A Novel DNA Synthesis Platform Design with High-Throughput Paralleled Addressability and High-Density Static Droplet Confinement.

Using DNA as the next-generation medium for data storage offers unparalleled advantages in terms of data density, storage duration, and power consumption as compared to existing data storage technologies. To meet the high-speed data writing requirements in DNA data storage, this paper proposes a novel design for an ultra-high-density and high-throughput DNA synthesis platform. The presented design mainly leverages two functional modules: a dynamic random-access memory (DRAM)-like integrated circuit (IC) responsible for electrode addressing and voltage supply, and the static droplet array (SDA)-based microfluidic structure to eliminate any reaction species diffusion concern in electrochemical DNA synthesis. Through theoretical analysis and simulation studies, we validate the effective addressing of 10 million electrodes and stable, adjustable voltage supply by the integrated circuit. We also demonstrate a reaction unit size down to 3.16 × 3.16 µm2, equivalent to 10 million/cm2, that can rapidly and stably generate static droplets at each site, effectively constraining proton diffusion. Finally, we conducted a synthesis cycle experiment by incorporating fluorescent beacons on a microfabricated electrode array to examine the feasibility of our design.

MAPK Signaling Pathway Plays Different Regulatory Roles in the Effects of Boric Acid on Proliferation, Apoptosis, and Immune Function of Splenic Lymphocytes in Rats.

Boron is one of the essential trace elements in animals. Although boron supplementation can enhance immune function and promote cell proliferation, high-dose boron supplementation can negatively affect immune function and inhibit cell proliferation. Furthermore, its action pathway is unknown. In this study, ERK1/2, JNK, and p38MAPK signaling pathways were blocked using specific blockers to investigate the impact of low-dose and high-dose boron on proliferation, apoptosis, and immune function of lymphocytes, and the expression of genes related to cell proliferation and apoptosis in rats. The addition of 0.4 mmol/L boron did not affect the ratio of CD4+/CD8+ T cells (P>0.05), IgG and IFN-γ contents (P>0.05), the proliferation rate of lymphocytes (P>0.05), and mRNA and protein expressions of PCNA (P>0.05) in the spleen after ERK1/2 signal pathway was selectively inhibited. Moreover, the addition of 40 mmol/L boron did not affect the proportion of CD4+ T cells, contents of IgG and cytokines (IL-2 and IL-4), proliferation and apoptosis rates of lymphocytes, and expression of proliferation- and apoptosis-related genes in the spleen. Meanwhile, the addition of 0.4 mmol/l boron increased the ratio of CD4+/CD8+ T cells (P<0.05 or P<0.01), IFN-γ or IgG contents (P<0.05), and the proliferation rate of lymphocytes (P<0.05) in spleen after selective inhibition of JNK or p38MAPK signaling pathways, while the protein expression of Caspase-3 decreased (P<0.05 or P<0.01). Furthermore, 40 mmol/L boron decreased the proportion of lymphocyte subsets, cytokine contents, proliferation rate of lymphocytes, and mRNA and protein expressions of PCNA. In contrast, the mRNA and protein expressions of Caspase-3 and protein expression of Bax were increased. These results indicate that ERK1/2 signaling pathway mainly regulates the effects of low-dose and high-dose boron on proliferation, apoptosis, and immune function of splenic lymphocytes.

DC-Dielectrophoretic Manipulation and Isolation of Microplastic Particle-Treated Microalgae Cells in Asymmetric-Orifice-Based Microfluidic Chip.

A novel direct-current dielectrophoretic (DC-DEP) method is proposed for the manipulation and isolation of microplastic particle (MP)-treated microalgae cells according to their dielectric properties in a microfluidic chip. The lateral migration and trajectory of the microalgae cells were investigated. To induce stronger DC-DEP effects, a non-homogeneous electric-field gradient was generated by applying the DC electric voltages through triple pairs of asymmetric orifices with three small orifices and one large orifice located on the opposite microchannel wall across the whole channel, leading to the enhanced magnitude of the non-uniform electric-field gradient and effective dielectrophoretic area. The effects of the applied voltage, the polystyrene (PS) adsorption coverage, and thickness on the DC-DEP behaviors and migration were numerically investigated, and it was found that the effect of the PS adsorption thickness of the Chlorella cells on the DC-DEP behaviors can be neglected, but the effect on their trajectory shifts cannot. In this way, the separation of 3 µm and 6 µm Chlorella coated with 100% PS particles and the isolation of the Chlorella cells from those coated with various coverages and thicknesses of PS particles was successfully achieved, providing a promising method for the isolation of microalgae cells and the removal of undesired cells from a target suspension.

Oxygen inhibition of free-radical polymerization is the dominant mechanism behind the "mold effect" on hydrogels.

Hydrogel surfaces are of great importance in numerous applications ranging from cell-growth studies and hydrogel-patch adhesion to catheter coatings and contact lenses. A common method to control the structure and mechanical/tribological properties of hydrogel surfaces is by synthesizing them in various mold materials, whose influence has been widely ascribed to their hydrophobicity. In this work, we examine possible mechanisms for this "mold effect" on the surface of hydrogels during polymerization. Our results for polyacrylamide gels clearly rule out the effect of mold hydrophobicity as well as any thermal-gradient effects during synthesis. We show unequivocally that oxygen diffuses out of certain molding materials and into the reaction mixture, thereby inhibiting free-radical polymerization in the vicinity of the molding interface. Removal of oxygen from the system results in homogeneously cross-linked hydrogel surfaces, irrespective of the substrate material used. Moreover, by varying the amount of oxygen at the surface of the polymerizing solutions using a permeable membrane we are able to tailor the surface structures and mechanical properties of PAAm, PEGDA and HEMA hydrogels in a controlled manner.

Versatile Surface Modification of Hydrogels by Surface-Initiated, Cu0-Mediated Controlled Radical Polymerization.

Surface-initiated controlled radical polymerization mediated by a Cu0 plate (SI-Cu0 CRP) emerges as a versatile and efficient method for the functionalization of the exposed surfaces of hydrogels with a wide variety of polymer brushes. When a Cu0 plate is placed in contact with initiator-bearing hydrogel surfaces in the presence of ligand and monomer and under ambient conditions, it rapidly consumes dissolved oxygen from the reaction mixture, further acting as a source of catalyst and leading to the rapid growth of hydrogel-bound polymer chains. Three types of functional surfaces have been prepared as examples of the wide range of potential materials that can be synthesized in this way, including a hydrogel with a protective, hydrophobic surface, a lubricious hydrogel, as well as a hydrogel with thermally switchable frictional properties.

Linking Friction and Surface Properties of Hydrogels Molded Against Materials of Different Surface Energies.

Biological tissues subjected to rubbing, such as the cornea and eyelid or articular cartilage, are covered in brushy, hydrated mucous structures in order to reduce the shear stress on the tissue. To mimic such biological tissues, we have prepared polyacrylamide (PAAm) hydrogels with various concentrations of un-cross-linked chains on their surfaces by synthesizing them in molds of different surface energies. The selected molding materials included hydrophilic glass, polyoxymethylene (POM), polystyrene (PS), polyethylene (PE), polypropylene (PP), and polytetrafluoroethylene (PTFE). After synthesis, demolding, and equilibration in water, the elastic modulus at the hydrogel surface decreased with increasing water contact angle of the mold. The softer, brushier surfaces did not completely collapse under compressive pressures up to 10 kPa, remaining better hydrated compared to their denser, cross-linked analogs. The hydrogels with brushier surfaces displayed an order of magnitude lower coefficient of friction than the cross-linked ones, which is attributed to the ability of their near-surface regions to retain larger amounts of liquid at the interface. The characteristic speed-dependent friction of the denser, cross-linked hydrogel surface is compared to the speed-independent friction of the brushy hydrogels and discussed from the perspectives of (elasto)hydrodynamic lubrication, permeability, and shear-induced hydrodynamic penetration depth.

Creating an Interface: Rendering a Double-Network Hydrogel Lubricious via Spontaneous Delamination.

Hydrogels engineered with specific surface chemistries and architectures have found myriad applications in electronics, biofouling, biolubrication, and biomedical devices. Free-radical polymerization is frequently employed to construct covalently bonded networks in hydrogels, and any inhibition of the radical reactions by oxygen at the surface of the reaction mixture is generally undesirable. The internal stress caused by the resulting gradient in the cross-linking density during polymerization can give rise to a physical deformation of the surface, resulting in wrinkles, creases, or cracks. However, this oxygen-inhibition effect can be positively utilized to create finely controlled surface structures. We describe a two-step cross-linking strategy for the fabrication of a P(AAm-AMPS)/alginate double-network hydrogel in the presence of air, which enables greater independent control over surface chemistry and functionality than homogeneously processed conventional double-network hydrogels. An alginate-rich "skin" layer is spontaneously delaminated due to the mechanical instability and osmotic mismatch between the swollen double-network hydrogel matrix and the rigid "skin" layer. Removal of the "skin" layer results in a lubricious surface with coefficients of friction as low as 0.02 against glass in aqueous solutions. The proposed strategy can be generalized to develop soft functional materials with unique structures and properties and precise control over the surface chemistry.

A Noncontact Dibutyl Phthalate Sensor Based on a Wireless-Electrodeless QCM-D Modified with Nano-Structured Nickel Hydroxide.

Dibutyl phthalate (DBP) is a widely used plasticizer which has been found to be a reproductive and developmental toxicant and ubiquitously existing in the air. A highly sensitive method for DBP monitoring in the environment is urgently needed. A DBP sensor based on a homemade wireless-electrodeless quartz crystal microbalance with dissipation (QCM-D) coated with nano-structured nickel hydroxide is presented. With the noncontact configuration, the sensing system could work at a higher resonance frequency (the 3rd overtone) and the response of the system was even more stable compared with a conventional quartz crystal microbalance (QCM). The sensor achieved a sensitivity of 7.3 Hz/ppb to DBP in a concentration range of 0.4-40 ppb and an ultra-low detection limit of 0.4 ppb of DBP has also been achieved.

Hydrogels with a Memory: Dual-Responsive, Organometallic Poly(ionic liquid)s with Hysteretic Volume-Phase Transition.

We report on the synthesis and structure-property relations of a novel, dual-responsive organometallic poly(ionic liquid) (PIL), consisting of a poly(ferrocenylsilane) backbone of alternating redox-active, silane-bridged ferrocene units and tetraalkylphosphonium sulfonate moieties in the side groups. This PIL is redox responsive due to the presence of ferrocene in the backbone and also exhibits a lower critical solution temperature (LCST)-type thermal responsive behavior. The LCST phase transition originates from the interaction between water molecules and the ionic substituents and shows a concentration-dependent, tunable transition temperature in aqueous solution. The PIL's LCST-type transition temperature can also be influenced by varying the redox state of ferrocene in the polymer main chain. As the polymer can be readily cross-linked and is easily converted into hydrogels, it represents a new dual-responsive materials platform. Interestingly, the as-formed hydrogels display an unusual, strongly hysteretic volume-phase transition indicating useful thermal memory properties. By employing the dispersing abilities of this cationic PIL, CNT-hydrogel composites were successfully prepared. These hybrid conductive composite hydrogels showed bi-stable states and tunable resistance in heating-cooling cycles.

Thermoresponsive Semi-IPN Hydrogel Microfibers from Continuous Fluidic Processing with High Elasticity and Fast Actuation.

Hydrogels with rapid and strong response to external stimuli and possessing high elasticity and strength have been considered as platform materials for numerous applications, e.g., in biomaterials engineering. Thermoresponsive hydrogels based on semi-interpenetrating polymer networks (semi-IPN) featuring N-isopropylacrylamide with copolymers of poly(N-isopropylacrylamide-co-hydroxyethyl methacrylate) p(NIPAM-HEMA) chains are prepared and described. The copolymer was characterized by FTIR, NMR, and GPC. The semi-IPN structured hydrogel and its responsive properties were evaluated by dynamic mechanical measurements, SEM, DSC, equilibrium swelling ratio, and dynamic deswelling tests. The results illustrate that the semi-IPN structured hydrogels possess rapid response and high elasticity compared to conventional pNIPAM hydrogels. By using a microfluidic device with double coaxial laminar flow, we succeeded in fabricating temperature responsive ("smart") hydrogel microfibers with core-shell structures that exhibit typical diameters on the order of 100 µm. The diameter of the fibers can be tuned by changing the flow conditions. Such hydrogel fibers can be used to fabricate "smart" devices, and the core layer can be potentially loaded with cargos to incorporate biological function in the constructs. The platforms obtained by this approach hold promise as artificial "muscles", and also "smart" hydrogel carriers providing a unique biophysical and bioactive environment for regenerative medicine and tissue engineering.

Highly Swellable, Dual-Responsive Hydrogels Based on PNIPAM and Redox Active Poly(ferrocenylsilane) Poly(ionic liquid)s: Synthesis, Structure, and Properties.

Highly swellable, dual-responsive hydrogels, consisting of thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) and redox-responsive poly(ferrocenylsilane) (PFS) based poly(ionic liquid)s (PILs) are formed by photo-polymerization. PFS chains bearing cross-linkable vinylimidazolium (VIm) side groups are copolymerized with NIPAM in aqueous solutions under ultraviolet light (λ = 365 nm) in the presence of a photoinitiator. The PFS-PILs serve as a macro-cross-linker and also provide redox responsiveness. The swelling ratio, morphology, and lower critical solution temperature (LCST) of the hydrogels are studied as a function of the PNIPAM/PFS ratio. The value of the LCST is dependent on the choice of the counterion of the PIL and the PNIPAM/PFS ratio. The hydrogel is employed as a reducing environment for the in situ fabrication of gold nanoparticles (AuNPs), forming AuNP-hydrogel composites. The localized surface plasmon resonance peak of the as-synthesized Au nanoparticles inside the hydrogel could be tuned by altering the temperature.

Enhanced Dibutyl Phthalate Sensing Performance of a Quartz Crystal Microbalance Coated with Au-Decorated ZnO Porous Microspheres.

Noble metals addition on nanostructured metal oxides is an attractive way to enhance gas sensing properties. Herein, hierarchical zinc oxide (ZnO) porous microspheres decorated with cubic gold particles (Au particles) were synthesized using a facile hydrothermal method. The as-prepared Au-decorated ZnO was then utilized as the sensing film of a gas sensor based on a quartz crystal microbalance (QCM). This fabricated sensor was applied to detect dibutyl phthalate (DBP), which is a widely used plasticizer, and its coating load was optimized. When tested at room temperature, the sensor exhibited a high sensitivity of 38.10 Hz/ppb to DBP in a low concentration range from 2 ppb to 30 ppb and the calculated theoretical detection limit is below 1 ppb. It maintains good repeatability as well as long-term stability. Compared with the undecorated ZnO based QCM, the Au-decorated one achieved a 1.62-time enhancement in sensitivity to DBP, and the selectivity was also improved. According to the experimental results, Au-functionalized ZnO porous microspheres displayed superior sensing performance towards DBP, indicating its potential use in monitoring plasticizers in the gaseous state. Moreover, Au decoration of porous metal oxide nanostructures is proved to be an effective approach for enhancing the gas sensing properties and the corresponding mechanism was investigated.

Breathing pores on command: redox-responsive spongy membranes from poly(ferrocenylsilane)s.

Redox-responsive porous membranes can be readily formed by electrostatic complexation between redox active poly(ferrocenylsilane) PFS-based poly(ionic liquid)s and organic acids. Redox-induced changes on this membrane demonstrated reversible switching between more open and more closed porous structures. By taking advantage of the structure changes in the oxidized and reduced states, the porous membrane exhibits reversible permeability control and shows great potential in gated filtration, catalysis, and controlled release.

Color-encoded microcarriers based on nano-silicon dioxide film for multiplexed immunoassays.

Multiplexed analysis allows researchers to obtain high-density information with minimal assay time, sample volume and cost. Currently, microcarrier or particle-based approaches for multiplexed analysis involve complicated or expensive encoding and decoding processes. In this paper, a novel optical encoding technique based on nano-silicon dioxide film is presented. Microcarriers composed of thermally grown silicon dioxide (SiO(2)) film and monocrystalline silicon (Si) substrate were fabricated. The nano-silicon dioxide film exhibited unique surface color by low-coherence interference. Hence the colors can be used for encoding at least 100 microcarriers loaded with films of different thickness. We demonstrated that color-encoded microcarriers loaded with antigens could be used for multiplexed immunoassays to detect goat anti-human IgG, goat anti-mouse IgG and goat anti-rabbit IgG, with fluorescent detection as the interrogating approach. This microcarrier-based method also exhibited improved analytical performance compared with a microarray technique. This approach will provide new opportunities for multiplexed target assay development.

Template free synthesis of hollow ball-like nano-Fe2O3 and its application to the detection of dimethyl methylphosphonate at room temperature.

This paper is focused on the template-free synthesis of nanosized ferric oxide (nano-Fe(2)O(3)) and its application in quartz crystal microbalance (QCM) resonators to detect dimethyl methylphosphonate (DMMP), a simulant of Sarin. The X-ray diffraction (XRD) patterns confirm that the synthesized samples are made of Fe(2)O(3) and the scanning electron microscopy (SEM) pictures show that the samples have ball-like shapes. The DMMP sensors with a sensing film of hollow ball-like and solid ball-like Fe(2)O(3) are fabricated and their sensing characteristics are compared. The sensitivity of the hollow ball-like Fe(2)O(3) sensor is more than 500% higher than the one of the solid ball-like Fe(2)O(3) sensor. The hollow ball-like nano-Fe(2)O(3) can be synthesized by a novel low temperature hydrothermal method. The sensors with the hollow ball-like Fe(2)O(3) film perform well in a range of 1 to 6 ppm, with a sensitivity of 29 Hz/ppm at room temperature, while the appropriate recoverability and selectivity are maintained. In addition, the performance of different thicknesses of the sensing film of the hollow ball-like nano-Fe(2)O(3) is investigated and the optimized relative film thickness of the hollow ball-like nano-Fe(2)O(3) is found to be 20 µg/mm(2).