Selectively metallized polymeric substrates by microcontact printing an aluminum(III) porphyrin complex.

We report a simple, low-cost method for the fabrication of copper wires and contacts on a wide range of flexible, rigid, and inert polymeric substrates. This method relies on procedures to oxidize the polymeric substrates to form surface-bound carboxylic acid groups. Patterning of an aluminum porphyrin ink using microcontact printing results in the formation of an aluminum porphyrin monolayer that is covalently anchored to the oxidized polymer surface via an aluminum-carboxylate bond. We characterize this monolayer using ultraviolet-visible absorption spectra, reflection-absorption infrared spectroscopy, and contact angle measurements. Patterned aluminum porphyrin monolayers bind a Pd/Sn colloidal catalyst from solution that subsequently initiates the selective deposition of copper in an electroless plating solution. We demonstrate the fabrication of patterned copper films on a variety of both flexible and rigid polymers with minimum feature sizes of 2 microm over 2 cm(2) substrates. Measurements of electrical resistivity of copper wires fabricated on flexible poly(ethylene naphthalate) (PEN) substrates as a function of the bending radius show no negative impact on electrical performance at bending radii as small as 500 microm. Permanently damaging the PEN substrate by creasing (corresponding to a bending radius of 100 microm) results in only a modest increase in resistivity.

Templated self-assembly of glass microspheres into ordered two-dimensional arrays under dry conditions.

This paper describes a new approach to mesoscale self-assembly in which a stream of nitrogen is used to propel micrometer-scale components toward a template of patterned liquid adhesive drops. This approach combines the use of capillary forces to hold the components in place with dry processing conditions. Eliminating the use of a liquid medium to suspend components is an important goal for mesoscale self-assembly methods because it eliminates the need for special encapsulation to protect electrically functional components. We demonstrate the dry self-assembly approach by assembling 100 microm glass microspheres into a variety of 2D patterns. A study of defects in these arrays relates parameters associated with the template--density of binding sites and volume of liquid adhesive comprising the drops--to the frequency of defects arising from the incorporation of additional microspheres into the array. Optimized template parameters and self-assembly conditions yield 2D arrays with defect rates of approximately 4-5%. We also demonstrate the versatility of this self-assembly method by producing ordered binary arrays of clear and black glass microspheres.

Controlling the ON/OFF threading of a terpyridine containing [2]pseudorotaxane ligand via changes in coordination geometry.

A 1,2-bis(pyridinium)ethane type axle containing a terpyridine chelate group, when combined with 24-membered crown ethers, forms [2]pseudorotaxanes, the stability of which can be controlled by coordination of metal ions with different geometries.

Coordination polymers based on aluminum(III) porphyrins.

Aluminum(III) porphyrin carboxylate complexes have shown an affinity for a sixth nitrogenous ligand. The use of isonicotinic or nicotinic acid, which offers both a carboxylate and a nitrogen donor in the same molecule, resulted in the formation of one-dimensional (1-D) coordination polymers. The complexes and their linear oligomers have been characterized by (1)H NMR spectroscopy and nanoelectrospray ionization spectrometry. X-ray analyses confirmed the formation of the 1-D polymers in the solid state.

Aluminium(III) porphyrins as supramolecular building blocks.

Aluminium(III) porphyrin-carboxylate complexes, including a porphyrin pentamer, have been characterised by NMR spectroscopy, MALDI spectrometry and single crystal X-ray diffraction; these complexes can also be coordinated by a sixth, nitrogenous, ligand to the aluminium(III) centre.

The role of muscle receptors in the detection of movements.

This review discusses the role of muscle receptors, in particular, that of muscle spindles, in the detection of movements, both passive and active. Emphasis is placed on the importance of conditioning the muscles acting at a joint before making measurements of thresholds to passive movements, to take into account muscle's thixotropic property. The detection threshold:movement velocity relation is discussed and described for a number of different joints. Implications for muscle spindles are considered from the generalisation that, when expressed in terms of proportion of muscle fascicle length change, detection thresholds are about the same at different joints. It is concluded that the available data supports the view that muscle spindles lie in parallel with only a portion of a muscle fascicle and not the whole fascicle. At the elbow joint, where it has been tested, movement detection threshold is lower during passive movements than during contraction of elbow muscles. Both peripheral mechanisms and mechanisms operating within the central nervous system may be responsible for the rise in threshold. The signalling of movements by spindles during a contraction raises the question of how the central nervous system is able to extract the length signal under such circumstances, given that there is likely to be co-activation of alpha and gamma motoneurones. The evidence for a central subtraction of fusimotor-evoked impulses and some recent experiments relevant to this idea are described. In conclusion, a number of points of uncertainly have been revealed in this area and these should be the subject of future experiments.

Damage to different motor units from active lengthening of the medial gastrocnemius muscle of the cat.

Slow-twitch motor units in the medial gastrocnemius muscle of the anesthetized cat were found to have an average optimum length for active tension that was 0.8 +/- 0.5 (SE) mm longer than the whole muscle optimum. For fast-twitch units (time to peak < 50 ms), the average optimum was 1.3 +/- 0.3 mm shorter than the whole muscle optimum. After the muscle had been subjected to 10 stretches while maximally activated, beginning at the whole muscle optimum length, the optimum lengths of the 27 fast-twitch motor units shifted significantly further in the direction of longer muscle lengths (mean 4.3 +/- 0.3 mm) than for the eight slow-twitch units (2.1 +/- 0.4 mm). A shift in the muscle's length-tension relation was interpreted as being due to sarcomere disruption. Statistical analysis showed that a motor unit's optimum length for a contraction, relative to the whole muscle optimum, was a better indicator of the unit's susceptibility to damage from active lengthenings than was motor unit type.

Rises in whole muscle passive tension of mammalian muscle after eccentric contractions at different lengths.

This is a report of experiments carried out on the medial gastrocnemius muscle of the anesthetized cat, investigating the effects of eccentric contractions carried out at different muscle lengths on the passive and active length-tension relationships. In one series of experiments, the motor supply to the muscle was divided into three approximately equal parts; in the other, whole muscles were used. Fifty eccentric contractions were carried out over different regions of the active length-tension curve for each partial or whole muscle. Active and passive length-tension curves were measured before and after the eccentric contractions. When eccentric contractions were carried out at longer lengths, there was a larger shift of the optimum length for active tension in the direction of longer muscle lengths and a larger fall in peak isometric tension. Passive tension was higher immediately after the eccentric contractions, and if the muscle was left undisturbed for 40 min, it increased further to higher values, particularly after contractions at longer lengths. A series of 20 passive stretches of the same speed and amplitude and covering the same length range as the active stretches, reduced the passive tension which redeveloped over a subsequent 40-min period. It is hypothesized that there are two factors influencing the level of passive tension in a muscle after a series of eccentric contractions. One is injury contractures in damaged muscle fibers tending to raise passive tension; the other is the presence of disrupted sarcomeres in series with still-functioning sarcomeres tending to reduce it.

Low-frequency depression of tension in the cat gastrocnemius muscle after eccentric exercise.

Subjecting a muscle to a series of eccentric contractions in which the contracting muscle is lengthened results in a number of changes in its mechanical properties. These include a fall in isometric tension that is particularly pronounced during low-frequency stimulation, a phenomenon known as low-frequency depression (LFD). Reports of LFD have not taken into account the shift in optimum length for active tension generation to longer muscle lengths that takes place after eccentric contractions. Given the length dependence of the stimulation frequency-tension curve, we tested the hypothesis that the change in this relationship after eccentric exercise is due to the shift in optimum length. We measured LFD by recording tension in response to a linearly increasing rate of stimulation of the nerve to medial gastrocnemius of anesthetized cats, over the range 0-100 pulses per second. Tension responses were measured before and after 50 eccentric contractions consisting of 6-mm stretches starting at 3 mm below optimum length and finishing at 3 mm above it. An index of LFD was derived from the tension responses to ramp stimulation. It was found that LFD after the eccentric contractions was partly, but not entirely, due to changes in the muscle's optimum length. An additional factor was the effect of fatigue. These observations led to the conclusion that the muscle length dependence of LFD was reduced by eccentric contractions. All of this means that after eccentric exercise the tension deficit at low rates of muscle activation is likely to be less severe than first thought.

Fatigue in mammalian skeletal muscle stimulated under computer control.

Functional electrical stimulation (FES) is used to provide paralyzed human subjects with postural support and a limited range of movements. Problems encountered with FES include jerky movements from tension oscillations during stimulation and rapid muscle fatigue. In this paper, we report experiments on anesthetized cats that test a new, computer-controlled method of stimulation of the muscle nerve supply, distributed across several inputs, which reduces these problems. After 5 min of continuous, distributed stimulation of the medial gastrocnemius muscle at 6 pulses per second (pps) across 6 channels, tension fell to 55.9 +/- 3.9% (SE) of its original value. In comparison, after 5 min of synchronous stimulation of one muscle portion at 36 pps, tension fell to 11 +/- 3.7%. At higher stimulation rates, 10 pps per channel (distributed) and 60 pps (synchronous), the differences in fatigue were even greater. Similar results were obtained when an intermittent, rather than a continuous, stimulation protocol was used. These findings indicate that distributed stimulation has important advantages over other methods for applications such as FES.

The medial and lateral cell groups of the sexually dimorphic area of the gerbil hypothalamus are essential for male sex behavior and act via separate pathways.

Male reptiles, birds and mammals do not copulate if the medial preoptic area (MPOA) is destroyed but the MPOA cell groups necessary for male sexual behavior were not known. Here, two cell groups essential for copulation are identified in the sexually dimorphic area (SDA) of the gerbil (Meriones unguiculatus) MPOA. Bilateral cell-body lesions of either the medial or lateral SDA eliminated mating in sexually experienced male gerbils given testosterone. Nearby MPOA lesions did not. The medial and lateral SDA affect sex behavior via separate pathways since lesioning the medial SDA on one side of the brain and the lateral SDA on the other did not stop sexual behavior.

The responses of muscle spindles to small, slow movements in passive muscle and during fusimotor activity.

We have previously shown that movement detection thresholds at the human elbow joint were less than a degree of joint rotation in the passive limb but were higher if they were measured while subjects co-contracted elbow muscles [A.K. Wise, J.E. Gregory, U. Proske, J. Physiol., 508 (1998) 325-330]. Here we report observations on the responses of muscle spindles of the soleus muscle of the anaesthetised cat to determine their ability to signal small length changes in the passive muscle and during a contraction, under conditions resembling those of the human experiments. After appropriate conditioning of the muscle to control for history effects, primary endings of muscle spindles showed thresholds to ramp stretch at 20 micrometers s-1 of between less than 5 micrometers and 15 micrometers, which translates to 0.05 degrees -0.15 degrees of human elbow joint rotation. Thresholds were much higher following conditioning to introduce slack in the muscle. Since during a voluntary contraction there is likely to be alpha:gamma co-activation, responses of spindles were also recorded during slow stretches (100 micrometers at 20 micrometers s-1) during static fusimotor stimulation, dynamic fusimotor stimulation, combined fusimotor stimulation and fusimotor plus skeletomotor stimulation. Invariably, responses to passive stretch were larger than during motor stimulation. It is concluded that spindles are sensitive enough to signal fractions of a degree of elbow joint rotation and that the rise in threshold observed during a voluntary contraction may be accounted for by the actions of fusimotor and skeletomotor axons on spindle stretch responses.

The effects of muscle conditioning on movement detection thresholds at the human forearm.

We have used the muscle history dependence of the sensitivity of muscle spindles to stretch, to provide evidence for their contribution to kinaesthesia, the sense of position and movement. Stretch sensitivity is altered depending on whether or not slack has been introduced in intrafusal fibres [13]. At the human elbow joint detection threshold was measured to passive movements applied at different speeds to the forearm after a conditioning co-contraction of muscles of the upper arm, with the arm held either flexed ('hold short') or extended ('hold long'). Test measurements were made with the elbow joint at 90 degrees. For the three speeds of movement, 2 degrees s-1, 0.2 degree s-1 and 0.02 degree s-1, after 'hold short' conditioning thresholds were lower for movements into extension, after 'hold long' conditioning they were lower for movements into flexion. It is concluded that when muscle conditioning introduces slack in the intrafusal fibres of muscle spindles, this must be taken up by the test movements before they can be detected by the subject. It means that whenever detection thresholds to passive movements are measured at a joint, the contraction history of the muscles acting at that joint must be taken into account.

Summation of responses of cat muscle spindles to combined static and dynamic fusimotor stimulation.

This is a study of the process of interaction between the responses of muscle spindles to stimulation of two fusimotor fibres. Combined stimulation of a static and a dynamic fusimotor fibre supplying the same muscle spindle in the soleus muscle of the anaesthetised cat gave a response which was larger than from stimulating each fibre separately, but less than their sum. A similar summation process was observed with pairs of static fusimotor fibres. The mean summation coefficient for the responses to stimulation of 14 pairs of static fusimotor fibres was 0.29 (range 0.14-0.52; S.D. 0.09), while for 42 static:dynamic pairs it was 0.30 (range 0.07-0.89; S.D. 0.20). Mechanisms considered for the summation process were probabilistic mixing of impulse traffic from two or more impulse generators within the terminals of the primary ending of the spindle, the spread of generator current from one encoding site to another and mechanical interactions between contracting intrafusal fibres. In an experiment where single static and dynamic fusimotor fibres were stimulated together, and then stimulation of the static fibre stopped, the size of the continuing dynamic response was larger than when the dynamic fibre had been stimulated alone. This finding suggested some kind of mechanical interaction between the contracting intrafusal fibres and implies that static and dynamic fusimotor effects within a spindle cannot be considered to be entirely independent of one another.

Can lactate-evoked cardiovascular responses be used to identify muscle ergoreceptors?

The increase in blood pressure and heart rate which accompanies muscular exercise is in part a reflex mediated by afferent nerve fibres in the group III and IV (small myelinated and unmyelinated) range. It has been reported that perfusion of lactate ions into hind limb muscles is an effective stimulus for these reflex responses. To investigate this hypothesis further, and to test adequacy of the controls used, a solution containing 15 mM lactic acid was perfused through a hind limb of urethane-anaesthetised rats, the leg's circulation being isolated from the rest of the body. During lactate perfusion, increases were seen in arterial blood pressure and heart rate. Denervation of the entire leg abolished the responses. To locate the receptors involved in the reflex, selective denervations of skin or muscle were performed. Clear responses were never seen when the leg was skinned or denervated by section of cutaneous nerves. On the other hand, responses to lactate perfusion were still seen following section of all nerves supplying the muscles of the leg, leaving the cutaneous innervation largely intact. It is concluded that perfusion of a hindlimb with lactate solutions is not an adequate technique to identify ergoreceptors in muscle.

Summing responses of cat soleus muscle spindles to combined static and dynamic fusimotor stimulation(1).

This is a study of the summation of responses of primary endings of muscle spindles to combined static and dynamic fusimotor stimulation in the soleus muscle of the anaesthetised cat. Summation, expressed as a summation coefficient, K, was measured under a variety of conditions including (1) at several, fixed muscle lengths using steady rates of stimulation, (2) using ramp-shaped increases in stimulation rates, (3) during passive stretches after muscle conditioning, and (4) during combined stretch plus stimulation. The predominant effect observed was occlusion, that is, the combined response was less than the sum of the two individual responses. The calculated mean K value for responses at fixed length was 0.156 (+/-0.005 S.E.M.). It was hypothesised that summation arose from electrotonic spread of generator current between the afferent terminals, either directly, or as a result of mechanical interactions between the contracting intrafusal fibres. Summation for responses from pairs of static fusimotor fibres gave a larger mean K value, 0.340 (+/-0.020 S.E.M.). These findings were interpreted in terms of a model of the muscle spindle where responses to dynamic fusimotor stimulation arise at one impulse generating site, and static fusimotor responses arise at another.

A comparison of the effects of concentric versus eccentric exercise on force and position sense at the human elbow joint.

It is generally accepted that our sense of limb position and movement is provided, in part, by signals from muscle spindles, while the sense of muscle force derives from signals in tendon organs. Experiments are described here, using human subjects, in which the effects of eccentric and concentric exercise of elbow flexor muscles are compared on the sense of forearm position and the sense of tension in elbow flexors. Subjects were required to compress a preloaded spring with one arm, carrying out a concentric contraction in elbow flexors, then flexors of the other arm released the spring from compression and thereby carried out an eccentric contraction. The force of the spring was adjusted to be 20% maximum voluntary contraction (MVC), and each subject carried out a minimum of 120 contractions. Position sense was measured in blindfolded subjects by placing one forearm at a set angle and asking subjects to match it by positioning the other arm. Over 4 days postexercise, subjects placed the eccentrically exercised arms in a more extended position than the concentrically exercised arm suggesting that they thought the muscle was shorter than it actually was. In a force-matching task, subjects systematically undershot the target 10% MVC with their eccentrically exercised arm. Since it is known that eccentric exercise is associated with damage to muscle fibres, it is postulated that this leads to a disturbance of muscle receptors, the muscle spindles and tendon organs.

Extrafusal and intrafusal motor units in the kitten.

In the lateral flexor digitorum longus muscle (FDL) of anaesthetized kittens aged 3-21 days, alpha (alpha) and gamma (gamma) motoneurone conduction velocities were measured together with motor unit tensions. Conduction velocity lay in the range 8-27 msec-1 for alpha motoneurones and 2-10 msec-1 for gamma motoneurones. Motor unit tetanic tensions were 3-47 mN with the largest units being 2-2.2% of whole muscle tension. The hypothesis was tested that motor axons conducting within the gamma range and presumed to be innervating the intrafusal fibres of muscle spindles, on stimulation, produced measurable tension. Stimulating gamma motoneurones in the adult produces no tension. The hypothesis was based on histological observations that while in the adult, intrafusal fibres were about one third of the size of extrafusal fibres, in kittens the two were nearly equal, both in length and diameter. It was shown by means of signal averaging during stimulation of ventral root filaments that whenever tension was recorded in the muscle an impulse could be detected in the muscle nerve conducting at alpha motoneurone tempo. It is concluded that in the kitten, despite the fact that intrafusal and extrafusal fibres are of similar size, stimulating single gamma motoneurones does not develop measurable tension.

Development of the sensory innervation of muscle spindles in the kitten.

This is a report of the changes observed in the pattern of sensory innervation of muscle spindles in hindlimb muscles of kittens during the first four weeks of life. The structural analysis, made on teased, silver-stained preparations, was complemented by a series of recordings of afferent responses of kitten spindles during ramp-and-hold stretches of the muscle. The primary endings of spindles from newborn animals showed a large degree of variability in their branching pattern and branches formed a network across the intrafusal fibres. In older animals there was less variability and lateral branches of stem axons began to encircle the intrafusal fibres. The process of maturation was characterized by a more uniform shape of the endings and more complete, evenly spaced, annulospiral terminals. Recordings of the responses of primary endings of spindles during muscle stretch showed that several features of the adult response were already present in the newborn, although the overall rate of discharge was very much lower. It was concluded that the changes observed in the structure of the sensory endings of kitten spindles did not have clearly identifiable physiological correlates. It appears that an annulospiral shape of the sensory terminals is not a necessary prerequisite for the generation of stretch responses. The predominant factor which appears to determine the responses of spindles to stretch is the maturity of the intrafusal fibres, in particular, the bag2 fibre.