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Table of contents
- The Weed Handbook Volume 2
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- Lab-on-a-Chip Technology (Vol. 2): Biomolecular Separation and Analysis
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Reversibility of tetraethyl pyrophosphate inhibition. Reactivation of alkyl phosphate-inhibited enzyme. Discus s. Acetyl- cholinesterase. Mechanism of the catalysis of acylation reactions. A powerful Deactivator of alkyd phosphate-inhibited acetylchol inesterase. Acta 18 , It is a chorine st era se deactivator and was tested alone and with anticholinesterase chemicals on human volun- teers at Edgewood.
It is manufactured by Ayerst Laboratories, approved by the F1 A, and wide1 y used in the United States as an antidote to alleviate the acute responses to poisoning by organo- phosphorus insecticides and other anticholinesterase chemicals. The latter, referred to as peeudocholinesterase, is a soluble enzyme that is synthesized in the liver and circulates in the plasma. Acetylcholine is the optimal substrate for acetylcholinesterase, whereas butyrY1choline is the optimal substrate for butyrylcholin- esterase.
Acetylcholinesterase can be extracted from tissues to various extents by saline buf fers, but often a detergent is necessary to solubi lize the larger part of the enzyme. Even a single tie sue usually yields a number of enzyme forms with different sedimentation coefficients. Although it contains a number of catal ytic subuni ts, there are no homotropic allosteric ef facts, nor do there appear to be any physiologic regulators of i ts activity. Acetylcholinesterase is sub] ect to substrate inhibition at high concentrations, but Michaelis kinetics are observed at lower concen- trations, because the substrate constant and the Michaelis constant differ by a factor of Most of the kinetic work has been done with the saline-extracted 1iS enzyme from electric eel and the detergent-extracted 6S enzyme from erythro- cytes.
The former is a tetramer derived f ram the net ive enzyme by the action of proteases; the latter is a dimer. The catalytic constant, kCat, refers to the overall decomposition of the enzyme intermediate E. S, E'. The enzymic nucleophile is the hydroxyl group of a specific serine residue. The mechanisms of both acetyl- at ion and deacetylat ion probably involve the formation of tetrahedral intermediates.
The active site contains an imidazole group that functions first as a general base and than as a genera' acid in each step and whose ionization determines in part the pH variation of enzyme activity. Details of enzyme-substrate and enzyme-inhibi tor reactions were described in Volume 1 p.
In summary, organophosphate esters wi th good leaving groups phosphorylate the enzyme by a mechanism similar to acetylation of the enzyme. This was recognized early in the quest for a practical reac- t tvating agent when choline was found to be a Deactivator. Because a hydroxyl group in an alcohol is a weak nucleophile at neutral pH, the capacity of choline to function as a Deactivator must be a con- sequence of its molecular complementarily with the enzyme and the increased acidity of the alcohol. The idea arose of f inding a rigid structure that would include a quaternary ammonium group and an acidic nucleophile that would be complementary with the phospho- rylated enzyme ire such a way that the nucleophilic oxygen would be positioned close to the elec trophilic phosphorus atom.
The reaction of 2-PAM with the phosphorylated enzyme is shown in the following diagram. Thus, ache biochemical characteristics affecting the reacti- vation of cholinesterase are complex and only partially understood. Knowledge of the kinetics of the various rate-determining processes is essential to the understanding of the inhibitox-reactivation process. The basic reaction believed to occur in the inhibition of acetylcholinesterase by some alkylphosphates is shown in Reaction 1. The reactivation or the inhibited enzyme can be achieved with selected oximes such as 2-PAM , as shown in Reaction 2.
Under some conditions--e. Reprinted with permission from Hackley et al. Reaction with a further molecule of GB would form the diphosphonylated compound. The inhibitory potency of phosphonylated oxides has been estimated from their effects on the course of the reactivation of phosphon;lated AChE when they were formed during the reaction. A prac tical limi tat ion on the usefulness of reac tivators comes about because cholinesterase inhibited by organophosphates undergoes a secondary reac tion termed "aging.
In brief an alkyd group is cleaved from the phosphorylated enzyme, leaving an "aged" enzyme that is resistant to reactivation by the oxime. This section touches on the highlights and restates the material from another viewpoint. This property allows them to function as nucleo- philes and displace organophosphate moieties from inhibited acetyl- cholinesterase. It also makes them vulnerable to decomposition by other mechanisms in the body. The oximes contain a quaternary ammonium group that contributes to their acidity and their strong binding to the inhibited enzyme. This appears to be a key struc tura1 element in known Deactivators, but it tends to make them poorly soluble in lipids.
Practically, this means that the drugs are slowly absorbed from the gastrointes- tinal tract, have dif ficulty entering the brain, do not easily enter hepatic cells to be biotransformed, and are not reabsorbed from the renal tubular urine. The overall absorp- tion rate is lower than the elimination rate ; that is, absorption is the rate-limiting step. Hence, blood concentrations are always low after oral administration, arid substantial blood concentrations are dif ficult to produce or maintain when the drug is given by this route.
Some anticholinesterases may also facilitate the entry of oximes into the central nervous system.grupoavigase.com/includes/399/35-jugar-al-golf.php
The Weed Handbook Volume 2
Investigators have therefore suggested that 2-PAM might be secreted into the urine. They imply dif ferent mecha- nisms of renal handling. Swartz and Sidell showed that in human beings both chemical groups are important. The more important of the two actions is the act ive secretion of the compound by the organic-base-secreting system of the kidney. This process can be slowed by one-third by coadministering high doses of thiamine. The net clearance of 2-PA approaches that of PAH, but is not as great; hence there may be some simultaneous active reabsorption of the material. The process here is complicated, in that the oxime has a pKa of 7.
Because of this, it is dif f icult to accumulate and maintain a substantial concentration of material. The smaller volume of distribution and slower clearance imply dif ferent distribution and handllog of the two oximes. These tables list only signif icant f indings. Although Hopff and Waser54 have listed mechanisms of action whereby reactivators of inhibited cholinesterase could be harmful, the real cause of most of the observed adverse ef fects is obscure.
One exception is the slight inhibition of cholinesterase caused by single dose of TMB-4 dibromide form. Many last only a few minutes; almost all disappear within a few hours after a single dose. A num- ber of investigations, especially those concerning metabolism or pharmacokinetics revealed no adverse effects, even though they were looked for. However, under identical conditions, 2-PAM chloride was somewhat more injurious than saline. Taste bitter, metallic 0. The investigators considered the icterus similar to that pro- duced by chlorpromazine. Ingestion of tablets of 2-PAM or related salts is often accompanied by transient diarrhea and cramps.
The full explanation is not known. The ef feet depends on concentration and is reversible. Nor are the long-term ef fects of such chronic administration and consequent fibrosis known. However, single doses, even oral' y, have not beer reported to produce tissue changes. These ef fects may be classified as hypertension characterized by moderate increased systolic and diastolic pressure with hypertension fold owed by hypotension, and ECG changes. In general, these effects were seen when large doses of the cholinesterase Deactivators were given intraven- ously or intramuscularly or af ter repetitive oral doses.
At least three classes of action have been attributed to the effects of altered calcium meta- bolism on autonomic ganglia. These results contradict the previous find- ing that phenoxybenzamine, an adrenergic blocking drug, decreased the press or effect of 2-PAM. Conflicting results have been reported in regard to the involve- ment of beta receptors in the mechanism of the isotropic effect of 2-PAM. It was concluded that the direct stimulation of the myocar- dium by 2-PAM that could be blocked by dichioroisoproterenol DCI was responsible for the locrease in blood pressure.
The studies reported above imp' icated calcium movement in the mechanism. Studies of the efflux of 45Ca by stimulated rabbit atria have characterized three calcium pools. Phase I may represent extra- cellular washout of the 45Ca that binds to the surface of muscle membrane arid is characterized by a high rate constant. Phase II may represent loosely bound calcium present in cell membrane and calcium red eased at the sarcoplasmic reticulum.
Calcium in this pool is directly related to contractility. Recent study has shown that the storage or release of calcium at the sarcoplasmic reticulum and other loosely bound calcium sites cell membrane that are involved in muscle contractility can be directly affected by 2-PAM. It has been postulated that 2-PAM exerts its cardiac action in rabbit atria through its alteration of calcium metabolism. The relaxation phase of skeletal muscle contraction seems to be directly affected by the sarcoplasmic reticulum because of its ability to sequester calcium actively. This contraction is later reduced by the increased calcium-sequestering activity of the sarcoplasmic reti- culum.
Thus, 2-PAM can affect this process by decreasing the rate of calcium uptake by the sarcoplasmic reticulum, which results in increasing the time required to reduce the calcium concentration enough to allow relaxation to take place. This was demonstrated by the increase in the relaxation phase.
The changes in gang- lionic function induced by 2-PAM will be reflected in sympathetic and parasympathetic activity, which may cause changes in cardiovascular functions. These are di scussed further in the next section.
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Similar effects were seen on isolated rabbit intestine and atriumi5 and on chicken muscle. No correlations were found, however, between atropine- like or curare-like actions of these compounds and their protective effects against organophosphate poisoning. Nicotinic Receptor Interactions. Af ter producing an initial. Excitatory muscarinic effects, such as temporary stimulation of salivation and stimulation of intes- tinal peristalsis, were seen with 2-PAM.
At low concentrations, neither compound affected normal intestinal peristalsis, but they did block peristalsis caused by lucreased vagal stimulation. There was transient hypotension due to block of ganglionic tranamission. None of the compounds or their in viva intermediates is likely to bind covalently with DNA and other macromolecules.
Other ways of binding with DNA, such as intercalation, cannot be ruled out. There is some membrane transport, albeit limited. It is not possible, therefore, to conclude that they are not mutagens, teratogens, or carcinogens. However, pralidoxime is an FDA-approved marketed drug in the U. That poisoning by diethoxy compounds can be treatedO'effectively by oximes is nearly universally agreed.
However, oxime treatment of patients poisoned by clime thoxy compounds has been beneficial in many cases. More reports deal with 2-PAM than with other oximes in the treat- ment of poisoned patients. High dosages have been used in patients who survived without sequelae. Milthers et al. Gitelson et al. Hiraki et al. However, no chronic studies were found. These findings certainly raise questions about the long-term use of these compounds in humans.
Another find- ing that needs further investigation, substantiation, and extension is ache apparent production of muscle necrosis from intramuscular in j action of 2-PAMi, 9 5 and P2S. Oral administration of cholinest erase reactlvators for up to 17 wk pro- duced erosion of the mucosa along ridges of the rugae in the fundus of the stomach and fibrosis in vicinities of the cardiac and pyloric sphincters.
The reports of physicians' examinations and physical findings were generally not included. Volunteers were identified by number. The procedures were described fully in Volume 1. In most cases, the analysis was based on summaries of drug admini s "rations prepared by a consultant to the Panel. In some instances, the compounds were given before or after anticholinesterase compounds or in conjunction with other drugs; thus, some of the results shown here were also presented in Volume 1.
The data on TMB-4 Table are difficult to interpret, because, in the instances on which clinical data are available, other potent drugs were given as well. Studies conducted: plasma and urine content, renal clearance, CNS ef fects, blood pressure, and in some cases, pupil size and number facility. Test conditions: heat and exercise in some tests.
Records on 79 subjects selected, on basis of high dose or high frequency of administration, from records on subjects tested. Results were in normal range after transitory manifestations. Nerve agent resulted in decrease in RBC cholinesterase content. Records on 75 of 95 subjects tested were summarized; each subject was tested once with P2S. In all but two instances described below , moderate effects disappeared within 24 h. He had minor symp tome, but in 12 h became anxious, restless, and agitated. He was transferred to Walter Reed Hospital. The discharge diagnosis from Walter Reed Hospital in specified acute, moderate anxiety reaction manifested by restless- ness, anxiety, agitation, and hysterical reaction.
He has experi- enced further problems requiring inpatient and outpatient psychi- atric care. This subject was also noted in Volume 1 p. He regained consciousness within 5 mini he had bitten his tongue.
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He was initially lethargic, but felt well 10 h later. He was trans- ferred to Walter Reed Hospital, but followup records are not avail- able. The only symptom on those occasions was local pain at the injection site. In seminary, with the possible exception of those two cases, the records contained no evidence of delayed or persistent effects after administration of the chorine at erase Deactivators. Such data cannot, however, address the issue of long-term effects or delayed sequelae. Albanus, L.
Lab-on-a-Chip Technology (Vol. 2): Biomolecular Separation and Analysis
The toxicity of some cholinesterase reactivating oximes. Aldridge, W. Enzyme Inhibitors as Substrates. Frontiers of Biology, Volume Malathion poisoning treated with protopam. Protopam R chloride Pralidoxime chloride. Professional brochure. Barckow, D.
English Summary 6. Barkman, R. Barr, A. Further experience in the treatment of severe organic phosphate poisoning. Poisoning by antic ho1 inesterase organic phosphates: Its significance in anaesthesia. Ame SOC. I8: , abet. Pharmacologist 4: , Heidelberg: Springer-Veriag Berlin, Bell, A. Cases of absorption and poisoning by the pesticide "Phosdrin. This difference remained statistically significant when controlled for CNS bleeds and administration of vitamin K.
Introduction: In many hospitals, off-hours emergency department ED radiographs are not read by a radiologist until the following morning and are instead interpreted by the emergency physician EP at the time of service. Studies have found conflicting results regarding the radiographic interpretation discrepancies between EPs and trained radiologists.
The aim of this study was to identify the number of radiologic interpretation discrepancies between EPs and radiologists in a community ED setting. We recorded the type of radiograph obtained for each patient. We also recorded the total number of radiographs formally interpreted by EPs during the prescribed time-frame to determine overall agreement between EPs and radiologists.
Results: There were discrepancies out of 16, EP reads, indicating Patients averaged The majority of discrepancies were minor with Only 1.
A small number of discrepancies, 0. Grade 4 discrepancies accounted for two of the 16, total reads, equivalent to 0. A slight disagreement in finding between EP and radiologist accounted for 8. Conclusion: Results suggest that plain radiographic studies can be interpreted by EPs with a very low incidence of clinically significant discrepancies when compared to the radiologist interpretation. Due to rare though significant discrepancies, radiologist interpretation should be performed when available.
Further studies are needed to determine the generalizability of this study to EDs with differing volume, patient population, acuity, and physician training. Introduction: Older patients frequently present to the emergency department ED with nonspecific complaints NSC , such as generalized weakness. They are at risk of adverse outcomes, and early risk stratification is crucial.
Triage using Emergency Severity Index ESI is reliable and valid, but older patients are prone to undertriage, most often at decision point D. The aim of this study was to assess the predictive power of additional clinical parameters in NSC patients. Physicians scored the coherence of history and their first impression. AUCs increased to 0. Maximal AUC was 0. This editorial addresses concerns of program directors that the new program requirements by the ACGME will adversely affect emergency medicine faculty and resident training.
In this editorial, we address the specific concerns of program directors in emergency medicine. Methods: Faculty who were present for the 10 consecutive study years at an allopathic emergency medicine residency retrospectively evaluated residents on their overall performance, medical knowledge, and interpersonal skills. Residency graduates were surveyed regarding their current position, hours of clinical practice, academic, teaching and leadership roles, and publications. We compared match position to performance using graphical techniques as the primary form of analysis.
Results: Ten faculty evaluated the residents who graduated from the program during these 10 years by class year. Eighty-four residents responded to the survey. In general, we found little correlation between NRMP rank and faculty rank of resident performance.
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There was also little correlation between position in the NRMP rank list and the probability of having an academic career, publishing research, or having a teaching or leadership role. Conclusion: We found that the position on our NRMP rank list was of little value in predicting which residents would do best in residency or take on academic or leadership roles once graduated. Residencies should evaluate the processes they use to generate their rank list to determine whether the ranking process is sufficiently predictive to warrant the effort expended. Introduction: Canadian emergency departments ED are struggling to provide timely emergency care.
Very few studies have assessed attempts to improve ED patient flow in the rural context. Methods: We implemented a set of commonly used methods for increasing ED efficiency with an innovative approach over 45 months. Our intervention involved seven parts comprised of an external review, Lean training, fast track implementation, patient-centeredness approach, door-to-doctor approach, performance reporting, and an action-based surge capacity protocol.
We also performed an interrupted time series ITS analysis. Results: During the study period, 80, people visited the ED. PIA decreased from The change over time decreased by 2. Conclusion: SurgeCon improved the key wait-time metrics in a rural ED in a country where average wait times continue to rise. The SurgeCon platform has the potential to improve ED efficiency in community hospitals with limited resources. Introduction: Emergency department ED patient care often hinges on the result of a diagnostic test.
Frequently there is a lag time between a test result becoming available for review and physician decision-making or disposition based on that result. We implemented a system that electronically alerts ED providers when test results are available for review via a smartphone- and smartwatch- push notification. We hypothesized this would reduce the time from result to clinical decision-making. Methods: We retrospectively assessed the impact of the implementation of a push notification system at three EDs on time-to-disposition or time-to-follow-up order in six clinical scenarios of interest: chest radiograph CXR to disposition, basic metabolic panel BMP to disposition, urinalysis UA to disposition, respiratory pathogen panel RPP to disposition, hemoglobin Hb to blood transfusion order, and abnormal D-dimer to computed tomography pulmonary angiography CTPA order.
All ED patients during a one-year period of push-notification availability were included in the study. The primary outcome was median time in each scenario from result availability to either disposition order or defined follow-up order. The secondary outcome was the overall usage rate of the opt-in push notification system by providers. Results: During the study period there were push notifications from ED encounters 2. Conclusion: Implementation of a push notification system for test result availability in the ED was associated with a decrease in lag time between test result and physician decision-making in the examined clinical scenarios.
Push notifications were used in only a minority of ED patient encounters. Introduction: Patients discharged from the emergency department ED may encounter difficulty finding transportation home, increasing length of stay and ED crowding. We sought to determine the preferences of patients discharged from the ED with regard to their transportation home, and their awareness and past use of ridesharing services such as Lyft and Uber.
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Methods: We performed a prospective, survey-based study during a five-month period at a university-associated ED and Level I trauma center serving an urban area. Subjects were adult patients who were about to be discharged from the ED. We excluded patients requiring ambulance transport home. However, we did detect age, education and income differences regarding awareness, but only age and education differences for past use. Logistic regression showed awareness and past use decreased with increasing patient age, but correlated positively with increasing education and income.
Half the subjects felt their medical insurance should pay for their transportation, whereas roughly one-third felt ED staff should pay for it. Conclusion: Patients most commonly prefer to be driven home by a family member or friend after discharge from the ED. Patients who are older, have limited income, and are less educated are less likely to be aware of or have previously used ridesharing services. ED staff may assist these patients by hailing ridesharing services for them at time of discharge.