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We report an amphiphilic block copolymer via poly(ethylene glycol) methyl ether-Dlabile-poly(caprolactone)-ferrocene (mPEG-Dlabile-PCL-Fc) to deliver anticancer drug doxorubicin (DOX). Lipase Novozyme-435 was used as a catalyst for ring-opening polymerization with e-caprolactone, and an acid-sensitive Schiff base was used to connect the hydrophilic and hydrophobic parts; the ferrocene provided ferrous ions and was introduced at the end of the amphiphilic copolymer. The resulting copolymers were characterized by 1H NMR/13C NMR and could be self-assembled in an aqueous solution to form nanomicelles with PCL-Fc as a hydrophobic core and mPEG as a hydrophilic shell. Transmission electron microscopy showed that the micelles were spherical and nanosized before and after DOX loading. The blank micelles also showed good biocompatibility. The drug-loaded polymeric nanomicelles exhibited a positive anticancer effect relative to the copolymers without ferrocene; the therapeutic effect of drug-loaded micelles containing ferrocene was more obvious. In vitro drug release results also showed that the polymer had a good pH response. Confocal microscopy also showed that polymeric micelles can effectively deliver and release the drug; the polymer containing ferrocene also leads to significantly improved ROS levels in tumor cells. Ferrocene can effectively and synergistically inhibit tumor cells with DOX.

In the cytosolic environment, protein crowding and Brownian motions result in numerous transient encounters. Each such encounter event increases the apparent size of the interacting molecules, leading to slower rotational tumbling. The extent of transient protein complexes formed in live cells can conveniently be quantified by an apparent viscosity, based on NMR-detected spin-relaxation measurements, that is, the longitudinal (T1) and transverse (T2) relaxation. From combined analysis of three different proteins and surface mutations thereof, we find that T2 implies significantly higher apparent viscosity than T1. At first sight, the effect on T1 and T2 seems thus nonunifiable, consistent with previous reports on other proteins. We show here that the T1 and T2 deviation is actually not a inconsistency but an expected feature of a system with fast exchange between free monomers and transient complexes. In this case, the deviation is basically reconciled by a model with fast exchange between the free-tumbling reporter protein and a transient complex with a uniform 143 kDa partner. The analysis is then taken one step further by accounting for the fact that the cytosolic content is by no means uniform but comprises a wide range of molecular sizes. Integrating over the complete size distribution of the cytosolic interaction ensemble enables us to predict both T1 and T2 from a single binding model. The result yields a bound population for each protein variant and provides a quantification of the transient interactions. We finally extend the approach to obtain a correction term for the shape of a database-derived mass distribution of the interactome in the mammalian cytosol, in good accord with the existing data of the cellular composition.

Polyoxometalate (POM)-based metal-organic framework (MOF)-derived Co3O4/CoMoO4 nanohybrids were successfully fabricated by a facile solvothermal method combined with a calcination process, in which a Co-based MOF, that is, ZIF-67 acts as a template while a Keggin-type POM (H3PMo12O40) serves as a compositional modulator. The materials were characterized through scanning electron microscopy (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), energy-dispersive spectroscopy (EDS) mapping, and electrochemical measurements. When the Co3O4/CoMoO4 nanohybrids were applied as anode materials for lithium-ion batteries (LIBs), they display large lithium storage capacity (around 900 mAh g-1 at 0.1 A g-1) and high cycling stability, and they can also exhibit good rate performances. This work might shed some light on the POM-based MOF host-guest synthesis strategy for the preparation of polymetallic oxides for enhanced electrochemical energy storage and further applications.

The zeolitic imidazolate framework (ZIF-8), composed of zinc ion and dimethylimidazole, is widely used in drug delivery because of the easy fabrication process and the good biosafety. However, ZIF-8 suffers from low affinity to nonelectric-rich drugs and does not have surface functional groups. Here, to deliver doxorubicin (DOX) with ZIF-8 to specific target sites, DOX was first modified with a pH-sensitive linker containing two carboxyl groups to form the inactive prodrug CAD and subsequently seeded inside ZIF-8 by a 5 min mineralization process. CAD has high affinity to ZIF-8 because of the carboxyl groups and can anchor to the ZIF-8 surface to enable the surface modification with folic acid for tumor targeting. Moreover, the DOX release is precisely controlled by three steps of acidic pH response, with the dissociation of the FA layer, the breakdown of the ZIF-8 structure, and the cleavage of the pH-sensitive linker in prodrug. This novel "prodrug-ZIF-8" strategy has opened a new horizon in drug delivery.

Thermal conductivity is an essential thermodynamic data in chemical engineering applications. Liquid aliphatic oxygen-containing organic compounds are important organic intermediates and raw materials. As a result, estimating thermal conductivity of liquid aliphatic oxygen-containing organic compounds is of significance in industry production. In this study, the genetic function approximation method was applied to screen descriptors and develop a 6-descriptor linear quantitative structure-property relationship model. The entire data set of these compounds covering 1064 thermal conductivity values was divided into 694-member training set, 298-member test set, and 72-member prediction set. The average absolute relative deviation of the training set, test set, and prediction set were 4.14, 4.41, and 4.16%, respectively. Model validation and Y-randomization test proved that the developed model has goodness-of-fit, predictive power, and robustness. In addition, the applicability domain of the developed model was visualized by the Williams plot. This study can provide a convenient method to estimate the thermal conductivity for researchers in chemical engineering production.

Poly(aspartic acid) (PAA) is a biodegradable water-soluble anionic polymer that can potentially replace poly(acrylic acid) for industrial applications and has shown promise for regenerative medicine and drug delivery. This paper describes an efficient and sustainable route that uses protease catalysis to convert l-aspartate diethyl ester (Et2-Asp) to oligo(β-ethyl-α-aspartate), oligo(β-Et-α-Asp). Comparative studies of protease activity for oligo(β-Et-α-Asp) synthesis revealed α-chymotrypsin to be the most efficient. Papain, which is highly active for l-glutamic acid diethyl ester (Et2-Glu) oligomerization, is inactive for Et2-Asp oligomerization. The assignment of α-linkages between aspartate repeat units formed by α-chymotrypsin catalysis is based on nuclear magnetic resonance (NMR) trifluoacetic acid titration, circular dichroism, and NMR structural analysis. The influence of reaction conditions (pH, temperature, reaction time, and buffer/monomer/α-chymotrypsin concentrations) on oligopeptide yield and average degree of polymerization (DPavg) was determined. Under preferred reaction conditions (pH 8.5, 40 °C, 0.5 M Et2-Asp, 3 mg/mL α-chymotrypsin), Et2-Asp oligomerizations reached maximum oligo(β-Et-α-Asp) yields of ∼60% with a DPavg of ∼12 (Mn 1762) in just 5 min. Computational modeling using Rosetta software gave relative energies of substrate docking to papain and α-chymotrypsin active sites. The substrate preference calculated by Rosetta modeling of α-chymotrypsin and papain for Et2-Asp and Et2-Glu oligomerizations, respectively, is consistent with experimental results.

Many researchers reported that a sigmoid kinetic curve was obtained in oil transesterification with methanol catalyzed by CaO and gave different explanations for this formation. In this paper, heterogeneously catalyzed transesterification of soybean oil with methanol using CaO has been investigated. The solid catalyst and the liquid reaction mixture under different reaction time periods were characterized by X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, and high-performance liquid chromatography (HPLC) to reveal the formation of an S-shape kinetic curve. The appearance of calcium hydroxide, calcium methoxide, calcium glyceroxide, fatty acid calcium, diglycerides, and monoglycerides and their contributions to the kinetic curve have been discussed. The low reaction rate in the induction period can be attributed to mass transfer in this three-phase system. However, the formation of surfactants, diglycerides and monoglycerides, promotes the emulsification of the reaction mixture and numerous emulsion reactors are generated. These emulsion reactors can improve the contact of the solid catalyst with the reactants and thus accelerate the reaction.

Xanthan, a highly stable polysaccharide which is not easily degraded by most microorganisms, contains a cellulosic backbone with trisaccharide side chains composed of mannosyl-glucuronyl-mannose attached α-1,3 to alternating glucosyl residues. Different digestion strategies were first applied to demonstrate the complexity about the proteomes of Microbacterium sp. XT11 in xanthan medium and glucose medium. Significantly up-regulated proteins induced by xanthan were screened out by the label-free quantitation of the proteomes of Microbacterium sp. XT11 in xanthan medium and glucose medium. Consequently, 2746 and 2878 proteins were identified in proteomes of Microbacterium sp. XT11 in xanthan medium and glucose medium individually, which represent 80.6 and 84.4% of total protein dataset predicted to be expressed by the gene. In the list of 430 induced proteins containing the proteins specifically expressed or up-regulated in xanthan medium, 19 proteins involved in carbohydrate-active enzymes database and 38 proteins annotated with transporter activity were critical in the degrading pathway of xanthan. Four CAZymes (GH3, GH38, GH9, and PL8) and one ABC transporter (LX1-1GL001097) were verified with quantitative real-time polymerase chain reaction. Four CAZymes (GH3, GH38, GH9, and PL8) were further verified with the enzyme assay. This study suggests a xanthan-degrading pathway in Microbacterium sp. XT11, and other potential xanthan degradation-related proteins still need further investigation.

Rapid, accurate, and real-time measurements of ocean salinity are of great importance for a host of scientific, commercial, and defense applications. We demonstrate a highly sensitive, fast-responding fiber-optic salinity sensor that integrates long-period fiber gratings (LPFGs) with ionic strength-responsive hydrogel. The submicron-thick hydrogel was synthesized via layer-by-layer electrostatic assembly of partially quaternized poly(4-vinylpyridine) (qP4VP) and poly(acrylic acid), followed by chemical cross-linking. Spectroscopic ellipsometry measurement of a hydrogel made of 37% quaternized qP4VP showed robust and reversible swelling/deswelling in solutions with salt concentrations ranging from 0.4 to 0.8 M (22.8-44.7 g/kg) around pH 8.1. The swelling/deswelling process induced large changes in the refractive index of the hydrogel, leading to resultant shift in the resonance wavelength (RW) of LPFGs. The salinity-dependent optical response of the hydrogel-coated LPFGs is in good agreement with ellipsometry measurement. LPFGs coated with the hydrogel exhibited a sensitivity of 7 nm RW shift/M (125.5 pm/‰) with a measurement time less than 5 s. The shift in the resonance wavelength correlated linearly with salt concentration, making quantification of measured salinity straightforward.

Fullerene cages are known as being able to participate in radical initiated copolymerization reactions with vinyl monomers for polymer-functionalized fullerenes. In this work, poly(N-vinylcarbazole) (PVK) was selected as a representative of electronic polymers in the functionalization of fullerene C60 by the same copolymerization reaction to yield the PVK–C60. Similarly found was that small carbon nanoparticles could also participate in the same copolymerization reaction for the nanoparticles to be surface-functionalized and -passivated by the attached PVK polymers, which are structurally adhering to the general definition on carbon dots (CDots), thus PVK–CDots. In the comparison between PVK–CDots and PVK–C60, the former was found to be more absorptive and therefore more effective in photon harvesting across the visible spectral region and also brightly fluorescent, orders of magnitude more so than the latter. Similar to the PVK–C60 and C60 cages in general, the PVK–CDots exhibited significant photoinduced electron accepting characteristics and, at the same time, also extraordinary electron donating abilities that are not available to fullerenes. Because fullerene-based composites with electronic polymers including PVK have found significant applications in optoelectronic devices and systems, the prospect of CDots represented by the PVK–CDots for similar purposes is discussed.