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Fibrin Clot Structure and Function: A Novel Risk Factor for Arterial and Venous Thrombosis Chapter | 3 35
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FXIIIa. As a result, studies have shown a direct relationship between final clot structure and FXIIIa in a manner that is dependent on fibrinogen concentration [72]. FXIII deficiency, resulting in clots that are weaker and more susceptible to lysis, is a risk factor for severe bleeding and hemostatic-related diseases [73]. Little is known about the effect of excess FXIII, likely because of the complex regulation of FXIII activation and fibrinogen concentration.
FIBRINOLYSIS
Fibrin clots are meant to be temporary structures formed to stop bleeding. After the process of wound healing has started, the ridged clot must be broken down to reduce the risk of thrombosis. The process of clot breakdown or fibrinolysis is orchestrated by the plasmin system. Physiologically, plasmin’s precursor, plasminogen, circulates in the blood and binds to fibrin at specific binding sites, mainly lysine side chains [14,74,75]. Once bound to fibrin, this 92-kDa glycoprotein is converted to plasmin by one of two different activators: tissue plasminogen activator (tPA) or urokinase plasminogen activator (uPA). Plasminogen and tPA binding sites as wel l as initial plasmin cleavage sites are shown in Fig. 3.3 (left). tPA and uPA act in two different ways to produce plasmin. tPA, which is released by endothelial cells found on the lumen of blood vessels, can bind directly to fibrin [27]. As plasmin begins to degrade the clot, newly created lysine binding sites allow for further degradation of the clot [76].Iffibrin is absent, tPA is very weakly bound to plasminogen, resulting in a weak activation, but in the presence of fibrin, tPA can activate plasminogen in a highly accelerated manner [77]. This acceleration is a result of plasminogen and tPA binding sites on fibrin being close together. Conversely, uPA does not bind to fibrin under normal physiological conditions and therefore does not require fibrin to convert plasminogen into plasmin
[78].
Due to the nature of normal clot structure and lateral aggregation of fibrin protofibrils during clot formation, plasmin degradation of aC-regions occurs early in the fibrinolysis process, resulting in aC fragments [79,80]. This is followed by degradation of the coiled-coil region [81]. The resulting by-product of this degradation, found only in the presence of cross-linked fibrin, is the geg cross-linked domain termed D-dimer [82,83]. In certain cases, although Aea and Beb interactions are not covalently cross-linked like geg chains are, the central E-region is still attached to the D-dimer [79]. This and other common proteolysis products are shown in Fig. 3.3 (right). The efficiency of clot lysis is determined by clot structure and fiber diameter. Clots made from thicker fibers are more porous and less densely packed than those made from thinner fibers. The resulting architecture allows for more plasminogen and tPA integration into clots with larger pores and accelerates fibrinolysis rates [84]. Due to the fragile balance of lysis inhibitors, the speed of clot lysis is a complex combination of many different factors.
FIGURE 3.3 Plasminogen and tissue plasminogen activator (tPA) binding sites, initial plasmin cleavage sites, and common fibrinolysis products.
Schematic showing the tPA and plasminogen binding sites on a fibrin molecule as well as the initial plasmin cleavage sites (left). Binding sites for tPA and plasminogen (green arrows) are located at residues a148e160 (low affinity) and in the aC domain (392e610, high affinity), likely attaching to lysine residues in the regions [184,185]. A lysine-independent tPA binding site (blue arrows) is located at residues g312e324 [186]. Plasmin first cleaves fibrin (red scissors) at residues aK583, aK206, and aK230, which removes the entire aC-region, leaving fragment X (shown on the right). Subsequent cleavage sites are located on each chain at residues a (K78, K81, R95, R104, R110), b (K122, K133), and g (K53, K58, K62, K85, K88), all located in the coiled­coil region of fibrin [187]. Other common fibrinolysis products are shown on the right, including fragment Y (one coiled-coil is cleaved), D-D (commonly referred to as the D-dimer, in which two cross-linked D domains are left following fibrinolysis), and D-E-D (a D-dimer with an un-cross-linked E-region still attached).
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Various factors in the blood are counteracting the conversion of plasminogen to plasmin while also competing with plasminogen to bind to fibrin. These regulators include a plasminogen activator inhibitor-1 and -2 (PAI-1 and PAI-2) [27]. The most potent of these inhibitors, a described earlier, is incorporated into the clot by FXIIIa. Through this incorporation into the clot, a plasminogen binding to fibrin [74]. In addition, a
a
-AP-deficient plasma have been shown to lyse very rapidly [85]. Lysis time can be increased by the addition of a2-AP,
2
-AP rapidly inactivates plasmin , regulating fibrinolysis. Clots made with
2
but this recovery is not as efficient a regulator as FXIIIa incorporation of a
TAFI is activated by thrombin with the help of thrombomodulin [87]. Similar to a
-AP, tissue activatable fibrinolysis inhibitor (TAFI), and
2
-AP, which was
2
-AP interferes with
2
-AP into the clot directly [86].
2
-AP, FXIIIa cross-links TAFI to
2
fibrin [66]. TAFI, in its activated form, cleaves C-terminal lysine residues from fibrin, thereby inhibiting plasminogen-to­plasmin conversion by tPA. As a result, the presence of TAFIa increases the lysis time and reduces the amount of plasmin generated.
PAI-1 and PAI-2 act similarly to prevent lysis by inhibit ing tPA and/or uPA. Both PAI-1 and PAI-2 actively bind fibrin and inhibit the ability of tPA or uPA to activate plasminogen into plasmin [88]. tPA is released by platelets and endothelial cells, and is therefore most important in the regulation of lysis in platelet-rich thrombi and in areas near the blood vessel wall where endothelial cells are present. PAI-2 is typically found at high volumes in the blood only during pregnancy [89].
CLOT MECHANICS
The mechanical properties of a clot are pivotal in supporting hemostasis. A clot must be stiff enough to stem the flow of blood, yet elastic enough to promote cell migration to the site of injury. There are two main mechanisms for deformation, elastic and plastic (inelastic), and fibrin clots display properties of both [90]. Elastic deformation is seen in a wide variety of biopolymers, including collagen and actin [91]. Similar to what is found in rubber, elastic deformation is a reversible process. In biopolymers, this property allows for cells and substrates to resist mechanical changes from an applied stress. Plastic or inelastic deformation is most commonly found in metals, in which local cracking due to stress can stop the overall failure of the substrate [92,93]. Physiologically, tissues can display plastic deformation as a defense mechanism against outside stimuli. If a polymer is able to display both elastic and inelastic proper ties it is known as viscoelastic. Fibrin’s remarkable viscoelastic properties make it unique among biological and synthetic polymers [94].
To truly understand the unique mechanical properties of fibrin clots, it is important to discuss each hierarchical level of a fibrin clot, starting at the molecular level and working our way up in scale from microscopic single fibers to the macroscopic fiber network. Fibrin molecules, when extended, first unfold in the coiled-coil region, which contributes to much of the individual molecule’s elasticity [95]. While this is occurring, aC-regions are lining up and beginning to stretch. This is followed by unfolding of the D-region and E-region, which contains elastic and plastic or irreversible deformation [94].
On the protofibril level, it is believed that slipping of protofibrils past one another and possible unbinding of non­covalent bonds contribute to the viscous or irreversible deformation of the clot. Single fibrin fibers have been shown to have extreme elasticity and extensibility, withstanding stretching up to 3.3 times their original length before breaking [95]. In the presence of FXIII, this extension occurs to a lesser degree, occurring at near 2.5 times their original length before rupturing. As might be expected, the presence of FXIII also stiffens individual fibers up to twofold higher than those that are un-cross-linked, maintaining a stiffness in the megapascal range. Here it should be noted that these elastic, mechanical properties behave in a nonlinear way [93,96]. Indicative of nonlinear response is the presence of strain hardening, an increase in stiffness while strain increases, during individual fiber mani pulations [97]. In the presence of FXIII, fibrin clots still display strain hardening, though to a lesser degree than in un-cross-linked fibers [95]. This is an important phenomenon in vivo, allowing clots to be more easily deformed at low strains while becoming stiffer at higher strains, preventing damage to the clot.
At the macroscopic level, individual fibers are branched and fiberefiber interactions can occur. The elasticity of fibrin can be further understood by looking at the effect FXIII has on the stiffness of these branch points. Carlisle et al. used an atomic force microscope to study how the branch points ruptured under strain [98]. This rupture could occur either at the node of the branch point or along the fibers connected to the branch point. In the absence of FXIII, ruptures occurred
68.5% of the time at the node and 31.5% of the time along the adjoining fiber. When fibers were cross-linked, these findings were nearly opposite, with ruptures occurring 39.5% of the time at the node and 60.5% of the time along the fiber. While this shows that the presence of covalent cross-links increases the stiffness at the node, it also suggests that cross­linked fibers are weaker along the fiber than along the nodes. When we look at the clot as a whole, individual fibers begin to align when they are under a mechanical strain, resulting in a reduced number of pores as the strain is further increased
[99,100].
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The mechanical properties and structure of the clot are at a delicate balance with various other factors found in blood plasma. Thrombin concentration can greatly affect clot structure and mechanics. Domingues et al. showed that increased thrombin concentration leads to thinner fibers made from less tightly packed protofibrils [101]. Fibrin clots were also found to be less stiff with increasing concentrations of thrombin. In whole blood, incorpo ration of red blood cells (RBCs) into the clot has been shown to increase the clot viscosity while also decreasing its stiffness. DesA-fibrin, which can be produced in the presence of a snake venomederived enzyme, batroxobin, cleaves only FpA and not FpB. Clots made with desA-fibrin are two to four times less stiff and up to eight times less elastic than clots formed with thrombin, cleaving both fibrino­peptides [102,103]. This suggests that Beb interactions play an important role in clot stiffness and elasticity. This delicate balance can also be greatly affected by changes in pH, calcium concentration, and concentrations of other plasma proteins that contribute to the coagulation cascade.
ALTERNATIVE mRNA FIBRINOGEN SPLICING
Two common fibrinogen variants occur due to alternative splicing in the mRNA transcription, which results in mu­tations on the a chain (fibrinogen-420) or the g chain (fibrinogen g
0
). Fibrinogen-420 is found at normal conc entratio ns of 1%e2% of the total fibrinogen concentration in b lood plasma [104]. Fibrinogen-420 gets its name from the high er molecular mass, 420 kDa, compared with the more abundant form of fibrinogen, which has a mo lecula r mass of 340 kDa [105]. The additional molecular mass comes from each of the normal a chains being replaced by an extended a chain (a
). This extended a chain leads to two additional globular domains now found at the C terminus named aEC
E
(Fig. 3.4, left). Although this additional globular domain does not contain a fibrin binding pocket similar to those found in the C terminus of the g and b chains, it does contain a binding site for b
-integrins, suggesting that it plays a role in
2
cellular adh esion [106]. Structurally, clots f ormed with purified fibrinogen-420 show less lateral aggregation than those formed with fibrinogen-340, which leads to thinner fibers that ar e more h ighl y branc he d.
Fibrinogen g chain found in normal fibrinogen (gA) contains 411 amino acid residues, whereas the g During transcription of the g additional amino acids (g heterodimer, gA/g at very low concentrations in normal blood plasma, mainly <1%. The g
0
is a much more abundant variant, found at normal concentrations of 8%e15% in blood plasma. The g
0
chain, the four terminal ends of the g chain (g408e411) are lost and replaced with 20
0
408e427), which are more negatively charged [30,107]. The majority of this variant occurs in a
0
, in which only one of the two g chains contains the g0sequence. The homodimer, g0/g0, is found only
0
mutation is found in the D-region and may
0
chain contains 427 residues.
interfere with DeD binding during polymerization [108]. These variants are shown in Fig. 3.4 (right).
0
The g
chain has also been shown to have a high binding affinity for thrombin [108]. It has been reported that this high-
affinity binding leads to decreased thrombin activity [109]. It should be noted, however, that g
0
does not inhibit FpA
cleavage from fibrinogen or FXIII activation, possibly even enhanci ng its activation. It has been proposed that fibrinogen
0
g
acts as a modulator of thrombin activity, specifically inhibiting acti vity driven through thrombin exosite II [110].Asa
result, g
0
does not have a direct inhibitory effect on fibrin clot formation due to its thrombin binding affinity and is believed
to be largely directed toward the intrinsic pathway through inhibition of FVIIIa and FVa [111,112].
FIGURE 3.4 Alternative fibrinogen mRNA splice variants. Schematic of fibrinogen-420 showing the extended aC-region (aEC, left). On the right are
shown the g splice variants, with one side of the fibrinogen molecule having the extended g chain (gA/g molecule having the extended g chain (g
0/g0
fibrinogen).
0
fibrinogen) and both sides of the fibrinogen
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Structurally, clots made from purified gA/g0have been shown to undergo altered polymerization, with resulting clots containing thinner fibers, a less porous architecture, and increased branching compared with clots made from gA/gA
[113e115]. Furthermore, it has been shown that protofibril packing of clots made from gA/g
0
contributes to the decrease in fiber radius [101]. This is contradictory to what would be expected from decreased thrombin activity since decreased thrombin activity would lead to larger fibers. Some of these results may be explained by studies looking into early fibrin oligomer and protofibril formation. Allan et al. showed that g
0
directly interferes with early fibrin polymerization, resulting in fibers that are thinner and mechanically weaker, but are more resistant to lysis [115]. The reduced lysis is due to reduced plasminogen and tPA binding leading to reduced plasmin generation [116].
FIBRIN CLOT STRUCTURE AND CORONARY ARTERY DISEASE
One of the major new developments in hemostasis and thrombosis research has been the recognition that the structure of the fibrin clot is an important player in determining risk of thrombotic vascular occlusion. The reasons for this are that the structure of the fibrin network determines the mechanical properties of the clot and its resistance to deformation and embolization. Furthermore, fibrin structure also regulates clot contractibility, its resistance to fibrinolysis by the plasmin generation system, interactions with blood cells during clotting, and interactions with other cells during processes involved in tissue repair. Fibrin clot structure has been implicated in thrombosis of both the arterial and the venous circulation, each of which is discussed in further detail later. Confocal micrographs of a loose and a dense fibrin clot are shown in Fig. 3.5.
The first studies showing a link between fibrin clot structure and risk of thrombosis were of fibrin clot structure in patients with CAD and MI. It was found that patients with MI produced clots that were denser, with smaller pores and increased resistance to fibrinolysis [117,118]. These early studies indicated that in patients with thrombosis and cardio­vascular occlusion, the structure of the fibrin clot was abnormal and contributed to the pathophysiology of cardiovascular disease.
Studies from our laboratory further showed that clot structure abnormalities also occur in the first-degree relatives of patients with CAD [119]. First-degree relatives of patients with CAD produced clots with reduced pore size and increased fiber branching compared with healthy age- and sex-matched controls. These studies suggest that patients with CAD may be predisposed to clot abnormalities that contribute to the increased risk of thrombosis. In support of this, studies of the heritability of fibrin clot structure in monozygous compared with heterozygous twins showed that as much as around 40% of the variation in clot structure is determined by genes, while the remaining 60% of the variation is determined by the environment [120]. Which genes contribute to this regulation of clot structure remains to be established.
It is of interest to note that such relatively high degree of heritability exists for a complex molecular phenotype like clot structure, which is the product of many factors from the coagulation system acting together to form the three-dimensional clot structure. In agreement with the significant heritability of complex biological and pathological pathways, high contributions of heritability have also been found in activation products of the coagulation cascade, including thrombineantithrombin complex, prothrombin fragment 1þ2, and cross-linked fibrin degradation product D-dimer [121].
While there is considerable genetic control of fibrin clot structure, which may help to explain the predisposition of patients with cardiovascular disease to thrombosis, this naturally does not preclude the beneficial effects of treatment
FIGURE 3.5 Confocal images of loose
and densely packed clots. Representative confocal micrographs of purified fibrin clots with loosely (left) and densely (right) packed fibers. Densely packed fibrin clots are asso­ciated with an increased risk of thrombosis in both the venous and arterial circulation. Both clots are imaged at the same magnification. Original scale of each micrograph is 160 160 mm. Images courtesy of Fraser
Macrae.
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directed toward clot structure. For example, statins, aspirin, and clopidogrel have all been reported to have a beneficial impact on clot structure in patients with cardiovascular disease; more about this later. Further studies are required to determine the mechanisms by which clot structure is regulated by genes. While genetic polymorphisms in fibrinogen and FXIII contribute to changes in clot structure [71,122,123], it is unlikely that they fully explain the genetic regulation of clot structure [124].
Studies have shown that a number of coagulation proteins are present in the atherosclerotic plaque [125]. Significant colocalization of FXII and fibrinogen has been shown in atherosclerotic plaque specimens obtained by atherectomy [126]. These findings suggest that coagulation factors and fibrin may contribute to plaque morphology and development. It also opens up the possibility that fibrin or other coagulation or fibrinolytic factors may affect plaque stability and possible rupture [127,128]. The mechanism(s) by which fibrin and coagulation factors recruit to the atherosclerotic plaque is not entirely clear. It may be that fibrin binds to monocytes and macrophages that infiltrate the plaque. Alternative ly, or in addition, subclinical plaque lesions may trigger clot formation without complete occlusion of the coronary artery, after which the formed fibrin clot is incorporated into the growing plaque. Furthermore, platelets incorporated into the clot and atherosclerotic plaques contain fibrinogen stored in the alpha granules [129]. Further studies into the role of fibrin and coagulation proteins in atherosclerosis and plaque formation are required to investigate mechanisms involved in some of these processes.
FIBRIN CLOT STRUCTURE AND VENOUS THROMBOSIS
Studies have indicated that fibrin clot structure is altered not only in arterial thrombotic diseases, but also in venous thromboembolic diseases. Patients with DVT produced clots with smaller pores that were more resistant to fibrinolysis compared with control clots [130]. Furthermore, the first-degree relatives of these patients also showed clot abnormalities compared with controls, in accordance with the reported heritability of fibrin clot structure and function [120]. Interest­ingly, patients with DVT who also developed pulmonary embol ism showed clots that were less compact and lysed more readily compared with those from patients with DVT alone [130]. These findings suggest that clot structure may play a role in the risk of clot embolization that occurs following DVT. In addition, studies show that clots from patients with pul­monary embolism differed from those with DVT alone by the accelerated establishment of viscoelastic properties [131]. How exactly the early establishment of clot viscoelastic properties increases the risk for clot embolization remains to be elucidated.
Venous thrombi are typically rich in fibrin and RBCs. Fibrin cross-linking by FXIIIa and clot elastic properties have been shown to play an important role in the retention of RBCs by the clot. In normal cross-linked clots, RBCs are retained inside the clots when they retract. Clot retraction is a physiological mechanism that follows clot formation. Activated platelets pull on the fibrin fibers and reduce the size of the clot, making it more compact [132]. Aleman et al. showed that clots made from mice that do not support fibrin cross-linking by FXIIIa (FXIII-deficient mice and fibrinogen g390e396A mice in which the FXIII binding site is mutated) retain many fewer RBCs during clot retraction [133]. Thrombus size was reduced due to the smaller number of RBCs retained, and human clots deficient in FXIII also retained fewer RBCs [133]. In a follow-up study, Byrnes et al. investigated the mechanism by which FXIII regulates RBC retention in the clot. FXIIIa does not appear to directly cross-link the RBC with fibrin, but cross-linking retains RBCs by strengthening the mechanical properties of fibrin, particularly through cross-linking of the fibrin a chains [134].
Around 20%e40% of patients with a DVT develop postthrombotic syndrome. Postthrombotic syndrome is a long-term complication due to residual vascular occlusion and may lead to limb ulceration. Studies showed augmented clot structure abnormalities in patients with postthrombotic syndrome, which may contribute to long-term complications [135]. Further studies are required to investigate the role of fibrin clot structure in pathological processes that underpin the postthrombotic syndrome and ulceration.
Air pollution has been reported to increase the risk of venous as well as atherothrombotic disease. Some of the increased risk of thrombosis by air pollution could be mediated through abnorm al clot structure. Studies by Metassan et al. have shown that particulate matter obtained from air pollution and diesel exhaust is capable of inducing changes in fibrin clot structure, leading to clots that are more tightly packed, with smaller pores and increased resistance to fibrinolysis [136]. However, in young healthy individuals who were transiently exposed to a controlled amount of diesel exhaust, while exercising moderately in an exposure chamber for 2 h, postexposure clot structure did not change compared with pre­exposure samples [137]. These data are in some way reassuring, as they suggest that healthy individuals may not be at increased risk for abnormal clots, if exposed to air pollution for a short period of time. In a study in patients with venous thrombosis, Pan et al. showed that patients with previous DVT living close to busy roads showed denser and compact clot structures compared with patients living farther away, while no changes were found for control subjects with high exposur e compared with low exposure. Together, these data indi cate that high levels of air poll ution provoke prothrombotic changes
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in clot structure in patients who are at risk for thrombosis, whereas healthy subjects remain unaffected [138]. Changes in clot structure represent a potential mechanism by which air pollution contributes to the risk of thrombosis in patients with previous thrombosis.
ROLE OF SMOKING, DIABETES, AND GLYCATION
In addition to the aforementioned effects of air pollution on clot structure, a number of other risk factors have been associated with prothrombotic clot alterations. Smoking is one of the strongest risk factors for atherothrombotic disease and has been associated with clear alterations in clot structure. In a group of healthy volunteers, smoking had acute effects on clots, producing thinner fibers, increased number of fibers per area in the clot, and increased maximum turbidity compared with nonsmokers [139]. In addition, clots were significantly stiffer after smoking as measured by thromboelastography
[139]. In a large group of patients with type 2 diabetes mellitus, smoking was significantly associated with prothrombotic
clot structural changes, independent of the patients’ gender [140]. Interestingly, Kovács et al. found that thrombi obtained by thromboaspiration in patients with acute MI showed a higher fibrin content in smokers compared with nonsmokers
[141]. In a separate study, Silvain et al. showed that thrombi obtained by thromboaspiration from patients with ST-segment
elevation MI were composed largely of fibrin (56%), followed by a minor contribution by platelets (17%), RBCs (12%), cholesterol (5%), and white blood cells (1.5%). In addition, the relative fibrin content of the thrombus was positively correlated with ischemic time [142]. These studies clearly show the importance of fibrin in coronary artery thrombosis, and warrant further studies into fibrin clot structure in patients with CAD. Furthermore, these studies indicate that some of the prothrombotic effects of smoking are mediated through fibrin and clot structure.
Studies have shown clear links between both type 1 and type 2 diabetes and abnormal, prothrombotic clot structures. Several mechanisms that drive these prothrombotic clot changes have also been identified. Jörneskog et al. was the first to show that clot porosity was reduced, indicative of a more compact clot structure, in a small study of 20 patients with type 1 diabetes compared with healthy control subjects [143]. Carr et al. showed that the clot elastic modulus was significantly increased in patients with chest pain and diabetes, compared with those without diabetes or normal controls [144]. In a larger study of 150 patients with type 2 diabetes compared with 50 controls, Dunn et al. showed that fibrinogen purified from patients with diabetes produced clots with reduced pore size, increased number of fiber branch points, and increased fiber density compared with those produced from fibrinogen from healthy controls. Furthermore, the prothrombotic changes correlated significantly with HbA1C (glycated hemoglobin) in the patients, a sensitive indicator of the glycemic index [145].
In a second study, Dunn et al. showed that the fibrinogen protein in patients with diabetes showed signs of glycation, particularly of the Bb and g chains, as determined by mass spectrometry [146]. It was also found that clots produced with fibrinogen from patients with type 2 diabetes were slower to lyse, bound tPA and plasminogen with lower affinity, supported less plasmin generation, and incorporated more a comprehensive studies of the effects of glycation in diabetes on fibrin clot structure and function as of this writing, and they clearly point to a mechanism by which increased glycation of the fibrinogen molecule in diabetes incurs prothrombotic changes at the level of the fibrin network.
The glycation of fibrinogen in diabetes can be reversed by improved glycemic control as shown in patients with uncontrolled diabetes treated with insulin by Pieters et al. [147]. However, no differences were observed in the clot structure characteristics between patients with diabetes and controls in this study. The reasons for this are unclear, but may be due to the relatively high fibrinogen concentrations in both patients and controls in this study, by itself a strong regulator of clot structure, which may have outweighed any effects of glycation on clot structure.
Diabetic retinopathy, a microvascular complication of diabetes, has been associated with denser clots that are slower to lyse [148]. Patients with diabetes are also at increased risk for macrovascular disease. Indeed, in patients with CAD, type 2 diabetes has been shown to exacerbate prothrombotic clot alterations [149,150]. In a large study of 875 patients, clot structure was further impaired in women compared with men when both had type 2 diabetes [140]. These studies indicate that abnormal clot structure is one of the mechanisms by which risk of thrombosis is increased in patients with diabetes. Furthermore, clot structure is a potential mechanism by which diabetes increases the risk for CAD and its atherothrombotic complications. Future treatments targeting fibrin clot structure may prove beneficial to treat risk of thrombosis in patients with CAD and diabetes.
-AP than control clots [146]. These are some of the most
2
STROKE, PERIPHERAL DISEASE, AND ANEURYSM
Several other atherothrombotic diseases have been associated with abnormal clot structure. Ischemic stroke has been associated with prothrombotic clots that were slower to lyse [151]. Furthermore, the presence of compact clots was
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associated with neurological deficit, at both admission and discharge of patients with acute ischemic stroke [152]. Also fractal dimension, a measure of clot architecture, is increased in patie nts with ischemic stroke, along with an increase in the elastic modulus at gel point [153]. Not much is known about the role of clot structure in hemorrhagic stroke, or in the resolution of ischemic stroke by thrombolysis with tPA or other thrombolytics.
In patients with peripheral arterial disease (PAD), intermittent claudication was associated with less permeable clots, with thicker fibers and increased resistance to fibrinolysis [154]. Moreover, the first-degree relatives of patients with PAD showed clot structure perturbations, indicative of a genetic basis for the observed changes [155]. Interestingly, thrombi obtained from patients with PAD by thrombendarterectomy showed thicker fibrin fibers overall than those obtained by thromboaspiration in patients with MI [141]. This may be related to the local vascular differences in the concentrations of thrombin and fibrinogen, as well as differences in flow rates and shear stress between the different arteries.
Abnormal clot structure that increases the risk of thrombosis has also been found in patients with abdominal aortic aneurysm (AAA) [156]. AAA is a progressive dilatation of the aorta, situated in the abdomen between the renal arteries and the femoral bifurcation. AAA may develop over many months or years, and once it exceeds 5.5 cm (2.75-fold the normal size of the aorta), the risk of rupture and life-threatening bleeding is very high. In approximately half of patients with a larger AAA, the aneurysm contains an intraluminal thrombus. The thrombus is composed of fibrin, RBCs, platelets, and leukocytes, and it increases the hypoxic and proinflammatory stress on the underlying aneurysmal aortic wall [157]. Furthermore, patients with AAA have a significantly increased risk of other cardiovascular diseases, which persists even after surgical repair of the AAA [158]. Patients with AAA have high levels of thrombineantithrombin complex and prothrombin fragment 1þ2, indicative of elevated coagulation activation, and also D-dimer, demonstrating fibrin depo­sition and turnover [159]. The only current therapeutic option for patients with large AAA is elective surgical repair. The complexity with treatment of coagulation abnormalities in AAA is that there is a need to reduce thrombotic burden in these patients, while avoiding exacerbation of the risk of fatal bleeding in the event of an AAA rupture.
Patients with AAA show a prothrombotic clot phenotype, characterized by densely packed fibrin fibers, reduced clot porosity, and increased resistance of the clot to fibrinolysis. Evidence was provided that the changes in clot structure depend on factors other than fibrinogen and thrombin generation in these patients [156]. Macrae et al. showed that His95Arg, a common genetic polymorphism in the FXIII B-subunit, is associated with risk of AAA, indicating a possible role for FXIII in the disease [160]. Furthermore, complement has been implicated in AAA pathogenesis, with evidence for activation of all three complement pathways, the lectin [161], alternative [162], and classical [163]. The complement and coagulation pathways are very closely linked, with several key players in coagulation playing a role in complement and vice versa [164]. There is strong evidence for at least three key compleme nt factors binding to fibrinogen and/or playing a role in clot structure, i.e., C1q inhibitor [165],C3[166e168], and MASP-1 complement interactions with fibrin and clot structure that elicit or promote AAA, deserving of further attention in future studies (Table 3.1).
[169]. These data suggest a possible role for
MEDICATION AND CLOT STRUCTURE
In view of the clear associations between clot structure and thrombosis risk in both the arterial and the venous circulation, fibrin seems an attractive target for the development of novel antithrombotic drugs. However, as of this writing there are no agents that selectively target clot structure. Future studies into the mechanisms that regulate the fibrin network, its mechanical properties, and resistance to lysis are required to identify possible targets for therapeutic intervention. Notwithstanding eagerly awaited future studies into new targets, a number of current medications used in cardiovascular disease have been shown to modify clot structure and function. The effects of these drugs on clot structure are important for our understanding of the drug’s antithrombotic action and also may help to illuminate novel mechanisms of disease and its treatment.
There are few studies on the effects of oral anticoagulation with vitamin K antagonists on clot structure, as patients on oral anticoagulation are normally excluded from studies because of the effects on thrombin generation. Thrombin gen­eration and prothrombin levels have an impact on clot structure, whereby reduced thrombin concentration produces clots with fibers that are thicker and more loosely packed [55,170]. Furthermore, a 2016 study showed that low concentrations of thrombin enhance fibrin intrafibrillar structure by increasing protofibril packing and thereby enhancing the elastic prop­erties of the fibers [101]. Since vitamin K antagonists inhibit g carboxylation of FVII, FIX, FX, and prothrombin, and thereby reduce their ability to bind to negatively charged phospholipid surfaces presented by the activated platelet, the catalytic activity of these enzymes and thrombin generation are impaired. Therefore, oral anticoagulants are expected to affect clot structure by producing thicker fibers that are more loosely packed. This is indeed the case, as demonstrated by Ząbczyk et al., who showed that fibrin clot porosity increased with the INR (international normalized ratio, a standardized
 
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TABLE 3.1 Cardiovascular Diseases, Risk Factors and Clot Structure
Cardiovascular Diseases and Risk Factors Effect on Clot Structure Reference
Myocardial infarction
First-degree relatives of CAD
DVT
First-degree relatives of DVT
DVT and pulmonary embolism
Air pollution
Smoking
Type 1 and type 2 diabetes
Diabetic retinopathy
Ischemic stroke
PAD
First-degree relatives of PAD Clot structure perturbations [155]
Abdominal aortic aneurysm
Green arrows indicate increased or decreased pore size, blue arrows indicate increased or decreased fiber size, and red arrows indicate increased or decreased fibrinolysis. CAD, coronary artery disease; DVT, deep vein thrombosis; PAD, peripheral arterial disease.
Increased branching [119]
 
(Compared with patients with DVT alone) [130]
Increased number of fibers and increased maximum turbidity [139]
Increased branching, increased number of fibers [143,145,146]
   
[117,118]
[130]
[120]
[136,138]
[148]
[151,152]
[154]
[156]
measure of oral anticoagulation), if clotting was triggered with low-dose tissue factor (10 pM) [171], a situation that relies on the intrinsic thrombin-generating capacity of the plasma sample. Interestingly, if 1 IU/mL thrombin was used to trigger clotting, clot pore size did not correlate with INR, which is in agreement with the fact that the intrinsic coagulation pathway in this situation is largely bypassed by the excess thrombin added to the sample [171].
Anticoagulation with heparin has clear effects on clot structure due to the inhibition of thrombin. Clots made in the presence of therapeutic doses of heparin show larger pores and thicker fibers and are less resistant to fibrinolysis [172]. Addition of low-molecular-weight heparin had similar effects, although perhaps somewhat less pronounced than those of unfractionated heparin [173]. Protamine has been shown to reverse these effects of heparin on clot structure, but excess protamine compromises clot structure in its own right [174].
Direct thrombin inhibitors such as dabigatran or argatroban affect clot structure by producing thicker fibers and larger pores, and increase fibrinolysis through their effects on clot structure, but also through effects on TAFI [175e177]. Also rivaroxaban, a direct inhibitor of FXa, showed beneficial effects on clot structure, with larger pores and reduced resistance to fibrinolysis
[178]. Further studies are needed to investigate the effects of other direct oral anticoagulants on clot structure and function.
Aspirin has been shown to directly modify fibrin clot structure, independent of its effects on platelet activation. Acetylsalicylic acid beneficially changed clot structure by increasing clot porosity [175,179]. Interestingly, low-dose aspirin (75 mg/day) showed increased beneficial effects on clot structure compared with a high dose (320 mg/day) [180] . Aspirin also reduced resistance of the clot to fibrinolysis [181]. Studies in cells expressing human fibrinogen showed that aspirin directly modifies fibrinogen, through acetylation of lysine residues, which leads to clots that are more permeable, less stiff, and easier to lyse [182]. Altogether, these studies indicate a mechanism by which aspirin acetylates lysine residues in fibrinogen, which then have an impact on clot structure and its stability. These actions of aspirin contribute to the antithrombotic effect of this commonly used prophylactic drug for the treatment of atherothrombotic diseases.
Other commonly prescribed drugs in atherothrombotic diseases such as statins have also been associated with beneficial effects on clot structure. Undas et al. showed that simvastatin and atorvastatin were associated with increased clot pore size, increased fiber thickness, and reduced resistance to fibrinolysis in patients with CAD [183]. Effects of simvastatin on clot structure were found even if C-reactive protein remained unaltered, and were independent of the effects of the drug on cholesterol levels. Fenofibrate, which controls lipids via a different mechanism, also had beneficial effects on clot structure. Furthermore, the angiotensin-converting enzyme inhibitor quinapril also showed modest beneficial effects on clot structure
[183]. These findings suggest important pleiotropic effects of statins and other common cardiovascular drugs, which may
contribute to the overall antithrombotic effects of these drugs and may indicate novel mechanisms that regulate clot structure (Table 3.2).
Fibrin Clot Structure and Function: A Novel Risk Factor for Arterial and Venous Thrombosis Chapter | 3 43
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TABLE 3.2 Common Cardiovascular Medications and Clot Structure
Medication Effect on Clot Structure Reference
Heparin (therapeutic doses)
Heparin (low molecular weight)
Protamine
Dabigatran (direct thrombin inhibitor)
Argatroban (direct thrombin inhibitor)
Rivaroxaban (direct factor Xa inhibitor)
Aspirin (low dose)
Simvastatin
Atorvastatin
Fenofibrate
Green arrows indicate increased or decreased pore size, blue arrows indicate increased or decreased fiber size, and red arrows indicate increased or decreased fibrinolysis. TAFI, thrombin-activatable fibrinolysis inhibitor.
(Less pronounced than unfractionated heparin) [173]
(Reverses the effects of heparin) [174]
Reduced TAFI activation [176]
Reduced TAFI activation [175,177]
Decreased fiber stiffness [175,179e182]
[172]
[178]
[183]
[183]
[183]
CONCLUSIONS
There is compelling evidence for a role of abnormal fibrin clot structure in thrombosis and cardiovascular disease. When produced by the coagulation system, fibrin polymerizes through a remarkable mechanism into a three-dimensional scaffold that supports the blood clot. Fibrin is stabilized by FXIIIa and orchestrates its own breakdown by the fibrinolytic system. Furthermore, fibrin has remarkable mechanical properties and is one of the most elastic biological polymers. Studies demonstrate that the structure of the fibrin network is a major determinant of its stability, resistance to fibrinolysis, and elastic characteristics under flow and shear stress. Consistent associations between clot structure and thrombosis in different vascular systems have been found. Compact clots, with increased numbers of fibers and small pores associate with increased risk for CAD, MI, stroke, venous thrombosis, PAD, diabetes, and abdominal aneurysms. Cardiovascular risk factors have detrimental effects on clot structure, while anticoagulation and cardiovascular medication can help to reverse these detrimental effects. Future developments of specific medicines targeting clot structure are eagerly awaited to assess their potential benefit in the treatment of thrombotic diseases.
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