Understanding the relevant permeability properties of ultrafiltration membranes is facilitated by using materials and procedures that allow a high degree of control on morphology and chemical composition. Here we present the first study on diffusion permeability through gyroid nanoporous cross-linked 1,2-polybutadiene (1,2-PB) membranes with uniform pores that, if needed, can be rendered hydrophilic. The gyroid porosity has the advantage of isotropic percolation with no need for structure prealignment. Closed (skin) or opened (nonskin) outer surface can be simply realized by altering the interface energy in the process of membrane fabrication. The morphology of the membranes' outer surface was investigated by scanning electron microscopy, contact angle, and X-ray photoelectron spectroscopy. The effective diffusion coefficient of glucose decreases from nonskin, to one-sided skin to two-sided skin membranes, much faster than expected by a naive resistance-in-series model; the flux through the two-sided skin membranes even increases with the membrane thickness. We propose a model that captures the physics behind the observed phenomena, as confirmed by flow visualization experiments. The chemistry of 1,2-PB nanoporous membranes can be controlled, for example, by hydrophilic patterning of the originally hydrophobic membranes, which allows for different active porosity toward aqueous solutions and, therefore, different permeability. The membrane selectivity is evaluated by comparing the effective diffusion coefficients of a series of antibiotics, proteins, and other biomolecules; solute permeation is discussed in terms of hindered diffusion. The combination of uniform bulk morphology, isotropically percolating porosity, controlled surface chemistry, and tunable permeability is distinctive for the presented gyroid nanoporous membranes.

Nanoporous polystyrene with hydrophilic pores was prepared from di- and triblock copolymer precursors. The precursor material was either a poly(tert-butyl acrylate)-b-polystyrene (PtBA-b-PS) diblock copolymer synthesized by atom transfer radical polymerization (ATRP) or a polydimethylsiloxane-b-poly(tert-butyl acrylate)-b-polystyrene (PDMS-b-PtBA-b-PS) triblock copolymer synthesized by a combination of living anionic polymerization and ATRP. In the latter copolymer, PS was the matrix and mechanically stable component, PtBA was converted by acidic deprotection to hydrophilic poly(acrylic acid) (PAA) providing at the same time part of the nanoporosity, and PDMS was quantitatively etched to provide additional nanoporosity. Both the deprotection of the PtBA block and the etching of PDMS were realized by one-step operations using either anhydrous hydrogen fluoride (HF) or trifluoroacetic acid (TFA). The finding that TFA can remove PDMS is important, not least as an alternative to the more hazardous HF. The investigated di- and triblock copolymer samples were of either hexagonal or lamellar morphology. The resulting nanoporous polymers were characterized by infrared spectroscopy, small-angle X-ray scattering, and scanning electron microscopy. In contact with water, all the prepared nanoporous polymers showed spontaneous water uptake close to the amounts expected from the precursor block copolymer compositions.

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We report a novel nanofabrication process via block copolymer lithography using solvent vapor annealing. The nanolithography process is facile and scalable, enabling fabrication of highly ordered periodic patterns over entire wafers as substrates for surface-enhanced Raman spectroscopy (SERS). Direct silicon etching with high aspect ratio templated by the block copolymer mask is realized without any intermediate layer or external precursors. Uniquely, an atomic layer deposition (ALD)-assisted method is introduced to allow reversing of the morphology relative to the initial pattern. As a result, highly ordered silicon nanopillar arrays are fabricated with controlled aspect ratios. After metallization, the resulting nanopillar arrays are suitable for SERS applications. These structures readily exhibit an average SERS enhancement factor of above 10(8), SERS uniformities of 8.5% relative standard deviation across 4 cm, and 6.5% relative standard deviation over 5 × 5 mm(2) surface area, as well as a very low SERS background. The as-prepared SERS substrate, with a good enhancement and large-area uniformity, is promising for practical SERS sensing applications.

Block copolymer (BC) self-assembly constitutes a powerful platform for nanolithography. However, there is a need for a general approach to BC lithography that critically considers all the steps from substrate preparation to the final pattern transfer. We present a procedure that significantly simplifies the main stream BC lithography process, showing a broad substrate tolerance and allowing for efficient pattern transfer over wafer scale. PDMS-rich poly(styrene-b-dimethylsiloxane) (PS-b-PDMS) copolymers are directly applied on substrates including polymers, silicon and graphene. A single oxygen plasma treatment enables formation of the oxidized PDMS hard mask, PS block removal and polymer or graphene substrate patterning.

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Hindlimb unweighting is a commonly used model to study skeletal muscle atrophy associated with disuse and exposure to microgravity. However, a discrepancy in findings between single fibers and whole muscle has been observed. In unweighted solei, specific tension deficits are greater in whole muscle than in single fibers. Also, metabolic enzyme activity when normalized per gram of mass is depressed in whole muscle but not in single fibers. These observations suggest that soleus muscle interstitial fluid volume may be elevated with atrophy caused by unweighting in rats. The purpose of this study was to determine if soleus muscle atrophy induced by unweighting is accompanied by alterations in muscle interstitial fluid volume and to calculate the effect of any such alterations on the muscle specific tension (N/cm2 muscle cross-sectional area). Nine female Wistar rats (200 g) were hindlimb unweighted (HU) by tail suspension. Soleus muscles were studied after 28 days and compared with those from five age-matched control (C) rats. Interstitial fluid volume ([3H]inulin space) and maximum tetanic tension (Po) were measured in vitro at 25 degrees C. Soleus muscles atrophied 58% because of unweighting (C = 147.8 +/- 2.3 mg; HU = 62.3 +/- 3.6 mg, P less than 0.001). Relative muscle interstitial fluid volume increased 107% in HU rats (35.5 +/- 2.8 microliters/100 mg wet mass) compared with the control value of 17.2 +/- 0.5 microliters/100 mg (P less than 0.001); however, absolute interstitial fluid volume (microliters) was unchanged.(ABSTRACT TRUNCATED AT 250 WORDS)