Visible Light-Regulated Ring-Opening Polymerization of Lactones by Employing Indigo as a Photoacid Catalyst.

The development of visible light-regulated polymerizations for precision synthesis of polymers has drawn considerable attention in the past years. In this study, an ancient dye, indigo, is successfully identified as a new and efficient photoacid catalyst, which can readily promote the ring-opening polymerization of lactones under visible light irradiation in a well-controlled manner, affording the desired polyester products with predictable molecular weights and narrow dispersity. The enhanced acidity of indigos by excitation is crucial to the H-bonding activation of the lactone monomers. Chain extension and block copolymer synthesis are also demonstrated with this method.

PEGylated Gambogic Acid Nanoparticles Enable Efficient Renal-Targeted Treatment of Acute Kidney Injury.

Acute kidney injury (AKI) is a common clinical syndrome lacking effective pharmacotherapy. Gambogic acid (GA), as an active ingredient of herbal medicines, exhibits antioxidant and anti-inflammatory effects that benefit the treatment of AKI, but its poor aqueous solubility limits effective renal delivery. We, for the first time, developed GA-based nanoparticles (GA-NPs) with preferential renal uptake for AKI treatment. By PEGylating with NH2-PEG5000-NOTA, hydrophobic GA was self-assembled into ∼4.5 nm nanoparticles, which showed the enhanced renal accumulation in AKI models from PET images. Importantly, the in vitro cell assays and in vivo tests of the two AKI models have confirmed the obvious nephroprotective effects and biosafety of GA-NPs. Therefore, this work indicates that GA-NPs can be a promising therapeutic candidate for the management of AKI.

Study of Crystallinity and Conformation of Poly(lactic acid) by Terahertz Spectroscopy.

During crystallization, conformational changes are often accompanied by the formation of interactions. Terahertz (THz) spectroscopy exhibits strong responses to the crystalline poly(lactic acid) (PLA). Therefore, we estimate the relative crystallinity and investigate the effect of conformational transition on the vibration of PLA by THz spectroscopy. By comparing with the results of X-ray diffraction (XRD) and differential scanning calorimetry (DSC), the validity of THz spectroscopy to calculate crystallinity is verified. Furthermore, the peak intensity of PLA at 2.01 THz increases with crystallinity. Combined with Fourier transform infrared spectroscopy (FTIR), the vibrational intensity of PLA at 2.01 THz is highly correlated with the contribution of gt conformation, showing a linear relationship. In addition, the vibrational peak of PLA also reflects the interchain interactions. We believe that the increase in peak intensity with increasing crystallinity originates from the effect of the dipole-dipole interactions between the carbonyl groups. Our study demonstrates the ability of THz spectroscopy to estimate the crystallinity of PLA, and the peak at 2.01 THz shows conformational and interaction sensitivities.

A finite element analysis on different bone cement forms and injection volumes injected into lumbar vertebral body in percutaneous kyphoplasty.

BACKGROUND: To investigate the stress changes between different bone cement forms and injection volumes in adjacent vertebrae after percutaneous kyphoplasty (PKP) by establishing a three-dimensional finite element model of osteoporosis. METHODS: A male healthy volunteer was selected. CT of scans L1 to L3 vertebrae were imported into Mimics 21.0 software.The vertebral model of osteoporosiswas established based on previous literature reference. The models were divided into three groups: unilateral, bilateral integration and bilateral separation groups, with each group injecting 2 ml, 4,ml and 6 ml of bone cement, respectively. In all models, a vertical compressive load of 500 N, anterior flexion/posterior extension, left/right bending, and left/right rotation were applied with a moment of 7.5 N/m, of which 85% was applied to the anterior mid-column and 15% to the posterior column. The stress changes between adjacent vertebrae under different conditions were calculated. RESULTS: After percutaneous kyphoplasty was applied to the L2 vertebral body, some differences can be found between the effects of different cement injection volumes and cement morphology on adjacent structures. There was no major difference between the groups when the bone cement injection volume was 2 ml. When the amount of bone cement injected was 4 ml, the bone cement morphology of the bilateral integration group (BIG) produced less stress between adjacent vertebral bodies. The minimum stress was 14.95 MPa in the L3 vertebral body in posterior extension. Whereas the stress levels on adjacent intervertebral structures, BIG shaped bone cement shows some superiority. In addition, the adjacent vertebrae and intervertebral structures are subjected to less stress during left and right rotation. CONCLUSIONS: The present finite element study suggested that bilateral integration bone cement is a suitable form of cement injection, and when the injection volume is 4 ml, reduces stress on adjacent segments by approximately 15% while maintaining the stability of the injected vertebral body.

A Facile and Unprecedented Route to a Library of Thermostable Formaldehyde-Derived Polyesters: Highly Active and Selective Copolymerization of Cyclic Acetals and Anhydrides.

The development of new strategies for producing polyesters can expand the category of biodegradable materials. Here, we disclose the alternating copolymerization of cyclic acetals (made from formaldehyde and diols) and anhydrides for the first time, using 5 cyclic acetals and 9 anhydrides to afford 45 unprecedented polyesters. At a wide range of reaction temperatures (25 to 140 °C), diverse metal-free Lewis/Brønsted acids are highly active catalysts for these copolymerizations via the cationic mechanism. Of interest, kinetic studies indicate that the copolymerization of cyclic acetals and anhydrides shifts the chemical equilibrium of "cyclic acetals ⇌ polyacetals" to the left, thus yielding polyesters with up to >99 % alternating degree. The obtained polyesters possess high oxygen content ([O] : [C] up to 6 : 7), molecular weights of 2.0-33.3 kDa, narrow polydispersities of 1.2-1.5, low glass transition temperatures (-64 to -27 °C), as well as high decomposition temperatures (275 to 324 °C).

NIR-II Absorbing Semiconducting Polymer-Triggered Gene-Directed Enzyme Prodrug Therapy for Cancer Treatment.

Exploration of facile strategies for precise regulation of target gene expression remains highly challenging in the development of gene therapies. Especially, a stimuli-responsive nanocarrier integrated with ability of noninvasive remote control for treating wide types of cancers is rarely developed. Herein, a NIR-II absorbing semiconducting polymer (PBDTQ) is employed to remotely activate the heat-inducible heat-shock protein 70 (HSP70) promoter under laser irradiation, further realizing regulation of gene-directed enzyme prodrug therapy (GDEPT) for cancer treatment in mild hyperthermia. In this multifunctional nanocomposite, the PBDTQ and double suicide gene plasmid (pSG) based on HSP70 promoter are incorporated into a lipid complex. Upon NIR-II laser excitation, the mild photothermal effect (≈43 °C) generated from PBDTQ can cause the release of pSG and activation of HSP70 promoter, and then upregulate suicide gene expression triggered by the HSP70 promoter which can further convert the nontoxic prodrug into its cytotoxic metabolites. Therefore, this work demonstrates a universal NIR-II laser-triggered GDEPT using semiconducting polymers as the photothermal generator for cancer treatment with minimized collateral damage and nontargeted side effects.

An Ester-Substituted Semiconducting Polymer with Efficient Nonradiative Decay Enhances NIR-II Photoacoustic Performance for Monitoring of Tumor Growth.

Photoacoustic agents have been of vital importance for improving the imaging contrast and reliability against self-interference from endogenous substances. Herein, we synthesized a series of thiadiazoloquinoxaline (TQ)-based semiconducting polymers (SPs) with a broad absorption covering from NIR-I to NIR-II regions. Among them, the excited s-BDT-TQE, a repeating unit of SPs, shows a large dihedral angle and narrow adiabatic energy as well as low radiative decay, attributing to its strongly electron-deficient ester-substituted TQ-segment. In addition, its more vigorous molecular motions trigger a higher reorganization energy that further yields an efficient photoinduced nonradiative decay, which has been carefully examined and understood by theoretical calculation. Thus, BDT-TQE SP-cored nanoparticles with twisted intramolecular charge transfer (TICT) feature exhibit a high NIR-II photothermal conversion efficiency (61.6 %) and preferable PA tracking of in situ hepatic tumor growth for more than 20 days. This study highlights a unique strategy for constructing efficient NIR-II photoacoustic agents via TICT-enhanced PNRD effect, advancing their applications for in vivo bioimaging.

Characterization of the Micromorphology and Topochemistry of Poplar Wood during Mild Ionic Liquid Pretreatment for Improving Enzymatic Saccharification.

Ionic liquids (ILs) as designer solvents have been applied in biomass pretreatment to increase cellulose accessibility and therefore improve the enzymatic hydrolysis. We investigated the characterization of the micromorphology and the topochemistry of poplar wood during 1-ethyl-3-methylimidazolium acetate pretreatment with mild conditions (90 °C for 20 and 40 min) by multiple microscopic techniques (FE-SEM, CLSM, and CRM). Chemical composition analysis, XRD, cellulase adsorption isotherm, and enzymatic hydrolysis were also performed to monitor the variation of substrate properties. Our results indicated that the biomass conversion was greatly enhanced (from 20.57% to 73.64%) due to the cell wall deconstruction and lignin dissolution (29.83% lignin was removed after incubation for 40 min), rather than the decrystallization or crystallinity transformation of substrates. The mild ILs pretreatment, with less energy input, can not only enhance enzymatic hydrolysis, but also provide a potential approach as the first step in improving the sequential pretreatment effectiveness in integrated methods. This study provides new insights on understanding the ILs pretreatment with low temperature and short duration, which is critical for developing individual and/or combined pretreatment technologies with reduced energy consumption.

Characterization of VP1 sequence of Coxsackievirus A16 isolates by Bayesian evolutionary method.

BACKGROUND: Coxsackievirus A16 (CV-A16), a major etiopathologic cause of pediatric hand, foot, and mouth disease (HFMD) worldwide, has been reported to have caused several fatalities. Revealing the evolutionary and epidemiologic dynamics of CV-A16 across time and space is central to understanding its outbreak potential. METHODS: In this study, we isolated six CV-A16 strains in China's Jilin province and construct a maximum clade credibility (MCC) tree for CV-A16 VP1 gene by the Bayesian Markov Chain Monte Carlo method using 708 strains from GenBank with epidemiological information. The evolution characteristics of CV-A16 VP1 gene was also analysed dynamicly through Bayesian skyline plot. RESULTS: All CV-A16 strains identified could be classified into five major genogroups, denoted by GI-GV. GIV and GV have co-circulated in China since 2007, and the CV-A16 epidemic strain isolated in the Jilin province, China, can be classified as GIV-3. The CV-A16 genogroups circulating recently in China have the same ancestor since 2007. The genetic diversity of the CV-A16 VP1 gene shows a continuous increase since the mid-1990s, with sharp increases in genetic diversity in 1997 and 2007 and reached peak in 2007. Very low genetic diversity existed after 2010. The CV-A16 VP1 gene evolutionary rate was 6.656E-3 substitutions per site per year. CONCLUSIONS: We predicted the dynamic phylogenetic trends, which indicate outbreak trends of CV-A16, and provide theoretical foundations for clinical prevention and treatment of HFMD which caused by a CV-A16.

Method for automatically identifying spectra of different wood cell wall layers in Raman imaging data set.

The technique of Raman spectroscopic imaging is finding ever-increasing applications in the field of wood science for its ability to provide spatial and spectral information about the sample. On the basis of the acquired Raman imaging data set, it is possible to determine the distribution of chemical components in various wood cell wall layers. However, the Raman imaging data set often contains thousands of spectra measured at hundreds or even thousands of individual frequencies, which results in difficulties accurately and quickly extracting all of the spectra within a specific morphological region of wood cell walls. To address this issue, the authors propose a new method to automatically identify Raman spectra of different cell wall layers on the basis of principal component analysis (PCA) and cluster analysis. A Raman imaging data set collected from a 55.5 µm × 47.5 µm cross-section of poplar tension wood was analyzed. Several thousand spectra were successfully classified into five groups in accordance with different morphological regions, namely, cell corner (CC), compound middle lamella (CML), secondary wall (SW), gelatinous layer (G-layer), and cell lumen. Their corresponding average spectra were also calculated. In addition, the relationship between different characteristic peaks in the obtained Raman spectra was estimated and it was found that the peak at 1331 cm(-1) is more related to lignin rather than cellulose. Not only can this novel method provide a convenient and accurate procedure for identifying the spectra of different cell wall layers in a Raman imaging data set, but it also can bring new insights into studying the morphology and topochemistry in wood cell walls.

Raman microspectroscopy imaging study on topochemical correlation between lignin and hydroxycinnamic acids in Miscanthus sinensis.

Confocal Raman microspectroscopy (CRM) has emerged as a powerful approach to visualize the compositional distribution in lignocellulosic biomass of cell walls. In this work, the applicability of CRM for imaging the topochemical correlation between lignin and hydroxycinnamic acids (HCA) in the Miscanthus sinensis internode was explored. Model compound [p-coumaric acid (PCA) and ferulic acid (FA)] analysis indicated that the band region from 1,152 to 1,197 cm(-1) can be used to characterize the distribution of HCA. Raman images calculated by integrating over the area intensity of characteristic spectral regions showed heterogeneous distribution of lignin and HCA at cellular and sub-cellular level. When overlaying the Raman image of lignin and HCA distribution, it was found that these two polymers were co-located in the middle lamella and secondary wall of corresponding cells. Raman images for the band intensity ratio (1,173 cm(-1)/1,603 cm(-1)) indicated a clear association between lignin and HCA distribution within morphologically distinct cell wall layers of sclerenchyma fibers and the parenchyma. This is the first time that the spatial correlation between lignin and HCA concentration has been illustrated by a microspectroscopy imaging approach. The results are of importance in extending the current understanding of lignin and aromatics topochemistry in herbaceous biomass.

Synthesis of grafted bromoisobutyryl esterified starch using electron transfer atom transfer radical polymerization method with high-performance adhesion and film properties.

Nowadays, few investigations on the process parameters of grafted starch synthesized using electron transfer atom transfer radical polymerization (ARGET ATRP) and its applications in warp sizing and paper-making are presented. Therefore, this study aimed to survey the appropriate process parameters of bromoisobutyryl esterified starch-g-poly(acrylic acid) (BBES-g-PAA) synthesized by the ARGET ATRP, and also aimed to provide a new biobased BBES-g-PAA adhesive. The appropriate synthesis process parameters were 1.2, 0.32, and 0.6 in the molar ratios of vitamin C, CuBr2, and pentamethyldivinyltriamine to BBES, respectively, at 40 °C for 5 h. The BBES-g-PAA samples with a grafting ratio range of 4.63-14.14 % exhibited bonding forces of 57.8-64.6 N to wool fibers [55.5 N (BBES) and 53.8 N (ATS)], and their films showed breaking elongations of 3.29-3.80 % [2.74 % (BBES) and 2.49 % (ATS)] and tensile strengths of 29.1-25.4 MPa [30.4 MPa (BBES) and 34.7 MPa (ATS)]. Compared with BBES, significantly increased bonding forces and film elongations, and decreased film strengths for the BBES-g-PAA samples with grafting ratios ≥10.54 % were displayed (p < 0.05). The time (100-42 s) taken for the BBES-g-PAA films was significantly shorter than that of ATS (246 s) and BBES (196 s) films (p < 0.05), corresponding to better desizability.

Recent developments in lignin-based fluorescent materials.

Biomass-based fluorescent materials are an alternative to plastic-based materials for their multifunctional applications. Lignin, an inexpensive and easily available raw material, demonstrates outstanding environment-responsive properties such as pH, metal ions, dyes sensing, bioimaging and so on. To date, only a little work has been reported on the synthesis of lignin-based fluorescent materials. In this review report, synthetic approaches and light-responsive applications of lignin-based fluorescent carbon dots and other materials are summarized. The results reveal that lignin-based fluorescent carbon dots are prepared by hydrothermal method, exhibit small size <10 nm, reveal significant quantum yield, biocompatibility, non-toxicity, photostability and display substantial tunable emission and can be efficiently employed for sensing, bioimaging and energy storage applications. Finally, the forthcoming challenges, investigations, and options open for the chemical and/or physical modification of lignin into fluorescent materials for future applications are well-addressed. To our knowledge, this is the first comprehensive review report on lignin-based fluorescent materials and their light-responsive applications. In addition, this review will attract remarkable consideration and thrust for the researchers and biochemical technologists working with the preparation of lignin-based fluorescent materials for broad applications.

[Preparation of self-microemulsion drug delivery system of the mixture of paeonol and borneol based on Xingbi Fang].

The aim of this study is to prepare self-microemulsifying drug delivery system (SMEDDS) of the mixture of paeonol (Pae) and borneol (Bor). Solubility test, ternary phase diagrams and simplex lattice method were employed to screen and optimize the formulation of the mixture of Pae and Bor-loaded SMEDDS. After formed into microemulsions, the particle diameter (PD) was determined and a TEM was employed to observe the microemulsions' morphology. The contents of Pae and Bor were determined by gas chromatography. As a result, while ethyl oleate (EO) as the oil phase, cremophor EL35 (EL35) as surfactant and Transcutol HP (HP) as cosurfactant, the range of the microemulsion on the ternary phase diagram was larger than other combinations. And at a ratio of 20:45:35, the microemulsions' PD was about 34 nm and the polydispersity index (PI) was about 0.2. There were 16% of Pae, 2% of Bor, 16% of EO, 37% of EL35 and 29% of HP in the prepared SMEDDS. The preparation process of the Pae and Bor-loaded SMEDDS based on Xingbi Fang is simple and feasible. This study provides a reference for the researches on the related traditional Chinese medicine and the related components.

[Application of the Raman spectroscopy to the study of plant cell walls].

Due to the deficiency of energy supply and negative environmental impacts. Much attentions have been paid to agnicultural these lignocellulosic the replacement of fossil resources with and forestry biomass for the production of bio-fuels, chemicals and biomaterials on a global scale. Highly effective utilization of biomass is dependent on full understanding of their chemical composition and structural characteristics. A state-of-the-art Raman spectroscopy has evolved an important and nondestructive technique for plant research as information concerning histochemistry and structural characteristics of plant cell walls can be investigated in a nearly native state. In this paper, the principle of Raman imaging was introduced briefly. Meanwhile, the research progress in structural analysis of major components, micro-area distribution and molecular organization of the cellulose and lignin in the plant cell walls by Raman spectroscopy was summarized. The aim of the review is to promote the application of Raman spectroscopy to the study of plant cell walls.

Recent studies on cellulose-based fluorescent smart materials and their applications: A comprehensive review.

The progress of bio-based fluorescent smart materials and their multifunctional applications have attained increasing interest in the recent decades. Cellulose is among the cheapest and widespread raw material on earth which can be modified into diverse useful materials. This review summarizes the chemical modification of cellulose into smart fluorescent materials. This further highlights on the fabrication of the prepared fluorescent materials into films, fibers, paper strips, carbon dots, hydrogels and solutions which are applied for the sensing of toxic metals and anions, pH, bioimaging, common organic solvents, aliphatic and aromatic amines, nitroaromatics, fluorescent printing, coating, and anti-counterfeiting applications. Finally, the discussion about the upcoming investigations, challenges, and options open for the cellulose-based luminescence sensors are communicated. We believe that this review will appeal more and more attention and curiosity for the chemists, biochemists, and chemical engineers working with the synthesis of cellulose-based fluorescent materials for widespread applications.

Microfluidic-based fabrication and characterization of drug-loaded PLGA magnetic microspheres with tunable shell thickness.

To overcome the shortcoming of conventional transarterial chemoembolization (cTACE) like high systemic release, a novel droplet-based flow-focusing microfluidic device was fabricated and the biocompatible poly(lactic-co-glycolic acid) (PLGA) magnetic drug-eluting beads transarterial chemoembolization (TACE) microspheres with tunable size and shell thickness were prepared via this device. Paclitaxel, as a model active, was loaded through O/O/W emulsion method with high efficiency. The size and the shell thickness vary when adjusting the flow velocity and/or solution concentration, which caters for different clinical requirements to have different drug loading and release behavior. Under the designed experimental conditions, the average diameter of the microspheres is 60 ± 2 µm and the drug loading efficiency has reached 6%. The drug release behavior of the microspheres shows the combination of delayed release and smoothly sustained release profiles and the release kinetics differ within different shell thickness. The microspheres also own the potential of magnetic resonance imaging (MRI) visuality because of the loaded magnetic nanoparticles. The microsphere preparation method and device we proposed are simple, feasible, and effective, which have a good application prospect.

PLGA-based biodegradable microspheres in drug delivery: recent advances in research and application.

Biodegradable microspheres have been widely used in the field of medicine due to their ability to deliver drug molecules of various properties through multiple pathways and their advantages of low dose and low side effects. Poly (lactic-co-glycolic acid) copolymer (PLGA) is one of the most widely used biodegradable material currently and has good biocompatibility. In application, PLGA with a specific monomer ratio (lactic acid and glycolic acid) can be selected according to the properties of drug molecules and the requirements of the drug release rate. PLGA-based biodegradable microspheres have been studied in the field of drug delivery, including the delivery of various anticancer drugs, protein or peptide drugs, bacterial or viral DNA, etc. This review describes the basic knowledge and current situation of PLGA biodegradable microspheres and discusses the selection of PLGA polymer materials. Then, the preparation methods of PLGA microspheres are introduced, including emulsification, microfluidic technology, electrospray, and spray drying. Finally, this review summarizes the application of PLGA microspheres in drug delivery and the treatment of pulmonary and ocular-related diseases.

Mimicking the rice leaf--from ordered binary structures to anisotropic wettability.

In this paper, we report a method to fabricate a series of surfaces with large-area ordered binary arrays by controllable dewetting. The binary structure arrays consist of an ordered-stripe array and droplet-row array. In order to expand the system, polystyrene (PS) and poly(methyl methacrylate) (PMMA) are introduced in this experiment for investigation in detail. Through adjustment of the polymer solution concentration and the modified underlying pattern on substrate, the surface topographies can be controlled simply. Accordingly, three types of topographies with ordered binary arrays have been obtained by thermal annealing. These unique surfaces mimic the natural rice leaf structurally, which also displays anisotropic wettability for water droplet as natural surfaces. This method points out a new way for the manufacture of functional surfaces.

A universal approach to fabricate ordered colloidal crystals arrays based on electrostatic self-assembly.

We present a novel and simple method to fabricate two-dimensional (2D) poly(styrene sulfate) (PSS, negatively charged) colloidal crystals on a positively charged substrate. Our strategy contains two separate steps: one is the three-dimensional (3D) assembly of PSS particles in ethanol, and the other is electrostatic adsorption in water. First, 3D assembly in ethanol phase eliminates electrostatic attractions between colloids and the substrate. As a result, high-quality colloidal crystals are easily generated, for electrostatic attractions are unfavorable for the movement of colloidal particles during convective self-assembly. Subsequently, top layers of colloidal spheres are washed away in the water phase, whereas well-packed PSS colloids that are in contact with the substrate are tightly linked due to electrostatic interactions, resulting in the formation of ordered arrays of 2D colloidal spheres. Cycling these processes leads to the layer-by-layer assembly of 3D colloidal crystals with controllable layers. In addition, this strategy can be extended to the fabrication of patterned 2D colloidal crystals on patterned polyelectrolyte surfaces, not only on planar substrates but also on nonplanar substrates. This straightforward method may open up new possibilities for practical use of colloidal crystals of excellent quality, various patterns, and controllable fashions.