The role of electrostatic interactions in the mechanism of peptide bond hydrolysis by a Ser-Lys catalytic dyad

General-base catalysis in the active site of serine proteasesis carried out by the imidazole side chain of a histidine. Duringformation of the transition state, an adjacent carboxylic acidgroup stabilizes the positive charge that forms on the general-basecatalyst and as a result contributes several orders of magnitudeto the catalytic efficiency of these enzymes. In the recentlydiscovered family of self-cleaving proteins exemplified by theLexA repressor of Escherichia coli, instead of the imidazoleof a histidine, the active-site general-base catalyst was foundto be the -amino of a lysine. The considerably higher capacityof the lysine side chain for proton acceptance raises interestingquestions concerning the role of electrostatic interactionsin the mechanism of proton transfer by this highly basic group.The negative charge elimination studies described here and theireffects on the k_max and pK of LexA self-cleavage are consistentwith a model in which electrostatic interactions between anacidic side chain and the general-base catalyst form a barrierto proton transfer. The implications are that the -amino group,unlike the imidazole group, is capable of effecting proton transferwithout the intervention of a countercharge.     

Color image segmentation using adaptive unsupervised clustering approach

This paper presents the Region Splitting and Merging-Fuzzy C-means Hybrid Algorithm (RFHA), an adaptive unsupervised clustering approach for color image segmentation, which is important in image analysis and in understanding pattern recognition and computer vision field. Histogram thresholding technique is applied in the formation of all possible cells, used to split the image into multiple homogeneous regions. The merging technique is applied to merge perceptually close homogeneous regions and obtain better initialization for the Fuzzy C-means clustering approach. Experimental results have demonstrated that the proposed scheme could obtain promising segmentation results, with 12% average improvement in clustering quality and 63% reduction in classification error compared with other existing segmentation approaches.     

Filler Wetting in Miscible ESBR/SSBR Blends and Its Effect on Mechanical Properties

The selective wetting behavior of silica in emulsion styrene butadiene rubber (ESBR)/solution styrene butadiene rubber (SSBR) blends is characterized by the wetting concept, which is further developed for filled blends based on miscible rubbers. It is found that not only the chemical rubber–filler affinity but also the topology of the filler surface significantly influences the selective filler wetting in rubber blends. The nanopore structure of the silica surface has been recognized as the main reason for the difference in the wetting behavior of the branched ESBR molecules and linear SSBR molecules. However, the effect of nanopore structure becomes more significant in the presence of silane. It is discussed that the adsorption of silane on silica surface constricts the nanopore to some extent that hinders effectively the space filling of the nanopores by the branched ESBR molecules but not by the linear SSBR molecules. As a result, in silanized ESBR/SSBR blends the dominant wetting of silica surface by the tightly bonded layer of SSBR molecules causes a low‐energy dissipation in the rubber–filler interphase. That imparts the low rolling resistance to the blends similar to that of a silica‐filled SSBR compound, while the ESBR‐rich matrix warrants the good tensile behavior, i.e., good abrasion and wear resistance of the blends.

     

Calcium phosphate nucleation on surface-modified PTFE membranes

Highly porous PTFE membranes are currently being used in facial reconstructive surgery. The present study aims at improving this biomaterial through creating a more bioactive surface by introducing ionic groups onto the surface. The unmodified PTFE membrane does not induce inorganic growth after immersion in simulated body fluid (SBF) for up to 4 weeks. Copolymeric grafting with acrylic acid (AAc) by means of gamma irradiation and subsequent in vitro testing in SBF reveals that this copolymer initially acts as an ion-exchange material and subsequently induces growth of a calcium phosphate phase (Ca/P=2.7) when large amounts (15%) of pAAc are introduced onto the membrane surface. This copolymer is not expected to function well from a biomaterials perspective since SEM showed the pores on the surface to be partly blocked. In contrast, the surface of monoacryloxyethyl phosphate (MAEP)-modified samples is altered at a molecular level only. Yet the modified materials are able to induce calcium phosphate nucleation when the external surface coverage is 44% or above. The initial inorganic growth on these membranes in SBF has a (Ca+Mg)/P ratio of 1.1 (presumably Brushite or Monetite). The secondary growth, possibly calcium-deficient apatite or tricalcium phosphate, has a (Ca+Mg)/P ratio of 1.5. This result is a promising indicator of a bioactive biomaterial.     

The elastic moduli and fatigue properties of canine trabecular bone tissue

The elastic modulus and fatigue properties of canine and human trabecular bone tissues (single trabeculae) were experimentally determined on a microstructural level using four-point bending cyclic test, and they were compared based on microstructural characteristics and mineral density. The results showed that canine trabecular bone tissue had significantly lower modulus and lower fatigue strength than human tissue. The observed microstructural differences between the two tissues may be more responsible for the differences, although the lower mineral density in canine tissue might also have contributed to the lower modulus and fatigue strength.     

Paraplegic standing controlled by functional neuromuscularstimulation. I. Computer model and control-system design

We have developed a planar computer model to investigate paraplegic standing induced by functional neuromuscular stimulation. The model consists of nonlinear musculotendon dynamics (pulse train activation dynamics and musculotendon actuator dynamics), nonlinear body-segmental dynamics, and a linear output-feedback control law. The model of activation dynamics is an analytic expression that characterizes the relation between the stimulus parameters (pulse width and interpulse interval) and the muscle activation. Hill's classic two-element muscle model was modified into a musculotendon actuator model in order to account for the effects of submaximal activation and tendon elasticity on development of force by the actuator. The three body-segmental, multijoint model accounts for the anterior-posterior movements of the head and trunk, the thigh, and the shank. We modeled arm movement as an external disturbance and imposed the disturbance to the body-segmental dynamics by means of a quasistatic analysis. Linearization, and at times linear approximation of the computer model, enabled us to compute a constant, linear feedback-gain matrix, whose output is the net activation needed by a dynamical joint-torque actuator. Motivated by an assumption that minimization of energy expenditure lessens muscle fatigue, we developed an algorithm that then computes how to distribute the net activation among all the muscles crossing the joint. In part II, the combined feedback control strategy is applied to the nonlinear model of musculotendon and body-segmental dynamics to study how well the body ought to maintain balance should the feedback control strategy be employed.     

Photolithographic Route to the Fabrication of Micro/Nanowires of III–V Semiconductors

Nano/microwires of semiconducting materials (e.g., GaAs and InP) with triangular cross‐sections can be fabricated by “top–down” approaches that combine lithography of high‐quality bulk wafers (using either traditional photolithography or phase‐shift optical lithography) with anisotropic chemical etching. This method gives good control over the lateral dimensions, lengths, and morphologies of free‐standing wires. The behaviors of many different resist layers and etching chemistries are presented. It is shown how wire arrays with highly ordered alignments can be transfer printed onto plastic substrates. This “top–down” approach provides a simple, effective, and versatile way of generating high‐quality single‐crystalline wires of various compound semiconductors. The resultant wires and wire arrays have potential applications in electronics, optics, optoelectronics, and sensing.     

Controlled release of bovine serum albumin using MPEG–PCL diblock copolymers as implantable protein carriers

MPEG–PCL diblock copolymers consisting of methoxy polyethylene glycol (MPEG) and poly(?‐caprolactone) (PCL) as drug carriers were synthesized by ring‐opening polymerization. It is possible to control the balance between hydrophilic and hydrophobic by changing the MPEG and the ratio of ?‐CL to MPEG. Implantable wafers were easily fabricated by the direct compression method after physical mixing of diblock copolymers and bovine serum albumin–fluorescein isothiocyanate (BSA‐FITC) as a model protein drug. The BSA release from wafers prepared by MPEG–PCL diblock copolymers were higher than that from PCL with the physical blending of MPEG. The wafers prepared by a variety of MPEG–PCL diblock copolymers exhibited the controlled BSA release profiles with a dependence on MPEG–PCL diblock copolymer compositions. In addition, the changing of MPEG and PCL molecular weights within MPEG–PCL diblock copolymer controlled the initial burst of BSA. We confirmed that the diblock copolymers could be served as protein delivery carrier in implantable wafer form. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:1561–1567, 2006     

A motion illusion from two-dimensional periodic patterns

The spatial properties of a motion illusion (the Ouchi illusion) that occurs in a stationary pattern were examined by means of a variety of two-dimensional periodic patterns (formed by multiplying pairs of various one-dimensional periodic functions). In two experiments, observers rated the magnitude of the illusion. The results showed that (1) patterns having large energy and steep saddle-shaped contrast gradients tended to generate stronger illusions, (2) the composite pattern made up of the sum of the fundamental and harmonic components exhibited a stronger illusion than either the fundamental or the harmonic pattern, (3) patterns possessing an element orientation and phase shift similar to those of a rectangular checkerboard, and with element sizes of 15-50 min in width and 4-8 min in height yielded a larger illusion, (4) equiluminant colors largely abolished the effect, and (5) blurring the boundary between the test and surround did not reduce the illusion. Interactions between spatially overlapping ON and OFF units was discussed as a possible underlying cause of this phenomenon.     

Investigating the client-related rework in building projects: The case of Singapore

Rework has become one of the most common concerns in construction projects. This study aims to investigate the client-related rework (CRR) in Singapore-based building projects. To achieve the objectives, a literature review and questionnaire survey was conducted and data were collected from 381 projects performed by 51 companies. The results confirmed that the client contributed most to rework. 41 of the 51 companies (80.4%) experienced CRR, and 226 of the 381 projects (59.3%) experienced CRR, which increased project cost by 7.1% and caused 3.3 weeks' delay on the average. Additionally, “replacement of materials by the client” was the cause with the highest frequency of occurrence, while “change of plans or scope by the client” contributed most to CRR and exerted most impact on project cost, schedule and quality performance. This study expands the literature and provides an in-depth understanding of the CRR in Singapore for both practitioners and researchers.