused as a block. Subsequently, autogenous bone regenerated successfully and artificial bone degraded thoroughly. For those with a defective cortical bone, partial fusion of the odontoid process, autograft ilium and third vertebra body could be seen three months after surgery, and complete fusion was seen nine months later. The odontoid process was preserved successfully, and the upper cervical spine was reconstructed effectively, without implant failure or infection. CONCLUSIONS: In this study, the odontoid process and function of upper cervical vertebra was preserved successfully through lesion curettage, combined with reconstruction with bone grafting, and adjuvant radiation therapy after surgery. During the follow-up periods, no recurrence or complications was observed.

A comparative study on improved Arrhenius-type and artificial neural network models to predict high-temperature flow behaviors in 20MnNiMo alloy.

The stress-strain data of 20MnNiMo alloy were collected from a series of hot compressions on Gleeble-1500 thermal-mechanical simulator in the temperature range of 1173 ∼ 1473 K and strain rate range of 0.01 ∼ 10 s(-1). Based on the experimental data, the improved Arrhenius-type constitutive model and the artificial neural network (ANN) model were established to predict the high temperature flow stress of as-cast 20MnNiMo alloy. The accuracy and reliability of the improved Arrhenius-type model and the trained ANN model were further evaluated in terms of the correlation coefficient (R), the average absolute relative error (AARE), and the relative error (η). For the former, R and AARE were found to be 0.9954 and 5.26%, respectively, while, for the latter, 0.9997 and 1.02%, respectively. The relative errors (η) of the improved Arrhenius-type model and the ANN model were, respectively, in the range of -39.99% ∼ 35.05% and -3.77% ∼ 16.74%. As for the former, only 16.3% of the test data set possesses η-values within ± 1%, while, as for the latter, more than 79% possesses. The results indicate that the ANN model presents a higher predictable ability than the improved Arrhenius-type constitutive model.

Evaluation of varying ductile fracture criteria for 42CrMo steel by compressions at different temperatures and strain rates.

Fracturing by ductile damage occurs quite naturally in metal forming processes, and ductile fracture of strain-softening alloy, here 42CrMo steel, cannot be evaluated through simple procedures such as tension testing. Under these circumstances, it is very significant and economical to find a way to evaluate the ductile fracture criteria (DFC) and identify the relationships between damage evolution and deformation conditions. Under the guidance of the Cockcroft-Latham fracture criteria, an innovative approach involving hot compression tests, numerical simulations, and mathematic computations provides mutual support to evaluate ductile damage cumulating process and DFC diagram along with deformation conditions, which has not been expounded by Cockcroft and Latham. The results show that the maximum damage value appears in the region of upsetting drum, while the minimal value appears in the middle region. Furthermore, DFC of 42CrMo steel at temperature range of 1123~1348 K and strain rate of 0.01~10 s(-1) are not constant but change in a range of 0.160~0.226; thus, they have been defined as varying ductile fracture criteria (VDFC) and characterized by a function of temperature and strain rate. In bulk forming operations, VDFC help technicians to choose suitable process parameters and avoid the occurrence of fracture.

Porous Titanium Scaffolds with Mechanoelectrical Conversion and Photothermal Function: A Win-Win Strategy for Bone Reconstruction of Tumor-Resected Defects.

Bone metastases severely threaten the lives of patients. Although surgical treatment combined with adjuvant chemotherapy significantly improves the survival rate of patients, tumor recurrence, or metastasis after surgical resection and bone defects caused by surgical treatment remain major challenges for clinicians. Given the abovementioned clinical requirements, barium titanate-containing iron-coated porous titanium alloy scaffolds have been proposed to promote bone defect repair and inhibit tumor recurrence. Fortunately, in vitro and in vivo experimental research confirms that barium titanate containing iron-coated porous titanium alloy scaffolds promote osteogenesis and bone reconstruction in defect repair via mechanoelectric conversion and inhibit tumor recurrence via photothermal effects. Furthermore, the underlying and intricate mechanisms of bone defect repair and tumor recurrence prevention of barium titanate-containing iron-coated porous titanium alloy scaffolds are explored. A win-win strategy for mechanoelectrical conversion and photothermal functionalization provides promising insights into bone reconstruction of tumor-resected defects.

Mechanical loading on cell-free polymer composite scaffold enhances in situ regeneration of fully functional Achilles tendon in a rabbit model.

Traditional tendon engineering using cell-loaded scaffold has limited application potential due to the need of autologous cells. We hypothesize that potent mechanical loading can efficiently induce in situ Achilles tendon regeneration in a rabbit model by using a cell-free porous composite scaffold. In this study, melt-spinning was used to fabricate PGA (polyglycolic acid) and PLA (polylactic acid) filament fibers as well as non-woven PGA fibers. The PLA/PGA (4:2) filament fibers were further braided into a hybrid yarn，which was knitted into a PLA/PGA tubular mesh with potent mechanical property for sustaining natural tendon strain. The results showed that a complete cross-section of Achilles tendon created a model of full mechanical loading on the bridging scaffold, which could efficiently induce in situ tendon regeneration by promoting host cell infiltration, matrix production and tissue remodeling. Histologically, mechanical loading assisted in forming parallel aligned collagen fibers and tenocytes in a fashion similar to those of native tendon. Transmission electron microscope further demonstrated that mechanical strain induced collagen fibril development by increasing fibril diameter and forming bipolar structure, which resulted in enhanced mechanical properties. Interestingly, the synergistic effect between mechanical loading and hyaluronic acid modification was also observed on the induced tenogenic differentiation of infiltrated host fibroblasts. In conclusion, potent mechanical loading is the key inductive microenvironment for in situ tendon regeneration for this polymer-based composite scaffold with proper matrix modification, which may serve as a universal scaffold product for tendon regeneration.

Porous titanium-6 aluminum-4 vanadium cage has better osseointegration and less micromotion than a poly-ether-ether-ketone cage in sheep vertebral fusion.

Interbody fusion cages made of poly-ether-ether-ketone (PEEK) have been widely used in clinics for spinal disorders treatment; however, they do not integrate well with surrounding bone tissue. Ti-6Al-4V (Ti) has demonstrated greater osteoconductivity than PEEK, but the traditional Ti cage is generally limited by its much greater elastic modulus (110 GPa) than natural bone (0.05-30 GPa). In this study, we developed a porous Ti cage using electron beam melting (EBM) technique to reduce its elastic modulus and compared its spinal fusion efficacy with a PEEK cage in a preclinical sheep anterior cervical fusion model. A porous Ti cage possesses a fully interconnected porous structure (porosity: 68 ± 5.3%; pore size: 710 ± 42 µm) and a similar Young's modulus as natural bone (2.5 ± 0.2 GPa). When implanted in vivo, the porous Ti cage promoted fast bone ingrowth, achieving similar bone volume fraction at 6 months as the PEEK cage without autograft transplantation. Moreover, it promoted better osteointegration with higher degree (2-10x) of bone-material binding, demonstrated by histomorphometrical analysis, and significantly higher mechanical stability (P < 0.01), shown by biomechanical testing. The porous Ti cage fabricated by EBM could achieve fast bone ingrowth. In addition, it had better osseointegration and superior mechanical stability than the conventional PEEK cage, demonstrating great potential for clinical application.

Ionic liquid-mediated regeneration of cellulose dramatically improves decrystallization, TEMPO-mediated oxidation and alkyl/alkenyl succinylation.

This work demonstrated a successful strategy that simple ionic liquids (ILs) mediated pretreatment could effectively reduce crystallinity of cellulose from 71 % to 46 % (by C2MIM.Cl) and 53 % (by C4MIM.Cl). The IL-mediated regeneration of cellulose greatly promoted its reactivity for TEMPO-catalyzed oxidation, which the resulting COO- density (mmol/g) increased from 2.00 for non-IL-treated cellulose to 3.23 (by C2MIM.Cl) and 3.42 (C4MIM.Cl); and degree of oxidation enhanced from 35 % to 59 % and 62 %, respectively. More significantly, the yield of oxidized cellulose increased from 4 % to 45-46 %, by 11-fold. IL-regenerated cellulose can also be directly subjected to alkyl/alkenyl succinylation without TEMPO-mediated oxidation, producing nanoparticles with properties similar to oxidized celluloses (55-74 nm in size, -70-79 mV zeta-potential and 0.23-0.26 PDI); but in a much higher overall yield (87-95 %) than IL-regeneration-coupling-TEMPO-oxidation (34-45 %). Alkyl/alkenyl succinylated TEMPO-oxidized cellulose showed 2-2.5 times higher ABTS* scavenging ability than non-oxidized cellulose; however, alkyl/alkenyl succinylation also resulted in a significant decline in Fe2+ chelating property.

UV Irradiation-Induced Cyclic-to-Linear Topological Changes of a Light/pH Dual-Sensitive Cyclic Copolymer for Enhanced Drug Delivery.

Cyclic polymers with cleavable backbones triggered by either external or internal stimuli can realize simultaneous extracellular stability and intracellular destabilization of cyclic polymer-based nanocarriers but remain seldom reported. To this end, we prepared herein cyclic-ONB-P(OEGMA-st-DMAEMA) (c-ONB-P(OEGMA-st-DMAEMA)) with a light-cleavable junction in the polymer backbone based on oligo (ethylene glycol) monomethyl ether methacrylate (OEGMA) and N,N-dimethylaminoethyl methacrylate (DMAEMA) using a light-cleavable atom transfer radical polymerization (ATRP) initiator containing an o-nitrobenzyl (ONB) ester group. Together with the pH-sensitivity of DMAEMA, c-ONB-P(OEGMA-st-DMAEMA) shows a light-cleavable mainchain and pH-sensitive side chains. Notably, doxorubicin (DOX)-loaded c-ONB-P(OEGMA4-st-DMAEMA38) (C2) micelles mediated an IC50 value of 2.28 µg/mL in Bel-7402 cells, which is 1.7-fold lower than that acquired without UV irradiation. This study thus reported the synthesis of a cyclic copolymer with a UV-cleavable backbone and uncovered the effects of topological modulation on the in vitro controlled release properties of cyclic polymers.

Computer-aided discovery of a novel thermophilic laccase for low-density polyethylene degradation.

Polyethylene (PE) and industrial dyes are recalcitrant pollutants calling for the development of sustainable solutions for their degradation. Laccases have been explored for removal of contaminants and pollutants, including dye decolorization and plastic degradation. Here, a novel thermophilic laccase from PE-degrading Lysinibaccillus fusiformis (LfLAC3) was identified through a computer-aided and activity-based screening. Biochemical studies of LfLAC3 indicated its high robustness and catalytic promiscuity. Dye decolorization experiments showed that LfLAC3 was able to degrade all the tested dyes with decolorization percentage from 39% to 70% without the use of a mediator. LfLAC3 was also demonstrated to degrade low-density polyethylene (LDPE) films after eight weeks of incubation with either crude cell lysate or purified enzyme. The formation of a variety of functional groups was detected using Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). Damage on the surfaces of PE films was observed via scanning electron microscopy (SEM). The potential catalytic mechanism of LfLAC3 was disclosed by structure and substrate-binding modes analysis. These findings demonstrated that LfLAC3 is a promiscuous enzyme that has promising potential for dye decolorization and PE degradation.

Enhanced catalytic activity of lipase encapsulated in PCL nanofibers.

Use of biocatalysis for industrial synthetic chemistry is on the verge of significant growth. Enzyme immobilization as an effective strategy for improving the enzyme activity has emerged from developments especially in nanoscience and nanotechnology. Here, lipase from Burkholderia cepacia (LBC), as an example of the luxuriant enzymes, was successfully encapsulated in polycaprolactone (PCL) nanofibers, proven by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). Evaluated in both organic and aqueous medium, the activation factor of the encapsulated enzymes in the hydrolysis reaction was generally higher than that in the transesterification reaction. Enhanced catalytic activities were found when 5-20 w/w % of LBC was loaded. The effect of different solvents pretreatment on the activity of immobilized LBC was also investigated. The highest activation factor was found up to 14 for the sample containing acetone-treated LBC/PCL (10 w/w %). The encapsulated lipase reserved 50% of its original activity after the 10th run in the transesterification reaction in hexane medium. The mechanism of activation of lipase catalytic ability based on active PCL nanofiberous matrix is proposed.