3D Printing of Silk Protein Structures by Aqueous Solvent‐Directed Molecular Assembly

Hierarchical molecular assembly is a fundamental strategy for manufacturing protein structures in nature. However, to translate this natural strategy into advanced digital manufacturing like three‐dimensional (3D) printing remains a technical challenge. This work presents a 3D printing technique with silk fibroin to address this challenge, by rationally designing an aqueous salt bath capable of directing the hierarchical assembly of the protein molecules. This technique, conducted under aqueous and ambient conditions, results in 3D proteinaceous architectures characterized by intrinsic biocompatibility/biodegradability and robust mechanical features. The versatility of this method is shown in a diversity of 3D shapes and a range of functional components integrated into the 3D prints. The manufacturing capability is exemplified by the single‐step construction of perfusable microfluidic chips which eliminates the use of supporting or sacrificial materials. The 3D shaping capability of the protein material can benefit a multitude of biomedical devices, from drug delivery to surgical implants to tissue scaffolds. This work also provides insights into the recapitulation of solvent‐directed hierarchical molecular assembly for artificial manufacturing.     

Effect of Hydration on Silk Film Material Properties

Effects of hydration on silk fibroin film properties were investigated for water‐annealed and MeOH‐treated samples. Hydration increased thickness by 60% for MeOH‐immersed films, while water‐annealed samples remained constant. MeOH‐immersed films showed an 80% mass loss due to water, while water‐annealed lost only 40%. O₂ permeability was higher in MeOH‐immersed films with Dk values of 10^?10 (mL O₂ · cm) · (cm^?1 · s^?1 · mmHg^?1), while those of water‐annealed films reached only one fifth of this value. All films showed a decrease in Young's modulus and increased plastic deformation by two orders of magnitude when submerged in saline solution. FT‐IR showed that β‐sheet content in water‐annealed films increased with increasing water vapor pressure, while MeOH‐immersed films showed no change.

     

Response of Human Corneal Fibroblasts on Silk Film Surface Patterns

Transparent, biodegradable, mechanically robust, and surface‐patterned silk films were evaluated for the effect of surface morphology on human corneal fibroblast (hCF) cell proliferation, orientation, and ECM deposition and alignment. A series of dimensionally different surface groove patterns were prepared from optically graded glass substrates followed by casting poly(dimethylsiloxane) (PDMS) replica molds. The features on the patterned silk films showed an array of asymmetric triangles and displayed 37–342 nm depths and 445–3 582 nm widths. hCF DNA content on all patterned films were not significantly different from that on flat silk films after 4 d in culture. However, the depth and width of the grooves influenced cell alignment, while the depth differences affected cell orientation; overall, deeper and narrower grooves induced more hCF orientation. Over 14 d in culture, cell layers and actin filament organization demonstrated that confluent hCFs and their cytoskeletal filaments were oriented along the direction of the silk film patterned groove axis. Collagen type V and proteoglycans (decorin and biglycan), important markers of corneal stromal tissue, were highly expressed with alignment. Understanding corneal stromal fibroblast responses to surface features on a protein‐based biomaterial applicable in vivo for corneal repair potential suggests options to improve corneal tissue mimics. Further, the approaches provide fundamental biomaterial designs useful for bioengineering oriented tissue layers, an endemic feature in most biological tissue structures that lead to critical tissue functions.

     

Reverse propagation of femtosecond pulses in optical fibers

We present a numerical technique for reversing femtosecond pulse propagation in an optical fiber, such that given any output pulse it is possible to obtain the input pulse shape by numerically undoing all dispersion and nonlinear effects. The technique is tested against experimental results, and it is shown that it can be used for fiber output pulse optimization in both the anomalous and normal dispersion regimes.     

Some considerations on the saturation parameter for 2- and 3-level systems in laser excited fluorescence

The parameter “saturation spectral irradiance”, defined for a spectrally continuum laser source interacting in a non-linear manner with a dilute atomic (molecular) vapor, is discussed for both 2 and 3 energy level systems. It is shown that the definition of such parameter is meaningful only when steady state conditions are warranted. For short excitation pulses, although steady state can still be attained when the optical transition is saturated, the saturation parameter cannot be evaluated from the conventional fluorescence saturation curve. Therefore, such a definition loses its meaning even for a simple 2-level system. As a consequence, serious experimental errors can occur. The same conclusions apply to a 3-level system. Several experimental possibilities of evaluating the saturation parameter are discussed. Finally, we show that when a 3-level system is compared with a 2-level system, the value of such parameter depends essentially upon the total coupling rate of the third level with the other levels.     

A review and tutorial discussion of noise and signal-to-noise ratios in analytical spectrometry—I. Fundamental principles of signal-to-noise ratios

This review consists of two parts which discuss signal-to-noise in a tutorial manner. The sources of noise, the mathematical representation of noise, and the major types of noises in emission and luminescence spectrometry are discussed. An extensive treatment of noise and signal-to-noise ratios of paired readings is given using the relation between the auto-correlation function and the spectral noise power. These signal-to-noise expressions under optimized measurement conditions are given in terms of currents and count rates as well as in terms of charge and counts for the cases of d.c. and a.c. measurements; the present treatment is limited to the cases when the background shows only either shot noise or flicker noise. Finally, the consequences of the combination of these noise sources is considered. Signal expressions for optical spectrometry are also given. Tables give the expressions for signal-to-noise ratios in the various cases.