Synthesis and Properties of Polybutylene (Succinate)-b-poly(dimethylsiloxane) with Unprecedented Combined Performance and Functions.

The excellent combined properties of poly(butylene succinate) (PBS) make it a promising biodegradable plastic. However, the lack of functionality and low impact strength limit its application. Poly(dimethylsiloxane) (PDMS) was introduced to prepare new high-performance and functional poly(butylene succinate)-b-poly(dimethylsiloxane) (PBS-b-PDMS) in this work. The resulting PBS-b-PDMS was found to possess high molecular weight, narrow molecular weight distribution, and excellent combined performance. PBS-b-PDMS had good thermal properties. The decomposition temperature of 5% weight loss (T5%) increased from 324 to 344 °C, and the temperatures at the maximum weight loss rate (Tmax) values increased from 385.1 to 396.7 °C. The impact strength increased significantly from 7.8 kJ/m2 of PBS to 53.9 kJ/m2 of PBS-b-PDMS. As the PDMS block endows copolymers with low surface energy and good liquid resistance, PBS-b-PDMS has excellent antismudge, self-cleaning, and solvent resistance. Finally, to minimize the surface energy, PDMS blocks preferentially enrich the surface, which imparts the polymers with self-cleaning properties.

Enzymatic preparation of hydrophobic biomass with one-pot synthesis and the oil removal performance.

Oil pollution is causing deleterious damage to aquatic ecosystems and human health. The utilization of agricultural waste such as corn stalk (CS) to produce biosorbents has been considered an ecofriendly and efficient approach for removing oil. However, most previous studies focused on the modification of the whole CS, which is inefficient due to the heterogeneity of CS. In this study, corn stalk pith (CP), which has excellent amphipathic characteristics, was selected to prepare a high-efficiency oil sorbent by grafting dodecyl gallate (DG, a long-chain alkyl) onto CP surface lignin via laccase mediation. The modified biomass (DGCP) shows high hydrophobicity (water contact angle = 140.2°) and superoleophilicity (oil contact angle = 0°) and exhibits a high oil sorption capacity (46.43 g/g). In addition, DGCP has good stability and reusability for adsorbing oil from the aqueous phase. Kinetic and isotherm models and two-dimensional correlation spectroscopy integrated with FTIR analyses revealed that the main sorption mechanism involves the H-bond effect, hydrophobic effect and van der Waals force. This work provides an ecofriendly method to prepare oil sorbents and new insights into the mechanisms underlying the removal of spilled oil from wastewater.

Delivery of Cationic Platinum Prodrugs via Reduction Sensitive Polymer for Improved Chemotherapy.

A cationic monofunctional platinum anticancer drug, phenanthriplatin (PhenPt(II)), exhibits promising anticancer effect on various cancer cell lines. Unlike the conventional platinum(II) drugs, PhenPt(II) is more likely to bind the N7 adenosine base of DNA in situ, and consequently resulting in a unique cellular response profile and unusual potency. However, since this drug is positively charged, it can easily bind to plasma protein that leads to rapid systematic clearance and deleterious toxicities, which greatly limits its in vivo application. Herein, a lipophilic phenanthriplatin (PhenPt(IV)) prodrug is synthesized. To further reduce its toxicity, a negatively charged polymer P1 with reduction responsiveness is assembled with PhenPt(IV) to form PhenPt(IV) NPs. In comparison to cisplatin, PhenPt(IV) NPs exhibit up to 30 times greater in vitro potency against various cancer cell lines. Additionally, in vivo, no obvious side effect is found on PhenPt(IV) NPs. Significant enhancement in tumor accumulation and improvement of drug efficacy in 4T1 tumor model are demonstrated. Taken together, this study provides a promising strategy for the clinical translation of phenanthriplatin.

Competitive adsorption behavior of typical heavy metal ions from acid mine drainage by multigroup-functionalization cellulose: qualitative and quantitative mechanism.

In response to Cd, Pb, and Cu pollution in acid mine drainage (AMD), a multigroup cellulose material (TCIS) containing thiol (-SH), carboxyl (-COOH), and imine (-C = N) groups was prepared through oxidation and grafting reactions. At pH 5, the maximum Cd(II), Pb(II), and Cu(II) adsorption performances of TCIS were 53.60, 120.6, and 36.01 mg/g, respectively. In the binary system, the interaction between metal ions was mainly inhibited by competitive adsorption. Cu(II) exhibited the most fierce inhibitory effect and had a relatively stable adsorption performance. In the ternary system, the adsorption order was Cu(II) > Cd(II) > Pb(II). In density functional theory (DFT) calculations, we combined the molecular electrostatic potentials, binding energies, differential charges, and total potentials to illustrate the competitive behavior of metal ions at different binding sites. Moreover, X-ray photoelectron spectroscopy (XPS) and DFT analysis revealed that the adsorption process of TCIS was dominated by the above functional groups, which caused competitive adsorption among Cd(II), Pb(II), and Cu(II).

Multiple adsorption systems and electron-scale insights into the high efficiency coadsorption of a novel assembled cellulose via experiments and DFT calculations.

In view of the characteristics of heavy metal and antibiotic compound pollution in the Pearl River Basin in Guangzhou. More scientifically modified cellulose, named HVUC, is characterized by multiple hydrophilic groups, long chains and large space and displays highly efficient adsorption of both Cd and sulfamethoxazole (SMZ) and good adaptability in a wide pH range and at high ion strength. Furthermore, the coadsorption mechanism was elaborated from multiple angles. Multiple adsorption experiments explained the competition and synergy effect in the adsorption process. The electrostatic potential maps indicated that HVUC had advantageous adsorption sites for both Cd and SMZ and that electrostatic interactions had the greatest impact on the adsorption of Cd and SMZ. The electron density and differential charge density images proved that Cd more easily overlapped electron clouds and transferred electrons with HVUC and that SMZ- and could act as a bridge for SMZ-. The equilibrium configuration indicated that the formation of Cd-SMZ- complexes led to the bending and folding of SMZ-, which was not conducive to overall adsorption when SMZ- was close to HVUC and could lead to the release of SMZ- when Cd was close to HVUC, which confirmed the proposed mechanism of complexation-decomplexation-complexation.

Mannose modified zwitterionic polyester-conjugated second near-infrared organic fluorophore for targeted photothermal therapy.

Cancer resistance has been the huge challenge to clinical treatment. A photothermal therapy of second near-infrared (NIR-II) organic dye small molecule has been used to conquer the cancer resistance. However, the available NIR-II dye lacks selectivity and spreads throughout the body. It has toxicity and indiscriminate burn injuries normal cells and tissues during therapy. Hence, to improve the therapeutic outcomes, herein, for the first time, we report the mannose-modified zwitterionic nanoparticles loading IR1048 dye, aiming to overcome cancer cellular resistance. The targeting molecule mannose has been applied to modify zwitterionic polyester, and the obtained polyester is employed to load IR1048 to prolong the circulation time in the blood and improve the stability of loaded dye, due to the good cytocompatibility of polyester and the antifouling properties of zwitterions. In vitro experimental results show that the pH-responsive targeted nanoparticles display satisfactory photophysical properties, prominent photothermal conversion efficiency (44.07%), excellent photothermal stability, negligible cytotoxicity for normal cells and strong photothermal toxicity to drug-resistant cancer cells. Moreover, due to the mannose targeting effect, cancer cells can endocytose the nanoparticles effectively. All these results demonstrate potential application of this alternative hyperthermal delivery system with remote-controllable photothermal therapy of tumor for accurate diagnosis by NIR-II fluorescence imaging.

Adsorption of sulfamethoxazole and sulfadiazine on phosphorus-containing stalk cellulose under different water pH studied by quantitative evaluation.

To improve the high-value application of corn stalk, phosphorus-containing stalk cellulose (PFC) was prepared, characterized, and utilized for the adsorption of sulfamethoxazole (SMZ) and sulfadiazine (SD), with maximum adsorption capacities of 1.385 and 2.527 mg/g at pH 7. As expected, the adsorption efficiency of PFC was strongly affected by pH, and the preferential adsorption order of SMZ- (SD0) > SMZ0 (SD-) > SMZ+ (SD+) was obtained from the experimental results and due to the charges of PFC and the SMZ and SD species. Furthermore, these results were qualitatively linked to the adsorption mechanism, e.g., π+-π electron donor-acceptor (EDA), anion-π bond electrostatic, and hydrophobic interactions. In particular, the adsorption mechanism was further characterized in terms of structure and analyzed systematically using density functional theory (DFT), frontier orbital theory (FOT), and molecular dynamics (MD) simulation, with the aim to explain the theoretical calculation and experimental results. As a result, the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) orbitals revealed the key role of the rings and functional groups of PFC and SMZ (or SD) and validated the optimized structures of PFC+ sulfonamides (SAs)+, PFC- SAs0, and PFC- SAs-, in which their binding energy values, energy gaps, and relevant molecular lengths determined their stability. Additionally, the van der Waals (vdW) energy confirmed the effect of various interactions on adsorption.

Adsorption behavior and mechanism of sulfonamides on phosphonic chelating cellulose under different pH effects.

Phosphonic chelating fiber (PCCSF) as a novel adsorbent was produced through alkalization, etherification, amination and phosphonation, and then it was applied to adsorb sulfonamides (SAs), such as sulfadiazine (SD), sulfamonomethoxine (SMM) and sulfamethoxazole (SMZ). Specially, their adsorption behavior at different pH values was studied. As a result, PCCSF was provided with amino (NH2 or NH) and PO(OH)2 (PO) groups, and its equilibrium data were generally represented by both Langmuir and Freundlich models. Combining adsorbent-to-solution distribution coefficients (Kd) values and the effect of pH, the primary mechanism suggested that adsorption capacity of PCCSF was lower in strong acid and alkali solution, due to the electrostatic repulsion and hydrophobic interactions. By contrast, its adsorption affinity became more excellent at 3 < pH < 9 owing to the π-π electron-donor-acceptor (EDA) charge-assisted H-bond, Lewis acid-base interaction and charge-assisted H-bond (CAHB).

Development of biodegradable polyesters based on a hydroxylated coumarin initiator towards fluorescent visible paclitaxel-loaded microspheres.

In this work, we developed a facile end-functionalization method using hydroxylated coumarin to initiate the ring-opening polymerization of cyclic esters to synthesize a series of fluorescent biodegradable aliphatic polyesters with tailorable properties. The resulting fluorescent functionalized poly(l-lactide) (PLLA-COU), poly(ε-caprolactone) (PCL-COU) poly(δ-valerolactone) (PVL-COU) and poly(trimethylene carbonate) (PTMC-COU) were investigated to evaluate the dependence of fluorescence on the chemical structure and molecular weight of the materials. The differences in the electron withdrawing ability and the density of ester groups are responsible for the changes in the fluorescence quantum yield. Then, two representative biodegradable materials, namely, PLLA-COU and PCL-COU, were used to prepare fluorescent paclitaxel-loaded microspheres. During in vitro drug release, the release rate of the PCL-COU microspheres is dramatically faster than that of the PLLA-COU microspheres due to the difference in the material nature and their surface morphologies, possibly achieving a tunable degradation and release rate for the drug carriers. Fluorescent functionalized polyester microspheres can retain their fluorescence properties and emit bright blue light for fluorescence tracing during the degradation process. Biological evaluations showed that both fluorescent polyesters are devoid of any significant toxicity and have good biocompatibility. The results demonstrated that the obtained fluorescent polyesters are promising for use in traceable and controlled drug delivery with tunable drug release.

A new amphoteric superabsorbent hydrogel based on sodium starch sulfate.

A new amphoteric superabsorbent hydrogels were synthesized by graft copolymerization blending based on acrylamide (AM), diallydimethylammonium chloride (DMDAAC) and sodium starch sulfate (SSS). The effect of polymerization conditions on swelling capacity was investigated. The results showed that the swelling capacity was affected by various factors, such as polymerization temperature, concentration of initiator and crosslinker, and dose of AM. Additionally, the results testified that salt bond was a potential crosslinking factor in the amphoteric hydrogel. The maximum swelling capacity in distilled water and saline solution reached 1493.1 and 91.0 g/g, respectively. These results were compared with those obtained from original starch-based hydrogel.

Synthesis and characterization of water-soluble chitosan grafted with hydrophilic aliphatic polyester.

Traditionally, hydrophobic aliphatic polyester has been employed to modify chitosan and organic soluble or swellable graft copolymers have been obtained. In this work, linear poly(butylene tartrate) (PBT) with hydrophilic pendant hydroxyl groups, which was synthesized by direct polycondensation of tartaric acid and butanediol under mild condition, was chosen to modify chitosan and synthesize PBT grafted chitosan (CS-g-PBT) with the mediation of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide in aqueous solution of an ionic liquid. The chain length of the grafted PBT could be facilely controlled by varying the molecular weight of PBT. The chemical structures of CS-g-PBT were systematically characterized by 1H NMR, attenuated total reflectance Fourier transform infrared and wide-angle X-ray diffraction. The thermal properties were investigated by thermogravimetric analysis and differential scanning calorimetry. The water solubility of chitosan has been effectively improved after grafting with PBT and a water-soluble chitosan derivative has been synthesized. Meanwhile, the water solubility of grafts varies regularly with chain length of grafted PBT.

A novel and simple procedure to synthesize chitosan-graft-polycaprolactone in an ionic liquid.

An ionic liquid, 1-ethyl-3-methylimidazolium acetate (EMIMAc), was synthesized and employed as a homogeneous and green reaction media to prepare chitosan-graft-polycaprolactone (CS-g-PCL) via ring-opening polymerization, using stannous octoate (Sn(Oct)2) as a catalyst. The structures and compositions of copolymers could be facilely controlled by the reaction conditions and feed ratios. The grafting content of polycaprolactone (PCL) could reach as high as 630%. The chemical structures of the copolymers were systematically characterized by (1)H NMR, Fourier transform infrared spectroscopy (FTIR) and wide-angle X-ray diffraction (WAXD), while thermal properties were studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). The thermal stability and glass transition temperature (Tg) of the graft copolymers vary regularly with the change of PCL grafting content.

Preparation of cellulose derived from corn stalk and its application for cadmium ion adsorption from aqueous solution.

Cellulose was isolated from corn stalk and modified by graft copolymerization to produce an absorbent material (AGCS-cell), which was characterized by scanning electron microscope and energy disperse spectroscopy (SEM-EDS), X-ray diffraction (XRD) and solid-state CP/MAS (13)C NMR. The results showed that AGCS-cell had better adsorption potential for cadmium ion than unmodified cellulose because of the addition of functional groups (CN and OH groups) and the lower crystallinity. The Langmuir isotherms gave the best fit to the data and gave an adsorption capacity was 21.37 mg g(-1), which was close to unpurified cellulose (AGCS) and reflected the feasibility of using AGCS-cell as an adsorbent to remove cadmium ions.

Removal of cadmium(II) from aqueous solution by corn stalk graft copolymers.

Corn stalk was modified using graft copolymerization to produce absorbent (AGCS), which was characterized by elemental analysis, fourier transform infrared, X-ray diffraction, solid-state CP/MAS (13)C NMR spectra, thermogravimetric analysis and differential scanning calorimeter. AGCS, having cyano group (-CN) after grafted successfully, exhibits more high adsorption potential for Cd(II) than unmodified forms. The efficiency of AGCS for removal of cadmium ions was evaluated. Factors affecting Cd(II) adsorption such as pH value and adsorbent dosage were investigated. More than 90% removal was achieved at pH 3.0-7.0 and the adsorption increased from 16.0% to 99.2% with increase of adsorbent dose. In addition, two isotherm models, namely, Langmuir and Freunlich were also analyzed to determine the best fit equation for adsorption of Cd(II) on AGCS.